Catalytic Effect of Hydrogen Bond on Oxhydryl Dehydrogenation in Methanol Steam Reforming on Ni(111)
Dehydrogenation of H<sub>3</sub>COH and H<sub>2</sub>O are key steps of methanol steam reforming on transition metal surfaces. Oxhydryl dehydrogenation reactions of H<i><sub>x</sub></i>COH (<i>x</i> = 0–3) and OH on Ni (111) were investigat...
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MDPI AG
2020-03-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/25/7/1531 |
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| author | Changming Ke Zijing Lin |
| author_facet | Changming Ke Zijing Lin |
| author_sort | Changming Ke |
| collection | DOAJ |
| description | Dehydrogenation of H<sub>3</sub>COH and H<sub>2</sub>O are key steps of methanol steam reforming on transition metal surfaces. Oxhydryl dehydrogenation reactions of H<i><sub>x</sub></i>COH (<i>x</i> = 0–3) and OH on Ni (111) were investigated by DFT calculations with the OptB88-vdW functional. The transition states were searched by the climbing image nudged elastic band method and the dimer method. The activation energies for the dehydrogenation of individual H<i><sub>x</sub></i>COH* are 68 to 91 kJ/mol, and reduced to 12–17 kJ/mol by neighboring OH*. Bader charge analysis showed the catalysis role of OH* can be attributed to the effect of hydrogen bond (H-bond) in maintaining the charge of oxhydryl H in the reaction path. The mechanism of H-bond catalysis was further demonstrated by the study of OH* and N* assisted dehydrogenation of OH*. Due to the universality of H-bond, the H-bond catalysis shown here, is of broad implication for studies of reaction kinetics. |
| first_indexed | 2024-03-11T10:12:02Z |
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| id | doaj.art-a60c75e9b0e04e698be87a0f645a8eda |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T10:12:02Z |
| publishDate | 2020-03-01 |
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| spelling | doaj.art-a60c75e9b0e04e698be87a0f645a8eda2023-11-16T14:28:56ZengMDPI AGMolecules1420-30492020-03-01257153110.3390/molecules25071531Catalytic Effect of Hydrogen Bond on Oxhydryl Dehydrogenation in Methanol Steam Reforming on Ni(111)Changming Ke0Zijing Lin1Hefei National Laboratory for Physical Sciences at Microscales, Department of Physics, School of Physical Sciences, University of Science and Technology of China, Hefei 230052, Anhui, ChinaCAS Key Laboratory of Strongly-Coupled Quantum Matter Physics, Department of Physics, School of Physical Sciences, University of Science and Technology of China, Hefei 230052, Anhui, ChinaDehydrogenation of H<sub>3</sub>COH and H<sub>2</sub>O are key steps of methanol steam reforming on transition metal surfaces. Oxhydryl dehydrogenation reactions of H<i><sub>x</sub></i>COH (<i>x</i> = 0–3) and OH on Ni (111) were investigated by DFT calculations with the OptB88-vdW functional. The transition states were searched by the climbing image nudged elastic band method and the dimer method. The activation energies for the dehydrogenation of individual H<i><sub>x</sub></i>COH* are 68 to 91 kJ/mol, and reduced to 12–17 kJ/mol by neighboring OH*. Bader charge analysis showed the catalysis role of OH* can be attributed to the effect of hydrogen bond (H-bond) in maintaining the charge of oxhydryl H in the reaction path. The mechanism of H-bond catalysis was further demonstrated by the study of OH* and N* assisted dehydrogenation of OH*. Due to the universality of H-bond, the H-bond catalysis shown here, is of broad implication for studies of reaction kinetics.https://www.mdpi.com/1420-3049/25/7/1531Reaction mechanismfirst-principle calculationBader charge analysisactivation energytransition state structure |
| spellingShingle | Changming Ke Zijing Lin Catalytic Effect of Hydrogen Bond on Oxhydryl Dehydrogenation in Methanol Steam Reforming on Ni(111) Molecules Reaction mechanism first-principle calculation Bader charge analysis activation energy transition state structure |
| title | Catalytic Effect of Hydrogen Bond on Oxhydryl Dehydrogenation in Methanol Steam Reforming on Ni(111) |
| title_full | Catalytic Effect of Hydrogen Bond on Oxhydryl Dehydrogenation in Methanol Steam Reforming on Ni(111) |
| title_fullStr | Catalytic Effect of Hydrogen Bond on Oxhydryl Dehydrogenation in Methanol Steam Reforming on Ni(111) |
| title_full_unstemmed | Catalytic Effect of Hydrogen Bond on Oxhydryl Dehydrogenation in Methanol Steam Reforming on Ni(111) |
| title_short | Catalytic Effect of Hydrogen Bond on Oxhydryl Dehydrogenation in Methanol Steam Reforming on Ni(111) |
| title_sort | catalytic effect of hydrogen bond on oxhydryl dehydrogenation in methanol steam reforming on ni 111 |
| topic | Reaction mechanism first-principle calculation Bader charge analysis activation energy transition state structure |
| url | https://www.mdpi.com/1420-3049/25/7/1531 |
| work_keys_str_mv | AT changmingke catalyticeffectofhydrogenbondonoxhydryldehydrogenationinmethanolsteamreformingonni111 AT zijinglin catalyticeffectofhydrogenbondonoxhydryldehydrogenationinmethanolsteamreformingonni111 |