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两种基于一维安德森型多金属氧酸盐的金属有机配合物作为用于CO光还原和硫氧化的双功能多相催化剂

Two 1D Anderson-Type Polyoxometalate-Based Metal-Organic Complexes as Bifunctional Heterogeneous Catalysts for CO Photoreduction and Sulfur Oxidation.

作者信息

Yang Jian-Bo, Pan Jia-Hang, Zhu Yin-Hua, Wang Ji-Lei, Mei Hua, Xu Yan

机构信息

College of Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 210009, P. R. China.

出版信息

Inorg Chem. 2022 Aug 1;61(30):11775-11786. doi: 10.1021/acs.inorgchem.2c01497. Epub 2022 Jul 20.

DOI:10.1021/acs.inorgchem.2c01497
PMID:35858285
Abstract

Sulfur oxides from the combustion of petrol and excessive emissions of carbon dioxide (CO) are currently the main causes of environmental pollution. Considerable interest has been paid to solving the challenge, and catalytic reactions seem to be the desired choice. Due to the high density of Lewis acid active sites, polyoxometalates are considered to be the ideal choice for these catalytic reactions. Herein, two captivating polyoxometalate-based metal-organic complexes, formulated as [Co(HO)DABT][CrMo(OH)O] () and [Zn(HO)DABT][CrMo(OH)O] () (DABT = 3,3'-diamino-5,5'-bis(1-1,2,4-triazole)) were successfully obtained under hydrothermal conditions. The structural analysis demonstrates that and are isostructural with two different transition metal (Co/Zn) ions based on quadridentate Anderson-type [CrMo(OH)O] polyanions. A fan-shaped unit of / is linked to generate a one-dimensional (1D) ladder-like structure. Intriguingly, benefitting from rich Co centers with a suitable energy band structure, displays better photocatalytic activity than for converting CO into CO, endowing the CO formation of 1935.3 μmol g h with high selectivity. Meanwhile, also exhibits a satisfactory removal rate of 99% for oxidizing dibenzothiophene at 50 °C, which suggests that may be utilized as a potential dual functional material with immense prospects in photocatalytic CO reduction and sulfur oxidation for the first time.

摘要

汽油燃烧产生的硫氧化物以及过量排放的二氧化碳(CO)是当前环境污染的主要原因。人们对解决这一挑战给予了极大关注,催化反应似乎是理想的选择。由于路易斯酸活性位点密度高,多金属氧酸盐被认为是这些催化反应的理想选择。在此,在水热条件下成功获得了两种引人注目的基于多金属氧酸盐的金属有机配合物,其化学式分别为[Co(HO)DABT][CrMo(OH)O]()和[Zn(HO)DABT][CrMo(OH)O]()(DABT = 3,3'-二氨基-5,5'-双(1-1,2,4-三唑))。结构分析表明,基于四齿安德森型[CrMo(OH)O]多阴离子,和具有两种不同的过渡金属(Co/Zn)离子的同构结构。/的扇形单元相连形成一维(1D)梯状结构。有趣的是,得益于具有合适能带结构的丰富Co中心,在将CO转化为CO方面表现出比更好的光催化活性,使CO的生成量达到1935.3 μmol g h且具有高选择性。同时,在50℃下对二苯并噻吩的氧化也表现出99%的令人满意的去除率,这表明可能首次被用作在光催化CO还原和硫氧化方面具有巨大前景的潜在双功能材料。

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