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Operando XAS and DFT Uncover Structure-Performance Relationships in Re/TiO2 for Selective CO2 Hydrogenation to Methanol

Journal Article · · ACS Catalysis

The conversion of CO2 into value-added chemicals, such as methanol, offers a promising pathway toward a renewable energy future. However, a precise kinetic control and a highly selective catalyst are necessary to overcome the thermodynamic preference for CO2 hydrogenation to methane. Rhenium-based catalysts, particularly Re/TiO2, demonstrate high activity and selectivity for methanol under high-pressure conditions. For example, at 100 bar and 200 °C, a methanol selectivity of 97−99% was obtained. Catalysts with 1 wt % Re and 5 wt % Re/ TiO2 were used to study the effect of cluster sizes. At 250 °C, the 1 wt % catalyst achieves 97% selectivity at 23% conversion, whereas 5 wt % Re/TiO2 achieves 74% selectivity at 40% conversion, corresponding to a drop in space-time yield from 65 to 16 gCH3OH·gRe−1·h−1, respectively. X-ray absorption spectroscopy provided insights into the structure of the active sites, while density functional theory calculations revealed the effects of cluster size on the energy barriers for H2 activation, CH3OH dissociation, and CH3OH desorption, all of which directly influence conversion and selectivity. These results underscore the importance of balancing cluster size for optimal catalyst performance and provide insights into the design of efficient and selective catalysts for renewable methanol production.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
3005244
Journal Information:
ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 22 Vol. 15; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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