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First-Principles Study of Hydrogen Evolution on M-N4 Sites in Porphyrin-Zigzag Graphene Nanoribbons
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DOI：10.1021/acs.jpcc.6c00452.png)
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Abstract
En 中文
The hydrogen evolution reaction (HER) is a key half-reaction in water electrolysis, motivating the development of efficient non-noble-metal electrocatalysts with well-defined active sites. Here, we employed recently synthesized metalloporphyrin-graphene nanoribbons (MPor-3ZGNRs) as a structurally precise model system to systematically investigate the intrinsic HER activity of atomically dispersed M-N4 sites (M = Sc-Zn). In MPor-3ZGNRs, metalloporphyrin units are periodically embedded into zigzag graphene nanoribbons via peri-fusion, enabling strong pi-d electronic coupling and continuous charge-transport pathways while preserving molecularly defined coordination environments. First-principles calculations show that the hydrogen adsorption free energy (Delta G *H) can be tuned over a wide range (0.12-2.26 eV) by metal selection, with V-N4 and Co-N4 sites exhibiting nearly thermoneutral hydrogen adsorption. Electronic structure analyses reveal that optimal HER activity arises from a balance between local M-H bonding and adsorption-induced electronic reorganization. Comparative studies with other porphyrin-based architectures further highlight the important roles of coupling mode and metal identity in governing HER thermodynamics.
Keywords:
HER
M-N4 sites
metalloporphyrin
graphene nanoribbons
hydrogen adsorption free energy
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3.2
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5.6W
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15.0W
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