Highly efficient continuous gas-phase dehydrogenation of formic acid by Ni induces β-Mo2C to α-MoC structural transformation

Abstract

Formic acid (FA) is a promising hydrogen storage carrier for high power density hydrogen fuel cells. However, dehydrogenation of FA usually produces CO by-products that poison the catalyst. The prevention of FA decomposition into CO within high-temperature proton exchange membrane (HT-PEM) systems operating at 130–200 °C remains a formidable scientific challenge. Here, we propose a Ni doping-induced active phase transition of molybdenum carbide on carbon-based catalysts, enhancing hydrogen production from FA. Ni-MoC/NC achieves complete FA conversion at 190 °C, maintaining stable catalytic performance over 170 h. In MoC/NC, Mo primarily exists as β-Mo₂C and γ-Mo₂N, while in Ni-MoC/NC, it predominantly forms α-MoC and γ-Mo₂N. XRD and XPS analyses reveal that Ni doping induces the transformation of β-Mo₂C into α-MoC, improving catalytic performance. Mechanistic studies identify HCOO* as a key intermediate in FA dehydrogenation on Ni-MoC/NC. The catalyst promotes the dissociation of HCOOH* into HCOO*, reduces the energy barrier for HCOO* conversion to CO₂*, and inhibits CO by-product formation, accelerating FA dehydrogenation. These findings highlight Ni-MoC/NC as a robust catalyst for efficient hydrogen production.

Keywords

Carbon-based catalyst / Active phase / FA Dehydrogenation / Hydrogen storage

CRediT authorship contribution statement

Peng Fu: Writing – original draft, Investigation, Formal analysis. Liang Zheng: Formal analysis, Data curation. Yujing Wu: Methodology, Investigation. Jinliang Yan: Writing – review & editing, Writing – original draft. Zhiyu Li: Supervision, Investigation, Funding acquisition, Formal analysis. Pingwen Ming: Methodology. Bing Li: Methodology. Ella Cebisa Linganiso: Methodology. Hailin Cong: Visualization, Methodology.

Data availability

All data generated and analyzed during this study are included in this article and its Supplementary Information or are available from the corresponding authors upon reasonable request.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

The authors gratefully thank the support for this research from Special Project Fund of “Taishan Scholar" of Shandong Province (No. tsqn202103066), Youth Innovation Support Program of Shandong Colleges and Universities [2023KJ333].

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