CO2-Assisted Oxidative Dehydrogenation of Propane over VOx/In2O3 Catalysts: Interplay between Redox Property and Acid–Base Interactions

Jiang, Xiao; Lis, Bar Mosevitzky; Purdy, Stephen C.; Paladugu, Sreya; Fung, Victor; Quan, Wenying; Bao, Zhenghong; Yang, Weiwei; He, Yang; Sumpter, Bobby G.; Page, Katharine; Wachs, Israel E.; Wu, Zili

doi:10.1021/acscatal.2c02099

Title: CO₂-Assisted Oxidative Dehydrogenation of Propane over VO_x/In₂O₃ Catalysts: Interplay between Redox Property and Acid–Base Interactions

Journal Article · Thu Sep 01 00:00:00 EDT 2022 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.2c02099· OSTI ID:1886495

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Lehigh University, Bethlehem, PA (United States)
University of Tennessee, Knoxville, TN (United States)
Georgia Institute of Technology, Atlanta, GA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); University of Tennessee, Knoxville, TN (United States)

Here, in this work, a series of VO_x-loaded In₂O₃ catalysts were prepared, and their catalytic performance was evaluated for CO₂-assisted oxidative dehydrogenation of propane (CO₂-ODHP) and compared with In₂O₃ alone. The optimal composition is obtained on 3.4V/In₂O₃ (surface V density of 3.4V nm^–2), which exhibited not only a higher C₃H₆ selectivity than other V/In catalysts and In₂O₃ under isoconversion conditions but also an improved reaction stability. To elucidate the catalyst structure–activity relationship, the VO_x/In₂O₃ catalysts were characterized by chemisorption [NH₃-temperature-programmed desorption (TPD), NH₃-diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), CO₂-TPD, and CO₂-DRIFTS], H₂-temperature-programmed reduction (TPR), in situ Raman spectroscopy, UV–vis diffuse reflectance spectroscopy, near-ambient pressure X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and further examined using density functional theory. The In–O–V structure and the extent of oligomerization, which play a crucial role in improving selectivity and stability, were identified in the VO_x/In₂O₃ catalysts. In particular, the presence of surface VO_x (i) inhibits the deep reduction of In₂O₃, thereby preserving the activity, (ii) neutralizes the excess basicity on In₂O₃, thus suppressing propane dry reforming and achieving a higher propylene selectivity, and (iii) introduces additional redox sites that participate in the dehydrogenation reaction by utilizing CO₂ as a soft oxidant. The present work provides insights into developing selective, stable, and robust metal-oxide catalysts for CO₂-ODHP by controlling the conversion of reagents via desired pathways through the interplay between acid–base interactions and redox properties.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725; SC0012577; AC02-06CH11357

OSTI ID:: 1886495

Journal Information:: ACS Catalysis, Vol. 12, Issue 18; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
oxidative dehydrogenation
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acid−base interaction
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Title: CO2-Assisted Oxidative Dehydrogenation of Propane over VOx/In2O3 Catalysts: Interplay between Redox Property and Acid–Base Interactions

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Title: CO₂-Assisted Oxidative Dehydrogenation of Propane over VO_x/In₂O₃ Catalysts: Interplay between Redox Property and Acid–Base Interactions