该文综述了无金属碳材料作为氧化还原反应电催化剂的最新研究进展，特别是理论与实验相结合对电催化机理的认识。来自中国科学院上海硅酸盐研究所高性能陶瓷与超微结构国家重点实验室的王家成研究员和北京航空航天大学仪器科学与光电工程学院的单光存教授共同领导的团队，评述了从高效氮掺杂碳纳米管的发现到最近兴起的缺陷碳材料机制研究方面的重要进展。将杂原子和缺陷引入碳材料的策略，能够暴露更多的活性位点且更有效地调节材料的电子结构，使氧还原优先通过四电子途径发生反应，有效提高电催化反应动力学，具有十分广阔的应用前景。因此，掺杂和缺陷协同作用，会进一步降低自由能和反应过电位，有可能赋予这种碳材料优于商用铂碳电催化剂的高效催化活性。而且，作者认为为了进一步揭示碳材料电催化机理，先进表征技术需要被广泛应用于组分、微结构和反应过程分析，例如，环境压力的X射线光电子能谱或时间分辨技术等。该综述近期发表于npj Computational Materials 5:78 (2019)。 

　　https://www.nature.com/articles/s41524-019-0210-3 　　

　　Summary 

　　Metal-free carbon-based electrocatalysts: Oxygen reduction mechanisms 

　　The latest advance in the research of metal-free carbon materials as electrocatalysts toward the oxygen reduction reaction (ORR), especially the understanding of mechanism on the electrocatalysis is reviewed. A team co-led by Prof. Jiacheng Wang and Guangcun Shan from the State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, and the School of Instrumentation Science and Opto-electronics Engineering, Beihang University, respectively, China, commented the significant progress on electrocatalytic mechanisms achieved from the finding of highly efficient N-doped carbon nanotube to the recently renascent defective carbon materials. As a result, the intentional introduction of both heteroatoms and defects into carbon materials can be a promising strategy to create catalytic active sites and boost the electrocatalytic kinetics via a preferential four-electron pathway. The synergistic effect of doping and defects may further lower the free energy and reaction overpotential, thus endowing such carbon materials with the potential to outperform the state-of-the-art Pt/C electrocatalyst during the catalytic process. Moreover, advanced characterization techniques are proposed to be extensively utilized to analyze the microstructure and composition of the carbon catalysts, especially in situ or operando  spectroscopy/microscopy characterization, such as ambient pressure X-ray photoelectron spectroscopy or time-resolved technique. This review was recently published in npj Computational Materials 5:78(2019). 　

　　原文Abstract及其翻译 

　　A review of oxygen reduction mechanisms for metal-free carbon-based electrocatalysts (无金属碳基电催化剂的氧还原机理综述) 

　　Ruguang Ma, Gaoxin Lin, Yao Zhou, Qian Liu, Tao Zhang, Guangcun Shan, Minghui Yang & Jiacheng Wang 

　　Abstract：The sluggish kinetics of Oxygen Reduction Reaction (ORR) at the cathode in proton exchange membrane fuel cells or metal-air batteries requires highly effective and stable electrocatalysts to boost the reaction. The low abundance and high price of Pt-based electrocatalysts hamper the widespread application of proton exchange membrane fuel cells and metal-air batteries. As promising alternatives, metal-free carbon materials, especially upon doping heteroatoms or creating defects demonstrated excellent ORR activity, which is as efficient as or even superior to commercial platinum on carbon. Significant progress on the development of advanced carbon materials as highly stable and durable catalysts has been achieved, but the catalytic mechanisms of these materials still remain undistinguished. In present review, we summarized the up-to-date progress in the studies of carbon materials, and emphasized on the combination of experiment and theory to clarify the underlying mechanisms of these materials. At last, we proposed the perspectives on the proper strategies of elucidating the mechanisms of carbon materials as electrocatalysts towards ORR. 

　　摘要： 

　　在质子交换膜燃料电池或金属-空气电池中，阴极氧还原反应动力学缓慢，需要高效且稳定的电催化剂来促进反应的进行。铂基电催化剂在地壳中的低丰度和高价格，阻碍了质子交换膜燃料电池和金属空气电池的大规模应用。作为应用潜力巨大的替代品，无金属碳材料，特别是掺杂杂原子或制造缺陷后，表现出优异的氧化还原反应活性，其电催化效果可与商业铂碳相媲美，甚至更加优异。作为高稳定性和耐久性催化剂，先进碳材料的开发近几年取得了重要进展，但这些材料的催化机理仍未被完全揭示。在本综述中，我们总结了无金属碳材料在这方面的最新研究进展，强调了实验与理论相结合来阐明这些材料催化功能的潜在机制。最后，我们讨论了探索碳材料电催化氧化还原反应机理所需要的表征技术和研究策略。 

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