Bifunctionality in Pt alloy nanocluster electrocatalysts for enhanced methanol oxidation and CO tolerance in PEM fuel cells: electrochemical and in situ synchrotron spectroscopy

Electrocatalysis of CO tolerance and direct methanol oxidation on PtMo/C (3:1 a/o) has been investigated in a PEM fuel cell environment. While a 3-fold enhancement is observed for CO tolerance when compared with PtRu/C (1:1), no such enhancement occurred for methanol oxidation. In situ XAS at the Pt L and alloying element K edges for Pt/C, PtRu/C and PtMo/C showed that in contrast to PtRu/C, both Mo and Pt surfaces play a distinct role for CO oxidation. While on the Ru surface there is a competition between oxide formation (from activation of water) and CO adsorption, Mo oxide surface showed no affinity for CO. This provided for efficient CO oxidation at low overpotentials on PtMo/C. However, the corresponding behavior for methanol oxidation showed that Mo oxy-hydroxides were inhibited from efficient removal of CO and CHO species in contrast to Ru oxides. The Mo surface oxides also showed a redox couple involving (V to VI) oxidation states in the presence of both CO and methanol.     

Preparation of supported PtRu/C electrocatalyst for direct methanol fuel cells

In this work, high-surface supported PtRu/C were prepared with Ru(NO)(NO₃)₃ and [Pt(H₂NCH₂CH₂NH₂)₂]Cl₂ as the precursors and hydrogen as a reducing agent. XRD and TEM analyses showed that the PtRu/C catalysts with different loadings possessed small and homogeneous metal particles. Even at high metal loading (40 wt.% Pt, 20 wt.% Ru) the mean metal particle size is less than 4 nm. Meanwhile, the calculated Pt crystalline lattice parameter and Pt (2 2 0) peak position indicated that the geometric structure of Pt was modified by Ru atoms. Among the prepared catalysts, the lattice parameter of 40-20 wt.% PtRu/C contract most. Cyclic voltammetry (CV), chronoamperometry (CA), CO stripping and single direct methanol fuel cell tests jointly suggested that the 40-20 wt.% PtRu/C catalyst has the highest electrochemical activity for methanol oxidation.     

Investigation of the CO tolerance mechanism at several Pt-based bimetallic anode electrocatalysts in a PEM fuel cell

The electrocatalysis of CO tolerance of Pt/C, PtRu/C, PtFe/C, PtMo/C, and PtW/C at a PEM fuel cell anode has been investigated using single cell polarization and online electrochemical mass spectrometry (EMS) measurements, and cyclic voltammetry, X-ray diffraction (XRD), in situ X-ray absorption near edge structure (XANES) analyses of the electrocatalysts. For all bimetallic electrocatalysts, which presented higher CO tolerance, EMS results have shown that the production of CO₂ start at lower hydrogen electrode overpotentials as compared to Pt/C, confirming the occurrence of the so-called bifunctional mechanism. On the other hand, XANES results indicate an increase in the Pt 5d-band vacancies for the bimetallic catalysts, particulary for PtFe/C, this leading to a weakening of the Pt-CO bond, helping to increase the CO tolerance (the so-called electronic effect). For PtMo/C and PtRu/C supplied with H₂/CO, the formation of CO₂ is observed even when the cell is at open circuit, confirming some elimination of CO by a chemical process, most probably the water gas shift reaction.     

Catalysed titanium mesh electrodes for ethylene glycol fuel cells

Electrodes comprising thermally deposited Pt, PtRu and PtRuW on titanium mesh were evaluated for the oxidation of ethylene glycol in acidic electrolyte. The electrodes were characterised using cyclic voltammetry, scanning electron microscopy and X-ray diffraction and the effect of reactant concentration and temperature were examined. Single fuel cell tests employing the titanium mesh anode with the PtRuW catalyst showed better performance than that of the PtRu catalyst. A peak power density of 15 mW cm⁻² was obtained at a temperature of 90 °C with 1.0 M ethylene glycol solution. The performance of the catalysed PtRu mesh electrode was comparable to that of a commercial, alcohol oxidation, PtRu carbon supported catalyst.     

Comparative study of carbon-supported Pt/Mo-oxide and PtRu for use as CO-tolerant anode catalysts

Carbon-supported Pt/Mo-oxide catalysts were prepared, and the reformate tolerances of Pt/MoOx/C and conventional PtRu/C anodes were examined to clarify the features and differences between these catalysts. Fuel cell performance was evaluated under various reformate compositions and operating conditions, and the CO concentrations at the anode outlet were analyzed simultaneously using on-line gas chromatography. Pt/MoOx showed better CO tolerance than PtRu with CO(80 ppm)/H₂ mixtures, especially at higher fuel utilization conditions, which is mainly due to the higher catalytic activity of Pt/MoOx for the water-gas shift (WGS) reaction and electro-oxidation of CO. In contrast, the CO₂ tolerance of Pt/MoOx was much worse than that of PtRu with a CO₂(20%)/H₂ mixture. The results of voltammetry indicated that the coverage of adsorbates generated by CO₂ reduction on Pt/MoOx was higher than that on PtRu, and therefore, the electro-oxidation of H₂ is partly inhibited on Pt/MoOx in the presence of 20% CO₂. With CO(80 ppm)/CO₂(20%)/H₂, the voltage losses of Pt/MoOx and PtRu are almost equal to the sum of the losses with each contaminant component. Although the adsorbate coverage on Pt/MoOx increases in the presence of 20% CO₂, CO molecules in the gas phase could still adsorb on Pt through an adsorbate ‘hole’ to promote WGS or electro-oxidation reactions, which leads to a reduction in the CO concentration under CO/CO₂/H₂ feeding conditions.     

Binary and ternary anode catalyst formulations including the elements W, Sn and Mo for PEMFCs operated on methanol or reformate gas

In an exploratory approach to find improved electrocatalyst formulations binary and ternary carbon supported catalysts with the elements Pt and Ru, W, Mo or Sn, respectively, amending the choice of Pt and Pt/Ru catalysts by addition of non-Pt metal cocatalysts were manufactured by impregnation and a colloid method and tested towards their activity for anodic oxidation of H₂ containing 150 ppm CO and of methanol. Membrane-electrode-assemblies with noble metal loadings of 0.4 mg cm⁻² were manufactured and tested in fuel cell operation at 75°C with H₂ fuel contaminated by CO and at 95°C for operation on methanol. Cocatalytic activities were found for the elements W and Mo for oxidation of H₂/CO and methanol while in the case of Sn a cocatalytic activity was only found for H₂/CO-oxidation. Both for oxidation of methanol and H₂/CO the system Pt/Ru/W was superior to the other systems tested. The colloid method was found to be highly suitable for synthesizing polymetallic PEM catalysts.     

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.     

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.     

Niobium Dioxide Facilitating Methanol Electrooxidation on Pt/C Catalyst by Synergistic Effect

In this work, Pt nanoparticles are deposited on NbO₂‐modified carbon composites and evaluated as promising direct methanol fuel cell (DMFC) electrocatalysts. Transmission electron microscopy (TEM) and X‐ray diffraction (XRD) indicate that Pt nanoparticles (about 2.5 nm) are uniformly dispersed on NbO₂‐modified carbon composites. Electrochemical measurements show that the mass activity toward methanol electrooxidation on Pt/NbO₂‐C is as high as 3.0 times that of conventional Pt/C. Meanwhile, the onset potential of CO oxidation is negatively shifted by about 46 mV as compared with that of Pt/C, which means that the synergistic effect between NbO₂ and Pt facilitates the feasible removal of poisoning intermediate CO during methanol electrooxidation. X‐ray photoelectron spectroscopy (XPS) characterizations reveal the electron transfer from Nb to Pt, which suppress the poisoning CO adsorption on Pt nanoparticles and facilitate methanol electrooxidation. NbO₂ nanoparticles facilitate methanol electrooxidation on Pt/C catalyst by synergistic effect and electronic effect, which represents a step in the right direction for the development of excellent fuel cell anode electrocatalysts.     

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.     

Effects of iron-tetrasulfophthalocyanine on the catalytic activities of Pt/C,PtRu/C,and Pd/C catalysts in a multi-anode direct formic acid fuel cell

This paper reports a systematic study of the effects of a promoter, iron-tetrasulfophthalocyanine (FeTSPc), on the catalytic activities of carbon supported Pt, PtRu, and Pd catalysts (Pt/C, PtRu/C, and Pd/C) for formic acid oxidation. A multi-anode direct formic acid fuel cell (DFAFC) was used to compare the effects on each catalyst of adding FeTSPc to the fuel stream. The FeTSPc significantly enhanced the activity of the Pt/C catalyst, but had little effect on the PtRu/C catalyst. The activity of the Pd/C catalyst was inhibited by the FeTSPc. A FeTSPc modified Pt/C was also evaluated in a conventional 5 cm² DFAFC.     

Ethanol oxidation on a high temperature PBI-based DEFC using Pt/C, PtRu/C and Pt3Sn/C as catalysts

A high temperature ethanol-fed polymer electrolyte membrane fuel cell has been implemented by using H₃PO₄-doped m-polybenzimidazole as polymeric electrolyte. Commercial Pt/C, PtRu/C and Pt₃Sn/C catalysts are used in the anode. The performance was assessed in terms of polarization curves at different temperatures, feeding the cell with a high concentration ethanol solution (water/ethanol mass ratio of 2). The product distribution was measured with the support of a gas chromatograph. The use of bimetallic catalysts increased the current density. PtRu/C showed the best performance up to 175 °C, but it is outperformed by Pt₃Sn/C at 200 °C. In terms of oxidation products, higher temperatures and current densities favour the oxidation of ethanol. However, Pt₃Sn/C promoted the generation of more oxidized products compared to PtRu/C (in which most of the ethanol is oxidized to acetaldehyde), especially at high temperature. This accounts for the large current density. In terms of complete oxidation of ethanol to CO₂, Pt/C was by far the most efficient catalyst for C–C scission, achieving percentages of 56 % of CO₂, although operating above 175 °C dramatically boosted an undesirable methanation process that slashed the efficiency. The combination of fuel cell results and product distribution helped to suggest the different oxidation routes on the surface of the different catalysts.     

Influence of temperature and relative humidity on performance and CO tolerance of PEM fuel cells with Nafion-Teflon-Zr(HPO4)2 higher temperature composite membranes

The carbon monoxide (CO) poisoning effect on carbon supported catalysts (Pt-Ru/C and Pt/C) in polymer electrolyte membrane (PEM) fuel cells has been investigated at higher temperatures (T > 100 °C) under different relative humidity (RH) conditions. To reduce the IR losses in higher temperature/lower relative humidity, Nafion^®-Teflon^®-Zr(HPO₄)₂ composite membranes were applied as the cell electrolytes. Fuel cell polarization investigation as well as CO stripping voltammetry measurements was carried out at three cell temperatures (80, 105 and 120 °C), with various inlet anode relative humidity (35%, 58% and 100%). CO concentrations in hydrogen varied from 10 ppm to 2%. The fuel cell performance loss due to CO poisoning was significantly alleviated at higher temperature/lower RH due to the lower CO adsorption coverage on the catalytic sites, in spite that the anode catalyst utilization was lower at such conditions due to higher ionic resistance in the electrode. Increasing the anode inlet relative humidity at the higher temperature also alleviated the fuel cell performance losses, which could be attributed to the combination effects of suppressing CO adsorption, increasing anode catalyst utilization and favoring OH_ads group generation for easier CO oxidation.     

Temperature dependence of co-adsorption of carbon monoxide and water on highly dispersed Pt/C and PtRu/C electrodes studied by in-situ ATR-FTIRAS

ATR-FTIRAS measurements were conducted to investigate nature of water molecules co-adsorbed with CO on highly dispersed PtRu alloy and Pt catalysts supported on carbon black in the temperature range between 23 °C and 60 °C. Each catalyst was uniformly dispersed and fixed by Nafion^® film of 0.0125 μm thickness on a chemically deposited gold film. Adsorption of CO was conducted and monitored by ATR-FTIRAS for 30 min in 1% CO saturated 0.1 M HClO₄ after stepping the potential from 1.2 V and 1.0 V to 0.05 V on Pt/C and PtRu/C, respectively. Similar atop and bridge bonded CO bands were observed on both PtRu/C and Pt/C, but a smaller relative band intensity, bridge bonded vs. atop CO, was observed on PtRu/C compared to Pt/C. A distinct O-H stretching band was found around 3643 cm⁻¹ and 3630 cm⁻¹ on PtRu/C and Pt/C, respectively, upon CO adsorption. They are assigned to non-hydrogen bonded water molecules co-adsorbed with CO on these catalysts. We found that the number of non-hydrogen bonded water molecules co-adsorbed with a given number of CO molecules decreases with increasing temperature and is higher on PtRu/C than Pt/C at each temperature. We interpret the higher ability of water co-adsorption at PtRu/C over Pt/C is due to stronger H₂O-metal interactions on the alloy surface. We present a model of the CO-H₂O co-adsorbed layer based on the bilayer model of water on metal surfaces.     

CO tolerance and catalytic activity of Pt/Sn/SnO2 nanowires loaded on a carbon paper

Electrochemical activities and structural features of Pt/Sn catalysts supported by hydrogen-reduced SnO₂ nanowires (SnO₂NW) are studied, using cyclic voltammetry, CO stripping voltammetry, scanning electron microscopy, and X-ray diffraction analysis. The SnO₂NW supports have been grown on a carbon paper which is commercially available for gas diffusion purposes. Partial reduction of SnO₂NW raises the CO tolerance of the Pt/Sn catalyst considerably. The zero-valence tin plays a significant role in lowering the oxidation potential of CO_ads. For a carbon paper electrode loaded with 0.1 mg cm⁻² Pt and 0.4 mg cm⁻² SnO₂NW, a conversion of 54% SnO₂NW into Sn metal (0.17 mg cm⁻²) initiates the CO_ads oxidation reaction at 0.08 V (vs. Ag/AgCl), shifts the peak position by 0.21 V, and maximizes the CO tolerance. Further reduction damages the support structure, reduces the surface area, and deteriorates the catalytic activity. The presence of Sn metal enhances the activities of both methanol and ethanol oxidation, with a more pronounced effect on the oxidation current of ethanol whose optimal value is analogous to those of PtSn/C catalysts reported in literature. In comparison with a commercial PtRu/C catalyst, the optimal Pt/Sn/SnO₂NW/CP exhibits a somewhat inferior activity toward methanol, and a superior activity toward ethanol oxidation.     

Effect of hydrogen partial pressure on a polymer electrolyte fuel cell performance

We first investigated the effect of partial pressure of hydrogen (H₂) on the performance of polymer electrolyte fuel cells (PEFCs) by controlling the ratio of hydrogen and nitrogen (N₂). The cell performance with Pt/C anode was significantly decreased with reduction of the partial pressure of H₂ in the presence of carbon monoxide (CO), while the performance variation was negligible in the absence of CO. Severe CO poisoning on Pt/C electrode at low partial pressure of H₂ might be attributed to the hindering effect by N₂ and CO. On the other hand, PtRu/C anode showed consistent power performance even at low partial pressure of H₂.     

Methanol oxidation at carbon supported Pt and Pt-Ru electrodes: an on line MS study using technical electrodes

Methanol oxidation at technical carbon based electrodes in 0.05 M H₂SO₄ has been investigated by cyclic voltammetry using online MS under the conditions of an acid methanol fuel cell (DMFC). 5% Pt on Norit BRX and 30% Pt/Ru (40/60) on Norit BRX were used as catalysts. It is shown that methanol oxidation at technical electrodes can be characterized by a combination of cyclic voltammetry and mass spectroscopy. The onset potentials and potential dependences of the methanol oxidation rate can be determined directly by monitoring the formation of CO₂. Onset potentials of 0.5V and 0.25 V/RHE have been measured for Pt and Pt-Ru catalysts, respectively. The onset of methanol oxidation can be shifted to even more cathodic potentials (0.2V) if the Pt-Ru electrode reduces oxygen simultaneously. Carbon monoxide gas was also purged into the methanol containing electroyte during measurement in order to investigate the catalyst performance under more adverse conditions. C¹³-labelled methanol was used to distinguish between CO₂. formed from methanol (m/e = 45) and CO-oxidation (m/e = 44). Without CO the use of C¹³-labelled methanol enabled a distinction between methanol oxidation and carbon corrosion. The methanol oxidation at the platinum catalyst is severely inhibited by the presence of CO, shifting its onset to 0.65 V/RHE. In contrast the performance of the Pt-Ru electrode is not seriously affected under these conditions. It is concluded that Pt-Ru is an excellent catalyst for a methanol anode in an acid methanol fuel cell (DMFC).     

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.     

Comparison of different promotion effect of PtRu/C and PtSn/C electrocatalysts for ethanol electro-oxidation

Well dispersed PtSn/C, PtRu/C and Pt/C electrocatalysts were synthesized by a modified polyol process and characterized by X-ray diffraction (XRD), transmission electron microscope (TEM) and inductively coupled plasma-atomic emission spectrometry techniques. XRD patterns show that Ru induces the contraction of Pt lattice parameter while Sn makes the Pt crystal lattice extended. Ethanol oxidation activities on the catalysts were studied via cyclic voltammetry (CV) and chronoamperometry (CA) methods at room temperature. It is found that the electrode potential plays an important role in the electrochemical behavior of ethanol oxidation on PtRu/C and PtSn/C catalysts. In the lower potential region, PtSn/C possesses higher performance for ethanol oxidation, while in the higher potential region PtRu/C is more active. The different promotion effects of PtSn/C and PtRu/C to ethanol oxidation can be explained by the structural effect and modified bi-functional mechanism in different potential region. Single cell test of a direct ethanol fuel cell (DEFC) was also carried out to elucidate the promotion effect of PtRu/C and PtSn/C catalysts on the ethanol oxidation at 90 °C.     

CO tolerance and CO oxidation at Pt and Pt-Ru anode catalysts in fuel cell with polybenzimidazole-H3PO4 membrane

CO tolerance of H₂-air single cell with phosphoric acid doped polybenzidazole (PA-PBI) membrane was studied in the temperature range 140-180 °C using either dry or humidified fuel. Fuel composition was varied from neat hydrogen to 67% (vol.) H₂-33% CO mixtures. It was found that poisoning by CO of Pt/C and Pt-Ru/C hydrogen oxidation catalysts is mitigated by fuel humidification. Electrochemical hydrogen oxidation at Pt/C and Pt-Ru/C catalysts in the presence of up to 50% CO in dry or humidified H₂-CO mixtures was studied in a cell driven mode at 180 °C. High CO tolerance of Pt/C and Pt-Ru/C catalysts in FC with PA-PBI membrane at 180 °C can be ascribed to combined action of two factors—reduced energy of CO adsorption at high temperature and removal of adsorbed CO from the catalyst surface by oxidation. Rate of electrochemical CO oxidation at Pt/C and Pt-Ru/C catalysts was measured in a cell driven mode in the temperature range 120-180 °C. Electrochemical CO oxidation might proceed via one of the reaction paths—direct electrochemical CO oxidation and water-gas shift reaction at the catalyst surface followed by electrochemical hydrogen oxidation stage. Steady state CO oxidation at Pt-Ru/C catalyst was demonstrated using CO-air single cell with Pt-Ru/C anode. At 180 °C maximum CO-air single cell power density was 17 mW cm⁻² at cell voltage U = 0.18 V.