Wang Yang, Lv Hao, Grape Erik Svensson, Gaggioli Carlo Alberto, Tayal Akhil, Dharanipragada Aditya, Willhammar Tom, Inge A Ken, Zou Xiaodong, Liu Ben, Huang Zhehao
College of Chemistry, Sichuan University, Chengdu 610064, China.
Key Laboratory for Soft Chemistry and Functional Materials, Nanjing University of Science and Technology, Ministry of Education, Nanjing 210094, China.
J Am Chem Soc. 2021 May 5;143(17):6333-6338. doi: 10.1021/jacs.1c01764. Epub 2021 Apr 26.
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 TiO. 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 ABOX 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 g min, a quantum efficiency of 4.25%, and a space time yield of 4.96 × 10 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.
光化学反应催化剂是我们生活中许多基础的核心，从自然光捕获到现代能量存储与转换，包括诸如TiO光解水等过程。最近，金属有机框架（MOF）在化学研究领域引起了广泛关注，因为它们的结构多样性和可调节性在设计光催化剂以应对能源和环境挑战方面具有优势。在此，我们报道了一系列新型多元金属有机框架（MTV-MOF），命名为MTV-MIL-100。它们通过连接芳香族羧酸盐和具有有序原子排列的ABOX双金属簇构建而成。通过溶剂辅助方法合成，这些有序的多元金属簇为增强和微调晶体材料的电子结构提供了机会。此外，利用MOF结构的高孔隙率改善了传质。结合这些关键优势，MTV-MIL-100（Ti，Co）在氨硼烷的光催化水解中表现出高光活性，周转频率为113.7 mol g min，量子效率为4.25%，时空产率为4.96×10。这项工作架起了钙钛矿和MOF领域之间的桥梁，为设计高活性光催化剂提供了一个新平台。
