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Synergizing Cu dimers and N atoms in graphene towards an active catalyst for hydrogen evolution reaction.

ABSTRACT: Moving forward from single atom catalysts, here we propose Cu mers coordinated with N atoms in graphene as a potential catalyst for hydrogen evolution reaction (HER) using first-principles calculations. Our study shows that Cu mers (monomer, dimer and trimer) with no N coordination adsorb H too strongly, whereas Cu mers with complete N coordination adsorb H too weakly, indicating that neither is catalytically active for HER. However, these results imply that Cu mers with partial N coordination may exhibit a better catalytic performance. Thus, we further explored all the Cu₂N _x complexes with different atomic coordination numbers and spatial distributions and find that one of the Cu₂N₄ atomic configurations possesses a ΔG _H* of -0.09 eV, exhibiting a superior catalytic performance for HER. The possible reason might be that this configuration tunes the p-band center to an optimum level. Our study here reveals a promising catalyst for HER and presents a practical route to design catalysts by introducing metal mers and tuning their coordination with high-valence non-metal elements.

SUBMITTER: Yang J

PROVIDER: S-EPMC9419068 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature

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Synergizing Cu dimers and N atoms in graphene towards an active catalyst for hydrogen evolution reaction.

Yang Jing J Yu Zhi Gen ZG Zhang Yong-Wei YW

Nanoscale advances 20210809 18

Moving forward from single atom catalysts, here we propose Cu mers coordinated with N atoms in graphene as a potential catalyst for hydrogen evolution reaction (HER) using first-principles calculations. Our study shows that Cu mers (monomer, dimer and trimer) with no N coordination adsorb H too strongly, whereas Cu mers with complete N coordination adsorb H too weakly, indicating that neither is catalytically active for HER. However, these results imply that Cu mers with partial N coordination m ...[more]

PMID: 36132635

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Project description:Hydrogen atom transfer (HAT) is the mechanism by which the vast majority of radical-trapping antioxidants (RTAs), such as hindered phenols, inhibit autoxidation. As such, at least one weak O-H bond is the key structural feature which underlies the reactivity of phenolic RTAs. We recently observed that quinone methide dimers (QMDs) synthesized from hindered phenols are significantly more reactive RTAs than the phenols themselves despite lacking O-H bonds. Herein we describe our efforts to elucidate the mechanism by which they inhibit autoxidation. Four possible reaction paths were considered: (1) HAT from the C-H bonds on the carbon atoms which link the quinone methide moieties; (2) tautomerization or hydration of the quinone methide(s) in situ followed by HAT from the resultant phenolic O-H; (3) direct addition of peroxyl radicals to the quinone methide(s), and (4) homolysis of the weak central C-C bond in the QMD followed by combination of the resultant persistent phenoxyl radicals with peroxyl radicals. The insensitivity of the reactivity of the QMDs to substituent effects, solvent effects and a lack of kinetic isotope effects rule out the HAT reactions (mechanisms 1 and 2). Simple (monomeric) quinone methides, to which peroxyl radicals add, were found to be ca. 100-fold less reactive than the QMDs, ruling out mechanism 3. These facts, combined with the poor RTA activity we observe for a QMD with a stronger central C-C bond, support mechanism 4. The lack of solvent effects on the RTA activity of QMDs suggests that they may find application as additives to materials which contain H-bonding accepting moieties that can dramatically suppress the reactivity of conventional RTAs, such as phenols. This reactivity does not extend to biological membranes owing to the increased microviscosity of the phospholipid bilayer, which suppresses QMD dissociation in favour of recombination. Interestingly, the simple QMs were found to be very good RTAs in phospholipid bilayers - besting even the most potent form of vitamin E.

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Synergizing Cu dimers and N atoms in graphene towards an active catalyst for hydrogen evolution reaction.

Publications

Synergizing Cu dimers and N atoms in graphene towards an active catalyst for hydrogen evolution reaction.

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