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

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

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

27 Scopus citations

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 Zn ^δ⁺ -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. Zn ^δ⁺ (0<δ<2 ) 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.

Original language	English
Article number	911
Journal	Nature Communications
Volume	15
Issue number	1
DOIs	https://doi.org/10.1038/s41467-024-44918-8
State	Published - Dec 2024
Externally published	Yes

Funding

The research was supported financially by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, US Department of Energy (Award No. DE-SC0022273). Spectroscopic and microscopic experiments were performed at the BL7.3.1 at the Advanced Light Source (ALS) and Molecular Foundry at LBNL under contract no. DE-AC02-05CH11231. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under contract no. DE-AC02-05CH11231. J.W. and H.Z. acknowledge the support of the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (BES), Materials Sciences and Engineering Division under Contract No. DE-AC02-05-CH11231 within the in-situ TEM program (KC22ZH). J.L.C. acknowledges the support of the Ministry of Science and Technology, Taiwan (110-2112-M-213-006). Work at Sandia National Laboratories supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (BES) under Field Work Proposal Number 23-024168. Sandia National Laboratories is a multimission laboratory managed and operated by the National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the U.S. Government. D.L. acknowledges the Kwanjeong Study Abroad Scholarship from the KEF (Kwanjeong Educational Foundation) (KEF-2019).

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Yang, J., Wang, L., Wan, J., El Gabaly, F., Fernandes Cauduro, A. L., Mills, B. E., Chen, J. L., Hsu, L. C., Lee, D., Zhao, X., Zheng, H., Salmeron, M., Wang, C., Dong, Z., Lin, H., Somorjai, G. A., Rosner, F., Breunig, H., Prendergast, D., ... Su, J. (2024). Atomically synergistic Zn-Cr catalyst for iso-stoichiometric co-conversion of ethane and CO₂ to ethylene and CO. Nature Communications, 15(1), Article 911. https://doi.org/10.1038/s41467-024-44918-8

@article{f4e18e72b4204306ae2fe9e14ac3ca8f,

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

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 Zn δ+ -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. Zn δ+ (0<δ<2 ) 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.",

author = "Ji Yang and Lu Wang and Jiawei Wan and \{El Gabaly\}, Farid and \{Fernandes Cauduro\}, \{Andre L.\} and Mills, \{Bernice E.\} and Chen, \{Jeng Lung\} and Hsu, \{Liang Ching\} and Daewon Lee and Xiao Zhao and Haimei Zheng and Miquel Salmeron and Caiqi Wang and Zhun Dong and Hongfei Lin and Somorjai, \{Gabor A.\} and Fabian Rosner and Hanna Breunig and David Prendergast and Jiang, \{De en\} and Seema Singh and Ji Su",

note = "Publisher Copyright: {\textcopyright} 2024, The Author(s).",

year = "2024",

month = dec,

doi = "10.1038/s41467-024-44918-8",

language = "English",

volume = "15",

journal = "Nature Communications",

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Yang, J, Wang, L, Wan, J, El Gabaly, F, Fernandes Cauduro, AL, Mills, BE, Chen, JL, Hsu, LC, Lee, D, Zhao, X, Zheng, H, Salmeron, M, Wang, C, Dong, Z, Lin, H, Somorjai, GA, Rosner, F, Breunig, H, Prendergast, D, Jiang, DE, Singh, S & Su, J 2024, 'Atomically synergistic Zn-Cr catalyst for iso-stoichiometric co-conversion of ethane and CO₂ to ethylene and CO', Nature Communications, vol. 15, no. 1, 911. https://doi.org/10.1038/s41467-024-44918-8

TY - JOUR

T1 - Atomically synergistic Zn-Cr catalyst for iso-stoichiometric co-conversion of ethane and CO2 to ethylene and CO

AU - Yang, Ji

AU - Wang, Lu

AU - Wan, Jiawei

AU - El Gabaly, Farid

AU - Fernandes Cauduro, Andre L.

AU - Mills, Bernice E.

AU - Chen, Jeng Lung

AU - Hsu, Liang Ching

AU - Lee, Daewon

AU - Zhao, Xiao

AU - Zheng, Haimei

AU - Salmeron, Miquel

AU - Wang, Caiqi

AU - Dong, Zhun

AU - Lin, Hongfei

AU - Somorjai, Gabor A.

AU - Rosner, Fabian

AU - Breunig, Hanna

AU - Prendergast, David

AU - Jiang, De en

AU - Singh, Seema

AU - Su, Ji

PY - 2024/12

Y1 - 2024/12

N2 - 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 Zn δ+ -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. Zn δ+ (0<δ<2 ) 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.

AB - 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 Zn δ+ -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. Zn δ+ (0<δ<2 ) 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.

UR - https://www.scopus.com/pages/publications/85183646285

U2 - 10.1038/s41467-024-44918-8

DO - 10.1038/s41467-024-44918-8

M3 - Article

C2 - 38291043

AN - SCOPUS:85183646285

SN - 2041-1723

VL - 15

JO - Nature Communications

JF - Nature Communications

IS - 1

M1 - 911

ER -

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

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