Comparative investigation of the resistance to electrochemical oxidation of carbon black and carbon nanotubes in aqueous sulfuric acid solution

The resistance to electrochemical oxidation of carbon black (Vulcan XC-72) and chemical vapor deposited multiwalled carbon nanotubes (CVD-MWNTs), both widely-used as catalyst supports for low temperature fuel cells, is investigated with potentiostatic oxidation in 0.5 mol L⁻¹ H₂SO_4, which mimics the working conditions of low temperature fuel cells. The surface oxygen of oxidized carbon black and MWNTs are analyzed with cyclic voltammetry and X-ray photoelectron spectroscopy (XPS). The increase in surface oxygen on MWNTs during 120 h holding at 1.2 V (versus Reversible Hydrogen Electrode, RHE) is much less than that on carbon black. The conclusion can be reached that CVD-MWNTs are more resistant to electrochemical oxidation than carbon black under the condition in the report. CVD-MWNTs therefore possess a higher potential for low temperature fuel cell applications.     

Electrochemical oxidation behavior of titanium nitride based electrocatalysts under PEM fuel cell conditions

Titanium nitride (TiN) is attracting attention as a promising material for low temperature proton exchange membrane fuel cells. With its high electrical conductivity and resistance to oxidation, TiN has a potential to act as a durable electrocatalyst material. Using electrochemical and spectroscopic techniques, the electrochemical oxidation properties of TiN nanoparticles (NP) are studied under PEM fuel cell conditions and compared with conventional carbon black supports. It is observed that TiN NP has a significantly lower rate of electrochemical oxidation than carbon black due to its inert nature and the presence of a native oxide/oxynitride layer on its surface. Depending on the temperature and the acidic media used in the electrochemical conditions, the open circuit potential (OCP) curves shows the overlayer dissolved in the acidic solution leading to the passivation of the exposed nitride surface. It is shown that TiN NP displays passive behavior under the tested conditions. The XPS characterization further supports the dissolution argument and shows that the surface becomes passivated with the O-H groups reducing the electrical conductivity of TiN NP. The long-term stability of the Pt/TiN electrocatalysts is tested under PEM fuel cell conditions and the trends of the measured electrochemical surface area at different temperatures is shown to agree with the proposed passivation model.     

Corrosion resistance and sintering effect of carbon supports in polymer electrolyte membrane fuel cells

The corrosion resistance of carbon black, carbon nanofiber and carbon nanocage used as catalyst supports in fuel cells was investigated by monitoring CO₂ emission using on-line mass spectrometry when 1.4 V was applied for 30 min. The changes associated with the carbon corrosion were assessed through electrochemical methods. In general, graphitized carbon supports were more corrosion-resistant than amorphous carbon black. However, the degree of graphitization did not directly correlate with higher resistance to corrosion. Hydrophobicity was critical in enhancing resistance to corrosion. When sintering of Pt particles was considered, carbon nanocages were more resistant than nanofibers. The present findings thus indicate that the carbon nanocage is an appropriate catalyst support in fuel cell systems.     

Mechanistic Study of Carbon Oxidation with NO2 and O2 in the Presence of a Ru/Na‐Y Catalyst

The oxidation of model soot by NO₂ and O₂ in the presence of a Ru/Na‐Y catalyst under conditions close to automotive exhaust gas after‐treatment systems is investigated. Isothermal oxidation experiments of a physical mixture of carbon black and catalyst were performed in a temperature range of 300–400 °C. A remarkable increase of the oxidation rate by NO₂ and O₂ in the presence of the Ru/Na‐Y catalyst was observed. An overall mechanism involving oxygen transfer from the Ru catalyst to the carbon surface leading to an increase of C(O) complexes is proposed. These C(O) complexes are destabilized in the presence of NO₂ increasing the carbon oxidation rate.     

Enhanced methanol electro-oxidation activity of PtRu catalysts supported on heteroatom-doped carbon

A typical heteroatom (nitrogen)-doped carbon materials were successfully synthesized through the carbonization of a hybrid containing traditional carbon black covered by in situ polymerized polyaniline. The nitrogen content onto carbon can be adjusted up to 5.1 at.% by changing the coverage of polyaniline. The effects of nitrogen doping on the surface physical and electrochemical properties of carbon were studied using XPS, XRD and HRTEM, as well as CV and EIS techniques. With increasing nitrogen doping, the carbon structure became more compact, showing curvatures and dislocations in the graphene stacking. The nitrogen-doped carbon also exhibited a higher accessible surface area in electrochemical reactions, and a lower charge transfer resistance at the carbon/electrolyte interface. Moreover, to investigate the influence of nitrogen doping on the electrocatalytic activity of the PtRu/C catalyst, comparisons in CO stripping and methanol oxidation were carried out on PtRu catalysts supported by non-doped and nitrogen-doped carbon. Since the promotional roles of nitrogen doping, including the high electrochemically accessible surface area, the richness of the disordered nanostructures and defects, and the high electron density on N-doped carbon supports, contribute to the synthesis of well-dispersed PtRu particles with high Pt utilization and stronger metal-support interactions, an enhanced catalytic activity for methanol oxidation was obtained in the case of the PtRu/N-C catalyst in comparison with the traditional PtRu/C catalyst.     

The role of nitrogen in a carbon support on the increased activity and stability of a Pt catalyst in electrochemical hydrogen oxidation

Nitrogen-containing carbon materials were prepared by acetonitrile pyrolysis on carbon black and used as a support for a Pt catalyst. The Pt particles on N-containing carbon exhibited increased activity and stability in electrochemical hydrogen oxidation relative to Pt on pristine carbon black. The N-doped carbon had a graphitic structure and contained pyridinic and quaternary nitrogen species. The Pt nanoparticles were better-dispersed because of increased hydrophilicity induced by the nitrogen species. The Pt/N-containing carbon showed higher stability in a potential cycling test than Pt/C, because of an increased metal-support interaction. Using XPS and EELS mapping, we demonstrated that the metal-support interaction became stronger and more specific by adding nitrogen into carbon.     

Effect of Preparation Conditions of Pt/C Catalysts on Oxygen Electrode Performance in Proton Exchange Membrane Fuel Cells

Supported Pt/C catalyst with 3.2 nm platinum crystallites was prepared by the impregnation—reduction method. The various preparation conditions, such as the reaction temperature, the concentration of precursor H₂PtCl₆ solution and the different reducing agents, and the relationship between the preparation conditions and the catalyst performance were studied. The carbon black support after heat treatment in N₂ showed improved platinum dispersion. The particle size and the degree of dispersion of Pt on the carbon black support were observed by transmission electron microscopy (TEM). The crystal phase composition of Pt in the catalyst was determined by X-ray diffraction (XRD). The surface characteristics of the carbon black support and the Pt/C catalyst were studied by X-ray photoelectron spectroscopy (XPS). The electrochemical characteristics of the Pt/C catalysts were evaluated from current—voltage curves of the membrane electrode assembly (MEA) in a proton exchange membrane fuel cell.     

Electrocatalytic activity mapping of model fuel cell catalyst films using scanning electrochemical microscopy

Scanning electrochemical microscopy has been employed to spatially map the electrocatalytic activity of model proton exchange membrane fuel cell (PEMFC) catalyst films towards the hydrogen oxidation reaction (the PEMFC anode reaction). The catalyst films were composed of platinum-loaded carbon nanoparticles, similar to those typically used in PEMFCs. The electrochemical characterisation was correlated with a detailed physical characterisation using dynamic light scattering, transmission electron microscopy and field-emission scanning electron microscopy. The nanoparticles were found to be reasonably mono-dispersed, with a tendency to agglomerate into porous bead-type structures when spun-cast. The number of carbon nanoparticles with little or no platinum was surprisingly higher than would be expected based on the platinum-carbon mass ratio. Furthermore, the platinum-rich carbon particles tended to agglomerate and the clusters formed were non-uniformly distributed. This morphology was reflected in a high degree of heterogeneity in the film activity towards the hydrogen oxidation reaction.     

Carbon cryogel as support of platinum nano-sized electrocatalyst for the hydrogen oxidation reaction

The kinetics of hydrogen oxidation reaction was studied in perchloric acid solution on carbon-supported Pt nanoparticles using the rotating disk electrode technique. Carbon cryogel and commercial carbon black. Vulcan XC-72 were used as catalyst supports. Pt/C catalysts were prepared by a modified polyol synthesis method in an ethylene glycol (EG) solution. Considerable effect has been observed for the specific surface area of carbon support on the fundamental properties of Pt/C catalyst, such as catalyst particle size distribution and dispersion as well as catalytic activity for the oxidation of hydrogen. X-ray diffraction (XRD) and transmission electron microscopy (TEM) images show that the particle size of the catalyst decreases with the increase of specific surface area of carbon support. Cyclic voltammetry (CV) was used for determination of the actual exposed surface area of catalyst particles. It was found that Pt catalyst prepared by using the novel carbon material displayed better hydrogen electrochemical oxidation activity than the catalyst prepared by using Vulcan XC-72.     

Carbon nanofibers as potential materials for catalysts support,a mini-review on recent advances and future perspective

The element carbon has been used as an active catalyst as well as a catalyst support. This dual nature of carbon has been attributed to its characteristics such as high porosity, large surface area, excellent electron conductivity and chemical inert nature. Besides, the availability of different forms of carbon like graphene, activated carbon, carbon nanotubes and carbon nanofibers have provided carbon a versatile material to be used for different applications. Carbon has been widely used in different applications like electrical, bio-electrochemical, dry cells, electrodes and as a lubricant. However, in the last decades, the catalytic applications of carbon materials especially carbon nanotubes and carbon nanofibers have gained tremendous attention of the researchers worldwide. Carbon nanofibers, in particular due to thier excellent catalytic support profile like, high surface area, thermal stability and its 3D access to the reacting molecules, have been utilized for different chemical reactions. Metal supported on carbon nanofibers have been observed with better activities as compared to the traditional supported counterparts for the several reactions. This mini-review attempts to document the role of carbon nanofibers and their catalytic support profile for the some common chemical processes. The mini-review also suggests about the future innovations and research work for carbon nanofibers as potential future catalysts support.     

Increased Metal Utilization in Carbon‐Supported Pt Catalysts by Adsorption of Preformed Pt Nanoparticles on Colloidal Silica

Pt/C electrocatalysts, aimed at maximizing the electrochemical surface area (ECSA) and consequently the specific mass activity of fuel cell reactions, are obtained by firstly depositing Pt nanoparticles on colloidal silica (Pt‐silica), followed by the adsorption of the latter onto a carbon support. This method of catalyst preparation increases Pt metal utilization and generates accessible void space in the interpenetrating particle network of carbon and silica for the facile transport of reactants and products. Both electrochemical hydrogen adsorption/desorption and CO oxidation measurements show an increase in the ECSA using this approach. Methanol electrooxidation is used as a test reaction to evaluate the catalytic activity. It is found that the silica modified catalyst is three times as active as a catalyst prepared without silica, under otherwise identical conditions.     

Carbon monoxide electrooxidation on porous Pt–Ru electrodes in sulphuric acid

CO electrooxidation on a Pt–Ru/C catalyst was investigated in sulphuric acid electrolyte. The physico-chemical properties of the Pt–Ru/C catalyst were studied by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The influence of temperature, CO partial pressure and proton concentration on the electrochemical oxidation rate was investigated by steady-state galvanostatic polarization measurements. The apparent activation energy decreased from 70 to 30kJmol–1 as the overpotential increased from 0.5 to 0.9V vs NHE. The reaction order with respect to carbon monoxide increased, passing from 0.4 to 1, with the increase of the overpotential from 0.5 to 0.7V vs NHE; a reaction order close to –1 with respect to the protonic concentration was observed, irrespective of the potential. Tafel slopes of about 136mVdec–1 were determined for oxidation of CO and CO/N2 mixtures.     

Improving of Micro Porous Layer based on Advanced Carbon Materials for High Temperature Proton Exchange Membrane Fuel Cell Electrodes

This work reports the study of four different carbon materials for their application as carbon material in microporous layers for high temperature proton exchange membrane fuel cells electrodes. The microporous layers were prepared with carbon black (a commercial one, Vulcan XC72), two different carbon nanofibers, CNF, (Ribbon and Platelet structure) and carbon nanospheres, all of them prepared in our lab. The microporous layers were characterized by XRD. The hydrophobicity, electrical conductivity, and permeability to different gases were also evaluated. The stability is an important issue to be overcome in the field of proton exchange membrane fuel cells. Thus, accelerated thermal and electrochemical degradation tests in phosphoric acid media were carried out to evaluate the stability of the different advanced materials tested under the same conditions. From all the performed essays, the carbon nanospheres were the best nano‐carbon materials because of the lower degradation degree shown by the microporous layer prepared with them and the good conductivity and permeability achieved, whereas CNF with a Platelet structure showed a low electrochemical stability due to their greater edge plane exposure which favors their corrosion.     

Low temperature synthesis of carbon nanofibres on carbon fibre matrices

Carbon nanofibres are grown on a carbon fibre cloth using plasma enhanced chemical vapour deposition from a gas mixture of acetylene and ammonia. A cobalt colloid is used as a catalyst to achieve a good coverage of nanofibres on the surface of the carbon fibres in the cloth. The low temperature growth conditions that we used would allow growth on temperature sensitive polymers and fibres. The nanofibres grown by a tip growth mechanism have a bamboo-like structure. A significant increase of the bulk electrical conductivity of the carbon cloth was observed after the nanofibre growth indicating a good electrical contact between carbon nanofibres and carbon fibres. The as-grown composite material could be used as high surface area electrodes for electrochemical applications like fuel cells and super-capacitors.     

Nanoscale graphite-supported Pt catalysts for oxygen reduction reactions in fuel cells

The nanoscale graphite particles were prepared and the Pt catalysts supported on such graphites were developed for oxygen reduction in the polymer electrolyte membrane fuel cells. Catalytic activity and carbon corrosion of the developed catalysts were evaluated using rotating disc electrode techniques and results were compared with those of a state-of-the-art commercial E-TEK Pt catalyst supported on carbon black Vulcan XC72. The results showed that the particle distribution and the structure of the developed Pt nanoparticles supported on the nanoscale graphite were similar to those of the commercial catalyst. The accelerated degradation testing results showed that the electrochemical active surface area losses after 1500 cycles were 46.92% and 62.2% for the developed catalyst and the commercial catalyst, respectively, while mass activity losses were 45.3% and 84.2%, respectively. The temperature-programmed oxidation results suggest that the developed catalysts had better corrosion resistance than the commercial catalyst. The developed Pt catalysts had similar catalytic performance to the commercial catalyst; however, the developed catalysts had much better corrosion resistance than the commercial catalyst. Overall, nanoscale graphite can be a promising electrocatalyst support to replace the currently used Vulcan XC72 carbon black.     

Carbon nanofibers supported Pt-Ru electrocatalysts for direct methanol fuel cells

Oxidized and reduced carbon nanofibers (OCNF and RCNF) were used as supports to prepare highly dispersed PtRu catalysts for the direct methanol fuel cells (DMFC). The structural and surface features and electrocatalytic properties of bimetallic PtRu/OCNF and PtRu/RCNF were extensively investigated. FT-IR spectra show that carboxyl groups exist on the surface of the OCNF, which greatly influence the morphology and crystallinity of the electrocatalysts. Transmission electron microscopy and X-ray diffraction consistently show that PtRu/RCNF has a smaller particle size and more uniform distribution than PtRu/OCNF. However, both catalysts have very similar methanol oxidation peak current densities that are significantly lower than commercial catalyst based on current-voltage (CV) results. These two catalysts also give very similar single cell performance except for some difference in the resistance polarization region. The OCNF supported catalysts give better performance than commercial catalysts when current density is higher than 50 mA cm⁻² in spite of low methanol oxidation peak current density. These results can be ascribed to the specific surface and structural properties of carbon nanofibers.     

Effects of ozone treatment of carbon support on Pt-Ru/C catalysts performance for direct methanol fuel cell

This research is aimed to increase the activity and utilization of Pt-Ru alloy catalysts and thus to lower the catalyst loading in anodes for methanol electrooxidation. The Pt-Ru/C catalysts were prepared by chemical reduction. The support of Vulcan XC-72 carbon black was pretreated by ozone at different temperatures for different times. The specific surface area of the samples was evaluated by the standard BET method. The surface concentrations of oxygen were determined by XPS. The results showed that the surface concentrations of oxygen on the carbon were first decreased and then increased with pretreating times, and the specific surface area of the carbon was decreased with pretreating times at the same temperature. The specific surface area was increased with increasing temperature, and the surface concentration of oxygen was first decreased and then increased with increasing temperature for the same pretreating time. Pt-Ru/C catalysts supported by untreated and O₃ treated carbon black were characterized and tested for methanol electrooxidation. X-ray diffraction (XRD) was used to characterize the influence of carbon treated with ozone on Pt-Ru/C catalysts. It was found that the catalysts were composed only of f.c.c. Pt-Ru alloy particles without metallic Ru or Ru oxide. Cyclic voltammetry (CV) and Tafel curves were used for methanol electrooxidation on Pt-Ru/C catalysts in a solution of 0.5 mol/L CH₃OH and 0.5 mol/L H₂SO₄, showing that the catalytic activity of Pt-Ru/C catalysts supported by ozone treated carbon was higher than that by the untreated one. The ozone treatment time and temperature, which affect the performance of Pt-Ru/C catalysts, were discussed. Electrochemical measurements showed that the catalysts supported by the carbon after ozone treatment for 6 min at 140 °C had the best performance.     

Bulk and Surface Properties of a VPO Catalyst Used in an Electrochemical Membrane Reactor: Conductivity-, XRD-, TPO- and XPS-study

In the first part of this work, the electrical conductivity of vanadium phosphorous oxide (VPO) catalyst was investigated by means of the 2-probe EIS method. The VPO showed an extremely low conductivity at low oxygen partial pressure, which is the prevailing condition in the anodic compartment in an electrochemical membrane reactor (EMR). In the second part of this study, fresh as well as VPO catalyst already used in an EMR were characterised with XRD, XPS and temperature programmed oxidation (TPO). The XRD measurements revealed an unchanged bulk phase structure after operation in the EMR. Significant differences in the average oxidation states of vanadium in the catalyst layer in the EMR were determined via XPS, where the catalyst surface facing the electrolyte membrane was more oxidised than the surface facing the anodic gas compartment. The lowered uptake and release of oxygen was observed in TPO experiments for the catalyst used in the EMR.     

Magnetron sputtering of platinum nanoparticles onto vertically aligned carbon nanofibers for electrocatalytic oxidation of methanol

The electrochemical activities of Pt-sputtered electrodes based on vertically aligned carbon nanofibers (Pt/VACNFs) directly grown on the carbon paper are investigated. Different Pt loading (0.01 mg cm⁻², 0.025 mg cm⁻² and 0.05 mg cm⁻²) electrodes are developed. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results show that the Pt nanoparticles are homogeneously dispersed on the surface of vertically aligned carbon nanofibers. TEM and X-ray diffraction (XRD) results reveal the Pt nanoparticles diameter increase with increasing Pt loading. The Pt/VACNFs electrodes show good electrochemical active surface area, methanol oxidation peak current density and CO tolerance. The electrochemical catalyst activities weaken as the diameter grows larger. Compared to common electrodes prepared by commercial catalyst in a conventional ink-process, the performance improvement suggests that unique structure of Pt/VACNFs electrode ensures the electronic pathway and Pt nanoparticles exposed to three-phase boundary, which leads to a significant improvement of the Pt utilization and a potential application in direct alcohol fuel cells.     

Platinum nanopaticles supported on stacked-cup carbon nanofibers as electrocatalysts for proton exchange membrane fuel cell

Inexpensive stacked-cup carbon nanofibers (SC-CNFs) supported Pt nanoparticles with a loading from 5 to 30 wt.% were prepared through a modified ethylene glycol method. XRD and TEM characterizations show that the average Pt particle sizes increase with increasing metal loading, and they can be controlled <5 nm with a uniform dispersion. A self-developed filtration process was employed to fabricate Pt/SC-CNFs film-based membrane electrode assembly (MEA), and the catalyst transfer efficiency can reach nearly 100% using a super-hydrophobic polycarbonate filter. The thickness of catalyst layer can be accurately controlled through altering Pt loadings of the catalyst and electrode, this is in good agreement with our theoretical calculation. For Pt/SC-CNFs-based-MEAs, Pt cathode loading was found more critical than Pt anode loading on proton exchange membrane fuel cell (PEMFC) performance. The Pt/SC-CNFs-based MEA with an optimized 50 wt.% Nafion content demonstrates higher PEMFC performance than the carbon black-based MEA with an optimized 30 wt.% Nafion content. SC-CNFs possess much larger length-to-diameter ratio than carbon black particles, it makes Pt/SC-CNFs more easily form continuously conductive networks in the Nafion matrix than carbon black. Therefore, the Pt/SC-CNFs-based MEA demonstrates higher Pt utilization than carbon black-based MEA, which implies possible reduction in Pt loading of MEA.