异金属取代的多金属氧酸盐@光响应型金属-有机框架用于高选择性光催化CO_(2)还原  

Highly selective photoreduction of CO_(2)catalyzed by the encapsulated heterometallic‐substituted polyoxometalate into a photo‐responsive metal‐organic framework

作　　者：李慧杰 池漫洲 辛兴 王瑞杰 刘天府 吕红金 杨国昱 Huijie Li;Manzhou Chi;Xing Xin;Ruijie Wang;Tianfu Liu;Hongjin Lv;Guo‐Yu Yang(MOE Key Laboratory of Cluster Science,Beijing Key Laboratory of Photoelectroic/Electrophotonic Conversion Materials,School of Chemistry and Chemical Engineering,Beijing Institute of Technology,Beijing 102488,China)

机构地区：[1]北京理工大学化学与化工学院,光电/电光转换材料北京重点实验室,原子分子簇科学教育部重点实验室,北京102488

出　　处：《Chinese Journal of Catalysis》2023年第7期343-351,共9页催化学报（英文）

基　　金：国家自然科学基金(21871025,21831001);国家海外高层次人才引进计划青年项目;北理工高层次人才科研启动计划项目.

摘　　要：传统化石燃料的过度消耗以及CO_(2)的持续排放,使开发可再生的碳中性燃料迫在眉睫.利用太阳能将CO_(2)光还原为能量密集的有机分子(CO,HCOOH,HCHO和CH_(3)OH等)被认为是一种绿色可持续但极具挑战性的方案.实现该方案所面临的关键难点是开发高效、廉价的光催化CO_(2)还原催化剂.作为一种具有前景的多电子转移催化剂,过渡金属取代的多金属氧酸盐(POM)因其结构丰富且物化性质可调,越来越多地被应用于光催化CO_(2)还原研究.其结构中的缺位多酸配体可用作电子存储海绵以实现光催化CO_(2)还原反应中的多电子转移过程.然而,目前均相催化体系面临的主要挑战在于可溶性POMs催化剂的可回收性不高和催化活性低等.为解决上述挑战,可行的策略是将可溶性POMs催化剂装载到多孔金属有机框架(MOFs)中,制备POM@MOF复合材料,从而将可溶性POMs催化剂优越的催化活性与多孔材料的可回收性结合起来.作为一类光敏型MOF材料,NU-1000具有良好的光响应能力和合适的孔道结构,可容纳不同尺寸的POMs客体分子.目前,基于POM@NU-1000的复合材料在光驱动分解水制氢领域已有一些报道;然而,该类复合材料在太阳能驱动的光催化CO_(2)还原中的应用研究仍然较少.本文构筑了一种异金属取代的POM@NU-1000复合材料(P_(2)W_(15)Ni_(3){Re(CO)_(3)}_(3)@NU-1000)通过浸渍法将Ni-Re异金属取代POMs(Na(NH4)5[P_(2)W_(15)O_(56)Ni_(3)(H_(2)O)3(μ3-OH)3{Re(CO)3}3]·18H_(2)O)锚定到NU-1000MOF孔道中.系列实验实验证实了P_(2)W_(15)Ni_(3){Re(CO)_(3)}_(3)客体团簇成功装载进NU-1000主体的孔道中.在最佳条件下,P_(2)W_(15)Ni_(3){Re(CO)_(3)}_(3)@NU-1000复合材料能有效地进行光催化CO_(2)还原,反应10 h的CO产量高达28982μmolg^(–1),选择性达93.5%.此外,该催化体系具有良好的光催化稳定性和至少4次连续循环的可重复性.催化反应机理研究表明,高效的光催化CO_(2)还原性The highly selective photoreduction of CO_(2 )into valuable chemical fuels such as CO has been considered as an effective strategy to address modern energy and environmental issues.In this work,we have adopted the well‐established impregnation approach to construct a P_(2)W_(15)Ni_(3){Re(CO)_(3)}_(3)@NU‐1000 composite by incorporating heterometallic‐substituted P_(2)W_(15)Ni_(3){Re(CO)_(3)}_(3)polyoxometalate(POM)into the pores of metal‐organic framework(NU‐1000)host.Upon light irradiation,the resulting P_(2)W_(15)Ni_(3){Re(CO)_(3)}_(3)@NU‐1000 composite can effectively photocatalyze CO_(2 )reduction,obtaining a CO production of 28982μmol g^(–1)with 93.5%selectivity during 10‐h photocatalysis.The catalytic system exhibits great long‐term recyclability and stability for at least four successive recycles.The proposed photocatalytic mechanism was confirmed by a series of photochemical and spectroscopic analyses.

关 键 词：CO_(2)还原 多金属氧酸盐 金属有机框架材料 异金属取代 光催化 

分 类 号：O643.36[理学—物理化学] X701[理学—化学]