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

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.