金属-空气电池中双功能电催化剂微纳结构设计（英文）

金属-空气二次电池在可再生电能的存储和转换方面具有广阔的应用前景.在金属-空气二次电池的空气侧,放电时发生氧还原反应(ORR),充电时发生氧析出反应(OER).然而, ORR和OER反应的动力学过程缓慢,因此限制了金属-空气二次电池的实际应用.因此,发展高性能ORR和OER电催化剂对金属-空气二次电池的发展尤为重要.目前,大多数的研究集中在ORR或OER的单功能电催化剂上,而关于双功能电催化剂的研究和综述相对较少.两个反应均具有较高的过电位和较缓慢的动力学过程,而且充电过程的高电压会导致ORR催化剂失活,反之亦然.因此,开发针对这两个反应均具有高活性和高稳定性的双功能电催化剂极具挑战性.近年来,研究者对具有低成本和高性能双功能电催化剂进行了探索.这些双功能电催化剂包括碳基材料,过渡金属材料和复合材料.双功能电催化剂可以通过提高本征活性和表观活性两种策略来提高其整体的活性.其中,本征活性与晶体结构和电子结构密切相关,即可以通过调节晶体结构和电子结构来提高其本征活性.例如,可以改变金属-氧键的强度、氧空位浓度等来调变电催化活性.在碳基材料中掺杂杂原子可以改变碳的电荷密度分布,从而实现对电催...     

Manganese-based bifunctional electrocatalysts for zinc-air batteries

Manganese-based materials have been attractive candidates for zinc-air batteries in the recent years. This is as a result of their natural abundance, low cost and level of toxicity. However, this review shows that the application still faces some challenges. In our opinion, continual fundamental information on strategies for improving the catalytic activity/performance could promote the commercialization of low cost with relatively high operating voltages profile of manganese-based materials for zinc-air batteries.     

Current progress of molybdenum carbide-based materials for electrocatalysis: potential electrocatalysts with diverse applications

Electrocatalysts are the cores of many electrochemical reactions including hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), nitrogen reduction reaction (NRR), and CO₂ reduction reaction (CO₂RR). Recent advances in research have demonstrated the potentials of molybdenum carbide-based catalysts for these reactions arising out of their unique electronic structure and physicochemical properties. In this review, we systematically summarize the recent advances of molybdenum carbide-based catalysts in these electrochemical processes. The corresponding synthesis strategies, structure and electrocatalytic performance of the catalysts are discussed and the relationships of the process-structure-property are highlighted. In addition, the catalytic mechanisms are analyzed based on the structure characterization and theoretical calculations results. Finally, the existing challenges and future perspectives are put forward for further development of molybdenum carbide-based catalysts.     

High Performance Bifunctional Electrocatalysts Designed Based on Transition-Metal Sulfides for Rechargeable Zn–Air Batteries

Due to the energy crisis by the excessive consumption of fossil fuels, Zinc–air batteries (ZABs) with high theoretical energy density have attracted people‘s attention. The overall performance of ZABs is largely determined by the air cathode catalyst. Therefore, it is necessary to develop high-efficiency and low-cost bifunctional catalysts to replace noble metal catalysts to promote the development of ZABs. Among a variety of cathode catalysts, TMS has become a research hotspot in recent years because of its better electrical conductivity than metal phosphides and metal oxides. In this work, we focus on the means of improving the electrocatalytic performance of transition-metal sulfides (TMS) providing ideas for us to rationally design high-performance catalysts. Furthermore, the performance improvement law between catalyst performance and ZABs is also discussed in this work. Finally, some challenges and opportunities faced in the research of TMS electrocatalysis are briefly proposed, and strategies for improving the performance of ZABs are prospected.     

中空四氧化三钴纳米球镶嵌的氮掺杂多孔碳纳米纤维:锂-氧电池氧电极双功能催化剂（英文）

随着全球人口数量快速增长和科技不断进步,对能源需求逐步增加,但化石能源日渐枯竭,同时环境问题日趋严重.因此,亟需开发新型、绿色、高效的能源以及能源装置,以保障清洁能源的可持续利用.锂-氧电池因其能量密度高、环境友好等优点受到了人们的广泛关注,并被认为是替代锂离子电池的新储能系统之一.然而,对于锂-氧电池仍需解决诸如能量密度低于理论值、倍率性能差和循环寿命短等难题.开发高效稳定的氧电极催化剂是解决上述问题的关键手段之一.在众多潜在的过渡金属氧化物催化剂中,四氧化三钴因其地壳丰度高、成本低和性能优异等优点成为研究热点.本文采用静电纺丝技术,结合热处理技术,成功制备了中空四氧化三钴纳米球镶嵌的多孔碳纳米纤维复合催化剂(H-Co3O4-CNFs),系统地研究了其氧还原反应(ORR)和析氧反应(OER)的电催化性能,以及作为锂-氧电池正极催化剂的电化学性能.结果表明,在碱性电解质中, H-Co3O4-CNFs具有较好的ORR/OER活性,展现出较好的双功能催化性能.H-Co3O4-CNFs作为锂-氧电池的氧电极催化剂材料,在100 mAg-1电流密度下的过电位为1.35 V,电池的放电比容量达到...     

导电金属有机框架材料在电催化中的成就，挑战和机遇

To fulfill the demands of green and sustainable energy, the production of novel catalysts for different energy conversion processes is critical. Owing to the intriguing advantages of the intrinsic active species, tunable crystal structure, remarkable chemical and physical properties, and good stability, metal-organic frameworks (MOFs) have been extensively investigated in various electrochemical energy conversions, such as the CO₂ reduction reaction, N₂ reduction reaction, oxygen evolution reaction, hydrogen evolution reaction, and oxygen reduction reaction. More importantly, it is feasible to change the chemical environments, pore sizes, and porosity of MOFs, which will theoretically facilitate the diffusion of reactants across the open porous networks, thereby improving the electrocatalytic performance. However, owing to the high energy barriers of charge transfer and limited free charge carriers, most MOFs show poor electrical conductivity, thus limiting their diverse applications. As reported previously, MOFs were used as a porous substrate to confine the growth of nanoparticles or co-doped electrocatalysts after annealing. The conductive MOFs can combine the advantages of conventional MOFs with electronic conductivity, which significantly enhance the electrocatalytic performance. In addition, conductive MOFs can achieve conductivity via electronic or ionic routes without post-annealing treatment, thereby extending their potential applications. Different synthesis strategies have recently been developed to endow MOFs with electrical conductivity, such as post-synthesis modification, guest molecule introduction, and composite formatting. The performance of conductive MOFs can even outperform those of commercial RuO₂ catalysts or Pt-group catalysts. However, it is difficult to endow most MOFs with high conductivity. This review summarizes the mechanisms of constructing conductive MOFs, such as redox hopping, through-bond pathways, through-space pathways, extended conjugation, and guest-promoted transport. Synthetic methods, including hydro/solvothermal synthesis and interface-assisted synthesis, are introduced. Recent advances in the use of conductive MOFs as heterogeneous catalysts in electrocatalysis have been comprehensively elucidated. It has been reported that conductive MOFs can demonstrate considerable catalytic activity, selectivity, and stability in different electrochemical reactions, revealing the immense potential for future displacement of Pt-group catalysts. Finally, the challenges and opportunities of conductive MOFs in electrocatalysis are discussed. Based on systematic synthesis strategies, more conductive MOFs can be constructed for electrocatalytic reactions. In addition, the morphology and structure of conductive MOFs, which can change the electrochemical accessibility between substrates and MOFs, are also crucial for catalysis, and thus, they should be extensively studied in the future. It is believed that a breakthrough for high-performance conductive MOF-based electrocatalysts could be achieved.     

导电金属有机框架材料在电催化中的成就，挑战和机遇

开发用于各种能量转化过程的新型催化剂对于满足绿色和可持续能源的需求至关重要。由于其具有可调节的晶体结构,显著的化学和物理性质以及稳定性,金属有机骨架(MOFs)已经广泛应用于电化学能量转换领域,比如CO₂还原反应、N₂还原反应、析氧反应、析氢反应和氧还原反应。更重要的是,MOFs具有可调节的化学环境、孔径和孔隙率,这些性质将促进反应物在多孔网络中的扩散,从而改善其电催化性能。但是,由于高的电荷转移能垒和受限的自由载流子,大多数MOFs展示了差的导电性,阻碍了其多样化应用。在先前的报道中,MOFs常被用作多孔基质来限制纳米颗粒生长或经退火处理作为共掺杂电催化剂。而导电MOFs不仅结合了传统MOFs的优点,还具有电子导电性和高电催化活性,使其无需退火处理就可以通过电子或离子途径实现导电,从而极大提高了电催化性能,这有助于拓宽其在电化学能源领域或其他方面的潜在应用。在一些催化反应中,导电MOFs的催化活性甚至超过了商业化的RuO₂催化剂或Pt基催化剂。本文主要总结了构建导电MOFs的机制,并概述了其合成方法,如水/溶剂热合成和界面辅助合成。此外,本文阐述了导电MOFs在电催化应用中的最新研究进展。值得一提的是,导电MOFs的形态和结构可改变底物与MOFs之间的界面接触,从而影响其催化性能,需要进一步深入研究。基于系统的合成策略,在未来可以根据各种电催化反应的需求设计合成更多的导电MOFs。高性能的导电MOF基催化剂将有望获得突破。     

基于金属有机框架化合物纳米电催化剂的研究进展

金属有机框架化合物具有比表面积大、孔隙率高、结构有序可控等特点,近年来作为电催化材料在电化学能源储存和转化应用中备受关注。本文从金属有机框架化合物作为前驱体制备电催化剂的独特优点入手,总结了目前该类材料在电催化领域的最新研究进展,并对其今后的发展趋势以及面临的机遇和挑战进行了简单的展望。     

Recent trends in hydrogen and oxygen electrocatalysis for anion exchange membrane technologies

This review aims at presenting recent findings in the understanding of oxygen and hydrogen electrocatalysis in alkaline electrolytes that are key processes for the emergence of sustainable energy storage and conversion devices such as anion exchange membrane fuel cells and electrolyzers. In these systems, the exchange of electrons through electrochemical reactions provides a unique pathway to reversibly convert the electricity vector into chemical one: hydrogen. A concise and critical review of advances made during the last past years in the design of catalysts is provided. Challenges and opportunities for the development of the next catalyst generation are also addressed.     

B， N共掺杂富勒烯C70作为氧还原和氧析出非金属电催化剂的理论研究

采用密度泛函理论研究了B; N共掺杂富勒烯C₇₀[C₆₈B(n)N(m); n; m=1~5; 分别代表B和N取代的C位点]的氧还原反应(ORR)和氧析出反应(OER)性能. 结果表明; C₆₈B(n)N(m)在热力学上是稳定的; 且其ΔG_*OOH和ΔG_*O与ΔG_*OH均呈良好的线性关系. 其中; C₆₈B(4)N(2)与C₆₈B(5)N(2)催化剂的ORR过电位为0.45 V; 与商业Pt催化剂相当; C₆₈B(4)N(1)的OER过电位最低（0.38 V）; 优于传统RuO₂催化剂(0.42 V); C₆₈B(1)N(3)也表现出与RuO₂相当的OER活性. 通过精确调控B; N共掺杂位置; 可显著降低ORR与OER过电位; 提升C₇₀的催化性能. 根据活性趋势图; C₆₈B(n)N(m)的最佳ORR和OER活性分别出现在ΔG_*O-ΔG_*OH=0.92 eV和ΔG_*O-ΔG_*OH=1.42 eV处. 研究结果为设计和发现新的非金属碳基电催化剂提供了线索.