Recent advances in one-dimensional nanostructures for energy electrocatalysis

Catalysts play decisive roles in determining the energy conversion efficiencies of energy devices. Up to now, various types of nanostructured materials have been studied as advanced electrocatalysts. This review highlights the application of one-dimensional (1D) metal electrocatalysts in energy conversion, focusing on two important reaction systems—direct methanol fuel cells and water splitting. In this review, we first give a broad introduction of electrochemical energy conversion. In the second section, we summarize the recent significant advances in the area of 1D metal nanostructured electrocatalysts for the electrochemical reactions involved in fuel cells and water splitting systems, including the oxygen reduction reaction, methanol oxidation reaction, hydrogen evolution reaction, and oxygen evolution reaction. Finally, based on the current studies on 1D nanostructures for energy electrocatalysis, we present a brief outlook on the research trend in 1D nanoelectrocatalysts for the two clean electrochemical energy conversion systems mentioned above.     

A review of transition metal‐based bifunctional oxygen electrocatalysts

Electrochemical energy storage and conversion devices play a key role in the development of clean, sustainable, and efficient energy systems to meet the sustainable growth of our society. However, challenging issues including the sluggish kinetics of oxygen electrode reactions involving the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are present, limiting the implementation of devices such as metal‐air batteries, water electrolyzers, and regenerative fuel cells. In this review, various monometallic and bimetallic transition metal oxides (TMOs) and hydroxides are summarized in terms of their application for ORR/OER, in which the merits and demerits of various precious metal and carbon‐based metal oxide materials are discussed, with requirements for better electrocatalysts and catalyst support being introduced as well. Following this, different approaches to improve catalytic activity such as the introduction of doping and defects, the manipulation of crystal facets, and the engineering of supports, compositions, and morphologies are summarized in which TMOs with improved ORR/OER catalytic activities can be synthesized, further improving the speed, stability, and polarization of electrochemical energy storage and conversion devices. Finally, perspectives into the improvement of performance and the better understanding of ORR/OER mechanisms for bifunctional electrocatalysts using in situ spectroscopic techniques and density functional theory calculations are also discussed.     

Noble-Metal-Free Doped Carbon Nanomaterial Electrocatalysts

Electrocatalytic processes, such as oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER) and carbon dioxide reduction reaction (CO₂RR), play key roles in various sustainable energy storage and production devices and their optimization in an ecological manner is of paramount importance for mankind. In this inclusive Review, we aspire to set the scene on doped carbon-based nanomaterials and their hybrids as precious-metal alternative electrocatalysts for these critical reactions in order for the research community not only to stay up-to-date, but also to get inspired and keep pushing forward towards their practical application in energy conversion.     

泡沫铜基底原位生长的铜基导电金属有机框架作为双功能电催化剂

以泡沫铜为基底生长氢氧化铜纳米线,通过原位转化合成二维导电金属有机框架(MOF)材料Cu_3HITP_2(HITP=2,3,6,7,10,11-六氨基三亚苯)作为双功能催化剂,可直接用作析氧及氧还原反应的工作电极,而无需使用额外的基底或粘合剂,且无需后续热处理。研究发现以氢氧化铜纳米线为模板的Cu_3HITP_2表现出了更大的电化学比表面积,这种新型的电极可在碱性溶液(0.1和1.0 mol·L~(-1) KOH)中可以稳定运行,析氧反应中在电流密度达到10 mA·cm~(-2)时的过电位仅为1.53 V,超越了商业二氧化钌的催化性能。此外,该催化剂在氧还原反应中的半波电位达到0.75 V,优于大多数MOF材料。     

导电MOFs在能源转化中的应用

可再生能源供应方案包括析氢反应(HER)、析氧反应(OER)、氧还原反应(ORR)和二氧化碳还原反应(CO2RR)等多种反应,电催化剂对这些反应至关重要。到目前为止,已有一系列导电MOFs作为与能源相关电催化电极材料的报道。本文从提高MOFs导电能力和对产物的选择性、增强MOFs的化学稳定性及增加MOFs的反应活性位点等方面介绍了导电MOFs作为电催化剂的设计策略,重点综述了其在能源转化涉及的HER、OER、ORR以及CO2RR方面的应用,并从材料制备和应用需求角度出发, 对高性能导电MOFs材料在电催化领域所面临的挑战和前景进行了展望。     

Bioinspired Transition-Metal Complexes as Electrocatalysts for the Oxygen Reduction Reaction

The oxygen reduction reaction (ORR) is one of the most important reactions in life processes and energy conversion systems. To alleviate global warming and the energy crisis, the development of high-performance electrocatalysts for the ORR for application in energy conversion and storage devices such as metal–air batteries and fuel cells is highly desirable. Inspired by the biological oxygen activation/reduction process associated with heme- and multicopper-containing metalloenzymes, iron and copper-based transition-metal complexes have been extensively explored as ORR electrocatalysts. Herein, an outline into recent progress on non-precious-metal electrocatalysts for the ORR is provided; these electrocatalysts do not require pyrolysis treatment, which is regarded as desirable from the viewpoint of bioinspired molecular catalyst design, focusing on iron/cobalt macrocycles (porphyrins, phthalocyanines, and corroles) and copper complexes in which the ORR activity is tuned by ligand variation/substitution, the method of catalyst immobilization, and the underlying supporting materials. Current challenges and exciting imminent developments in bioinspired ORR electrocatalysts are summarized and proposed.     

钙钛矿型稀土氧化物的合成及其能源转化储存应用研究进展

钙钛矿型稀土氧化物价格低廉、结构可控、性质多样,在催化领域有着广阔的应用前景。本文从钙钛矿型稀土氧化物的结构类型、合成方法及电化学催化反应出发,总结了传统高温合成方法、火焰喷雾法、静电纺丝法和脉冲激光沉积法等几种最常用的合成方法,以及提升其氧析出反应(OER),氢析出反应(HER)和氧还原反应(ORR)催化能力的典型有效方法,概述了近年来钙钛矿型稀土氧化物在电解水、金属空气电池和固体氧化物燃料电池等能源转化储存装置的主要研究进展,进而对钙钛矿型稀土氧化物在能源转化储存领域的应用进行了展望。     

单原子催化剂的合成及其能源电催化应用的研究进展

基于电化学反应的能源储存与转化技术为全球能源结构的转型提供了一条绿色、 可持续的途径, 高效的电催化剂在其中扮演着重要的角色. 得益于在物理、 化学性质上的独特优势, 单原子催化剂在电催化能源转化方面展现出巨大的应用前景. 本文综合评述了单原子催化剂的合成及其能源电催化应用的研究进展, 介绍了单原子催化剂的常见表征手段, 总结了单原子催化剂的合成方法(湿化学法、 高温热解法、 原子沉积法、 电化学沉积法等), 并介绍了该类材料在氧还原、 二氧化碳电还原、 电解水及氮气电还原反应中的研究进展, 重点探讨了催化剂微观结构与其性能之间的关系, 最后, 对单原子能源电催化领域所面临的挑战进行了总结, 并对该领域未来的发展方向进行了展望.     

石墨烯基催化剂的设计合成与电催化应用

为了解决能源匮乏和环境污染的问题,研究人员正致力于寻找清洁可持续的新能源。 其中,氧气还原、氧气析出、析氢反应等是紧密联系新型清洁能源获取和存贮的重要电化学反应。 为了提高其能量转化效率,电催化剂(如碳载铂Pt/C)被广泛地用于降低其反应活化能、提高能量转化效率。 近年来,石墨烯作为一种具有高比表面积和优异导电性的二维碳材料受到了广泛关注。 通过表面杂原子掺杂、缺陷调控和引入催化活性组分等方式,获得了催化性能与贵金属催化剂相媲美,且低价格和高稳定性的非贵金属石墨烯基催化材料。 针对氧气还原、氧气析出和析氢反应在燃料电池、金属-空气电池和电催化水分解中的应用,本文概括综述了通过表/界面结构性质调控提高石墨烯电催化性能和稳定性,获得具有双功能或复合催化性能的石墨烯基催化剂的最新研究进展。 最后总结和展望了亟待解决的问题及未来的发展趋势。     

高效氧催化反应中的金属有机骨架材料（英文）

氧电催化反应包括氧气还原反应(ORR)和氧气析出反应(OER).作为核心电极反应,这两个反应对诸多能源存储与转换技术(比如燃料电池、金属空气电池以及全水分解制氢等)的能量效率起决定性作用.然而,ORR和OER涉及多个反应步骤、多个电子转移过程以及多相界面传质过程.这些复杂的过程较大程度上限制了ORR和OER的反应速率.从理论和实践两个方面来看,ORR和OER都需要高效电催化剂的参与来促进其反应速率,从而能够最终提高上述能源存储与转换技术的能量转换或利用效率.目前,以Pt,Pd,Ir,Ru为代表的贵金属基电催化剂具有十分突出的电催化性能.但是,过高的成本和过低的储量始终制约着贵金属基电催化剂在催化ORR和OER反应方面,乃至在能源存储与转换技术领域的规模化应用.因而,开发高效非贵金属基氧电催化剂成为近年来能源存储与转换领域的研究重点之一.在众多已经报道的非贵金属基氧电催化剂中,金属有机骨架材料(MOFs)备受瞩目.MOFs是一类由有机配体和金属节点通过配位键自组装而成的晶态多孔材料.它们具备超高比表面积、超高孔隙率以及规则性纳米孔道.相比较其他传统的多孔材料(比如活性炭、分子筛、介孔炭、介孔氧化硅等),MOFs最主要的优势在于它们的结构和功能可以依据需求通过选择合适的有机配体和金属节点进行便利地设计,或通过后处理进行必要的改性和调节.基于独特的多孔特性以及结构与功能的可设计、可调节性,MOFs在气体分离与存储、异相催化、化学传感、药物输送、环境保护以及能源存储与转化等领域都具有潜在的应用价值.因而,近年来,MOFs备受基础研究领域和工业界的青睐.针对MOFs开展的基础研究和应用开发逐渐成为诸多领域的研究焦点.也正由于MOFs具有的上述优异特性,尤其是结构与功能的可设计、可调节性,使得设计制备基于单纯MOFs以及MOFs衍生材料成为开发高效非贵金属基氧电催化剂的新途径.本综述首先论述了基于单纯MOFs的氧电催化剂(包括纯MOFs、活性物种修饰的MOFs以及与导电材料构成的复合MOFs)的合成以及它们在ORR或OER催化反应中应用的研究进展.在第二部分论述中,本综述主要针对MOFs衍生的各类氧电催化剂(包括无机微米-纳米结构/多孔碳复合材料、纯多孔碳材料、纯无机微米-纳米结构材料以及单原子型电催化材料)的研究进展进行了简要介绍和讨论.最后,本综述对MOFs基氧电催化剂目前存在的挑战进行了简要分析;同时,也对这类氧电催化剂的通用设计准则以及未来发展方向进行了展望.尽管存在诸多挑战,MOFs始终被认为是极好的"平台"材料.充分利用它们将有利于开发高效且实用的非贵金属基氧电催化剂.     

Recent Advances in Two-dimensional Materials for Electrochemical Energy Storage and Conversion

With the increased energy demand,developing renewable and clean energy technologies becomes more and more significant to mitigate climate warming and alleviate the environmental pollution.The key point is design and synthesis of low cost and efficient materials for a wide variety of electrochemical reactions.Over the past ten years,two-dimensional(2D)nanomaterials that graphene represents have been paid much attention as a class of the most promising candidates for heterogeneous electrocatalysts in electrochemical storage and conversion.Their unique properties,such as good chemical stability,good flexibility,and good electronic properties,along with their nanosized thickness and large specific area,make them exhibit comprehensively good performances for energy storage and conversion.Here,we present an overview on the recent advances in electrochemical applications of graphene,graphdiyne,transition metal dichalcogenides(TMDs),and MXenes for supercapacitors(SCs),oxygen reduction reaction(ORR),and hydrogen evolution reaction(HER).     

金属有机骨架及其衍生材料在电解水和锌-空气电池中的应用

电解水和锌-空气电池(ZABs)技术为解决能源危机、实现碳中和目标开辟了一条新的途径。然而,这些技术的实际应用在很大程度上受到析氢反应(HER)、析氧反应(OER)以及氧还原反应(ORR)缓慢动力学的限制。因此,迫切需要开发高效、稳定的电催化剂有效降低反应过电位,加快电催化反应进程。金属有机骨架(MOFs)由于其灵活可调的组成和精确可控的结构,已成为催化领域研究最广泛的材料之一。本文聚焦于MOFs基电催化剂的制备策略和结构特性,主要介绍它们在电解水和ZABs方面近期的研究进展,并对该领域存在的问题和发展趋势进行了总结和展望。     

金属有机骨架及其衍生材料在电解水和锌-空气电池中的应用

电解水和锌-空气电池(ZABs)技术为解决能源危机、实现碳中和目标开辟了一条新的途径。然而,这些技术的实际应用在很大程度上受到析氢反应(HER)、析氧反应(OER)以及氧还原反应(ORR)缓慢动力学的限制。因此,迫切需要开发高效、稳定的电催化剂有效降低反应过电位,加快电催化反应进程。金属有机骨架(MOFs)由于其灵活可调的组成和精确可控的结构,已成为催化领域研究最广泛的材料之一。本文聚焦于MOFs基电催化剂的制备策略和结构特性,主要介绍它们在电解水和ZABs方面近期的研究进展,并对该领域存在的问题和发展趋势进行了总结和展望。     

Hydrogen energy currency: Beyond state-of-the-art transition metal oxides for oxygen electrocatalysis

In this opinion piece, we highlight and discuss beyond state-of-the-art transition metal oxide materials for the oxygen evolution reaction and oxygen reduction reaction, which are essential for the renewable energy conversion and storage of H₂ to electricity. We pinpoint some of the synthetic routes taken and discuss essential measurements required in the highlighted works, which others should undertake to achieve highly active and stable oxygen evolution reaction and oxygen reduction reaction catalysts in both acidic and alkaline media.     

Recent advances of layered double hydroxides–based bifunctional electrocatalysts for ORR and OER

The oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) have attracted increasing attention for the sake of clean, renewable, and efficient energy technologies in recent years. The design of ORR/OER bifunctional electrocatalysts is a challenging task in the promotion of highly efficient rechargeable metal-air batteries as well as regenerative fuel cells. Owing to the wide adaptability of different types and ratios of metals in the interlayer space as well as the adjustable interlayer distance, composite materials with layered double hydroxides (LDHs) and their derivatives have recently been registered as electrode materials and catalysts supports for various electrochemical reactions. This study examines the recent development of bifunctional electrocatalysts based on LDHs for ORR/OER to expand the application of LDHs in the field of energy storage and conversion. Various bifunctional electrocatalysts associated with LDHs are discussed in detail to improve their performance. Finally, existing problems and future prospects for improving the performance of LDHs bifunctional electrocatalysts are proposed.     

Two-dimensional hybrid nanomaterials derived from MXenes(Ti_3C_2T_x)as advanced energy storage and conversion applications

The development of two-dimensional hybrid nanomaterial derived from MXenes as high performance electrode material is the key component for the advanced ene rgy storage and conversion systems.In the past decades,MXene derived nanomaterials have attracted greatly interest in scientific activity and potential applications because of their unique synergistic properties such as high thermal stability,excellent electrical conductivity,large surface area,easy to handle and outstanding electro and photo chemical properties.This review is focused on the synthesis of hybrid nanomaterials from MXene(Ti_3C_2T_x) for renewable energy conversion and storage application including hydrogen evolution reaction,supercapacitor,lithium-ion batteries and photocatalysis.Finally,we also summarized the prospect and opportunities of novel two-dimensional hybrid nanomaterials derived MXene(Ti_3C_2T_x) fo r futuristic sustainable energy technology.     

Silica-Derived Nanostructured Electrode Materials for ORR,OER, HER,CO2RR Electrocatalysis,and Energy Storage Applications: A Review**

Silica-derived nanostructured catalysts (SDNCs) are a class of materials synthesized using nanocasting and templating techniques, which involve the sacrificial removal of a silica template to generate highly porous nanostructured materials. The surface of these nanostructures is functionalized with a variety of electrocatalytically active metal and non-metal atoms. SDNCs have attracted considerable attention due to their unique physicochemical properties, tunable electronic configuration, and microstructure. These properties make them highly efficient catalysts and promising electrode materials for next generation electrocatalysis, energy conversion, and energy storage technologies. The continued development of SDNCs is likely to lead to new and improved electrocatalysts and electrode materials. This review article provides a comprehensive overview of the recent advances in the development of SDNCs for electrocatalysis and energy storage applications. It analyzes 337,061 research articles published in the Web of Science (WoS) database up to December 2022 using the keywords “silica”, “electrocatalysts”, “ORR”, “OER”, “HER”, “HOR”, “CO₂RR”, “batteries”, and “supercapacitors”. The review discusses the application of SDNCs for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO₂RR), supercapacitors, lithium-ion batteries, and thermal energy storage applications. It concludes by discussing the advantages and limitations of SDNCs for energy applications.     

扫描电化学显微镜在电催化氧反应研究中的应用

本综述首先简单介绍了扫描电化学显微镜的基本概况,尤其是不同的工作模式. 其次,有针对性地介绍了SECM的不同工作模式在氧还原和水解析氧反应相关研究中的应用. 最后,对扫描电化学显微镜未来在新能源转换存储系统研究领域的应用进行了展望.     

高熵纳米合金在电化学催化中的应用

The implementation of clean energy techniques, including clean hydrogen generation, use of solar-driven photovoltaic hybrid systems, photochemical heat generation as well as thermoelectric conversion, is crucial for the sustainable development of our society. Among these promising techniques, electrocatalysis has received significant attention for its ability to facilitate clean energy conversion because it promotes a higher rate of reaction and efficiency for the associated chemical transformations. Noble-metal-based electrocatalysts typically show high activity for electrochemical conversion processes. However, their scarcity and high cost limit their applications in electrocatalytic devices. To overcome this limitation, binary catalysts prepared by alloying with transition metals can be used. However, optimization of the activity of the binary catalysts is considerably limited because of the presence of the miscibility gap in the phase diagram of binary alloys. The activity of binary electrocatalysts can be attributed to the adsorption energy of molecules and intermediates on the surface. High-entropy alloys (HEAs), which consist of diverse elements in a single NP, typically exhibit better physical and/or chemical properties than their single-element counterparts, because of their tunable composition and inherent surface complexity. Further, HEAs can improve the performance of binary electrocatalysts because they exhibit a near-continuous distribution of adsorption energy. Recently, HEAs have gained considerable attention for their application in electrocatalytic reactions. This review summarizes recent research advances in HEA nanostructures and their application in the field of electrocatalysis. First, we introduce the concept, structure, and four core effects of HEAs. We believe that this part will provide the basic information about HEAs. Next, we discuss the reported top-down and bottom-up synthesis strategies, emphasizing on the carbothermal shock method, nanodroplet-mediated electrodeposition, fast moving bed pyrolysis, polyol process, and dealloying. Other methods such as combinatorial co-sputtering, ultrashort-pulsed laser ablation, ultrasonication-assisted wet chemistry, and scanning-probe block copolymer lithography are also highlighted. Among these methods, wet chemistry has been reported to be effective for the formation of nano-scale HEAs because it facilitates the concurrent reduction of all metal precursors to form solid-solution alloys. Next, we present the theoretical investigation of HEA nanocatalysts, including their thermodynamics, kinetic stability, and adsorption energy tuning for optimizing their catalytic activity and selectivity. To elucidate the structure–property relationship in HEAs, we summarize the research progress related to electrocatalytic reactions promoted by HEA nanocatalysts, including the oxygen reduction reaction, oxygen evolution reaction, hydrogen evolution reaction, methanol oxidation reaction, and CO₂ reduction reaction. Finally, we discuss the challenges and various strategies toward the development of HEAs.     

基于微生物作为智能模板的电催化剂制备与应用研究进展

通过电催化实现可再生能源的存储与转化对于改善能源结构、保护生态环境、实现碳达峰和碳中和的国家战略具有重大意义。而开发低成本、高效的电催化剂成为全世界科学家共同面对的挑战。微生物在自然界中广泛存在,具有结构、组成和代谢丰富的特点,可以成为电催化剂的模板以及碳、磷、硫等非金属元素以及金属元素的来源,而且具有无毒、生产可重复性好、易于规模化等优点,已成为电催化剂制备的新趋势。对此,本文综述了微生物“智能”引导制备电催化剂的发展及在电催化析氢(HER)、电催化析氧(OER)、氧还原反应(ORR)、二氧化碳还原(CO₂RR)、锂电池(LBs)等领域的应用现状。希望有助于推动微生物代谢与催化剂微纳结构关系以及与催化反应的构效关系的深入理解,最后针对这类材料的问题挑战及其未来发展方向进行了探讨与展望。