CO2-mediated oxidative dehydrogenation of propane enabled by Pt-based bimetallic catalysts

Zhai, Peng; Xie, Zhenhua; Huang, Erwei; Aireddy, Divakar R.; Yu, Haoran; Cullen, David A.; Liu, Ping; Chen, Jingguang G.; Ding, Kunlun

doi:10.1016/j.chempr.2023.07.002

CO₂-mediated oxidative dehydrogenation of propane enabled by Pt-based bimetallic catalysts

Journal Article · Tue Aug 01 00:00:00 EDT 2023 · Chem

DOI:https://doi.org/10.1016/j.chempr.2023.07.002· OSTI ID:2224166

Zhai, Peng ^[1]; Xie, Zhenhua ^[2]; Huang, Erwei ^[3]; Aireddy, Divakar R. ^[1]; ^[4]; ^[4]; Liu, Ping ^[5]; Chen, Jingguang G. ^[2]; Ding, Kunlun ^[1]

Louisiana State Univ., Baton Rouge, LA (United States)
Columbia Univ., New York, NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Brookhaven National Laboratory (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)

The greenhouse gas CO₂ is a promising soft oxidant for the oxidative dehydrogenation of light alkanes. However, the occurrence of side reactions including cracking, hydrogenolysis, and reforming results in lower olefin yields compared with direct dehydrogenation. Here, we report that Pt-M (M = Sn/In/Zn) bimetallic catalysts on non-redox-active silica support can break the equilibrium limit of direct propane dehydrogenation using CO₂ as a co-reactant to consume the hydrogen formed in propane dehydrogenation. Unlike the commonly postulated direct CO₂-assisted dehydrogenation mechanism, we confirm that CO₂-oxidative dehydrogenation of propane (ODHP) proceeds in two tandem steps on these bimetallic catalysts, i.e., propane dehydrogenation and reverse water-gas shift, with the latter being the rate-determining step. In situ X-ray absorption studies and density functional theory calculations suggest that the Pt_mM_n-MO_x (e.g., Pt₃Sn-SnO_x) interfaces are likely active sites.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725; SC0012653; SC0012704

OSTI ID:: 2224166

Alternate ID(s):: OSTI ID: 2281331

Report Number(s):: BNL--225163-2024-JAAM

Journal Information:: Chem, Journal Name: Chem Journal Issue: 11 Vol. 9; ISSN 2451-9294

Publisher:: Cell PressCopyright Statement

Country of Publication:: United States

Language:: English

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