Electrolysis Can Be Used to Resolve Hydrogenation Pathways at Palladium Surfaces in a Membrane Reactor
| Autor: | Ryan P. Jansonius, Roxanna S. Delima, Aoxue Huang, Aiko Kurimoto, Camden Hunt, Tengxiao Ji, Curtis P. Berlinguette, Noah J. J. Johnson, Jingfu He, Zishuai Zhang, Yang Cao |
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| Rok vydání: | 2021 |
| Předmět: |
Materials science
benzaldehyde chemistry.chemical_element 02 engineering and technology catalytic mechanism 010402 general chemistry 01 natural sciences Article law.invention Benzaldehyde chemistry.chemical_compound Adsorption law reaction pathways QD1-999 Electrolysis Membrane reactor Substrate (chemistry) 021001 nanoscience & nanotechnology palladium membrane reactor palladium nanocubes 0104 chemical sciences Chemistry chemistry Chemical engineering hydrogenation 0210 nano-technology Palladium |
| Zdroj: | JACS Au JACS Au, Vol 1, Iss 3, Pp 336-343 (2021) |
| ISSN: | 2691-3704 |
| Popis: | For common hydrogenation chemistries that occur at high temperatures (where H2 is adsorbed and activated at the same surface which the substrate must also adsorb for reaction), there is often little consensus on how the reactions (e.g., hydro(deoxy)genation) actually occur. We demonstrate here that an electrocatalytic palladium membrane reactor (ePMR) can be used to study hydrogenation reaction mechanisms at ambient temperatures, where the catalyst does not necessarily undergo structural reorganization. The ePMR uses electrolysis and a hydrogen-selective palladium membrane to deliver reactive hydrogen to a catalyst surface in an adjacent compartment for reaction with an organic substrate. This process forms the requisite metal-hydride surface for hydrogenation chemistry, but at ambient temperature and pressure, and without a H2 source. We demonstrate the utility of this analytical tool by studying the hydrogenation of benzaldehyde at palladium nanocubes with dimensions of 13–24 nm. This experimental design enabled us to resolve that the alcohol product forms at the facial sites, whereas the hydrodeoxygenation step occurs at edge sites. These observations enabled us to develop the first site-specific definition of how a carbonyl species undergoes hydro(deoxy)genation. |
| Databáze: | OpenAIRE |
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