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

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

doi:10.1016/j.chempr.2023.07.002

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

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

Materials MicroAnalysis

Research output: Contribution to journal › Article › peer-review

19 Scopus citations

Abstract

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. 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.

Original language	English
Pages (from-to)	3268-3285
Number of pages	18
Journal	Chem
Volume	9
Issue number	11
DOIs	https://doi.org/10.1016/j.chempr.2023.07.002
State	Published - Nov 9 2023

Funding

We thank J. Spivey for access to the IR instrument. K.D. acknowledges the LIFT2 grant and the Provost's Fund for Innovation in Research from the Louisiana State University. Electron microscopy (HAADF-STEM and EDS) studies were conducted at the Center for Nanophase Materials Sciences, which is a U.S. DOE Office of Science User Facility. X-ray photoelectron spectroscopy was performed at the Shared Instrumentation Facility (SIF) at Louisiana State University. In situ characterization and DFT calculations were supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under contract no. DE-SC0012704. This research used beamline 7-BM (QAS) of the National Synchrotron Light Source II (NSLS-II) at BNL (contract no. DE-SC0012704) and was supported in part by the Synchrotron Catalysis Consortium (grant no. DE-SC0012653). DFT calculations were performed using computational resources of the Center for Functional Nanomaterials (CFN) at BNL under contract no. DE-SC0012704. K.D. J.G.C. and P.L. supervised the project; P.Z. carried out catalyst synthesis, screening, and IR studies; Z.X. performed in situ XAS studies; E.H. carried out DFT studies; D.R.A. conducted IR and XPS characterizations; H.Y. and D.A.C. performed HAADF-STEM and EDS characterizations; and all coauthors contributed to the manuscript writing. The authors declare no competing interests. We thank J. Spivey for access to the IR instrument. K.D. acknowledges the LIFT2 grant and the Provost’s Fund for Innovation in Research from the Louisiana State University . Electron microscopy (HAADF-STEM and EDS) studies were conducted at the Center for Nanophase Materials Sciences, which is a U.S. DOE Office of Science User Facility. X-ray photoelectron spectroscopy was performed at the Shared Instrumentation Facility (SIF) at Louisiana State University. In situ characterization and DFT calculations were supported by the U.S. Department of Energy , Office of Basic Energy Sciences , under contract no. DE-SC0012704 . This research used beamline 7-BM (QAS) of the National Synchrotron Light Source II (NSLS-II) at BNL (contract no. DE-SC0012704 ) and was supported in part by the Synchrotron Catalysis Consortium (grant no. DE-SC0012653 ). DFT calculations were performed using computational resources of the Center for Functional Nanomaterials (CFN) at BNL under contract no. DE-SC0012704 .

Funders	Funder number
National Synchrotron Light Source II
Provost's Fund for Innovation in Research
Provost’s Fund for Innovation in Research
Synchrotron Catalysis Consortium	DE-SC0012653
U.S. Department of Energy
Office of Science
Basic Energy Sciences	DE-SC0012704
Brookhaven National Laboratory
Louisiana State University

Keywords

SDG13: Climate action
SDG7: Affordable and clean energy
bimetallic
carbon dioxide
density functional theory
in situ characterization
oxidative dehydrogenation

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1016/j.chempr.2023.07.002

Cite this

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title = "CO2-mediated oxidative dehydrogenation of propane enabled by Pt-based bimetallic catalysts",

abstract = "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. 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 PtmMn-MOx (e.g., Pt3Sn-SnOx) interfaces are likely active sites.",

keywords = "SDG13: Climate action, SDG7: Affordable and clean energy, bimetallic, carbon dioxide, density functional theory, in situ characterization, oxidative dehydrogenation",

author = "Peng Zhai and Zhenhua Xie and Erwei Huang and Aireddy, {Divakar R.} and Haoran Yu and Cullen, {David A.} and Ping Liu and Chen, {Jingguang G.} and Kunlun Ding",

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AU - Zhai, Peng

AU - Xie, Zhenhua

AU - Huang, Erwei

AU - Aireddy, Divakar R.

AU - Yu, Haoran

AU - Cullen, David A.

AU - Liu, Ping

AU - Chen, Jingguang G.

AU - Ding, Kunlun

PY - 2023/11/9

Y1 - 2023/11/9

N2 - 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. 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 PtmMn-MOx (e.g., Pt3Sn-SnOx) interfaces are likely active sites.

AB - 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. 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 PtmMn-MOx (e.g., Pt3Sn-SnOx) interfaces are likely active sites.

KW - SDG13: Climate action

KW - SDG7: Affordable and clean energy

KW - bimetallic

KW - carbon dioxide

KW - density functional theory

KW - in situ characterization

KW - oxidative dehydrogenation

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