Photocatalytic CO2 reduction by Ni-substituted polyoxometalates: Structure-activity relationships and mechanistic insights

IF 20.2 1区化学 Q1 CHEMISTRY, PHYSICAL Applied Catalysis B: Environmental Pub Date : 2024-01-02 DOI:10.1016/j.apcatb.2023.123681

Khadija Talbi , Francesc Penas-Hidalgo , Amanda L. Robinson , Philipp Gotico , Winfried Leibl , Pierre Mialane , Maria Gomez-Mingot , Marc Fontecave , Albert Solé-Daura , Caroline Mellot-Draznieks , Anne Dolbecq

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Abstract

The photocatalytic activity for CO₂ reduction of a series of Ni-substituted polyoxometalates (POMs) differing in nuclearity, shape and size, has been investigated under visible light irradiation, with [Ru(bpy)₃]²⁺ (bpy = 2,2′-bipyridine) as photosensitizer and triethanolamine as sacrificial donor. The tetrabutylammonium salt of the Ni₄ tetranuclear species was found to exhibit the highest CO production and its stability under photocatalytic conditions was demonstrated. The catalytic performance was significantly lower for the alkaline salt due to the separation of the POM from its counter-ions occurring only for the tetrabutylammonium salt. Photophysical experiments evidenced a bimolecular electron transfer from the reduced photosensitizer [Ru(bpy)₃]⁺ to the Ni₄ POM, the former arising from the reductive quenching of the [Ru(bpy)₃]²⁺ excited state by triethanolamine. This was further supported by DFT calculations, which also showed that the Ni₄ POM accumulates at least two electrons and four protons to carry out the CO₂ reduction catalytic process.

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镍取代的多氧金属卤化物光催化二氧化碳还原：结构-活性关系和机理启示

以[Ru(bpy)3]2+（bpy = 2,2'-联吡啶）为光敏剂，以三乙醇胺为牺牲供体，研究了一系列在核性、形状和尺寸上各不相同的镍取代的多氧金属盐（POMs）在可见光照射下还原二氧化碳的光催化活性。研究发现，Ni4 四核物种的四丁基铵盐具有最高的 CO 产率，并证明了其在光催化条件下的稳定性。碱性盐的催化性能明显较低，这是因为只有四丁基铵盐才会出现 POM 与反离子分离的现象。光物理实验证明了还原型光敏剂 [Ru(bpy)3]+ 与 Ni4 POM 之间的双分子电子转移，前者产生于三乙醇胺对 [Ru(bpy)3]2+ 激发态的还原淬灭。DFT 计算进一步证实了这一点，计算结果还表明，Ni4 POM 至少积累了两个电子和四个质子，以进行二氧化碳还原催化过程。

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

Applied Catalysis B: Environmental 环境科学-工程：化工

CiteScore

38.60

自引率

6.30%

发文量

1117

审稿时长

24 days

期刊介绍： Applied Catalysis B: Environment and Energy (formerly Applied Catalysis B: Environmental) is a journal that focuses on the transition towards cleaner and more sustainable energy sources. The journal's publications cover a wide range of topics, including: 1.Catalytic elimination of environmental pollutants such as nitrogen oxides, carbon monoxide, sulfur compounds, chlorinated and other organic compounds, and soot emitted from stationary or mobile sources. 2.Basic understanding of catalysts used in environmental pollution abatement, particularly in industrial processes. 3.All aspects of preparation, characterization, activation, deactivation, and regeneration of novel and commercially applicable environmental catalysts. 4.New catalytic routes and processes for the production of clean energy, such as hydrogen generation via catalytic fuel processing, and new catalysts and electrocatalysts for fuel cells. 5.Catalytic reactions that convert wastes into useful products. 6.Clean manufacturing techniques that replace toxic chemicals with environmentally friendly catalysts. 7.Scientific aspects of photocatalytic processes and a basic understanding of photocatalysts as applied to environmental problems. 8.New catalytic combustion technologies and catalysts. 9.New catalytic non-enzymatic transformations of biomass components. The journal is abstracted and indexed in API Abstracts, Research Alert, Chemical Abstracts, Web of Science, Theoretical Chemical Engineering Abstracts, Engineering, Technology & Applied Sciences, and others.