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Engineering of HO−Zn−N2 Active Sites in Zeolitic Imidazolate Frameworks for Enhanced (Photo)Electrocatalytic Hydrogen Evolution

Zheao Huang recently developed a highly selective ligand removal (SeLiRe) strategy to engineer open metal sites (OMS) in zeolitic imidazolate frameworks (ZIFs) without disrupting their inherent framework structure. By altering the Zn coordination environment from saturated Zn−N4 to unsaturated Zn−N2, Huang introduced open zinc sites as active centers for (photo)electrocatalytic hydrogen evolution reaction (HER).

Featured image: A selective ligand removal strategy was developed to engineer active catalytic sites of unsaturated HO−Zn−N2 in zeolitic imidazolate frameworks, which significantly accelerate the hydrogen evolution reaction by reducing the overpotential water adsorption from 0.31 V to 0.07 V at 10 mA cm−2.

Through a combination of advanced in situ and ex situ characterization techniques, as well as theoretical calculations, Huang demonstrated that these open Zn−N2 sites chemisorb hydroxyl groups from alkaline electrolytes under operational conditions, forming high-valence HO−Zn−N2 active sites.

The introduction of HO−Zn−N2 sites significantly reduced the overpotential for HER from 0.31 V (ZIF-8) to 0.07 V at 10 mA cm−2, substantially enhancing the electrocatalytic efficiency. Furthermore, the presence of these active sites decreased the band gap of the material, enabling visible light activity compared to the UV-limited ZIF-8. Density functional theory (DFT) simulations supported these findings, revealing that the HO−Zn−N2 sites facilitated water adsorption and dissociation, thus improving the overall HER performance. His work offers a promising pathway for designing advanced materials with optimized catalytic properties for energy-related applications.

 

The paper was recently published Open Access in Angewandte chemie and can be assessed through the following link: https://doi.org/10.1002/anie.202419913, opens an external URL in a new window