Product Control in Visible-Light-Driven CO2 Reduction by Switching Metal Centers of Binuclear Catalysts

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-01-27 DOI:10.1021/acscatal.4c0480010.1021/acscatal.4c04800

Chao Su, Hai-Hua Huang, Zubing Huang, Zilu Chen*, Anna Mo, Jia-Wei Wang, Huancheng Hu, Huahong Zou, Zhuofeng Ke, Fupei Liang*, Tong-Bu Lu* and Dongcheng Liu*,

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Abstract

Controlled selectivity of products for visible-light-driven photocatalytic reduction of CO₂ in water-containing systems is highly desirable. Here, we report two highly efficient and selective binuclear complex catalysts, [Co₂(^MeL-S)(OAc)₂](OAc) (CoCo) and [Cu₂(^MeL-S)(H₂O)](CF₃SO₃)₂·2H₂O (CuCu), bearing a N₆S-type polypyridine sulfur ligand (^MeL-S^–) in situ formed from 2,6-bis[(bis(pyridylmethyl)amino)methyl]-4-methylmercaptophenylsulfide (^MeL-S-S-L^Me), which can promote the selective reduction of CO₂ into CO and HCOOH employing [Ru(phen)₃](PF₆)₂ as photosensitizer, respectively, under the irradiation of visible light in CH₃CN/H₂O (4/1 v/v) solution. We found that CoCo can catalyze the conversion of CO₂ to CO with a high selectivity (96%) and a TON value of 6188. However, HCOOH was found for the CuCu case with a high selectivity (98%) and TON value (7540). Experimental results and DFT calculations revealed that the close Cu···Cu distance in CuCu facilitates the hydrogenation process through a 3-center-4-electron (3c-4e^–) bond to give high efficiency and high HCOOH selectivity. However, 3c-4e^– is absent in CoCo due to the well-separated Co centers and high total valence of the Co atoms, which lead to a high CO selectivity.

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双核催化剂金属中心开关在可见光驱动CO2还原中的产物控制

在含水系统中，可见光驱动光催化还原CO2的产物的选择性控制是非常可取的。本文报道了两种高效、选择性的双核配合物催化剂[Co2(MeL-S)(OAc)2](OAc) （CoCo）和[Cu2(MeL-S)(H2O)](CF3SO3)2·2H2O (CuCu)，它们含有由2,6-二[（双（吡啶基甲基）氨基）甲基]-4-甲基巯基苯基硫化物（MeL-S- s - lme）原位形成的n2s型多吡啶硫配体（MeL-S-），分别可以促进以[Ru(phen)3](PF6)2为光敏剂的Co2选择性还原为CO和HCOOH。在CH3CN/H2O （4/ 1v /v）溶液中可见光照射下。我们发现CoCo催化CO2转化为CO的选择性高（96%），TON值为6188。然而，在CuCu病例中发现HCOOH具有高选择性（98%）和TON值（7540）。实验结果和DFT计算表明，CuCu中的Cu···Cu距离较近，有利于通过3中心-4电子键（3c-4e -）氢化过程，具有较高的氢化效率和高的HCOOH选择性。然而，由于Co中心分离良好和Co原子的高总价，在CoCo中不存在3c-4e -，这导致了Co的高选择性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.