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通过金属有机骨架转化诱导预成核实现固溶氧化物异质结光催化剂的通用制备。

A General Preparation of Solid Solution-Oxide Heterojunction Photocatalysts through Metal-Organic Framework Transformation Induced Pre-nucleation.

机构信息

State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, China.

Key Laboratory of Magnetism and Magnetic Materials of Ministry of Education, School of Physical Science and Technology, Lanzhou University, Lanzhou, 730000, China.

出版信息

Angew Chem Int Ed Engl. 2023 Jun 26;62(26):e202302986. doi: 10.1002/anie.202302986. Epub 2023 May 15.

Abstract

Solid solution-oxide heterostructures combine the advantages of solid solution and heterojunction materials to improve electronic structure and optical properties by metal doping, and enhance charge separation and transfer in semiconductor photocatalysts by creating a built-in electric field. Nevertheless, the effective design and synthesis of these materials remains a significant challenge. Here, we develop a generally applicable strategy that leverages the transformable properties of metal-organic frameworks (MOFs) to prepare solid solution-oxide heterojunctions with controllable structural and chemical compositions. The process consists of three main steps. First, MOFs with different topological structures and metal centers are transformed, accompanied by pre-nucleation of a metal oxide. Second, solid solution is prepared through calcination of the transformed MOFs. Finally, a heterojunction is formed by combining solid solution with another metal oxide group through endogenous overflow. DFT calculations and study on carrier dynamics show that the structure of the material effectively prevents electrons from returning to the bulk phase, exhibiting superior photocatalytic reduction performance of CO . This study is expected to promote the controllable synthesis and research of MOF-derived heterojunctions.

摘要

固溶体氧化物异质结构结合了固溶体和异质结材料的优点,通过金属掺杂来改善电子结构和光学性能,并通过在半导体光催化剂中创建内置电场来增强电荷分离和转移。然而,这些材料的有效设计和合成仍然是一个重大挑战。在这里,我们开发了一种普遍适用的策略,利用金属有机骨架(MOFs)的可变形特性来制备具有可控结构和化学成分的固溶体氧化物异质结。该过程包括三个主要步骤。首先,具有不同拓扑结构和金属中心的 MOFs 发生转化,同时伴随着金属氧化物的预成核。其次,通过转化后的 MOFs 的煅烧来制备固溶体。最后,通过内源溢出将固溶体与另一个金属氧化物组合形成异质结。DFT 计算和载流子动力学研究表明,该材料的结构有效地阻止了电子返回到体相,表现出优异的 CO 光催化还原性能。本研究有望促进 MOF 衍生异质结的可控合成和研究。

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