Hydrogen Activation via Dihydride Formation on a Rh1/Fe3O4(001) Single-Atom Catalyst
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| Auteurs principaux: | , , , , , , , , , , , , |
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| Format: | Preprint |
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2026
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| _version_ | 1866914269181771776 |
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| author | Wang, Chunlei Sombut, Panukorn Puntscher, Lena Barama, Nail Hao, Maosheng Kraushofer, Florian Pavelec, Jiri Meier, Matthias Libisch, Florian Schmid, Michael Diebold, Ulrike Franchini, Cesare Parkinson, Gareth S. |
| author_facet | Wang, Chunlei Sombut, Panukorn Puntscher, Lena Barama, Nail Hao, Maosheng Kraushofer, Florian Pavelec, Jiri Meier, Matthias Libisch, Florian Schmid, Michael Diebold, Ulrike Franchini, Cesare Parkinson, Gareth S. |
| contents | Hydrogen activation is a key elementary step in catalytic hydrogenation. In heterogeneous catalysis, it usually proceeds through dissociative adsorption on metal nanoparticles followed by surface diffusion or spillover, whereas homogeneous catalysts activate H2 through dihydride or dihydrogen intermediates at a single metal center. Here, we show that isolated Rh adatoms supported on Fe3O4(001) activate hydrogen through formation of a stable dihydride species without atomic H spillover. Temperature-programmed desorption, X-ray photoelectron spectroscopy, and scanning tunneling microscopy collectively reveal strong (approximately 1 eV) hydrogen adsorption exclusively at isolated Rh1 sites, while isotope-exchange experiments further demonstrate that hydrogen remains localized. Density-functional theory based calculations indicate a barrierless conversion from molecular H2 to the dihydride, and random-phase approximation calculations further confirm the relative stability of the dihydride. Together, these results show that single-atom Rh sites cleave and bind H2 through a dihydride pathway analogous to homogeneous complexes, establishing a mechanistic bridge between homogeneous and heterogeneous catalysis. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2601_14756 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | Hydrogen Activation via Dihydride Formation on a Rh1/Fe3O4(001) Single-Atom Catalyst Wang, Chunlei Sombut, Panukorn Puntscher, Lena Barama, Nail Hao, Maosheng Kraushofer, Florian Pavelec, Jiri Meier, Matthias Libisch, Florian Schmid, Michael Diebold, Ulrike Franchini, Cesare Parkinson, Gareth S. Materials Science Hydrogen activation is a key elementary step in catalytic hydrogenation. In heterogeneous catalysis, it usually proceeds through dissociative adsorption on metal nanoparticles followed by surface diffusion or spillover, whereas homogeneous catalysts activate H2 through dihydride or dihydrogen intermediates at a single metal center. Here, we show that isolated Rh adatoms supported on Fe3O4(001) activate hydrogen through formation of a stable dihydride species without atomic H spillover. Temperature-programmed desorption, X-ray photoelectron spectroscopy, and scanning tunneling microscopy collectively reveal strong (approximately 1 eV) hydrogen adsorption exclusively at isolated Rh1 sites, while isotope-exchange experiments further demonstrate that hydrogen remains localized. Density-functional theory based calculations indicate a barrierless conversion from molecular H2 to the dihydride, and random-phase approximation calculations further confirm the relative stability of the dihydride. Together, these results show that single-atom Rh sites cleave and bind H2 through a dihydride pathway analogous to homogeneous complexes, establishing a mechanistic bridge between homogeneous and heterogeneous catalysis. |
| title | Hydrogen Activation via Dihydride Formation on a Rh1/Fe3O4(001) Single-Atom Catalyst |
| topic | Materials Science |
| url | https://arxiv.org/abs/2601.14756 |