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Low-dose transmission electron microscopy study on halide perovskites: Application and challenges 卤化物钙钛矿的低剂量透射电镜研究:应用与挑战
IF 25.1 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-09-01 DOI: 10.1016/j.enchem.2023.100105
Libing Yao , Liuwen Tian , Shaochen Zhang , Yuan Tian , Jingjing Xue , Siying Peng , Rui Wang

Transmission electron microscopy (TEM) is widely used in the materials science community because of its high spatial, temporal and energy resolution. However, for electron beam-sensitive halide perovskites (HPs), the achievements offered by TEM are still in their infancy due to the nonnegligible structural damage caused by the incident electron beams to the fragile structure. Despite these challenges, the potential for TEM to provide unique insights into the microstructure and phase evolution of HPs at the atomic scale, to track the dynamic ion migration behaviors, and to explore the effects of lattice defects on physicochemical properties is still fascinating. In this review, we summarize recent achievements in HPs through advanced analytical methods embedded in the TEM, including high-resolution/scanning TEM (HRTEM/STEM) imaging, electron diffraction (ED) analysis, X-ray energy dispersive spectroscopy (EDS), and electron energy-loss spectroscopy (EELS) measurement, and in-situ TEM observation, with the aim of providing a multi-dimensional and multi-scale understanding of the intrinsic properties of HPs that have not yet been discovered. In addition, we delve into the inherent beam-damage mechanisms affecting the delicate HPs crystal, thereby emphasizing the significant hurdles associated with employing TEM in HPs research. Finally, we present a number of effective strategies that may be beneficial in reducing the damage caused by beams. In particular, the introduction of a direct-detection electron-counting (DDEC) camera has contributed significantly to the advancement of low-dose imaging and the suppression of beam damage to the intrinsic structure of HPs. With the improvement of low-dose imaging technology, TEM characterization is expected to promote a comprehensive understanding of the intrinsic properties of HPs in terms of structure-property-performance and to expand the wide range of applications of HPs in optoelectronic devices.

透射电子显微镜(TEM)由于具有较高的空间、时间和能量分辨率,在材料科学界得到了广泛的应用。然而,对于电子束敏感的卤化物钙钛矿(HPs),由于入射电子束对脆弱结构造成不可忽略的结构损伤,透射电镜所提供的成果仍处于起步阶段。尽管存在这些挑战,但透射电镜在原子尺度上为hp的微观结构和相演化提供独特见解,跟踪动态离子迁移行为,以及探索晶格缺陷对物理化学性质的影响方面的潜力仍然令人着迷。在本文中,我们通过TEM中嵌入的先进分析方法,包括高分辨率/扫描TEM (HRTEM/STEM)成像,电子衍射(ED)分析,x射线能量色散谱(EDS)和电子能量损失谱(EELS)测量以及原位TEM观测,总结了近年来在hp方面取得的进展,旨在为hp尚未发现的内在性质提供一个多角度和多尺度的理解。此外,我们还深入研究了影响精细HPs晶体的固有光束损伤机制,从而强调了在HPs研究中使用TEM的重大障碍。最后,我们提出了一些有效的策略,可能有利于减少梁造成的损伤。特别是,直接探测电子计数(DDEC)相机的引入对低剂量成像的进步和抑制光束对hp固有结构的损伤做出了重大贡献。随着低剂量成像技术的进步,透射电镜表征有望促进人们从结构-性能-性能方面全面了解高分子材料的内在特性,并扩大高分子材料在光电器件中的广泛应用。
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引用次数: 0
Critical review on the degradation mechanisms and recent progress of Ni-rich layered oxide cathodes for lithium-ion batteries 锂离子电池用富镍层状氧化物阴极降解机理及研究进展综述
IF 25.1 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-09-01 DOI: 10.1016/j.enchem.2023.100103
Qingmeng Gan , Ning Qin , Huimin Yuan , Li Lu , Zhenghe Xu , Zhouguang Lu

Ni-rich layered transition metal oxides possess remarkably high capacity and thus are very competitive cathode materials in high-energy lithium-ion batteries (LIBs) for electric vehicles, but encounter the critical problems of fast degradation caused by the highly reactive nickel component. Here in this review we intensively summarize thedegradation mechanism of Ni-rich cathode materials including e.g., residual lithium species, cation mixing, gas generation, surface structure reconstruction, crack, thermal instability, and transition metal dissolution. Furthermore, the state-of-art strategies e.g., new preparation methods, single-crystal, doping, structure design, coating and new binders, to tackle these degradation problem are accounted. This review might be inspiring for better understanding the degradation mechanism and relevant coping approaches of high-energy cathode materials for lithium ion batteries.

富镍层状过渡金属氧化物具有非常高的容量,是电动汽车高能锂离子电池极具竞争力的正极材料,但由于其高活性的镍成分而面临快速降解的关键问题。本文综述了富镍正极材料的降解机理,包括锂残留、阳离子混合、气体生成、表面结构重构、裂纹、热不稳定性和过渡金属溶解等。此外,还介绍了解决这些降解问题的最新策略,如新的制备方法、单晶、掺杂、结构设计、涂层和新型粘合剂等。本文的研究对进一步认识高能锂离子电池正极材料的降解机理及相应的应对方法具有一定的启发意义。
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引用次数: 4
Recent advances and challenges of anodes for aqueous alkaline batteries 碱性电池阳极的研究进展与挑战
IF 25.1 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-09-01 DOI: 10.1016/j.enchem.2023.100102
Lijun Zhou , Jinhao Xie , Diyu Xu , Yanxia Yu , Xingyuan Gao , Xihong Lu

The ongoing surge in demand for energy conversion and storage spurs the development of high-efficiency batteries. In recent decades, aqueous alkaline batteries (AABs) have been the focus point owing to the high safety, low cost, environmental benefits, impressive output voltage and theoretical energy density. However, the large-scale application of AABs is hindered by the poor cyclability and insufficient capacity utilization, especially in anodes. To circumvent the issues, great research efforts have been dedicated to the electrode design and electrolyte optimization. In this review, reaction mechanisms, modification strategies, application feasibility and existing challenges are systematically summarized and highlighted. Additionally, insightful perspectives and research orientations are proposed for further development of AABs anodes.

能源转换和存储需求的持续激增刺激了高效电池的发展。近几十年来,水碱性电池(AABs)因其高安全性、低成本、环保效益、高输出电压和理论能量密度而成为研究的热点。然而,AABs的大规模应用受到循环性差和容量利用率不足的阻碍,特别是在阳极方面。为了解决这些问题,人们在电极设计和电解质优化方面进行了大量的研究。本文对反应机理、改性策略、应用可行性和存在的挑战进行了系统的总结和强调。此外,还对AABs阳极的进一步发展提出了有见地的观点和研究方向。
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引用次数: 0
Design strategies of electrocatalysts for acidic oxygen evolution reaction 酸性析氧反应电催化剂的设计策略
IF 25.1 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-09-01 DOI: 10.1016/j.enchem.2023.100104
Shubham Kaushik, Xin Xiao, Qiang Xu

Electrochemical water splitting, especially in acidic media, is a promising technology for hydrogen production and sustainable energy conversion. However, it remains a challenge to synthesize suitable acidic oxygen evolution reaction (OER) electrocatalysts that provide high activity and long-term stability according to the industrial standards. Up to date, quite few reviews provide a systematic summarization of the strategies and approaches to improve the electrocatalytic performances of the catalysts in acidic electrolytes. Herein, we analyze the electrochemical behavior of the reported state-of-the-art OER catalysts and provide a comprehensive review of the systematic strategies for preparing high-performance electrocatalysts. First, we introduce some fundamentals of OER mechanism to give readers a deeper understanding of this field. Then, we summarize and discuss various design strategies, including electronic state modulation, structural manipulation, etc. Finally, the challenges, opportunities, and future outlook regarding acidic OER electrocatalysts are delivered. This review will serve as a useful guiding resource for researchers seeking in-depth understanding of the OER mechanism in acidic media as well as learning approaches for synthesizing highly efficient and cost-effective OER electrocatalysts.

电化学水分解是一种很有前途的制氢和可持续能源转换技术,特别是在酸性介质中。然而,如何合成符合工业标准、具有高活性和长期稳定性的酸性析氧反应(OER)电催化剂仍然是一个挑战。目前,国内外对提高催化剂在酸性电解质中的电催化性能的策略和方法进行了较为系统的综述。在此,我们分析了目前报道的最先进的OER催化剂的电化学行为,并对制备高性能电催化剂的系统策略进行了全面的综述。首先,我们将介绍OER机制的一些基本原理,以便读者对该领域有更深入的了解。然后,我们总结和讨论了各种设计策略,包括电子状态调制,结构操纵等。最后,介绍了酸性OER电催化剂的挑战、机遇和未来展望。本文将为研究人员深入了解酸性介质中OER的机理以及合成高效、经济的OER电催化剂提供有益的指导资源。
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引用次数: 3
Synthetic porous carbons for clean energy storage and conversion 用于清洁能源储存和转化的合成多孔碳
IF 25.1 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-07-01 DOI: 10.1016/j.enchem.2023.100099
Xiao-Ling Dong, Lu Hou, Xu Hu, Yu-Tai Wu, Ling-Yu Dong, Xiao-Fei Yu, Guang-Ping Hao, An-Hui Lu

Synthetic porous carbons (SPCs) are important materials in fundamental research and industrial applications due to their diverse structures at different dimensions, intriguing physio-chemical properties, exceptional thermal and chemical stability, etc. In particular, the features including high electron conductivity, accessible active surface/interface, and developed porosity warrant their superior performances in clean energy storage and conversion. In this review, we summarize the latest advances in SPCs, serving as electrodes for this ever-increasing energy storage and conversion-related directions, e.g., supercapacitors, rechargeable batteries, fuel cells, etc. We emphasized rational design and targeted synthesis of SPCs based on bottom-up strategy, the effective methods for precise tuning of their core parameters, and the disclosure of their structure-performance correlations. The challenges of fine-tuning surface chemistry by doping heteroatoms, engineering defective sites, and optimizing compositions are discussed, which could endow the SPCs with new functions and potential applications. Finally, we outlined the developing trend and design principle of the new generation of SPCs for clean energy storage and conversion. We expect that this review could inspire interdisciplinary activities between the synthesis, physical and chemical studies of SPCs and other potential applications in addition to energy storage and conversion.

合成多孔碳(SPCs)具有不同尺寸的结构、独特的物理化学性质、优异的热稳定性和化学稳定性等特点,是基础研究和工业应用的重要材料。特别是高电子导电性、易接近的活性表面/界面和发达的孔隙度等特点,保证了其在清洁能源存储和转换方面的优越性能。在这篇综述中,我们总结了SPCs的最新进展,作为电极在这个日益增长的能量存储和转换相关的方向,如超级电容器,可充电电池,燃料电池等。我们强调了基于自底向上策略的SPCs的合理设计和有针对性的合成,精确调整其核心参数的有效方法,以及揭示其结构-性能相关性。讨论了通过杂原子掺杂、缺陷位点工程和优化组成来微调表面化学的挑战,这将赋予SPCs新的功能和潜在的应用前景。最后,我们概述了用于清洁能源存储和转换的新一代SPCs的发展趋势和设计原则。我们希望这篇综述能够激发SPCs的合成、物理和化学研究之间的跨学科活动,以及除能量存储和转换之外的其他潜在应用。
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引用次数: 5
Advanced porous adsorbents for radionuclides elimination 用于消除放射性核素的先进多孔吸附剂
IF 25.1 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-07-01 DOI: 10.1016/j.enchem.2023.100101
Mengjie Hao , Yanfang Liu , Weijin Wu , Shiyu Wang , Xinyi Yang , Zhongshan Chen , Zhenwu Tang , Qifei Huang , Suhua Wang , Hui Yang , Xiangke Wang

With the rapid development of nuclear industry, effective management of nuclear waste and oversight of nuclear fuel cycle are critical. Radionuclides such as uranium (U), plutonium (Pu), neptunium (Np), americium (Am), curium (Cm), technetium (Tc), rhenium (Re), iodine (I), selenium (Se), thorium (Th), cesium (Cs), and strontium (Sr) transferred into environment are dangerous. It is crucial to design the corresponding materials to exhibit high adsorption capacity and selectivity among competing species in nuclear waste. Herein, this review comprehensively summarizes the application of advanced porous materials, including metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and amorphous porous organic polymers (POPs) as porous adsorbents for radionuclides removal. These porous materials feature uniform composition, large porosity, and good stability, which lay a good foundation for various applications. The tunable pore sizes, high specific surface areas, exchangeable sites, and functional groups are designed as accessible platforms for nuclides diffusion and adsorption. Specific binding mechanisms toward various radionuclides, such as complexation, electrostatic interaction, and ion exchange are presented. Beyond traditional adsorbents, the superior capacity, kinetics, selectivity, and reusability of COFs, MOFs, and POPs make them broad application prospects in radionuclides removal, providing a way for effective applications in environmental remediation.

随着核工业的快速发展,有效的核废料管理和对核燃料循环的监督至关重要。铀(U)、钚(Pu)、镎(Np)、镅(Am)、锔(Cm)、锝(Tc)、铼(Re)、碘(I)、硒(Se)、钍(Th)、铯(Cs)和锶(Sr)等放射性核素转移到环境中是危险的。设计相应的材料,使其在核废料的竞争物种中具有较高的吸附能力和选择性是至关重要的。本文综述了金属有机骨架(MOFs)、共价有机骨架(COFs)和无定形多孔有机聚合物(pop)等先进多孔材料在放射性核素去除中的应用。这些多孔材料成分均匀,孔隙率大,稳定性好,为各种应用奠定了良好的基础。可调孔径,高比表面积,交换位点和官能团被设计为核素扩散和吸附的可访问平台。介绍了与各种放射性核素的特殊结合机制,如络合、静电相互作用和离子交换。在传统吸附剂的基础上,COFs、mof和POPs具有优良的吸附能力、动力学、选择性和可重复使用性,在放射性核素去除方面具有广阔的应用前景,为其在环境修复中的有效应用提供了途径。
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引用次数: 53
Design of ammonia oxidation electrocatalysts for efficient direct ammonia fuel cells 高效直接氨燃料电池氨氧化电催化剂的设计
IF 25.1 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-05-01 DOI: 10.1016/j.enchem.2022.100093
Zhen-Hua Lyu , Jiaju Fu , Tang Tang , Jianan Zhang , Jin-Song Hu

In the past few decades, renewable-energy-driven fuel cell technologies have been widely investigated as promising approaches to alleviate the energy and environmental crisis caused by fossil fuel consumption. Similar to hydrogen, ammonia provides a potential solution due to its comparable energy density and carbon-free emissions. Besides, the convenient storage and transportation of ammonia make the direct ammonia fuel cell (DAFC) a more secure technology than the hydrogen-based fuel cell system. However, the sluggish kinetics of ammonia oxidation reaction significantly hindered the performance of low-temperature DAFCs, urgently demanding systematic guidance for designing high-efficiency electrocatalysts. In this review, with an in-depth study of the basic principle of DAFC and the mechanism of AOR, we systematically summarized and discussed the recently reported strategies for developing high-performance AOR electrocatalysts, including size regulating, crystal facet engineering, morphology controlling, defect engineering, alloying, heterostructure constructing, and molecular engineering strategies. Finally, we propose perspectives and challenges for future AOR electrocatalyst development and high-performance DAFC construction. We hope this review could provide significant insights into fabricating active and stable AOR electrocatalysts for practical low-temperature DAFC.

在过去的几十年里,可再生能源驱动的燃料电池技术作为缓解化石燃料消耗造成的能源和环境危机的有希望的方法得到了广泛的研究。与氢类似,由于其相当的能量密度和无碳排放,氨提供了一种潜在的解决方案。此外,氨的方便储存和运输使直接氨燃料电池(DAFC)成为比氢基燃料电池系统更安全的技术。然而,氨氧化反应的缓慢动力学严重阻碍了低温DAFCs的性能,迫切需要系统的指导来设计高效的电催化剂。本文在深入研究DAFC的基本原理和AOR机理的基础上,系统地总结和讨论了近年来报道的制备高性能AOR电催化剂的策略,包括尺寸调节、晶面工程、形貌控制、缺陷工程、合金化、异质结构构建和分子工程策略。最后,对未来AOR电催化剂的发展和高性能DAFC的构建提出了展望和挑战。希望本综述能为制备高效稳定的AOR电催化剂提供参考。
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引用次数: 4
Aqueous transition-metal ion batteries: Materials and electrochemistry 水性过渡金属离子电池:材料与电化学
IF 25.1 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-05-01 DOI: 10.1016/j.enchem.2022.100097
Sheng Zhu , Qian Wang , Jiangfeng Ni

The constant pursuit of alternative energy sources stimulates the rapid exploitation of energy storage systems. Compared to alkali metal-ion batteries, aqueous transition-metal ion batteries have captured increasing attention because of their high safety, eco-friendliness, abundant resources, and low cost. More importantly, their multivalent chemistry offers opportunities to realize storage technologies with higher energy. Although these bright prospects have fostered progress in recent years, practical deployment of these batteries has been denied by several scientific and technological issues including sluggish reaction kinetics, poor electrochemical reversibility, and low material stability. In this comprehensive overview, we focus on the materials and electrochemistry of several booming aqueous transition-metal ion batteries such as Zn, Cu, Fe, and Mn-ion systems. State-of-the-art progress accompanied with the solutions to addressing the above-mentioned issues are highlighted. A particular focus is laid on zinc-ion batteries, which are ready to become commercially available. Finally, the remaining challenges and future directions in the field are also outlined. We anticipate that this review will supply a clear understanding of the current status and meaningful guidelines for researchers in developing aqueous transition-metal ion batteries.

对替代能源的不断追求刺激了储能系统的快速开发。与碱金属离子电池相比,水过渡金属离子电池因其安全性高、生态友好、资源丰富、成本低等优点而受到越来越多的关注。更重要的是,他们的多价化学为实现更高能量的存储技术提供了机会。尽管这些光明的前景促进了近年来的进展,但这些电池的实际部署一直受到一些科学和技术问题的阻碍,包括反应动力学缓慢、电化学可逆性差和材料稳定性低。在这篇全面的综述中,我们重点介绍了几种蓬勃发展的水性过渡金属离子电池的材料和电化学,如锌、铜、铁和锰离子系统。强调了最新进展以及解决上述问题的办法。特别关注的是锌离子电池,它已经准备好商业化了。最后,对该领域存在的挑战和未来发展方向进行了概述。我们期望这篇综述将为研究人员开发水过渡金属离子电池的现状提供一个清晰的认识和有意义的指导。
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引用次数: 3
Alloy electrocatalysts 合金electrocatalysts
IF 25.1 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-03-01 DOI: 10.1016/j.enchem.2022.100083
Meng Du , Xinran Li , Huan Pang , Qiang Xu

The development of clean sustainable energy conversion technologies to deal with energy shortage and environmental pollution has aroused a widespread concern. To improve the rate and selectivity of the pivotal chemical reactions involved in these technologies, high-performance electrocatalysts are crucial. Alloys have sparked research hotspot in electrocatalysis because of their higher catalytic activity, stability, and selectivity than their single-metal counterparts. In this review, the design strategies for alloy electrocatalysts are firstly introduced with a focus on how to achieve optimal performance by composition regulation, size optimization and morphology control. Subsequently, we offer a comprehensive overview of the electrocatalytic applications of binary, ternary, quaternary, and high-entropy alloys to different types of electrochemical energy conversion processes, including the hydrogen evolution, oxygen evolution, oxygen reduction, CO2 reduction, formic acid oxidation, methanol oxidation, and ethanol oxidation reactions. Finally, the challenges and future outlook are presented for the rational design of advanced alloy electrocatalysts.

发展清洁的可持续能源转换技术以应对能源短缺和环境污染已引起广泛关注。为了提高这些技术中关键化学反应的速率和选择性,高性能的电催化剂是至关重要的。合金具有较高的催化活性、稳定性和选择性,已成为电催化领域的研究热点。本文首先介绍了合金电催化剂的设计策略,重点介绍了如何通过成分调节、尺寸优化和形貌控制来实现合金电催化剂的最佳性能。随后,我们全面概述了二元、三元、四元和高熵合金在不同类型的电化学能量转换过程中的电催化应用,包括析氢、析氧、氧还原、CO2还原、甲酸氧化、甲醇氧化和乙醇氧化反应。最后,对先进合金电催化剂的合理设计提出了挑战和展望。
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引用次数: 18
Surface reconstruction-derived heterostructures for electrochemical water splitting 电化学水分解的表面重构异质结构
IF 25.1 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-03-01 DOI: 10.1016/j.enchem.2022.100091
Xu Luo , Xin Tan , Pengxia Ji , Lei Chen , Jun Yu , Shichun Mu

Electrocatalytic water splitting for green hydrogen generation is of great significance for renewable energy conversion and storage. The development of efficient electrocatalysts to reduce the energy barriers of the two half-reactions of hydrogen evolution (HER) and oxygen evolution (OER) is the key to realize the high-efficiency industrialization of electrochemical water splitting. With the continuous investment of research efforts, diverse transition metal-based catalysts have flourished, and their dynamic structural reconstruction during electrocatalytic OER and HER has also been pushed into a research upsurge. Since most transition metal compounds are thermodynamically unstable under electrochemical OER or HER conditions, they tend to undergo dynamic structural evolution to reach a relatively stable state, whereby the in situ reconstructed surface as the real reactivity species induces the changes in catalytic activity, which brings challenges to understanding the real catalytic mechanism and also motivates the development of surface reconstruction as a novel strategy to design superior heterostructure catalysts. At present, how to rationally utilize surface reconstruction to achieve breakthroughs in catalytic performance has become a critical focus area. This review summarizes the recent progress of surface reconstruction-derived heterostructures for electrocatalytic OER and HER, highlighting the fundamental understanding of surface reconstruction behaviors, the correlation between the intrinsic structure and dynamic reconstruction process of pristine catalysts, and some possible catalytic mechanisms that responsible for the enhanced catalytic activity. Moreover, several instructive design strategies of catalysts for modulating structural reconstruction to obtain optimized activity including heteroatom doping/substitution, anion/cation induction, structural defects, and heterostructure construction, are then introduced. Finally, we put forward the challenges and outlooks for surface reconstruction engineering, providing new insights and directions for future research development.

电催化水裂解绿色制氢技术对可再生能源转换和储存具有重要意义。开发高效电催化剂,降低析氢(HER)和析氧(OER)两个半反应的能垒,是实现电化学水分解高效产业化的关键。随着研究工作的不断投入,各种过渡金属基催化剂蓬勃发展,其在电催化OER和HER过程中的动态结构重构也被推向了研究热潮。由于大多数过渡金属化合物在电化学OER或HER条件下热力学不稳定,它们倾向于通过动态结构演化达到相对稳定的状态,从而原位重构表面作为真正的反应活性物质引起催化活性的变化。这给理解真正的催化机理带来了挑战,也激发了表面重构作为设计优质异质结构催化剂的新策略的发展。目前,如何合理利用表面重构实现催化性能的突破已成为一个关键的关注领域。本文综述了电催化OER和HER的表面重构异质结构的最新进展,重点介绍了对表面重构行为的基本认识,原始催化剂的内在结构与动态重构过程之间的关系,以及催化活性增强的一些可能的催化机制。此外,还介绍了几种调节结构重构以获得最佳活性的催化剂设计策略,包括杂原子掺杂/取代、阴离子/阳离子诱导、结构缺陷和异质结构构建。最后,我们提出了表面重建工程面临的挑战和展望,为未来的研究发展提供了新的见解和方向。
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引用次数: 22
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