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氮掺杂多孔碳负载Fe纳米颗粒用于高性能电催化还原CO_(2)与Zn-CO_(2)电池 被引量:2
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作者 杨文倩 薛自前 +9 位作者 杨俊 冼家慧 刘庆林 范雅楠 郑凯 廖锫钦 苏徽 刘庆华 李光琴 苏成勇 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 2023年第5期185-194,共10页
电催化CO_(2)还原为CO因其技术与经济上的可行性而被认为是推进碳中和最有前景的反应之一.然而,水溶液中激烈的竞争性析氢反应阻碍生成单一高选择性产物.目前,贵金属纳米催化剂表现出较好的CO选择性,但稀缺性和高成本限制了其进一步应用... 电催化CO_(2)还原为CO因其技术与经济上的可行性而被认为是推进碳中和最有前景的反应之一.然而,水溶液中激烈的竞争性析氢反应阻碍生成单一高选择性产物.目前,贵金属纳米催化剂表现出较好的CO选择性,但稀缺性和高成本限制了其进一步应用.Fe纳米颗粒(NPs)具有电催化活性,且储量丰富成本低,被认为是一种潜在可替代贵金属的电催化剂,但Fe存在易氧化、团聚、稳定性差、吸附CO_(2)能力低等问题.因此,探索同时具有良好活性和稳定性的新型Fe NPs催化剂仍具有重要意义.金属-有机骨架(MOFs)衍生物被认为是合成锚定和激活金属纳米颗粒的良好前驱体.因此,将Fe NPs固定在MOFs衍生物中为开发稳定、高活性的Fe NPs催化剂提供了可行的机会.本文通过修饰MOFs前驱体的策略,对IRMOF-3(Zn)进行少量含铁配体单羧酸二茂铁的取代,结合一步热解碳化,制备了Fe NPs负载在海绵状氮掺杂多孔碳的复合催化剂(Fe@NPC).同时对配体为对苯二甲酸的MOF-5和配体为2-氨基-对苯二甲酸的IRMOF-3(Zn)进行热解碳化,制备了对照样品多孔碳MOF-5-D和氮掺杂多孔碳IRMOF-3-D.光电子能谱(XPS)和X射线吸收精细结构谱(XAFS)结果表明,在Fe@NPC中含有大量的Fe-Fe键以及极少量的Fe-N/C键,说明Fe主要以纳米颗粒形式存在,少量Fe-N/C分布在Fe NPs表面,在Fe NPs与氮掺杂碳基底间起到良好的连接作用.此外,Fe@NPC具有较大的比表面积(1264 m^(2)g^(-1))和高于MOF-5-D与IRMOF-3-D的CO_(2)吸附能力(93.5 cm^(3)g^(-1)),这种具有CO_(2)强吸附和丰富活性位点的多级孔结构为加速传质、加快CO_(2)转化奠定了良好的基础.在H-cell与-0.6 V_(RHE)的条件下,IRMOF-3-D的最大CO法拉第效率(FECO)为65.3%,是MOF-5-D(49.9%)的1.3倍,说明氮掺杂在一定程度上促进了CO_(2)的电还原.此外,Fe@NPC在-0.3 V_(RHE)到1.0 V_(RHE)的宽电位化学区间均表现出较好的性能,即最大的电流密度,最低的起始电位以及92.1%的最高的FECO.而且Fe@NPC在流动池中可以获得更高的FECO(96.4%),同时能够在H-cell与流动池中均保持良好的稳定性.由于*COOH高能垒,它的产生被认为是高效电化学CO_(2)-CO转换的瓶颈.进一步采用原位衰减全反射-傅里叶变换红外(ATR-IR)来实时监测中间体,并深入探究Fe@NPC作用于CO_(2)还原过程的机理,观测到中间体*COOH的逐渐形成和积累,以及同一反应时间内*COOH在Fe@NPC上的更快动力学形成过程;进一步说明Fe位点与氮掺杂多孔碳之间的协同作用显著提高了Fe@NPC的CO_(2)的捕获能力和传质能力并加速了CO生成的动力学.本文以Fe@NPC为阴极组装了Zn-CO_(2)电池,发现该电池具有良好的充电放电性能,放电过程中可提供3.0 mW cm^(-2)的峰值功率密度,同时表现出良好的稳定性(120个循环),实现CO_(2)电还原与储能的良好结合,并表现出高效的能量转换装置的良好应用潜力.综上,本文为设计用于高选择性的CO_(2)还原反应和能量转换器件的铁基催化剂提供了一种新方法. 展开更多
关键词 Fe纳米颗粒 MOFs衍生物 氮掺杂多孔碳 CO_(2)电催化 Zn-CO_(2)电池
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Recent Progress of Metal Organic Frameworks-Based Electrocatalysts for Hydrogen Evolution,Oxygen Evolution,and Oxygen Reduction Reaction 被引量:1
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作者 Yaling Jia ziqian xue +1 位作者 Yinle Li Guangqin Li 《Energy & Environmental Materials》 SCIE EI CAS CSCD 2022年第4期1084-1102,共19页
Exploring efficient and cost-saving electrocatalysts is essential to the renewable energy storage and utilization,which is still in its embryonic period.MOFs have drawn tremendous attention due to their adjustability,... Exploring efficient and cost-saving electrocatalysts is essential to the renewable energy storage and utilization,which is still in its embryonic period.MOFs have drawn tremendous attention due to their adjustability,abundant active sites,and plentiful pores.Notably,satisfactory electrocatalytic performance has been achieved by MOFs-based electrocatalysts comparable to traditional electrocatalysts.State-of-the-art works about the MOFs-based electrocatalysts for hydrogen evolution reaction(HER),oxygen evolution reaction(OER),and ORR were summarized in this review.This review comprises a series of modifying strategies of MOFs and their derivatives,from aspects of structure,composition,and morphology.Furthermore,the active sites and functional mechanisms’recognition are involved in this review expecting to provide reference for rationally designing efficient electrocatalysts.At last,the current status,challenges,and perspectives of MOFs-based electrocatalysts are also discussed. 展开更多
关键词 ELECTROCATALYSTS hydrogen evolution metal organic frameworks oxygen evolution oxygen reduction reaction
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Metal organic frameworks-based cathode materials for advanced Li-S batteries: A comprehensive review
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作者 Zhengkun Xie Boyong Cao +5 位作者 Xiyan Yue Ruixue Wang ziqian xue Jiajia Wang Guoqing Guan Weihua Chen 《Nano Research》 SCIE EI CSCD 2024年第4期2592-2618,共27页
Li-S batteries(LSBs)have been considering as new and promising energy storage systems because of the high theoretical energy density and low price.Nevertheless,their practical application is inhibited by several facto... Li-S batteries(LSBs)have been considering as new and promising energy storage systems because of the high theoretical energy density and low price.Nevertheless,their practical application is inhibited by several factors,including poor electrical conductivity of electrode materials,greatly volumetric variation,as well as the polysulfide formation upon the cycling.To address these problems,it is imperative to develop and design effective and suitable sulfur host anode materials.Metal organic frameworks(MOFs)-based cathode materials,possessing their good conductivity and easy morphology design,have been extensively studied and exhibited enormously potential in LSBs.In this review,a comprehensive overview of MOFs-based sulfur host materials is provided,including their electrochemical reaction mechanisms,related evaluation parameters,and their performances used in LSBs in the past few years.In particular,the recent advances using in-situ characterization technologies for investigating the electrochemical reaction mechanism in LSBs are presented and highlighted.Additionally,the challenges and prospects associated with future research on MOF-related sulfur host materials are discussed.It is anticipated to offer the guidance for the identification of suitable MOFs-based sulfur cathode materials for high-performance LSBs,thereby contributing for the achievement of a sustainable and renewable society. 展开更多
关键词 lithium metal anode sulfur cathode metal organic frameworks HOST energy density in-situ characterization
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