CO2 Reduction by Transition‐Metal Complex Systems: Effect of Hydrogen Bonding on the Second Coordination Sphere DOI Open Access

Xiangming Liang,

Zhijun Ruan,

Gui‐Quan Guo

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 21, 2024

Abstract Homogeneous electrocatalysts typified by transition‐metal complex show transcendent potency in efficient energy catalysis through molecular design. For example, metal complexes with elaborate design performed wonderful activity and selectivity for electrocatalytic CO 2 reduction. Primary coordination sphere of plays a key role regulating its intrinsic redox properties catalytic activity. However, the overall reduction efficiency is also bound up substrate activation process. Transition‐metal are hoped to exhibit reasonable potential, reactive activity, stability, while binding activating molecules achieve Construction second sphere, especially hydrogen‐bonding network complexes, reported be “kill two birds one stone” strategy realize via systematic catalyst modulation activation. Herein, we present recent progress on construction ligand modification or introduction exogenous organic ligand, resulted productive enhancement performance improvement adsorption capacity , proton transfer rate, stability reaction intermediates, so forth.

Language: Английский

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

Chao Su,

Haihua Huang,

Zubing Huang

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 2522 - 2530

Published: Jan. 27, 2025

Language: Английский

Citations

1
Synergistic Effect Promotes Visible‐Light–Driven CO2‐To‐CO Conversion by Macrocyclic Dinuclear Mixed‐Valence Co (II)/Co (III) Complexes DOI Open Access
Chunzhao Huang, Zi‐Lu Chen,

Hongmei Hao

et al.

Applied Organometallic Chemistry, Journal Year: 2025, Volume and Issue: 39(2)

Published: Jan. 12, 2025

ABSTRACT The catalytic conversion of carbon dioxide (CO 2 ) into valuable energy under light sources is one the effective ways to achieve cycle. reported nonprecious metal complex catalysts still show shortcomings low activity and selectivity in visible‐light–driven CO reduction, especially aqueous systems. Herein, we report three dinuclear mixed‐valence Co (II)/Co (III) complexes 1 – 3 bearing macrocyclic ligands that exhibit high for photocatalytic reduction an system. Moreover, TON reach as 4100 96%, respectively, which about 4.9 times higher than mononuclear (II) 4 . Through electrochemical DFT calculations, found increase due synergistic effect between two centers, site stabilizes *COOH intermediate reduces barrier rate‐determining step, thereby increasing activity.

Language: Английский

Citations

0
Theoretical Study on the Mechanism of the Electrocatalytic CO2 Reduction to Formate by an Iron Schiff Base Complex DOI

Ya-Qiong Zhang,

Jiayi Chen, Man Li

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

The iron(III) chloride compound 6,6'-di(3,5-ditert-butyl-2-hydroxybenzene)-2,2'-bipyridine (Fe(tbudhbpy)Cl) can effectively catalyze the electrochemical CO2 reduction in N,N-dimethylformamide. Density functional calculations were conducted to investigate mechanism and unravel governing factors of product selectivity. results suggest that initial catalyst, Fe(tbudhbpy)Cl (formally FeIII-Cl), undergoes two steps, accompanied by dissociation Cl-, leading formation active ferrous radical intermediate 2 FeI). Without phenol, attacks generate FeIII-carboxylate FeIII-CO2, followed a one-electron FeII-CO2, which reacts with another produce CO. This aligns experimental result CO is main when phenol absent. In contrast, presented, triple reduced species 3 protonated at its ligand N site yield 3pt(N) Fe0-NH), subsequently performs nucleophilic attack on afford formate. process occurs via an orthogonal electron/proton transfer mechanism, where electrons one proton are transferred from moiety. redox noninnocent nature thus crucial for formate formation, as it facilitates electron shuttling, enabling through this unusual effectively.

Language: Английский

Citations

0
Highly efficient photocatalytic reduction of CO2 to CO under visible light using rhenium benzo[d]oxazole complexes DOI
Uday Shee,

Biswajit Khutia,

S. Ray

et al.

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A series of six isomeric Re( i ) tricarbonyl complexes bearing benzo[d]oxazole ligands exhibit tunable photocatalytic and electrochemical CO 2 reduction activity. Ligand design offers key insights into optimizing catalysts for solar-to-fuel conversion.

Language: Английский

Citations

0
CO2 Reduction by Transition‐Metal Complex Systems: Effect of Hydrogen Bonding on the Second Coordination Sphere DOI Open Access

Xiangming Liang,

Zhijun Ruan,

Gui‐Quan Guo

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 21, 2024

Abstract Homogeneous electrocatalysts typified by transition‐metal complex show transcendent potency in efficient energy catalysis through molecular design. For example, metal complexes with elaborate design performed wonderful activity and selectivity for electrocatalytic CO 2 reduction. Primary coordination sphere of plays a key role regulating its intrinsic redox properties catalytic activity. However, the overall reduction efficiency is also bound up substrate activation process. Transition‐metal are hoped to exhibit reasonable potential, reactive activity, stability, while binding activating molecules achieve Construction second sphere, especially hydrogen‐bonding network complexes, reported be “kill two birds one stone” strategy realize via systematic catalyst modulation activation. Herein, we present recent progress on construction ligand modification or introduction exogenous organic ligand, resulted productive enhancement performance improvement adsorption capacity , proton transfer rate, stability reaction intermediates, so forth.

Language: Английский

Citations

2