Sulfate residuals on Ru catalysts switch CO2 reduction from methanation to reverse water-gas shift reaction

Min Chen; Longgang Liu; Xueyan Chen; Xiaoxiao Qin; Jianghao Zhang; Shaohua Xie; Fudong Liu; Hong He; Changbin Zhang

doi:10.1038/s41467-024-53909-8

Sulfate residuals on Ru catalysts switch CO₂ reduction from methanation to reverse water-gas shift reaction

Nat Commun. 2024 Nov 2;15(1):9478. doi: 10.1038/s41467-024-53909-8.

Authors

Min Chen¹, Longgang Liu², Xueyan Chen¹, Xiaoxiao Qin¹, Jianghao Zhang¹, Shaohua Xie³, Fudong Liu⁴, Hong He^{1

5}, Changbin Zhang^{6

7}

Affiliations

¹ State Key Joint Laboratory of Environment Simulation and Pollution Control, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, China.
² School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu, China.
³ Department of Chemical and Environmental Engineering, Bourns College of Engineering, Center for Environmental Research and Technology (CE-CERT), Materials Science and Engineering (MSE) Program, University of California, Riverside, CA, USA.
⁴ Department of Chemical and Environmental Engineering, Bourns College of Engineering, Center for Environmental Research and Technology (CE-CERT), Materials Science and Engineering (MSE) Program, University of California, Riverside, CA, USA. [email protected].
⁵ University of Chinese Academy of Sciences, Beijing, China.
⁶ State Key Joint Laboratory of Environment Simulation and Pollution Control, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, China. [email protected].
⁷ University of Chinese Academy of Sciences, Beijing, China. [email protected].

PMID: 39488527
DOI: 10.1038/s41467-024-53909-8

Abstract

Efficient heterogeneous catalyst design primarily focuses on engineering the active sites or supports, often neglecting the impact of trace impurities on catalytic performance. Herein, we demonstrate that even trace amounts of sulfate (SO₄^2-) residuals on Ru/TiO₂ can totally change the CO₂ reduction from methanation to reverse-water gas shift (RWGS) reaction under atmospheric pressure. We reveal that air annealing causes the trace amount of SO₄^2- to migrate from TiO₂ to Ru/TiO₂ interface, leading to the significant changes in product selectivity from CH₄ to CO. Detailed characterizations and DFT calculations show that the sulfate at Ru/TiO₂ interface notably enhances the H transfer from Ru particles to the TiO₂ support, weakening the CO intermediate activation on Ru particles and inhibiting the further hydrogenation of CO to CH₄. This discovery highlights the vital role of trace impurities in CO₂ hydrogenation reaction, and also provides broad implications for the design and development of more efficient and selective heterogeneous catalysts.

Abstract

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