\r\n\tPainful attack commonly occurs in the big toe, the ankle joint, the achilles tendon, the knee joint and the wrist joint. Sometimes gouty nodules can occur even in the auricle. The occurance of urinary stones is a common complication. Administration of anti-inflammatory drugs including steroid or joint injection of steroid are used for the treatment. \r\n\tGout often occurs in patients with renal impairment, we should check renal function before the treatment. \r\n\tIt requires time to improve serum uric acid level and to disappear gout attack, and care of the patients might continue for their lifetime. \r\n\tOur goal is to provide effective treatments and prevention methods.
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1. Introduction
Buildings within urban areas today already communicate to a certain extent. Communication is inherent within their design, as a building’s architect must create an environment that “speaks” to its surrounding context of other buildings through its design. In other words, as a design is being realized, it is responding to its future surrounding context as its architect imagines it into being. Yet, once constructed, the design is often static, as it stands without adapting to the ever-changing context that surrounds it.
At times, such buildings work hard to meet certain needs and goals, but because they do not adapt to changing demands and desires, they remain limited. Also, there are times where other buildings within an urban area may conflict with the way a particular building reaches certain individual or collective goals. In this case, another building can actually undo the hard work a different particular building has been designed to do.
Thus, the way buildings communicate today is often fragmented, contradictory, and static. This is why it is important to better understand how buildings can use communication in positive ways that strengthen their design and performance. By thinking and designing consciously about the inter-building communication network within an urban area, new goals can be achieved in dynamic ways. After all, communication between architecture is more than just about making a statement; it becomes more about designing for consistent optimization for learning—where a design, once built, improves over time as it communicates.
This chapter serves as a guide on how to design a framework for inter-building communication by taking a biomimetic approach that parallels eye accommodation (eye focusing) and stereopsis in vision to how buildings can communicate to focus and harness performance. In simplest terms, the human eyes work together as a team that serves as a model for how to design inter-communicating buildings. This framework allows building communication to advance greatly as it would no longer be fragmented, contradictory, and static. Instead, communication between buildings would be convergent, collaborative, and adaptive.
For buildings to communicate successfully, they must pull from the power of adaptive sensory environments. These buildings are prime for an urban communication network since they are sensory designed environments that engage with occupants, other buildings, and surrounding contexts, in dynamic and adaptive ways. For this reason, inter-building communication for adaptive sensory environments holds the most promise for positive benefit at city-wide and individual levels.
This chapter demonstrates why such inter-building communication is important, as well as illustrating how, by learning from the design of the human eyes, it can be designed to work for maximum value at all scales.
Built-environments are gaining in their ability to not only interact with occupants and their surrounding context, but to also adapt. This occurs as new developments in sensor technology become integrated along with emerging design processes. Together, they yield environments that change in real time to meet occupant short-term needs and longer-term goals [1].
Within adaptive sensory environments, static and transient materials work together tuning to occupants, supporting them both directly and indirectly. This stems from the occupant-centered approach to design, which holds sensory design as a guiding principle. By adjusting a building’s characteristics moment-by-moment, it becomes possible to not only meet a one-time occupant need but also meet ongoing occupant needs, which help achieve longer-term goals through processes such as learning.
Adaptive sensory environments bring great benefit to occupants because they allow for greater personalization through real-time tuning. This creates built-environments that do not just “house” function, but proactively work to “foster” function. For example, this is the difference between a hospital that contains healing, versus a hospital that nurtures healing [1]. In other words, the hospital environment becomes a participant of the “healing team.”
In order for such adaptive buildings to function optimally, they engage in a two-way dialog with occupants. Thus, as occupants’ needs and goals change and grow, the architectural environment does so as well. Each teaches and learns from the other.
In efforts to optimize such adaptive sensory environments, it is necessary to understand how communication between such buildings affects both the occupants that inhabit them as well as their surrounding natural environment. In this sense, adaptive buildings act as a “bridge” between occupants and their natural surrounding context. To do this, it is advantageous for such buildings to communicate with one another.
3. Inter-building communication for optimization
An inter-building communication network can work to help such adaptive environments cooperate and collaborate with each other. By pulling from the best of what each building does, regardless of the building type, other buildings can learn and use what works to help both their occupants and their natural surroundings. And this can all happen in real time, moment-by-moment.
When adaptive sensory environments communicate with one another, they are able to grasp a “bigger picture” of not only what their occupant needs, but also of how they can help their occupants. Thus, the boundary of a particular building may shift as its occupant and their needs shift as well. For example, a hospital may learn from its patient’s home environment about how their hospital room should function regarding light levels, daily habits, or ideal temperatures within which this particular occupant can thrive.
Inter-building communication between adaptive sensory environments helps occupants both individually and collectively. Yes, the adaptive architecture tunes to a specific occupant’s needs and goals, but it also can coordinate and pull from the collective needs and goals of a group, city, or culture. This allows for a type of “teamwork” to occur where the built-environment works as a conductor, helping to pull the best from occupants, while also coordinating their efforts to meet a greater good that benefits all. Thus, inter-building communication allows occupants that are located in different places at different times to work together.
It is important to pull from the power of collective behaviors because larger positive impact can be achieved for certain goals. For example, one person that is engaging in greener behaviors to benefit the natural environment will have positive effect, but when an entire collective urban area engages in greener behaviors in a coordinated manner, a much larger positive impact will benefit the natural environment.
4. Objectives for the design of a communication framework
Inter-building communication matters, but so does the way in which this communication happens. It is not simply enough to design buildings that exchange information interactively. These buildings must also use information to help them adapt to the needs of their occupants and ever-changing surrounding natural context. Yet, what should buildings do with such information? What is their objective and goal?
With an adaptable inter-building communication framework, built-environments can learn from each other. By better understanding and incorporating what works, and what does not work with occupants and surrounding natural contexts, adaptive sensory environments can adapt and improve in entirely new ways. For example, a hospital building can learn how to better personalize its healing environments by interpreting information from a home. Conversely, a home can interpret information from a hospital to help a patient recover from illness post hospital stay.
Multiple simultaneous dialogs are critical for the successful design of an inter-building communication framework. Such built-environments must not only communicate with each other, but also must exchange information with occupants and the surrounding natural environment. In reality, adaptive sensory environments become a “bridge” that adaptively re-presents nature to occupants in harmonious, beautiful, and beneficial ways.
To optimize the learning and subsequent adaptation of sensory environments, it is important for designers to engage in a “growth mindset” during design [2]. This means that building occupants, and their buildings, strive to grow and change by learning from successes as well as failures. Thus, as buildings exchange information, it becomes important for each to learn from the other by not simply replicating what the other building is doing, but by adapting their architectural behavior to their own functional needs for occupants. In other words, a hospital building that receives information from a home is not to behave exactly as a home would behave, but instead can interpret the information to improve upon its own hospital behavior. For example, a hospital can synchronize a postoperative room for improved patient sleep, but it can do this by learning specifically how to personalize the sleep environment per particular patient by learning from their home environment sleep habits.
By achieving an inter-building communication framework, it becomes possible for buildings, the natural environment, and occupants to all benefit in unique ways. For example, by coordinating efforts, a “network” of communicating buildings can pull from the power of the occupant collective to promote, sustain, and enhance green behaviors. This becomes even more empowering as buildings exchange information to work together as a team, instead of having each building work in isolation. With such inter-building communication framework designs, advancements can help to mitigate the negative effects of a changing climate.
5. Learning from human eye accommodation
The human eye holds principles by which to better understand how buildings can work together through the exchange and interpretation of information. By uncovering how the human eye focuses, a biomimetic model forms. Eye accommodation, or eye focusing, allows the eye to adapt to ever-changing object distances with the goal of seeing clearly. Similarly, the buildings that comprise a city must adapt to meet the ever-changing goals of its citizens. But how can they coordinate efforts to change their “focus” as citizen needs and goals change in real time?
Within the human eye, there are muscles that simultaneously move to allow for the expansion and contraction of the eye’s lens. In essence, this muscle behavior allows for the harnessing of the lens’ power, which is to focus [3]. In following this model, one can see that buildings are akin to the eye muscles, while occupants are akin to the eye lens. In other words, adaptive sensory environments can adapt to harness and enhance the power of their occupants. This can help them to coordinate efforts and achieve milestones and goals not previously possible.
Communication between buildings can foster coordination and collaboration for learning and subsequent improvement. It is important to note that adaptive sensory environments, behaving in a muscle-like manner, are able to help boost occupant efforts through both teamwork and learning. The environment can help occupants with better collaboration, which in turn, can improve learning and overall goal attainment. For example, if city citizens want to engage in greener behaviors, then communicating buildings can target and focus upon different and complementary goals including increased recycling, reduced energy consumption, and less unnecessary waste. The inter-communicating buildings act as muscles that help empower the effort of city citizens to not only support their efforts, but to also coordinate and reward them.
6. Learning from stereopsis for 3D vision
The human eyes provide an excellent example and model for how adaptive sensory buildings can communicate with one another. By studying and decoding how the biological system of the human eyes function together, architects and urban planners can expand their thinking about how to design beyond the typical boundaries within architectural and urban conditions. In particular, the eyes model how a design can work by continuously focusing on visual targets that are ever-changing, much like the real-world dynamics within which architecture and urban environments must adapt. It is by using the way human eyes coordinate as a biomimetic model that a “communication bridge” can be developed to allow for the “sensemaking” of data flowing from and to buildings so they can communicate. Just as muscles help the human eyes to focus vision, the communication bridge helps buildings to focus design behavior.
One human eye that focuses is quite powerful, but two eyes that focus simultaneously unlock the power of three-dimensional vision. Without both eyes focusing, depth of vision is not as evident. Thus, as buildings engage in communication with each other, just as two eyes do to create stereopsis; an entirely new third behavior is born. In other words, one eye focuses on an object, but both eyes can focus to see that object in perspective with depth. The same becomes true with the design of inter-communicating adaptive sensory environments. As buildings communicate, entirely new third behaviors are born.
Without inter-building communication, environments can work against one another. One building can literally undo what another has worked so hard to accomplish within a city. Similarly, a lack of stereopsis where both the eyes are not communicating with the brain as a team, can result in double vision; thus, detracting from the ultimate goal of the eyes, which is to see perspective clearly [4]. For this reason, when designers can learn from the way stereopsis works, they can begin to create urban inter-communicating environments that work together to unleash new collective building behaviors. Hence, adaptive sensory environments create a type of compound effect as can be seen in Figure 1.
Figure 1.
The compound effect of collective behaviors.
In Figure 1, Building A and Building B communicate through a real-time collaboration where environmental features learn from each other to optimize building performance for goal-attainment. In essence, communicating buildings can “tune” their behaviors to guide, teach, and reward occupants as they strive to meet their goals, whether they are for an individual or for the collective. As both buildings work together to optimize their performance, a compound effect emerges as focused behaviors generate smarter citizen decision-making that positively impacts entire urban areas. Thus, a two-way dialog between buildings and occupants becomes critical as each does their part to meet a particular goal.
7. Inter-building communication to target goals in real time
Buildings that learn from each other by cooperating and collaborating make a city more nimble in responding to needs. The third behavior formed as buildings cooperate with each other means that the built-environment is not working against itself. Instead, it is harnessing its resources to yield a cumulative positive impact. In addition, as needs and goals change over time, this third behavior can be focused upon different targets because adaptive sensory buildings can change and “tune” in real time.
For example, if a city experiences a drought, citizens can work together to conserve water, “bridged” and supported by the adaptive sensory buildings. As these buildings communicate, they will nimbly optimize the way they guide, enhance, and reward city citizens. Then, as extreme weather conditions change, the city can adapt to mitigate new challenges, as these become new goals. Just as the human eyes are continuously focusing on different objects at different distances, the adaptive sensory buildings that communicate with one another can continuously adjust their aim as they target different needs and goals over time.
Inter-building communication amplifies and empowers collective occupant behaviors in real time. By using emerging technologies, such buildings can utilize social media, gamification, and even website design principles to optimize themselves with interpreted information from other buildings. These digital “doors” help adaptive sensory environments to have dialog with each other, with their occupants, and with the surrounding natural context. For example, information can be interpreted by a hospital through social media created by an individual or the collective, by recognizing winning or losing design behaviors through gamification, or by analyzing data regarding the design of different postoperative recovery rooms to see which configurations work best for a particular situation.
Thus, communication that is coordinated and collaborative is the linchpin to “focusing” or meeting ever-changing needs and goals. This becomes quite important as an overarching equilibrium point to keep the planet and occupants healthy is a primary aim, but the way in which to achieve health for the planet and occupants changes over time. Adaptability of an entire city can be harnessed through its buildings by pulling from the power of both the individual and the collective.
In Figure 2, one can see how buildings can work to exchange information that helps them to create a third behavior—where both occupants and buildings are working synergistically to focus on different urban needs and goals. As Building A and Building B engage with one another, the way they communicate and interpret information changes as goals shift over time. In other words, communicating buildings can collaborate in real time to meet simultaneous goals and/or shifting goals set by citizens. Buildings act as eye muscles that help occupants to focus their behaviors toward helping them reach their desired goals at micro- and macro-scales. Thus, through inter-building communication, it becomes possible to have urban buildings work both independently and collectively for the good of both the citizen and the planet. All of this becomes possible with inter-communicating adaptive sensory environments.
Figure 2.
System design using the human eye as a model.
8. Evoking beneficial occupant behaviors
Buildings that communicate can engage individuals to contribute beneficially through collective behaviors that achieve urban goals. Adaptive sensory environments that exchange information create a third behavior that is a hybrid behavior, which can tackle goals differently than if individual buildings never communicated. The benefit of this resides in the way such buildings can learn from each other—through designed competition, by applying tested design methods, or by learning directly from the preferences of city citizens.
For instance, inter-building communication evokes greener behavior in citizens, and thus, brings impact that is more positive to the planet. As weather has potential to become extreme, citizens need to coordinate their efforts to mitigate negative weather effects. An inter-building communication framework provides the amplifier by which citizens can pull individual efforts together to make a real difference.
An adaptive sensory environment can help its building occupants to engage in greener behaviors like recycling, using less energy, and walking or cycling instead of driving an automobile. Using gamification, it becomes possible to not only guide, enhance, and reward citizens for their greener behaviors, but it also becomes possible for the whole urban area to optimize itself as each building can adapt to incorporate design integrations that are successfully working in other buildings. Thus, the city is made up of self-optimizing buildings that work together, and not in isolation—as they learn through testing, correction, and adaptation. Citizens benefit as their usage of such buildings impacts what and how environments in such a city get optimized.
9. Creating an inter-building “communication bridge”
Creating an inter-building “communication bridge” is like seeing the city as a brain that flexes its muscles (the buildings) to focus its lenses (the occupants) to meet more collective needs faster and with higher quality. In essence, a city can mirror the plasticity of the human brain as it adjusts and changes over time to meet citizen needs and goals. The inter-building communication framework enhances such plasticity, as the third behaviors resulting from collaborating buildings allow for new kinds of evolutionary growth.
As a city works to optimize itself for its citizens, it must pull from its best features to uplift those weaker ones. As adaptive sensory environments communicate with each other, new ways in which to collaborate surface and city optimization can turn into faster and more profound evolution.
A framework for how such a city-wide inter-building communication system can be realized arises with the proliferation of nanotechnology, ubiquitous computing, wearables, micro-architectures, and the interconnection of everyday things. These sensing and data collecting devices can relay real-time data into the communication bridge. Cities can use one or multiple bridges by which to facilitate inter-building collaboration. By interpreting and correlating in-flowing data through pattern-detection methods, a “sensemaking” action occurs at the bridge, by which to make optimal city-wide decisions. From these data, building actuators can interact and engage with their occupants at more micro-levels. Thus, the communication bridge makes inter-building communication and collaboration possible (Figure 3).
Figure 3.
Inter-building communication bridge.
An example of present-day technology that would help such a communication bridge to be realized can be seen in the Hexagon Geospatial Smart Maps. These smart maps create interfaces by which to visualize and assess quality and incidents of aspects like urban or building infrastructure and resources through a real-time dashboard that provides insights on conditions as they occur. Such maps have been used for the 2016 Brazil Olympics to help with real-time safety in Rio de Janeiro where the smart map interface allowed for 360-degree views through a digital model of the real Olympic city along with the map interface by which to monitor and analyze incident place, time, and patterns. Again, all of this was key to help keep safety throughout the Olympic city [5]. Smart maps are also being used in the Netherlands to help assess and make decisions about infrastructure that is so critical in this location where road traffic, weather patterns, and water infrastructure must be monitored and evaluated continuously [6].
Smart maps are an example of how real-time data can be collected through sensors, analyzed, correlated, and used to make decisions not only after an event occurs, but also while it is occurring or even before it occurs (through predictive measures). With smart maps it becomes possible to engage in the sensemaking of data for building collaboration and coordination. These maps become a critical piece of the communication bridge.
Yet, the role of technology in creating an inter-building communication bridge is critical. While technology contributing to the Internet of Everything (IoE) helps to make inter-building communication possible, there are certain challenges that arise. For example, such technology should not isolate or confuse. In other words, one must beware of having a particular building or feature design become the majority that isolates or diminishes the minority [7]. In addition, inter-building communication technology should not create such complex design solutions that they become useless.
It also is important to preserve certain functions within building types that could become more hybrid. In this case, it may be beneficial to redefine building types to innovate functions that are better suited for meeting occupant needs and goals in this adaptive sensory design manner. For example, an office building may innovate its functionality by learning from a school, as it places more emphasis upon learning and free “play” time for creative thinking by workers. As such buildings communicate, new goals and priorities will arise—perhaps creativity becomes more important than productivity within certain businesses.
Furthermore, it also becomes important for adaptive sensory environments to nurture the occupant cultures they serve. In this case, a particular office building culture may be very different from another office building culture. Such inter-building communication that helps buildings optimize themselves must customize the way in which it interprets information from another building. An office building can learn from another without sacrificing what makes it unique.
In the end, inter-building communication between adaptive sensory environments is most effective when buildings learn from one another while also fusing into third behaviors that allow the city to “focus” on its prioritized citizen needs and goals.
10. The role of gamification, social media, and augmented reality
Technologies for inter-building communication frameworks give rise to such usages as gamification, social media, and augmented reality. And these all can converge to form the real-time design and optimization of place. As gamification provides incentive, guidance, and reward to occupants, social media can help such occupants to coordinate and collaborate for the common good. Augmented reality can help occupants to make more informed decisions since, with this technological advancement, they can see deeper into their environments. In this way, there will be a convergence between the digital and physical.
Just as the human eye works to form perception from physical objects, inter-building communication technologies will help occupants make smarter decisions from physical environments. These decisions can lead to greener, healthier, safer, and even more productive or creative behaviors. The guiding principle of all of this is to not only have adaptive sensory environments communicate with occupants within each building, but to also have buildings communicate with each other city-wide, so the collective of citizen behaviors can have more profound positive impact upon their future, particularly as these behaviors become smarter over time.
11. A/B split test for behavioral optimization
The brain adapts as it forms visual perceptions from what the eyes see, and this ability to compensate for visual discrepancies is very important. For example, if one eye is focusing more weakly than the other, then the brain will bias the stronger eye. Thus, a similar approach to inter-building communication can work as a healthy competition, or A/B Split Test can be used to optimize buildings in real time.
Healthy competition between buildings can work if a learning approach is at the core of the competition. An A/B Split Test, a term and practice used in website design, can be applied to inter-communicating adaptive sensory buildings. Since each building adapts to its occupants’ needs and goals in real time, it is important for environments to not become design “echo chambers”—where architectural features optimize themselves in a closed loop.
In Figure 4, the difference between closed loop and open loop optimization can be seen. The key is to have adaptive sensory buildings interconnect through a communication network that allows collaborating building clusters to participate proactively in real-time city-wide goals. Furthermore, such a city-wide communication network can help building clusters to learn from one another. For example, one cluster may create a better A/B Split Test that can be replicated in another cluster. In the end, it is important for inter-communicating buildings to be connected for local, city, and global benefits. After all, highly successful building clusters can impact environments in different cities as they learn, interpret, and apply the positive results. An open loop design framework is vital for inter-building adaptive sensory communication.
Figure 4.
Closed loop versus open loop design optimization.
Within an open loop design optimization of place, environments both reference themselves and other buildings outside of themselves to help them learn, adapt, and grow. This type of evolution can be empowered by adapting an A/B Split Test approach.
During a website design A/B Split Test, a webpage design element is tested against another alternative by tracking how website visitors interact with the element and page. For example, the winning design element may have the most visitor clicks.
A/B Split Testing can be used to help encourage the positive learning and growth of inter-communicating adaptive sensory design buildings. By allowing two or even three buildings to enter into such an A/B Split Test, particular design elements can be compared against one another to see which performs best. And since these sensory buildings adapt in real time, the winning design element can be interpreted and then incorporated to optimize the other designs.
Within an A/B Split Test, design features from one hospital can be compared against another hospital’s feature. Or a hospital feature in a postoperative recovery room can be compared against a patient’s home bedroom. In this case, the hospital room can better “tune” as it adapts itself to optimize for ideal patient healing.
Such A/B Split Tests can be used for any building type, as long as there is a network for the inter-building communication system. In essence, Split Tests can help buildings to improve themselves by not being so self-referential. At the city scale, this allows buildings to learn from each other, and at the global scale this allows cities to collaborate.
12. Competition for growth and healing
By learning from other buildings, adaptive sensory environments can grow, as they evolve into better forms of themselves. However, they may also be able to heal themselves in real time, at a multitude of scales—from building-scale to urban-scale.
Similarly, healthy competition can be used within one building as rooms can also learn from one another. Essentially, the inter-building communication system allows environments to optimize—by reaching out to distinctly separate other environments, be they right around the corner within the city, or within another city across the globe.
The human eyes cooperate with one another, and their “competing” views are actually very critical to how the human brain and mind work to form perspective and perception. Similarly, as two buildings compete with one another, they are simply offering alternative design solutions.
It is important to note that just because building designs may be involved in an A/B Split Test, the winning design is not necessarily the better overall design. Two buildings can learn from one another, as one environment may perform better with certain functions, while another environment performs better with other functions. Inter-building communication allows for the best design integrations to influence others.
The A/B Split Testing method is not a means by which designs should simply copy other designs. The interpretation of design usage in one place can influence the way a design operates in another. However, care should be taken to ensure that a place does not lose its authenticity.
As inter-building communication unifies city buildings through form, function, and even meaning, it becomes important for the authenticity of place to remain standing. After all, the certain culture of a particular office building, or the way a hospital nurtures its patients in a particular part of the world will likely differ. Yet, universal lessons can be learned, interpreted, and applied from building to building within different cultures.
By using healthy competition to improve designs in real time, larger leaps in design evolution can be taken. Adaptive sensory environments that communicate with each other become innovators, driven by the thumbprint of their original architectural designers.
In the end, such healthy competition helps to strengthen what works, and helps to eliminate design weaknesses. This is particularly advantageous as certain citizen goals surface. The aim of A/B Split Testing environments through inter-building communication is to find those key leverage points where optimal benefit can be pulled from a design to positively impact more people. Yet, healthy competition is only one way in which to use the system framework of inter-building communication.
As buildings advance in the way they are able to communicate and learn from each other, greater occupant customization will become possible through occupant control points. For example, an occupant can “bridge” their home office preferences with their office building workplace preferences—to either keep them different or similar. The key with inter-building communication is to allow personal choice for occupants when they need it, while also being versatile enough as a design to be able to present them with those choices.
As environmental designs learn from each other, the choices and variations they can provide occupants for certain situations will grow as well. Thus, buildings will be better able to adapt, to nurture, and to grow with the occupants they serve. This will strengthen design so as to help it “fit” occupants at a more nuanced level. Again, this will help them to learn better, to make smarter decisions better, and to engage in more beneficial behaviors.
13. The emergence of symbiotic ecosystems
As inter-building communication links buildings together into a type of network, an ecosystem emerges. Much like the natural environment ecosystem, the city ecosystem cultivates the power to heal itself, particularly as buildings use such information “bridges” to learn from each other. And when both urban and natural ecosystems interact adaptively with one another, they become symbiotic.
By using teamwork at all scales: rooms within buildings learn from each other to optimize a building, buildings within cities learn from each other to optimize a city, and cities within the world can learn from each other to optimize for global goals. All of this teamwork can be thought of as an important collective “challenge” with missions that serve different scales.
As buildings work together through learning and adapting, they help to empower and enhance citizen efforts to improve their own individual quality of life, and the collective quality of life that serves the greater good. Similarly, the eyes that help the human body to see empower the person to improve their quality of life in new ways. In other words, citizens are the lenses of the city—giving the city focus through adapting buildings that work to meet goals by acting collaboratively.
In essence, the built-environment ecosystem can enter into a new type of dialog with the natural environment ecosystem. This symbiotic relationship serves to help each ecosystem enhance, grow, and heal itself. For example, as cities harness built-environment and citizen behaviors, they can positively impact the natural environment by adapting or even reversing disturbances.
Inter-building communication for adaptive sensory environments is key to magnifying the positive effects of beneficial behaviors. As the built and natural ecosystems enter into a two-way dialog, architectural design will keep occupants at the center, but in additional new ways. Inter-building communication extends the reach of beneficial citizen behaviors, while also pulling from these behaviors to harmonize with nature anew.
By strategically designing inter-building communication within cities, a renewed relationship between the built and natural worlds arises. This way of designing will raise the consciousness of citizens so they engage in smarter decision-making while also knowing that their behaviors have a tangible impact upon the greater context that is the planet. Thus, buildings can be designed to communicate so they can retain their individual authenticity but can also act together to create maximized positive impact.
Just as the eyes see to help a person visualize where they are going, with communication, the city can “see” to help citizens visualize where they are going. Furthermore, as inter-building communication is applied to adaptive sensory environments, those citizens will have the ability to optimize, enhance, and take action on behaviors that lead to their goals—including a safer environment, a healthier planet, and a happier world.
\n',keywords:"adaptive architecture, interactive architecture, sensory design, biomimicry, eye accommodation, inter-building communication, green design, occupant-centered design",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/58436.pdf",chapterXML:"https://mts.intechopen.com/source/xml/58436.xml",downloadPdfUrl:"/chapter/pdf-download/58436",previewPdfUrl:"/chapter/pdf-preview/58436",totalDownloads:376,totalViews:160,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:0,dateSubmitted:"February 22nd 2017",dateReviewed:"December 5th 2017",datePrePublished:null,datePublished:"March 28th 2018",readingETA:"0",abstract:"Adaptive sensory environments optimize in real time to consistently improve performance. One optimization method involves communication between buildings to dramatically compound positive effects—but the way these buildings communicate, matters. To design such a communication framework, this chapter uses a biomimetic approach to derive lessons from the human eye and its focusing abilities. With each focusing action, coordination occurs as muscles move to expand and contract the eye’s lens to achieve varying focal distances. And when both eyes focus together, they are able to achieve stereopsis, a field of depth and perception not attainable with only the focus of one eye. By dissecting this collaboration between eye muscle coordination and stereopsis, this chapter uncovers how a communication framework between adaptive sensory environments can create indirect, yet powerful, collective occupant and building behaviors. For example, communicating adaptive sensory environments evoke greener occupant behaviors, which, in turn, bring added benefit to the natural environment. Communication framework aspects include gamification, social media, and augmented reality that blur the boundaries between built-environments in different ways. These “communication bridges” allow buildings to take on new symbiotic relationships with each other to harness and enhance how entire urban areas uplift quality of life.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/58436",risUrl:"/chapter/ris/58436",book:{slug:"interdisciplinary-expansions-in-engineering-and-design-with-the-power-of-biomimicry"},signatures:"Maria Lorena Lehman",authors:[{id:"205780",title:null,name:"Maria Lorena",middleName:null,surname:"Lehman",fullName:"Maria Lorena Lehman",slug:"maria-lorena-lehman",email:"mll@sensingarchitecture.com",position:null,institution:null}],sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. Adaptive sensory environments improve performance",level:"1"},{id:"sec_3",title:"3. Inter-building communication for optimization",level:"1"},{id:"sec_4",title:"4. Objectives for the design of a communication framework",level:"1"},{id:"sec_5",title:"5. Learning from human eye accommodation",level:"1"},{id:"sec_6",title:"6. Learning from stereopsis for 3D vision",level:"1"},{id:"sec_7",title:"7. Inter-building communication to target goals in real time",level:"1"},{id:"sec_8",title:"8. Evoking beneficial occupant behaviors",level:"1"},{id:"sec_9",title:"9. Creating an inter-building “communication bridge”",level:"1"},{id:"sec_10",title:"10. The role of gamification, social media, and augmented reality",level:"1"},{id:"sec_11",title:"11. A/B split test for behavioral optimization",level:"1"},{id:"sec_12",title:"12. Competition for growth and healing",level:"1"},{id:"sec_13",title:"13. The emergence of symbiotic ecosystems",level:"1"}],chapterReferences:[{id:"B1",body:'Lehman ML. Adaptive Sensory Environments. Oxon/New York: Routledge; 2017. p. 1'},{id:"B2",body:'Dweck CS. Mindset: The New Psychology of Success. New York: Ballantine Books; 2008. pp. 3-14'},{id:"B3",body:'Nave R. HyperPhysics: Accommodation. [Internet]. 2016. Available from: http://hyperphysics.phy-astr.gsu.edu/hbase/vision/accom.html [Accessed: Mar 29, 2017]'},{id:"B4",body:'Ang B. Vision and Eye Health: Stereopsis. [Internet]. 2017. Available from: http://www.vision-and-eye-health.com/stereopsis.html [Accessed: Mar 29, 2017]'},{id:"B5",body:'Hexagon Geospatial. Hexagon Smart City Rio Project. [Internet]. 2016. Available from: https://www.youtube.com/watch?v=YtOoLovYZZo [Accessed: Oct 11, 2017]'},{id:"B6",body:'Hexagon Geospatial. Making Smart Cities in the Netherlands. [Internet]. 2016. Available from: https://www.youtube.com/watch?v=q1gbzJQfv2c [Accessed: Oct 11, 2017]'},{id:"B7",body:'Johnson S. Emergence. New York: Scribner; 2001. p. 161'}],footnotes:[],contributors:[{corresp:"yes",contributorFullName:"Maria Lorena Lehman",address:"mll@sensingarchitecture.com",affiliation:'
MLL Design Lab, LLC, Sensing Architecture® Academy, Massachusetts, United States
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\n
1. Introduction
\n
Oxygen reduction reaction (ORR) has been the subject of extensive investigation over the last century [1]. This is largely because ORR is of major importance to energy conversion, in particular in the field of fuel cells and metal-air batteries [1, 2, 3]. ORR is the most important cathodic process in polymer electrolyte membrane fuel cells (PEMFCs) [4]. Among all catalysts evaluated, Pt is still the best catalyst for ORR. The major obstacle with Pt is that it belongs to the platinum group of metals, which are rare metals, hence too expensive for feasible commercialisation of fuel cells. This has led to more research being conducted in an effort to find alternate electrocatalysts that can be used.
\n
Oxygen reduction in aqueous solutions occurs mainly through two different pathways: either a four-electron reduction pathway from O2 to H2O or a two-electron pathway from O2 to H2O2. The most accepted mechanism of ORR was first proposed by Damjanovic et al. [5, 6] and later modified by Wroblowa et al. [7], making it easier to understand the complicated reaction pathway of oxygen on the metal surface. They suggest that ORR proceeds along two parallel reaction pathways with rates that are comparable. In PEMFCs, a four-electron transfer is preferred.
\n
The ORR is alkaline media versus reversible hydrogen electrode (RHE) at 25°, and its thermodynamic potentials at standard conditions are presented as follows [3, 8, 9]:
It is desirable for the ORR to occur at potentials close to thermodynamic potentials as much as possible. For the thermodynamic potentials to be obtained, the charge transfer kinetics of the ORR must be quick. It has been reported that the kinetics of fuel cells at cathode are slow, hence show over-potential ƞ as in Eq. (7) [3, 11]:
\n
\n\n\n\nƞ\n=\nE\n−\n\nE\neq\n\n\n\n\nE7
\n
E is the resultant potential and Eeq is the equilibrium potential.
\n
The difference between E and Eeq is called polarisation.
\n
There are three distinct types of polarisation expressed in Eq. (8):
ƞact is the activation over-potential, a function describing the charge transfer kinetics of an electrochemical reaction. ƞact is always present and mostly dominant at small polarisation currents.
\n
ƞconc is the concentration over-potential, a function describing the mass transport limitations associated with electrochemical processes. ƞconc is predominant at larger polarisation currents.
\n
iR is the ohmic drop. This function takes into account the electrolytic resistivity of an environment when the anodic and cathodic elements of a corrosion reaction are separated by this environment while still electrically coupled.
\n
The graph in Figure 1 depicts a polarisation curve showing the electrochemical efficiency of a fuel cell.
\n
Figure 1.
The polarisation curve shows the electrochemical efficiency of the PEMFC at any operating current [12].
\n
The expression relating the over-potential, ƞ, and the net current is known as the Butler-Volmer equation and is given as follows [13]:
where i is the ORR current density, io is the exchange current density, n is the number of electrons transferred in the rate-determining step, β is the transfer coefficient, β is the over-potential of ORR, F is the Faraday constant, R is the gas constant and T is the temperature in K. The first term in the Butler-Volmer equation represents the anodic reaction/metal dissolution, while the second term represents the cathodic reaction/metal deposition. A plot of the Butler-Volmer equation gives the polarisation curve as shown in Figure 2.
\n
Figure 2.
Current-potential relationship of a metal dissolution (M → Mn+)/deposition (Mn+ → M) process [13].
\n
There are two limitations in the Butler-Volmer equation.
A low over-potential region, also known as polarisation resistance/charge transfer resistance, where the Butler-Volmer equation simplifies to [13]
A plot of ƞ versus log ic also known as the Tafel plot and gives a linear relationship, with slope \n\n\n\n2.303\n\n\nRT\n\nβ\nnF\n\n\n\n\n\n\n, known as the Tafel slope and the intercept yielding the io. The Tafel slope gives the information about the mechanism of the ORR. The higher the Tafel slope, the faster the over-potential increases with current density. With a low Tafel slope, the electrochemical reaction is able to obtain a high current density, at low over-potential. For ORR, two Tafel slopes, 60 mV dec−1 and 120 mV dec−1, respectively, are obtained, depending on the potential range and the electrode material used.
\n
\n
\n
3. Electrocatalysts for ORR
\n
The kinetics of the ORR at the cathode are very important, as they are the factors for the performance of PEMFCs [14, 15]. There are several issues that need to be addressed, including slow reaction kinetics at the cathode, which are due to highly irreversible ORR, and fuel crossover in the cathode, which causes a mixed potential, leading to potential loss and 25% reduction in efficiency, hence reducing the ORR performance [16, 17, 18, 19]. An electrocatalyst is used to induce a four-electron reduction of O2 to water by utilising the protons that permeate from the anode. Pt is the electrocatalyst that is currently used for ORR reactions, as it is the only commercially available catalyst with sensible activity and stability for PEMFCs, although it offers limited commercialisation of fuel cells due to its limited availability and high cost [4, 20]. It is also reported that Pt still shows over-potentials of over 400 mV from the equilibrium reversible potentials (1.19 V at 80°C) [21]. These high potentials result in the formation of adsorbed species on a platinum surface that restrain the ORR and hence result in performance loss [2]. Considerable research has been conducted to try to (1) reduce the costs of fuel cells, which is one of the stumbling blocks in fuel cell commercialisation using low-cost non-Pt catalysts such as supported platinum group metals Pd, Ir and Ru; (2) improve the electrocatalytic activity of the cathode catalyst, which includes using bimetallic alloy catalysts, transition metal macrocyanides, transition metal chalcogenides and metal oxides in order to improve the ORR kinetics on the new catalyst; and (3) fabricate Pt with novel nanostructures such as nanotubes, graphene and carbon nanofibres (CNFs), as it is known that supports may significantly affect the performance of the catalyst. However, these efforts are still in the research stage, as their activity and stability are still lower than that of the Pt catalyst.
\n
\n
3.1. Single-metal catalyst
\n
Other noble metals, such as Pd, Ag, Rh, Ir and Ru, have also been used as cathode materials for ORR [22]. Among these, Pd, which has the same electron configuration and lattice constant as Pt, as they belong to the same row in the periodic table, showed the most improved ORR towards alcohol in an alkaline medium, while it is reported to be inactive in an acid medium [4, 23]. It has been showed that Pd/C is less sensitive to alcohol contamination compared to Pt/C, hence more tolerant to alcohol crossover [16, 24, 25]. However, when comparing the ORR activity of Pd/C to Pt/C, the former has less activity and high potentials of amount 0.8 V versus NHE, hence less stability, which prevents its replacement as the preferred ORR catalyst over Pt/C [26]. The noble metals in terms of ORR activity follow the trend: Pt > Pd > Ir > Rh [27]. Wang [18] reports that Ru can undergo a four-electron reduction reaction. Ag is reported to show less electrocatalytic activity towards ORR compared to Pt, but is more stable than Pt cathodes during long-term operations [4].
\n
There are several metals other than noble metals that were also evaluated as cathode catalysts for ORR. Figure 3 shows a comparison of the activities of various catalysts as a function of binding energy. These catalysts showed less catalytic activity towards ORR compared to Pt, with less electrochemical stability [28].
\n
Figure 3.
Oxygen reduction activities as a function of oxygen-binding energy [27].
\n
\n
\n
3.2. Bimetallic-alloyed catalysts
\n
Transition metals such as Fe, Ni, Co and Cr have been extensively studied due to their improved ORR electrocatalytic activity as alloys for Pt in the presence of a support [17, 28]. Yuan et al. [17] prepared PtFe/C using the impregnation method. Current densities of PtFe/C for ORR in methanol were higher (78.6 mA cm−2) than in Pt/C (65.0 mA cm−2), but was lower in methanol-free solutions, indicating that PtFe/C is a better methanol-tolerant catalyst compared to Pt/C. In terms of power density, the PtFe/C showed an improvement of 20–30% compared to Pt/C [17]. Other researchers [29, 30] also reported better performance of PtFe/C for ORR. Yang et al. [31] report on PtNi/C prepared via the carbonyl complex route an improved mass and specific activity of PtNi/C compared to Pt/C with an improved electrocatalytic activity towards ORR. Pt-Bi/C showed improved methanol tolerance for ORR compared to Pt/C [3]. Remona and Phani [32] synthesised PtBi/C by micro-emulsion. The PtBi/C displayed a higher methanol tolerance compared to mass activity (1.5 times higher) for ORR compared to Pt/C. The high ORR activity of PtBi/C was due to distortion (internal stress) of three Pt sites by Bi.
\n
The effect of Pd on Pt catalysts has been reported by various researchers [33, 34, 35, 36], who all reported an improved electrocatalytic activity towards ORR. The improved electrocatalytic activity of Pt alloys has been ascribed to geometric effect, namely a decreased Pt-Pt bond distance, the dissolution of more oxidisable alloying components, a change in surface structure and electronic effect, that is, an increase in Pt d-band vacancy [31, 37]. Other noble metals (Au, Ir, Rh and Ru) were also studied as Pt alloys. PtAu/CNT (carbon nanotubes) was reported to show an improved electrocatalytic activity in an alkaline membrane compared to Pt/CNT [38, 39, 40]. Pd-Pt alloy had the highest electrocatalytic activity towards ORR compared to other Pt-alloyed noble metals. Fu et al. [41] report on an improved ORR electrocatalytic activity and a larger diffusion-limiting current density compared to commercial Pd black. The improvement of Pt with noble metals (Pd, Ag and Au) is attributed to these metals having a fully occupied d-orbital. The d-orbital coupling effect between metals decreases the Gibbs free energy for the electron-free steps in ORR, resulting in improved ORR kinetics [37].
\n
Binary Pd catalysts (Cu, Ni, Fe, Co, W and Mo) have been identified as promising cathode catalysts for ORR with an improved electrocatalytic activity and stability compared to Pd alone due to changes in Pd-Pd bond length, modification of the electron configuration and change of surface species and compositions [4, 25]. Kim et al. [42] used PdSn/C as a cathode for direct methanol fuel cells. Their results exhibited a high performance in high methanol concentrations compared to commercial Pt/C. Wang [18] reports on PdCo catalysts tested for ORR. The results showed improved activities towards ORR, with PdCo improvement only observed when less than 20% Co was used. Meng et al. [4] report on PdFe, PdCu, PdAg and PdCo, which all showed an improved electrocatalytic activity compared to Pd alone. In the presence of alcohol, the binary Pd catalysts showed an improved electrocatalytic performance for ORR compared to Pt.
\n
Although bimetallic catalysts (Pt with Fe, Ni, Co, etc.) have shown improvement in the performance of the ORR compared to Pt [27], the lack of preparation methods to control large synthesis has limited its use in commercial devices [33]. In addition, the dissolution of transition metals alloyed in the Pt-M catalyst is a major drawback, because these transition metals are electrochemically soluble at a potential range between 0.3 and 1.0 V versus NHE in acidic media [43].
\n
One possible way to overcome the dissolution of transition metals and improve stability of catalysts is by preparing multi-component catalysts (three and more electrocatalyst alloys). The multi-component catalysts are able to shift the d-band centre by a strain effect (caused by the lattice mismatch in the multi-component system) and lower the adsorption energy of surface oxygenated intermediates, thereby enhancing the surface catalytic activity.
\n
Tiwari et al. [37] report on various multi-component catalysts that have been synthesised over the years with either Pt or Pd, including PtTiM (M = Co, Cr, Cu, Fe, Mn, Mo, Ni, Pd, Ta, V, W and Za), PtCuCo, PtCoSe2, PtIrCo, PdFePt, PtCuCoNi, PdSnPt and PdCoPt. From the multi-component catalysts, they reported an improved electrocatalytic activity towards ORR compared to pure Pt and the possibility of reducing the costs of the electrocatalysts for PEMFCs.
\n
More research is also done on trying to improve the kinetics of Pt catalysts through the development of new and the optimisation of existing synthesis methods that can control the shape and surface structure of the electrocatalyst in order to improve its performance [8, 33, 44, 45]. There has been contracting reports on particle size and specific activity. Some researchers report a decrease in specific activity with a decrease in particle size, while other researchers report an increase in specific activity with a decrease in particle size. The discrepancy may be the result of different electrocatalysts with different shapes and degree of agglomeration [46]. It has been reported that metallic nanostructures with different shapes display unique chemical and physical properties [47]. Significant progress has been made for size-controlled spherical nanostructures, but only limited progress has been made with non-spherical nanostructures, which are reported to show more improved ORR electrocatalytic activity for fuel cells compared to spherical-shaped electrocatalysts, the reason being that the highly symmetric face-centred cubic crystal structure of Pt-based catalysts makes it not easy to obtain a non-spherical shape, which involves a competition over the desire to minimise the surface energy through the formation of thermodynamically stable spherical shapes. Hao et al. [48] report that cubic Pd nanocrystals exhibit better performance in methanol compared to the spherical Pd catalyst of a similar size. The improvement was attributed to cubic nanocrystals that contain a more electroactive surface area compared to its spherical counterpart. It has also been reported that Pt electrocatalysts with a tetrahedral shape showed much improved reaction kinetics compared to the spherical Pt nanoparticles. It has been reported that low-index crystal planes give poor electrocatalytic properties, while high-index planes give a high electrocatalytic activity and stability [47, 49]. Pt nanocubes have been reported to have much improved specific activity for ORR compared to commercial Pt catalysts (spherical) [47, 50]. Kuai et al. [50] report on uniform, high-yield icosahedral Ag and Au nanoparticles prepared using a hydrothermal system in the presence of polyvinylpyrrolidone and ammonia. The prepared Au and Ag nanoparticles showed an improved ORR electrocatalytic activity and excellent stability compared to spherical Pt/C nanoparticles.
\n
The form or shape of the electrocatalysts depends on the synthesis method and the various parameters used. Figure 4 shows the formation of various forms of Pt nanocubes using different strategies based on the polyol method [47]. The formation of Pt tubes can be obtained through two different routes, either galvanic displacement or using selected templates [47]. Researchers have synthesised metal nanoparticles with various shapes [32].
\n
Figure 4.
Different routes for the synthesis of Pt nanocubes along with their electron micrographs [47].
\n
Researchers are reporting an improved electrocatalytic activity of ORR using various synthesis methods focusing on surface structure. Lim et al. [14] report on the synthesis of Pt/C using the modified polyol method using ethylene glycol as the reducing agent. The prepared catalyst had the highest mass activity, which was 1.7 times higher than the commercial Pt/C [14]. The improvement was attributed to small and uniform particle size and better dispersion. Adonisi et al. [51] report on various Pt-based catalysts synthesised using the Bonnemann method. Some of those catalysts showed an improved ORR electrocatalytic activity compared to commercial Pt/C. Figure 5 shows a graph depicting 20% Pt/C commercial compared to 20% Pt/C synthesised catalysts using the Bonnemann method. From the graph, it can be observed that the 20% Pt/C commercial catalyst was found at lower current densities than the prepared 20% Pt/C catalyst. The mass activities of the 20% Pt/C commercial and 20% Pt/C prepared catalysts were found to be 12.6 and 15.8 A/g, respectively, and the specific activities were found to be 0.060 and 0.063 A cm−2, respectively. This improvement was attributed to the particle size of the prepared catalysts, which was smaller than the particle size for the commercial Pt/C catalyst.
\n
Figure 5.
Cyclic voltammograms for ORR of 20% Pt/C commercial and prepared electrocatalysts in O2-saturated 0.5 M H2SO4 at a scan rate of 20 mV [51].
\n
Post-treatment after synthesis has been reported to change the physicochemical properties of the electrocatalysts. Heat treatment is considered as one of the important and sometimes necessary steps to improve the activity of the catalysts [52]. Heat treatment involves heating the catalyst under inert (N2, Ar or He) or reducing H2 atmosphere in the temperature range of 80–900°C for 1–4 h [52]. The benefit of heat treatment is the removal of impurities resulting from the preparation stages, allowing uniform dispersion and stable distribution of the catalyst on the support, thereby improving the electrocatalytic activity of the prepared catalyst. It has been determined that the electrocatalytic reduction of oxygen on the catalyst can be influenced by the particle size and surface structure, and hence treatment can have an effect on ORR activity and stability by altering the surface structure of the catalyst [32]. Various researchers have worked on heat treatment of mono and bimetallic catalysts for ORR [50]. They all concluded that heat treatment improves alloying of the catalysts, which decreases the Pt-Pt distance and hence d-band vacancy of the Pt and thus improves the electroactivity of the catalyst [53]. Jeyabharathi et al. [54] report on improved methanol tolerance of PtSn/C after heat treatment, while the ORR activity remained intact. Sarkar et al. report on PdW synthesised using thermal composition followed by annealing at 800°C with an improved electrocatalytic activity for ORR and catalyst durability with an improved methanol tolerance compared to Pt [32].
\n
\n
\n
3.3. Transition metal macrocycles and chalgogenides
\n
Transition metals such as macrocycles and chalgogenides have been used as ORR catalysts since the 1960s due to their inactivity towards the oxidation of methanol [55]. Other than noble metals, they are the most-studied electrocatalysts for oxygen reduction. The study of ruthenium chalgogenides RuxSey and Pt for ORR has shown that the performance of RuxSey is slightly weaker than Pt and that the difference was their behaviour in the presence or absence of methanol. Under these conditions, the electroactivity of RuxSey is not changed, while for Pt, the potential shifts to the negative direction (120–150 mV). A similar behaviour was observed when RuxSey was embedded in a polymetric matrix, such as polyaniline. RuSM (M = Rh, Re, Mo, etc.) when used as catalysts, methanol oxidation on the cathode was suppressed or avoided leading to a reduced mixed potential. The results confirm that the chalgogenide of Ru is insensitive to methanol, in contrast to the Pt catalyst [56]. The main concern with this approach was the low power output due to low activity of these catalysts for ORR, compared to the Pt catalyst [17]. Cobalt and iron phthalocyanide are the most-studied transition metals as centres for macrocycling rings as catalysts for ORR in fuel cells [56, 57]. These ORR catalysts have shown that a number of metal chelates will chemisorb oxygen [58]. A fuel cell with an iron phthalocyanide cathode can only be stable for up to 10 h [17], but has shown improved activity towards ORR in alkaline media [44]. Zagal et al. [59] report that when Fe chelates with N4, a four-electron ORR occurs. Co phthalocyanide has demonstrated similar ORR kinetics as commercial Pt/C, as it also leads to a four-electron process per oxygen molecule, that is, to water, but at lower potentials (0.25 and −0.25 versus RHE) [44, 56]. However, these compounds are not completely stable under strong acid conditions [17, 56]. They decompose via hydrolysis in the electrolyte and attack the macrocyanide via peroxide, causing poor performance and stability [58, 60, 61]. Transition metal chalgogenides are more stable and show an improved electrocatalytic activity at temperatures above 800°C.
\n
\n
\n
3.4. Metal oxides
\n
Another route to stabilising nanoparticles is the development of metal oxide composite supports. Metal oxides such as IrO2, NiO, CeO2, ZrO2, TiO2 and SnO2 have also been studied as ORR catalysts in basic acidic media [62, 63, 64, 65, 66]. Nanoparticles on metal oxides are not able to improve the electrocatalytic activity due to their limited electron conductivity, but are reported to have excellent corrosion resistance in various electrolyte media [66, 67]. Researchers use metal oxides in combination with carbon supports that have desirable properties such as a high surface area and a high electric conductivity. The metal oxides combined with carbon supports are reported to improve the stability and the electrocatalytic activity of the electrode material. Carbon surfaces are functionalised before they are used as supports for catalysts in order to improve their surface properties, but the disadvantage of functionalisation is that it accelerates the degradation process of the support material. The presence of the metal oxide delays the corrosion process. Montero-Ocampo et al. [68] report on PtTiO2 and PtTiO2/CNT synthesised using metal organic chemical vapour deposition. The PtTiO2/CNT was more electrocatalytically active compared to PtTiO2, while good stability was observed for both PtTiO2 and PtTiO2/CNT that was provided by the TiO2 support. This was attributed to the high conductivity of CNT compared to TiO2, which has limited electron conductivity. Pt/TiO2/C showed improvement in activity and thermal stability for ORR compared to Pt/C [69]. Khotseng et al. [70] compared the activity for PtRu/TiO2 to commercial PtRu/C and Pt/C. They reported a high electroactive surface area and activity of commercial Pt/C and PtRu/C compared to PtRu/TiO2 towards ORR. When durability studies were performed for the same catalysts, the PtRu/TiO2 recorded a loss of 29% compared to Pt/C and PtRu/C, which recorded a loss of 64 and 32%, respectively. Li et al. [71] reported an improved oxygen reduction activity, a better durability and a higher methanol tolerance capability in alkaline solution compared to Pt/C.
\n
Most metal oxides were found to be unstable in acidic media. To overcome this instability, conducting polymer polypyrrole (Ppy) was used against the dissolution of metal oxides. During synthesis, the metal oxides were sandwiched between the Ppy layers. Through this research, an improved electrochemical stability of the metal oxides was achieved [18]. Singh et al. [72] report on CoFe2O4 oxides sandwiched between Ppy layers. A high electrocatalytic activity towards ORR at high cathodic potentials was obtained with stability in acidic media [72].
\n
\n
\n
3.5. Novel nanostructures with electrocatalysts
\n
Although Pt-based catalysts have been widely studied due to their high current density and low over-potential, when used as cathode catalysts, their activity is lowered due to slow reaction kinetics. More research is required to try to improve the catalyst activity. One of the focus areas is looking into loading Pt nanostructures with a high activity on the surface of supporting materials with (1) low cost, (2) good electrical conductivity, (3) strong catalyst-support interaction that is influenced by its surface functionalities to limit the possible deactivation of the electrocatalyst and allow for efficient charge transport, (4) large surface area and (5) good resistance to corrosion to allow high stability [8, 22, 24, 73, 74, 75]. Carbon black (CB) is the most-used support for Pt and Pt alloy catalysts. CB is thermochemically unstable and hence suffers from corrosion, leading to performance degradation and durability issues and high potential [66, 76]. Nanostructured carbon materials, for example, mesoporous carbon, CNFs, CNTs and graphene, have been studied extensively as support materials for electrocatalysts, as they have been identified as some of the most promising materials for PEMFCs due to their high chemical stabilities, high electric conductivities and improved mass transport capabilities [32, 77].
\n
CNTs are attractive support materials in fuel cell applications and are by far the most-explored carbon nanostructures as catalyst supports in fuel cells due to their excellent mechanical strength, a high surface area and a high electric conductivity and because they have reported to show an improved catalytic activity [22, 32, 78] compared to CB. The carbon surface is functionalised to provide oxygen-binding groups for the growth of metal catalyst ions [79]. CNTs can be single-walled (SWCNT) or multi-walled (MWCNT), depending on the structure. Both SWCNT and MWCNT have been used as support materials to disperse the electrocatalyst and have been reported to show an enhanced electrocatalytic activity towards ORR. SWCNTs have unique electrical and electronic properties, a wide electrochemical stability and high surface areas [9]. When compared to commercial Pt/C (from ETEK) in acidic media, the SWCNT showed an improved electrocatalytic activity performance, with the negative shift of onset potential by 10 mV compared to Pt/C, whose onset potential moved to a higher potential by 15 mV [15, 73]. Jukk et al. [80] report on Pd/MWCNT having an enhanced electrocatalytic activity compared to Pd/C for ORR. Wang et al. [81] reported on Pt/MWCNT, which showed an improved electrocatalytic activity for ORR compared to Pt/C. Khotseng et al. [70] compared PtRu/MWCNT with commercial Pt/C, PtRu/C and prepared PtRu/TiO2 and PtRu/MoO2. From Figure 6 and Table 1, it is observed that PtRu/MWCNT has the highest mass and specific activity at 0.9 V compared to commercial Pt/C, PtRu/C and prepared PtRu/TiO2 PtRu/MoO2 with the highest current density towards ORR.
\n
Figure 6.
ORR polarisation curves of PtRu/MWCNT PtRu/MWCNT compared to Pt/C, PtRu/C PtRu/TiO2 and PtRu/MoO2 commercial catalysts in O2-saturated 0.1 M HClO4 at 20 m V/s and 1600 rpm [70].
\n
\n
\n
\n
\n\n
\n
\n
ORR catalytic activity at 0.9 V
\n
\n
\n
Catalyst
\n
MA (mA mg−1)
\n
SA (mA cm−2)
\n
\n\n\n
\n
Pt/C
\n
85.85
\n
0.188
\n
\n
\n
PtRu/C
\n
463
\n
1.66
\n
\n
\n
PtRu/MWCNT
\n
35.6 \n\n×\n\n 103
\n
111
\n
\n
\n
PtRu/TiO2
\n
18.94
\n
1.04
\n
\n
\n
PtRu/MoO2
\n
997
\n
17.82
\n
\n\n
Table 1.
Studying the activity of electrocatalysts towards ORR in comparison with commercial Pt/C, PtRu/C and PtRu/TiO2.
\n
The two main functionalities are oxygen, namely carboxyl (▬COOH), hydroxyl (▬OH) and carbonyl (▬C=O), and nitrogen groups. Modified CNTs with nitrogen functional groups have been reported to show a much improved electrocatalytic activity towards ORR through forming thermally stable structures during heat treatment [82, 83]. Nitrogen is known to efficiently create defects on carbon materials, which might increase the edge plane exposure and thus improve the ORR activity [29]. Ghosh and Raj [84] report on an improved electrocatalytic activity towards ORR for N-doped CNTs. Wang et al. [85] report on a sponge-like nitrogen containing carbon with a high electrocatalytic ORR activity compared to commercial Pt/C with a considerably higher methanol tolerance. One distinct advantage offered by CNTs is their high resistance towards corrosion compared to CB, and hence they have an enhanced electrochemical stability compared to CB [66, 84].
\n
CNFs have been reported to show an improved electrocatalytic activity towards ORR compared to CB [66]. Yang et al. [86] report on an improved electrocatalytic activity for ORR for Pd/CNF. The biggest difference between CNTs and CNFs is their exposure of active edge planes. For CNTs, the basal planes are exposed, while for CNFs, edge planes are exposed [66].
\n
Graphene and graphene oxide (GRO) have also been investigated as another support material for electrocatalysts in fuel cells due to their high electron transfer rate, a large surface area and a high conductivity [64]. When compared to CNTs, they have a higher surface area and a similar electric conductivity for electrochemical applications and can also be produced at a lower cost compared to CNTs [21]. In graphene, both basal and edge planes interact with the electrocatalysts, while for CNTs, only basal planes are exposed [66]. A surface built up only of basal planes is said to have a homogeneous surface, while a surface built up of both basal and edge planes is said to have a heterogeneous surface. Heterogeneous surfaces are reported to better stabilise the metal in a highly dispersed state. It has been reported that Pd/GRO shows a better ORR activity and forms a four-electron oxygen-reduction process compared to Pt [87, 88, 89]. N-doped graphene has been reported to show an improved electrocatalytic activity towards ORR compared to graphene in acidic and alkaline media [90]. Lu et al. [91] report a superior electrocatalytic activity of N-GRO compared to GRO. The fast electron transfer rate of graphene can particularly facilitate ORR much quicker in fuel cells [66].
\n
Other nanostructured carbon supports such as mesoporous carbon, carbon nanocoils and carbon aerogel have also been used as support material for cathode catalysts and have been reported to show an improved ORR electrocatalytic activity [76].
\n
Although carbon supports have been reported to show an improved ORR electrocatalytic activity, carbon oxidation or corrosion due to the presence of O2 and/or high electrode potential has been identified as one of the major causes of failure for PEMFC degradation [67]. Non-carbon supports such as electrically conducting polymers, for example, polyaniline, Ppy and mesoporous silica, have also been used as supports to improve the stability of the electrode materials. Shurma and Pollet [66] and Wang et al. [67] report on various non-carbon supports for electrocatalysts for fuel cells. However, it is reported that with non-carbon supports, no major breakthrough has been achieved as yet [66].
\n
\n
\n
3.6. Anion exchange membranes
\n
ORR is also studied in alkaline media using anion exchange membranes (AEMs) [92]. The significant reason for the change in electrolyte membrane from acid to alkaline is the improved electrokinetics of ORR in alkaline [93]. Pd is emerging as an alternative catalyst compared to Pt in alkaline. It is reported that more ORR catalysts are available for alkaline solutions compared to acidic solutions, due to excessive corrosion in acidic media. Pt/C in basic media is said to enhance ORR towards alcohol [94, 95], while non-Pt catalysts also showed an improved ORR when employed. In addition, in alkaline media, Pt/C is more tolerant to alcohol crossover due to its inactivity in alcohol oxidation reaction. Pd alloys are reported to be comparable or slightly better than Pt/C [4]. Kim et al. reported on PdSn using anion exchange membrane (AEM) which showed an improved ORR electrocatalytic activity with a high methanol tolerance compared to commercial Pt/C tested in proton exchange membrane [42]. He and Cairns [96] report on various electrocatalysts for ORR in AEM.
\n
\n
\n
\n
4. Mechanisms for ORR in the presence of an electrocatalyst
\n
Oxygen reduction on Pt is one of the most extensively studied mechanisms [3]. It involves a multi-electron process with a number of elementary steps, involving different reaction intermediates. The mechanism can be shown schematically as follows [97] (Figure 7).
\n
Figure 7.
A simplified schematic pathway of oxygen reduction reaction for both acidic and alkaline media [7].
\n
From the mechanism, only two products are observed with ORR on Pt, either H2O, which can directly form through a four-electron reduction with the rate constant k1, or adsorbed hydrogen peroxide (H2O2, ads), which is through a two-electron process with the rate constant k2, which can be reduced further by another two-electron process to form water with rate constant k3, or be chemically decomposed on the electrode surface (k4), or be desorbed in the electrolyte solution (k5). For ORR in fuel cells, the direct four-electron process is required.
\n
Oxygen reduction on a Pt catalyst in acid media occurs via dissociative adsorption of O2 followed by the protonation of the adsorbed species, with the former being the rate-determining step [55].
\n
The main steps in the mechanism of ORR are given subsequently. One is known as dissociative mechanism for a low current density range and the other associative mechanism for a high current density range:
In this mechanism, no H2O2 is formed. On the Pt surface, the O2 adsorption breaks the O▬O bond and forms adsorbed atomic O with further gain of two electrons, in the two consecutive steps, forming H2O. Because there is no adsorption of O2 on the surface, no H2O2 can be formed. This mechanism can be considered as the direct four-electron reduction reaction.
In this mechanism, no H2O2 is involved as well. Because there is adsorbed O2 on the surface, O▬O may not be broken down in the following steps, resulting in the formation of H2O2, which can be reduced further to form water.
\n
Pt shows two Tafel slope regions. At a high potential, low current density (>0.8 V), the electrode surface is a mixture of Pt and PtO with the Tafel slope of 60 mV dec−1 and the reaction order 0.5 with respect to pH in alkaline media. The fractional reaction order was represented in terms of the first electrochemical step as a rate-determining step under the Temkin isotherm, that is, the adsorption of reaction intermediates Oads, OHads and HO2ads [98, 99].
\n
The rate expression under Temkin conditions of adsorption is
where k is the rate constant and ƞ is the over-potential.
\n
At a low potential, high current density (<0.8 V), the electrode surface is a pure Pt with the Tafel slope of 120 mV dec−1 and the reaction order 0 with respect to pH in alkaline media, with H2O as the reacting species. The adsorption of intermediate species to a Langmuir isotherm under Temkin conditions no longer holds.
The reaction is of the first order with respect to O2 in solutions. It was found that the H2O2 formed was greater in an alkaline solution than in an acidic one [4, 94]. In alkaline solutions, about 80% of the reduction current is through the direct reduction and the other current forms H2O2, which leads to a complicated mechanism.
\n
Various models representing the adsorbed states of oxygen are represented in Figure 8.
\n
Figure 8.
Oxygen reduction on Pt from the (a) bridge model, (b) Griffiths model and (c) Pauling model [100].
\n
Figure 8(a) is known as the bridge model. It is a 2:2 complex of metal oxygen where the bonding arises from the interaction between the d-orbital on the metal with a Π* and Π orbital combination on O2 [101]. This gives rise to a singlet or a triplet nature of di-oxygen orbitals and determines the bridge or a transmode of interaction of di-oxygen with the metal [101]. Figure 8(b) is known as the Griffiths model. It is a 2:1 metal-di-oxygen complex structure, which involves a side on the interaction of oxygen with metal. This type of bonding can be viewed as rising from two contributions: (1) σ-type bonding is formed by overlapping between the Π orbitals of oxygen and the dz2 orbitals on the metal; (2) Π back-bond interaction between the metal d Π orbitals and partially occupied Π* antibonding orbital on O2 arises [102]. Figure 8(c) is known as the Pauling model. It is a 1:1 metal-oxygen complex structure, which is an end-on interaction of O2 with metal. In this model, the σ bond is formed by the donation of electron density from the σ-rich orbital of di-oxygen to the acceptor dz2 orbital on the metal. The metal’s two d-orbitals, namely dxz and dyz, then interact with the Π* orbitals of di-oxygen, with the corresponding charge transfer from the metal to the O2 molecule. The Griffiths and Pauling models are the preferred models due to the donating abilities of the filled Π and σ orbitals of the di-oxygen molecule, respectively [103].
\n
\n
\n
5. Conclusion
\n
ORR has a huge role to play in fuel cell development. Comparing the ORR electrocatalytic activity of Pt with other single metals, Pt shows the most improved electrocatalytic activity, but its large-scale applications are limited by its high cost and scarcity. The addition of a second metal to a metal electrocatalyst decreases its particle size (large surface area), which leads to an increased lattice strain and hence an increased electrocatalytic activity [28]. It has been concluded that multi-component catalysts improve ORR activity, although it is not conclusive on which multi-catalyst shows the most improved ORR activity, as various researchers report on different multi-component catalysts as the most improved. Although improvement has been obtained, the Pt loading required is still too high to produce PEMFCs at commercially viable prices [22]. The transition metal phthalocyanine is offering reasonable performance as an ORR catalyst, although it suffers from lack of long-term stability.
\n
The challenge remaining is optimising the synthesis method in order to control the shape and the surface structure of especially non-spherical electrocatalysts, which are reported to show the most improved ORR electrocatalytic activity with most stable electrocatalysts, while they contribute to the lowering of Pt usage and hence cost reduction of the PEMFC.
\n
Catalyst support is one of the critical components in improving the electrocatalytic activity of PEMFCs, as they are responsible for parameters that govern the performance of the fuel cell, that is, particle size, catalyst dispersion and stability [8]. Comparison of the carbon supports, CNTs and graphene supports provides considerable advantages concerning mass and charge transport. The disadvantage of using these supports is the costs [25]. In addition, the deposition, distribution and crystallite size of metal nanoparticles are affected by the synthesis method and oxidation treatment of carbon supports.
\n
Using an alkaline medium, Pt-free nanoparticles can be used as electrocatalysts for fuel cells, with a reduced alcohol crossover, an improved ORR kinetics and limited risks of corrosion. Recently, research has been focused on using AEMs. The main advantage of using AEM fuel cells over PEMFCs is that it allows for the use of less expensive, Pt-free electrocatalysts. AEM fuel cells promise to solve the cost barriers of PEMFCs.
\n
\n
Acknowledgments
\n
I thank ESKOM (TESP), NRF (THUTHUKA), Ithemba Labs, Physics Department (UWC), Chemical Engineering Department (UCT) and Chemistry Department (UWC).
\n
Conflict of interest
I have no conflict of interest to declare.
\n
Nomenclature
\n
\n\n\nAEM\n\n
anion exchange membrane
\n\n\n\nCB\n\n
carbon black
\n\n\n\nCNF\n\n
carbon nanofibre
\n\n\n\nCNT\n\n
carbon nanotube
\n\n\n\nGRO\n\n
graphene oxide
\n\n\n\nMWCNT\n\n
multi-walled carbon nanotube
\n\n\n\nNHE\n\n
normal hydrogen electrode
\n\n\n\nORR\n\n
oxygen reduction reaction
\n\n\n\nPEMFC\n\n
polymer electrolyte membrane fuel cell
\n\n\n\nPpy\n\n
polypyrrole
\n\n\n\nRHE\n\n
reversible hydrogen electrode
\n\n\n\nSWCNT\n\n
single-walled carbon nanotube
\n\n\n
\n
\n',keywords:"oxygen reduction reaction, electrocatalysts, reaction kinetics, mechanism, novel nanostructures, polymer membrane fuel cells",chapterPDFUrl:"https://cdn.intechopen.com/pdfs/62242.pdf",chapterXML:"https://mts.intechopen.com/source/xml/62242.xml",downloadPdfUrl:"/chapter/pdf-download/62242",previewPdfUrl:"/chapter/pdf-preview/62242",totalDownloads:1629,totalViews:4145,totalCrossrefCites:0,dateSubmitted:"November 24th 2017",dateReviewed:"May 24th 2018",datePrePublished:"November 5th 2018",datePublished:"December 5th 2018",readingETA:"0",abstract:"In this chapter, the oxygen reduction reaction (ORR), which is one of the most important reactions in energy conversion systems such as fuel cells, including its reaction kinetics, is presented. Recent developments in electrocatalysts for ORR in fuel cells, including low and non-Pt electrocatalysts, metal oxides, transition metal macrocycles and chalgogenides, are discussed. Understanding of the interdependence of size, shape and activity of the electrocatalysts is evaluated. The recent development of ORR electrocatalysts with novel nanostructures is also reported. The mechanism catalysed by these electrocatalysts is presented. Finally, the perspectives of future trends for ORR are discussed.",reviewType:"peer-reviewed",bibtexUrl:"/chapter/bibtex/62242",risUrl:"/chapter/ris/62242",signatures:"Lindiwe Khotseng",book:{id:"6778",title:"Electrocatalysts for Fuel Cells and Hydrogen Evolution",subtitle:"Theory to Design",fullTitle:"Electrocatalysts for Fuel Cells and Hydrogen Evolution - Theory to Design",slug:"electrocatalysts-for-fuel-cells-and-hydrogen-evolution-theory-to-design",publishedDate:"December 5th 2018",bookSignature:"Abhijit Ray, Indrajit Mukhopadhyay and Ranjan K. Pati",coverURL:"https://cdn.intechopen.com/books/images_new/6778.jpg",licenceType:"CC BY 3.0",editedByType:"Edited by",editors:[{id:"174737",title:"Dr.",name:"Abhijit",middleName:null,surname:"Ray",slug:"abhijit-ray",fullName:"Abhijit Ray"}],productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"}},authors:null,sections:[{id:"sec_1",title:"1. Introduction",level:"1"},{id:"sec_2",title:"2. Kinetics of ORR",level:"1"},{id:"sec_3",title:"3. Electrocatalysts for ORR",level:"1"},{id:"sec_3_2",title:"3.1. Single-metal catalyst",level:"2"},{id:"sec_4_2",title:"3.2. Bimetallic-alloyed catalysts",level:"2"},{id:"sec_5_2",title:"3.3. Transition metal macrocycles and chalgogenides",level:"2"},{id:"sec_6_2",title:"3.4. Metal oxides",level:"2"},{id:"sec_7_2",title:"3.5. Novel nanostructures with electrocatalysts",level:"2"},{id:"sec_8_2",title:"3.6. Anion exchange membranes",level:"2"},{id:"sec_10",title:"4. Mechanisms for ORR in the presence of an electrocatalyst",level:"1"},{id:"sec_11",title:"5. Conclusion",level:"1"},{id:"sec_12",title:"Acknowledgments",level:"1"},{id:"sec_15",title:"Conflict of interest",level:"1"},{id:"sec_12",title:"Nomenclature",level:"1"}],chapterReferences:[{id:"B1",body:'Liu B, Bard AJ. Scanning electrochemical microscopy. 45. Study of the kinetics of oxygen reduction on platinum with potential programming on tip. Journal of Physical Chemistry B. 2002;106(49):12801-12806. DOI: 10.1021/jp026824f\n'},{id:"B2",body:'Song C, Zhang J. Electrocatalytic oxygen reduction reaction. In: Zhang J, editor. PEM Fuel Cell Electrocatalyst: Fundamentals and Applications. London: Springer; 2008. pp. 89-134. DOI: 10.1007/978-1-84800-936-3\n'},{id:"B3",body:'Raghuveer V, Kumar K, Viswanathan B. Nanocrystalline lead ruthenium pyrochlore as oxygen reduction electrode. Indian Journal of Engineering and Material Science. 2002;9:137-140\n'},{id:"B4",body:'Meng H, Zeng D, Xie F. 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Role of electronic property of Pt and Pt alloys on electrocatalytic reduction of oxygen. Journal of the Electrochemical Society. 1998;145(12):4185-4188. DOI: 10.1149/1.1838934\n'},{id:"B101",body:'Tatsumi K, Hoffman R. Metalloporphyrins with unusual geometries. 1. Mono-, di-, tri atom-bridged porphyrin dimers. Journal of the American Chemical Society. 1981;103:3328-3341. DOI: 10.1021/ja00402a018\n'},{id:"B102",body:'Griffith JS. On the magnetic properties of some haemoglobin complexes. Proceedings of the Royal Society of London. 1956;A235:23-36. DOI: 10.1098/rspa.1956.0062\n'},{id:"B103",body:'Pauling L. Nature of the iron-oxygen bond in oxyhaemoglobin. Nature. 1964;203:182-183. DOI: 10.1038/203182b0\n'}],footnotes:[],contributors:[{corresp:"yes",contributorFullName:"Lindiwe Khotseng",address:"lkhotseng@uwc.ac.za",affiliation:'
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