Effect of heat treatment on PtRu/C catalyst for methanol electro-oxidation

The effect of heat treatment on a commercial PtRu/C catalyst was investigated with a focus on the relationship between electrochemical and surface properties. The heat treated PtRu/C catalysts were prepared by reducing the commercial PtRu/C catalyst at 300, 500, and 600 °C under hydrogen flow. The maximum mass activity for the methanol electro-oxidation reaction (MOR) was observed in the catalyst heat treated at 500 °C, while specific activity for the MOR increased with increasing heat treatment temperature. Cyclic voltammetry (CV) results revealed that the heat treatment caused Pt rich surface formation. The increase in surface Pt was confirmed by X-ray photoelectron spectroscopy; the surface (Pt:Ru) ratio of the fresh catalyst (81:19) changed to (87:13) in the 600 °C heat treated catalyst. Quantitative analysis of the Ru oxidation state showed that the ratio of metallic Ru increased with an increase in heat treatment temperature. On the other hand, RuO_xH_y completely reduced at 500 °C and the ratio of RuO₂ slightly decreased with increasing heat treatment temperature.     

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.     

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.     

High activity PtRu/C catalysts synthesized by a modified impregnation method for methanol electro-oxidation

A modified impregnation method was used to prepare highly dispersive carbon-supported PtRu catalyst (PtRu/C). Two modifications to the conventional impregnation method were performed: one was to precipitate the precursors ((NH₄)₂PtCl₆ and Ru(OH)₃) on the carbon support before metal reduction; the other was to add a buffer into the synthetic solution to stabilize the pH. The prepared catalyst showed a much higher activity for methanol electro-oxidation than a catalyst prepared by the conventional impregnation method, even higher than that of current commercially available, state-of-the-art catalysts. The morphology of the prepared catalyst was characterized using TEM and XRD measurements to determine particle sizes, alloying degree, and lattice parameters. Electrochemical methods were also used to ascertain the electrochemical active surface area and the specific activity of the catalyst. Based on XPS measurements, the high activity of this catalyst was found to originate from both metallic Ru (Ru⁰) and hydrous ruthenium oxides (RuO_xH_y) species on the catalyst surface. However, RuO_xH_y was found to be more active than metallic Ru. In addition, the anhydrous ruthenium oxide (RuO₂) species on the catalyst surface was found to be less active.     

Characterization and electrocatalytic properties of PtRu/C catalysts prepared by impregnation-reduction method using Nd2O3 as dispersing reagent

A simple impregnation-reduction method introducing Nd₂O₃ as dispersing reagent has been used to synthesize PtRu/C catalysts with uniform Pt-Ru spherical nanoparticles. X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) analysis have been used to characterize the composition, particle size and crystallinity of the catalysts. Well-dispersed catalysts with average particle size about 2 nm are achieved. The electrochemically active surface area of the different PtRu/C catalysts is determined by the CO_ad-stripping voltammetry experiment. The electrocatalytic activities of these catalysts towards methanol electrooxidation are investigated by cyclic voltammetry measurements and ac impedance spectroscopy. The in-house prepared PtRu/C catalyst (PtRu/C-03) in 0.5 M H₂SO₄ + 1.0 M CH₃OH at 30 °C display a higher catalytic activity and lower charge-transfer resistance (R_t) than that of the standard PtRu/C catalyst (PtRu/C-C). It is mainly due to enhanced electrochemically active specific surface, higher alloying extent of Ru and the abundant Pt⁰ and Ru oxides on the surface of the PtRu/C catalyst.     

Pt-CeO2/C anode catalyst for direct methanol fuel cells

In order to develop a cheaper and durable catalyst for methanol electrooxidation reaction, ceria (CeO₂) as a co-catalytic material with Pt on carbon was investigated with an aim of replacing Ru in PtRu/C which is considered as prominent anode catalyst till date. A series of Pt-CeO₂/C catalysts with various compositions of ceria, viz. 40 wt% Pt-3–12 wt% CeO₂/C and PtRu/C were synthesized by wet impregnation method. Electrocatalytic activities of these catalysts for methanol oxidation were examined by cyclic voltammetry and chronoamperometry techniques and it is found that 40 wt% Pt-9 wt% CeO₂/C catalyst exhibited a better activity and stability than did the unmodified Pt/C catalyst. Hence, we explore the possibility of employing Pt-CeO₂ as an electrocatalyst for methanol oxidation. The physicochemical characterizations of the catalysts were carried out by using Brunauer Emmett Teller (BET) surface area and pore size distribution (PSD) measurements, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) techniques. A tentative mechanism is proposed for a possible role of ceria as a co-catalyst in Pt/C system for methanol electrooxidation.     

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.     

Effect of electrochemical polarization of PtRu/C catalysts on methanol electrooxidation

To determine the influence of electrochemical polarization of PtRu/C catalysts on methanol electrooxidation, this work investigated methanol electrooxidation on as received and different electrochemically polarized PtRu/C catalysts. Thermogravimetric analysis (TGA) and X-ray diffraction (XRD) were used to characterize the redox state of PtRu/C after different electrochemical polarization. The methanol electrooxidation activity was measured by cyclic voltammetry (CV), Tafel steady state plot and electrochemical impedance spectroscopy (EIS). The results indicate that the metallic state Pt⁰Ru⁰ can be formed during cathodic polarization and contribute to electrooxidation of methanol, while the formation of inactive ruthenium oxides during anodic polarization cause the negative effect on methanol electrooxidation. Different Tafel slopes and impedance behaviors in different potential regions also reveal a change of the mechanism and rate-determining step in methanol electrooxidation with increasing potentials. The kinetic analysis from Tafel plots and EIS reveal that at low potentials indicate the splitting of the first CH bond of CH₃OH molecule with the first electron transfer is rate-determining step. However, at higher potentials, the oxidation reaction of adsorbed intermediate CO_ads becomes rate-determining step.     

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.     

Preparation and characterization of a PtRu/C nanocatalyst for direct methanol fuel cells

PtRu/C nanocatalysts were prepared by changing the molar ratio of citric acid to platinum and ruthenium metal salts (CA:PtRu) from 1:1, 2:1, 3:1 to 4:1 using sodium borohydride as a reducing agent. Transmission electron microscopy analysis indicated that well-dispersed smaller PtRu particles (2.6 nm) were obtained when the molar ratio was maintained at 1:1. X-ray diffraction analysis confirmed the formation of PtRu alloy; the atomic percentage of the alloy analyzed by the energy dispersive X-ray spectrum indicated an enrichment of Pt in the nanocatalyst. X-ray photoelectron spectroscopy measurements revealed that 83.34% of Pt and 79.54% of Ru were present in their metallic states. Both the linear sweep voltammetry and chronoamperometric results demonstrated that the 1:1 molar ratio catalyst exhibited a higher methanol oxidation current and a lower poisoning rate among all the other molar ratios catalysts. The CO stripping voltammetry studies showed that the E-TEK catalyst had a relatively higher CO oxidation current than did the 1:1 molar ratio catalyst. Testing of the PtRu/C catalysts at the anode of a direct methanol fuel cell (DMFC) indicated that the in-house PtRu/C nanocatalyst gave a slightly higher performance than did the E-TEK catalyst.     

The inclusion of Mo, Nb and Ta in Pt and PtRu carbon supported electrocatalysts in the quest for improved CO tolerant PEMFC anodes

The effect of the inclusion of Mo, Nb and Ta in Pt and PtRu carbon supported anode electrocatalysts on CO tolerance in proton exchange membrane fuel cells (PEMFC) has been investigated by cyclic voltammetry and fuel cell tests. CO stripping voltammetry on binary Pt_xM/C (M: Mo, Nb, Ta) reveals partial oxidation of the CO adlayer at low potential, with PtMo (4:1)/C exhibiting the lowest value. At 80 °C, the operating temperature of the fuel cell, CO oxidation was observed at potentials close to 0 V versus the reversible hydrogen electrode (RHE). No significant difference for CO electro-oxidation at the lower potential limit, compared to PtRu/C, was observed for PtRuM_y/C (M: Mo, Nb). Fuel cell tests demonstrated that while all the prepared catalysts exhibited enhanced performance compared to Pt/C, only the addition of a relatively small amount of Mo to PtRu results in an electrocatalyst with a higher activity, in the presence of carbon monoxide, to PtRu/C, the current catalyst of choice for PEM fuel cell applications.     

Combinatorial Search for Quaternary Methanol Tolerant Oxygen Electro‐Reduction Catalyst

A combinatorial library containing 645 different compositions was synthesised and characterised for methanol tolerant oxygen electro‐reduction reaction (ORR) catalytic performance. The library was composed of compositions involving between 1 and 4 metals among Pt, Ru, Fe, Mo and Se. In an optical screening test, Pt(50)Ru(10)Fe(20)Se(10) composition exhibited the highest ORR activity in the presence of methanol. This composition was further investigated by synthesis and characterisation of a powder version catalyst [Pt(50)Ru(10)Fe(20)Se(10)/C]. At 0.85 V [vs. reversible hydrogen electrode (RHE)] in the absence of methanol, the Pt/C catalyst exhibited higher ORR current (0.0990 mA) than the Pt(50)Ru(10)Fe(20)Se(10)/C catalyst (0.0902 mA). But much higher specific activity (12.7 μA cm_pt^–2) was observed in the Pt(50)Ru(10)Fe(20)Se(10)/C catalyst than for the Pt/C catalyst 6.51 μA cm_pt^–2). In the presence of methanol, the ORR current decreased by 0.0343 and 0.247 mA for the Pt(50)Ru(10)Fe(20)Se(10)/C and Pt/C catalysts, respectively, which proved the excellent methanol tolerance of the Pt(50)Ru(10)Fe(20)Se(10)/C catalyst.     

The efficiency of methanol conversion to CO2 on thin films of Pt and PtRu fuel cell catalysts

Yields were determined for the CO₂ produced upon the electrochemical oxidation of 1.0 M methanol in 0.1 M HClO₄ at the following four fuel cell catalyst systems: Pt black, Pt at 10 wt.% metal loading on Vulcan XC-72R carbon (C/Pt, 10%), PtRu black at 50 at.% Pt, 50 at.% Ru (PtRu (50:50) black), and PtRu at 30 wt.% Pt, 15 wt.% Ru loading on Vulcan XC-72R carbon (C/PtRu, 30 wt.% Pt, 15 wt.% Ru). Samples were electrolyzed in a small volume (50 μl) arrangement for a period of 180 s keeping the reactant depletion in the cell below 1%. The dissolved CO₂ produced was determined ex situ by infrared spectroscopy in a micro-volume transmission flow cell. For the PtRu materials, the efficiencies for CO₂ formation were near 100% at reaction potentials in the range between 0.4 V (versus the reversible hydrogen electrode (RHE), V_RHE ) and 0.9 V_RHE. At the Pt catalysts, the yields of CO₂ approached 80% between 0.8 and 1.1 V_RHE and declined rapidly below 0.8 V_RHE.     

Enhanced activity of carbon-supported PdCo electrocatalysts toward electrooxidation of ethanol in alkaline electrolytes

Carbon-supported Pd and PdCo (1: 2, 1: 1, 2: 1 and 3: 1) catalysts were synthesized by chemical reduction with NaBH₄. Their electrochemical properties were investigated by cyclic voltammetry, chronoamperometry and CO stripping voltammetry in alkaline electrolytes, and compared with commercial Pt/C and PtRu(1: 1)/C catalysts. In electrochemical oxidation of ethanol in an alkaline electrolyte, marked improvements in the current density and onset potential were observed by incorporating Co into Pd/C to form PdCo/C alloy electrocatalysts. The best catalyst PdCo (1: 1)/C showed performance superior to the commercial Pt/C or PtRu/C catalysts. It is shown that the incorporated Co facilitates the oxidation of strongly-adsorbed carbonaceous intermediate species on the surface of Pd by forming OH^? group and reacts away the intermediates from Pd surface. Thus, PdCo(1: 1)/C catalyst is a promising anode catalyst for direct ethanol fuel cells with alkaline electrolytes.     

Study of Methanol‐tolerant Oxygen Reduction Reaction at Pt–Bi/C Bimetallic Nanostructured Catalysts

The nanostructured platinum–bismuth catalysts supported on carbon (Pt₃Bi/C, PtBi/C and PtBi₃/C) were synthesised by reducing the aqueous metal ions using sodium borohydride (NaBH₄) in presence of a microemulsion. The amount of metal loading on carbon support was found to be 10 wt.‐%. The catalyst materials were characterised by X‐ray diffraction (XRD), X‐ray fluorescence (XRF), transmission electron microscope (TEM) and electroanalytical techniques. The Pt₃Bi/C, PtBi/C and PtBi₃/C catalysts showed higher methanol tolerance, catalytic activity for oxygen reduction reaction (ORR) than Pt/C of same metal loading. The electrochemical stability of these nano‐sized catalyst materials for methanol tolerance was investigated by repetitive cycling in the potential range of –250 to 150 mV_MSE. Bi presents an interesting system to have a control over the activity of the surface for MOR and ORR. All Pt–Bi/C catalysts exhibited higher mass activities for oxygen reduction (1–1.5 times) than Pt/C. It was found that PtBi/C catalyst exhibits better methanol‐tolerance than the other catalysts.     

Kinetic study of methanol oxidation on carbon-supported PtRu electrocatalyst

Methanol electrooxidation was investigated on the carbon-supported PtRu electrocatalyst (1:1 atomic ratio) in acid media. X-ray diffraction measurement indicated alloying of Pt and Ru. Cyclic voltammetry of the sample reflects the amount of Ru in the catalyst and its ability to adsorb OH radicals. Tafel plots for the oxidation of 0.02-3 M methanol in the solutions containing 0.05-1 M HClO₄ and in the temperature range 27-40 °C showed reasonably well-defined linear region with the slope of about 115 mV dec⁻¹ at the low currents, irrespective of the experimental conditions employed. Reaction order with respect to methanol was found to be 0.5. A correlation between methanol oxidation rate and pseudocapacitive current of OH adsorption on Ru sites was established. It was proposed that bifunctional mechanism is operative with the reaction between methanol residues adsorbed on Pt sites and OH radicals adsorbed on Ru sites as the rate-determining step.     

Electro-oxidation of dimethyl ether on Pt/C and PtMe/C catalysts in sulfuric acid

The electro-oxidation of dimethyl ether (DME) on PtMe/Cs (Me = Ru, Sn, Mo, Cr, Ni, Co, and W) and Pt/C electro-catalysts were investigated in an aqueous half-cell, and compared to the methanol oxidation. The addition of a second metal enhanced the tolerance of Pt to the poisonous species during the DME oxidation reaction (DOR). The PtRu/C electro-catalyst showed the best electro-catalytic activity and the highest tolerance to the poisonous species in the low over-potential range (<0.55 V, 50 °C) among the binary electro-catalysts and the Pt/C, but at the higher potential (>ca. 0.55 V, 50 °C), the Pt/C behaved better than PtRu/C. The apparent activation energy for the DOR decreased in the order: PtRu/C (57 kJ mol⁻¹) > Pt₃Sn/C (48 kJ mol⁻¹) ≈ Pt/C (46 kJ mol⁻¹). On the other hand, the activation energy for the MOR showed a different turn, decreased in the following order: Pt/C (43 kJ mol⁻¹) > Pt₃Sn/C (35 kJ mol⁻¹) ≈ PtRu/C (34 kJ mol⁻¹). The temperature dependence of the DOR was greater than that of the oxidation of methanol (MOR) on the PtRu/C.     

Ethanol oxidation on novel, carbon supported Pt alloy catalysts—Model studies under defined diffusion conditions

The structure, surface composition and activity/selectivity for ethanol oxidation of carbon supported Pt alloy catalysts with different composition and catalyst loading, which were synthesized via the polyol-route, were investigated and characterized by microscopic/spectroscopic methods (TEM, EDX, XRD) and electrochemical (RDE, on-line DEMS) measurements under well-defined transport and diffusion conditions. The performance of the polyol-type Pt/C (20 wt.%), PtRu/C (20, 40 and 60 wt.%), and Pt₃Sn/C (20 wt.%) catalysts was compared with that of commercial Pt/C, PtRu/C and Pt₃Sn/C (E-Tek) catalysts. The metal particle sizes of the polyol-type catalysts are significantly smaller than those of the corresponding commercial catalysts, nevertheless both the mass specific activities and, more pronounced, the inherent, active surface area specific activities are lower than those of the commercial catalysts, which is related to the lower degree of alloy formation in the polyol-type catalysts. For all catalysts, incomplete ethanol oxidation to C2 products (acetaldehyde and acetic acid) prevails under conditions of this study, CO₂ formation contributes by ≤1% for potentiostatic reaction conditions. The lower activity of the polyol-type catalysts is mainly due to the lower activity for acetaldehyde formation. Implications and further strategies for fuel cell applications are discussed.     

Highly active PtRu catalysts supported on carbon nanotubes prepared by modified impregnation method for methanol electro-oxidation

A simple and rapid synthesis method (denoted as modified impregnation method, MI) for PtRu/CNTs (MI) and PtRu/C (MI) was presented. PtRu/CNTs (MI) and PtRu/C (MI) catalysts were characterized by transmission electron microscopy (TEM) and X-ray diffractometry. It was shown that Pt-Ru particles with small average size (2.7 nm) were uniformly dispersed on carbon supports (carbon nanotubes and carbon black) and displayed the characteristic diffraction peaks of Pt face-centered cubic structure. Cyclic voltammetry and chronoamperometry showed that the Pt-Ru/CNTs (MI) catalyst exhibited better methanol oxidation activities than Pt-Ru/C (MI) catalyst and commercial Pt-Ru/C (E-TEK) catalyst. The single cells with Pt-Ru/CNTs (MI) catalyst exhibited a power density of 61 mW/cm², about 27% higher than those single cells with commercial Pt-Ru/C (E-TEK) catalyst.     

Facile Preparation of an Excellent Pt/RuO2‐MnO2/CNTs Nanocatalyst for Anodes of Direct Methanol Fuel Cells

RuO₂‐MnO₂ complex supported by multi‐wall carbon nanotubes (CNTs) was firstly synthesised by the oxidation–reduction precipitation of RuCl₃ and KMnO₄ in one step. Then Pt was loaded onto the obtained RuO₂‐MnO₂/CNTs to fabricate a novel anodic catalyst Pt/RuO₂‐MnO₂/CNTs for direct methanol fuel cells (DMFCs). The catalyst was characterised by transmission electron microscopy (TEM), X‐ray diffraction (XRD), temperature programmed reduction (TPR), X‐ray photoelectron spectroscopy (XPS) and BET specific surface areas (BET). Pt nanoparticles were found uniformly dispersed on the surface of CNTs, with the average diameter of about 2.0 nm. The activities of methanol and CO electrocatalytic oxidation were analysed, and the reaction mechanism of methanol electro‐oxidation on Pt/RuO₂‐MnO₂/CNTs catalyst was discussed. The MnO₂ in the catalysts improves the proton conductivity and electrochemical active surface area (EAS) for the catalysts. RuO₂ improves the CO oxidation activity and Pt dispersion. CNTs provide effectively electron channels. Thus, the Pt/RuO₂‐MnO₂/CNTs catalyst has high utilisation of the noble metal Pt, high CO oxidation ability and excellent methanol electro‐oxidation activity, being an outstanding anode catalyst for DMFC.