Enhanced activity and stability of Pt/C fuel cell anodes by the modification with ruthenium-oxide nanosheets

Ruthenium-oxide nanosheet (RuO₂ns) crystallites with thickness less than 1 nm were prepared via chemical exfoliation of a layered potassium ruthenate and deposited onto carbon supported platinum (Pt/C) as a potential co-catalyst for fuel cell anode catalysts. The electrocatalytic activity towards carbon monoxide and methanol oxidation was studied at various temperatures for different RuO₂ns loadings. An increase in electrocatalytic activity was evidenced at temperatures above 40 °C, while little enhancement in activity was observed at room temperature. The RuO₂ns modified Pt/C catalyst with composition of RuO₂:Pt = 0.5:1 (molar ratio) exhibited the highest methanol oxidation activity. CO-stripping voltammetry revealed that RuO₂ns promotes oxidation of adsorbed CO on Pt. In addition to the enhanced initial activity, the RuO₂ns modified Pt/C catalyst exhibited improved stability compared to pristine Pt/C against consecutive potential cycling tests.     

ESTIMATION OF KINETIC PARAMETERS FOR ELEMENTARY SURFACE PROCESSES FROM INTEGRAL REACTOR DATA. CO OXIDATION OVER Pt/ Al2O3

A novel method has been developed which can be used for kinetic parameter estimation from laboratory reactor data. It is based on discrete modeling and variational techniques applied to an integral reactor packed with supported catalyst pellets. This new method, similar to the McCabe-Thiele method in distillation column design, has been used to determine kinetic parameters of adsorption, desorption and surface reaction steps for CO oxidation over Pt/ AI₂ O₃catalysts at 500° C and atmospheric pressure. The results clearly indicate the importance of the coverage dependency of CO desorption activation energy in the steady state kinetics of CO oxidation. The good agreement of the results with those on single crystal Pt surfaces indicates no significant metal-support interactions for the Pt/ Al₂O₃ system during CO oxidation     

H2 and H2/CO oxidation mechanism on Pt/C, Ru/C and Pt–Ru/C electrocatalysts

The oxidation kinetics of H₂ and H₂ + 100 ppm CO were investigated on Pt, Ru and Pt–Ru electrocatalysts supported on a high-surface area carbon powder. The atomic ratios of Pt to Ru were 3, 1 and 0.33. XRD, TEM, EDS and XPS were used to characterize the electrocatalysts. When alloyed with ruthenium, a decrease in mean particle size and a modification of the platinum electronic structure were identified. Impedance measurements in H₂SO₄, at open circuit potential, indicated different mechanisms for hydrogen oxidation on Pt/C (Tafel–Volmer path) and Pt–Ru/C (Heyrowsky–Volmer path). These mechanisms also occur in the presence of CO. Best performances, both in H₂ and H₂ + CO, were achieved by the catalyst with the ratio Pt/Ru = 1. This is due to a compromise between the number of free sites and the presence of adsorbed water on the catalyst. For CO tolerance, an intrinsic mechanism not involving CO electroxidation was proposed. This mechanism derives from changes in the electronic structure of platinum when alloyed with ruthenium.     

Reduction of CO2 on bismuth modified Pt(1 1 0) single-crystal surfaces. Effect of bismuth and poisoning intermediates on the rate of hydrogen evolution

The reduction of CO₂ on bismuth modified Pt(1 1 0) single crystal surfaces has been studied voltammetrically. The effect of bismuth and the amount of formed CO species on the rate of hydrogen evolution has also been investigated. A decrease in the rate of CO₂ reduction is observed due to the modification of the surface with bismuth adsorption. This decrease goes beyond the simple third body effect expected from the blockage of active sites on the platinum surface after bismuth adsorption. However, the hydrogen evolution reaction is relatively insensitive to the presence of adsorbed species, in contrast with previous result reported for Pt(1 1 1) and Pt(1 0 0) surfaces.     

Potential dependence of segregation and surface alloy formation of a Ru modified carbon supported Pt catalyst

Ruthenium modified carbon supported platinum catalysts have been shown to have a similar activity towards carbon monoxide oxidation as conventionally prepared bimetallic PtRu alloy catalysts. In this study the effect of the applied electrode potential and potential cycles on the location and oxidation state of the Ru species in such Ru modified Pt/C catalysts was investigated using in situ EXAFS collected at both the Ru K and Pt L₃ absorption edges. The as prepared catalyst was found to consist of a Pt core with a Ru oxy/hydroxide shell. The potential dependent data indicated alloying to form a PtRu phase at 0.05 V versus RHE and subsequent dealloying to return to the Ru oxy/hydroxide decorated Pt surface at potentials greater than 0.7 V. The Ru-O distances obtained indicate that both Ru³⁺ and Ru⁴⁺ species are present on the surface of the Pt particles at oxidising potentials; the former is characteristic of the as prepared Ru modified Pt/C catalyst and following extensive periods at potentials above 0.7 V and the latter of the Ru oxide species on the PtRu alloy.     

ESTIMATION OF KINETIC PARAMETERS FOR ELEMENTARY SURFACE PROCESSES FROM INTEGRAL REACTOR DATA. CO OXIDATION OVER Pt/ Al2O3

A novel method has been developed which can be used for kinetic parameter estimation from laboratory reactor data. It is based on discrete modeling and variational techniques applied to an integral reactor packed with supported catalyst pellets. This new method, similar to the McCabe-Thiele method in distillation column design, has been used to determine kinetic parameters of adsorption, desorption and surface reaction steps for CO oxidation over Pt/ AI₂ O₃catalysts at 500° C and atmospheric pressure. The results clearly indicate the importance of the coverage dependency of CO desorption activation energy in the steady state kinetics of CO oxidation. The good agreement of the results with those on single crystal Pt surfaces indicates no significant metal-support interactions for the Pt/ Al₂O₃ system during CO oxidation     

Preferential oxidation of CO over CuO/CeO2 and Pt-Co/Al2O3 catalysts in micro-channel reactors

Micro-channel plates with dimension of 1 mm × 0.3 mm × 48 mm were prepared by chemical etching of stainless steel plates followed by wash coating of CeO₂ and Al₂O₃ on the channels. After coating the support on the plate, Pt, Co, and Cu were added to the plate by incipient wetness method. Reaction experiments of a single reactor showed that the micro-channel reactor coated with CuO/CeO₂ catalyst was highly selective for CO oxidation while the one coated with Pt-Co/Al₂O₃ catalyst was highly active for CO oxidation. The 7-layered reactors coated with two different catalysts were prepared by laser welding and the performances of each reactor were tested in large scale of PROX conditions. The multi-layered reactor coated with Pt-Co/Al₂O₃ catalyst was highly active for PROX and the outlet concentration of CO gradually increased with the O₂/CO ratio due to the oxidation of H₂ which maintained the reactor temperature. The multi-layered reactor coated with CuO/CeO₂ showed lower catalytic activity than that coated with Pt catalyst, but its selectivity was not changed with the increase of O₂/CO ratios due to the high selectivity. In order to combine advantages (high activity and high selectivity) of the two individual catalysts (Pt-Co/Al₂O₃, CuO/CeO₂), a serial reactor was prepared by connecting the two multi-layered micro-channel reactors with different catalysts. The prepared serial reactor exhibited excellent performance for PROX.     

Pt-Fe催化剂次表层Fe结构表面的CO氧化反应性能

利用紫外光电子能谱等表面科学方法,研究了Pt-Fe模型催化剂的次表层Fe结构[即Pt/Fe/Pt(111)结构]在不同条件下CO的吸附及其氧化反应。结果表明,Pt/Fe/Pt(111)结构在H_2气氛或者超高真空中是种稳定结构,最外层的原子与Pt(111)相同,是密排的铂原子面;但次表层的原子中有约0.5单层的铁原子,使费米边附近(0~2.0)e V的电子态密度明显低于Pt(111)表面,从而改变表面的CO和O_2吸附以及反应性能。程序升温的紫外光电子能谱结果显示,Pt/Fe/Pt(111)表面在(100~300)K,CO的吸附受温度的影响不明显,且O_2能够吸附、活化并使共吸附的CO发生氧化反应;当温度为300 K时,O_2无法在Pt/Fe/Pt(111)表面吸附、活化,所以CO氧化反应无法进行。Pt/Fe/Pt(111)结构虽然能有效地减弱CO的吸附从而避免CO毒化的问题,但O_2的吸附和活化也受到显著抑制并影响到一定条件下CO的氧化反应。     

Needle in a haystack catalysis

A new configuration of catalyst loading in the Temporal Analysis of Products (TAP) reactor is presented. It is a single Pt particle packed in a bed with approximately 100,000 inert quartz particles. In TAP studies, the single particle configuration was proven to be sensitive enough to monitor and compare kinetic characteristics of the same catalyst particle at both high vacuum and atmospheric pressures. Catalytic CO oxidation reaction over platinum was used to illustrate these new possibilities. In the TAP single particle experiments under high vacuum conditions, a single particle provides high conversion (up to a total conversion of 95%) despite the catalyst particle occupies less than 0.1% of the total reactor volume. This phenomenon was proven in a variety of pulse response experiments. A mathematical probabilistic theory of this counterintuitive phenomenon will be published in the next paper. Also, an interesting similarity was found from both TAP vacuum and atmospheric pressure data, i.e. both sets of data are characterized by a “turning point” at the same temperature of 170 °C indicating a transition from an O₂ dominated regime to a CO dominated regime. This observation of pressure independent characteristic of the Pt particle creates a new possibility for bridging across the pressure gap.     

Composite electrocatalysts for anodic methanol and methanol-reformate oxidation

Binary anode electrocatalyst formulations were prepared by adsorption of phthalocyanine and tetraphenylporphyrin complexes of different transition metals on a commercial carbon supported platinum catalyst. Only after pyrolyzing the complexes at 700 °C under nitrogen were catalysts of some activity obtained. A binary Pt/Ni electrocatalyst prepared by this procedure exhibits considerable anodic catalytic activity in the acidic environment of the Nafion^® electrolyte for reformate and direct methanol oxidation for more than 400 h without deterioration. Ternary electrocatalyst formulations Pt/Ru/W = 1/1/y were produced according to the Bönnemann method. The Pt/Ru/W catalyst of 1/1/1.5 (mol/mol/mol) composition is optimal. Compared to the Pt/Ru catalyst, it enhances the performance of reformate (H₂ + 150 ppm CO) fuel cells by 50% and of direct methanol fuel cells (steam/methanol vapour = 50:1 mol/mol) by 80%. Attached to a GC electrode by a thin Nafion^® film, the catalysts were also tested for methanol oxidation in aqueous methanol solutions in half cells by slow potential stepping. This procedure is useful for fast initial screening.     

One-Step Flame Synthesis of an Active Pt/TiO2 Catalyst for SO2 Oxidation—A Possible Alternative to Traditional Methods for Parallel Screening

Flame synthesis as a route for production of composite metal oxides has been employed for the one-step synthesis of a supported noble metal catalyst, i.e., a Pt/TiO₂ catalyst, by simultaneous combustion of Ti-isopropoxide and platinum acetylacetonate in a quench-cooled flame reactor. The average size of the platinum particles supported on aggregated nanoparticles of TiO₂ is approximately 2 nm. The high SO₂ oxidation activity of the catalyst proves that platinum is not “hidden” in the titania matrix. The flame-produced catalyst showed catalytic activity similar to that of samples prepared by wet platinum impregnation of pure titania.     

Effect of sintering on the catalytic activity of a Pt based catalyst for CO oxidation: Experiments and modeling

The goal of this paper was to make the link between sintering of a 1.6% Pt/Al₂O₃ catalyst and its activity for CO oxidation reaction. Thermal aging of this catalyst for different durations ranging from 15 min to 16 h, at 600 and 700 °C, under 7% O₂, led to a shift of the platinum particle size distributions towards larger diameters, due to sintering. These distributions were studied by transmission electron microscopy. The number and the surface average diameters of platinum particles increase from 1.3 to 8.9 nm and 2.1 to 12.8 nm, respectively, after 16 h aging at 600 °C. The catalytic activity for CO oxidation under different CO and O₂ inlet concentrations decreases after aging the catalyst. The light-off temperature increased by 48 °C when the catalyst was aged for 16 h at 600 °C. The CO oxidation reaction is structure sensitive with a catalytic activity increasing with the platinum particle size. To account for this size effect, two intrinsic kinetic constants, related either to platinum atoms on planar faces or atoms on edges and corners were defined. A platinum site located on a planar face was found to be 2.5 more active than a platinum site on edges or corners, whatever the temperature. The global kinetic law {r (mol m⁻² s⁻¹) = 103 × exp(−64,500/RT)[O₂]^0.74[CO]^−0.5)} related to a reaction occurring on a platinum atom located on planar faces allows a simulation of the CO conversion curves during a temperature ramp. Modeling of the catalytic CO conversion during a temperature ramp, using the different aged catalysts, allows prediction of the CO conversion curves over a wide range of experimental conditions.     

Deuterium isotope analysis of methanol oxidation on mixed metal anode catalysts

The widely accepted mechanism for methanol oxidation on Pt based catalyst surfaces has held that the rate determining step is activation of water, and/or oxidation of surface-bound CO to CO₂. In fact on pure Pt, water activation is always rate limiting at potentials negative of 0.6 V. Anode potentials greater than 0.4 V are outside the useful potential window of direct methanol fuel cells when using Nafion 117 at 60 °C. Enhancement of the water activation kinetics on Pt has been effected by the use of oxophilic transition metal promoters including Ru, W and Sn. For decades the search for improved methanol oxidation electrocatalysts has focused on water activation. A systematic deuterium isotope study on Pt black and two active mixed metal catalysts (PtRu and PtRuOsIr) shows that for each catalyst there is a characteristic transition potential above which the primary reaction in the rate-determining step changes from water activation to CH bond activation. On the mixed metal catalysts, this crossover potential is ca. 0.35 V, which is within the direct methanol fuel cell potential window (0-0.400 V). This study confirms that on these active catalysts there is a potential above which further improvements in water activation must be concomitant with acceleration of CH bond activation. Thus the catalyst search strategy involving Pt promoter metals must also consider the kinetic importance of CH bond activation.     

N掺杂石墨烯负载Pt-Sn催化剂的制备及电催化性能研究

氮掺杂石墨烯负载Pt在直接乙醇燃料电池（DEFCs）中表现出较好的性能。Pt的高成本极大地限制了DEFCs的商业化应用。因此,采用一系列不同浓度水合肼还原氧化石墨烯的简单方法,合成了氮掺杂石墨烯负载Pt-Sn （Pt-Sn/G-N）。研究了Pt-Sn/G-N催化剂纳米粒子的均匀分散对乙醇氧化的电催化活性影响。通过控制不同的氮含量,进一步研究了Pt和Sn金属颗粒最适宜协同效应的比例。结果表明：当氧化石墨烯与水合肼的质量比为1∶7时,催化剂的Pt和Sn负载均最大,Pt与Sn的比值为1.41,Pt/Sn合金的平均粒径最小（1.8 nm）。此外,与其他催化剂相比,Pt-Sn/G-N （1∶7）具有最高的电催化活性,稳定性好,抗CO中毒能力强。即Pt-Sn/G-N （1∶7）的Pt与Sn实现了催化协同作用,为Pt-Sn催化剂在直接乙醇燃料电池（DEFCs）中的应用提供了更多的途径。     

Platinum-macrocycle co-catalysts for the electrochemical oxidation of methanol

Metal phthalocyanines (Fe, Co, Ni and Sn) and ruthenium tetramethylcyclam 14 and 15 were studied as cocatalysts for methanol oxidation on platinum supported catalysts. The formation of well defined monolayers of the adsorbed complexes was inferred from the Langmuirian form of the adsorption isotherms in solutions of macrocycles. The coverage at monolayer levels was low, e.g. 1.25 to 2.25×10¹³ molecules cm⁻² or 400 to 800 Ų molecule⁻¹. Enhancement for the methanol oxidation reaction was observed for Pt co-catalyzed with Sn phthalocyanine and Ru tetramethylcyclam. Ru tetramethylcyclam showed an enhancement for methanol oxidation on a per unit weight basis over pure Pt, approaching the activity of PtRu at lower potentials. Increasing the size of the nitrogen ring from 14 to 15 resulted in a lower redox potential and increase in the activity of methanol oxidation. The activity of Pt co-catalyzed with Ru TMC 15 decreased with time suggesting that the macrocycle was desorbing from the supported catalyst surface.     

High utilization platinum deposition on single-walled carbon nanotubes as catalysts for direct methanol fuel cell

This research aims to enhance the activity of Pt catalysts, thus to lower the loading of Pt metal in fuel cell. Highly dispersed platinum supported on single-walled carbon nanotubes (SWNTs) as catalyst was prepared by ion exchange method. The homemade Pt/SWNTs underwent a repetition of ion exchange and reduction process in order to achieve an increase of the metal loading. For comparison, the similar loading of Pt catalyst supported on carbon nanotubes was prepared by borohydride reduction method. The catalysts were characterized by using energy dispersive analysis of X-ray (EDAX), transmission electron micrograph (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectrum (XPS). Compared with the Pt/SWNTs catalyst prepared by borohydride method, higher Pt utilization was achieved on the SWNTs by ion exchange method. Furthermore, in comparison to the E-TEK 20 wt.% Pt/C catalyst with the support of carbon black, the results from electrochemical measurement indicated that the Pt/SWNTs prepared by ion exchange method displayed a higher catalytic activity for methanol oxidation and higher Pt utilization, while no significant increasing in the catalytic activity of the Pt/SWNTs catalyst obtained by borohydride method.     

IN-SITU FT-IR SPECTROSCOPIC STUDIES OF FUEL CELL ELECTRO-CATALYSIS: FROM SINGLE-CRYSTAL TO NANOPARTICLE SURFACES

The work presented in this article shows the power of the variable temperature, in-situ FT-IR spectroscopy system developed in Newcastle with respect to the investigation of fuel cell electro-catalysis. On the Ru(0001) electrode surface, CO co-adsorbs with the oxygen-containing adlayers to form mixed [CO + (2 × 2)-O(H)] domains. The electro-oxidation of the Ru(0001) surface leads to the formation of active (1 × 1)-O(H) domains, and the oxidation of adsorbed CO then takes place at the perimeter of these domains. At 20°C, the adsorbed CO is present as rather compact islands. In contrast, at 60°C, the CO_ads is present as a relatively looser and weaker adlayer. Higher temperature was also found to facilitate the surface diffusion and oxidation of CO_ads. No dissociation or electro-oxidation of methanol was observed at potentials below approximately 950 mV; however, the Ru(0001) surface at high anodic potentials was observed to be very active. On both Pt and PtRu nanoparticle surfaces, only one linear bond CO adsorbate was formed from methanol adsorption, and the PtRu surface significantly promoted both methanol dissociative adsorption to CO and its further oxidation to CO₂. Increasing temperature from 20° to 60°C significantly facilitates the methanol turnover to CO₂.     

Mechanistic pathways during oxidation of cyanate on platinum single crystal faces

Adsorption and oxidation processes of cyanate (OCN⁻) were studied on polycrystalline platinum and Pt(1 0 0), Pt(1 1 0) and Pt(1 1 1) surfaces in alkaline solution (pH 9). On Pt(poly), Pt(1 0 0) and Pt(1 1 0), it has been found that cyanate chemisorbs dissociatively, with production of adsorbed CO. Oxidation of cyanate thus follows a pathway involving CO_ad on polycrystalline Pt and these single crystal faces. CO_ad has not been observed during oxidation of cyanate on Pt(1 1 1); thus another pathway, involving direct oxidation of OCN⁻, has been identified for cyanate oxidation on platinum surfaces.     

Synthesis of Ultrafine Size Platinum Nanoparticles on Defective Graphene with Enhanced Performance Towards Methanol Electro‐Oxidation

Graphene nanosheets (GS) were formed by the thermal‐expansion method. Large micropores about 1–2 nm were produced, which might provide abundant anchor sites for fixing catalyst. Platinum nanoparticles (NPs) supported on exfoliated GS (Pt/GS) were synthesized through an improved impregnation approach and mixture gas (5% H₂ in N₂) reduction. SEM and TEM images indicated the simple and clean method can effectively synthesize Pt with uniform dispersion and small size (below 3 nm) on the 2D specific and stratiform GS. The different amounts of Pt loaded on carbon carriers have been investigated respectively to evaluate the preferable electrocatalyst. Experimental results showed that Pt/GS of 20 wt.% initiated CO oxidation at the lowest onset potential in comparison with the commercial Pt/C (JM), indicating a higher CO tolerance of Pt/GS catalysts. In addition, Pt/GS of 20 wt.% exhibited enhanced electrocatalytic activity and high durability towards methanol oxidation. The high performance is exclusively attributed to synergistic effects of exfoliated GS and ultrafine size Pt NPs. Combining a melt‐diffusion strategy with the effective reduction of Pt precursors by the hydrogen gas, this present method is easy to scale up and possesses a significant potential for synthesizing anode electro‐catalyst of direct methanol fuel cells.     

An Extremely Active Pt/Carbon Nano-Tube Catalyst for Selective Oxidation of CO in H2 at Room Temperature

Pt catalyst supported on carbon nano-tube (CNT) was extremely active for the selective oxidation of CO in H₂ at room temperature, which was remarked contrast to the Pt supported on an active carbon (Vulcan carbon) and a graphite powder. Complete oxidation of CO was attained on a 5 wt.% Pt/CNT catalyst (0.8 g) at ca. 40 °C when the O₂/CO ratio in a flow of H₂ (20 mL/min) + CO (3.0 mL/min) + O₂ + N₂ was adjusted to be larger than 0.75 at the total flow rate of 100 mL/min. Specific activity of the Pt/CNT catalyst was explained by efficient provision of reactant molecules diffusing on CNT surface to Pt particles.