Preparation of PtSnSb/C by an alcohol reduction process for direct ethanol fuel cell (DEFC)

PtSn/C and PtSnSb/C electrocatalysts (20 wt.% metal loading) were prepared by an alcohol reduction process using H₂PtCl₆.6H₂O, SnCl₂.2H₂O, and Sb(OOCCH3) as metal sources, ethylene glycol as solvent and reducing agent, and Vulcan XC72 as carbon support. The electrocatalysts were characterized by energy dispersive X-ray analysis, X-ray diffraction, and transmission electron microscopy, while that the performance for ethanol oxidation was investigated by cyclic voltammetry and chronoamperommetry (chrono) at room temperature. The diffractograms of the PtSn/C and PtSnSb/C electrocatalysts showed four peaks associated to Pt face-centered cubic structure and two peaks that were related to a SnO₂ phase. For PtSb/C and PtSnSb/C electrocatalysts, no Sb (antimony) peaks corresponding to a metallic antimony or antimony oxide phases were observed. Transmission electron microscopy images showed that the metal particles were homogeneously distributed over the support. The PtSnSb/C (50:45:05) electrocatalyst showed an increase of performance for ethanol oxidation in relation to PtSn/C electrocatalyst at room temperature. In the tests at 100 °C on a single cell of a direct ethanol fuel cell, the maximum power density of PtSnSb/C (50:45:05) electrocatalyst was slightly higher than that of PtSn/C electrocatalyst.     

Oxygen Electroreduction by Single PtPd Nanocubes Encaged in Hollow Carbon Nanospheres: Improved Durability and Strong Effect of Carbon‐Shell Thickness

As a cathode reaction in fuel cells, oxygen reduction reaction (ORR) plays a critical role in determining the overall performance of a fuel cell. It is still a big challenge to find effective ways to improve the catalytic activity, efficiency, and especially stability of ORR electrocatalysts. In the present study, single nanoparticle electrocatalysis for ORR is realized for the first time by encaging PtPd nanocube in hollow and porous carbon nanosphere (PtPd@HCS). Through tuning the carbon‐shell thickness by carbonization temperature, the effects of carbon‐shell thickness on ORR catalytic performance of PtPd@HCS are systematically investigated. The PtPd@HCS calcinated at 800 °C (PtPd@HCS‐800) with the thinnest carbon shell (3.52 nm) and rich pore structure exhibits enhanced ORR catalytic activity and stability. The strategy mentioned here is expected to provide a new method to design single nanoparticle electrocatalysts for fuel cells with high catalytic performance and reduced loading of precious metals.     

A Self‐Assembly Route to an Iron Phthalocyanine/Reduced Graphene Oxide Hybrid Electrocatalyst Affording an Ultrafast Oxygen Reduction Reaction

Graphene oxide (GO) is an attractive freestanding support that can be decorated with ultrathin organic layers for facile and low‐cost fabrication of novel devices with controllable functional properties and microstructures. Here, it is reported that a hybrid material consisting of an ultrathin iron phthalocyanine (FePc) layer self‐assembled on reduced graphene oxide (rGO) exhibits excellent catalytic activity that is superior to that of commercial Pt/C for an oxygen reduction reaction (ORR). During solution processing, the FePc layer is first self‐organized onto GO sheets and then reduced electrochemically to form an FePc/rGO hybrid electrocatalyst. Kinetics studies reveal that the hybrid architecture affords an ultrafast ORR rate caused by a strongly dominant four‐electron process, and the durability of the catalyst shows significant improvement by forming the hybrid structure. Spectroscopic studies suggest that these advantages are afforded by synergistic effects between FePc and rGO, which are enriched by the hybrid structure and the appropriate reduction step.     

A high-throughput search for direct methanol fuel cell anode electrocatalysts of type PtxBiyPbz

We used a high-throughput method to screen for direct methanol fuel cell anode electrocatalysts in the Pt-Bi-Pb system. Previous studies showed that PtBi and PtPb (both NiAs structure type) were active electrocatalysts for the oxidation of formic acid, but only PtPb was active in oxidizing methanol. We synthesized thin films with continuous composition spreads of the three elements by magnetron sputtering at deposition temperatures from ambient to 510 °C. A fluorescence method was then used to identify compositions that were active toward methanol oxidation. Only films deposited between temperatures of 160 and 400 °C showed electrocatalytic activity. The areas that were active for methanol oxidation showed predominantly the NiAs structure type according to XRD, with optimal activity for compositions near PtBi_0.01Pb_0.53.     

Deactivation of carbon supported palladium catalyst in direct formic acid fuel cell

A new carbon black supported palladium catalyst for direct formic acid fuel cell applications has been prepared and characterized by X-ray diffraction. Bi-modal distribution of Pd crystallite sizes was observed. The average Pd size for crystallites in small size and large size ranges were about 2.7 nm and 11.2 nm, respectively. The initial activity of the catalyst in the oxidation of formic acid tested in a fuel cell was similar to a commercial well dispersed 20 wt.% Pd/Vulcan. The rates of the fuel cell power decay were measured for formic acid of two purities for various current loadings. The results showed that various mechanisms contribute to the decrease of cell power with time. In direct formic acid fuel cell (DFAFC) fed with a very pure HCOOH accumulation of CO₂ gas bubbles in anode catalyst layer is responsible for observed power decay. In DFAFC fed with a pure for analysis (p.a.) grade formic acid the formation of CO_ads poison from the formic acid impurities is the main deactivation reason.     

Efficient electrocatalysis of formic acid oxidation onto Pd-Cu/poly (2-methoxyaniline)-SDS nanocomposite film

In this work, porous poly (2-methoxyaniline) film prepared in the presence of sodium dodecyl sulfate (P2MA-SDS) is used as a potent support for dispersion of bimetallic palladium-copper nanoparticles (Pd-Cu NPs) towards the electrooxidation of formic acid (HCOOH) in sulfuric acid solution. The Pd-Cu NPs are prepared through galvanic replacement reaction between Pd^II ions and Cu particles. The SEM, EDS, and electrochemical methods were used to characterize the prepared Pd-Cu NPs. The obtained results show that the Pd-Cu exhibited significantly high current density of HCOOH oxidation compared to other catalysts and utilization of Cu NPs enhances the electrocatalytic activity towards electrooxidation. The enhanced performance is related to the synergetic effect between Pd-Cu NPs and P2MA-SDS film. The effects of galvanic replacement time, potential sweep rates, and concentration of HCOOH on the catalytic activity of the electrocatalyst as well as long-term stability are investigated by the various electrochemical techniques.     

Effect of Ni proportion on the performance of proton exchange membrane fuel cells using PtNi/C electrocatalysts

PtNi/C electrocatalysts were synthesised by borohydride method on functionalised carbon support. Energy-dispersive X-ray spectroscopy, X-ray diffraction, transmission electron microscopy and both cyclic and linear voltammetry were employed to characterise the composition, crystalline structure, morphology and catalytic properties of the PtNi/C electrocatalysts. Different Ni proportions in the PtNi/C electrocatalysts were evaluated in the cathode or anode in a H₂/air proton exchange membrane fuel cells (PEMFC) by polarisation curves. PtNi particles uniformly dispersed with different proportions of metals obtained. The increase of Ni proportion in the electrocatalyst led to materials with higher mass activity values toward the oxygen reduction reaction and a greater electrochemical-active surface area. PtNi/C electrocatalysts in the cathode presented higher mass activity values at high potential in the PEMFC. The best PEMFC performance was obtained with PtNi 13 at.% Ni (cathode) and Pt/C (anode) relative to the Pt/C (cathode and anode) with identical Pt loadings. PtNi/C electrocatalysts in PEMFC may be used as an alternative to Pt/C electrocatalyst.     

Co9S8 Nanoparticles Incorporated in Hierarchically Porous 3D Few‐Layer Graphene‐Like Carbon with S,N‐Doping as Superior Electrocatalyst for Oxygen Reduction Reaction

Electrochemical oxygen reduction reaction (ORR), using nonprecious metal catalysts, has attracted great attention due to the importance in renewable energy technologies, such as fuel cells and metal–air batteries. A simple and scalable synthetic route is demonstrated for the preparation of a novel 3D hybrid nanocatalyst consisting of Co₉S₈ nanoparticles which are incorporated in N,S‐doped carbon (N, S–C) with rational structure design. In particular, the hybrid catalyst is prepared by direct pyrolysis and calcination of a gel mixture of Mg,Co nitrate‐thiourea‐glycine under Ar atmosphere, with subsequent HCl washing. The properties of obtained hybrid catalyst are quite dependent on calcination temperature and added glycine amount. Under a molar ratio of Co5‐Mg15‐tu10‐gl45 and a calcination temperature of 900 °C, Co₉S₈ nanoparticles are embedded in a well‐developed carbon matrix which shows a porous 3D few‐layer graphene‐like N, S–C with open and hierarchical micro–meso–macro pore structure. Because of the synergistic effect between Co₉S₈ nanoparticles and well‐developed carbon support, the composite exhibits high ORR activity close to that of commercial Pt/C catalyst. More importantly, the composite displays superior long‐term stability and good tolerance against methanol. The strategy developed here provides a novel and efficient approach to prepare a cost‐effective and highly active ORR electrocatalyst.     

Ceramic materials as supports for low-temperature fuel cell catalysts

The performance and durability of low-temperature fuel cells seriously depend on catalyst support materials. Catalysts supported on high surface area carbons are widely used in low temperature fuel cells. However, the corrosion of carbonaceous catalyst-support materials such as carbon black has been recognized as one of the causes of performance degradation of low-temperature fuel cells, in particular under repeated start-stop cycles or high-potential conditions. To improve the stability of the carbon support, materials with a higher graphitic character such as carbon nanotubes and carbon nanofibers have been tested in fuel cell conditions. These nanostructured carbons show a several-fold lower intrinsic corrosion rate, however, do not prevent carbon oxidation, but rather simply decrease the rate. Due their high stability in fuel cell environment, ceramic materials (oxides and carbides) have been investigated as carbon-substitute supports for fuel cell catalysts. Moreover, the higher specific electrocatalytic activity of some ceramic supported metals than unsupported and carbon supported ones, suggests the possibility of a synergistic effect by supporting metal catalyst on ceramic supports. This paper presents an overview of ceramic materials tested as a support for fuel cell catalysts, with particular attention addressed to the electrochemical activity and stability of the supported catalysts.     

石墨烯基PtCu二元金属催化剂对甲醇吸附性能的理论研究

直接甲醇燃料电池作为最有潜力的能源越来越受到人们的关注。本文主要采用密度泛函理论（DFT),对石墨烯基PtCu催化剂吸附甲醇的结构进行了理论研究。通过分析甲醇吸附前后前线分子轨道、电荷和吸附能的变化,发现PtCu二元金属催化剂与甲醇相互作用中,甲醇容易吸附于Pt位点上。对于PtCu二元金属的Cu位点的吸附能力与纯Cu相比变化不大,但是PtCu二元金属的Pt位点相对于纯Pt催化剂对甲醇的吸附能力却有明显的提高。因此Cu的掺杂对于提高Pt位点的活性起到促进作用     

Role of Acid Treatment of the Carbon Support in the Growth of Atomic-Layer-Deposited Pt Nanoparticles for PEMFC Fabrication

Ultrathin films or particles of atomic layer deposition (ALD) on high surface can improve the activity and durability of catalyst fields, so depending on the surface state, the ALD growth mechanism on porous materials should be systematically investigated and optimized to improve their characteristics of catalysts. Herein, a Pt catalyst used in polymer electrode membrane fuel cell (PEMFC) applications is synthesized through fluidized-bed-reactor ALD on carbon black whose surface is modified through treatment with citric acid. The functional groups, analyzed through X-ray photoelectron spectroscopy (XPS), are found to be maximized after 60 min of acid treatment with stirring. Compared with bare carbon (untreated), the acid-treated carbon presents rich oxidized functional groups and abundant defects but lower surface areas and pore volumes. After ALD Pt deposition, highly dense, uniform, and well-dispersed Pt nanoparticles (NPs) are observed on the carbon black subjected to acid treatment, because of the favorable surface modifications for ALD growth resulting from the acid treatment. The ALD-Pt NPs on the acid-treated carbon exhibit larger electrochemical active surface areas, improved oxygen reduction reactions, and PEMFC performances, when compared with that of NPs on bare carbon with similar Pt weight loading.     

Substrate‐Induced Synthesis of Nitrogen‐Doped Holey Graphene Nanocapsules for Advanced Metal‐Free Bifunctional Electrocatalysts

The development of efficient metal‐free electrocatalysts for oxygen electrocatalysis is of great significance for various energy conversion devices. Herein, novel nitrogen‐doped holey graphene nanocapsules (NHGNs) are reported prepared by self‐assembly of graphene oxide nanosheets on the surface of amino‐functionalized silica template and NH₃ activation with simultaneously enhanced nitrogen doping and etching of nanopores in graphene, followed by template etching. The silica template is demonstrated to show a substrate‐enhanced effect on nitrogen doping and etching of nanopores in graphene based on density functional theory calculations. Benefiting from the large surface area, unique pore distribution, and high surface functionality of nitrogen doping, the resulting NHGNs exhibit superior bifunctional electrocatalytic activity and durability for both oxygen reduction reaction and oxygen evolution reaction, which is similar to that of the commercial Pt/C and RuO₂ electrocatalysts, respectively. This work presents an advance in developing new nitrogen‐doped graphene species for highly efficient metal‐free electrocatalysis.     

NiWO3 Nanoparticles Grown on Graphitic Carbon Nitride (g‐C3N4) Supported Toray Carbon as an Efficient Bifunctional Electrocatalyst for Oxygen and Hydrogen Evolution Reactions

Catalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are at the heart of water oxidation reactions. Despite continuous efforts, the development of OER/HER electrocatalysts with high activity at low cost remains a big challenge. Herein, a composite material consisting of TC@WO₃@g‐C₃N₄@Ni‐NiO complex matrix as a bifunctional electrocatalyst for the OER and HER is described. Though the catalyst has modest activity for HER, it exhibits high OER activity thereby making it a better nonprecious electrocatalyst for both OER and HER and is further improved by g‐C₃N₄. The catalytic activity arises from the synergetic effects between WO₃, Ni‐NiO, and g‐C₃N₄. A Ni‐NiO alloy and WO₃ nanoparticles decorated on the g‐C₃N₄ surface supported toray carbon (TC) matrix (TC@WO₃@g‐C₃N₄@Ni‐NiO) by a facile route that show an excellent and durable bifunctional catalytic activity for OER and HER in the alkaline medium are developed. This carbon nitride with binary metal/metal‐oxide matrix supported with TC exhibit an overpotential of 0.385 and 0.535 V versus RHE at a current density of 10 mA cm^?2 (Tafel slopes of 0.057 and 0.246 V dec^?1 for OER and HER, respectively), in 0.1 m NaOH . The catalyst is tested in water electrolysis for 17 h.     

Nitrogen‐Doped Carbon with Mesopore Confinement Efficiently Enhances the Tolerance,Sensitivity, and Stability of a Pt Catalyst for the Oxygen Reduction Reaction

Electrocatalysts for the oxygen reduction reaction (ORR) present some of the most challenging vulnerability issues reducing ORR performance and shortening their practical lifetime. Fuel crossover resistance, selective activity, and catalytic stability of ORR catalysts are still to be addressed. Here, a facile and in situ template‐free synthesis of Pt‐containing mesoporous nitrogen‐doped carbon composites (Pt‐m‐N‐C) is designed and specifically developed to overcome its drawback as an electrocatalyst for ORR, while its high activity is sustained. The as‐prepared Pt‐m‐N‐C catalyst exhibits high electrocatalytic activity, dominant four‐electron oxygen reduction pathway, superior stability, fuel crossover resistance, and selective activity to a commercial Pt/C catalyst in 0.1 m KOH aqueous solution. Such excellent performance benefits from in situ covalent incorporation of Pt nanoparticles with optimal size into N‐doped carbon support, dense active catalytic sites on surface, excellent electrical contacts between the catalytic sites and the electron‐conducting host, and a favorable mesoporous structure for the stabilization of the Pt nanoparticles by pore confinement and diffusion of oxygen molecules.     

Exploration of bimetallic Pt-Pd/C nanoparticles as an electrocatalyst for oxygen reduction reaction

In this study, carbon supported Pt and Pt-Pd were synthesized as oxygen reduction reaction electrocatalysts for polymer electrolyte membrane fuel cells (PEMFCs). Pt and Pt-Pd nanoparticles have been synthesized by reduction of metal precursors in presence of NaBH₄. Various techniques such as X-ray diffraction (XRD), energy dispersive X-ray analysis (EDX) and scanning electron microscopy (SEM) were utilized to study the prepared samples. Furthermore, electrochemical properties of the prepared samples were evaluated from cyclic voltammetry (CV), linear sweep voltammetry (LSV), chronoamperometry and electrochemical impedance spectroscopy (EIS). The results showed, the crystallite size of electrocatalysts (Pt and Pt-Pd) is below 10 nm. The higher catalytic activity was detected for Pt-Pd/C electrocatalyst for oxygen reduction reaction (ORR). In addition, it is believed that the better performance of electrocatalyst is related to the synergic effect between Pt and Pd nanoparticles, weakening of the OO bond on Pd-modified Pt nanoparticles in ORR, uniform dispersion of Pd and Pt on the carbon support and higher electrochemical active surface area (EAS) of Pt-Pd/C electrocatalyst.     

Metal–Organic Framework Supported Palladium Nanoparticles: Applications and Mechanisms

Heterogeneous palladium (Pd)‐based catalysts are extensively applied to improve the catalytic performance and/or expand the reaction scope in many catalytic processes, involving the cross‐coupling, hydrogenation, reduction, and oxidation reactions. Among them, metal–organic framework (MOF)‐supported Pd nanoparticles (Pd NPs) are becoming the most popular one for their excellent catalytic performance and reusable property. To motivate the development of this technology, the applications of MOF‐supported Pd NPs (Pd NPs/MOFs) in heterogeneous catalysis are critically summarized herein, including the hydrogenation reduction of nitro‐ and polyunsaturated compounds, synthesis of carbon–carbon (C? C) bonds compounds, chromium (Cr(VI)) reduction, dehalogenation, alcohol oxidation, CO₂ conversion, and CO oxidation. The influences of base, solvents, electron character of substitutes, and type of halogen on the catalytic performance are comprehensively discussed. Finally, the application prospects of Pd NPs/MOFs and existing shortcomings in the catalytic field are proposed.     

Preparation of PdAu/C-Sb2O5·SnO2 electrocatalysts by borohydride reduction process for direct formic acid fuel cell

Pd/C-Sb₂O₅·SnO₂ and PdAu/C-Sb₂O₅·SnO₂ electrocatalysts with different PdAu atomic ratio (90:10, 70:30, and 50:50) were prepared by borohydride reduction method, and characterized by X-ray diffraction, transmission electron microscopy, cyclic voltammetry, chronoamperommetry, and performance test on direct formic acid fuel cell at 100 °C. X-ray diffraction showed for Pd/C-Sb₂O₅·SnO₂ the presence of Pd face-centered cubic (fcc) system, while for PdAu/C-Sb₂O₅·SnO₂ it showed the presence of Pd fcc phase, PdAu fcc alloys and a segregated phases fcc Pd-rich and Au-rich phases. TEM micrographs and histograms for all electrocatalysts showed that the nanoparticles where not well dispersed on the support and some agglomerates were present. The electrochemical studies showed that PdAu/C-Sb₂O₅·SnO₂ (70:30) had superior performance for formic acid electro-oxidation at 25 °C compared to others electrocatalysts prepared while PdAu/C-Sb₂O₅·SnO₂ (90:10) showed superior performance in direct formic acidic fuel cell at 100 °C. These results indicated that the addition of 10–30 % Au to Pd favor the electro-oxidation of formic acid. This effect could be attributed to the synergy between the constituents of the electrocatalyst (metallic Pd and Au, SnO₂, and Sb₂O₅·SnO₂).     

Carbon‐Doped Metal Oxide Nanoparticles Prepared from Metal Nitrates in Supercritical CO2‐Enabled Polymer Nanoreactors

Various C‐doped metal oxide nanoparticles (NPs) are prepared from metal nitrates in poly‐(methyl vinyl ether‐co‐maleic anhydride) (PVM/MA) nanoreactors. The loading of metal nitrates in the nanoreactors is realized via a process of solution‐enhanced dispersion by supercritical CO₂. When the temperature exceeds the thermal decomposition temperature of the nitrates, the nitrates‐loaded nanoreactors transform into C‐doped metal oxide NPs. ZnO, NiO, and Co₃O₄ NPs as representative of the doped oxides are successfully fabricated. A precise control over the doping concentration and doping site in the lattice is achieved by changing the mass ratio between PVM/MA and metal nitrate. The controllable carbon doping avoids undesirable aggregation of carbon species and metal oxide NPs, endows the NPs with broad and strong absorption bands in the visible light region, and creates channels for separation of photo‐generated electrons and holes. In this regard, the resultant C‐doped metal oxide NPs exhibit excellent photocatalytic, photo‐induced antibacterial, and photothermal performances.     

Electro-oxidation of ethylene glycol on PtSn/C and PtSnNi/C electrocatalysts

A PtSn/C electrocatalyst with a Pt–Sn molar ratio of 50:50 and A PtSnNi/C electrocatalyst with a Pt–Sn–Ni molar ratio of 50:40:10 were prepared by alcohol-reduction process using ethylene glycol as solvent and reducing agent. The electrocatalysts were characterized by energy dispersive X-ray, X-ray diffraction, and cyclic voltammetry. The electro-oxidation of ethylene glycol was studied by cyclic voltammetry and chronoamperometry using the thin porous coating technique. PtSnNi/C electrocatalyst showed a superior performance compared to PtSn/C electrocatalysts in the potential range of interest for a direct ethylene glycol fuel cell.     

Quantifying phosphoric acid in high‐temperature polymer electrolyte fuel cell components by X‐ray tomographic microscopy

Synchrotron‐based X‐ray tomographic microscopy is investigated for imaging the local distribution and concentration of phosphoric acid in high‐temperature polymer electrolyte fuel cells. Phosphoric acid fills the pores of the macro‐ and microporous fuel cell components. Its concentration in the fuel cell varies over a wide range (40–100 wt% H₃PO₄). This renders the quantification and concentration determination challenging. The problem is solved by using propagation‐based phase contrast imaging and a referencing method. Fuel cell components with known acid concentrations were used to correlate greyscale values and acid concentrations. Thus calibration curves were established for the gas diffusion layer, catalyst layer and membrane in a non‐operating fuel cell. The non‐destructive imaging methodology was verified by comparing image‐based values for acid content and concentration in the gas diffusion layer with those from chemical analysis.