Deciphering the active species and reaction mechanism in water oxidation catalyzed by a copper complex with redox-active ligands

Fan, Qing; Yang, Cong; Li, Mengdi; Wang, Chen; Wang, Guixia; Kong, Xiangfei; Zhu, Qiping

doi:10.1039/d4qi00163j

Inorg. Chem. Front.

2024

DOI: 10.1039/d4qi00163j

|View full text |Cite

Deciphering the active species and reaction mechanism in water oxidation catalyzed by a copper complex with redox-active ligands

Qing Fan,

Cong Yang,

Mengdi Li

et al.

Abstract: Homogeneous water oxidation catalysts play a crucial role in the efficient utilization of hydrogen energy. The exploration of cost-effective metal catalysts based on redox-active ligands represents a promising approach in...

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...

Citation Types

Supporting

Mentioning

Contrasting

Year Published

2024

Publication Types

Select...

Article1

Relationship

Self Cite0

Independent1

Authors

Journals

Cited by 1 publication

References 47 publications

(64 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

Toward Rational Design of Mononuclear Nickel Complexes as Water Oxidation Catalysts Exploring the Ligand Effects on the Rate‐Determining Step

Kumar Singh,

Roy

2024

ChemPhysChem

View full text Add to dashboard Cite

The major impediment in realizing a carbon‐neutral hydrogen fuel economy is the cost and inadequacy of contemporary electrochemical water splitting approaches towards the energy intensive oxygen evolution reaction (OER). The O‐O bond formation in the water oxidation half‐cell reaction is both kinetically and thermodynamically challenging and amplifies the overpotential requirement in most of the active water oxidation catalysts. Herein, density functional theory is employed to interrogate 20 Ni(II) complexes, out of which 17 are in silico designed molecular water oxidation catalysts, coordinated to electron‐rich tetra‐anionic redox non‐innocent phenylenebis(oxamidate) and dibenzo‐1,4,7,10‐tetraazacyclododecane‐2,3,8,9‐tetraone parent ligands and their structural analogues, and identify the role of substituent changes or ligand effects in the order of their reactivity. Importantly, our computational mechanistic analyses predict that the activation free energy of the rate‐determining O‐O bond formation step obeys an inverse scaling relationship with the global electrophilicity index of the intermediate generated on two‐electron oxidation of the starting complex. Additionally, the driving force is directly correlated with this OER descriptor which enables two‐dimensional volcano representation and thereby extrapolation towards the ideal substitution with the chosen ligand. Our study, therefore, establish fundamental insights to overcome the imperative overpotential issue with simple and precise computational rationalization preceding experimental validation.

show abstract

Toward Rational Design of Mononuclear Nickel Complexes as Water Oxidation Catalysts Exploring the Ligand Effects on the Rate‐Determining Step

Kumar Singh,

Roy

2024

ChemPhysChem

View full text Add to dashboard Cite

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

Deciphering the active species and reaction mechanism in water oxidation catalyzed by a copper complex with redox-active ligands

Abstract: Homogeneous water oxidation catalysts play a crucial role in the efficient utilization of hydrogen energy. The exploration of cost-effective metal catalysts based on redox-active ligands represents a promising approach in...

Cited by 1 publication

References 47 publications

Toward Rational Design of Mononuclear Nickel Complexes as Water Oxidation Catalysts Exploring the Ligand Effects on the Rate‐Determining Step

Toward Rational Design of Mononuclear Nickel Complexes as Water Oxidation Catalysts Exploring the Ligand Effects on the Rate‐Determining Step

Contact Info

Product

Resources

About