Alcohol-Induced Low-Temperature Blockage of Supported-Metal Catalysts for Enhanced Catalysis

Polo-Garzon, Felipe; Blum, Thomas F.; Fung, Victor; Bao, Zhenghong; Chen, Hao; Huang, Zhennan; Mahurin, Shannon M.; Dai, Sheng; Chi, Miaofang; Wu, Zili

doi:10.1021/acscatal.0c02452

Alcohol-Induced Low-Temperature Blockage of Supported-Metal Catalysts for Enhanced Catalysis

Journal Article · Mon Jul 20 00:00:00 EDT 2020 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.0c02452· OSTI ID:1651365

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division and Center for Nanophase Materials Sciences (CNMS)

The partial or complete blockage of active sites of metal nanoparticles (NPs) on supported-metal catalysts has been of interest for tuning the stability, selectivity, and rate of reactions. In this study, we show that Au-sites in Au/TiO₂ surprisingly become blocked upon treatment in common alcohols (2-propanol and methanol), with 2-propanol causing a greater extent of blockage. Nearly 95% of Au-sites are covered after treatment in 2-propanol at room temperature, followed by desorption at 150 °C. Infrared spectroscopy of CO adsorption unambiguously confirms the occurrence of this phenomenon. Electron energy loss spectroscopy (EELS), temperature-programmed desorption (TPD), Raman spectroscopy, and DFT simulations suggest that the formation of carbon deposits from 2-propanol decomposition and/or the migration of a TiO_x layer over the supported NPs may be responsible for the blockage of Au-sites. Nearly full coverage of Au NPs after treatment in 2-propanol led to negligible activity for catalytic CO oxidation, whereas partial retraction of the overlayer led to enhanced activity with time-on-stream, suggesting a self-activating catalytic performance.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1651365

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 15 Vol. 10; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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