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  

Fe nanoparticles embedded in N‐doped porous carbon for enhanced electrocatalytic CO_(2)reduction and Zn‐CO_(2)battery

作　　者：杨文倩 薛自前 杨俊 冼家慧 刘庆林 范雅楠 郑凯 廖锫钦 苏徽 刘庆华[3] 李光琴 苏成勇 Wenqian Yang;Ziqian Xue;Jun Yang;Jiahui Xian;Qinglin Liu;Yanan Fan;Kai Zheng;Peiqin Liao;Hui Su;Qinghua Liu;Guangqin Li;Cheng‐Yong Su(State Key Laboratory of Optoelectronic Materials and Technologies,MOE Laboratory of Bioinorganic and Synthetic Chemistry,Lehn Institute of Functional Materials,School of Chemistry,Sun Yat‐Sen University,Guangzhou 510006,Guangdong,China;Institute for Integrated Cell‐Material Sciences,Kyoto University,Institute for Advanced Study,Kyoto University,Yoshida,Ushinomiya‐cho,Sakyo‐ku,Kyoto 606‐8501,Japan;National Synchrotron Radiation Laboratory,University of Science and Technology of China,Hefei 230026,Anhui,China)

机构地区：[1]中山大学化学学院,莱恩功能材料研究所,光电材料与技术国家重点实验室,教育部生物无机与合成化学实验室,广东广州510006 [2]京都大学综合细胞材料科学研究所,京都大学高级研究所,日本京都 [3]中国科学技术大学国家同步辐射实验室,安徽合肥230026

出　　处：《Chinese Journal of Catalysis》2023年第5期185-194,共10页催化学报（英文）

基　　金：国家重点研发计划(2021YFA1500401);广东省珠江人才计划引进创新团队(2017ZT07C069);广东省珠江人才计划本土创新团队(2017BT01C161);国家自然科学基金(22075321,21821003,21890380).

摘　　要：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�The selective electrochemical reduction of CO_(2)to CO is a promising solution for the design of carbon‐neutral,sustainable processes.Achieving a highly selective single reduction product is still challenging because of the energetically favorable competing hydrogen evolution reaction.We report the fabrication of N‐doped sponge‐like porous graphitic carbon structures embedded with Fe nanoparticles(Fe@NPC)via the pre‐modification of a metal‐organic framework(IRMOF‐3(Zn))with carboxyferrocene,followed by pyrolysis.The as‐prepared Fe@NPC exhibited a 96.4%CO Faradaic efficiency at–0.5 V_(RHE)and good stability.The exceptional CO_(2)reduction performance is attributed to the unique structure of the composite catalyst,which provides abundant hierarchical pores that increase CO_(2)adsorption and mass transfer,and active Fe sites that synergistically accelerate the kinetics of CO generation.The in situ attenuated total reflectance‐Fourier transform infrared analysis provided proof of the improved ability of Fe@NPC to accumulate the crucial intermediate*COOH compared with other pyrolyzed porous carbons.Fe@NPC was used in a Zn‐CO_(2)battery that delivered a maximum power density of 3.0 mW cm^(-2),evidencing its potential for application in energy‐converting devices.

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 

分 类 号：TB383.1[一般工业技术—材料科学与工程] O643.36[理学—物理化学] TM911.41[理学—化学]