Room temperature hydrogen generation from aqueous ammonia-borane using noble metal nano-clusters as highly active catalysts

Nano-clusters of noble metals Ru, Rh, Pd, Pt and Au have been supported on γ-Al₂O₃, C and SiO₂, of which the catalytic activities have been investigated for hydrolysis of NH₃BH₃. Among these catalysts, the Ru, Rh and Pt catalysts exhibit high activities to generate stoichiometric amount of hydrogen with fast kinetics, whereas the Pd and Au catalysts are less active. Support effect has been studied by testing the hydrogen generation reaction in the presence of Pt supported on γ-Al₂O₃, VULCAN^® carbon and SiO₂, and it is found that Pt on γ-Al₂O₃, which has the smallest particle size, is the most active. Concentration dependence of the hydrogen generation from aqueous NH₃BH₃ solutions has been investigated in the presence of Pt/γ-Al₂O₃ by keeping the amount of Pt/γ-Al₂O₃ catalyst unchanged, which exhibits that the hydrogen release versus time (ml H₂ min⁻¹) does not significantly change with increasing the NH₃BH₃ concentration, indicating that the hydrogen release rate is not dependent on the NH₃BH₃ concentration and the high activity of the Pt catalyst can be kept at high NH₃BH₃ concentrations. Activation energies have been measured to be 23, 21 and 21 kJ mol⁻¹ for Ru/γ-Al₂O₃, Rh/γ-Al₂O₃ and Pt/γ-Al₂O₃ catalysts, respectively, which may correspond to the step of B–N bond breaking on the metal surfaces. The particle sizes, surface morphology and surface areas of the catalysts have been obtained by TEM and BET experiments.     

Sn-modified carbon-supported Pt nanoparticles synthesized using spontaneous deposition as electrocatalysts for direct alcohol fuel cells

Sn-modified carbon-supported Pt nanoparticles (Sn(Pt)/C electrocatalysts) were prepared by spontaneous deposition. Sn species were deposited on Pt/C by immersion in 2.0 × 10⁻⁴ M SnCl₂ + 0.1 M HClO₄ for different times, which allowed achieving an adequate control of the coverage (θ). Cyclic voltammetry (CV) in 0.5 M H₂SO₄ was carried out to determine θ and to evaluate the Sn(Pt)/C performance. The activity towards the oxidation reactions of methanol (MOR) and ethanol (EOR) was analyzed using CV in 0.5 M H₂SO₄ + 1.0 M alcohol. A promotional effect for the MOR and the EOR after the partial coverage by the Sn species was shown, as indicated by the significant reduction of the overpotential and the higher oxidation currents in both cases. This activation was explained by the formation of hydroxylated species on the tin deposits, thus facilitating the removal of the adsorbed intermediates. The best performance was achieved for θ ≈ 0.3 in the case of the MOR and for θ ≈ 0.5 in the case of the EOR. The reaction pathway for both alcohols was analyzed according to the obtained kinetic parameters, which significantly depended on the coverage.     

Effect of operating parameters and anode diffusion layer on the direct ethanol fuel cell performance

A parametric study was conducted on the performance of direct ethanol fuel cells. The membrane electrode assemblies employed were composed of a Nafion^® 117 membrane, a Pt/C cathode and a PtRu/C anode. The effect of cathode backpressure, cell temperature, ethanol solution flow rate, ethanol concentration, and oxygen flow rate were evaluated by measuring the cell voltage as a function of current density for each set of conditions. The effect of the anode diffusion media was also studied. It was found that the cell performance was enhanced by increasing the cell temperature and the cathode backpressure. On the contrary, the cell performance was virtually independent of oxygen and fuel solution flow rates. Performance variations were encountered only at very low flow rates. The effect of the ethanol concentration on the performance was as expected, mass transport loses observed at low concentrations and kinetic loses at high ethanol concentration due to fuel crossover. The open circuit voltage appeared to be independent of most operating parameters and was only significantly affected by the ethanol concentration. It was also established that the anode diffusion media had an important effect on the cell performance.     

Nanostructured polypyrrole/carbon composite as Pt catalyst support for fuel cell applications

A novel catalyst support was synthesized by in situ chemical oxidative polymerization of pyrrole on Vulcan XC-72 carbon in naphthalene sulfonic acid (NSA) solution containing ammonium persulfate as oxidant at room temperature. Pt nanoparticles with 3–4 nm size were deposited on the prepared polypyrrole–carbon composites by chemical reduction method. Scanning electron microscopy and transmission electron microscopy measurements showed that Pt particles were homogeneously dispersed in polypyrrole–carbon composites. The Pt nanoparticles-dispersed catalyst composites were used as anodes of fuel cells for hydrogen and methanol oxidation. Cyclic voltammetry measurements of hydrogen and methanol oxidation showed that Pt nanoparticles deposited on polypyrrole–carbon with NSA as dopant exhibit better catalytic activity than those on plain carbon. This result might be due to the higher electrochemically available surface areas, electronic conductivity and easier charge-transfer at polymer/carbon particle interfaces allowing a high dispersion and utilization of deposited Pt nanoparticles.     

Investigation of AuNi/C anode catalyst for direct methanol fuel cells

AuNi nanoparticles supported on the activated carbon (AuNi/C) are synthesized by the impregnation method in the ethyleneglycol system using NH₂NH₂·H₂O as a reducing agent. The alloying of Au and Ni and the removal of unalloyed Ni in the AuNi/C composition are achieved by heat and acid treatments in sequence. Research results reveal that the average size and alloying degree of the AuNi nanoparticles in the AuNi/C catalyst increase with the enhancement of the annealing temperature. However, the Ni content of the AuNi/C catalyst firstly goes up and then down with the rising of heat treatment temperature due to the AuNi system phase-separates. Moreover, the electrocatalytic activity normalized by the electrochemically active surface area of each AuNi/C catalyst is far better than that of the Au/C catalyst, because of the bifunctional mechanism and the electrocatalytic activity of the NiOOH. In particular, the AuNi/C catalyst annealed at 400 °C exhibits the most excellent activity, due to its small AuNi particles and proper alloying degree. Furthermore, its mass-specific electrochemical activity is higher than that of the Au/C catalyst, although the mean diameter of the AuNi nanoparticles in this catalyst is larger than that of the Au nanoparticles.     

Addition of rhenium (Re) to Pt-Ru/f-MWCNT anode electrocatalysts for enhancement of ethanol electrooxidation in half cell and single direct ethanol fuel cell

Pt-Ru and Pt–Re and Pt-Ru-Re nanoparticles supported on functionalized multi-walled carbon nanotubes (f-MWCNT) were synthesized via modified polyol reduction method and tested thoroughly in a half cell and single direct ethanol fuel cell for ethanol electrooxidation in acidic medium. The MWCNTs were functionalized in a mixture of HNO₃/H₂SO₄ solution for depositing a more active metal alloy nanoparticle on support material. The alloy formation of bi-metallic and tri-metallic electrocatalysts were examined by XRD analysis and more clearly explained by FE-SEM element mapping. The TEM analyses reveal that electrocatalysts nanoparticles are well dispersed on f-MWCNT, with spherical shapes and nano sizes range of 1.5–4 nm. The electrochemical analyses by cyclic voltammetry and chronoamperometry measurements reveal that tri-metallic electrocatalyst Pt-Ru-Re (1:1:0.5)/f-MWCNT exhibits the highest electrocatalytic activity and stability towards ethanol electrooxidation among all the synthesized electrocatalysts. The same electrocatalyst as anode in single DEFC results in excellent performance in comparison to all other synthesized electrocatalysts, with a maximum power density of 9.52 mW/cm² at a cell temperature of 30 °C. The bi-metallic Pt-Ru (1:1)/f-MWCNT and Pt–Re (1:1)/f-MWCNT produced power density of 7.48 mW/cm² and 4.74 mW/cm² at room temperature of 30 °C. The power density of DEFC enhanced 2.44 times, when cell operating temperature was increased from 30 °C to 80 °C using anode electrocatalyst Pt-Ru-Re (1:1:0.5)/f-MWCNT and keeping other parameters constant. The best result obtained in half cell and single DEFC using Pt-Ru-Re (1:1:0.5)/f-MWCNT electrocatalyst may be attributed to the synergistic effect of Pt, Ru and Re combined with bi-functional and ligand effects.     

Graphene-multi walled carbon nanotube hybrid electrocatalyst support material for direct methanol fuel cell

Nanostructured PtRu and Pt dispersed functionalized graphene-functionalized multi walled carbon nanotubes (PtRu/(f-G-f-MWNT)), (Pt/(f-G-f-MWNT)) nanocomposites have been prepared. Electrochemical studies have been performed for the methanol oxidation using cyclic voltammetry (CV) and chronoamperometry technique. Full cell measurements have been performed using PtRu nanoparticles dispersed on the mixture of functionalized graphene (f-G) and functionalized multi walled carbon nanotubes (f-MWNT) in different ratios as anode electrocatalyst for methanol oxidation and Pt/f-MWNT as cathode catalyst for oxygen reduction reaction in direct methanol fuel cell (DMFC). In addition, full cell measurements have been performed with PtRu/(50 wt% f-MWNT + 50 wt% f-G) and Pt/(50 wt% f-MWNT + 50 wt% f-G) as anode and cathode electrocatalyst respectively. With PtRu/(50 wt% f-MWNT + 50 wt% f-G) as anode electrocatalyst, a high power density of about 40 mW/cm² has been obtained, in accordance with cyclic voltammetry studies. Further enhancement in the power density of about 68 mW/cm² has been observed with PtRu/(50 wt% f-MWNT + 50 wt% f-G) and Pt/(50 wt% f-MWNT + 50 wt% f-G) as electrocatalyst at anode and cathode respectively. These results have been discussed based on the change in the morphology of the f-G sheets due to the addition of f-MWNT.     

Sodium borohydride as an additive to enhance the performance of direct ethanol fuel cells

The effect of adding small quantities (0.1-1 wt.%) of sodium borohydride (NaBH₄) to the anolyte solution of direct ethanol fuel cells (DEFCs) with membrane-electrode assemblies constituted by nanosized Pd/C anode, Fe-Co cathode and anion-exchange membrane (Tokuyama A006) was investigated by means of various techniques. These include cyclic voltammetry, in situ FTIR spectroelectrochemistry, a study of the performance of monoplanar fuel cells and an analysis of the ethanol oxidation products. A comparison with fuel cells fed with aqueous solutions of ethanol proved unambiguously the existence of a promoting effect of NaBH₄ on the ethanol oxidation. Indeed, the potentiodynamic curves of the ethanol-NaBH₄ mixtures showed higher power and current densities, accompanied by a remarkable increase in the fuel consumption at comparable working time of the cell. A ¹³C and ¹¹B {¹H}NMR analysis of the cell exhausts and an in situ FTIR spectroelectrochemical study showed that ethanol is converted selectively to acetate while the oxidation product of NaBH₄ is sodium metaborate (NaBO₂). The enhancement of the overall cell performance has been explained in terms of the ability of NaBH₄ to reduce the PdO layer on the catalyst surface.     

Electrochemical and mechanical behavior of carbon composite bipolar plate for fuel cell

Composite bipolar plates for fuel cells were prepared by a compression molding technique using novolac type phenol formaldehyde resin as a binder and natural graphite, carbon black and carbon fiber as reinforcements. The plates were characterized for electrical conductivity, mechanical strength and corrosion resistance. The flexural strength of the bipolar plate for optimum composition (PF:30%; NG:60%; CB:5%; CF:5%) was 55.28 MPa, with a deflection of 5.2% at mid-span, while the in-plane and through-plane electrical conductivities were 286 and 92 S cm⁻¹, respectively. Corrosion analyses were conducted in normal and rigorous simulated polymer electrolyte membrane fuel cell and alkaline fuel cell environments. The corrosion current density was close to the limit set by the USA Department of Energy. The corrosion current density at the optimum composition was found to be 0.99 μA cm⁻² for polymer electrolyte membrane fuel cell and 17.62 μA cm⁻² for alkaline fuel cell environments.     

Graphene oxide supported Pd-Fe nanohybrid as an efficient electrocatalyst for proton exchange membrane fuel cells

The experimental realization and computational validation for graphene oxide (GO) supported palladium (Pd)-iron (Fe) nanohybrids as a new generation electrocatalyst for proton-exchange membrane fuel cells (PEMFCs) has been reported. The experimental apprehension of the present catalyst system has been initiated with the graphene oxide, followed by the doping of Pd and Fe via thermal inter calation of palladium chloride and iron chloride with the in-situ downstream reduction to get nanohybrids of the GO-Pd-Fe. These nanohybrids are subsequently characterized by RAMAN, FT-IR, UV–Vis, XRD, SEM, EDS, TEM and HRTEM analysis. Furthermore, the first principle calculations based on Density Functional Theory (DFT) with semi-empirical Grimme DFT-D₂ correction has been performed to support the experimental findings. Computational results revealed the alteration of graphene electronic nature from zero-band gaped to metallic/semi-metallic on adsorption of transition metal clusters. Moreover, the defect sites of the graphene surface are more favorable than the pristine sites for transition metal adsorption owing to the strong binding energies of the former. Electrochemical studies show that GO-Pd-Fe nanohybrids catalyst (Pd: Fe = 2:1) demonstrates excellent catalytic activity as well as the higher electrochemical surface area of (58.08 m²/g Pd–Fe)⁻¹ which is higher than the commercially available Pt/C catalyst with electrochemical surface area 37.87 m²/(g Pt)⁻¹.     

Development of new test instruments and protocols for the diagnostic of fuel cell stacks

In the area of fuel cell research, most of the experimental techniques and equipments are still devoted to the analysis of single cells or very short stacks. However, the diagnosis of fuel cell stacks providing significant power levels is a critical aspect to be considered for the integration of fuel cell systems into real applications such as vehicles or stationary gensets. In this article, a new instrument developed in-lab is proposed in order to satisfy the requirements of electrochemical impedance studies to be led on large FC generators made of numerous individual cells. Moreover, new voltammetry protocols dedicated to PEMFC stack analysis are described. They enable for instance the study of membrane permeability and loss of platinum activity inside complete PEMFC assemblies.     

Electrooxidation of formaldehyde as a fuel for fuel cells using Fe2+-nano-zeolite modified carbon paste electrode

This study aimed to investigate the application of nano ZSM-5 zeolite for preparation of modified carbone paste electrode for electrocatalytic oxidation of formaldehyde. The electrochemical behavior of modified carbon paste electrodes in the forms of Fe/FeZSM-5CPE and unmodified carbon paste electrode were studied using cyclic voltammetric and chronoamprometric techniques. The obtained results show that the modified carbon paste electrode (Fe/FeZSM-5CPE) is the suitable electrode for electrooxidation of formaldehyde in the acidic solution. The transfer coefficient and current density for formaldehyde were calculated 0.23 and 19.8 mA/cm², respectively. The rate constant for catalytic reaction was calculated as 3.6 × 10³ cm³ s^?1 mol^?1 via Cottrell equation.     

Reduced graphene oxide supported nickel tungstate nano-composite electrocatalyst for anodic urea oxidation reaction in direct urea fuel cell

In recent time direct urea fuel cell (DUFC) emerges as a potential candidate for sustainable urea reach wastewater treatment and power generation. The efficiency of DUFC mainly governed by the anodic urea oxidation reaction (UOR) kinetics. The design and development of efficient electrocatlysts for UOR remains a key factor for practical utilization of DUFC. In current study, we present a single step hydrothermal synthesis of NiWO₄ NPs/rGO (h-NiWO₄ NPs/rGO) composite for UOR catalysis in alkaline medium. The synthesized NiWO₄ NPs/rGO composite offers a 218 mA/cm² UOR catalytic current density. Moreover, the h-NiWO₄ NPs/rGO composite retains its 94% UOR catalytic current after 1000 cyclic voltammetric cycles. Further, h-NiWO₄ NPs/rGO composite shows superior UOR catalytic performance than physical mixture of NiWO₄ NPs and rGO, NiWO₄ NPs, NiO/WO₃ physical mixture and only NiO with reference to catalytic current density, onset potential, and durability. The enhanced electrocatalytic activity of the h-NiWO₄ NPs/rGO composite attributed to the synergetic coupling of physiochemical properties of NiWO₄ NPs and rGO which improves the charge transfer generates larger electroactive surface and reduces catalyst poisoning. An air cathode DUFC with h-NiWO₄ NPs/rGO composite modified anode and Pt/C cathode produces a maximum power density of 5.1 mW/cm² and 927 mV open circuit potential.     

Carbon nanostructure grown using bi-metal oxide as electrocatalyst support for proton exchange membrane fuel cell

A novel carbon nanostructure grown by catalytic chemical vapour deposition technique has been applied as an electrocatalyst support for oxygen reduction reaction in proton exchange membrane fuel cell. The growth of carbon nanostructure (CNS) is carried over a low cost bi-metal oxide catalyst (Fe–Sn–O) synthesized by sol–gel technique. Platinum nanoparticle decoration on Fe–Sn–O incorporated CNS (CNS-FSO) is performed by ethylene glycol reduction method. The structural as well as morphological analysis confirms the formation of CNS-FSO and platinum decoration on CNS-FSO. The electrochemically active surface area (ECSA) of platinum decorated CNS-FSO (Pt/CNS-FSO) is 68 m² g⁻¹, as revealed from cyclic voltammetry. Polarization studies are carried out at different temperatures (40 °C, 50 °C and 60 °C) to exploit the oxygen reduction reaction activity of Pt/CNS-FSO. A maximum power density of 449 mW cm⁻² (without back pressure) at 60 °C shows the potential of this novel CNS-FSO as an electrocatalyst support in proton exchange membrane fuel cell.     

Compositional effect on oxygen reduction reaction in Pr excess double perovskite Pr1+xBa1-xCo2O6-δ cathode materials

The kinetics of oxygen reduction reaction (ORR), being a prime requisite for electrode materials after the higher conductivity. Further, electrodes are observed to dissolute on reaction at triple phase boundary. However, the compositional effect on ORR is least understood. In order to inspect the ORR mechanism with substitution, a series of (1 + x) PrCoO₃ − (1 − x) BaCoO₃ (x = 0.2 to 1.0 with step of 0.2) compositions are prepared using conventional solid-state route method. The Rietveld refinement of X-ray diffractograms and specific heat curves confirms the formation of double phase comprising orthorhombic Pmmm phase corresponding to PrBaCo₂O_6-δ and Pnma phase corresponding to PrCoO₃ for x = 0.2 to 0.8 with well connected and porous microstructure. The triple phase boundary reactions suggest the formation of Co(OH)₃ along with H₂ gas on reaction of these composite electrodes with H₂O during electrochemical dissolution. However, chronoamperometric studies prove the suitability of x = 0.6 sample with higher ORR and liberation of H₂ gas at room temperature.     

Hydroxyapatite-supported palladium(0) nanoclusters as effective and reusable catalyst for hydrogen generation from the hydrolysis of ammonia-borane

Herein we report the preparation, characterization and catalytic use of hydroxyapatite-supported palladium(0) nanoclusters in the hydrolysis of ammonia-borane. Palladium(0) nanoclusters were formed in situ from the reduction of palladium(II) ion exchanged hydroxyapatite during the hydrolysis of ammonia-borane and supported on hydroxyapatite. The hydroxyapatite-supported palladium(0) nanoclusters are stable enough to be isolated as solid materials and characterized by using a combination of advanced analytical techniques. They are isolable, redispersible and reusable as an active catalyst in the hydrolysis of ammonia-borane even at low concentration and temperature. They provide a maximum hydrogen generation rate of ∼1425 mL H₂ min⁻¹ (g Pd)⁻¹ and 12300 turnovers in the hydrolysis of ammonia-borane at 25 ± 0.1 °C before deactivation. The work reported here also includes the full experimental details for the collection of a wealth of kinetic data to determine the activation energy (E_a = 54.8 ± 2.2 kJ/mol) and the effect of catalyst concentration on the rate for the catalytic hydrolysis of ammonia-borane.     

Nickel nanorods over nickel foam as standalone anode for direct alkaline methanol and ethanol fuel cell

A highly electroactive nickel nanorod (NNR)/nickel foam (NF) electrode was fabricated for direct alcohol fuel cells (DAFCs) using a simple and cost-effective hydrothermal process. The Ni/NiO nanorods were successfully grown on the surface of an NF electrode, which strongly enhanced the anode wettability and increased surface area by 18 times (11.9 m² g⁻¹), resulting in interfacial polarization resistance reduction. The NNR/NF electrode shows high electro-catalytic activity and great stability during alcohol oxidation. The current densities obtained for NNR/NF were four (479 mA cm⁻²) and six (543 mA cm⁻²) times higher than that for pristine NF in the cases of methanol and ethanol oxidations, respectively. This high current density can be attributed to the superhydrophilic surface of the Ni/NiO nanorods and corresponding high mass transfer capability between the electrolytes and Ni/NiO nanorods embedded on the surface of the electrodes. This study presents a new approach for using the novel NNR/NF as a cheap and high performance anode in DAFCs.     

Direct borohydride fuel cell using Ni-based composite anodes

In this study, nickel-based composite anode catalysts consisting of Ni with either Pd on carbon or Pt on carbon (the ratio of Ni:Pd or Ni:Pt being 25:1) were prepared for use in direct borohydride fuel cells (DBFCs). Cathode catalysts used were 1 mg cm⁻² Pt/C or Pd electrodeposited on activated carbon cloth. The oxidants were oxygen, oxygen in air, or acidified hydrogen peroxide. Alkaline solution of sodium borohydride was used as fuel in the cell. High power performance has been achieved by DBFC using non-precious metal, Ni-based composite anodes with relatively low anodic loading (e.g., 270 mW cm⁻² for NaBH₄/O₂ fuel cell at 60 °C, 665 mW cm⁻² for NaBH₄/H₂O₂ fuel cell at 60 °C). Effects of temperature, oxidant, and anode catalyst loading on the DBFC performance were investigated. The cell was operated for about 100 h and its performance stability was recorded.     

Hydrogen generation from the hydrolysis of ammonia-borane using intrazeolite cobalt(0) nanoclusters catalyst

Previously being used as highly active catalyst in the hydrolysis of sodium borohydride, intrazeolite cobalt(0) nanoclusters were also employed as catalyst in the hydrolysis of ammonia-borane (H₃NBH₃). Intrazeolite cobalt(0) nanoclusters were found to be active catalyst in this hydrolysis reaction of ammonia-borane providing 5450 total turnovers at room temperature before deactivation. The results of the kinetic study shows that the catalytic hydrolysis of AB is first order with respect to the catalyst concentration and zero order with respect to substrate concentration. Activation parameters could be obtained from the evaluation of the rate constants at different temperature. The results reveal that intrazeolite cobalt(0) nanoclusters can be considered as promising candidate to be used as catalyst in developing highly efficient portable hydrogen generation systems using ammonia-borane as solid hydrogen storage material.     

Microwave assisted synthesis of nitrogen doped and oxygen functionalized carbon nano onions supported palladium nanoparticles as hybrid anodic electrocatalysts for direct alkaline ethanol fuel cells

In this study, we present the synthesis of pristine carbon (p-CNO), nitrogen doped (N–CNO) and oxygen functionalized (ox-CNO) nano onions, using flame pyrolysis, chemical vapour deposition, and reflux methods, respectively. Pd/p-CNO, Pd/N–CNO and Pd/ox-CNO electrocatalysts are prepared using a simple and quick microwave-assisted synthesis method. The various CNO and Pd/CNO electrocatalysts are fully characterized and the FTIR and XPS results reveal that the synthesized CNOs contain oxygen and nitrogen functional groups that facilitates the attachment and dispersion of the Pd nanoparticles. Electrochemical tests show that the N–CNO and Pd/N–CNO electrocatalysts exhibit high current density (4.2 mA cm ^?2 and 17.4 mA cm ^?2), long-term stability (1.2 mA cm ^?2 and 6.9 mA cm ^?2), and fast electron transfer when compared to the equivalent pristine and oxidized catalysts (and their Pd counterparts), and a commercial Pd/C electrocatalyst, towards ethanol oxidation reactions in alkaline medium.