Carbon nanotube supported platinum-palladium nanoparticles for formic acid oxidation

Pt, Pd and Pt_xPd_y alloy nanoparticles (Pt₁Pd₁, Pt₁Pd₃, atomic ratio of Pt to Pd is 1:1, 1:3, respectively) supported on carbon nanotube (CNT) with high and uniform dispersion were prepared by a modified ethylene glycol method. Transmission electron microscopy images show that small Pt and Pt_xPd_y nanoparticles are homogeneously dispersed on the outer walls of CNT, while Pd nanoparticles have some aggregations and comparatively larger particle size. The average particle sizes of Pt/CNT, Pt₁Pd₁/CNT, Pt₁Pd₃/CNT and Pd/CNT obtained from the Pt/Pd (2 2 0) diffraction peaks in the X-ray diffraction patterns are 2.0, 2.4, 3.1 and 5.4 nm, respectively. With increasing Pd amount of the catalysts, the mass activity of formic acid oxidation reaction (FAOR) on the CNT supported catalysts increases in both cyclic voltammetry (CV) and chronoamperometry (CA) tests, although the particle size gets larger (thus, the relative surface area gets smaller). The CV study indicates a ‘direct oxidation pathway’ of FAOR occurred on the Pd surface, while on the Pt surface, the FAOR goes through ‘CO_ads intermediate pathway’. Pd/CNT demonstrates 7 times better FAOR mass activity than Pt/CNT (2.3 mA/mgPd vs. 0.33 mA/mgPt) at an applied potential of 0.27 V (vs. RHE) in the CA test.     

Size-controlled synthesis and impedance-based mechanistic understanding of Pd/C nanoparticles for formic acid oxidation

This work provides a detailed electrochemical impedance study for formic acid electro-oxidation on size-controlled Pd/C nanoparticles, the synthesis of which was done by a simple protocol using ethylene glycol as a reducing agent. By controlling KOH concentration, this strategy provides a synthesis method for Pd nanoparticles with a selective size range of 3.9–7.5 nm. The as-prepared Pd nanoparticles exhibited size-dependent electrochemical property and electrochemical characterizations of four different Pd/C nanocatalysts (3.9, 5.2, 6.1, and 7.5 nm) showed that Pd particle with average size of 6.1 nm has the highest formic acid oxidation activity. Electrochemical impedance-based characterizations of formic acid oxidation on Pd/C suggested that at high potentials the adsorbed oxygen species could block the catalyst surface and inhibit the oxidation reaction, as reflected by the negative polarization resistance. Unlike Pd/C, the intermediate adsorbed CO species (CO_ads) plays a critical role for formic oxidation on Pt/C and thus the impedance spectra of Pd/C and Pt/C appear different potential-dependent patterns in the second quadrant. The issue of CO was investigated by an impedance investigation of Pd/C in a mixture of formic acid containing dissolved CO.     

Improved electrocatalytic performance of Pd nanoparticles with size-controlled Nafion aggregates for formic acid oxidation

This work focuses on the effect of Nafion ionomer aggregation within the Pd catalytic electrode on electrocatalytic oxidation of formic acid. By a simple heat-treatment, the particle sizes of both Nafion ionomers in Nafion solution and congeries formed between Pd nanoparticles and Nafion ionomers in the catalyst ink decrease and their size distribution becomes narrow. Heat treatment of the catalyst ink leads to a significantly enhanced catalytic activity for formic acid oxidation on the Pd catalytic electrode. Such an enhancement is ascribed to the improvement in catalyst utilization verified by CO stripping voltammograms and to the decrease in charge-transfer resistance of oxidation reaction confirmed by impedance analysis. Typical XPS analysis shows that there are at least two kinds of Pd and S surface states within the catalytic electrode with the ink pre-heated at 25 °C and only one kind of Pd and S surface state at 80 °C, indicative of a better dispersion between Pd nanoparticles and smaller Nafion ionomers at a higher heat treatment temperature. Furthermore, the decrease in congeries size within the anode catalyst ink leads to a significant decrease in Nafion loading within the catalytic layer and a remarkable improvement in direct formic acid fuel cell's performance.     

Controlled synthesis of Pt-decorated Au nanostructure and its promoted activity toward formic acid electro-oxidation

Highly active Pt-decorated Au nanoparticles on carbon support with Pt:Au mole ratio ranging from 1:10 to 1:2 was successfully synthesized based on successive reduction strategy. The successful formation of this structure was suggested by transmission electron microscopy, UV-vis and voltammetry analyses. The electrocatalytic activity of this decorated structure toward formic acid oxidation surprisingly increases despite the low amount of Pt being used. At 0.1 V, the specific activity of PtAu/C with Pt/Au mole ratio 1:8 was more than one order of magnitude higher than the conventional Pt/C. The enhancement was attributed to the less Pt ensemble sites that the decorated structure possesses (ensemble effect) and the increase in the Pt atom reactivity on Au nanocrystal. The formic acid oxidation mechanism on this decorated structure was also elucidated using electrochemical impedance spectroscopy technique. It is proposed that besides the dehydrogenation reaction pathway happening on clean Pt sites, the reactive intermediate i.e. formate species could also be oxidized by the adsorbed water species on Pt at higher potential.     

The origin of high activity of Pt–Au surfaces in the formic acid oxidation

We have investigated the oxidation of HCOOH on Au-modified Pt (Au@Pt) and Pt-modified Au (Pt@Au) electrodes to establish the role of the ensemble and the electronic effect in the catalysis of this reaction. The surfaces were modified by the electrodeposition of sub-monolayers. Cyclic voltammetry in the supporting electrolyte and CO_ads stripping have shown that the electronic Pt–Au interactions are insignificant on Au@Pt, but considerable on Pt@Au. Oxidation of CO_ads on Au@Pt commenced at the same potentials as on bare Pt, whereas on Pt@Au the oxidation was delayed for 0.2 V. Both types of Pt–Au surfaces were found to be more active toward the oxidation of HCOOH compared to bare Pt, exhibiting the maximum activity at Pt fraction between 0.15 and 0.25 with the enhancement factor of more than two orders of magnitude. On bimetallic surfaces the amount of CO_ads formed by HCOOH dehydration was low and decreased with decreasing Pt fraction. It was concluded that the high activity of Pt–Au surfaces is caused by the increased selectivity toward the HCOOH dehydrogenation. Similar behavior of Pt–Au surfaces in the HCOOH oxidation, regardless on the Pt–Au electronic interactions, leads to the conclusion that the ensemble effect plays dominant role in the catalysis of HCOOH oxidation.     

Electrooxidation of methanol and formic acid on PtCu nanoparticles

Improving the catalytic activity of the anode catalyst is an important task in direct methanol and formic acid fuel cell development. In the present work, catalytic activity of shape-controlled PtCu nanoparticles toward methanol and formic acid oxidation was investigated. The results show that the addition of Cu to Pt increases the catalytic activity of both reactions. In addition, the shape of PtCu nanoparticles plays an important role on improving the reactivity of both reactions. Cubic PtCu nanoparticles are more active for methanol oxidation while spheres are better for formic acid oxidation. The present study demonstrates controlling shape of Pt alloy catalysts is an effective way of improving catalytic activity. Likely mechanisms of the activity enhancement are briefly discussed.     

Preparation of high performance Pd catalysts supported on untreated multi-walled carbon nanotubes for formic acid oxidation

Due to the inherent inertness of carbon nanotubes (CNTs), one of the most significant challenges in the preparation of CNT-supported catalysts is achieving a uniform deposition of nanoparticles on the surface of the nanotubes. In this paper, we report on the preparation and characterization of Pd nanoparticles supported on untreated multi-walled carbon nanotubes (MWCNTs), synthesized in the presence of glutamate. The results of Raman spectroscopy revealed that this synthetic procedure does not have a detrimental effect on the surface structure of MWCNTs. Transmission electron microscopy (TEM) measurements indicated that the dispersion of Pd nanoparticles on untreated-MWCNTs in the presence of glutamate were uniform, and a narrow particle size was observed. X-ray diffraction (XRD) patterns indicated that the Pd/MWCNT catalyst possessed a face-centered cubic crystal structure. Cyclic voltammetry and chronoamperometry tests demonstrated that the obtained Pd/MWCNT catalyst displayed superior electrocatalytic activity and stability in formic acid oxidation, as compared to both a Pd/MWCNT catalyst synthesized without glutamate and a Pd catalyst on acid-oxidized MWCNTs, under otherwise identical experimental conditions. These results indicate that the catalyst developed in this study is a superior candidate for direct formic acid fuel cells (DFAFCs).     

Electrocatalytic properties of Pd clusters on Au nanoparticles in formic acid electro-oxidation

Pd clusters were formed on highly dispersed Au nanoparticles (∼3.5 nm in diameter) using a seed-mediated growth process. The structural information and electrocatalytic activities of these Pd clusters on Au nanoparticles were confirmed by high-resolution-transmission-electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). The resulting nanoparticles, which had a uniform size (<5 nm in diameter), were highly dispersed on carbon particles, and Pd clusters (<0.44 nm in size, <2 atomic layers) were formed selectively on Au nanoparticles. XPS results show that the Pd 3d_5/2 peak shifted to lower binding energies and that the amount of surface oxide decreased as the Pd content was decreased on the Au nanoparticles. In formic acid electro-oxidation, these Pd clusters exhibit enhanced electrocatalytic activity relative to that of carbon-supported Pd nanoparticles. These results may be due to the modified electronic and geometric structure of the Pd clusters on the Au nanoparticle substrate.     

Pd nanoparticles supported on carbon-modified rutile TiO2 as a highly efficient catalyst for formic acid electrooxidation

In this article, Pd nanoparticles supported on carbon-modified rutile TiO₂ (CMRT) as a highly efficient catalyst for formic acid electrooxidation were investigated. Pd/CMRT catalyst was synthesized by using liquid phase reduction method in which Pd nanoparticles was loaded on the surface of CMRT obtained through a chemical vapor deposition (CVD) process. Pd/CMRT shows three times the catalytic activity of Pd/C, as well as better catalytic stability towards formic acid electrooxidation. The enhanced catalytic property of Pd/CMRT mainly arises from the improved electronic conductivity of carbon-modified rutile TiO₂, the dilated lattice constant of Pd nanoparticles, an increasing of surface steps and kinks in the microstructure of Pd nanoparticles and slightly better tolerance to the adsorption of poisonous intermediates.     

Electrosynthesis of Pd/Au hollow cone-like microstructures for electrocatalytic formic acid oxidation

Pd/Au hollow cone-like microstructures (HCMs) have been electrodeposited on indium tin oxide (ITO) using a two-step protocol, which involves the nucleation pulse and succedent constant potential reduction in the presence of metal precursors and polyvinylpyrrolidone (PVP). Scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscope (XPS) were used to characterize the Pd/Au HCMs. The electrochemical results (cyclic voltammetry and chronoamperometry) testify that the Pd/Au HCMs exhibit significantly higher electrocatalytic activity and stability for the oxidation of formic acid than that of Pd/Au solid microhemispheres (SMHs). These attractive features are attributable to the unique hollow structures of Pd/Au with much higher electrochemical active surface areas and the exposure of favorable planes. Our work points to a new path for the preparation of Pd/Au HCMs, which are promising as electrocatalysts in direct formic acid fuel cell (DFAFC).     

Influence of Au contents of AuPt anode catalyst on the performance of direct formic acid fuel cell

We reported that various compositions of AuPt nanoparticles synthesized as an anode material for formic acid fuel cell were investigated. Its surface characteristics were systematically analyzed using XRD and TEM and anodic electrocatalytic activity was studied using a linear sweep voltammetry technique in 0.5 M H₂SO₄ + 1 M HCOOH. In addition, the voltage-current curve and power density of home-made AuPt-based membrane-electrode-assembly (MEA) and commercial Pt_0.5Ru_0.5-based MEA was measured at 60 °C in 9 M formic acid. The maximum power density of Au_0.6Pt_0.4-based MEA was 30% higher than that of PtRu-based MEA which were 200 mW cm⁻² and 155 mW cm⁻², respectively.     

络合还原法制备的Pd/C催化剂对甲酸氧化的电催化性能

分别以硼氢化钠和乙二醇为还原剂,经络合还原法制备了炭载钯（Pd/C）催化剂。透射电镜（TEM）和X射线粉末衍射谱（XRD）结果表明,以乙二醇为还原剂制备的Pd/C催化剂中Pd粒子具有较小的粒径、均匀的粒径分布和较大的相对结晶度,Pd粒子的平均粒径和相对结晶度分别为4.2±2 nm和1.88。电化学测试结果显示,以乙二醇为还原剂制备的Pd/C催化剂具有较大的电化学活性面积,对甲酸氧化表现出较高的电催化活性和稳定性。     

Pb and Sb modified Pt/C catalysts for direct formic acid fuel cells

PtPb/C and PtSb/C bi-metallic catalysts were synthesized by chemical deposition of Pb or Sb on a commercial 40% Pt/C catalyst. The performances of catalysts with a range of compositions were compared in a multi-anode direct formic acid fuel cell in order to optimize compositions and evaluate the statistical significance of differences between catalysts. The catalytic activity for formic acid oxidation increased approximately linearly with adatom coverage for both PtPb/C and PtSb/C, to maxima at fractional coverages of ca. 0.7. At a cell voltage of 0.5 V, the currents at the optimum Pb or Sb coverages were ca. 8 times higher than at unmodified Pt/C. CO-stripping results indicate that the presence of Pb or Sb facilitates the oxidation of adsorbed CO. In addition, both metals appear to produce electronic effects that inhibit poison formation on the modified Pt surface.     

A catalytic study of formic acid oxidation on preferentially oriented platinum electrodes

The oxidation of formic acid was examined by cyclic voltammetry and chronoamperometry in order to determine the rate of catalytic activity (reaction turnover) as a function of surface crystallography on preferentially oriented (electrochemically modified) platinum electrodes. The resulting turnover rates indicated a maximum fourfold current enhancement for an approximately 60% (111)-oriented surface versus a polycrystalline surface, suggesting that preferentially oriented electrodes are of potential practical significance.     

One-step synthesis of Ni@Pd/NH2-Fe3O4 nanoparticles as affordable catalyst for formic acid dehydrogenation

Currently, one of the critical issues in the world is finding an appropriate green alternative to fossil fuels due to the concerns about global warming. As a hydrogen source, formic acid has been given particular attention owing to the attractive features such as high-energy density, no toxicity, high stability at ambient temperature and high hydrogen content. Introducing an affordable and highly efficient catalyst with easy recovery from the reaction mixture for selective dehydrogenation of formic acid is still demanding.In this report, we used a simple one-step process to synthesize Ni@Pd core shell nanoparticles on 3-aminopropyltriethoxysilane modified Fe_3O_4 nanoparticles. The existence of Ni and Pd results in a synergic effect on the catalytic activity. The —NH_2 groups play an important role for obtaining well-dispersed ultrafine particles with high surface area and active sites. In addition, Fe_3O_4 lead to convenient magnetic recovery of the catalyst from reaction mixture. Our results indicate that the as-prepared catalyst give the superb turnover frequency of 5367.8 h~(-1) with no additive, which is higher than most of the previously reported catalysts.     

Study of the kinetics and the influence of Biirr on formic acid oxidation at Pt2Ru3/C

Electrochemical oxidation of HCOOH in H₂SO₄ and HClO₄ solutions was examined on thin film Pt₂Ru₃/C electrode. XRD pattern revealed that Pt₂Ru₃ alloy consisted of the solid solution of Ru in Pt and the small amount of Ru or solid solution of Pt in Ru. According to STM images, Pt₂Ru₃ particles size was between 2 and 6 nm. It was established that electrochemical oxidation of HCOOH commenced at −0.1 V versus SCE at Pt sites in the catalyst. Kinetic parameters indicated that dehydrogenation path was predominant. Dehydration occurs in parallel, but without significant poisoning by CO_ad owing to oxidative removal by OH species on Ru atoms. The coverage of Pt₂Ru₃ surface by CO preadsorbed from the solution was found to be 24% lower when the surface was modified by irreversibly adsorbed Bi. Modification by Bi also shifted the onset potential for HCOOH oxidation for about 50 mV towards more negative values and consequently, increased the reaction rate for a factor of two. It was proposed that Ru acts through bifunctional mechanism, i.e. OH species adsorbed on Ru oxidizes CO_ad from Pt sites, while Bi hinders the adsorption of CO on Pt sites via electronic and/or ensemble effects.     

Activity of a novel titanium-supported bimetallic PtSn/Ti electrode for electrocatalytic oxidation of formic acid and methanol

Bimetallic platinum–tin nanoparticles were co-deposited on a titanium surface using a simple one step hydrothermal method process. The electrochemical catalytic activity of this titanium-supported nanoPtSn/Ti electrode towards the oxidation of formic acid and methanol in 0.5 M H₂SO₄ was evaluated by voltammetric techniques, chronoamperometric responses and electrochemical impedance spectra (EIS). According to the cyclic voltammograms of the oxidation of both formic acid and methanol, the nanoPtSn/Ti presents high anodic current densities and low onset potentials. Potential-time transient measurements show that the nanoPtSn/Ti exhibits high steady-state current densities for the oxidation of both formic acid and methanol. The EIS data indicate that the nanoPtSn/Ti presents very low electrochemical impedance values, showing that for the oxidation of both formic acid and methanol, low charge transfer resistances are present on the nanoPtSn/Ti catalyst. This confirms the high electrocatalytic activity of the nanoPtSn/Ti for the formic acid and methanol oxidation.     

High efficient electrocatalytic oxidation of formic acid on Pt/polyindoles composite catalysts

Four novel composite catalysts have been developed by the electrodeposition of Pt onto glassy carbon electrode (GCE) modified with polyindoles: polyindole, poly(5-methoxyindole), poly(5-nitroindole) and poly(5-cyanoindole). As-formed composite catalysts are characterized by SEM, XRD and electrochemical analysis. Compared with Pt nanoparticles, respectively, deposited on the bare GCE and on the GCE modified with polypyrrole, the four newly developed composite catalysts exhibit higher catalytic activity towards formic acid electrooxidation by improving selectivity of the reaction via dehydrogenation pathway and thus mostly suppressing the generation of poisonous CO_ads species. The enhanced performance is proposed to come from the synergetic effect between Pt and polyindoles and the increase of electrochemical active surface area (EASA) of Pt on polyindoles.     

Sonochemical synthesis of Pt-doped Pd nanoparticles with enhanced electrocatalytic activity for formic acid oxidation reaction

Pt-doped Pd nanoparticle catalysts (Pd _n Pt, n is 12, 15 and 19) supported on carbon were synthesized by an ultrasound assisted polyol method. The catalysts were characterized by X-ray diffraction, transmission electron microscopy, and energy dispersive X-ray spectroscopy. The electrochemical activity of the electrocatalysts was investigated in terms of formic acid oxidation reaction (FAOR) at low concentration of formic acid in 0.1 M perchloric acid at room temperature. Formic acid oxidation on the Pd _n Pt/C commences at lower potential than a commercial Pt/C. Pd₁₉Pt/C catalyst showed the highest catalytic activity in FAOR compared to that of other catalysts. The obtained electrochemical results from voltammograms indicate that Pt-doped Pd catalysts can be a promising candidate for the anode material in direct formic acid fuel cells. The synthesis procedure is not only a very facile route but also a mass producible method for preparing carbon supported alloy nanoparticles.     

不同体系Pd/C催化剂的制备及对甲酸的电催化氧化

采用不同体系制备了碳载Pd催化剂(Pd/C),发现在乙二醇体系中制备的Pd/C催化剂对甲酸氧化具有最负的峰电位和最低的起始氧化电位,Tafel斜率最小为155mV,并且在1h的计时电流曲线测试表明,用乙二醇体系制备的Pd/C-3催化剂具有较高的稳定电流。TEM结果可以看出,用乙二醇体系制备的Pd/C催化剂Pd粒子在活性碳表面分散得最好,Pd粒径的大小约为4～5nm。