Pt-based bimetallic catalysts for SO2-depolarized electrolysis reaction in the hybrid sulfur process

SO₂-depolarized electrolysis (SDE) is pivotal in the hybrid sulfur process, which is a promising approach for mass hydrogen production without CO₂ emission. The anode overpotential of SDE is the key component of electrolysis potential. This factor can be reduced by improving anode reaction kinetics. Such improvement is commonly achieved by employing Pt/AC as anode electrode and catalyst, thus also improving economic and electrocatalytic performances. In this work, anode catalysts for SO₂ oxidation reaction are experimentally studied. Platinum-based bimetallic catalysts, including Pt–Pd/C, Pt–Rh/C, Pt–Ru/C, Pt–Ir/C, and Pt–Cr/C, are prepared and characterized. Their electrochemical characteristics for SDE in a once-through mode are investigated in SO₂-saturated 30 wt% sulfuric acid at room temperature by various approaches such as cyclic voltammetry, linear sweep voltammetry, and polarization curves. Results show that 60 wt% Pt–Cr/C exhibits the highest electrocatalytic activity for SDE. Further studies on the metal proportion in Pt–Cr/C show that at a Pt:Cr atomic ratio of 1:2, this bimetallic catalyst demonstrates equal or even better electrolysis performance than 60 wt% Pt/C at a significantly lower economic cost.     

Carbon supported nano-sized Pt–Pd and Pt–Co electrocatalysts for proton exchange membrane fuel cells

Nano-sized Pt–Pd/C and Pt–Co/C electrocatalysts have been synthesized and characterized by an alcohol-reduction process using ethylene glycol as the solvent and Vulcan XC-72R as the supporting material. While the Pt–Pd/C electrodes were compared with Pt/C (20 wt.% E-TEK) in terms of electrocatalytic activity towards oxidation of H₂, CO and H₂–CO mixtures, the Pt–Co/C electrodes were evaluated towards oxygen reduction reaction (ORR) and compared with Pt/C (20 wt.% E-TEK) and Pt–Co/C (20 wt.% E-TEK) and Pt/C (46 wt.% TKK) in a single cell. In addition, the Pt–Pd/C and Pt–Co/C electrocatalyst samples were characterized by XRD, XPS, TEM and electroanalytical methods. The TEM images of the carbon supported platinum alloy electrocatalysts show homogenous catalyst distribution with a particle size of about 3–4 nm. It was found that while the Pt–Pd/C electrocatalyst has superior CO tolerance compared to commercial catalyst, Pt–Co/C synthesized by polyol method has shown better activity and stability up to 60 °C compared to commercial catalysts. Single cell tests using the alloy catalysts coated on Nafion-212 membranes with H₂ and O₂ gases showed that the fuel cell performance in the activation and the ohmic regions are almost similar comparing conventional electrodes to Pt–Pd anode electrodes. However, conventional electrodes give a better performance in the ohmic region comparing to Pt–Co cathode. It is worth mentioning that these catalysts are less expensive compared to the commercial catalysts if only the platinum contents were considered.     

Support effect of anode catalysts using an organic metal complex for fuel cells

The carbon support effect of Pt–Ni(mqph) electrocatalysts on the performance of CO tolerant anode catalysts for polymer electrolyte fuel cells (PEFCs) was investigated using carbon black and multi-walled carbon nanotubes (MWCNTs), with and without defect preparation. 20%Pt–Ni(mqph)/defect-free CNTs showed a very high CO tolerance (75% compared to the CO-free H₂ case) under 100 ppm CO level in the half-cell system of the hydrogen oxidation reaction. On the other hand, the hydrogen oxidation current on Pt–Ni(mqph)/defective CNTs, Pt–Ni(mqph)/VulcanXC-72R and Pt–Ru/VulcanXC-72R significantly decreased with increasing concentration of CO up to 100 ppm (25–47% compared to the CO-free H₂ case). It is thus considered that the carbon support materials strongly affect the CO tolerance of anode catalysts. This is ascribed to a change in the electronic structure of the Pt particles due to the interaction with the graphene surface, leading to a reduction in the adsorption energy of CO. Ni(mqph) also mitigates CO poisoning due to its ability of CO coordination on Ni metal center.     

Comparison of structure and catalytic performance of Pt–Co and Pt–Cu bimetallic catalysts supported on Al2O3 and CeO2 synthesized by electron beam irradiation method for preferential CO oxidation

In order to investigate the effect of transition metal addition to platinum with different support materials on preferential CO oxidation, structure and chemical properties of supported bimetallic catalysts prepared by electron beam irradiation method were correlated to the catalytic performance. On Al₂O₃, decoration of Pt by small amount of Co (Co/Pt ∼ 0.03) drastically increased CO and O₂ conversions while addition of equimolar Cu to Pt increased them only above 100 °C, where the rate-controlling factor was suggested to change from oxygen transport to CO activation. On CeO₂, either addition of Co or Cu to Pt had minor or negative effect on high O₂ conversion inherent to high oxygen transport at Pt–CeO₂ interface. On Pt–Cu/CeO₂, however, metal-CuO_x interface dominates the reaction characteristics to give improved selectivity, which is suitable for deep CO removal in excess O₂/CO condition. The order of selectivity above 100 °C, Pt–CoO_x > Pt(alloy)–CuO_x > Pt–CeO₂ interfaces, was derived from structural analysis and catalytic tests.     

On the activity of bimetallic catalysts for ethanol steam reforming

The performance of CeO₂-supported Pt–Ni and Pt–Co catalysts in the low temperature-Ethanol Steam Reforming (ESR) reaction has been evaluated studying the effect of the preparation method (impregnation/coprecipitation) and parameters such as dilution ratio, temperature, water-to-ethanol feed ratio and Gas Hourly Space Velocity (GHSV). The results show that impregnated samples perform better. In particular, the Pt/Ni/CeO₂ catalyst starting from 350 °C leads to a products distribution very close to the equilibrium calculations, with a low CO content that is ideal for fuel cells devices. In addition, the Co-based catalysts appear attractive in terms of hydrogen yield and coking tendency.     

Electrochemical synthesis and characterization of carbon-supported Pt and Pt–Ru nanoparticles with Cu cores for CO and methanol oxidation in polymer electrolyte fuel cells

Pt and Pt–Ru shells on Cu cores supported on Vulcan carbon XC72R have been synthesized and tested as possible anode electrocatalysts for polymer electrolyte fuel cells. Pt(Cu)/C was prepared by Cu electrodeposition on the black carbon support at constant potential followed by Pt deposition on Cu by galvanic exchange, whereas Pt–Ru(Cu)/C was prepared by spontaneous deposition of Ru species on Pt(Cu)/C. The corresponding cyclic voltammograms in 0.5 M H₂SO₄ solution showed the hydrogen adsorption/desorption peaks and no Cu oxidation. The respective CO stripping peak potentials of Pt(Cu)/C and Pt–Ru(Cu)/C were about 0.1 and 0.2 V more negative than those corresponding to Pt/C and Ru-decorated Pt/C. The best conditions for CO oxidation were found for Cu deposition potentials between −0.2 and −0.4 V vs. Ag/AgCl/KCl(sat). The Pt economy of the Pt–Ru(Cu)/C system was proved for the methanol oxidation, with specific currents more than twice those obtained on the Ru-decorated commercial Pt/C catalysts.     

CeO2-supported Pt–Cu alloy nanoparticles synthesized by radiolytic process for highly selective CO oxidation

CeO₂-supported Pt–Cu bimetallic catalysts were synthesized by radiolytic process and their PROX activities were evaluated in relation to structural properties of the catalysts. Irradiating the aqueous precursor solution yielded Pt–Cu alloy nanoparticles and amorphous-like CuO on CeO₂ which are thermodynamically stable products formed from reduced Pt and Cu. Addition of Cu to Pt significantly improved CO selectivity in PROX reaction. The Pt–Cu catalysts had wide temperature window for 100% CO conversion in contrast to very narrow window for monometallic Pt and Cu catalysts. Much lower light-off temperature for Pt–Cu catalysts than Cu catalyst revealed that Pt-Cu alloy surface is the active center. Regardless of the amount of CuO phase, the bimetallic catalyst exhibited high catalytic performance, which further revealed that Cu in close contact with Pt is responsible for the improved selectivity. The CuO phase was suggested to promote oxygen supply to CO chemisorbed on Pt–Cu alloy surface.     

Study on water–gas shift reaction performance using Pt-based catalysts at high temperatures

The water–gas shift reaction (WGSR) performance was experimentally studied using Pt-based catalysts for temperature, time factor and steam to carbon (S/C) molar ratio at ranges of 750–850 °C, 10–20 g_cat h/mol_CO, and 1–5, respectively. Al₂O₃ spheres were used as the catalyst support. For the high S/C cases, it was found that CO conversion can be enhanced when Pt/CeO₂/Al₂O₃ catalyst was used as compared with Pt/Al₂O₃. For the low S/C ratio cases, CO conversion enhancement was not significant with the addition of CeO₂. It was also found that CO conversion was not influenced by the CeO₂ amount to a large extent. Using bimetallic Pt–Ni/CeO₂/Al₂O₃ catalyst, it was found that higher CO conversion can be obtained as compared with CO conversions obtained from monometallic catalysts (Pt/Al₂O₃ or Pt/CeO₂/Al₂O₃). The experimental data also indicated that good thermal stability can be obtained for the Pt-based catalysts studied.     

Comparative study of CeO2/CuO and CuO/CeO2 catalysts on catalytic performance for preferential CO oxidation

The CeO₂/CuO and CuO/CeO₂ catalysts were synthesized by the hydrothermal method and characterized via XRD, SEM, H₂-TPR, HRTEM, XPS and N₂ adsorption–desorption techniques. The study shows that the rod-like structure is self-assembled CeO₂, and both hydrothermal time and Ce/Cu molar ratio are important factors when the particle-like CeO₂ is being self-assembled into the rod-like CeO₂. The CuO is key active component in the CO-PROX reaction, and its reduction has a negative influence on the selective oxidation of CO. The advantage of the inverse CeO₂/CuO catalyst is that it still can provide sufficient CuO for CO oxidation before 200 °C in the hydrogen-rich reductive gasses. The traditional CuO/CeO₂ catalyst shows better activity at lower temperature and the inverse CeO₂/CuO catalysts present higher CO₂ selectivity when the CO conversion reaches 100%. The performance of mixed sample verifies that they might be complementary in the CO-PROX system.     

A novel co-precipitation method for preparation of Pt-CeO2 composites on multi-walled carbon nanotubes for direct methanol fuel cells

Ceria (CeO₂) as co-catalytic material with Pt on multi-walled carbon nanotubes (Pt-CeO₂/MWCNT) is synthesized by a co-precipitation method. The physicochemical characterizations of the catalysts are carried out by using transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) techniques. Electrocatalytic activities of the catalysts for methanol oxidation is examined by cyclic voltammetry and chronoamperometry techniques and it is found that Pt-CeO₂/MWCNT catalysts exhibited a better activity and stability than did the unmodified Pt/MWCNT catalyst. CO-stripping results indicate the facile removal of intermediate poisoning species CO in the presence of CeO₂, which is helpful for CO and methanol electro-oxidation.     

Carbon supported Pt–Pd alloy as an ethanol tolerant oxygen reduction electrocatalyst for direct ethanol fuel cells

A carbon supported Pt–Pd catalyst with a Pt:Pd atomic ratio 77:23 was prepared by reduction of metal precursors with formic acid and characterized by EDX, XRD and XPS techniques. A decrease of the lattice parameter compared with that of pure Pt was observed, indicating the formation of a Pt–Pd alloy. Tests in H₂SO₄ solution in the absence of ethanol showed that the Pd-containing is slightly more active than pure Pt for the oxygen reduction reaction (ORR). In the presence of ethanol a larger increase in overpotential of the ORR on pure Pt than that on Pt–Pd was found, indicating a higher ethanol tolerance of the binary catalyst. The enhanced performance at 90 °C of the direct ethanol fuel cell with Pt–Pd/C as cathode material confirmed the results of half cell tests, and was essentially ascribed to a reduced ethanol adsorption on Pt–Pd.     

CeO2 nanoparticles improved Pt-based catalysts for direct alcohol fuel cells

We developed an ultrasonic co-deposition technique to enhance the activity of Pt/C catalyst (and Pt/CNT, PtRu/C catalysts) for direct alcohol fuel cells (DAFCs) by CeO₂ nanoparticles. The composite catalyst architecture is obtained by an ultrasonically mixing commercial Pt/C catalyst and CeO₂ nanoparticles. Both Pt and CeO₂ are dispersed uniformly in the electrodes resulting in a great deal of CeO₂–Pt–C triple junction interfaces. Unlike traditional preparation of metal oxide supported Pt catalysts, CeO₂ will not cut the connection between Pt and C in this composite catalyst structure. Electrochemical measurements confirm that CeO₂ can improve almost all Pt based catalysts (Pt/C, Pt/CNT, and PtRu/C) for almost all small molecular alcohols (methanol, ethanol, ethylene glycol, and glycerol) electro-oxidation. EIS measurement shows that reaction resistance between Pt and alcohols is decreased much by adding small CeO₂ nanoparticles. Besides, these composite catalysts have high stability. It proves CeO₂ a very promising co-catalyst of Pt based catalysts for DAFCs.     

The effect of Ni:Pt ratio on oxidative steam reforming performance of Pt–Ni/Al2O3 catalyst

Oxidative steam reforming of propane was tested over four Pt–Ni/δ-Al₂O₃ bimetallic catalysts aiming to investigate the effect of metal loadings and Ni:Pt loading ratio on catalyst performance. A trimetallic Pt–Ni–Au/δ-Al₂O₃ catalyst was additionally studied aiming to understand the effect of Au presence. Reaction temperature, carbon to oxygen ratio, and residence time were taken as the reaction parameters. The effect of C/O₂ ratio on the hydrogen production and H₂/CO selectivity was found dependent on the Pt and Ni loadings. The results underlined the importance of C/O₂ ratio as an optimization parameter for product distribution. The highest hydrogen production and H₂/CO ratio levels were obtained for the highest C/O₂ ratio tested. An optimum Ni:Pt weight ratio was found around 50 due to suppressed methanation and enhanced hydrogen production activities of these catalysts. The presence of gold in the trimetallic catalyst caused poor activity and selectivity in comparison to bimetallic catalysts.     

Defect configuration of ceria for Pt anchoring toward efficient methanol oxidation

As a potential next-generation power source for portable electronic devices, commercialization process of direct methanol fuel cell (DMFC) technology is hindered by the high dependence of anode methanol oxidation reaction (MOR) on precious Pt catalyst. In order to improve the efficiency of Pt toward MOR catalysis, a Ni doping strategy is proposed for defect engineering on ceria substrate to achieve uniform dispersion of Pt nanoparticles. Besides, Ni could also act as electron donor for Pt and hence favor the removal of CO intermediate on Pt and act as a co-catalyst toward MOR. Superior MOR activity and great stability is therefore achieved for the as-prepared Pt/CeO₂@Ni catalyst with 3 times higher peak MOR current density compared with Pt/C catalyst. Due to the evenly anchored Pt and enhanced CO oxidation ability caused from Ni doped ceria substrate, Pt utilization of the Pt/CeO₂@Ni catalyst is calculated to be 3.24 times higher than that of the commercial Pt/C catalyst. By considering the significantly improved stability, the Pt/CeO₂@Ni catalyst has the potential for application in DMFC devices.     

Enhanced performance of Ca-doped Pt/γ-Al2O3 catalyst for cyclohexane dehydrogenation

The promotion effects of Ca on catalytic performance of Ca-doped Pt/Al₂O₃ catalyst were investigated by varying Ca content and impregnation orders. The Ca-doped Pt/Al₂O₃ catalyst with atomic rate Ca/Pt = 5 exhibited the highest catalytic activity and stability. Detailed analyses show that low Ca content (Ca/Pt ＜ 5) could not efficiently promote hydrogen spillover from Pt-Al interface to the support and reduce the strong acid sites on the support. However, high Ca content (Ca/Pt > 5) decreases the initial activity due to the coverage of Ca on the support and increases the amount of Pt strongly interacting with Ca, which inhibits Pt reduction. Furthermore, the Ca promotion effect is more pronounced when Ca is added prior to Pt due to surface modification of Ca on Al₂O₃ support. This modified catalyst possesses more dispersed Pt, lower acidity and larger amount of spilled-over hydrogen.     

Preferential oxidation of CO in H2 stream on Au/CeO2–TiO2 catalysts

A series of Au catalysts supported on CeO₂–TiO₂ with various CeO₂ contents were prepared. CeO₂–TiO₂ was prepared by incipient-wetness impregnation with aqueous solution of Ce(NO₃)₃ on TiO₂. Gold catalysts were prepared by deposition–precipitation method at pH 7 and 65 °C. The catalysts were characterized by XRD, TEM and XPS. The preferential oxidation of CO in hydrogen stream was carried out in a fixed bed reactor. The catalyst mainly had metallic gold species and small amount of oxidic Au species. The average gold particle size was 2.5 nm. Adding suitable amount of CeO₂ on Au/TiO₂ catalyst could enhance CO oxidation and suppress H₂ oxidation at high reaction temperature (>50 °C). Additives such as La₂O₃, Co₃O₄ and CuO were added to Au/CeO₂–TiO₂ catalyst and tested for the preferential oxidation of CO in hydrogen stream. The addition of CuO on Au/CeO₂–TiO₂ catalyst increased the CO conversion and CO selectivity effectively. Au/CuO–CeO₂–TiO₂ with molar ratio of Cu:Ce:Ti = 0.5:1:9 demonstrated very high CO conversion when the temperature was higher than 65 °C and the CO selectivity also improved substantially. Thus the additive CuO along with the promoter and amorphous oxide ceria and titania not only enhances the electronic interaction, but also stabilizes the nanosize gold particles and thereby enhancing the catalytic activity for PROX reaction to a greater extent.     

In-situ investigation on the CO tolerance of carbon supported Pd–Pt electrocatalysts with low Pt content by electrochemical impedance spectroscopy

Carbon supported Pd–Pt electrocatalysts (Pd–Pt/C) with low Pt content were investigated in proton exchange membrane fuel cells (PEMFCs) with pure H₂ and CO/H₂ as the feeding fuels, respectively. The Pd–Pt/C catalysts showed high activity for hydrogen oxidation reaction (HOR) and improved CO tolerance. Electrochemical impedance spectroscopy (EIS) was employed to probe the in-situ information of the improved CO tolerance. The dependence of Nyquist plots and Bode plots on current density and feeding gas was investigated in low polarization region. The results of EIS analysis indicated that the improved CO tolerance of Pd–Pt/C catalysts can be attributed to the lower coverage of CO on the Pd–Pt bimetal than that on the pure Pt.     

A novel Rh–Ir electrocatalyst for the oxygen reduction reaction and the hydrogen and methanol oxidation reactions

A novel Rh–Ir based material was synthesized by pyrolysis of an Ir₄(CO)₁₂/Rh₆(CO)₁₆ mixture in a reductive (H₂) atmosphere. The material was characterized by FTIR spectroscopy, X-ray diffraction, energy dispersive spectroscopy and scanning electron microscopy, and was evaluated as electrocatalyst for oxygen reduction and hydrogen and methanol oxidation by rotating disk electrode measurements. The bimetallic material shows a high catalytic activity for the oxygen reduction reaction and is also capable to carry out the hydrogen oxidation reaction even in the presence of carbon monoxide in different concentrations (100 ppm and 0.5%), in contrast with commercial platinum catalysts, which become easily deactivated by CO. The activity of the catalyst for methanol oxidation is acceptable but still low in comparison with Pt–Ru. The results show that the new bimetallic catalyst is a potential candidate to be evaluated as both cathode and anode in a reforming hydrogen PEMFC, and as an anode in a direct methanol fuel cell.     

Selective CO oxidation on Cu promoted Pt/Al2O3 and Pt/Nb2O5 catalysts

Pt–Cu catalysts supported on Al₂O₃ and Nb₂O₅ were studied for use in selective CO oxidation. The addition of copper enhanced the activity and selectivity of Pt–Cu/Nb₂O₅ at lower temperatures when compared to Pt/Nb₂O₅. On the other hand, copper addition was not beneficial in the case of Al₂O₃ supported catalysts.     

Effect of polyoxometalate amount deposited on Pt/C electrocatalysts for CO tolerant electrooxidation of H2 in polymer electrolyte fuel cells

Polyoxometalate-deposited Pt/C electrocatalysts are prepared by impregnation with various amounts of polyoxometalate (POM) anions (from 2 to 16.7 wt.% PMo₁₂O₄₀^3–) on the Pt/C catalyst. The prepared electrocatalysts show a high CO electrooxidation performance over a half-cell system for CO stripping voltammetry, and CO tolerant electrooxidation of H₂ is further demonstrated over a proton exchange membrane fuel cell by using CO-containing H₂ gas feeds (0, 10, 50, and 100 ppm CO in H₂). In the CO stripping voltammograms, the onset and peak potentials for the CO oxidation appear to decrease as the POM deposition is increased, indicating that the electrooxidation of CO undergoes more efficiently on the catalyst surface with the deposited POMs on the Pt/C catalysts. In the single fuel cell tests with the CO-containing H₂ gases, the higher current density is also generated with the larger amounts of deposited POMs on the Pt/C catalysts. Importantly, the charge transfer resistance R_p appears to decrease monotonically with the POM amounts, which was measured by electrochemical impedance spectroscopy. Physico-chemical characterizations with electrocatalytic analyses show that the deposited POMs hardly affect the active phase of Pt catalyst itself but can help the electrooxidation of H₂ by efficiently oxidizing CO to prevent the Pt catalyst from poisoning. Consequently, this POM-deposited Pt/C catalyst can serve as a promising CO tolerant anode catalyst for the polymer electrolyte fuel cells that are operated with hydrocarbons-reformed H₂ fuel gases.