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能源和环保问题是现代社会可持续发展的重要挑战[1]。特别是在面临人口持续增长、化石燃料日益枯竭、气候变化影响日益恶化的情况下,开发新的清洁和可持续能源至关重要。氢能具有无污染、能量密度高、资源丰富等特点,是最具潜力的传统化石燃料替代品之一[2]。在众多制氢技术中,电催化分解水是一种很有前途的大规模制氢技术[3]。析氧反应(Oxygen Evolution Reaction,OER)作为电解水制氢技术的阳极反应,由于反应机理复杂,其反应速率很大程度上决定了装置的运行效率。一般来说,最被广泛认可的OER机制是吸附质演化机制(Adsorbate Evolution Mechanism,AEM),它涉及到在过渡金属阳离子位点上四个电子-质子协同转移生成O2,如图1和式(1)~式(5)所示。通常,*OH(*表示电催化剂上的活性位点)最初是在活性位点(1)上生成的。然后经过质子耦合的电子转移过程,转化为*O(2)。随后,*O经过以下两种可能的途径之一产生分子O2:两个*O(3)的直接耦合或通过与另一个OH–反应生成*OOH,该OH–通过另一个质子耦合电子转移过程(4)和(5)进一步转化为O2[4]。
$$ \text{O}{{\text{H}}^{-}}+*{{\to }^{*}}\text{OH}+{{\text{e}}^{-}}$$ (1) $$ ^{*}\text{OH}+\text{O}{{\text{H}}^{-}}{{\to }^{*}}\text{O}+{{\text{H}}_{2}}\text{O}+{{\text{e}}^{-}}$$ (2) $$ ^{*}\text{O}{{+}^{*}}\text{O}\to {{\text{O}}_{2}} $$ (3) 或:
$$ ^{*}\text{O}+\text{O}{{\text{H}}^{-}}{{\to }^{*}}\text{OOH}+{{\text{e}}^{-}}$$ (4) $$ ^{*}\text{OOH}+\text{O}{{\text{H}}^{-}}{{\to }^{*}}+{{\text{O}}_{2}}+{{\text{e}}^{-}}+{{\text{H}}_{2}}\text{O}$$ (5) 然而,发生在阳极上的四电子析氧反应(OER)具有动力学迟缓、能量转换效率低等特点,成为电催化分解水的技术瓶颈。为了克服OER过程的能量障碍,必须开发能在低过电位下传递高电流密度并具有长期稳定性的电催化剂。目前,铱(Ir)和钌(Ru)及其氧化物(IrO2和RuO2)等贵金属催化剂被广泛用于OER应用中。虽然这些材料对OER具有良好的催化活性,但原材料储量丰度低、成本高以及在碱性介质中的化学稳定性差等特性,严重阻碍了它们的大规模应用[5]。因此,开发一种更高效、稳定、低成本的OER非贵金属电催化剂来替代昂贵的Ir和Ru基催化剂是发展电催化分解水技术的关键。
镍(Ni)和钴(Co)等第一排过渡金属因其独特的晶体和电子结构类型、可调节的化学反应性、理论上的高效率和热力学稳定性而备受关注[6]。然而,单一类型的镍基催化剂和钴基催化剂仍然存在活性位点不足、固有活性差、电导率低等问题。而双金属催化剂的合成促进了金属原子的重排,使其具有更有利于催化的原子和电子结构。特别是镍-钴(Ni-Co)双金属基电催化剂由于其存在合适的界面原子和电子结构,丰富的活性位点以及耦合金属之间的协同效应,在OER过程中表现出优异的活性、稳定性和耐蚀性[7]。研究表明,Ni-Co基材料,包括二者的合金、氧化物和氢氧化物、氮化物、磷化物以及硫化物等,都可作为高效的OER催化剂。此外,通过调整Ni-Co基电催化剂的微观形貌、晶体结构、成分和氧化态、异质结结构以及与导电材料复合等策略可以有效改善OER性能[8]。然而,关于Ni-Co基电催化剂活性位点的结构和催化机理尚不清楚,对用于OER的Ni-Co基电催化剂的设计合成、活性来源、催化机理以及结构-活性关系等方面的综述也鲜有报道。
文章综述了近几年Ni-Co基电催化剂的在OER应用中的研究进展,包括Ni-Co合金、氧化物、氢氧化物、氮化物、磷化物、硫化物以及其他用于OER的Ni-Co基电催化剂,重点介绍了催化剂的设计合成、结构组成以及提高OER性能的策略。最后,提出了Ni-Co基电催化剂面临的挑战和未来的发展方向,希望这篇综述将有助于研究人员设计和开发更有效的Ni-Co基电催化剂,实现电催化水技术的可持续发展。
Research Progress of Bimetallic NiCo-Based Electrocatalysts for Oxygen Evolution Reaction
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摘要:
目的 能源消耗的持续增长和化石燃料燃烧带来的环保和能源安全问题已经引起世界各国的广泛关注。因此,发展清洁能源生产技术已成为世界范围内的主要研究重点。氢能具有无污染、比能密度高、资源丰富等特点,是最具潜力的传统化石燃料替代品之一。电催化分解水被认为是最有希望的制氢方法,但阳极上的析氧反应动力学缓慢,能量转换效率低,是大规模制氢的主要瓶颈。与稀有和昂贵的贵金属催化剂相比,镍-钴(Ni-Co)基电催化剂由于具有可调的电子结构、高导电性和低成本优势,有望在碱性溶液中实现卓越的OER活性和耐久性。 方法 文章总结并讨论了在OER中Ni-Co基电催化剂的最新研究发展。重点讨论了Ni-Co基电催化剂的设计和合成,以及在OER过程中提高其电催化性能的研究策略。 结果 为了代替钌、铱等贵金属催化剂,研究者们对Ni-Co基非贵金属催化剂进行了大量研究。包括氧化物、氢氧化物、合金、氮化物、硫化物、磷化物等在内的多种Ni-Co基催化剂通过化学结构的调控,从阳极角度提高了电催化制氢的活性。但这些催化剂又分别面临不同的缺陷,有待进一步研究克服。 结论 开发具有高OER活性的非贵金属催化剂是降低电解水制氢成本,促进氢能产业发展的重要途径。虽然仍有一些技术问题尚未解决限制了Ni-Co基催化剂替代贵金属催化剂,但作为重要的贵金属催化剂替代品,Ni-Co基催化剂的研究为新型催化剂的开发提供了重要选择。 Abstract:Introduction The persistently increasing energy consumption and the environmental protection and energy security issues brought about by the burning of fossil fuels have raised widespread concerns all over the world. Thus, the development of technology for clean-energy production has become the major research priority worldwide. Hydrogen energy with zero pollution, high specific energy density, and abundant resources is one of the most promising alternatives to traditional fossil fuels. Electrocatalytic water splitting is considered as the most promising method for hydrogen production. However, the oxygen evolution reaction (OER) at the anode side has sluggish kinetics and low energy conversion efficiency, which is the major bottleneck for large-scale hydrogen production. Method The latest development of NiCo-based electrocatalysts for OER was summarized and discussed, especially the design and synthesis of NiCo-based electrocatalysts and the research strategies for improving their electrocatalytic performance in the OER process. Result In order to replace the noble-metal catalysts such as ruthenium and iridium, researchers have carried out a lot of research on NiCo-based non-noble metal catalysts. By regulating the chemical structure of a variety of NiCo-based-catalysts, including oxides, hydroxides, alloys, nitrides, sulfides, and phosphides, the activity of electrocatalytic hydrogen production is improved from the anode perspective. However, these catalysts have different defects, which need to be overcome by further research. Conclusion The development of non-noble metal catalysts with high OER activity is an important way to reduce the cost of hydrogen production from water electrolysis and promote the development of hydrogen energy industry. Although there are still some unsolved technical problems that limit the substitution of NiCo-based catalysts for noble metal catalysts, the research of NiCo-based catalysts, as an important substitute for noble metal catalysts, provides an important choice for the development of new catalysts. -
图 6 三金属NiCo2–xFexO4 NBs的形成过程示意图[32]
Fig. 6 Formation process of trimetallic NiCo2–xFexO4 NBs
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