A Tunable Multivariate Metal-Organic Framework as a Platform for Designing Photocatalysts

Yang Wang; Hao Lv; Erik Svensson Grape; Carlo Alberto Gaggioli; Akhil Tayal; Aditya Dharanipragada; Tom Willhammar; A Ken Inge; Xiaodong Zou; Ben Liu; Zhehao Huang

doi:10.1021/jacs.1c01764

A Tunable Multivariate Metal-Organic Framework as a Platform for Designing Photocatalysts

J Am Chem Soc. 2021 May 5;143(17):6333-6338. doi: 10.1021/jacs.1c01764. Epub 2021 Apr 26.

Authors

Yang Wang^{1

2}, Hao Lv¹, Erik Svensson Grape³, Carlo Alberto Gaggioli⁴, Akhil Tayal⁵, Aditya Dharanipragada³, Tom Willhammar³, A Ken Inge³, Xiaodong Zou³, Ben Liu^{1

6}, Zhehao Huang³

Affiliations

¹ College of Chemistry, Sichuan University, Chengdu 610064, China.
² Key Laboratory for Soft Chemistry and Functional Materials, Nanjing University of Science and Technology, Ministry of Education, Nanjing 210094, China.
³ Department of Materials and Environmental Chemistry, Stockholm University, Stockholm SE-106 91, Sweden.
⁴ Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United States.
⁵ Photon Science, Deutsches Elektronen-Synchrotron, Hamburg 22607, Germany.
⁶ Jiangsu Key Laboratory of New Power Batteries, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China.

Abstract

Catalysts for photochemical reactions underlie many foundations in our lives, from natural light harvesting to modern energy storage and conversion, including processes such as water photolysis by TiO₂. Recently, metal-organic frameworks (MOFs) have attracted large interest within the chemical research community, as their structural variety and tunability yield advantages in designing photocatalysts to address energy and environmental challenges. Here, we report a series of novel multivariate metal-organic frameworks (MTV-MOFs), denoted as MTV-MIL-100. They are constructed by linking aromatic carboxylates and AB₂OX₃ bimetallic clusters, which have ordered atomic arrangements. Synthesized through a solvent-assisted approach, these ordered and multivariate metal clusters offer an opportunity to enhance and fine-tune the electronic structures of the crystalline materials. Moreover, mass transport is improved by taking advantage of the high porosity of the MOF structure. Combining these key advantages, MTV-MIL-100(Ti,Co) exhibits a high photoactivity with a turnover frequency of 113.7 mol_H2 g_cat.^-1 min^-1, a quantum efficiency of 4.25%, and a space time yield of 4.96 × 10^-5 in the photocatalytic hydrolysis of ammonia borane. Bridging the fields of perovskites and MOFs, this work provides a novel platform for the design of highly active photocatalysts.