基于金属-有机框架同分异构体构建MOFs相结用以增强CO_(2)光还原活性  

Assembling phase-junctions based on metal-organic framework polymophism for enhanced overall CO_(2) photoreduction activities

作　　者：黄海波 李兰 王瑞 AR Mahammed Shaheer 刘天赋 刘海雄 曹荣 Haibo Huang;Lan Li;Rui Wang;AR Mahammed Shaheer;Tianfu Liu;Haixiong Liu;Rong Cao(School of Environmental Science and Engineering,Qingdao University,Qingdao 266071,China;State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China;University of Chinese Academy of Sciences,Chinese Academy of Sciences,Beijing 100049,China;College of Materials and Chemistry,China Jiliang University,Hangzhou 310018,China)

机构地区：[1]School of Environmental Science and Engineering,Qingdao University,Qingdao 266071,China [2]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China [3]University of Chinese Academy of Sciences,Chinese Academy of Sciences,Beijing 100049,China [4]College of Materials and Chemistry,China Jiliang University,Hangzhou 310018,China

出　　处：《Science China Materials》2024年第6期1839-1845,共7页中国科学（材料科学）（英文版）

基　　金：the support from the National Natural Science Foundation of China (2220102005,22071246,and 22033008);Shandong Provincial Natural Science Foundation (ZR2023QB173);the Technology Support Program for Youth Innovation Team of Shandong Higher Education Institutions (2023KJ225);the Postdoctoral Application Project of Qingdao (QHBSH20230102024)。

摘　　要：利用太阳能将CO_(2)光转化为化学燃料是前沿研究的热点.当前,科研的重点在于开发和优化各类光催化材料的性能.异质结构不仅用于增强无机半导体催化剂的活性,而且用于金属-有机框架(MOFs)光催化剂的构建.随着异质结技术的不断进步,新的相结概念应运而生.尽管关于无机半导体中的相结研究已取得一定进展,但是MOFs相结结构的探索尚处于起步阶段.本文中,我们成功设计并构建了一种具有卓越光催化CO_(2)还原性能的MOFs相结杂化材料.这种材料由具有高度连接性的卟啉配体(TCPP-Ni)与Zr6团簇紧密结合而成,在溶剂热反应条件下,PCN-222-Ni能够快速且均匀地成核.通过精准调控调节剂的用量,我们实现了同分异构体PCN-224-Ni在类似条件下较慢的晶体形成过程.最终制得的P@P杂化材料展现出高表面积、多孔性和卓越的结晶度.由于PCN-222-Ni和PCN-224-Ni之间的带隙匹配,光生载流子的分离和迁移得以促进,从而使P@P杂化材料展现出卓越的光还原CO_(2)性能.这一重大突破不仅标志着MOFs相结结构研究的重大进展,还拓宽了MOFs相结在CO_(2)光转化领域的应用前景.The conversion of solar energy into chemical fuels stands at the forefront of promising applications for metal-organic frameworks(MOFs),but the rapid re-combination of photo-induced charge carriers within these frameworks poses a significant challenge to their photo-catalytic performance.Despite heterojunction construction has potential as a viable approach,its synthesis involves con-siderable complexity.Here,we present a distinct and well-defined phase junction based on polymorphic MOFs,achieved through an efficient one-pot synthesis process.This work not only paves the way for a robust platform for designing so-phisticated MOFs complexes,but also illuminates the intricate hierarchical structure-function dynamics inherent in MOFs.The fabricated PCN-222-Ni@PCN-224-Ni(P@P)hybrid ma-terial exhibits extensive surface area,a porous matrix,and superior crystallinity.The harmonious alignment of the band-gap between PCN-222-Ni and PCN-224-Ni,establishing a phase junction for type-II carrier transfer,endows the re-sultant photocatalysts with exceptional visible-light-induced photoreduction capabilities for CO_(2),along with augmented stability.This significant advancement represents a significant milestone in the applications of MOFs,especially in harnes-sing solar energy for the production of sustainable chemical fuels through the process of CO_(2) photo-conversion.

关 键 词：MOFs polymorphism phase-junctions photo-catalytic CO_(2)reduction 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学]