Synthesis of Pd/C Catalyst by Modified Polyol Process for Formic Acid Electrooxidation

Pd catalyst supported on Vulcan XC‐72 carbon black was prepared by a modified polyol process. Its performance was compared with that of Pd/C catalyst prepared by impregnation reduction method by using NaBH₄ as a reducing agent for formic acid electrooxidation. Their physical characterisations were tested by means of energy dispersive analysis of X‐ray, X‐ray diffraction and transmission electron micrographs. Their activities were presented by cyclic voltammetry and chronoamperometry. The results show that the particle sizes of Pd/C catalysts prepared by modified polyol process and impregnation reduction method are 3.9 and 7.9 nm, respectively. The size dispersion of the former is narrower and more homogeneous than that of the latter. However, both of Pd/C catalysts display the characteristic diffraction peaks of a Pd face‐centred cubic (f.c.c.) crystal structure. The results of electrochemical measurements present that the Pd/C catalyst prepared by modified polyol process has the higher electrocatalytic activity and stability for formic acid electrooxidation in comparison to the Pd/C one by impregnation reduction method due to the particle size effect, and its peak current density of CV and the current of chronoamperometric curve at 1,000 s reach 33.2 and 11.2 mA cm^–2, respectively.     

Effect of pH Value and Temperatures on Performances of Pd/C Catalysts Prepared by Modified Polyol Process for Formic Acid Electrooxidation

The highly active Pd/C catalysts for formic acid electrooxidation have been prepared by a modified polyol process at different pH values of reaction solutions and different reducing temperatures, respectively. Their physical properties have been characterised by energy dispersive analysis of X‐ray, X‐ray diffraction and transmission electron microscopy. Their electrochemical performances for formic acid electrooxidation have been tested by cyclic voltammetry and amperometric i–t curves. The results of physical characterisations show that all the Pd/C catalysts present an excellent face centered cubic crystalline structure. Their particle sizes are decreasing firstly and then increasing with the increasing of the pH values of reaction solutions. The reducing temperatures also markedly affect the Pd particle sizes. And their nanoparticles have narrow size distributions and are highly dispersed on the surface of carbon support, and Pd metal loading in Pd/C catalyst is similar to the theoretical value of 20 wt.%. The results of electrochemical measurements present that the Pd/C catalyst prepared by waterless polyol process at the pH value of 10 and the reducing temperature of 120 °C has the smallest particle size of about 5.6 nm, and exhibits the highest catalytic activity (1172.0 A · g_Pd<?h‐2.85>^–1<?h.8>) and stability for formic acid electrooxidation.     

Evaluation of the Performance of Carbon Supported Pt–Ru–Ni–P as Anode Catalyst for Methanol Electrooxidation

This research is aimed to improve the activity and stability of ternary alloy Pt–Ru–Ni/C catalyst. A novel anodic catalyst for direct methanol fuel cell (DMFC), carbon supported Pt–Ru–Ni–P nanoparticles, has been prepared by chemical reduction method by using NaH₂PO₂ as a reducing agent. One glassy carbon disc working electrode is used to test the catalytic performances of the homemade catalysts by cyclic voltammetric (CV), chronoamperometric (CA) and amperometric i–t measurements in a solution of 0.5 mol L^–1 H₂SO₄ and 0.5 mol L^–1 CH₃OH. The compositions, particle sizes and morphology of home‐made catalysts are evaluated by means of energy dispersive analysis of X‐ray (EDAX), X‐ray diffraction (XRD) and transmission electron micrographs (TEM), respectively. TEM images show that Pt–Ru–Ni–P nanoparticles have an even size distribution with an average diameter of less than 2 nm. The results of CV, CA and i–t curves indicate that the Pt–Ru–Ni–P/C catalyst shows significantly higher activity and stability for methanol electrooxidation due to the presence of non‐metal phosphorus in comparison to Pt–Ru–Ni/C one. All experimental results indicate that the addition of non‐metallic phosphorus into the Pt–Ru–Ni/C catalyst has definite value of research and practical application for enhancing the performance of DMFC.     

Investigations of Compositions and Performance of PtRuMo/C Ternary Catalysts for Methanol Electrooxidation

PtRuMo/C catalyst was prepared by impregnation reduction method and characterised. Comparison is made between a home‐made PtRu/C prepared by similar method and Pt/C (E‐Tek Co., Pt/C‐ET) catalysts. One glassy carbon disc electrode for ternary alloy catalyst was used to evaluate the catalytic performances by cyclic voltammetric, chronoamperometric, amperometric i–t curves, and electrochemical impedance spectra (EIS). The electrochemical measurement results indicated that the performance of PtRuMo/C with a molar ratio of 6:3:1 was the highest among 15 Pt_xRu_yMo_10–x–y/C catalysts with different molar ratios. The composition, particle size, lattice parameter and morphology of the PtRuMo(6:3:1)/C catalyst were determined by means of X‐ray energy dispersive analysis, X‐ray diffraction (XRD) and transmission electron micrographs (TEM). The result of XRD analysis exhibits that PtRuMo(6:3:1)/C has the fcc structure with the smaller lattice parameter than the home‐made PtRu/C and Pt/C‐ET. Its typical particle sizes is only about 5 nm. With respect to the catalytic activity and stability, the PtRuMo(6:3:1)/C catalyst is superior to PtRu/C despite their comparable active areas. Though the electrochemically active surface area of Pt/C‐ET is the biggest, its performance is the lowest. EIS results also indicate that the reaction resistances for methanol electrooxidation on the PtRuMo(6:3:1)/C catalyst are smaller than those of PtRu/C at different polarisation potentials.     

The Promoting Effect of Europium on PtSn/C Catalyst for Ethanol Oxidation

Well‐dispersed PtSnEu/C and PtSn/C catalysts were prepared by the impregnation–reduction method using formic acid as a reductant and characterised by X‐ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersion X‐ray spectroscopy (EDX) and X‐ray photoelectron spectroscopy (XPS). The synthesised catalysts with different atomic ratios of Pt/Sn/Eu have the Pt face centered cubic (fcc) structure and their particle sizes are 3–4 nm. The PtSnEu/C catalyst is composed of many Pt (0), SnO₂, Eu(OH)₃, a small amount of Pt(II) and partly alloyed PtSn, but no metallic Eu. The electrochemical measurements indicate that in comparison with Pt₃Sn₁/C catalyst, the Pt₃Sn₁Eu₁/C catalyst for ethanol oxidation has more negative onset potential, smaller apparent activation energy and lower electrochemical impedance so that it exhibits very high catalytic activity. Its peak current density increases by 135% and 40%, compared with Pt₃Sn₁/C and Pt₁Ru₁/C (JM) catalysts, respectively. This is because the Eu(OH)₃ formed by adding Eu to PtSn/C catalyst can provide the OH group which is in favour of the removal of adsorbed intermediates and ethanol oxidation.     

The effect of CeO2 on Pt/CeO2/CNT catalyst for CO electrooxidation

Pt/CeO₂/CNT catalysts were prepared by adsorbing Pt nanoparticles on the supports of CNTs coated with CeO₂. The electrocatalytic performances in respect to the electrooxidation of chemisorbed CO were tested using potential step and stripping voltammetry methods under variable sweep rate and temperature conditions. At 10 mV s^–1, the CO stripping voltammogram exhibited the peak splitting phenomenon. The oxidation charge and the peak potential of the two voltammetric peaks changed regularly with the number of Pt and CeO₂ neighbours, the sweep rate, and the temperature. We considered that the low potential peak originated from the reaction of CO_ads with hydroxyl groups on CeO₂ adjacent to Pt sites, while the high potential peak came from the reaction of CO_ads with hydroxyl groups produced on pure Pt. Furthermore, the experimental results of the peak potential against the logarithm of the sweep rate and the logarithm of the current maximum time against the step potential were plotted and intersecting lines with different slopes in high and low potential regions in the plot were observed. The lines intersected at lower potentials on the Pt/CeO₂/CNT electrode than on the Pt/CNT electrode, which was attributed to the contribution of hydroxyl groups on CeO₂.     

Effect of pH Value on Performance of PtRu/C Catalyst Prepared by Microwave‐Assisted Polyol Process for Methanol Electrooxidation

PtRu/C catalysts with different mean particle sizes have been synthesised by microwave‐assisted polyol process at various pH values and characterised by transmission electron microscopy (TEM), energy dispersive analysis of X‐ray (EDAX) and X‐ray diffraction (XRD). Their electrochemical performances have been tested by cyclic voltammetry, amperomeric i–t, and CO‐stripping techniques. The effects of pH values on performances of the PtRu/C catalysts have been mainly investigated. It has been found that the particle size, composition and catalytic activity of the PtRu/C catalyst are very sensitive to the pH value of reducing solution, and the PtRu/C catalyst prepared at the pH value of 8 exhibits the better performance for methanol electrooxidation than the other samples. The size of the nanoparticles decreases as the pH value increases from 0.2 to 10 with the largest size of 4.4 nm and the smallest one of 2.1 nm. The two metal elements distribute uniformly in the catalyst and their metal loadings are similar to the theoretical value.     

Effects of pH Value on Composition Structure and Catalytic Activity of Pt‐SnOx/C Prepared by Ethylene Glycol Method

Pt‐SnO_x nanoparticles were synthesized by the ethylene glycol (EG) method in solution of H₂PtCl₆ and SnCl₂, with the same concentrations of Pt and Sn, but different pH values. The pH value after the end of platinum reduction reaction was not changed any more, except that a certain amount of water was added to deposit the Pt‐SnO_x nanoparticles on the carbon support. The pre‐nanocatalysts were characterized by X‐ray photoelectron spectroscopy (XPS) to investigate the contents of Pt and Sn, and their catalytic activities for ethanol electrooxidation were tested by cyclic voltammetry (CV). The result was that the Sn contents were increasing as the Pt/Sn atomic ratios of 2.2, 2.6, 5.1, 7.4, 8.7, with the decreasing end pH values of 4.5, 5.0, 5.5, 6.5, 7.5, and the Pt contents became less than the addition in the preparation solution while the end pH values were <5.5, but the catalytic activities for ethanol electrooxidation were not so much regularly changed. Besides, from the end pH value of 5.5 to the increasing 9.0, all the platinum nanoparticles could be completely deposited on the carbon support, under the condition that only a certain amount of water was added.     

Preparation of Low Loading Pt/C Catalyst by Carbon Xerogel Method for Ethanol Electrooxidation

Low platium loading Pt/C catalyst was prepared by direct Pt-embedded carbon xerogel method. The Pt content of the as-prepared Pt/C is about 4.32 wt% and has a typical polycrystalline phase. Textural and structural characteristics of the catalysts were characterized by XRD, EDS and BET. Pt-embedded in carbon xerogel increases the specific surface area and pore volume of the X-Pt/C during carbon gelation and the carbonization process. Electrochemical characteristics of the catalysts for ethanol electrooxidation were measured. The results indicated that the as-prepared 4.32 wt% Pt/C has higher mass current density in ethanol electrooxidation as compared to the 20 wt% Pt/C. This may be due to the high roughness of the Pt surface that is formed during the carbon gelation and carbonization process.     

Influence of the Temperature for the Ethanol Oxidation Reaction (EOR) on Pt/C,Pt‐Rh/C and Pt‐Rh‐SnO2/C

The electrocatalytic activity of Pt/C, Pt‐Rh/C and Pt‐Rh‐SnO₂/C electrocatalysts toward the ethanol oxidation reaction (EOR) was investigated in a three‐electrode assembly at 25 °C, 40 °C and 70 °C in acidic medium. The 10 wt.% electrocatalysts were prepared with a modified polyol method and physically characterized by both X‐Ray Diffraction (XRD) and Transmission Electron Microscopy (TEM). The CO‐stripping study revealed that CO_ad oxidation initiates at lower potential on Pt‐Rh/C and Pt‐Rh‐SnO₂/C than on Pt/C and shifts negatively when the temperature increases. The positive effect of the temperature is maintained for the EOR: the three electrocatalysts exhibit a higher activity and a negative shift of the EOR wave at higher temperature. Pt‐Rh‐SnO₂/C demonstrates the lowest EOR onset potential of the three electrocatalysts. The steady‐state Tafel slopes and apparent activation energies E_a were determined in 0.5 M H₂SO₄ + 0.1 M EtOH between E = 0.4 and 0.7 V vs. RHE in the temperature range 25–70 °C. The results show rather comparable rate determining steps (rds) for the ethanol electrooxidation on Pt/C and Pt‐Rh/C in the ranges of potential and temperature studied. The EOR on Pt‐Rh‐SnO₂/C seems less influenced by the potential than on Pt/C and Pt‐Rh/C electrocatalysts, but is more temperature sensitive.     

Effect of Mo addition on the electrocatalytic activity of Pt–Sn–Mo/C for direct ethanol fuel cells

Carbon-supported Pt–Sn–Mo electrocatalysts have been synthesized by a polyol reduction method and characterized for ethanol electro-oxidation reaction (EOR). While the percent loading of the synthesized nanoparticles on the carbon support is higher than 35%, energy dispersive spectroscopy (EDS) reveals that the Mo contents in the nanoparticle catalysts are lower than the nominal value, indicating incomplete reduction of the Mo precursor. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analyses reveal that the Sn and Mo exist as oxide phases at the surface layers of the nanoparticles and the degree of alloying is very low. The electrochemical properties of the electrocatalysts have been evaluated by cyclic voltammetry (CV) and chronoamperometry. The catalytic activity for EOR decreases in the order PtSnMo_0.6/C > PtSnMo_0.4/C > PtSn/C. Single cell direct ethanol fuel cell (DEFC) tests also confirm that the PtSnMo_0.6/C anode catalyst exhibit better performance than the PtSn/C anode catalyst. An analysis of the electrochemical data suggests that the incorporation of Mo to Pt–Sn enhances further the catalytic activity for EOR.     

A Novel Carbon‐Encapsulated Cobalt‐Tungsten Carbide as Electrocatalyst for Oxygen Reduction Reaction in Alkaline Media

Carbon‐encapsulated cobalt‐tungsten carbides (CoWC@C) were synthesized by reduction and carbonization method and used as the electrocatalyst for oxygen reduction reaction (ORR) in direct methanol fuel cells. The as‐prepared samples were characterized by transmission electron microscope, X‐ray diffraction, and X‐ray photoelectron spectroscopy. The results show that CoWC@C consists of outer layer carbon and internal Co₃W₃C, WC, and Co. The cyclic voltammetry results show that CoWC@C has high ORR activity, long‐term durability, and good methanol‐tolerant performance. It is revealed that the main active phase for ORR of CoWC@C is Co₃W₃C, and the outer layer carbon plays the role in improving the durability of the catalyst.     

Pd–Co/MWCNTs Catalyst for Electrooxidation of Hydrazine in Alkaline Solution

Multiwall carbon nanotubes supported Pd–Co electrocatalysts (Pd–Co/MWCNTs) for hydrazine electrooxidation in alkaline electrolytes were prepared. Their morphology and structure were characterized by scanning electron microscopy, transmission electron microscope, and X‐ray diffraction. The effect of the mass ratio of Pd to Co on the catalytic performance was examined via cyclic voltammetric and chronoamperometric measurements. The Pd–Co/MWCNTs with a mass ratio of 1:1 for Pd:Co shows higher catalytic performance than both Pd/MWCNTs and Co/MWCNTs and it has good stability for catalyzing the electrooxidation of hydrazine. The gas collection measurements indicated that hydrazine electrooxidation on Pd–Co/MWCNTs proceeded via a near 4‐electron pathway.     

Investigation on Electrocatalytic Activity and Stability of Pt/C Catalyst Prepared by Facile Solvothermal Synthesis for Direct Methanol Fuel Cell

Pt nanoparticles supported on Vulcan XC‐72 carbon black have been synthesized by a facile solvothermal method. The obtained Pt/C catalysts are characterized by X‐ray diffraction (XRD), energy dispersive X‐ray analysis (EDAX), and transmission electron microscopy (TEM) analysis to identify Pt mean size and Pt content. The results of electrochemical measurements demonstrate that the Pt/C catalyst prepared at the reaction temperature of 140 °C and the reaction time of 2 h shows the biggest initial electrochemical area with an initial electrochemically active specific surface area (ESA) of 70.6 m²g_Pt⁻¹, the highest electrocatalytic stability with an ESA loss of 48.7% after 1,000 CV cycles, and the best electrocatalytic activity and stability toward methanol oxidation reaction (MOR) with a specific activity of 0.6 mA cm⁻² and a retention rate (the ratio of the final current density to the maximum current density) after 3,600 s of 42.8%. Moreover, the electrochemical performance of homemade Pt/C catalyst is superior to that of commercial Pt/C catalyst, suggesting that the solvothermal synthesis is a promising method for preparing Pt based catalyst.     

Ternary Pt<Subscript>45</Subscript>Ru<Subscript>45</Subscript>M<Subscript>10</Subscript>/C (M=Mn,Mo and W) catalysts for methanol and ethanol electro-oxidation

Ternary Pt₄₅Ru₄₅Mn₁₀/C, Pt₄₅Ru₄₅Mo₁₀/C and Pt₄₅Ru₄₅W₁₀/C catalysts were synthesized and physical and electrochemical properties were characterized. Particle sizes of the catalysts were determined by X-ray diffraction to be 3.9, 4.8 and 4.6 nm for the Mn, Mo and W incorporated catalysts, respectively. Electrochemically active surface areas were calculated from CO stripping results, which were 17.7, 17.2 and 15.7 m²/g _catal for the Pt₄₅Ru₄₅Mn₁₀/C, Pt₄₅Ru₄₅Mo₁₀/C and Pt₄₅Ru₄₅W₁₀/C catalysts, respectively. In methanol electro-oxidation, the Pt₄₅Ru₄₅W₁₀/C catalyst showed highest mass and specific activities of 2.78 A/g _cat. and 177 mA/m², respectively, which were 22 and 100% higher than those of commercial PtRu/C. In the case of ethanol electro-oxidation, the Pt₄₅Ru₄₅Mo₁₀/C catalyst exhibited highest mass and specific activities of 4.8 A/g _catal and 280 mA/m², respectively. Specific activity of the Pt₄₅Ru₄₅Mo₁₀/C catalyst was 56% higher than that of the commercial PtRu/C.     

Improving the Stability and Ethanol Electro‐Oxidation Activity of Pt Catalysts by Selectively Anchoring Pt Particles on Carbon‐Nanotubes‐Supported‐SnO2

To improve the stability and activity of Pt catalysts for ethanol electro‐oxidation, Pt nanoparticles were selectively deposited on carbon‐nanotubes (CNTs)‐supported‐SnO₂ to prepare Pt/SnO₂/CNTs and Pt/CNTs was prepared by impregnation method for reference study. X‐ray diffraction (XRD) was used to confirm the crystalline structures of Pt/SnO₂/CNTs and Pt/CNTs. The stabilities of Pt/SnO₂/CNTs and Pt/CNTs were compared by analyzing the Pt size increase amplitude using transmission electron microscopy (TEM) images recorded before and after cyclic voltammetry (CV) sweeping. The results showed that the Pt size increase amplitude is evidently smaller for Pt/SnO₂/CNTs, indicating the higher stability of Pt/SnO₂/CNTs. Although both catalysts exhibit degradation of electrochemical active surface area (EAS) after CV sweeping, the EAS degradation for the former is lower, further confirming the higher stability of Pt/SnO₂/CNTs. CV and potentiostatic current–time curves were recorded for ethanol electro‐oxidation on both catalysts before and after CV sweeping and the results showed that the mass specific activity of Pt/CNTs increases more than that of Pt/SnO₂/CNTs, indicating that Pt/CNTs experiences more severe evolution and is less stable. The calculated area specific activity of Pt/SnO₂/CNTs is larger than that of Pt/CNTs, indicating SnO₂ can co‐catalyze Pt due to plenty of interfaces between SnO₂ and Pt.     

Pd‐RuSe/C as ORR Specific Catalyst in Alkaline Solution Containing Methanol

Carbon supported RuSe (RuSe/C) catalyst in varying atomic ratios of Ru to Se, namely, 1:1, 2:1, and 3:1 were prepared and their performances were compared with carbon supported Ru (Ru/C). Based on the performance, Palladium was incorporated into as prepared RuSe(2:1)/C and heat treated HTRuSe(2:1)/C. Ru/C, RuSe/C, and Pd‐RuSe/C were characterized by X‐ray diffraction (XRD) and transmission electron microscopy techniques. The XRD analyses of Ru/C, RuSe/C and Pd‐HTRuSe/C show the formation of the hcp structure of Ru particles and the mean particle size was obtained from Ru(101) peak. The electrochemical characterizations of Ru/C, RuSe/C, Pd‐HTRuSe(2:1)/C and Pd‐RuSe(2:1)/C were conducted by cyclic voltammetry. Linear Sweep Voltammetric studies showed that incorporation of Pd in HTRu‐Se(2:1)/C resulted in better catalytic activity toward oxygen reduction with resistance to methanol oxidation. The quantity of hydrogen peroxide produced was obtained from rotating ring disk electrode studies.     

Pt–Sn/C electrocatalysts for methanol oxidation synthesized by reduction with formic acid

Carbon supported Pt–Sn alloy catalysts were prepared by reduction of Pt and Sn precursors with formic acid, and their electrocatalytic activity for methanol oxidation was compared with commercial Pt/C and Pt₇₅Sn₂₅/C electrocatalysts. By X-ray diffraction analysis it was found that the Pt lattice parameter increases with the addition of Sn, indicative of alloy formation. It was confirmed that Sn exhibits cocatalytic activity for CO oxidation. The onset potential for the methanol oxidation reaction of the Pt–Sn electrode was approximately 0.1 V smaller than that on Pt both at room temperature and at 90 °C. The best performance in a direct methanol fuel cell was obtained using the Pt₇₅Sn₂₅/C alloy catalyst prepared by the formic acid method as the result of an optimal balance of Sn content, degree of alloying and metal particle size.     

Synthesis of Truncated‐Octahedral Pt–Pd Nanocrystals Supported on Carbon Black as a Highly Efficient Catalyst for Methanol Oxidation

A novel PtPd/C nanocrystals catalyst with truncated‐octahedral structure has been successfully prepared by ethylene glycol reduction to induce anisotropic growth in an isotropic medium by adding a small amount of Fe³⁺ species. Its structure, composition, and morphology are characterized by X‐ray diffraction, transmission electron microscopy, and scanning transmission electron microscopy‐energy dispersive spectroscopy elemental maps, respectively. The electrochemical measurements demonstrate that the highly dispersed and uniform PtPd/C nanocrystals have excellent poisoning tolerance, significantly higher electrocatalytic activity and durability for the methanol oxidation, as compared to solid solution PtPd/C and Pt/C catalysts. This may be ascribed to the stepped atoms and dangling bonds, which served as active sites for breaking chemical bonds during oxidation–reduction reaction; the high density of preferred crystal planes of (111) facets greatly enhanced the oxidation of poisonous residues during reaction.     

Methanol‐Tolerant Heterogeneous PdCo@PdPt/C Electrocatalyst for the Oxygen Reduction Reaction

We have prepared carbon‐supported nanoparticles with the heterogeneous structure of a PdPt shell on a PdCo core which are effective for the oxygen reduction reaction (ORR) in the presence of methanol. The preparation was based on the galvanic replacement reaction between PdCo/C nanoparticles and PtCl₄^2–, a method of general utility which can be extended to the preparation of other core‐shell electrocatalysts. The heterogeneous PdCo‐core and PtPd‐shell architecture was confirmed by multiple techniques including high resolution transmission electron microscopy, energy dispersive X‐ray spectroscopy, powder X‐ray diffraction and X‐ray photoelectron spectroscopy. The activity of the PdCo@PdPt/C catalyst in ORR was evaluated in acidic solutions both with and without methanol (0.1 M). The results showed four to sixfold increases in activity over a standard Pt/C catalyst with no apparent loss of catalyst stability. It is inferred that the strain effect from the lattice mismatch between the shell and core components is the major contributor for the enhancement of ORR activity and selectivity.