Stable Co-valorization of Carbon Dioxide and Methane via Dynamic Reconstruction of a Metal Oxide Solid Solution Catalyst

Junyan Zhang; Meijia Li; Yuanyuan Li; Nabihan B. Abdul Rahman; Hailing Yu; Kevin Siniard; Alexander S. Ivanov; Xin Wang; Harry M. Meyer; Shize Yang; Leighanne C. Gallington; Victoria Cooley; J. Anibal Boscoboinik; Zili Wu; Zhenzhen Yang; Felipe Polo-Garzon; Sheng Dai

doi:10.1021/acscatal.5c07343

Stable Co-valorization of Carbon Dioxide and Methane via Dynamic Reconstruction of a Metal Oxide Solid Solution Catalyst

Junyan Zhang
, Meijia Li
, Yuanyuan Li
, Nabihan B. Abdul Rahman
, Hailing Yu
, Kevin Siniard
, Alexander S. Ivanov
, Xin Wang
, Harry M. Meyer
, Shize Yang
, Leighanne C. Gallington
, Victoria Cooley
, J. Anibal Boscoboinik
, Zili Wu
, Zhenzhen Yang
, Felipe Polo-Garzon
, Sheng Dai

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

Abstract

Dry reforming of methane (DRM) is a process that converts two greenhouse gases (methane and carbon dioxide) into syngas, a mixture of H₂ and CO, that can lead to a variety of value-added chemicals. Owing to its endothermic nature, high reaction temperatures up to 800 °C are typically required, and the grand challenge lies in developing robust catalysts without sintering and coking-induced deactivation during the long-term on-stream operation. Toward this aim, herein, a robust complex oxide-supported NiCu alloy catalyst was generated in situ during DRM. By leveraging the configurational stability of a solid oxide solution precursor, tightly anchored NiCu bimetallic nanoparticles were in situ exsoluted and acted as the active sites in DRM. The as-afforded catalyst exhibited stable performance for DRM due to the ability to repel coke off the surface as the reaction proceeds. Kinetic experiments along with top surface characterization detail the reconstruction behavior of the solid oxide solution under the DRM reaction conditions. The fundamental insights from this work provide guidance on generating resistant and flexible catalysts via in situ active site formation from easily synthesized metal oxide solid solutions.

Original language	English
Pages (from-to)	2340-2352
Number of pages	13
Journal	ACS Catalysis
Volume	16
Issue number	3
DOIs	https://doi.org/10.1021/acscatal.5c07343
State	Published - Feb 6 2026

Funding

This research was sponsored by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, Catalysis Science program. Part of the research were carried out at National Synchrotron Light Source II (NIST beamline 6-BM), a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. Part of the research was performed on APS beam time award 10.46936/APS-188511/60013158 , from the Advanced Photon Source, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Some of the work including Raman spectral measurement was conducted as part of a user project at the Center for Nanophase Materials Science (CNMS), which is a U.S. DOE Office of Science User Facility located at Oak Ridge National Laboratory. We thank Dr. Ryan Thorpe (Lehigh University Institute for Functional Materials and Devices) for performing LEIS analysis. This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). Acknowledgments

Keywords

Complex metal oxide
Dry reforming of methane
Exsolution
NiCu alloy
Solid solution catalyst

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10.1021/acscatal.5c07343

Cite this

Zhang, J., Li, M., Li, Y., Abdul Rahman, N. B., Yu, H., Siniard, K., Ivanov, A. S., Wang, X., Meyer, H. M., Yang, S., Gallington, L. C., Cooley, V., Boscoboinik, J. A., Wu, Z., Yang, Z., Polo-Garzon, F., & Dai, S. (2026). Stable Co-valorization of Carbon Dioxide and Methane via Dynamic Reconstruction of a Metal Oxide Solid Solution Catalyst. ACS Catalysis, 16(3), 2340-2352. https://doi.org/10.1021/acscatal.5c07343

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title = "Stable Co-valorization of Carbon Dioxide and Methane via Dynamic Reconstruction of a Metal Oxide Solid Solution Catalyst",

abstract = "Dry reforming of methane (DRM) is a process that converts two greenhouse gases (methane and carbon dioxide) into syngas, a mixture of H2 and CO, that can lead to a variety of value-added chemicals. Owing to its endothermic nature, high reaction temperatures up to 800 °C are typically required, and the grand challenge lies in developing robust catalysts without sintering and coking-induced deactivation during the long-term on-stream operation. Toward this aim, herein, a robust complex oxide-supported NiCu alloy catalyst was generated in situ during DRM. By leveraging the configurational stability of a solid oxide solution precursor, tightly anchored NiCu bimetallic nanoparticles were in situ exsoluted and acted as the active sites in DRM. The as-afforded catalyst exhibited stable performance for DRM due to the ability to repel coke off the surface as the reaction proceeds. Kinetic experiments along with top surface characterization detail the reconstruction behavior of the solid oxide solution under the DRM reaction conditions. The fundamental insights from this work provide guidance on generating resistant and flexible catalysts via in situ active site formation from easily synthesized metal oxide solid solutions.",

keywords = "Complex metal oxide, Dry reforming of methane, Exsolution, NiCu alloy, Solid solution catalyst",

author = "Junyan Zhang and Meijia Li and Yuanyuan Li and \{Abdul Rahman\}, \{Nabihan B.\} and Hailing Yu and Kevin Siniard and Ivanov, \{Alexander S.\} and Xin Wang and Meyer, \{Harry M.\} and Shize Yang and Gallington, \{Leighanne C.\} and Victoria Cooley and Boscoboinik, \{J. Anibal\} and Zili Wu and Zhenzhen Yang and Felipe Polo-Garzon and Sheng Dai",

note = "Publisher Copyright: {\textcopyright} 2026 American Chemical Society",

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month = feb,

day = "6",

doi = "10.1021/acscatal.5c07343",

language = "English",

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Zhang, J, Li, M, Li, Y , Abdul Rahman, NB, Yu, H, Siniard, K, Ivanov, AS, Wang, X, Meyer, HM, Yang, S, Gallington, LC, Cooley, V, Boscoboinik, JA, Wu, Z , Yang, Z , Polo-Garzon, F & Dai, S 2026, 'Stable Co-valorization of Carbon Dioxide and Methane via Dynamic Reconstruction of a Metal Oxide Solid Solution Catalyst', ACS Catalysis, vol. 16, no. 3, pp. 2340-2352. https://doi.org/10.1021/acscatal.5c07343

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T1 - Stable Co-valorization of Carbon Dioxide and Methane via Dynamic Reconstruction of a Metal Oxide Solid Solution Catalyst

AU - Zhang, Junyan

AU - Li, Meijia

AU - Li, Yuanyuan

AU - Abdul Rahman, Nabihan B.

AU - Yu, Hailing

AU - Siniard, Kevin

AU - Ivanov, Alexander S.

AU - Wang, Xin

AU - Meyer, Harry M.

AU - Yang, Shize

AU - Gallington, Leighanne C.

AU - Cooley, Victoria

AU - Boscoboinik, J. Anibal

AU - Wu, Zili

AU - Yang, Zhenzhen

AU - Polo-Garzon, Felipe

AU - Dai, Sheng

PY - 2026/2/6

Y1 - 2026/2/6

N2 - Dry reforming of methane (DRM) is a process that converts two greenhouse gases (methane and carbon dioxide) into syngas, a mixture of H2 and CO, that can lead to a variety of value-added chemicals. Owing to its endothermic nature, high reaction temperatures up to 800 °C are typically required, and the grand challenge lies in developing robust catalysts without sintering and coking-induced deactivation during the long-term on-stream operation. Toward this aim, herein, a robust complex oxide-supported NiCu alloy catalyst was generated in situ during DRM. By leveraging the configurational stability of a solid oxide solution precursor, tightly anchored NiCu bimetallic nanoparticles were in situ exsoluted and acted as the active sites in DRM. The as-afforded catalyst exhibited stable performance for DRM due to the ability to repel coke off the surface as the reaction proceeds. Kinetic experiments along with top surface characterization detail the reconstruction behavior of the solid oxide solution under the DRM reaction conditions. The fundamental insights from this work provide guidance on generating resistant and flexible catalysts via in situ active site formation from easily synthesized metal oxide solid solutions.

AB - Dry reforming of methane (DRM) is a process that converts two greenhouse gases (methane and carbon dioxide) into syngas, a mixture of H2 and CO, that can lead to a variety of value-added chemicals. Owing to its endothermic nature, high reaction temperatures up to 800 °C are typically required, and the grand challenge lies in developing robust catalysts without sintering and coking-induced deactivation during the long-term on-stream operation. Toward this aim, herein, a robust complex oxide-supported NiCu alloy catalyst was generated in situ during DRM. By leveraging the configurational stability of a solid oxide solution precursor, tightly anchored NiCu bimetallic nanoparticles were in situ exsoluted and acted as the active sites in DRM. The as-afforded catalyst exhibited stable performance for DRM due to the ability to repel coke off the surface as the reaction proceeds. Kinetic experiments along with top surface characterization detail the reconstruction behavior of the solid oxide solution under the DRM reaction conditions. The fundamental insights from this work provide guidance on generating resistant and flexible catalysts via in situ active site formation from easily synthesized metal oxide solid solutions.

KW - Complex metal oxide

KW - Dry reforming of methane

KW - Exsolution

KW - NiCu alloy

KW - Solid solution catalyst

UR - https://www.scopus.com/pages/publications/105029480753

U2 - 10.1021/acscatal.5c07343

DO - 10.1021/acscatal.5c07343

M3 - Article

AN - SCOPUS:105029480753

SN - 2155-5435

VL - 16

SP - 2340

EP - 2352

JO - ACS Catalysis

JF - ACS Catalysis

IS - 3

ER -

Stable Co-valorization of Carbon Dioxide and Methane via Dynamic Reconstruction of a Metal Oxide Solid Solution Catalyst

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