Fabrication of a Hierarchical Ni(OH)2@Ni3S2/Ni Foam Electrode from a Prussian Blue Analogue-Based Composite with Enhanced Electrochemical Capacitive and Electrocatalytic Properties

Developing high-efficiency, cost-effective, and durable electrodes is significant for electrochemical capacitors and electrocatalysis. Herein, a 3D bifunctional electrode consisting of nickel hydroxide nanosheets@nickel sulfide nanocubes arrays on Ni foam (Ni(OH)₂@Ni₃S₂/NF) obtained from a Prussian blue analogue-based precursor is reported. The 3D higher-order porous structure and synergistic effect of different compositions endow the electrode with large specific surface area, facile ion/electron transport path, and improved conductivity. As a result, the Ni(OH)₂@Ni₃S₂/NF electrode exhibits a high specific capacity of 211 mA h g⁻¹ at a current density of 1 A g⁻¹ and 73 % capacity retention after 5000 cycles at 5 A g⁻¹. Moreover, the Ni(OH)₂@Ni₃S₂/NF electrode has superior electrocatalytic activity for the hydrogen evolution reaction with low overpotentials of 140 and 210 mV at current densities of 10 and 100 mA cm⁻², respectively. The synthetic strategy for the unique higher-order porous structure can be extended to fabricate other composite materials for energy storage and conversion.     

Electrocatalysts Based on Transition Metal Borides and Borates for the Oxygen Evolution Reaction

Electrochemical water splitting is a clean and sustainable process for hydrogen production on a large scale as the electrical power required can be obtained from various renewable energy resources. The key challenge in electrochemical water splitting process is to develop low-cost electrocatalysts with high catalytic activity for the hydrogen evolution reaction (HER) on the cathode and the oxygen evolution reaction (OER) on the anode. OER is the most important half-reaction involved in water splitting, which has been extensively studied since the last century and a large amount of electrocatalysts including noble and non-noble metal-based materials have been developed. Among them, transition metal borides and borates (TMBs)-based compounds with various structures have attracted increasing attention owing to their excellent OER performance. In recent years, many efforts have been devoted to exploring the OER mechanism of TMBs and to improving the OER activity and stability of TMBs. In this review, recent research progress made in TMBs as efficient electrocatalysts for OER is summarized. The chemical properties, synthetic methodologies, catalytic performance evaluation, and improvement strategy of TMBs as OER electrocatalysts are discussed. The electrochemistry fundamentals of OER are first introduced in brief, followed by a summary of the preparation and performance of TMBs-based OER electrocatalysts. Finally, current challenges and future directions for TMBs-based OER electrocatalysts are discussed.     

酸性和碱性溶液中金属氮碳材料氧还原和氢析出反应的理论研究

单原子催化剂(SAC)由于其低成本和在各种电催化反应中潜在的高催化活性而被认为是铂族金属的有前景的替代材料,但仍然缺乏对不同金属氮碳材料催化剂之间活性差异的原子机理的理解.在此,通过实验和理论研究相结合,研究了非贵金属氮碳材料(Me-N-C,Me = Fe和Co)作为模型催化剂,以探索在普遍的pH值下氧还原反应(ORR...     

铂和钯上丙三醇电氧化研究进展：从反应机理到催化材料

生物柴油工业的蓬勃发展带来大量副产品丙三醇(甘油),因此如何将甘油转化为高附加值产品具有重要的研究价值。在各种方法中, 电催化氧化由于其条件温和、环境友好和高效率而备受关注。然而,甘油的电氧化非常复杂,涉及许多反应途径和多个电子和质子转移过程,如何合理设计对目标产物具有高选择性的催化剂是很大的挑战。在本文中, 我们主要概述了铂和钯基催化剂上甘油电氧化研究的最新进展。我们首先总结了基于原位和在线谱学研究以及理论计算获得的影响其电催化活性和选择性的因素。然后,选择代表性文献来说明这些因素如何应用于研制高效甘油电氧化催化剂。最后,提出了未来研究中要解决的关键问题。     

Carbon Nanofiber and Poly[2-(methacryloyloxy) ethyl] Trimethylammonium Chloride Composite as a New Benchmark Carbon-based Electrocatalyst for Sulfide Oxidation

There is an overwhelming desire to develop new sulfide oxidation electrocatalysts that perform at low potentials and exhibit high current density for the removal and efficient sensing of sulfide. This article describes a comparative electrochemical analysis of various commercially available carbon materials and polymer/surfactant composite electrocatalysts for direct electrooxidation of sulfide in an aqueous solution. The composites were prepared from five different carbon materials multiwalled carbon nanotubes, fullerene-C₆₀, graphene, glassy carbon, and carbon nanofibers (CNF) and four different polymers: chitosan, polyvinylidene fluoride, Nafion, and indigenously synthesized poly[2-(methacryloyloxy)ethyl] trimethylammonium chloride (PMTC). The carbon@polymer composites were prepared by a simple ultrasonication technique, and the electrodes were prepared by drop-drying the prepared composite on indium tin oxide (ITO) substrates. The CNF@PMTC showed the highest positive zeta potential that allowed an accumulation of many negatively charged sulfide ions at the CNF@PMTC surface. Cyclic voltammetry was used for the electrooxidation of sulfide in an aqueous solution of tris buffer (0.05 M; pH 8.0) and KNO₃ (0.1 M). The lowest sulfide oxidation peak potential (i. e., −51 mV vs. standard hydrogen electrode) with a high catalytic current response (730 μA/cm²) of the CNF@PMTC-modified ITO electrode among the tested and previously reported carbon-based electrode materials make it ideal for direct sulfide electrooxidation. Taking this and its simple preparation method into account, CNF@PMTC can be considered a benchmark carbon-based electrocatalyst for sulfide oxidation.     

Pt-Cu合金纳米枝晶的合成及其氧还原催化性能

纳米材料的结构和化学成分对其催化性能的显著影响已经得到验证. 因此,本文通过一种简易的蚀刻方法,合成出具有均匀合金结构且尺寸和形貌均一的Pt-Cu纳米枝晶（NDs）作为高效氧还原（ORR）催化剂. 其树枝状形貌的形成得益于由Br^-/O₂氧化蚀刻剂引起的蚀刻效应. 通过改变Pt/Cu前驱体的比例可以容易地调节Pt-Cu NDs的Pt/Cu原子比,而不会使其树枝状形貌发生改变. 活性最高的碳载Pt₁Cu₁ NDs（Pt₁Cu₁ NDs/C）的面积比活性为1.17 mA·cm^-2@0.9V（vs. RHE）,约为商业Pt/C的5.32倍. 此外,Pt₁Cu₁ NDs/C还具有卓越的电化学耐久性,即使在经过加速衰减实验的12000个电势循环后仍保持其优异的ORR催化活性. Pt₁Cu₁ NDs/C优异的ORR催化活性和电化学耐久性得益于由其合金结构和枝晶形貌产生的电子效应和结构效应.     

PdCo/C氧还原催化剂及其抗甲醇性能(英文)

以柠檬酸钠为络合剂,在乙二醇体系中采用有机溶胶法制备出了PdCo/C催化剂,XRD研究结果表明催化剂具有面心立方结构,粒度小,分散性好,同时元素钴的加入使催化剂的Pd-Pd间距缩小。采用电化学方法评价了催化剂对于氧气还原反应的活性,结果表明:PdCo/C催化剂具有比Pd/C要好的氧还原活性,同时具有Pt/C催化剂无法比拟的抗甲醇中毒能力。     

Dimethoxymethane (DMM) electrooxidation on carbon-supported Pt-based nanosized catalysts for PEMFC

Previous studies on dimethoxymethane (DMM: CH₃OCH₂OCH₃) on platinum poly- and single crystals allowed us to propose a general mechanism of DMM electrooxidation. At the time, making electrodes for proton exchange membrane fuel cells (PEMFC) with nanoparticles (based on Pt) was encouraged. It is well known that the improvement of Pt activity for electrocatalysis is possible by modifying platinum with other metals able to increase the kinetics of specific steps of the reaction (activation of water for example). Nanosized PtM/C electrocatalysts have been synthesized by the Bönneman method and characterized for DMM electrooxidation. Voltammetry, in situ IRTF spectroscopy and fuel cell tests were carried out to better understand DMM oxidation reaction. Voltammetry and fuel cell tests showed that PtRuMo and PtRu are the most active catalysts at high potential, whereas PtSn and PtMo have a best activity at low potentials. In situ IR experiments allowed the observation of CO_ads and CO₂ bands.