用于优化光催化产氢的三明治结构金属有机框架复合材料的连接体工程

Linker Engineering of Sandwich-Structured Metal-Organic Framework Composites for Optimized Photocatalytic H Production.

作者信息

Wang Siyuan, Ai Zhiwen, Niu Xinwei, Yang Weijie, Kang Rong, Lin Zhongyuan, Waseem Amir, Jiao Long, Jiang Hai-Long

机构信息

Hefei National Research Center for Physical Sciences at the Microscale, Department of Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), University of Science and Technology of China, Hefei, Anhui, 230026, P. R. China.

School of Energy and Power Engineering, North China Electric Power University, Baoding, Hebei, 071003, P. R. China.

出版信息

Adv Mater. 2023 Sep;35(39):e2302512. doi: 10.1002/adma.202302512. Epub 2023 Aug 4.

DOI:10.1002/adma.202302512

PMID:37421606

Abstract

While the microenvironment around catalytic sites is recognized to be crucial in thermocatalysis, its roles in photocatalysis remain subtle. In this work, a series of sandwich-structured metal-organic framework (MOF) composites, UiO-66-NH @Pt@UiO-66-X (X means functional groups), is rationally constructed for visible-light photocatalytic H production. By varying the ─X groups of the UiO-66-X shell, the microenvironment of the Pt sites and photosensitive UiO-66-NH core can be simultaneously modulated. Significantly, the MOF composites with identical light absorption and Pt loading present distinctly different photocatalytic H production rates, following the ─X group sequence of ─H > ─Br > ─NA (naphthalene) > ─OCH > ─Cl > ─NO . UiO-66-NH @Pt@UiO-66-H demonstrates H production rate up to 2708.2 µmol g h , ≈222 times that of UiO-66-NH @Pt@UiO-66-NO . Mechanism investigations suggest that the variation of the ─X group can balance the charge separation of the UiO-66-NH core and the proton reduction ability of Pt, leading to an optimal activity of UiO-66-NH @Pt@UiO-66-H at the equilibrium point.

摘要

虽然催化位点周围的微环境在热催化中被认为至关重要，但其在光催化中的作用仍不明确。在这项工作中，一系列三明治结构的金属有机框架（MOF）复合材料UiO-66-NH@Pt@UiO-66-X（X表示官能团）被合理构建用于可见光光催化产氢。通过改变UiO-66-X壳层的─X基团，可以同时调节Pt位点和光敏UiO-66-NH核的微环境。值得注意的是，具有相同光吸收和Pt负载量的MOF复合材料呈现出明显不同的光催化产氢速率，遵循─X基团顺序为─H > ─Br > ─NA（萘）> ─OCH > ─Cl > ─NO。UiO-66-NH@Pt@UiO-66-H的产氢速率高达2708.2 μmol g⁻¹ h⁻¹，约为UiO-66-NH@Pt@UiO-66-NO的222倍。机理研究表明，─X基团的变化可以平衡UiO-66-NH核的电荷分离和Pt的质子还原能力，从而使UiO-66-NH@Pt@UiO-66-H在平衡点处具有最佳活性。