Harnessing the Cobalt-Catalyzed Hydrogen Evolution Reaction through a Data-Driven Approach

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

Published: Feb. 4, 2025

The design of cobalt complexes for the hydrogen evolution reaction (HER) has garnered significant attention over past few decades. To address limitations traditional trial-and-error method, we introduced strategy a simplified mechanism-based approach with data-driven practice (SMADP) in this study. Our results indicate that polypyridyl DPA-Bpy family (DPA-Bpy = N,N-bis(2-pyridinylmethyl)-2,2′-bipyridine-6-methanamine) generally follow electron transfer (E)–chemical proton (C)–electron (C) pathway HER. However, involvement proton-coupled (PCET) formation [CoII(L)–H]+ intermediate been observed PY5Me2 (PY5Me2 2,6-bis(1,1-di(pyridin-2-yl)ethyl)pyridine). Furthermore, hydricity (ΔGH–) and CoIII–H/CoII–H reduction potential (ERed°) are found to be active descriptors cobalt-catalyzed Excellent two-parameter regression models (ΔGH– ERed°) H2 molecule have obtained (R2 0.9429 R2 0.9854 family). demonstrate SMADP is groundbreaking method delineating This could also accelerate novel enhanced

Language: Английский

Effect of Ligand Backbone on the Electrochemical Hydrogen Evolution Reaction and Hydrogen-Atom-Transfer Reactivity Using a Nickel Polypyridine Quinoline Complex

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

Published: April 16, 2025

Redox-active quinoline-containing [NiII(2PyN2Q) (H2O)]2+ complex (1) has been developed for the electrocatalytic (e) hydrogen evolution reaction (HER) in presence of organic acids and water hydrogen-atom-transfer (HAT) with styrene acids. Complex 1 shows promising e-HER performance up to pH 9. It exhibits a stepwise (E)ECEC mechanism AcOH, while potential-dependent bimolecular homolytic pathway CEEC is operative p-toluene sulfonic acid during e-HER. The one- two-electron-reduced species are characterized by spectro-electrochemistry, optical, EPR studies. Moreover, inverse kinetic isotope effect (KIE = 0.83) between AcOH d4-AcOH e-HAT hydro-functionalization using catalyst possibly suggests involvement nickel hydride species. reactivity have compared redox-inactive [NiII(N4Py)(H2O)]2+ (2), demonstrating prominent quinoline pyridine e-HAT. proposed well supported DFT

Language: Английский

Molecular Ru(II) complexes with universal pH hydrogen evolution performance

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

Published: Jan. 1, 2025

The development of efficient and robust hydrogen evolution reaction (HER) catalysts that operate across a wide pH range is critical for advancing sustainable production. Previously, series molecular complexes have been immobilized on solid supports to achieve HER activity. However, achieving activity with universal still remains challenging. Herein, we demonstrated two Ru(II) systematically characterized them using spectroscopic techniques. (MeTBEN)Ru(II) complex (2) exhibited outstanding range, specifically in alkaline, neutral, acidic electrolytes, the highest performance observed electrolytes compared (BnTBEN)Ru(II) (1). 2 demonstrates electrocatalytic low overpotential 115 mV at 10 mA cm-2 0.5 M H2SO4, along an excellent turnover frequency. Furthermore, electrochemical stability, sustaining its up 8 hours under conditions.

Language: Английский