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Molecularly Defined Manganese Catalyst for Low-Temperature Hydrogenation of Carbon Monoxide to Methanol
Methanol synthesis from syngas (CO/H2 mixtures) is one of the largest manmade chemical processes with annual production reaching 100 million tons. The current industrial method proceeds at high temperatures (200–300 °C) and pressures (50–100 atm) using a copper–zinc-based heterogeneous catalyst. In...
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Published in: | Journal of the American Chemical Society 2019-10, Vol.141 (42), p.16923-16929 |
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Main Authors: | , , , , |
Format: | Article |
Language: | English |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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Summary: | Methanol synthesis from syngas (CO/H2 mixtures) is one of the largest manmade chemical processes with annual production reaching 100 million tons. The current industrial method proceeds at high temperatures (200–300 °C) and pressures (50–100 atm) using a copper–zinc-based heterogeneous catalyst. In contrast, here, we report a molecularly defined manganese catalyst that allows for low-temperature/low-pressure (120–150 °C, 50 bar) carbon monoxide hydrogenation to methanol. This new approach was evaluated and optimized by quantum mechanical simulations virtual high-throughput screenings. Crucial for this achievement is the use of amine-based promoters, which capture carbon monoxide to give formamide intermediates, which then undergo manganese-catalyzed hydrogenolysis, regenerating the promoter. Following this conceptually new approach, high selectivity toward methanol and catalyst turnover numbers (up to 3170) was achieved. The proposed general catalytic cycle for methanol synthesis is supported by model studies and detailed spectroscopic investigations. |
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ISSN: | 0002-7863 1520-5126 |
DOI: | 10.1021/jacs.9b08990 |