Open access peer-reviewed chapter

Mesoporous Carbons for Energy-Efficient Water Splitting to Produce Pure Hydrogen at Room Temperature

Written By

Mohindar S. Seehra and Vishal Narang

Submitted: October 23rd, 2015 Reviewed: February 15th, 2016 Published: August 24th, 2016

DOI: 10.5772/62503

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Abstract

Theoretical and experimental aspects of the use of mesoporous carbons in carbon-assisted water electrolysis (CAWE) to produce pure hydrogen at room temperature are presented. It is shown that the electrical energy requirements for CAWE can be as low as 20% of the energy needed for conventional water electrolysis, the extra energy coming from the electrochemical oxidation of carbon occurring at room temperature. Although CO2 is produced at the anode in this process, it is well separated from pure H2 produced at the cathode. Experimental results are reviewed for a variety of carbons with the major focus on the results obtained with carbon BP2000, which has both mesopores and micropores and a nanocarbon produced by the hydrothermal treatment of microcrystalline cellulose.

Keywords

  • Hydrogen
  • Carbons
  • Electrolysis
  • Energy efficiency
  • Carbon dioxide

1. Introduction

Mesoporous materials with pore size from 2 to 50 nm fall in the middle range between microporous (pore size <2 nm) and macroporous (pore size >50 nm) materials. In a recent book edited by Titirici [1] and a review by Liang et al. [2], various processes for producing mesoporous carbon materials have been described. Sevilla and Fuertes [3] and Seehra et al. [4, 5] used hydrothermal treatment of cellulose and lignin to produce nanoparticles of carbon. Liu and Guo [6] compared the characteristics of carbons produced by the hydrothermal treatment of holocellulose and crude biomass. Other methods of preparing mesoporous carbons have been reported by Zhou et al. [7] for supercapacitor applications. Such carbons produced by different methods have applications in separation processes, catalysis, energy storage (such as super capacitors), and energy conversion. A very popular commercial source of mesoporous and microporous carbons is non-graphitized Black Pearls (BP) carbon blacks manufactured by Cabot Corporation. The pore structures of the BP carbons have been reported by Kruk et al. [8].

The focus of this review is on the use and the science of mesoporous/microporous carbons for the electrochemical production of pure hydrogen at room temperature employing electrical energy as low as 20% of the energy used in ordinary water electrolysis (WE). This process was first proposed and demonstrated by Coughlin and Farooque [9, 10] and developed more fully in the recent investigations of Seehra et al. using a variety of carbons and termed as carbon-assisted water electrolysis (CAWE) [11, 12]. Some follow-up studies of this process have been reported by Dubey et al. [13] using a carbon nanotube anode and by Giddy et al. [14] using a solid-state electrolytic cell. A different variation of this process involving hydrogen generation by laser irradiation of a carbon powder suspension in water has been reported by Akimoto et al. [15]. Results of the hydrogen evolution rate RH using a variety of carbons show some proportionality to the surface area of a carbon which in turn is related to the pore structure of the carbons. The best results so far have been obtained with carbon BP2000, which as shown later has both micropores and mesopores and a surface area of about 1500 m2/g.

This review covers the science behind CAWE followed by select experimental results and a comparative energy analysis of the process vis-à-vis conventional WE. Such comparative energy assessment of different processes to produce H2 is essential for considering practical applications of the different processes. The remaining sections are organized as follows. In Section 2, prominent analytical techniques used in the structural characterization of porous carbons are reviewed with some examples imported from the published literature. Section 3 deals with the science behind CAWE and the experimental results on the electrochemical production of hydrogen reported in the literature using different carbons. The comparative energy analysis of the CAWE and WE processes is presented in Section 4. Concluding remarks of this review are given in Section 5.

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2. Structural characterization of porous carbons

The porous structure of materials is often determined by means of adsorption of gases such as nitrogen and argon over a wide range of pressures. For activated carbons, the resulting structure depends on the process of activation, the activation agent, and the nature of the raw material used for producing a carbon. Kruk et al. [8] reported the surface and structural parameters (standard BET surface area SBET, external surface area Sex, micropore volume Vmi, and total pore volume Vt) of six carbon blacks produced by Cabot Corporation. These are named as Cabot BP120, BP280, BP460, BP800, BP1300, and BP2000 with SBET = 30, 41, 78, 242, 520, and 1450 m2/g, respectively. The pore volume distribution of these six carbons determined from nitrogen adsorption and desorption isotherms at 77.35 K and reproduced from Ref. [8] is shown in Figure 1. From these graphs, it is evident that BP 120 and BP 280 have only small amount of pores, mostly in macroregion. BP460 has some mesoporosity, whereas BP800 and BP1300 are largely mesoporous with some microporosity. In contrast, BP2000 contains large fraction of micropores in addition to mesopores and some macropores. The ratio of SBET/Vt for BP120, BP280, BP460, BP800, BP1300, and BP2000, based on the numbers given in Ref. [8] are 375, 410, 269, 356, 571, and 829 m2/mL, respectively, showing that shapes and sizes of the particles and pores for the BP1300 and BP 2000 are quite different from the other four carbons.

Figure 1.

Pore size distribution of the six carbon blacks. (Reproduced with permission from Kruk et al. [8], copyright Elsevier 1996).

Characterization of seven activated carbons from PICA-USA for supercapacitor applications is reported by Gamby et al. [16]. Their BET surface areas ranged from a low of 1200 m2/g to a high of SBET = 2315 m2/g. These carbons contained roughly equal fractions of microporous and mesoporous volume fractions with total porous volume ≈1 cm3/g for pore sizes <50 nm. The microporous volume increases nearly linearly with increase in the surface area. The specific capacitance increased by about 40% with increase in SBET from about 1000 m2/g to about 2000 m2/g. This improvement in specific capacitance was tentatively related to increase in the mesoporous volume of the carbons.

Figure 2.

Wide-angle X-ray diffraction patterns of the three PICA carbons. (Reproduced with permission from Manivannan et al. [17], copyright Elsevier 1999).

Manivannan et al. [17] reported characterization of three PICA carbons viz. GX203, P1400, and Med50 with SBET = 1000, 1150 and 2000 m2/g, respectively, using the experimental techniques of wide-angle X-ray diffraction (WAXD), Raman spectroscopy, magnetometry, and electron spin resonance (ESR) spectroscopy. In Figure 2, we show the WAXD patterns of the three carbons using Cu-Kα source, with the broad lines near 2θ = 24° and 44° due to graphitic crystallites corresponding to the (002) and (101)/(101) Bragg lines, respectively. The widths of these lines are then used to determine Lc (La) as the crystallite sizes along the c(a) directions, yielding Lc ≈ 1 nm and La ≈ 3 nm for these carbons. The Raman spectra of the three carbons, shown in Figure 3, can also be used to determine La from the empirical relation: La (nm) = 4.4/R, where R = I(1350)/I(1600) is the ratio of the intensities of the D band near 1350 cm−1 and the G band near 1600 cm−1. This analysis also showed La ≈ 3 nm in agreement with the results from WAXD. A similar comparison of the use of WAXD and Raman spectroscopy for characterizing carbons is given by Cuesta et al. [18]. ESR and magnetometry was used by Manivannan et al. [17] to determine the density of ESR active surface dangling bonds and nature of magnetic impurities which otherwise could not be detected by WAXD.

From the WAXD data shown in Figure 2, it is evident that for the lower 2θ values, the scattered intensity of X-ray photons increases sharply with decrease in 2θ. This is a characteristic feature of many amorphous materials. Measurements of the intensity of scattered X-rays covering smaller angles from 2θ = 0.1° to 10° are termed small angle X-ray scattering (SAXS), and it can provide very useful information about pore sizes and structural aspects of macromolecules between 5 and 25 nm. In this case, the quantity plotted is the intensity I(q) of the scattered X-rays of wavelength λ as a function of momentum transfer q = 4π·sinθ/λ and such a plot can separate out contributions from micro and macropores [19]. In general, the intensity I(q) ~ q−α where α = 6−D, with D being the dimensionality of pore-boundary surface [20]. Experiments of SAXS in a lignite coal showed α = 3.5 and so D = 2.5 signifying fractal nature of the surface. Peaks in the I(q) versus q provides information on the size of macromolecules as for example observed in carbon nanotube suspensions [21].

Figure 3.

Raman spectra of the three PICA carbons. (Reproduced with permission from Manivannan et al. [17], copyright Elsevier 1999).

Techniques other than those described above that have also been used for the characterization of carbons include Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). FTIR spectroscopy is particularly useful for determining the nature of surface functional groups. The use of all these techniques except XPS was employed in the characterization of the carbons produced from the hydrothermal carbonization of microcrystalline cellulose [4]. SEM/TEM is indispensable tools for visualization of the size and morphology of the particles [15], and TGA provides good information on the decomposition and oxidation characteristics of carbons [4]. The technique of XPS is often used for determining the elemental composition of a material. In summary, techniques that are used for structural characterization of other materials can also be used for carbons.

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3. Carbon-assisted WE

The basic reactions for the well-known process of WE and Carbon-assisted water electrolysis (CAWE), the latter proposed by Coughlin and Farooque [9, 10], are given below:

3.1. Water electrolysis (WE)

Anode : 2 H 2 O O 2 + 4 H + + 4 e E1
Cathode : 4 H + + 4 e 2 H 2 E2
N e t reaction : 2 H 2 O 2 H 2 + O 2 E3

3.2. Carbon-assisted water electrolysis (CAWE)

Anode : C s + 2 H 2 O C O 2 + 4 H + + 4 e E4
Cathode : 4 H + + 4 e 2 H 2 g E5
N e t reaction : C s + 2 H 2 O l C O 2 g + 2 H 2 g E6

To understand why CAWE is more energy efficient than WE, the change in the Gibbs-free energy ΔG = ΔH—TΔS needs to be determined where ΔH (ΔS) is the change in enthalpy (entropy) of the system at temperature T. This is valid for the reactions under constant temperature and constant pressure conditions. Enthalpy is best understood as standard heat of formation of a compound from its basic elements at 25°C, the enthalpy being zero for the elements. For a compound to be stable, ΔH has to be negative. A reaction is favored if ΔG = ΔG (products) − ΔG (reactants) < 0 which implies that a reaction is favored if, ΔH < 0 and ΔS > 0. We now apply these concepts to reactions for WE and CAWE listed in Eqs. (1)–(6).

At 25°C, ΔH (l) = −68.32 kcal/mol for water and ΔH (g) = −94.05 kcal/mol for CO2 [22]. The standard molar entropies (in units of cal/mol K) are 31.2, 49.0, 16.7, and 51.0 for H2(g), O2(g), H2O(l), and CO2(g), respectively. Using these numbers for reaction (3) gives ΔH = 136.64 kcal and TΔS = 23.23 kcal for 298 K, yielding ΔG = ΔH−TΔS = 113.41 kcal > 0. ΔG being >0 means that the reaction (3) is not favored and energy must be supplied to split water into H2 and O2. Finally, ΔG is related to the electrical potential Eo generated in the reaction by the relation [22]:

ΔG=nFEoE7

Here, n is the number of electrons involved in the reaction and F = 96484.56 C/mol is the Faraday constant. For WE, n = 4 according to Eq. (1) leading to Eo = −1.23 V. The negative sign implies that a minimum of Eo = 1.23 V must be applied to split water. Note that we have used 1 cal = 4.184 J and volt = Joules /Coulomb.

For CAWE, defined by reaction (6), a similar analysis yields ΔH = 42.59 kcal, ΔS = 80.05 cal leading to ΔG = 18.74 kcal and Eo = −0.20 V. This suggests that for reaction (6) to proceed, a minimum Eo = 0.20 V needs to be applied which is a factor of 1.23/0.20 ≃ 6 smaller than that needed for reaction (3) of WE. This extra energy comes from carbon which gets oxidized to CO2 in the process, making CAWE six times more energy efficient than WE, at least theoretically. This process of CAWE may thus be classified as electrochemical gasification of carbon at room temperature producing pure H2 at the cathode which is well separated from pure CO2 produced at the anode.

Figure 4.

A schematic diagram of the three-electrode cell with Pt plate as anode (surface area = 6.8 cm2) and Pt coil as cathode (surface area = 2.5 cm2). A magnetic stirrer was used to stir the contents of the anode. (Reproduced with permission from Seehra et al. [11], copyright AIP Publishing LLC 2007).

Experimentally, an electrochemical cell of the type shown in Figure 4 is often used. Because of the over-potentials of the electrodes which are related to their intrinsic properties and surface structure, Eo considerably greater than the theoretical 1.23 V in WE and the theoretical 0.20 V in CAWE needs to be applied to initiate H2 evolution. Electrodes made of Pt and Pd are often used because they have the lowest over-potentials [23]. For each applied voltage Eo between the cathode and the anode, the quantities measured are as follows: (i) current Io; (ii) the time tH needed to produce the same amounts of H2 for each Eo as measured by gas chromatography; and the computed quantities such as the hydrogen evolution rate RH = 1/tH and the efficiency factor AH = RH/EoIo representing evolved H2 per kWh of energy used. The voltage Eo is with respect to the standard hydrogen electrode (SHE), and it is determined from the Eq.: Eo = E(P) + 0.22 V where E(P) is the voltage measured by the potentiostat with respect to the reference electrode Ag/AgCl with Eo = 0.22 V (SHE). It is noted that in many publications, voltages listed are simply E(P), and this needs to be kept in mind while comparing with the theoretical estimates.

Figure 5.

Forward and reverse current–voltage characteristics of the reaction, with and without adding carbon BP2000. (Reproduced with permission from Seehra and Bollineni [12], copyright Elsevier 2009).

In Figure 5, the effect of adding carbon BP2000 to the anode in the amount of 0.08 gm/cm3 of the electrolyte (3.7 M H2SO4) is shown in terms of current–voltage plot. Without added carbon, an increase in current indicative of the start of WE only begins for Eo > 2 V. With the addition of carbon BP2000 to the anode, a rapid increase in current accompanied by evolution of H2 gas at the cathode was observed for Eo > 0.4 V. These results are consistent with the theoretical predictions mentioned earlier in that the presence of carbon in the anode significantly lowers the threshold voltage to initiate WE and produce H2 gas at the cathode.

It is noted that 3.7 M H2SO4 is chosen for the electrolyte since this particular concentration was found to have the highest electrical conductivity [10]. Similarly, the carbon concentration of 0.08 g/cm3 was determined to be most efficient and practical by varying the concentration of the added carbon [11, 12]. A number of carbons were tried for their effects on the hydrogen generation rate RH (Figure 6). As evident in Figure 6, carbon BP2000 yielded the best RH values and so most of the follow up experiments were made with carbon BP2000 [12]. Another carbon that produced similar RH values was the carbon produced by the hydrothermal treatment of microcrystalline cellulose using water as solvent and treated at 250°C for 60 min under the maximum pressure of 800 psi. This hydrothermal carbonization yielded spherical carbon particles of about 210 nm [4]. In the following section, the results obtained with carbon BP2000 [12] and hydrothermally treated cellulose are compared. The liquid-phase products obtained in the hydrothermal treatment of microcrystalline cellulose have also been analyzed [24].

Figure 6.

Comparison of hydrogen evolution rate RH measured at Eo = 1.12 V for several carbons plotted vs. oxidation temperatures of carbons determined by thermo-gravimetric analysis. MWCNT and SCNT stand for multi-walled and single-walled carbon nanotubes, respectively (Reproduced with permission from Seehra and Bollineni [12], copyright Elsevier 2009).

In the experiments reported in Refs. [4] and [12], H2 was produced electrochemically first by conventional WE using 3.7 M H2SO4 as the electrolyte and then by adding carbons and cellulose-derived nanocarbons to the anode in separate experiments, repeating the experiments each time by measuring current Io and hydrogen solution rate RH as a function of the voltage Eo applied between the cathode and anode. Evolved hydrogen at the cathode was measured by a calibrated gas chromatograph. The efficiency factor AH = RH/Eo Io representing evolved H2 per kWh of energy used is then computed for each Eo. The plots of current in the circuit, RH and AH as a function of applied voltage Eo (relative to the SHE) are shown in Figure 7 for three cases: (i) electrolyte only, (ii) carbon BP2000 added to the anode in the amount of 0.08 gm/mL of the electrolyte, and (iii) the carbon produced by the hydrothermal treatment of cellulose added to the anode in the amount of 0.08 gm/mL of the electrolyte. In the WE process, a noticeable current and RH is observed only if Eo > 2 V. However, for both BP2000 and hydrothermally treated cellulose, significant Io and RH are observed at Eo = 0.7 V. In Figure 7, the horizontal dotted line is drawn to show that using commercial carbon BP2000 with surface area of 1500 m2/g, same RH is obtained at applied voltage Eo = 0.7 V using carbon BP2000 as obtained by applying Eo = 2.6 V in conventional WE. For carbon produced by hydrothermal treatment of cellulose, Eo = 1.2 V is needed to produce the same RH. A detailed analysis of the comparison of the efficiencies of the three processes is given in Section 4.

Figure 7.

Comparison of current, hydrogen evolution rate RH, and efficiency factor AH against applied voltage Eo (vs. standard hydrogen electrode) for HTP-cellulose treated at 250°C for 60 min, carbon BP2000 and electrolyte only. (Reproduced with permission from Seehra et al. [4], copyright Elsevier 2012).

According to the Eqs. (4) and (5) valid for CAWE, H2 should be produced at the cathode and CO2 at the anode in the molar ratio of H2/CO2 =2. With careful quantitative measurements, this indeed was found to be valid using carbon BP2000 [12]. However, using carbon produced from the hydrothermal treatment of cellulose, CO2 at the anode could not be detected with certainty suggesting that the reaction with this carbon is more complicated perhaps because of the presence of surface group present in this carbon [4]. Another difficulty in the quantification of CO2 is that its peak in gas chromatography is quite weak relative to peaks from H2 and O2. Regardless, CO2 produced in CAWE at the anode is well separated from H2 produced at the cathode. This is important since CO2 is a green-house gas and so it can be collected in relatively pure form and so appropriately used or sequestered.

Of all the carbons results for which are shown in Figure 6, BP2000 was found to be the most efficient for producing H2. It is very likely that this is due to surface area effect since BP2000 has high surface area of 1500 m2/g. However, a direct correlation between the surface area and RH has not yet been established experimentally. It may be possible to do so by comparing RH yields for the various BP carbons with different surface areas shown in Figure 1.

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4. Comparative energy analysis

Understanding the efficiencies of various processes to produce hydrogen is very important for practical considerations. In this regard, Rosen and Scott [25] have published a comparative energy analysis of the various processes currently in use for producing H2. The summary of this analysis, reproduced from their paper, is given in Table 1. According to this analysis, the energy efficiency of the conventional WE for producing H2 gas is only about 30% compared to about 85% for the steam methane reforming (SMR) and about 60% for coal gasification (CG) processes. If heat losses to the environment are also included (exergy) in the analysis, then these efficiencies are reduced by an additional few percent. The energy efficiency here is defined as the ratio of the energy contained in the produced hydrogen to the input energy. Because of the higher efficiencies of the SMR and CG processes, these are currently the favored techniques for producing H2 although both of these processes also produce CO2.

Category Process Efficiency (%)
Energy Exergy
Hydrocarbon-based Steam-methane reforming (SMR) 86 78
Coal gasification 59 49
Non-hydrocarbon-based Current-technology water electrolysis 30 26
Advanced-technology water electrolysis 49 41
Thermochemical water decomposition 21 19
Integrated SMR/current-technology water electrolysis 55 48
SMR/advanced-technology water electrolysis 70 62
SMR/thermochemical water decomposition 45 40

Table 1.

Hydrogen production processes and their efficiencies considering fuel and/or a hypothetical heat source as the external energy inputs.

Reproduced with permission from Rosen and Scott [25] copyright Elsevier 1998

In the recent paper [4], energy efficiencies of the WE and CAWE processes were considered in terms of the energy equivalence of electrical energy in kWh (kilo-watt-hour) and liters (L) of produced H2. Using the data available in the literature, it can be shown that one gasoline gallon equivalent (GGE) equals 33.4 kWh of electricity which in turn equals 10.1 m3 of H2 gas at STP (standard temperature and pressure). According to this equivalence, one kWh of electricity equals 300 L (liters) of hydrogen implying that one kWh of electricity used in electrolysis must produce 300 L of H2 @ STP for 100% energy efficiency. This equivalence is used here to determine the energy efficiencies of WE and CAWE processes, the latter using carbon BP2000 and the carbon produced from the hydrothermal treatment of microcrystalline cellulose [4].

Examining the results shown in Figure 7, it is evident that for electrolyte only representing conventional WE, Eo > 2 V is needed to start the reaction, reaching close to saturation at Eo = 2.6 V. At this voltage, RH is about 15 mL/h of hydrogen and AH equals 100 L of H2 produced per kWh of electrical energy used. As noted earlier, if process was 100% energy efficient, AH = 300 L/kWh should have been produced. Thus, conventional WE is only about 33% (100/300) efficient, in close agreements with the results from the analysis of Rosen and Scott shown in Table 1.

Following the horizontal dotted line drawn in Figure 7, it is evident that using commercial carbon BP2000 with surface area of 1500 m2/g, same RH is obtained at applied voltage Eo = 0.7 V using carbon BP2000 as obtained by applying Eo = 2.6 V in conventional WE. However, at Eo = 0.7 V with carbon BP2000, AH = 450 L/kWh of H2 is produced resulting in energy efficiency of 150% (450/300) compared to about 33% for conventional WE. This extra energy representing nearly fivefold improvement in energy efficiency over conventional WE is coming from the extra electrons provided by use of carbon BP2000. This electrochemical gasification occurring at room temperature does produce CO2 at the anode, but it is well separated from the H2 produced at the cathode.

In Figure 7, the data of H2 production using carbon produced from hydrothermally treated cellulose instead of carbon BP2000 is also shown. With the use of carbon produced from hydrothermally treated cellulose, again following the horizontal line, somewhat lower AH ≃ 350 L/kWh is obtained at Eo = 0.7 V with essentially similar evolution rate RH of H2. This yields slightly lower energy efficiency of about 120% (350/300) which is still a factor of four improvement over conventional WE. This electrochemical process with cellulose-derived nanocarbon has the added advantage that no CO2 could be detected at the anode presumably because cellulose-derived nanocarbons have surface functional groups [4] unlike carbon BP2000. It is noted that in doing these comparisons of energy efficiencies, the cost of producing the carbons is not included. However, BP2000 is available commercially in large quantities and hydrothermal carbonization is environmentally friendly process employing water as solvent under subcritical temperature–pressure conditions [24].

In summary, the comparative energy analysis described here shows factors of four to five improvements in the energy efficiencies for producing H2 electrochemically using commercial carbon BP2000 and cellulose-derived nanocarbons. Pure CO2 is produced with the use of carbon BP2000, but it is well separated from H2. The use of post-HTP cellulose has the advantage that no CO2 could be detected in the process. For more practical issues related to the electrochemical production of hydrogen from WE, the reader is referred to the recent review by Wang et al. [23].

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5. Concluding remarks

In this review, the focus has been on just one application of mesoporous/microporous carbons viz. in CAWE to produce H2 at energy-efficient voltages. Theoretical considerations and experimental results have established that the electrical energy requirements for CAWE are a factor of about five smaller than those needed for conventional WE. CO2 is produced at the cathode in CAWE resulting from the room temperature oxidation of carbon. However, it is well separated from pure H2 produced at the anode. Whether this energy advantage of CAWE vis-à-vis conventional WE can be commercially exploited still remain to be seen since there are often other technical issues that must be overcome as described in the recent review of Wang et al. [23]. Comparing the results in Figure 6 obtained with the use of a variety of carbons, it is evident that the best H2 evolution rate RH was obtained using carbon BP2000 with high surface area of about 1500 m2/g. Since smaller pore size leads to higher surface area, a correlation quite likely exists between RH and pore size of the carbons. Additional studies along these lines using different carbons with known pore-size structure and surface areas might be fruitful. As mentioned in the Introduction, there are of course many other applications of mesoporous and microporous carbons and some of these are addressed in the other chapters of this book.

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Written By

Mohindar S. Seehra and Vishal Narang

Submitted: October 23rd, 2015 Reviewed: February 15th, 2016 Published: August 24th, 2016