Modification of platinum surfaces by spontaneous deposition: Methanol oxidation electrocatalysis

The presence of a second metal on platinum surfaces affects the performance of methanol oxidation. However, most of the electrocatalytic reactions are studied by using electrochemically deposited platinum alloys, but in the case of spontaneous deposition the situation is not so clear since the surface distribution, stability and morphology are usually not well documented. The formation of surface decorated samples on mono- and poly-crystalline platinum is followed by electrochemical and spectroscopic techniques and analysis of their performance towards methanol adsorption and oxidation compared with that on pure platinum. Pt/Sn and Pt/Ru are of special interest because of their well-known performance in methanol fuel cells. Methanol oxidation on Pt(111)/Ru, Pt(111)/Sn and Pt(111) shows that ruthenium is the only one able to promote the reaction since the simultaneous dissolution of tin occurs and competes with the process of interest. The in situ infrared spectroscopy is used to compare methanol oxidation on Pt(111)/Ru and Pt(111) in acid media using p-polarized light. The formation of bridge bound carbon monoxide is inhibited in the presence of ruthenium ad-species, whereas on Pt(111) the three adsorption configurations are observed. Linear sweep polarization curves and Tafel slopes (calculated from steady state potentiostatic plots) for methanol oxidation are compared on polycrystalline surfaces modified by tin or ruthenium at different coverages. There is almost no change in the Tafel slopes due to the presence of the foreign metal except for Pt/Ru, where a 0.09 V decade⁻¹ slope was calculated below 0.55 V due to hydroxyl adsorbates on ruthenium islands. The anodic stripping of methanol residues on the three surfaces indicates a lower amount of carbon monoxide-type adsorbates on Pt/Ru, and the simultaneous tin dissolution process leading to residues oxidation on Pt/Sn electrodes.     

Platinum supported catalysts for carbon monoxide preferential oxidation: Study of support influence

The aim of this work is to study the influence of the addition of different oxides to an alumina support, on surface acidity and platinum reducibility in platinum-based catalysts, as well as their effect on the activity and selectivity in CO preferential oxidation, in presence of hydrogen. A correlation between surface acidity and acid strength of surface sites and metal reducibility was obtained, being Pt-support interaction a function of the acid sites concentration under a particular temperature range. In platinum supported on alumina catalysts, CO oxidation follows a Langmuir-Hinshelwood mechanism, where O₂ and CO compete in the adsorption on the same type of active sites. It is noteworthy that the addition of La₂O₃ modifies the reaction mechanism. In this case, CO is not only adsorbed on the Pt active sites but also on La₂O₃, forming bridge bonded carbonates which leads to high reactivity at low temperatures. An increase on temperature produces CO desorption from Pt surface sites and favours oxygen adsorption producing CO₂. CO oxidation with surface hydroxyl groups was activated producing simultaneously CO₂ and H₂.     

Well dispersed Pt nanoparticles on commercial carbon black oxidized by ozone possess significantly high electro-catalytic activity for methanol oxidation

In this paper, the electro-catalytic methanol oxidation on the commercial carbon black treated with ozone at different temperatures to support platinum (Pt) nanoparticles was investigated. The necessary techniques like transmission electron microscopy (TEM), Raman spectroscopy, nitrogen adsorption-desorption techniques, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) have been used to discovery the composition, morphology and structure of the catalysts. The electro-catalytic methanol oxidation activity and durability of the catalysts was estimated by the cyclic voltammetry and chronoamperometric techniques. The results indicated that the platinum nanoparticles with average sizes of 2.04 nm can be uniformly dispersed on the surfaces of carbon black oxidized by ozone at 140 °C. In the meanwhile it has significantly high electro-catalytic activity for methanol oxidation. This phenomenon is attributed to the fact that ozone oxidation increase the content of oxygen-containing groups on the carbon black, which is helpful for improving the dispersion and decreasing the size of platinum nanoparticles. Oxygen-containing groups play a critical role in enhancing the performance of methanol electro-oxidation.     

Alkaline direct alcohol fuel cells

The faster kinetics of the alcohol oxidation and oxygen reduction reactions in alkaline direct alcohol fuel cells (ADAFCs), opening up the possibility of using less expensive metal catalysts, as silver, nickel and palladium, makes the alkaline direct alcohol fuel cell a potentially low cost technology compared to acid direct alcohol fuel cell technology, which employs platinum catalysts. A boost in the research regarding alkaline fuel cells, fuelled with hydrogen or alcohols, was due to the development of alkaline anion-exchange membranes, which allows the overcoming of the problem of the progressive carbonation of the alkaline electrolyte. This paper presents an overview of catalysts and membranes for ADAFCs, and of testing of ADAFCs, fuelled with methanol, ethanol and ethylene glycol, formed by these materials.     

Influence of Pb2+ ions in the H2 oxidation on Pt catalyzed hydrogen diffusion anodes in sulfuric acid: presence of oscillatory phenomena

The influence of Pb²⁺ ions in sulfuric acid medium on the behavior of a platinum catalyzed hydrogen diffusion electrode (HDE) in a filter press reactor has been studied. A voltammetric study of the H₂ oxidation reaction on a polyoriented platinum electrode and a platinum rotating disk electrode (RDE) in presence of lead ions in solution has also been carried out. Potential oscillations were found in galvanostatic experiments of H₂ oxidation using a HDE catalyzed with platinum when Pb²⁺ ions are present in solution. This oscillatory phenomenon was also observed when hydrogen oxidation was carried out in presence of Pb²⁺ ions using a platinum RDE. The oscillatory behavior observed has been attributed to an adsorption–oxidation–desorption process of lead on the platinum surface. Due to the low solubility of Pb²⁺ in sulfuric acid, at high values of coverage, lead is oxidised to insoluble lead sulfate that blocks the Pt surface. The coupling of the dissolution of lead sulfate and the Pb electrochemical adsorption–oxidation processes cause the oscillatory phenomenon.     

Platinum decorated Ru/C: Effects of decorated platinum on catalyst structure and performance for the methanol oxidation reaction

Platinum decorated Ru/C catalysts are prepared by successive reduction of a platinum precursor on pre-formed Ru/C. Pt:Ru atomic ratios are varied from 0.13:1 to 0.81:1 to investigate the platinum decoration effects on the catalyst's structure and electrochemical performance towards the methanol oxidation reaction (MOR) at room temperature. The catalysts are extensively characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Ru@Pt/C catalysts show enhanced mass-normalized activity and specific activity for the MOR relative to Pt/C. For the anodic oxidation of methanol, the ratio of forward to reverse oxidation peak current R (I_f/I_b) varies considerably: R decreases from 5.8 to 0.8 when the Pt:Ru ratio increases from 0.13:1 to 0.81:1. When the ratio of Pt:Ru is 0.42:1, R reaches 0.99 (close to that of Pt/C), and further increase of the Pt:Ru ratio leads to almost no decrease in R. Coincidentally, maximum mass-normalized activity is also obtained when Pt:Ru is 0.42:1.     

Heteroatom doped 3D graphene aerogel supported catalysts for formic acid and methanol oxidation

In this study, nitrogen (N) and boron (B) heteroatom doped graphene aerogel support materials have been employed for the dispersion of platinum (Pt) nanoparticles to improve their electrocatalytic activities for formic acid and methanol oxidation. Pt nanoparticles dispersed on the heteroatom doped graphene aerogel (GA) support materials by a microwave heating method. The as-prepared catalysts were characterized by a variety of means such as SEM, EDS, ICP-MS, TEM, XRD, BET and XPS. The electrocatalytic activities, stability and impedance of the synthesized catalysts were investigated for formic acid and methanol oxidation using electrochemical measurements. The 3D graphene aerogels have higher capacitive currents than the Vulcan XC-72 in the double layer region. The results of electrochemical chronoamperometry tests reveal that Pt/BGA shows the best stability for methanol oxidation and also exhibited superior electrocatalytic activity towards the oxidation of methanol in cyclic voltammetry. In addition to, heteroatom doped GA supported catalysts higher activity compared to the Vulcan XC-72 supported catalyst for formic acid oxidation.     

Investigating the addition of silicon oxide to carbon: Effects of amount and heat treatment on anti-aggregation and electrochemical performance of Pt catalysts

Small nanoparticles offer high surface areas and are certainly desirable for electrocatalytic reactions and fuel cells. However, the drawback of using small nanoparticles is their tendency towards particle aggregation. This paper aims to inhibit platinum agglomeration by adding silicon oxide to a carbon support for enhanced catalytic activity in low-temperature fuel cells. The catalysts are characterized by X-ray diffraction and transmission electron microscopy. Physical characterization and cyclic voltammetry techniques at room temperature are used to assess the effects of silicon oxide amount, post-heating temperature, and holding time on particle size and dispersion of active components, and the catalysts’ activity towards the methanol oxidation and oxygen reduction reactions. It is found that using a support of carbon powder with 3 wt.% silicon oxide can enhance the electrochemically active surface area of Pt catalysts and their activity towards the anodic oxidation of methanol and reduction of oxygen. The active components are also more resistant than Pt/C to agglomeration upon heating.     

Electrodeposited Pd nanoparticles on polypyrole/nickel foam for efficient methanol oxidation

The present work describes the Ni foam (Ni–F)/polypyrrole (PPy)/palladium (Pd) (Ni–F/PPy/Pd) multilayered catalysts via a facile electrochemical technique. Potentiostatic deposition of PPy on the surface of Ni–F is followed by galvanostatic deposition of Pd nanoparticles on Ni–F/PPy acted as supports for electrochemical deposition of Pd nanoparticles. The produced catalysts are utilized for electrocatalytic methanol oxidation in alkaline media. Chronoamperometry (CA), cyclic voltammetry (CVs), and electrochemical impedance spectroscopy (EIS) techniques are used to examine the electrocatalytic performance of Ni–F/PPy/Pd based electrodes for methanol oxidation. The polypyrrole modification on Ni–F leads to an improvement in the electrocatalytic activity of the Ni-F/PPY-Pd catalysts toward methanol oxidation. As an open-pored, porous metal with high electrical conductivity, nickel foam produces a substantial amount of active area during the modification of Pd and polypyrrole, which results in significant catalytic activity and a rapid rate charge transfer reaction kinetics on methanol oxidation. The Ni–F/PPy/Pd10 catalyst exhibits enhanced specific activity than its counterparts and a reduced onset potential for methanol oxidation, as well as a low Tafel slope. Based on these results, Ni–F/PPy/Pd10 is suggested as a good material for the anode in the electrocatalytic oxidation of methanol.     

Recent advances in two-dimensional Pt based electrocatalysts for methanol oxidation reaction

Direct methanol fuel cells (DMFCs) had been attracted considerable attention for its advantages of high energy density, simplified systems and readily transportation and storage of methanol. However, the notoriously sluggish kinetics of methanol oxidation reaction (MOR) of the anode reaction, had greatly affected the commercialization of DMFCs. On one hand, Pt based catalyst are still the most effective MOR catalysts, while the high cost caused by the high loadings of electrocatalyst to compensate the low MOR activity impedes the wide accessible of DMFCs. In addition, the occurrence of catalyst poisoning owing to the strong interaction between Pt and carbon monoxide (CO) generated during the MOR processing, further leading to the fast decay in the performance and stability of MOR electrocatalysts. Two-dimensional (2D) Pt based nanostructures is regarded to be one promising and effective class of MOR electrocatalysts, and attracted much attention due to the high electron mobility, highly exposed active sites, and extraordinary thermal conduction. In this review, the mechanism of MOR was firstly introduced, and then the synthesis conditions, structure characteristics and methanol oxidation performances both in acidic and alkaline dielectric of 2D Pt based nanocatalysts were introduced. Subsequently, we briefly analyzed the structural characteristics of 2D Pt based nanocatalysts and their advantages, including the low platinum loadings, high specific surface area and majority of atomic active sites exposed. Finally, the opportunities and challenges for designing of advanced 2D Pt based nanocatalysts was proposed and discussed.     

Metamorphosis of the mixed phase PtRu anode catalyst for direct methanol fuel cells after exposure of methanol: In situ and ex situ characterizations

The change in the mixed phase heavily oxidized PtRu anode with the exposure of methanol in a direct methanol fuel cell (DMFC) has been investigated by electrochemical impedance spectroscopy (EIS) and X-ray diffraction (XRD). The investigation had two major objectives: (i) to explore the original state of the active catalyst and (ii) to understand if alloying of Pt and Ru is a requirement for higher methanol oxidation activity. It was found that the methanol oxidation activity gradually improved for ∼2 h of exposure. The impedance spectra were taken at different times within this time of improvement of activity. The impedance spectra were deconvoluted in different contributions like membrane resistance (R_m), charge transfer resistance (R_Ct), adsorption resistance (R_ad), and oxidation resistance (R_ox). The improvement of the activity was explained in terms of the effect of the pretreatment on different contributions. XRD was done on the virgin and methanol exposed sample as a possible mean to identify the difference. It was postulated that the reduction of the as prepared PtRu after exposure was responsible for the activity improvement. Also, it was shown that bulk alloy formation is not a necessary condition for higher methanol activity of PtRu catalysts.     

Catalysts for direct ethanol fuel cells

By comparing the performance of fuel cells operating on some low molecular weight alcohols, it resulted that ethanol may replace methanol in a direct alcohol fuel cell. To improve the performance of a direct ethanol fuel cell (DEFC), it is of great importance to develop anode catalysts for ethanol electro-oxidation more active than platinum alone. This paper presents an overview of catalysts tested as anode and cathode materials for DEFCs, with particular attention on the relationship between the chemical and physical characteristics of the catalysts (catalyst composition, degree of alloying, and presence of oxides) and their activity for the ethanol oxidation reaction.     

A novel Rh–Ir electrocatalyst for the oxygen reduction reaction and the hydrogen and methanol oxidation reactions

A novel Rh–Ir based material was synthesized by pyrolysis of an Ir₄(CO)₁₂/Rh₆(CO)₁₆ mixture in a reductive (H₂) atmosphere. The material was characterized by FTIR spectroscopy, X-ray diffraction, energy dispersive spectroscopy and scanning electron microscopy, and was evaluated as electrocatalyst for oxygen reduction and hydrogen and methanol oxidation by rotating disk electrode measurements. The bimetallic material shows a high catalytic activity for the oxygen reduction reaction and is also capable to carry out the hydrogen oxidation reaction even in the presence of carbon monoxide in different concentrations (100 ppm and 0.5%), in contrast with commercial platinum catalysts, which become easily deactivated by CO. The activity of the catalyst for methanol oxidation is acceptable but still low in comparison with Pt–Ru. The results show that the new bimetallic catalyst is a potential candidate to be evaluated as both cathode and anode in a reforming hydrogen PEMFC, and as an anode in a direct methanol fuel cell.     

Polypyrrole and platinum deposited onto carbon substrate to enhance direct methanol fuel cell electrodes behaviour

The aim of this work is to study the ability of polypyrrole to reduce the platinum load of low temperature methanol fuel cell electrodes. Platinum was deposited onto carbon paper and a layer of polypyrrole electrodeposited onto carbon paper, using electron beam evaporation and electrodeposition by pulses. Subsequently, the morphology and electrochemical behaviour of the synthesised samples were analysed in sulphuric acid solution, determining their electrochemically active surface area; and in a solution of sulphuric acid and methanol, to analyse their catalytic performance. The electrochemical measurements showed that the electrochemically active surface area and the catalytic performance of the electrodes prepared by evaporating platinum are increased when prepared on the polypyrrole film. Electrodes prepared using the pulse electrodeposition technique presented fairly homogeneous coatings that led to the reduction of the oxidation potential of methanol and the increase of their resistance to CO poisoning.     

Methanol oxidation on carbon-supported platinum-tin electrodes in sulfuric acid

A study is made of the electrooxidation of methanol in sulfuric acid on carbon-supported electrodes containing platinum-tin bimetal catalysts that are prepared by an in situ potentiometric-characterization route. The catalysts are investigated by employing chemical analyses, X-ray diffraction (XRD), X-ray absorption-near-edge spectroscopy (XANES) and X-ray photoelectron spectroscopy (XPS) data in conjunction with electrochemical measurements. From the electrochemical data, it is inferred that while an electrode with (3:1) Pt-Sn/C catalyst involves a two-electron rate-limiting step akin to platinum-on-carbon electrodes, it is shifted to a one-electron mechanism on electrodes with (3:2)Pt-Sn/C, (3:3)Pt-Sn/C, and (3:4)Pt-Sn/C catalysts. The study suggests that the tin content in the platinum-tin bimetal catalyst produces: (i) a charge transfer from tin to platinum; (ii) an increase in the coverage of adsorbed methanolic residues with increase in the tin content, as indicated by the shift in rest potential of the electrodes towards the reversible value for oxidation of methanol (0.043 V versus SHE), and (iii) a decrease in the overall content of higher valent platinum sites in the catalyst.     

Electrooxidation of methanol on polyaniline without dispersed catalyst particles

Electrooxidation of methanol in H₂SO₄ is studied on platinum and polyaniline (PANI) deposited platinum electrodes by cyclic voltammetry. In contrast to reports in the literature, which suggest the need of fine particles of a catalyst dispersed in PANI matrix for occurrence of electrooxidation of CH₃OH, in the present study, the reaction is shown to take place on PANI without additional catalyst particles at CH₃OH concentrations higher than 1 M. At lower concentrations, adsorption of CH₃OH occurs on PANI resulting in a reduction in intrinsic voltammetric peak currents of PANI in H₂SO₄. The kinetics of adsorption follows Langmuir isotherm. By a comparison of cyclic voltammetric peak currents of methanol on platinum and PANI deposited platinum electrodes, the catalytic efficiency of PANI towards oxidation of CH₃OH is evaluated.     

Kinetics of methanol electrooxidation on Pt/C and PtRu/C catalysts

This paper analyzes the performance of platinum and platinum:ruthenium carbon-supported catalysts modified by the application of in-situ cathodic polarizations towards the methanol oxidation reaction. These new electrodes are characterized by electrochemical techniques together with transmission electron microscopy images to envisage the dispersion of the catalyst. We measure methanol electrooxidation current transients, fitting the results with a general kinetic equation for a mixed mass and charge transfer processes for adsorbed reactant species. The kinetic equation also helps to predict the exponent of the chronoamperometric decay as directly related to the fractal dimension of the catalyst surface and to discuss the possible processes involved in the electrocatalytic reaction.     

CO oxidation on carbon-supported PtMo electrocatalysts: Effect of the platinum particle size

The electrochemical oxidation of CO on carbon-supported electrocatalysts was studied with different amounts of platinum and molybdenum as active phases. These materials were synthesized by the metal carbonyl thermolysis method. Molybdenum hexacarbonyl and large or small polymeric chains of Pt carbonyl complex were used as metal precursors. The catalysts were characterized by XRD, HRTEM and SEM–EDX. The platinum active area was determined by voltammetric CO stripping. The electrochemical methods revealed an enhanced performance of the platinum–molybdenum materials for the CO oxidation, in comparison with those formulated only with Pt. The best results were obtained for low molybdenum loadings. The lowest onset oxidation potential was obtained with a 4:1 relationship in the Pt:Mo content, which indicates the highest activity for this catalyst for CO oxidation. The presence of molybdenum caused a decrease in the catalytic active area of the materials synthesized with large platinum particles, whereas the opposite was observed with the catalysts synthesized with small Pt particles, where the addition of Mo results in higher active areas than the Pt catalyst.     

废银催化剂中银的回收技术进展

银可用作多种氧化反应催化剂的活性组分,尤其是作为乙烯氧化制环氧乙烷和甲醇氧化制甲醛的催化剂已工业化应用多年。甲醇氧化制甲醛废银催化剂采用草酸除铁后,主要采用电解工艺进行回收。目前废环氧乙烷银催化剂中银的回收采用湿法,银的溶解方法包括硫酸溶解法、硝酸溶解法、亚硫酸钠溶解法、硫代硫酸盐溶解法、硫脲溶解法和强碱溶解法,高含量废银催化剂常采用硝酸溶解法。无论是从降低硝酸的消耗量,还是从降低NOx的排放量上看,选用稀硝酸溶解银都是有利的。从银离子得到单质银的工艺包括还原法(溶液中还原和干态还原)、熔炼-筛选-脱碳法、热解法和吸附法,通常采用还原法。常用的还原剂有硼氢化钠、双氧水、硫酸亚铁及Fe、Zn、Al等无机还原剂和醛类、醇类、水合肼、抗坏血酸等有机还原剂。硝酸与金属反应时,首先被还原成中间体HNO2,反应产物的种类及组成随硝酸浓度和金属种类而发生变化。有研究认为,硝酸溶解废银催化剂中银的最佳工艺条件为:反应温度85℃,反应及恒温时间70min,酸量为理论耗量的1.2倍,固液比1:4。NOx尾气的处理主要有碱吸收法、分子筛吸附法、催化还原法和稀硝酸吸收法等。硝酸溶解-NaCl沉淀-Fe粉还原法是将废银催化剂中的银回收为单质银的较好工艺。今后努力的方向是进一步提高银回收率。     

Electro-oxidation of methanol and ethanol using PtRu/C electrocatalysts prepared by spontaneous deposition of platinum on carbon-supported ruthenium nanoparticles

PtRu/C electrocatalysts were prepared by spontaneous deposition of Pt(II) and Pt(IV) ions on carbon-supported ruthenium nanoparticles, characterized by EDAX, TEM, cyclic voltammetry and tested for methanol and ethanol oxidation using the thin porous coating technique. The spontaneous deposition of Pt(II) ions was about two times more effective than Pt(IV) ions. The electrocatalysts were active for methanol and ethanol oxidation. For methanol oxidation good performance was obtained with high platinum coverage and for ethanol oxidation with low platinum coverage.