UHMS- and FDA-approved indications for hyperbaric oxygen therapy.
\r\n\tIn sum, the book presents a reflective analysis of the pedagogical hubs for a changing world, considering the most fundamental areas of the current contingencies in education.
",isbn:"978-1-83968-793-8",printIsbn:"978-1-83968-792-1",pdfIsbn:"978-1-83968-794-5",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"b01f9136149277b7e4cbc1e52bce78ec",bookSignature:"Dr. María Jose Hernandez-Serrano",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/10229.jpg",keywords:"Teacher Digital Competences, Flipped Learning, Online Resources Design, Neuroscientific Literacy (Myths), Emotions and Learning, Multisensory Stimulation, Citizen Skills, Violence Prevention, Moral Development, Universal Design for Learning, Sensitizing on Diversity, Supportive Strategies",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"September 14th 2020",dateEndSecondStepPublish:"October 12th 2020",dateEndThirdStepPublish:"December 11th 2020",dateEndFourthStepPublish:"March 1st 2021",dateEndFifthStepPublish:"April 30th 2021",remainingDaysToSecondStep:"3 months",secondStepPassed:!0,currentStepOfPublishingProcess:4,editedByType:null,kuFlag:!1,biosketch:"Dr. Phil. Maria Jose Hernandez Serrano is a tenured lecturer in the Department of Theory and History of Education at the University of Salamanca, where she currently teaches on Teacher Education. She graduated in Social Education (2000) and Psycho-Pedagogy (2003) at the University of Salamanca. Then, she obtained her European Ph.D. in Education and Training in Virtual Environments by research with the University of Manchester, UK (2009).",coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"187893",title:"Dr.",name:"María Jose",middleName:null,surname:"Hernandez-Serrano",slug:"maria-jose-hernandez-serrano",fullName:"María Jose Hernandez-Serrano",profilePictureURL:"https://mts.intechopen.com/storage/users/187893/images/system/187893.jpg",biography:"DPhil Maria Jose Hernandez Serrano is a tenured Lecturer in the Department of Theory and History of Education at the University of Salamanca (Spain), where she currently teaches on Teacher Education. She graduated in Social Education (2000) and Psycho-Pedagogy (2003) at the University of Salamanca. Then, she obtained her European Ph.D. on Education and Training in Virtual Environments by research with the University of Manchester, UK (2009). She obtained a Visiting Scholar Postdoctoral Grant (of the British Academy, UK) at the Oxford Internet Institute of the University of Oxford (2011) and was granted with a postdoctoral research (in 2021) at London Birbeck University.\n \nShe is author of more than 20 research papers, and more than 35 book chapters (H Index 10). She is interested in the study of the educational process and the analysis of cognitive and affective processes in the context of neuroeducation and neurotechnologies, along with the study of social contingencies affecting the educational institutions and requiring new skills for educators.\n\nHer publications are mainly of the educational process mediated by technologies and digital competences. Currently, her new research interests are: the transdisciplinary application of the brain-based research to the educational context and virtual environments, and the neuropedagogical implications of the technologies on the development of the brain in younger students. Also, she is interested in the promotion of creative and critical uses of digital technologies, the emerging uses of social media and transmedia, and the informal learning through technologies.\n\nShe is a member of several research Networks and Scientific Committees in international journals on Educational Technologies and Educommunication, and collaborates as a reviewer in several prestigious journals (see public profile in Publons).\n\nUntil March 2010 she was in charge of the Adult University of Salamanca, by coordinating teaching activities of more than a thousand adult students. She currently is, since 2014, the Secretary of the Department of Theory and History of Education. Since 2015 she collaborates with the Council Educational Program by training teachers and families in the translation of advances from educational neuroscience.",institutionString:"University of Salamanca",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"0",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"University of Salamanca",institutionURL:null,country:{name:"Spain"}}}],coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"23",title:"Social Sciences",slug:"social-sciences"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"301331",firstName:"Mia",lastName:"Vulovic",middleName:null,title:"Mrs.",imageUrl:"https://mts.intechopen.com/storage/users/301331/images/8498_n.jpg",email:"mia.v@intechopen.com",biography:"As an Author Service Manager, my responsibilities include monitoring and facilitating all publishing activities for authors and editors. From chapter submission and review to approval and revision, copyediting and design, until final publication, I work closely with authors and editors to ensure a simple and easy publishing process. I maintain constant and effective communication with authors, editors and reviewers, which allows for a level of personal support that enables contributors to fully commit and concentrate on the chapters they are writing, editing, or reviewing. I assist authors in the preparation of their full chapter submissions and track important deadlines and ensure they are met. I help to coordinate internal processes such as linguistic review, and monitor the technical aspects of the process. As an ASM I am also involved in the acquisition of editors. Whether that be identifying an exceptional author and proposing an editorship collaboration, or contacting researchers who would like the opportunity to work with IntechOpen, I establish and help manage author and editor acquisition and contact."}},relatedBooks:[{type:"book",id:"6942",title:"Global Social Work",subtitle:"Cutting Edge Issues and Critical Reflections",isOpenForSubmission:!1,hash:"222c8a66edfc7a4a6537af7565bcb3de",slug:"global-social-work-cutting-edge-issues-and-critical-reflections",bookSignature:"Bala Raju Nikku",coverURL:"https://cdn.intechopen.com/books/images_new/6942.jpg",editedByType:"Edited by",editors:[{id:"263576",title:"Dr.",name:"Bala",surname:"Nikku",slug:"bala-nikku",fullName:"Bala Nikku"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"1591",title:"Infrared Spectroscopy",subtitle:"Materials Science, Engineering and Technology",isOpenForSubmission:!1,hash:"99b4b7b71a8caeb693ed762b40b017f4",slug:"infrared-spectroscopy-materials-science-engineering-and-technology",bookSignature:"Theophile Theophanides",coverURL:"https://cdn.intechopen.com/books/images_new/1591.jpg",editedByType:"Edited by",editors:[{id:"37194",title:"Dr.",name:"Theophanides",surname:"Theophile",slug:"theophanides-theophile",fullName:"Theophanides Theophile"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"3092",title:"Anopheles mosquitoes",subtitle:"New insights into malaria vectors",isOpenForSubmission:!1,hash:"c9e622485316d5e296288bf24d2b0d64",slug:"anopheles-mosquitoes-new-insights-into-malaria-vectors",bookSignature:"Sylvie Manguin",coverURL:"https://cdn.intechopen.com/books/images_new/3092.jpg",editedByType:"Edited by",editors:[{id:"50017",title:"Prof.",name:"Sylvie",surname:"Manguin",slug:"sylvie-manguin",fullName:"Sylvie Manguin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"3161",title:"Frontiers in Guided Wave Optics and Optoelectronics",subtitle:null,isOpenForSubmission:!1,hash:"deb44e9c99f82bbce1083abea743146c",slug:"frontiers-in-guided-wave-optics-and-optoelectronics",bookSignature:"Bishnu Pal",coverURL:"https://cdn.intechopen.com/books/images_new/3161.jpg",editedByType:"Edited by",editors:[{id:"4782",title:"Prof.",name:"Bishnu",surname:"Pal",slug:"bishnu-pal",fullName:"Bishnu Pal"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"72",title:"Ionic Liquids",subtitle:"Theory, Properties, New Approaches",isOpenForSubmission:!1,hash:"d94ffa3cfa10505e3b1d676d46fcd3f5",slug:"ionic-liquids-theory-properties-new-approaches",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/72.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"1373",title:"Ionic Liquids",subtitle:"Applications and Perspectives",isOpenForSubmission:!1,hash:"5e9ae5ae9167cde4b344e499a792c41c",slug:"ionic-liquids-applications-and-perspectives",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/1373.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"57",title:"Physics and Applications of Graphene",subtitle:"Experiments",isOpenForSubmission:!1,hash:"0e6622a71cf4f02f45bfdd5691e1189a",slug:"physics-and-applications-of-graphene-experiments",bookSignature:"Sergey Mikhailov",coverURL:"https://cdn.intechopen.com/books/images_new/57.jpg",editedByType:"Edited by",editors:[{id:"16042",title:"Dr.",name:"Sergey",surname:"Mikhailov",slug:"sergey-mikhailov",fullName:"Sergey Mikhailov"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"371",title:"Abiotic Stress in Plants",subtitle:"Mechanisms and Adaptations",isOpenForSubmission:!1,hash:"588466f487e307619849d72389178a74",slug:"abiotic-stress-in-plants-mechanisms-and-adaptations",bookSignature:"Arun Shanker and B. Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"878",title:"Phytochemicals",subtitle:"A Global Perspective of Their Role in Nutrition and Health",isOpenForSubmission:!1,hash:"ec77671f63975ef2d16192897deb6835",slug:"phytochemicals-a-global-perspective-of-their-role-in-nutrition-and-health",bookSignature:"Venketeshwer Rao",coverURL:"https://cdn.intechopen.com/books/images_new/878.jpg",editedByType:"Edited by",editors:[{id:"82663",title:"Dr.",name:"Venketeshwer",surname:"Rao",slug:"venketeshwer-rao",fullName:"Venketeshwer Rao"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"4816",title:"Face Recognition",subtitle:null,isOpenForSubmission:!1,hash:"146063b5359146b7718ea86bad47c8eb",slug:"face_recognition",bookSignature:"Kresimir Delac and Mislav Grgic",coverURL:"https://cdn.intechopen.com/books/images_new/4816.jpg",editedByType:"Edited by",editors:[{id:"528",title:"Dr.",name:"Kresimir",surname:"Delac",slug:"kresimir-delac",fullName:"Kresimir Delac"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"66258",title:"Historical Aspects of Hyperbaric Physiology and Medicine",doi:"10.5772/intechopen.85216",slug:"historical-aspects-of-hyperbaric-physiology-and-medicine",body:'Since 4500 BC, breath-holding dives for mother-of-pearl, sea sponges, and coral was a distinct occupation. These free divers could hold their breath for extended periods of time, and their work was confined to waters less than 30 m (100 ft) deep. It was undoubtedly a hazardous occupation, and many of them succumbed to decompression sickness after rapid surfacing. Persian king Xerxes the Great (520–465 BC) employed divers to salvage sunken goods and treasures from the wrecks of Greek ships he had sunk in numerous battles at sea. Some of these dives were recorded to depths of 20–30 m and lasting 4 minutes at a time. The ancient Greek historians Herodotos and Pausanias wrote about a Greek hero named Scyllias from Scione, who used a reed and diving capsule made from animal skins to cut the mooring lines of enemy ships. Pausanias even taught his own daughter Hydna to dive. Alexander the Great (365–323 BC), under the advice of a reputed astronomer named Ethicus, dived into the Bosphorus straits in a bathysphere, accompanied by a dog, a cat, and a rooster, after entrusting the security of the hoisting chain to his most loyal mistress. Taking advantage of the moment, she chose to elope with her lover after casting the chain into the sea, abandoning Alexander and leaving him to figure out his escape on his own! In 300 BC, Aristotle described the ruptured eardrum as a complication of undersea diving.
While living in Venice in the late fifteenth century, Leonardo da Vinci designed diving suits to enable divers cut holes in the hulls of invading ships, but none seem to have been developed or used [1].
In 1620, Dutch inventor Cornelis Jacobszoon Drebbel (1572–1633) designed a wooden diving boat, sealed against water by greased leather, to travel in the River Thames at a depth of around 4 m, from Westminster to Greenwich. Air was supplied by two tubes with floats to maintain one end above water [2]. In sixteenth century England and France, full diving suits made of leather were used to depths of 60 ft with air being pumped down from the surface with the aid of manual pumps.
The first documented use of hyperbaric therapy was in 1662, when a British clergyman and physician named Nathaniel Henshaw used a system of organ bellows with unidirectional valves to change the atmospheric pressure in a sealed chamber called a domicilium (Figure 1). Without any scientific rationale whatsoever, Henshaw claimed that high air pressures would remedy acute conditions while lower pressures would yield salutary results in chronic disorders. His domicilium therapy was touted to improve digestion and prevent lung diseases by manipulating ambient pressures without increasing oxygen concentrations, as oxygen was not discovered until nearly a century later [2].
Henshaw and his domicilium.
In 1690, Edmond Halley designed a diving bell ventilated with weighted barrels of air sent down from the surface. Employing this device, Halley, escorted by five of his close friends, undertook a dive to a depth of 60 ft in the River Thames in that bell and remained submerged at that depth for 90 minutes. Too heavy for salvage work, Halley made improvements to his bell, extending his underwater exposure time to over 4 hours. The first deep-sea diving suit was invented in 1819 by Augustus Siebe. It used compressed air supplied to the helmet for ease of movement underwater.
All of these early submersibles used ambient air and were called “pneumatic chambers” or “compressed air baths.”
Nearly two centuries later, in the 1830s, there was a rebirth of interest in hyperbaric medicine in France. In 1834, the French physician Junod built a hyperbaric chamber designed by the steam engine inventor James Watt, who was well-versed in pressure physics. This appliance could generate a maximum of 4 atmospheres pressure and used to treat pulmonary afflictions using pressures between 2 and 4 ATA. Junod referred to his treatment as “Le Bain d’air com-primé” (the compressed air bath), and claimed that it increased circulation to the internal organs and the brain, resulting in feelings of well-being and better general health.
Taberie designed a spherical pneumatic chamber made of cast iron with two pipes, one to provide pressure from a hydraulic compressor run by steam and the other to allow for ventilation. Carpet covered the floor to conceal the pipes, and it featured an antechamber to allow the physician to enter and exit without disturbing the pressure. The passage was also used to stock books, newspapers, and drinks for the patients (Figure 2).
Taberie’s pneumatic chamber.
Lange had a cylindrical chamber constructed out of wrought iron, designed to accommodate four persons. The temperature of the compressed air within the chamber was lowered in two ways. The first employed a stream of cold water directed against the force pump and the supply pipes. The second method was by filling a cup-shaped space at the top of the chamber with cold water and allowing it to cascade down the sides to soak sheets of linen and cool the air by evaporation. In winter the chamber was kept at a comfortable temperature by heating. The chamber was also provided with a device for regulating the flow of the incoming air so that it entered in a steady stream (instead of a succession of puffs in earlier versions) by a force pump. The pressure was secured, as in Tabarie’s system, by regulating the inflow and outflow of the air (Figure 3).
Lange’s pneumatic chamber.
Leibig’s pneumatic chamber was located at Dianabad in Reichenhall, Bavaria, Germany. This pneumatic chamber had three chambers, each one capable of accommodating three persons. One antechamber connected all three rooms, allowing the physician to enter and exit without affecting the ambient pressure. The antechamber also acted as a large pressure regulator, preventing the patients from being affected by sudden surges of pressure. A ventilation pipe through an opening in the ceiling provided good ventilation (Figure 4). The temperature and pressures within each chamber could also be individually controlled [3].
Leibig’s pneumatic chamber.
In 1837, Pravaz built the largest hyperbaric chamber in Lyon, France, to seat 12 patients and treat patients with pulmonary conditions including tuberculosis, laryngitis, tracheitis, and pertussis, as well as unrelated conditions such as cholera, conjunctivitis, deafness, menorrhagia, and rickets. In 1855, Bertin wrote a book on compressed air therapy and even constructed his own hyperbaric chamber.
Compressed air therapy was first introduced into the USA by JL Corning in 1871. In 1876, Kelly treated a patient in a “Compressed Air Bath Apparatus” having two locking plates operated from outside to seal pressures. In 1877, French surgeon Fontaine developed the first mobile hyperbaric operating theater. The high ambient pressure was claimed to facilitate the reduction of hernias and provide relief for patients with lung diseases. Over the next 3 months, 27 surgeries were successfully performed within this mobile hyperbaric chamber (Figure 5). Spurred by the results, Fontaine ventured to erect a mammoth hyperbaric surgical amphitheater to accommodate 300 patients in one sitting. This did not see the light of day as Fontaine died from an accident at the Pneumatic Institute to become the first physician to be martyred in the history of hyperbaric medicine [4].
Fontaine’s mobile hyperbaric operation theater.
In 1885, C Theodore Williams published his “Lectures on the Compressed Air Bath and its Uses in the Treatment of Disease” in the British Medical Journal, extolling the use of atmospheric air under different degrees of atmospheric pressure to treat diseases. He remarked that this mode of therapy was among the most important advances in modern medicine and expressed astonishment at its being ignored in England [5].
Back in the USA, during the closing days of the World War I, Kansas-bavsed physician Orval J Cunningham built a hyperbaric chamber in 1921 at Lawrence, Kansas. He used the facility to treat victims of the Spanish influenza epidemic that swept North America. Noticing that people in the valley fared better than those living in the mountains, Cunningham theorized that atmospheric pressure or barometric factors were responsible for the higher mortality rates in those residing at higher elevations. He observed remarkable improvements in patients treated with HBO, especially those who were cyanotic and comatose. In 1923, heat from open gas burners warming the chambers in winter scorched the insulation and started a fire, but all patients were safely evacuated. In another incident, a mechanical failure caused a complete loss of pressure within the chamber and all patients died. This did not, however, deter Cunningham’s enthusiasm for hyperbaric air. He went on to treat diseases such as syphilis, hypertension, diabetes mellitus, and cancer, believing that anaerobic infections played a role in the etiology of all these afflictions. In 1928, with the financial backing of Henry H. Timken, a roller bearing manufacturer and tycoon, Cunningham built the largest hyperbaric chamber in the world along the shores of Lake Erie in Cleveland, Ohio, at a cost of 1 million dollars. This “Steel Ball Hospital” or “Cunningham’s Sanitarium” was a five-story high steel sphere, 64 ft in diameter with 60 rooms and weighing 900 tons. Each floor of this structure had 12 rooms, with all the amenities of a good hotel (Figures 6 and 7). The growing popularity of Cunningham’s treatments prompted the Bureau of Investigation of the American Medical Association (AMA) to request the doctor to validate his claims regarding the effectiveness of hyperbaric therapy. Cunningham refused to share the details or cooperate with the AMA, leading to his being labeled a quack and a fraud. The chamber was dismantled in 1937 and sold for scrap during World War II [6].
Cunningham’s hyperbaric hotel—outside and inside view.
Cunningham’s hyperbaric hotel—exterior and interior views.
In 1840, Charles Pasley, charged with the recovery of the sunken warship HMS Royal George, commented that, of those who made frequent dives, “not a man escaped the repeated attacks of rheumatism and cold.” In 1841, Trigger, a French mining engineer, used a pressure chamber to deliver workers to the bottom of the river to extract coal. In 1845, he reported that some of his miners complained of joint pains and nervous disorders after surfacing. The first recorded death from “caisson disease” (which later came to be known as decompression illness (DCI) or acute decompression sickness) occurred in 1859 during the building of the Royal Albert Bridge, a railway bridge in England spanning the River Tamar from Saltash to Plymouth. Several workers were taken ill after emerging from deep underground after long hours of work under high atmospheric pressure conditions. In 1871, during the construction of the Eads Bridge in St. Louis, 352 compressed air workers, including Alphonse Jaminet, the physician in charge, were employed. Thirty workers developed serious conditions with 12 ending fatally. Jaminet himself suffered decompression sickness, and his personal description was the first such recorded. It was in 1873 that Andrew Smith first utilized the term “caisson disease” to describe 110 cases of decompression sickness that occurred during construction of the Brooklyn Bridge. The project employed 600 compressed air workers, and recompression treatment was not available on site. In 1882, during the Hudson tunnel construction in New York, every fourth worker died of bends until a recompression chamber was installed to treat the condition. Only three workers died of bends over the next 18 months.
Paul Bert, a French professor of physiology and a student of Claude Bernard, is considered the father of pressure physiology (Figure 8). In 1878, while working closely with Dr. Alphonse Gal, the first doctor to actually dive in order to study how the body reacted underwater, Bert studied Gal’s reports on divers who became symptomatic or died while surfacing. He conducted a series of dog experiments, exposing them to 7–9¾ atmospheres and subjecting them to rapid decompression. A majority of them died and exhibited grossly distended bodies with their right heart chambers filled with gas. When decompression was done at slowly over 1–2 hours after exposure to similar pressures, none of the dogs succumbed. Applying Dalton’s and Henry’s gas laws, Bert concluded that too rapid a decompression induced a pathophysiologic insult secondary to supersaturation of body tissues with nitrogen, causing the formation of nitrogen bubbles. He also went on to suggest that divers stop halfway to the surface to allow for slow decompression after a deep dive—what is now known as deep stops. Bert was also the first to describe oxygen toxicity at pressures in excess of 1.75 ATA. This adverse effect on the central nervous system came to be known as the “Paul Bert effect” [7, 8].
Dr. Paul Bert (1883–1886).
In 1908, Scottish physiologist John Scott Haldane conducted experiments at the Lister Institute of Preventive Medicine in London assisted by Lieutenant Guybon Damant of the Royal Navy, an expert diver and amateur scientist, and a physiologist Edwin Arthur Boycott. A herd of 85 goats was assembled, and the researchers put groups of up to eight goats inside compression chambers for specific periods of time. Pressures were then normalized before releasing the animals into the institute’s yard for observation. These studies confirmed that those goats decompressed by stages did not exhibit signs of the bends (Figure 9). Haldane then introduced the concept of half times—the time required for a particular tissue to become half saturated with a gas—and recommended staged decompression, especially at shallower depths. He prepared detailed practical dive tables for the Royal Navy to prevent acute decompression sickness. These guidelines remained the foundation of all diving operations until 1956 [10]. Heinrich Drager was the first to explore the use of pressurized oxygen in decompression sickness (Figure 10). His protocols were put into practice by Behnke and Shaw, who used HBOT for treating decompression sickness in the late 1930s. They replaced oxygen in place of compressed air, and their work resulted in the use of the first nitrogen-oxygen mixtures and hyperbaric treatment being tailored to the severity of the injury [11]. In 1939, the US Navy began treating divers suffering decompression sickness with hyperbaric oxygen therapy. After World War II, the US military conducted extensive research in HBOT, and this expanded the existing knowledge about survivable pressures and popularized HBOT in the late 1950s and early 1960s. In the 1980s, Paul Harch began an in-depth study of brain decompression illness (DCI) and evaluated divers with this disorder. He concluded that it was not residual gas that was being treated but ischemic brain injury. He went on to develop individualized treatment protocols for over 50 different chronic neurological disorders. Harch is considered to be the foremost authority in the use of HBOT and SPECT brain blood flow imaging in neurology [12, 13, 14]. In 1990, former microbiology professor Igor Gamow invented and patented the Gamow Bag that provided mountaineers with a mobile and effective method to treat high-altitude sickness. This bag is a single-place portable hyperbaric chamber, pressurized with a foot pump, to simulate a descent to 7000 ft (Figure 11). In 1992, Harch treated the first delayed decompression sickness, which led to the treating of “dementia pugilistica” in boxers and cerebral palsy and autism in children [15].
Bends in the foreleg of a goat after experiments performed by physiologist Haldane [9].
Drager and his recompression chamber.
The Gamow Bag.
In 1937, Brazilians Ozorio de Almeida and Costa pioneered the use of HBOT in treating leprosy [16]. In the 1950s, Ite Boerema, a cardiac surgeon from the Netherlands, conceived the idea of “flooding” the body’s tissues with extra oxygen. Working with the help of the Royal Dutch Navy, Boerema conducted a series of animal experiments and operations within a hyperbaric oxygen chamber (Figure 12). These went off without a hitch and led to the installation of a large operating hyperbaric chamber at the University of Amsterdam. Many children with congenital heart diseases like tetralogy of Fallot, transposition of great vessels, and pulmonic stenosis were operated in this facility with great success. Boerema mooted the concept of “Life without blood” using HBO, when dissolved oxygen sufficed to meet the entire body’s oxygen needs without the need for red cells or hemoglobin. Boerema is credited with being the father of modern-day hyperbaric medicine [17].
Dr. Boerema with children operated by him.
In 1955–1956, I Churchill-Davidson evaluated clinical trials on HBOT as a potentiator for radiation therapy in cancer patients at St. Thomas Hospital in London [18]. Public interest in hyperbaric oxygen therapy started to grow in the 1960s after publicity about its use in treating President John F Kennedy’s sick infant. In 1961, a colleague of Boerema, W. H. Brummelkamp, published a paper on inhibition of anaerobic infections by HBOT [19]. In 1962, Smith and Sharp reported the enormous benefits of HBO in carbon monoxide poisoning. They recommended that all those having a verified carboxyhemoglobin level above 25% needed immediate HBOT at 3 ATA for 90 minutes, followed by two or three more sessions for full recovery, making HBO very cost-effective [20]. Global interest in HBOT was rekindled by this finding, resulting in hyperbaric units being installed at many centers like Duke University, New York Mount Sinai Hospital, Presbyterian Hospital and Edgeworth Hospital in Chicago, Good Samaritan in Los Angeles, St. Barnabas Hospital in New Jersey, Harvard Children’s Hospital, and St. Luke’s Hospital in Milwaukee. In 1965, Perrins from the UK demonstrated the effectiveness of HBOT in osteomyelitis [21]. In 1966, Saltzman and coworkers from the USA proved the effectiveness of HBOT in stroke patients [22].
In 1970, Boschetty and Cernoch of Czechoslovakia conducted a trial of HBOT for multiple sclerosis. In their series 15 out of 26 patients with multiple sclerosis showed improvement after HBOT at 2 atmospheres [23]. In 1971, Lamm of West Germany used HBOT for treatment of sudden deafness. It was shown that HBOT shortens the course of healing in high-pitch perception dysacusis by upregulating constitutive nitric oxide synthase in the substructure of the cochlea [24]. In 1973, Thurston pioneered studies that showed lower mortality figures in patients with myocardial infarction treated with HBO. HBOT was shown to improve oxygen supply to the threatened heart and reduce the volume of infarct size and other major adverse outcomes [25]. In 1972, Richard A Neubauer set up the Ocean Hyperbaric Neurologic Center in Lauderdale-by-the-Sea exclusively for HBOT in the management of various central nervous system disorders. He mooted the concept of “idling” neurons capable of surviving for years or even decades after the original injury. He claimed that these injured neurons could be re-activated with HBOT and that the greater the number of idling neurons, the better would be the patient’s response to HBOT [26]. Neubauer was also the co-founder and executive director of the American College of Hyperbaric Medicine. After his death in 2007 at the age of 83, his clinical research center in Florida was renamed the Neubauer Hyperbaric Neurologic Center. In 1976, Hollbach and Wasserman determined that 1.5 ATA (atmospheres absolute) maximizes oxygen content and glucose metabolism in the brain [27].
In 1985, RE Marx and his colleagues observed that the rate of osteoradionecrosis was 30%/patient in patients treated with penicillin alone while rates in those treated with HBO was only 5% [28]. In 1987, Jain successfully treated patients with paralytic stroke using HBOT [29, 30]. In 2002, a US Army study confirmed that HBOT repairs white matter damage in children with cerebral palsy. In 2005, Stoller of the USA treated the first case of a child with fetal alcohol syndrome using HBOT and with good outcome [31]. In 2006, Thom of the USA discovered that HBO causes stem cell mobilization [32]. In 2010, Godman discovered that HBOT activated 8101 genes, resulting in reduction of inflammation and increase in growth in body tissues [33, 34]. In 2011, Stoller treated the first retired National Football League (NFL) player for chronic traumatic encephalopathy [35]. In 2012, Harch and his colleagues demonstrated that blast-induced post-concussion syndrome and post-traumatic stress disorders responded to HBOT [15].
The UHMS and FDA approved HBOT for treatment of conditions like autism, stroke, air embolism, ischemic limbs, split-thickness skin graft acceptance, failed grafts, flap survival and salvage, wound reepithelialization, acute thermal burns, etc. (Table 1) [36, 37].
Air or gas embolism |
Carbon monoxide poisoning; cyanide poisoning; smoke inhalation |
Clostridial myositis and myonecrosis (gas gangrene) |
Crush injuries, compartment syndromes, and other acute traumatic peripheral ischemias |
Decompression sickness |
Enhancement of healing in selected problem wounds |
Exceptional blood loss anemia |
Intracranial abscess |
Necrotizing soft tissue infections |
Refractory osteomyelitis |
Skin flaps and grafts (compromised) |
Delayed radiation injury (soft tissue and bony necrosis) |
Thermal burns |
UHMS- and FDA-approved indications for hyperbaric oxygen therapy.
Many patients do not respond to aggressive acid-suppressing medications. HBOT has a beneficial effect in patients with blunt duodenal trauma, duodenal ulcers, and indomethacin-/radiation-induced gastritis. This salubrious effect is mediated by decreased production of oxidative stress markers like tumor necrosis factor-alpha, interleukin-1beta, neopterin, myeloperoxidase, and malondialdehyde. HBOT is seen to improve the acid-neutralizing function of the stomach, normalize gastric motility, reduce the duodenum acidification, decrease edema, and improve the blood flow both in human and equine studies [38, 39]. These effects were also seen in cases of inflammatory bowel diseases like Crohn’s [40].
In September 1961, the First International Congress on the clinical applications of hyperbaric oxygen was held in Amsterdam. The Second International Conference on HBO was held in Glasgow in September 1964, with detailed deliberations on various aspects of HBOT. In November 1965, the Third International Congress on HBOT was organized at the Duke University at Durham, North Carolina. The Fourth and Fifth International Congresses were held in Sapporo, Japan, and Vancouver, respectively, in 1969 and 1973. The University of Aberdeen, Scotland, hosted the sixth conference in August 1977. The subsequent International Congress was held in Moscow in 1981 and is an annual event thereafter. The deliberations during these academic forums threw fresh light on the basic physiology, oxygen toxicity, and therapeutic applications of HBO in human disease.
The Undersea Medical Society (it added hyperbaric to its name in 1986), an organization made up largely of naval and ex-navy physicians, was founded in 1967 in the USA. It reviewed the indiscriminate and inappropriate use of the HBO chamber for a variety of medical conditions by practitioners searching for a “cure-all” therapy, tarnishing the credibility of hyperbaric medicine. This nonprofit organization, now known as the Undersea and Hyperbaric Medical Society (UHMS), set up a Committee on Hyperbaric Oxygen Therapy in the 1970s to systematically review all the available scientific evidence for HBOT and formulate absolute indications for HBOT. This was accepted by insurance providers, including Medicare. The UHMS is committed to providing, promoting, developing, and raising the quality of care across the spectrum in scientific communication, life sciences, and clinical practices of hyperbaric medicine by promoting high standards of patient care and operational safety. It offers accreditation and certificate of competency and credibility and has over 2500 members in 50 countries. UHMS also awards board certification in Undersea and Hyperbaric Medicine through the American Board of Emergency Medicine (ABEM), the American Board of Preventive Medicine (ABPM), and fellowship training in Undersea and Hyperbaric Medicine.
In 1980, Dr. Richard A. Neubauer and Dr. William S. Maxfield formed the American College of Hyperbaric Medicine (ACHM) to foster the ethical advancement and expansion of hyperbaric medicine. The International Society of Hyperbaric Medicine was founded in 1988.
Hyperbaric medicine was approved by the American Board of Medical Specialties as a sub-specialty of emergency and preventative medicine in 2000.
In 1860, the first hyperbaric chamber in the North American continent was constructed in Oshawa, Ontario, Canada. A year later, a neurologist, James Leonard Corning, built the first hyperbaric chamber in the USA in New York. This chamber was used to treat “nervous and related disorders.” The first decompression chamber was invented by the Italian engineer Alberto Gianni in 1916 [39, 40]. In 1928, the Harvard Medical School built a hyperbaric chamber for medical research. Among the largest HBOT chambers is the 22 ton 32 ft wide 14 ft wide one at the Utah Valley Regional Medical Center, USA.
In modern times, many traditional hard-shell hyperbaric chambers and soft-shell, portable hyperbaric chambers (Figures 13–18) are manufactured by several companies and available in every major city. The latest chambers must comply with NFPA-992012 Edition Chapter 14 Code in the USA and European 1997 CEN pressure vessels 97/23E standards as well as the 1998 ECHM recommendations for safety. The newer chambers feature hingeless pressure-sealed doors, antifriction bearings, antibacterial leather upholstery, and high-quality resin fiber loop mattresses and pillows that dissipate heat and moisture generated by the body during therapy. The newer low-pressure monoplace chambers are portable and less expensive. Operating between 1.2 and 1.3 ATA pressures, they are eminently suited for use in homes and spas and also find use to improve results after plastic surgery.
The evolution of hyperbaric chambers.
Monoplace HBO chamber.
Recompression chamber.
Multiplace HBOT chamber.
Hyperbaric operation suite.
Hyperbaric operation suite. (Image courtesy: CONE Health Wound Care and Hyperbaric Center, Greensboro, North Carolina, USA).
The earliest documentation of therapeutic use of HBOT in animals was in 1998. The Veterinary Hyperbaric Medicine Society was formed in 2006. Veterinary-specific hyperbaric chambers are available.
The evolution of HBOT chambers over time is chronicled in Figure 13.
HBOT was called the Cinderella of modern medicine since it was not taught in medical schools and had no pharmaceutical companies to nurture and protect it. Over the course of time, it has shed the label of being a mysterious therapy and become a major tool in the armamentarium of clinicians either as a primary or adjunctive therapy for a spectrum of diseases. Stroke, cancer, heart disease, and chronic lung disease account for almost 60% of the total number of deaths. Hypoxia is a significant component of the pathology of these conditions, and this leads to metabolic acidosis, organ dysfunction, and death. Conventional oxygen therapy may not have desired results, when HBOT yields remarkable clinical improvement. HBOT prevents 75 percent of all major amputations that would otherwise be necessary for diabetic wounds and a 450% increase in complete recovery in patients with traumatic brain injury receiving HBOT vs. standard intensive care. Newer application of HBOT is in emergency care for resuscitation in cases of acute blood loss, near drowning, hanging and poisoning, and cardiorespiratory arrest.
Athletic associations like the NFL employ hyperbaric oxygen therapy as part of the recovery regimen for its athletes, and some players own their own HBOT chambers. Joe Namath experienced remarkable recovery from the head injuries he sustained during his career, leading him to be part of an FDA-approved study of HBOT at the Joe Namath Neurological Center of the Jupiter Medical Center in Florida. Ace swimmer Michael Phelps and football stars Maurice Jones-Drew and James Harrison have endorsed the benefits of HBOT, along with professional boxers like Evander Holyfield [41].
With the utilization of isotopic tracers, magnetic resonance imaging (MRI), and single-photon emission computed tomography (SPECT), HBOT is getting evidence-based recognition. Various conditions like brain injuries, stroke, and neurological diseases with poor prognosis are now amenable to improved outcomes with the application of HBOT. There are more than 500 hyperbaric facilities in the USA alone. Much research remains to be done regarding the efficacy of HBO2 therapy to develop treatment plans for those in extremes of age. The use of hyperbaric medicine to treat wounds in the foot or in the brain is a divine gift, and great advances in this field are on the horizon. The future of healthcare is here!
Over the last decades, sonochemistry has been a fast developing branch of chemistry, which revolves around the ultrasound (US) effect and acoustic cavitation. USs include frequencies above the audible limit of human hearing (20 kHz). The effects of high-energy US arise from the acoustic cavitation rather than interactions of acoustic waves and matter at a molecular or atomic level. The pressure fluctuations generated by US in a liquid medium lead to the formation, growth, and implosive collapse of bubbles. More specifically, the liquid continuously expands (negative pressure) and compresses (positive pressure) until it reaches a critical diameter, which depends on the nature of the liquid and the US frequency.
The collapse of the bubble is almost an adiabatic process, and it results in a massive buildup of energy within the bubble. The microscopic bubbles can also collapse near the surface of the solid substrate and activate it, split larger particles to smaller ones or deagglomerate nanoparticles. Other than the elevated temperature and pressure, those localized hotspots can result in powerful cavitation-generated shock waves and microjets, which can cause effective stirring/mixing of the adjusted layer of liquid [1, 2].
The first region is the interior of the bubble itself, which can be visualized as a micro-/nano-reactor, dictated by extreme temperature (>5000 K) and pressure conditions (>1000 atm) along with rapid heating/cooling rates (1010 K/s). The second one is the interface between the bubble and the bulk solvent. The reaction efficiency of nonvolatile solutes depends on their hydrophobicity, which determines their ability to accumulate at the gas-liquid interface [3]. The third region is the vicinity of the bubble, where the bulk solution is at ambient temperature, and free radicals can form in the hot regions.
As the globe encounters constant rise of energy demand to survive, the need to exploit efficiently renewable energy sources is vital. Electrochemical energy production can be a promising power source, while electrochemical devices constitute an energy storage option as well. Among these devices, batteries possess commensurate attention the last decades, due to their various applications and potential [4].
A battery cell, regardless its shape and configuration, is a device consisted of two electrodes, the anode and the cathode, an electrolyte between them having the role of the ionic conductor and a separator positioned between the electrodes that converts chemical energy to electricity or the reverse if the cell is rechargeable. Thus, the performance of the cell depends on the properties of all the components and the consistency of the system [5]. Τhe current challenges are to advance the energy density of batteries, extend their conversion efficiency and rechargeability, and eliminate the charging time and cost while meeting the safety and environmental standards [5, 6].
In this direction, research has been emphasized toward developing nanostructured materials and implementing them in batteries as they deliver enriched performance, which is unapproachable by conventional materials. Some crucial aspects about nanomaterials are their large electrochemically active surface area, their electronic and ionic conductivity, thermal and mechanical endurance, and flexibility [7, 8]. In order to ameliorate redox reaction rates and accelerate kinetic mechanisms, a wide range of methods have been proposed including the possible incorporation of nanomaterials in each component of a cell [9].
Though the effectiveness of nanomaterials remains undisputed, only a minority of them is currently commercially utilized apparently as a result of the high cost to synthesize and manufacture them [7]. Sonochemistry may provide feasible tools to resolve many obstacles concerning the cost, safety, and environmental liability while fabricating the nanomaterials for batteries. As an example, we refer to Gu et al., who give a nice overview of graphene preparation by exfoliation in liquid media by using US as energy source and compared the results with those from other methods [10]. Graphene has excellent electrical, chemical, and mechanical properties and can, for example, boost the activity of electrodes especially of the oxygen electrodes in Zn-air batteries [11, 12, 13].
High intensity USs have been used to prepare iron-graphene hybrid electrodes for Li-batteries, whereby it was found that the ultrasonication step is of key importance for obtaining hybrid electrode material with small particle size and outstanding capacity and cyclability [14].
Olivine-structured LiFePO4 is a very promising cathode material; has benefits such as nontoxicity, low cost of raw materials, and good structural stability at high temperature; is safe; and has relatively high-specific capacity (170 mA h g−1) with a flat discharge-charge potential (3.45 V vs. Li+/Li) [15, 16]. However, the low diffusion coefficients (10−17 to 10−14 cm2 s−1) of the Li-ions lead to a poor rate performance of LiFePO4, and the poor electronic conductivity (10−9 to 10−8 S cm−1) is hindering its practical applications and must be tackled [15, 16, 17]. The preparation of nanomaterials for cathodes in Li-ion batteries (LIBs) has been proved to be one of the effective ways to overcome the problem of the slow Li diffusion and facilitate the reaction kinetics on the cathode. It is well known that porous structures can also increase the electrode/electrolyte interface area ensuring effective electrolyte permeation in cathode materials and substantially improve the performance of LiFePO4 and thus of the LIBs [17, 18]. It has been demonstrated that the adoption of ultrasonic-assisted impinging stream reaction is an effective method to produce positive electrode precursor particles for LIBs with high electrochemical performance [19].
(NH4)Fe2(PO4)2(OH)·2H2O has been prepared as positive electrode material for LIBs. The ultrasonication step was followed by a hydrothermal treatment step [20].
Apart from LiFePO4, the preparation of Li-Mn-O electrode materials for secondary Li-batteries has been examined. Kim et al. fabricated mesoporous LiMn2O4 nanospheres with upgraded properties and observed their performance in 50 cycles [21]. Sonochemical treatment of the surface of a corresponding Li-Mn-O electrode by coating particles with a porous film of MgO enhances its electrochemical properties, especially in high temperatures [22].
Mn3O4 is used as a precursor in the preparation of LiMn2O4 and can be synthesized using US in a direct step. Co3O4 used as key material in energy applications can be prepared by the same procedure [23]. Co3O4 nanoparticles (NPs) can be obtained by sonochemical synthesis also out of ionic liquids or azo ligands, using Co(CH3COO)2·2H2O as starting material [24, 25]. In both reports, the diameter of the particle size of Co3O4 could be decreased lower than 50 nm.
A plethora of carbon morphologies has been extensively investigated as potential material appropriate for anode electrode in LIBs. Carbon spheres constitute an example applicable in LIBs [26, 27]. It has been demonstrated that the use of US provides an opportunity to prepare the mentioned material in a nontoxic accessible manner under mild conditions and competent dimensions (150–400 nm) [28].
Furthermore, recently Kumar et al. [29] outlined the progress in sonochemical synthesis of carbon dots, while Gedanken et al. [30] presented an advanced hybrid electrode of Cu foil coated by a layer of Sn@C-dots@Sn NPs ranging from 50 to 200 nm. These NPs were formed via sonication and contributed in promising cycling endurance of the cell.
A novel approach for the preparation of electrodes is the use of composite materials based on graphene. Therefore, Fe(III) oxide was sonochemically coprecipitated on graphene nanosheets in order to obtain nanocomposites for rechargeable Li batteries with stable charge-discharge kinetics for ca. 120 cycles [31]. Wu et al. also prepared magnetite NPs on reduced graphene by using a one-pot US-assisted method. These nanocomposites allow for high performance lithium ion storage devices [32].
Reduced graphene oxide (RGO) nanosheets dispersed under ultrasonic irradiation in NV (Ni3(VO4)2) NPs prove to eliminate their agglomeration; thus, the highly conductive electrode fabricated by the composite NV/RGO can preserve 88% of its initial capacity (117.22 mA h g−1) after 1000 cycle tests [33].
Polyacrylonitrile (PAN) can be used as a component of solid composite electrolyte lithium battery [34]. A sonochemical method has been used to prepare negative electrode materials containing encapsulated intermetallic NPs in PAN. The use of US leads to very small particles of CoSn2, which favors the formation of amorphous Li-Co-Sn and CoSn2 alloys, while the carbonaceous matrix helps to maintain the small particle size. The resulting CoSn2-carbonaceous phase electrode (CoSn2@C) shows improved electrochemical behavior and is stable upon cycling (ca. 450 mA h g−1 after 50 cycles) in comparison with reports on pure crystalline CoSn2 [35].
Cu2O-based graphene composites have been prepared and tested for use as anode materials in lithium ion batteries [36] with superior performance than Cu2O and can be used also for photocatalytic applications, sensors, and energy storage, especially for supercapacitors [37].
Various reports investigate copper (II) oxide (CuO) and CuO/carbon composites as a possible anode material for LIBs [38, 39, 40, 41]. Studies exploiting sonochemical methods for fabricating these materials involve the synthesis of copper complexes in an ultrasonic bath and the following calcination of compounds between 400 and 500°C. In this way, CuO particle size can be decreased until 12.1 nm. However, the specific structure and dimensions of particles differ depending on the precursor and the treatment conditions [42, 43, 44]. Hajnorouzi proposed a new method called “direct sonoelectrochemistry” incorporating ultrasonic irradiation in the process of electrolysis of a Cu tip and a physical top-down method, “US ablation” with Cu foil as the starting material to produce CuO NPs [45]. In comparison with conventional electrochemical methods, the produced amount of NPs was increased, and their dimensions were controlled, while the total time of preparation was reduced.
Nanoporous silicon structures are considered to be an attractive material in the design of LIBs as they have a large theoretical specific capacity [46, 47, 48]. Bedini et al. reported the synthesis of hydrogenated amorphous Si NPs under ultrasonic irradiation in mild conditions [49]. The product was highly porous with dimensions of particle ranging from 1.5 to 50 nm.
Two-dimensional molybdenum disulfide (MoS2) NPs have high potential implementation not only in LIBs but also in sodium-ion [50], Li-sulfur [50], zinc-ion [50, 51], and Mg batteries [52]. Liquid-phase ultrasonic exfoliation method can be an attractive process to disperse nanosheets of MoS2 in various solvents [53]. One more layered 2D material that can be obtained with the contribution of US is V2O5 nanosheets according to Li et al., who fabricated and evaluated the electrochemical performance of the respective electrode [54].
Among the oxides of manganese, manganese dioxide (MnO2) finds application as energy storage material in alkaline batteries, rechargeable lithium batteries, and dry cells. Highly dispersed and nonagglomerated nano a-MnO2 with a needle form of 1–2 nm diameter and up to 50 nm length have been synthesized by ultrasonication of an aqueous manganese(ΙΙΙ)acetate solution with pH close to 7 followed by mild drying [55]. Reduction of KMnO4 has been also investigated as an alternative manner to exploit ultrasonic irradiation to prepare MnO2 [56, 57]. Okitsu et al. [56] provided useful data in order to comprehend the mechanism of basification, assisted by H2O2 molecules formed during sonication, while Gnana Sundara Raj et al. [57] used also polyethylene glycol so as to achieve reduction and prepare spherical MnO2 particles with dimensions from 10 up to 20 nm. This proved to exhibit proper electrochemical endurance (after 500 cycles, 87% of the initial capacitance was preserved, while in the end of 1000 cycles, 78% of the initial specific capacitance was preserved).
Not always is it possible to obtain the result one is looking for, during the preparation of nanomaterials using US. Ganesh Kumar et al. did not obtain lithiated manganese oxide suitable for lithium batteries by treating Mn(III) salts using US and hot-hydrolysis, but the study showed the superiority of the ultrasonication regarding the adjustment of particle properties [58]. In another attempt of the same group, LiNi0.5Mn1.5O4 was synthesized sonochemically as cathode with high redox potential for LIBs with better cyclability [59].
Zinc-air batteries (ZABs) exhibit a high energy density being at the same time a low-cost product. Therefore, a tremendous interest is present in meeting the demands for flexible and portable electronics. A novel porous-structured poly vinyl alcohol (PVA)-based nanocomposite gel polymer electrolyte (GPE) with silica (SiO2) was synthesized and used as electrolyte in a flexible ZAB. The fabricated porous material exhibited a high ionic conductivity (57.3 mS cm−1), excellent water retention capability, and improved thermal and mechanical properties under ambient condition, and the ZAB showed an excellent cyclability, discharge performance, and power density [60].
It has been reported that cerium metallic particles deposited on Zn anode for alkali batteries lead to an improved electrochemical performance, whereby US power and sonication time influence strongly the battery efficiency, increase the corrosion resistance of the anode, and suppress the Zn-dendrite formation [61].
Regarding the oxygen reduction reaction (ORR), highly efficient cathodes for ZABs have been prepared based by decorating Fe2P on 3D N,P-codoped porous carbon. The later has been prepared using pore-forming agents [62]. Further, bimetallic oxides like perovskites can be immobilized on different substrates and used as air electrodes in ZABs. As an example, one can use nafion, which has antifouling properties and is very interesting in electrochemical application owing to its interesting electronic and catalytic properties. As an example, we refer to Chen et al., who have immobilized SrWO3 on nafion by using US [63].
Nickel-iron layered double hydroxide (NiFe LDH) constitutes one more competitive catalyst with potential use in air cathodes, due to its layered structure. Sonication-assisted liquid exfoliation has been proposed to be competent to deliver highly functional NiFe LDH/CB nanosheets considering their oxygen evolution (OER) catalytic properties and stability [64].
Xie et al. prepared active cathodes for Ag2V4O11/Li battery systems through a reaction between V2O5 gel and Ag2O powder, which has been accelerated by using US [65]. The prepared cathodes (Ag2V4O11 and Ag1.4V3O8) exhibited superior electrochemical properties as compared to the ones prepared by this solid-state method.
In Li-S batteries, the sulfur host plays an important role. With respect to this, hierarchically ordered micro/mesoporous carbon (HPC) has been prepared by US-assisted spray pyrolysis obtaining HPC-S cathodes, which exhibited an excellent cycle retention of 77% in tests with 500 cycles at 2.4°C [66, 67].
An electrochemical mechanism for the direct combustion (chemical oxidation) of fuels, which bypasses the intermediate stage of heat generation (so-called “cold combustion”), allows for the direct conversion of chemical energy of a fuel to electrical energy without the losses due to the Carnot process. This direct energy conversion is possible in devices called fuel cells, and the underlying electrochemical mechanism has analogies in living beings [68].
There are several types of fuel cells, mostly categorized based on the used electrolyte. A second classification is based on the temperature needed by the electrolyte to achieve sufficient ionic conductivity and one speaks about low-, intermediate-, and high-temperature fuel cells.
The most important reaction in fuel cells is the provision with enough oxidant in order to keep the reaction running and thus the electricity production at the maximum level. This reaction is the reduction of the oxygen molecule (oxygen reduction reaction—ORR) as this is the source of the ions either to be transported through the solid electrolyte in solid oxide fuel cells (SOFCs) or to react with the protons arriving through the electrolyte in polymer electrolyte membrane (PEM) fuel cells.
In PEMs, the operating temperature is low, and therefore, the kinetics of the ORR is not high enough without the use of catalysts [69].
We prepared using the sonoelectrochemical method a Pt and carbon black-based nanocomposite as electrocatalyst for PEM fuel cells. We used pulsed electrodeposition in combination with pulsed ultrasonication to obtain Pt NPs on carbon black substrates, and we have shown the beneficial role of polyvinylpyrrolidone (PVP) against the agglomeration of the produced NPs [70].
Despite the reports of many research groups that Pt-based materials are considered to be the best electrocatalyst for ORR in fuel cells, there is no doubt that their reserves in nature are very limited making them expensive. Further, their durability is not as high as needed to use them in commercial applications. Therefore, reduction of the Pt consumption and most importantly their replacement with nonprecious metal catalysts in the ORR are considered essential. Therefore, the development of non-Pt or metal-free ORR electrocatalysts is extremely important and urgent [71].
Pd-based catalysts are one of the most attractive choices for the replacement of Pt catalysts as their cost is significantly lower, and at the same time, they possess a high catalytic activity for ORR not only because of the Pd itself but also due to synergistic effects between the Pd and the other components and supports [72]. Until now, different Pd-based composite materials have been proposed and investigated as catalysts for ORR [73, 74].
A very useful overview on sonochemically prepared multicomponent electrocatalytic materials for low-temperature fuel cells is given by Lee and Kwon [75]. Most of the efforts are focusing on the partial replacement of Pt by low-cost metals, for example, Ni [76], or the Pt replacement by Pd and respective nanoalloys with low-cost metals (Mn and Fe as core-shell with Pd) as well [77]. Carbon-supported Sn NPs for electrochemical applications and especially for improving the kinetics of the ORR have been sonochemically synthesized and showed high reduction overpotential for the ORR mainly due to the high surface area of the resulting carbon-supported Sn electrode [78].
Further improvement in the catalytic activity of the developed catalysts is expected through core-shell architecture materials and also through the use of active supports with high porosity leading to high active centers on the catalyst surface. Unique Pd@Pt/C core-shell NPs as methanol-tolerant catalysts have been prepared by Zheng et al. in a sonochemical multistep approach [79]. The high performance of the Pd3Pt/C catalyst is ascribed to the unique combination of preferable growth of the Pd (1 1 1) plane, small particle size (∼4 nm), unique core/shell structure, and the electronic effects between Pd and Pt.
Alternative electrocatalytic materials for the ORR have been also prepared starting from biomass and turned out to be promising alternatives to noble metal catalytic materials. The resulting catalysts exhibit an excellent catalytic activity as compared to commercial catalysts with reduced methanol crossover [80].
Also, oxides of transition metals have been sonochemically prepared as electrocatalysts for the ORR. Highly active porous MnO2 with superior electrocatalytic activity as compared to commercial Pt/C catalyst has been sonochemically prepared and tested by Zuo et al. as a promising catalyst for direct methanol fuel cells [81].
US has been used also for the preparation of electrolyte membranes for PEMs. Nanocomposite membranes based on sulfonated polybenzimidazole (PBI) with cellulose and silica precursors have been made with improved mechanical properties and decreased methanol permeability [82].
Zuo et al. prepared a composite cathode material for alkaline fuel cells based on MoS2 decorated with Pd using a simple sonochemical route [83]. They found that the new electrocatalyst has better performance than commercial Pt/C catalysts.
Fuel cells working at temperatures higher than 500°C are referred to as intermediate (<700°C) and high temperature (700–850°C) fuel cells. These are proton conducting ceramic fuel cells (PCFCs), molten carbonate fuel cells (MCFCs), and solid oxide fuel cells (SOFCs). In all these fuel cells, the ORR is important, but in general, the use of catalysts is not necessary on the cathode side because of the high service temperatures.
In SOFCs, the ORR is as important as mentioned in the PEM section, but here the temperature is high enough to accelerate the ORR without the use of specific catalysts [84]. SOFC cathodes must be efficient mixed ionic-electronic conductors (MIECs) as they need to transport both electrons and ions especially in intermediate SOFCs (IT-SOFCs) [85].
Once the cathode reaction is providing a sufficient amount of oxygen ions in SOFCs, the anode material is of outmost importance as it has to catalyze the oxidation reaction.
One of the critical components for such a device is hydrogen, which is the fuel to be oxidized. Hydrogen can be produced by not only the classical methods such as reforming of hydrocarbons, gasification of coal or heavy oil fractions, and electrolysis using renewable or nuclear energy sources but also sonochemically and sonoelectrochemically, as reported in a recent review [86]. Other groups have developed electrocatalysts for hydrogen evolution using US. High intensity ultrasonic irradiation of AlNi alloy has led to an electrocatalyst for water splitting with high surface area and changes in its composition, which can be controlled by the selection of the right fluid during sonication [87]. Nitrogen doped reduced graphene oxide supported on N-titania as efficient catalysts for the production of hydrogen through water splitting has been prepared in a combined sonochemical/hydrothermal step [88].
As oil and natural gas supply is well established, feeding SOFCs directly with natural gas would be an ideal solution [89]. For natural gas fed SOFCs, the catalytic activity of the anode materials is critical as it needs not only to accelerate the oxidation reaction but also to prevent poisoning of the active centers by coking and sulfur and to be stable against other components that may be contained in the natural gas.
In our group, several efforts have been made in order to improve the preparation methods of SOFCs [90, 91, 92, 93, 94] and SOFC materials [95, 96] with a focus on the anode compartment [97, 98, 99]. Emphasis was given on the implementation of US in order to reduce the preparation time or to follow a facile and/or alternative path for materials with improved properties. In most cases, we prepared nanomaterials because they offer special properties to the fuel cells as they are catalytically active to a wide range of chemical reactions. One can prepare novel SOFC anodes by decorating state-of-the-art anode powder with nanometric metals and metal oxides [100]. We decorated anode materials based on GDC/Nickel and YSZ/Nickel cermets with molybdenum and tungsten oxide NPs and improved the catalytic activity and stability of the resulting composite anodes against coking and sulfur poisoning [101].
Not only electrodes for SOFCs have been made using ultrasonication but also electrolytes. Okkay et al. prepared samaria doped ceria (SDC—Ce0.8Sm0.2O1.9) using an US-assisted coprecipitation method [102]. It has been found that the lattice parameter of the produced nanomaterial increased with increasing ultrasonic acoustic power and is linearly related to the ionic conductivity of the resulting electrolyte after sintering at 1200°C. Pinjari and Pandit prepared sonochemically at room temperature ceria nanopowders with particle size less than 30 nm with clear benefits regarding energy efficiency and reaction time as compared to the conventional preparation method [103]. Sonochemistry has been also used to prepare Ce(III) nano-sized precursors for nanoceria [104].
USs can be used not only in batteries and fuel cells but also in many other electrochemical and sonoelectrochemical applications. Ultrasonication has been used for the preparation of electrocatalysts for the direct electrooxidation of ethanol. A facile US-assisted method was proposed to fabricate the Pd-Pt alloy/multiwalled carbon nanotube (Pd-Pt/CNTs) nanocomposites for the ethanol and methanol electrooxidation reaction in alkaline media [105].
In another attempt, a catalyst made of graphene supported Ag decorated Pd NPs with exceptional activity and uniformity. In this respect, it has been shown that graphene is very important as substrate as it minimizes the coalescence of the NPs, which would decrease both the surface area and the electrocatalytic activity [106]. A multifunctional nanostructured electrocatalyst has been prepared by replacing carbon copper nanowires by Pd resulting to Pd@CuNWs and supported them by multiwalled carbon nanotubes (MWCNTs) using chitosan (CH) as a binder. Electrochemical catalytic activity and durability evaluation results proved the superiority of the resulting Pd@CuNWs/MWCNTs/CH regarding electrocatalytic activity and long-term stability compared to Pd/MWCNTs and commercial Pd/C electrocatalysts for ethanol electrooxidation [107].
An overview on fundamental studies of sonochemical and sonoelectrochemical nanomaterial preparation is given in recent publications of our group on fuel cells [108, 109] and others on nanomaterials [110].
Silica gels have been considered as appropriate matrices for the preparation of complex center doped materials for a variety of applications such as controlled-release carrier implantable materials for low weight drugs in biological systems and as substitute materials for membrane processes in fuel cells [111, 112].
Ultrasonication can be used for the atomization of methanol in order to have a smooth and continuous feed in direct methanol fuel cells, leading to a high and stable open circuit voltage (OCV) [113] or to enable improvement of direct methanol fuel cells using sonication in parallel with a novel cell design with integrated ultrasonic transducer [114].
Photocatalysis is a phenomenon based on redox reactions, which take place at the surface of a semiconductor material under UV or visible light irradiation. The photocatalytic activity of the catalyst depends on its ability to create electron-hole pairs, which are then taking part in a redox reaction to generate hydroxyl and superoxide radicals, which are able to undergo secondary reactions [115].
The improvement of the photocatalytic efficiency is a strategy, which was developed to push the absorption onset of TiO2 toward longer wavelengths (anatase band gap, 3.2 eV) by doping TiO2 with anions and/or cations and metal ions [116, 117, 118]. Zinc oxide can be either a n-type or a p-type semiconductor with a wide band gap (Eg ≈ 3.3 eV at 300 K), while its composites are very interesting materials because of possible synergistic effects on photoelectrochemical properties and photocatalytic activity [119, 120]. The primary ways to improve the photocatalytic effect can incorporate a sonocatalytic technique [121], doping [122], or stratified films [123, 124].
The photocatalytic degradation of organic pollutants such as dyes, pesticides, and pharmaceutical waste is a crucial application for the safety of the ecological system, mainly due to their toxicity and degradation complexity. The main application areas in catalysis are photocatalytic electrolysis of water, environmental protection, and solar cells. The pollutants in wastewater can be roughly divided into organic and inorganic pollutants, where organic compounds can be degraded by TiO2 photocatalytic technology [125].
Converting CO2 waste into valuable carbon fuels is undoubtedly one of the most viable and economical alternatives to reduce the CO2 emissions and resolve the energy crisis. UV irradiation and visible light have been used as sources of excitement for semiconductor catalysts to produce energy-bearing products such as methane, methanol, carbon monoxide, formic acid, and formaldehyde. Photocatalytic reduction of CO2 can not only reduce the carbon dioxide emissions but also solve the energy crisis [126, 127, 128]. Some of the catalysts that can be used for the photocatalytic reduction of CO2 include WO3 [120], ZnIn2S4 [129], CdS [130], Cu2O [117], CuInS2 [131, 132], and BiVO4 [133].
Stucchi et al. used sonochemistry to both form NPs from the precursor and achieve a good distribution on the TiO2 decoration surface [117]. In fact, US energy accelerates the diffusion of the dissolved substance into the reaction system and also affects the selective adsorption of the surfactant on copper, causing elongation or compression in certain directions, thus affecting the morphology of the particles. The utilization of Cu, CuO, and Cu2O NPs on TiO2 surface can greatly enhance the photodegradation of acetone and acetaldehyde [118].
CdS/TiO2 can be prepared at a relatively low temperature (70°C) with small particle sizes (11 nm) using US in a short time (1.5 h) [130]. On the other hand, the use of conventional methods requires at least 20–24 h and elevated temperatures (200–400°C). The properties of complex core-shell materials are combinations of the properties of both materials in the core and the shell. Those materials can be used in photovoltaic cells, optical sensor photocatalysts, and catalysts. In addition, CdS/TiO2 NPs can selectively bind heavy metal ions, such as Cr (VI), on their surface [134].
The irradiation of W(CO)6 in diphenylmethane in the presence of an Ar-O2 mixture for 3 h can lead to tungsten oxide NPs consisting of both orthomolecular and monoclinic WO2, partial oxidation of which produces tricyclic WO3 [135]. WO3 acts as a catalyst in reducing CO2 in fuels (CH4 and CH3OH) with significant catalytic efficiency [136]. The introduction of CdS on WO3 can enhance carbon dioxide adsorption and increase CH4 selectivity, while the existence of two different regions can minimize undesirable back reactions of the photocatalytic products [137]. Those material CdS/WO3 can also use for the photocatalytic degradation of organic dye rhodamine B [138].
Xin et al. synthesized ZnIn2S4 nanosheets with hexagonal and cubic structures. The samples were prepared and used to form methyl formate by photochemically reducing CO2 to methanol. The efficiency of the hexagonal form was better than the cubic one. In addition, both hexagonal and cubic nanosheets exhibited much higher activity than ZnIn2S4 microspheres prepared by the hydrothermal method [129]. The ZnIn2S4-In2O3 structure is effectively used as a photocatalyst in CO2 reduction, by offering a large surface area for CO2 adsorption, while it exhibits abundant active sites for surface catalysis, leading to significant CO production rate and high stability [139].
Copper can also be used to prepare a CuInS2 NP structure. The study of various parameters, such as the different crystallographic structures of sulfur, the concentration of precursors, the reaction time, and the power of ultrasonic radiation on the morphology and particle size, showed that the crystallinity of sulfur plays an important role in the morphology of CuInS2 [131, 132]. Reducing CO2 to solar fuel can be essential for both decreasing CO2 emissions and increasing energy production. This photoelectrochemical reduction of CO2 to methanol is carried out by using p-CuInS2 as a photocathode [140].
BiVO4 NPs can be synthesized sonochemically at room temperature at different pH values (3, 5, and 10) of the original precursor without further heat treatment. The morphologies of the final samples are different depending on the pH value of the original precursor. The BiVO4 sample, which was prepared at a higher pH value, has an advantage in photocatalytic performance. The excellent photocatalytic efficiency can be attributed to the superior crystallinity and the large active surface of the BiVO4 structure [133], while its photocatalytic activity was studied during the degradation of organic dyes [134].
Metal-organic frameworks (MOFs) are a new class of porous crystalline hybrid materials that have achieved a tremendous growth over the last decades, with attention not only in chemistry but also in general science and technology. They consist of inorganic metal-based centers (ions or clusters) and organic ligands, assembled through strong coordination bonds in order to create an open crystalline framework with permanent porosity.
These ordered crystalline structures possess physicochemical properties, such as high surface area, open metal sites, and large void space. The easy tuning of the shape, size, and chemical nature of pores has led to unique chemical versatility and various morphologies, such as micro- or nano-spheres, -cubes, -sheets, and -rods [141, 142, 143]. Furthermore, accessing the molecular adsorption sites has opened the way to host-guest interactions and the ability to capture materials in both chemisorption and physisorption states [144]. Due to their controllable composition and targeted preparation, MOFs can be manipulated, so they can be used in specific applications.
MOFs have been very promising in a wide spectrum of applications, ranging from the well-known gas storage/adsorption [145] and separation [146], catalysis [147], sensing [148], and dye/toxic material removal [149] to recently rising fields, such as luminescence [150], membranes [151], and drug delivery [152]. In terms of energy-related applications, they have been used for solar energy conversion [153], supercapacitors [154], batteries [155], and fuel cells [156].
MOFs have been traditionally synthesized either at room temperature [157] or via a hydrothermal/solvothermal approach by using electrical heating, an oil bath, or an autoclave at high temperatures, for a prolonged time of hours or even days. Recently, new methods have arisen to avoid these conditions. Similar to conventional, as a heating-based technique, microwaves (MWs) have lately been used widely for the synthesis of MOFs [158, 159], by offering phase selectivity, fast crystallization, and control over the crystal morphology. Electrochemical [160] and mechanochemical syntheses [161] are alternative methods, which appeared in 2005 and 2006, respectively. Other than the above popular methods, slow diffusion [162], reverse micelle [163], and combinations like sonoelectrochemical [164] have been tested as well.
This section is focused on the effect that US synthesis conditions have on the final product along with the use of sonochemically prepared MOFs in environmental applications with regard to harmful substance removal. (Zn3BTC2)·12H2O (BTC = 1,3,5-benzenetricarboxylate) was the first MOF that was successfully prepared by applying a sonochemical method in 2008 [165], followed by MOF-5 [166] and ZnBDC (BDC = 1,4-benzenedicarboxylate) [167] later that year.
In order to reveal the determining factors of the reaction rates, a kinetic study was performed in 2010, by comparing conventional, microwave, and US syntheses [168]. Fe-MIL-53 was chosen for the comparison due to its mild synthesis conditions. The average reaction time to obtain the product is 1.5–3 days at 70–80°C for the conventional synthesis, 1.5–2.5 h at 60–70°C for microwaves, and 0.5–1 h at 50–70°C for the US, which is a result of increased preexponential factors in the sonochemical method.
Synthesis conditions can heavily affect the quality of crystals, the particle size, the surface area, and the morphology; thus, various studies have been published in an effort to optimize the reaction time, US power, solvent ratios, reagent concentration, and modulators/additives and achieve the best results in targeted applications [169, 170].
The contamination of the environment is becoming an aggravating problem [171, 172]. As a result of the accelerated expansion of chemical, pharmaceutical, and agricultural industries, many hazardous compounds, such as dyes, antibiotics, and pesticides, reach the aquatic environment. Therefore, many scientists have dedicated their work for the production of materials that can remove harmful substances.
Abbasi et al. compared the sonochemical synthesis of HKUST-1 with a mechanochemical one [173]. The majority of the mechanochemically prepared particles had a size of at least 60 nm, while the US led to particles mainly around 35–65 nm. Their adsorption efficiency was tested via the removal of two dyes. After 24 h, 19.52% of methylene blue and 10.86% of crystal violet had been adsorbed by the mechanochemical MOFs, while the US one had managed to remove 31.91 and 27.43%, respectively. The increased adsorption of methylene blue could be explained due to its smaller size, so it can be captured more easily than crystal violet.
In order to improve the methylene blue adsorption performance of TMU-23, a composite was prepared with graphene oxide (GO) in a US bath within 60 min at room temperature [174]. About 30 mg of GO-TMU-23 (10% GO) was added in 20 mL of 10 ppm aqueous solution, as well as 27 mg TMU-23 and 3 mg GO were also examined separately for comparison purposes. After only 2 min, TMU-23, GO, and GO-TMU-23 have removed 50, 47, and 89% of MB, respectively, while after 15 min, they have removed 78, 90, and 97%, respectively. Another GO composite is GO-Ni-BTC, which was prepared via an US-assisted ball milling technique [175]. Water was used as the only solvent as the coupling effect of mechanical force and ultrasonic waves can promote the reaction without an organic solvent. The Ni-BTC and GO-Ni-BTC were compared by studying the thermodynamics, along with adsorption kinetics by using the congo red dye, resulting in capacities of 2046 and 2489 mg/g, respectively.
[Zn(ATA)(BPD)]∞ nanoplates (ATA = 2-aminoterephthalic acid, BPD = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene) were prepared at room temperature in a US bath within the optimized duration of 120 min [176]. The addition of triethylamine accelerated the crystal growth, and crystals could get separated after 60 min, but 120 min was still needed to receive fully uniform nanoplates. The modulator implementation led to an increase in 2,4-dichlorophenol adsorption from 68 to 91%. Pyridine had also been tested as a modulator agent during the synthesis of [Zn(TDC)(4-BPMH)]n·n(H2O) (TDC = 2,5-thiophene dicarboxylic acid, 4-BPMH=N,N-bis-pyridin-4-yl-methylene-hydrazine) [177]. Its addition led to better morphology of uniform sheet-shaped nanoplates with a thickness of 20–35 nm instead of NPs without order, while it also increased the removal efficiency of dichlorophenol and amoxicillin from 92.5 to 95% and from 87 to 94.5%, respectively, after 3 h.
The adsorption of rifampicin (antibiotic drug) [178] and imatinib (anti-cancer drug) [179] was tested as well with HKUST-1. The MOF was prepared by both a sonochemical method within 60 min and a conventional one after 24 h at 80°C. The US synthesized particles had an average size of 80 nm, while the majority of the conventional ones had a size over 150 nm. Regarding the uptake properties, the former could adsorb 26.6% of rifampicin after 3 h and 98% after 48 h, while the latter could reach 19% and 59.6%, respectively. Similarly, although a greater time period was needed, after 144 h, 96.7% of imatinib was adsorbed by the US HKUST-1 and 81.1% by the conventional one.
Among the several types of fuel cells, the use of nanoparticles has been implemented for improving the ORR in cathodes and the stability and poisoning of the anodic catalysts enhancing mainly the mass transfer phenomena. US-assisted preparation methods have been enabling more facile and cost-effective preparation methods of producing mono- and bimetallic nanoparticles in the absence and presence of various surfactants than conventional methods of preparations. The produced nanoparticles were decorated onto cathode surfaces used in low- and high-temperature fuel cells acting synergistically with the surface toward an enhanced catalytic activity. The use of US and/or sono(electro)chemical methods also produces a controllable variety in the shape of the exposed planar sites of the moieties onto electrode surfaces and was proven to be a powerful tool for reducing metal precursors to mono- or/and bimetallic nanoparticles. Especially, in the case of carbon-supported nanocatalysts, the use of US, in general, has been proposed toward a high-value product production to meet the needs of energy applications.
US-assisted preparation methods are also a very promising tool in developing highly efficient materials for batteries. Significant efforts have been focused on creating functional nanomaterials in a variety of morphologies while decreasing the time and cost of preparation for meeting the commercial requirements. Substantial research has been reported in the field of Li and Li-ion batteries, where certain materials were directly tested in custom-made batteries with promising performance. Concerning other battery systems such as zinc-based and metal-air batteries, research showed promising results, although various nanomaterial candidates for electrodes, electrolytes, or catalysts have been prepared but not thoroughly tested. A more focused research trend in implementing the synthesized US-assisted nanomaterials in battery applications is currently toward a complete range definition of characteristics and stability in order to overcome possible failures and limitations.
In terms of environmental studies, semiconductor nanoparticles and composites prepared via US technology have shown promising results toward photocatalysis. Carbon dioxide reduction has achieved great process on both the reaction mechanisms and the pathways; thus, such materials can display better product selectivity.
Finally, USs have opened the way to fast and facile synthesis of metal-organic frameworks by further offering smaller particle size and enhanced morphologies. Compared to conventional methods, the accelerated nucleation and crystallization times have made sonochemistry very attractive over the last few years, although proper handling is necessary in regard to synthesis conditions for the acquisition and optimization of desired properties.
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