Electrodepositing Pt on a Nafion-bonded carbon electrode as a catalyzed electrode for oxygen reduction reaction

The research aims to increase the utilization of platinum (Pt) catalysts and thus to lower the catalyst loadings in the electrode for oxygen reduction reaction (ORR). The electrodeposition of Pt was performed on a rotation disk electrode (RDE) of glass carbon (GC), on which a layer of Nafion-bonded carbon of Vulcan XC 72R was dispersed in advance. The behaviors of Pt RDE and GC RDE in an aqueous solution containing HCl and H₂PtCl₆ were firstly studied. It was found that Pt deposition could be achieved if the electrode potential is controlled below −0.20 V versus (saturated-potassium-chloride silver chloride electrode) SSCE. However, quite a high overpotential is necessary if a quick and apparent deposition were required. Unfortunately, at a high overpotential, the hydrogen evolution would be unavoidable and even accelerated by the formation of nanometer size of Pt particles on the RDE. It was found that it is futile to increase platinum deposits just through extending the deposition time. It was also found that too large deposition current is not helpful for increase of platinum deposition because most of the current was consumed on hydrogen evolution in this case. It has been confirmed that it is conducive to richen Pt ions, present in the form of anionic complex in solution, onto the working electrode to be deposited. It is also helpful to eliminate the hydrogen bubbles formed on the working electrode, i.e., uncatalyzed carbon electrode (UCE), by imposing a positive current on the UCE for a length of time in advance of each cathodic deposition. The potential changes during deposition were recorded. Cyclic voltammograms (CV) of electrodes in 0.5 M H₂SO₄ before and after the deposition were used to assess loading of metal catalysts in a wide range of potential from −0.20 to 1.1 V versus SSCE. The results have shown that the performance of such an electrode with loadings estimated to be 50 μg Pt/cm² is much better than those of a conventional electrode with loadings of 100 μg Pt/cm².     

Rapid optical screening technology for direct methanol fuel cell (DMFC) anode and related electrocatalysts

We describe here the development of an optical high-throughput screening method for direct methanol fuel cell catalysts based on the fluorescence of protonated quinine generated during electro-oxidation of methanol. The design of the working electrode allows the parallel quantification of the fluorescence development for up to 60 materials. For the preparation of the working electrode a coating routine has been developed, which allows the use of sol–gel derived materials. Due to the required stability of the electrode catalysts towards the acidic polymer membrane, a fast optical pre-screening method for acid stable materials has been developed. The electrochemical high-throughput system has been validated with Pt-Ru catalysts. Automation of data acquisition and data processing led to a fast and reliable high-throughput screening setup.     

Experimental and density functional theory studies on PtPb/C bimetallic electrocatalysts for methanol electrooxidation reaction in alkaline media

Carbon-supported bimetallic Pt_mPb₁ (m = 1, 2, 3) electrocatalysts with different Pt/Pb atomic ratios were synthesized by a polyol method. The X-ray diffraction results reveal that a PtPb alloy formed in the Pt_mPb₁/C electrocatalysts. TEM images show that the PtPb nanoparticles distribute uniformly on the carbon support, and are about 4–5 nm in size. The Pt_mPb₁/C bimetallic catalysts show superior activities toward methanol electrooxidation reaction (MOR) than the Pt/C in alkaline media. Both CO stripping measurements and density functional theory studies reveal that CO adsorption decreased significantly on the Pt_mPb₁/C bimetallic catalysts compared with on pure Pt, which may offer an explanation for the enhanced MOR activity of the Pt_mPb₁/C bimetallic catalysts.     

Development of bifunctional Mo doped ZnAl2O4 spinel nanorods array directly grown on carbon fiber for supercapacitor and OER application

Electrochemical energy storage and water splitting strategies may be greatly improved with proper structural design and doping techniques. In the present study, molybdenum-doped ZnAl₂O₄ loaded on carbon fiber (Mo–ZnAl₂O₄/CF) was fabricated via a simple hydrothermal synthetic approach. Due to its unique hierarchical nanostructures and enhanced electrical, structural topologies, Mo-doped ZnAl₂O₄ demonstrates exceptional supercapacitor performance and electrocatalytic oxygen evolution reaction activity. The Mo-doped ZnAl₂O₄ electrode material exhibited 1477.63 F g^?1 specific capacitance, 46.57 Wh Kg^?1 specific energy and specific power of 476.4 W kg^?1 at 1 A g^?1. After 5000 cycles, the pseudo supercapacitor retains 97.46% of its capacitance and displays stable behavior over 50 h. During the OER reaction, the Mo–ZnAl₂O₄/CF as an electrocatalyst rapidly self-reconstructs, resulting in many oxygen vacancies, and causes a lower 38 mV dec^?1 Tafel slope and overpotential potential of 255 mV to achieved 10 mA cm^?2 current flow and responsible for the excellent stability of the electrocatalyst. These findings suggest that multifunctional materials based electrode for electrical energy conversion and storage become more efficient and stable by using Mo for doping to generate porous hierarchical structures and local amorphous phases.     

Hollow graphitic carbon spheres for Pt electrocatalyst support in direct methanol fuel cell

Hollow graphitic carbon spheres (HGCSs) with a high surface area are produced by the carbonization of hollow polymer spheres obtained by the polymerization of core/shell-structured pyrrole micelles. HGCSs are employed as a carbon support material in a direct methanol fuel cell catalyst, and their effect on the electrocatalytic activity toward methanol oxidation is investigated. Pt catalyst supported on HGCSs shows a better electrocatalytic activity compared to that on Vulcan XC-72, which has been commonly used in fuel cell catalysts. The observed enhancement in the electrocatalytic activity is attributed to the improved electronic conductivity and high surface area of HGCSs.     

Model interpretation of electrochemical impedance spectroscopy and polarization behavior of H2/CO mixture oxidation in polymer electrolyte fuel cells

A mathematical model is proposed based on electrode kinetics analysis for the oxidation of 2% CO+H₂ mixture in polymer electrolyte fuel cells. Successful simulation of the polarization curve and experimental impedance spectra for Pt/C electrode system confirm the validity of the model which shows that the impedance is strongly dependent on electrode potential. With the increase of potential, an inductive behavior will occur. It is believed that the appearance of this inductive pattern can be used as a criterion for the onset of CO oxidation by the coincidence of the potential at which inductive behavior occurs with the ignition potential for CO oxidation. The effects of change of CO oxidation rate constant and CO adsorption equilibrium constant on impedance pattern, as well as on CO surface coverage and Faradaic current are also delineated with the use of the proposed model.     

Palygorskite Hybridized Carbon Nanocomposite as PtRuIr Support for the Methanol Oxidation Reaction

A palygorskite/carbon heterogeneous nanocomposite, a unique hybrid of palygorskite and carbon, was prepared and designed as an electrocatalyst support material for PtRuIr nanoparticles and evaluated for methanol electrooxidation. X‐ray diffraction and transmission electron microscopy results showed that PtRuIr nanoparticles were well‐dispersed on the composite support with highly dispersed tiny crystal alloy phase on the surface of PtRuIr amorphous alloy. X‐ray photoelectron spectroscopy results indicated that the formation of Ru and Ir oxides on the surface of the PtRuIr nanoparticles. The electrochemical results show that the palygorskite hybridized carbon used as electrocatalysts support can improve the electrocatalytic activity towards methanol oxidation and CO tolerance.     

Recent advances in metals and metal oxides as catalysts for vanadium redox flow battery:Properties,structures,and perspectives

Vanadium redox flow battery(VRFB)is a kind of battery with wide application prospect.Electrode mate-rial is one of the key components of VRFB,and its stability directly affects the performance of battery.Among all kinds of electrode materials,carbon-based material has the best comprehensive properties.However,carbon-based electrodes still have disadvantages such as poor hydrophilicity and low electro-chemical activity which need to be improved.One of the effective ways to improve the performance of electrode is to modify carbon-based material with metals and metal oxides.The metal catalysts have excellent electrical conductivity and high catalytic activity.The metal oxide catalysts have the advan-tages of low cost,wide variety and strong oxidizing properties.This work introduced the application of metal and metal oxide modified electrodes in VRFB in recent years,classified the catalysts,studied their catalytic performance and mechanism.The metal catalysts were reviewed from precious metals and base metals.The metal oxide catalysts were classified and discussed according to the similar proper-ties of the same group elements.This work compared different modification methods,summarized the research progress of metal and metal oxide modification,and proposes the future development direction of electrodes and catalysts.     

固体聚合物电解质水电解催化剂的研究进展

鉴于固体聚合物电解质(SPE)水电解技术的发展现状,着重介绍了目前在SPE水电解析氢、析氧催化剂方面的研究进展,对催化剂的制备方法进行了分析,并对近来以纳米氮化钛粉体为前驱体通过浸渍—热分解法制备水电解催化剂的研究工作进行了总结,提出了开发高耐蚀性的催化剂载体和降低贵金属载量是SPE水电解催化剂的重要发展方向。     

石墨烯负载Pt-Co纳米粒子及其在氧化还原反应中的应用

采用微波-乙二醇方法还原氧化石墨烯和Pt(v)、Co(Ⅱ)粒子混合物,再经300℃H2还原,制备了石墨烯负载Pt-Co合金催化剂(Pt-Co/G).利用透射电镜、X-射线能谱、X-射线衍射和光电子能谱对所制催化剂进行表征.Pt-Co合金的粒径为3nm～8 nm,均匀地分散在石墨烯片上.与单金属的Pt/G和商品化的Pt/C催化剂相比,所制合金化的Pt-Co/G催化剂对氧还原反应展现出高的催化活性和可比拟的稳定性,显示了其在燃料电池中的应用潜力.