Enabling hydrogen chemisorption on charged graphene

Shea, Patrick T.; Rowberg, Andrew J. E.; Wood, Brandon C.

doi:10.1039/D5CP00150A

Enabling hydrogen chemisorption on charged graphene

Journal Article · Wed Jan 01 00:00:00 EST 2025 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/D5CP00150A· OSTI ID:2571694

Shea, Patrick T. ^[1]; ^[1]; ^[1]

Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States). Laboratory for Energy Applications for the Future (LEAF)

Two-dimensional (2D) materials, including graphitic derivatives, have long been of interest for hydrogen storage applications, due to their high theoretical storage capacity, low weight, and other useful properties. However, poor kinetics for hydrogen adsorption and surface diffusion as part of the proposed spillover process for hydrogenation have limited their technological potential. Here, we use first-principles calculations to study electronic doping as a means to improve hydrogen chemisorption on graphene, which we use here as a proxy for graphitic derivatives more broadly. We find that positively charged graphene sheets have vastly improved kinetics for hydrogen diffusion and adsorption, while they limit unwanted hydrogen desorption. This combination of effects should favor hydrogen chemisorption via spillover. We connect these trends to the C–H bond, which introduces states near the Fermi level. These states are depopulated as electrons are removed, thereby lowering the bond energy and permitting more facile movement of hydrogen. Our results suggest that spillover mechanisms for hydrogen chemisorption should be revisited if strategies to apply a large charge to graphitic systems can be realized. Moreover, switchable application of the charge may lead to the reversible chemisorption of hydrogen. While the large magnitude of charging required suggests that graphene itself may not be suitable for reversible hydrogen chemisorption, the factors we identify and discuss could significantly boost the prospects of graphitic derivatives and other 2D or layered materials for hydrogen storage applications.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 2571694

Report Number(s):: LLNL--JRNL-871854

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 26 Vol. 27; ISSN 1463-9076; ISSN 1463-9084

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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