Acetylacetonate Derived Cobalt(III) Complexes as Photocatalysts and Electrocatalysts for Energy Conversion.

IF 2.8 4区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

ChemPlusChem Pub Date : 2025-10-06 DOI:10.1002/cplu.202500305

Thamilarasan Vijayan, Abida Batool, Yu Mi Park, Jinheung Kim, Rodrigo Arancibia, Nallathambi Sengottuvelan

{"title":"Acetylacetonate Derived Cobalt(III) Complexes as Photocatalysts and Electrocatalysts for Energy Conversion.","authors":"Thamilarasan Vijayan, Abida Batool, Yu Mi Park, Jinheung Kim, Rodrigo Arancibia, Nallathambi Sengottuvelan","doi":"10.1002/cplu.202500305","DOIUrl":null,"url":null,"abstract":"Developing systems that facilitate the conversion of solar energy into fuel by reducing carbon dioxide and producing hydrogen could bridge the gap between production and consumption. In this work, a new method to study the reaction intermediates of carbon dioxide reduction reaction (CO2RR) and hydrogen elimination reaction (HER) catalyzed by Cobalt(III) catalysts with high photocatalytic activity in a water/acetonitrile solvent system is proposed. The optimization of the cobalt catalysts ([Co(acac)(bpy)(N3)2].H2O 1, [Co(acac)(en)(N3)2] 2 and [Co(acac)(2-pic)(N3)2] 3) for photocatalytic activities in visible light irradiation (>420 nm) is performed by varying solvents systems (v/v) (CH3COCH3/H2O, CH3CN/H2O, DMF/H2O, EtOH/H2O and H2O), sacrificial electron donors (1-benzyl-1,4-dihydronicotinamide (BNAH), diethanolamine (DEOA), triethylamine (TEA), and triethanolamine (TEOA), photosensitizers (Eosin Y, Erythrosin B, Fluorescein (Fl), Rose Bengal, Rhodamine-B, and Ru(bpy)3 (Ru)), pH (7-12.5) and different catalyst concentrations (0-2 mM). The arrangement around the Cobalt(III) ion is an octahedral coordination geometry. A combination of experimental characterization and density functional theory (DFT) is used to identify the mechanism of the photocatalytic CO2 reduction reaction. DFT calculations and experimental results for the photocatalytic activity of the catalysts 1-3 reveal the involvement of multi-electron metal-ligand exchange coupling in promoting CO2RR and HER, and provide a starting point for the integration of these strategies into catalyst design.","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202500305"},"PeriodicalIF":2.8000,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ChemPlusChem","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/cplu.202500305","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}

引用次数: 0

Abstract

Developing systems that facilitate the conversion of solar energy into fuel by reducing carbon dioxide and producing hydrogen could bridge the gap between production and consumption. In this work, a new method to study the reaction intermediates of carbon dioxide reduction reaction (CO₂RR) and hydrogen elimination reaction (HER) catalyzed by Cobalt(III) catalysts with high photocatalytic activity in a water/acetonitrile solvent system is proposed. The optimization of the cobalt catalysts ([Co(acac)(bpy)(N₃)₂].H₂O 1, [Co(acac)(en)(N₃)₂] 2 and [Co(acac)(2-pic)(N₃)₂] 3) for photocatalytic activities in visible light irradiation (>420 nm) is performed by varying solvents systems (v/v) (CH₃COCH₃/H₂O, CH₃CN/H₂O, DMF/H₂O, EtOH/H₂O and H₂O), sacrificial electron donors (1-benzyl-1,4-dihydronicotinamide (BNAH), diethanolamine (DEOA), triethylamine (TEA), and triethanolamine (TEOA), photosensitizers (Eosin Y, Erythrosin B, Fluorescein (Fl), Rose Bengal, Rhodamine-B, and Ru(bpy)₃ (Ru)), pH (7-12.5) and different catalyst concentrations (0-2 mM). The arrangement around the Cobalt(III) ion is an octahedral coordination geometry. A combination of experimental characterization and density functional theory (DFT) is used to identify the mechanism of the photocatalytic CO₂ reduction reaction. DFT calculations and experimental results for the photocatalytic activity of the catalysts 1-3 reveal the involvement of multi-electron metal-ligand exchange coupling in promoting CO₂RR and HER, and provide a starting point for the integration of these strategies into catalyst design.

查看原文本刊更多论文

乙酰丙酮酸衍生钴（III）配合物作为光催化剂和电催化剂的能量转换。

开发通过减少二氧化碳和产生氢气来促进太阳能转化为燃料的系统可以弥合生产和消费之间的差距。本文提出了一种在水/乙腈溶剂体系中研究高光催化活性钴（III）催化剂催化的二氧化碳还原反应（CO2RR）和消氢反应（HER）中间体的新方法。钴催化剂[Co(acac)(bpy)(N3)2]的优化。H2O 1, [Co(acac)(en)(N3)2] 2和[Co(acac)（2-pic)(N3)2] 3）在可见光照射（>420 nm）下的光催化活性由不同的溶剂体系（v/v）（CH3COCH3/H2O, CH3CN/H2O, DMF/H2O， EtOH/H2O和H2O），牺牲电子供体（1-苄基-1,4-二氢烟碱酰胺（BNAH），二乙醇胺（DEOA），三乙胺（TEA）和三乙醇胺（TEOA）），光敏剂（伊红Y，红素B，荧光素（Fl），玫瑰，罗丹明-B和Ru(bpy)3），pH（7-12.5）和不同催化剂浓度（0- 2mm）。钴离子周围的排列是八面体配位几何。结合实验表征和密度泛函理论（DFT）对光催化CO2还原反应机理进行了研究。1-3催化剂光催化活性的DFT计算和实验结果揭示了多电子金属-配体交换耦合在促进CO2RR和HER中的作用，并为将这些策略整合到催化剂设计中提供了一个起点。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

ChemPlusChem CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

5.90

自引率

0.00%

发文量

200

审稿时长

1 months

期刊介绍： ChemPlusChem is a peer-reviewed, general chemistry journal that brings readers the very best in multidisciplinary research centering on chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. Fully comprehensive in its scope, ChemPlusChem publishes articles covering new results from at least two different aspects (subfields) of chemistry or one of chemistry and one of another scientific discipline (one chemistry topic plus another one, hence the title ChemPlusChem). All suitable submissions undergo balanced peer review by experts in the field to ensure the highest quality, originality, relevance, significance, and validity.