Hydrogen evolution catalysis by terminal molybdenum-oxo complexes
Summary: Stable complexes with terminal triply bound metal-oxygen bonds are usually not considered as valuable catalysts for the hydrogen evolution reaction (HER). We now report the preparation of three conceptually different (oxo)molybdenum(V) corroles for testing if proton-assisted 2-electron redu...
| Main Authors: | , , , , , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Elsevier
2021-08-01
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| Series: | iScience |
| Subjects: | |
| Online Access: | http://www.sciencedirect.com/science/article/pii/S2589004221008920 |
| _version_ | 1818645060911104000 |
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| author | Pinky Yadav Izana Nigel-Etinger Amit Kumar Amir Mizrahi Atif Mahammed Natalia Fridman Sophia Lipstman Israel Goldberg Zeev Gross |
| author_facet | Pinky Yadav Izana Nigel-Etinger Amit Kumar Amir Mizrahi Atif Mahammed Natalia Fridman Sophia Lipstman Israel Goldberg Zeev Gross |
| author_sort | Pinky Yadav |
| collection | DOAJ |
| description | Summary: Stable complexes with terminal triply bound metal-oxygen bonds are usually not considered as valuable catalysts for the hydrogen evolution reaction (HER). We now report the preparation of three conceptually different (oxo)molybdenum(V) corroles for testing if proton-assisted 2-electron reduction will lead to hyper-reactive molybdenum(III) capable of converting protons to hydrogen gas. The upto 670 mV differences in the [(oxo)Mo(IV)]-/[(oxo)Mo(III)]−2 redox potentials of the dissolved complexes came into effect by the catalytic onset potential for proton reduction thereby, significantly earlier than their reduction process in the absence of acids, but the two more promising complexes were not stable at practical conditions. Under heterogeneous conditions, the smallest and most electron-withdrawing catalyst did excel by all relevant criteria, including a 97% Faradaic efficiency for catalyzing HER from acidic water. This suggests complexes based on molybdenum, the only sustainable heavy transition metal, as catalysts for other yet unexplored green-energy-relevant processes. |
| first_indexed | 2024-12-17T00:24:45Z |
| format | Article |
| id | doaj.art-36209de32d024c208c40cce258fda381 |
| institution | Directory Open Access Journal |
| issn | 2589-0042 |
| language | English |
| last_indexed | 2024-12-17T00:24:45Z |
| publishDate | 2021-08-01 |
| publisher | Elsevier |
| record_format | Article |
| series | iScience |
| spelling | doaj.art-36209de32d024c208c40cce258fda3812022-12-21T22:10:30ZengElsevieriScience2589-00422021-08-01248102924Hydrogen evolution catalysis by terminal molybdenum-oxo complexesPinky Yadav0Izana Nigel-Etinger1Amit Kumar2Amir Mizrahi3Atif Mahammed4Natalia Fridman5Sophia Lipstman6Israel Goldberg7Zeev Gross8Schulich Faculty of Chemistry, Technion - Israel Institute of Technology, Haifa, IsraelSchulich Faculty of Chemistry, Technion - Israel Institute of Technology, Haifa, IsraelSchulich Faculty of Chemistry, Technion - Israel Institute of Technology, Haifa, IsraelSchulich Faculty of Chemistry, Technion - Israel Institute of Technology, Haifa, Israel; Chemistry Department, Nuclear Research Centre Negev, Beer Sheva 84190, IsraelSchulich Faculty of Chemistry, Technion - Israel Institute of Technology, Haifa, IsraelSchulich Faculty of Chemistry, Technion - Israel Institute of Technology, Haifa, IsraelSchool of Chemistry, Sackler Faculty of Exact Sciences, Tel Aviv University, Tel Aviv 6997801, IsraelSchool of Chemistry, Sackler Faculty of Exact Sciences, Tel Aviv University, Tel Aviv 6997801, IsraelSchulich Faculty of Chemistry, Technion - Israel Institute of Technology, Haifa, Israel; Corresponding authorSummary: Stable complexes with terminal triply bound metal-oxygen bonds are usually not considered as valuable catalysts for the hydrogen evolution reaction (HER). We now report the preparation of three conceptually different (oxo)molybdenum(V) corroles for testing if proton-assisted 2-electron reduction will lead to hyper-reactive molybdenum(III) capable of converting protons to hydrogen gas. The upto 670 mV differences in the [(oxo)Mo(IV)]-/[(oxo)Mo(III)]−2 redox potentials of the dissolved complexes came into effect by the catalytic onset potential for proton reduction thereby, significantly earlier than their reduction process in the absence of acids, but the two more promising complexes were not stable at practical conditions. Under heterogeneous conditions, the smallest and most electron-withdrawing catalyst did excel by all relevant criteria, including a 97% Faradaic efficiency for catalyzing HER from acidic water. This suggests complexes based on molybdenum, the only sustainable heavy transition metal, as catalysts for other yet unexplored green-energy-relevant processes.http://www.sciencedirect.com/science/article/pii/S2589004221008920ChemistryInorganic chemistryMolecular inorganic chemistryChemical reactionCatalysis |
| spellingShingle | Pinky Yadav Izana Nigel-Etinger Amit Kumar Amir Mizrahi Atif Mahammed Natalia Fridman Sophia Lipstman Israel Goldberg Zeev Gross Hydrogen evolution catalysis by terminal molybdenum-oxo complexes iScience Chemistry Inorganic chemistry Molecular inorganic chemistry Chemical reaction Catalysis |
| title | Hydrogen evolution catalysis by terminal molybdenum-oxo complexes |
| title_full | Hydrogen evolution catalysis by terminal molybdenum-oxo complexes |
| title_fullStr | Hydrogen evolution catalysis by terminal molybdenum-oxo complexes |
| title_full_unstemmed | Hydrogen evolution catalysis by terminal molybdenum-oxo complexes |
| title_short | Hydrogen evolution catalysis by terminal molybdenum-oxo complexes |
| title_sort | hydrogen evolution catalysis by terminal molybdenum oxo complexes |
| topic | Chemistry Inorganic chemistry Molecular inorganic chemistry Chemical reaction Catalysis |
| url | http://www.sciencedirect.com/science/article/pii/S2589004221008920 |
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