Deoxydehydration of Biomass-Derived Polyols with a Reusable Unsupported Rhenium Nanoparticles Catalyst
- Univ. of California, Santa Barbara, CA (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States)
Oxorhenium catalysts effectively transform biomass derived polyols into corresponding alkenes, via deoxydehydration (DODH) with a secondary alcohol as a hydrogen donor. This report describes the preparation of unsupported rhenium oxide nanoparticles (ReOx NPs), their use as DODH heterogeneous catalyst, and changes in the speciation and structure of Re during catalysis leading to a mechanism for DODH by a heterogeneous catalyst. The unsupported nanoparticles catalyze various polyols transformation to produce alkenes with high efficiency and recyclability. X-ray spectroscopy analysis shows the structure of as-prepared ReOx NPs is similar to perrhenate with oxidation state between Re(VI) and Re(VII). Under reaction conditions and post catalysis, the ReOx NPs are reduced by approximately two oxidation units. Kinetic isotope effect demonstrates that dissociation of a C-H bond during reduction of ReOx NPs by 3-octanol is part of the rate-determining step. Based on all experimental observations, the mechanism of DODH catalysis with unsupported ReOx NPs involving a Re(VII)/Re(V) redox-pair is introduced.
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Grant/Contract Number:
- AC02-06CH11357
- OSTI ID:
- 1559530
- Journal Information:
- ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 13; ISSN 2168-0485
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
Web of Science
Recent Advances in the Deoxydehydration of Vicinal Diols and Polyols
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journal | October 2019 |
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