Atomically synergistic Zn-Cr catalyst for iso-stoichiometric co-conversion of ethane and CO2 to ethylene and CO

Ji Yang; Lu Wang; Jiawei Wan; Farid El Gabaly; Andre L Fernandes Cauduro; Bernice E Mills; Jeng-Lung Chen; Liang-Ching Hsu; Daewon Lee; Xiao Zhao; Haimei Zheng; Miquel Salmeron; Caiqi Wang; Zhun Dong; Hongfei Lin; Gabor A Somorjai; Fabian Rosner; Hanna Breunig; David Prendergast; De-En Jiang; Seema Singh; Ji Su

doi:10.1038/s41467-024-44918-8

Atomically synergistic Zn-Cr catalyst for iso-stoichiometric co-conversion of ethane and CO₂ to ethylene and CO

Nat Commun. 2024 Jan 30;15(1):911. doi: 10.1038/s41467-024-44918-8.

Authors

Ji Yang^#^{1

2}, Lu Wang^#³, Jiawei Wan^#⁴, Farid El Gabaly^#⁵, Andre L Fernandes Cauduro⁵, Bernice E Mills⁵, Jeng-Lung Chen⁶, Liang-Ching Hsu⁷, Daewon Lee⁴, Xiao Zhao⁴, Haimei Zheng⁴, Miquel Salmeron⁴, Caiqi Wang⁸, Zhun Dong⁸, Hongfei Lin⁸, Gabor A Somorjai⁹, Fabian Rosner¹⁰, Hanna Breunig¹⁰, David Prendergast², De-En Jiang^{11

12}, Seema Singh¹³, Ji Su^{14

15}

Affiliations

¹ Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA.
² The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA.
³ Department of Chemistry, University of California, Riverside, CA, USA.
⁴ Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA.
⁵ Sandia National Laboratories, Livermore, CA, US.
⁶ National Synchrotron Radiation Research Center, Science-Based Industrial Park, Hsinchu, Taiwan.
⁷ Department of Soil and Environmental Sciences, National Chung Hsing University, Taichung, Taiwan.
⁸ Gene and Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, WA, USA.
⁹ Department of Chemistry, University of California, Berkeley, CA, USA.
¹⁰ Energy Analysis and Environmental Impacts Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA.
¹¹ Department of Chemistry, University of California, Riverside, CA, USA. de-en.jiang@vanderbilt.edu.
¹² Department of Chemical and Biomolecular Engineering, Vanderbilt University, Nashville, TN, USA. de-en.jiang@vanderbilt.edu.
¹³ Sandia National Laboratories, Livermore, CA, US. seema.rose.singh@gmail.com.
¹⁴ Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA. jisu@lbl.gov.
¹⁵ The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA. jisu@lbl.gov.

^# Contributed equally.

Abstract

Developing atomically synergistic bifunctional catalysts relies on the creation of colocalized active atoms to facilitate distinct elementary steps in catalytic cycles. Herein, we show that the atomically-synergistic binuclear-site catalyst (ABC) consisting of [Formula: see text]-O-Cr⁶⁺ on zeolite SSZ-13 displays unique catalytic properties for iso-stoichiometric co-conversion of ethane and CO₂. Ethylene selectivity and utilization of converted CO₂ can reach 100 % and 99.0% under 500 °C at ethane conversion of 9.6%, respectively. In-situ/ex-situ spectroscopic studies and DFT calculations reveal atomic synergies between acidic Zn and redox Cr sites. [Formula: see text] ([Formula: see text]) sites facilitate β-C-H bond cleavage in ethane and the formation of Zn-H^δ- hydride, thereby the enhanced basicity promotes CO₂ adsorption/activation and prevents ethane C-C bond scission. The redox Cr site accelerates CO₂ dissociation by replenishing lattice oxygen and facilitates H₂O formation/desorption. This study presents the advantages of the ABC concept, paving the way for the rational design of novel advanced catalysts.

Abstract

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