Boosting CO2 Hydrogenation to Formate over Edge-Sulfur Vacancies of Molybdenum Disulfide
Zifeng Wang
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
These authors contributed equally to this work.
Search for more papers by this authorYiran Kang
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
University of Chinese Academy of Sciences, Beijing, 100039 China
These authors contributed equally to this work.
Search for more papers by this authorJingting Hu
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
Search for more papers by this authorQinqin Ji
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
University of Chinese Academy of Sciences, Beijing, 100039 China
Search for more papers by this authorZhixuan Lu
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
Search for more papers by this authorGuilan Xu
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
Search for more papers by this authorYutai Qi
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
Search for more papers by this authorMo Zhang
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
Search for more papers by this authorWangwang Zhang
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
Search for more papers by this authorRui Huang
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
Search for more papers by this authorCorresponding Author
Liang Yu
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
University of Chinese Academy of Sciences, Beijing, 100039 China
Search for more papers by this authorZhong-qun Tian
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
Search for more papers by this authorCorresponding Author
Dehui Deng
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
University of Chinese Academy of Sciences, Beijing, 100039 China
Search for more papers by this authorZifeng Wang
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
These authors contributed equally to this work.
Search for more papers by this authorYiran Kang
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
University of Chinese Academy of Sciences, Beijing, 100039 China
These authors contributed equally to this work.
Search for more papers by this authorJingting Hu
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
Search for more papers by this authorQinqin Ji
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
University of Chinese Academy of Sciences, Beijing, 100039 China
Search for more papers by this authorZhixuan Lu
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
Search for more papers by this authorGuilan Xu
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
Search for more papers by this authorYutai Qi
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
Search for more papers by this authorMo Zhang
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
Search for more papers by this authorWangwang Zhang
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
Search for more papers by this authorRui Huang
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
Search for more papers by this authorCorresponding Author
Liang Yu
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
University of Chinese Academy of Sciences, Beijing, 100039 China
Search for more papers by this authorZhong-qun Tian
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
Search for more papers by this authorCorresponding Author
Dehui Deng
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 China
State Key Laboratory of Catalysis, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian, 116023 China
University of Chinese Academy of Sciences, Beijing, 100039 China
Search for more papers by this authorGraphical Abstract
Edge-rich MoS2 is presented as a promising catalyst for CO2 hydrogenation to formate with superior activity and stability. The selective formation of formate is enabled by using surface OH* and H* species from H2O dissociation on the edge-sulfur vacancies as moderate hydrogenating agents.
Abstract
Synthesis of formate from hydrogenation of carbon dioxide (CO2) is an atom-economic reaction but is confronted with challenges in developing high-performance non-precious metal catalysts for application of the process. Herein, we report a highly durable edge-rich molybdenum disulfide (MoS2) catalyst for CO2 hydrogenation to formate at 200 °C, which delivers a high selectivity of over 99 % with a superior turnover frequency of 780.7 h−1 surpassing those of previously reported non-precious metal catalysts. Multiple experimental characterization techniques combined with theoretical calculations reveal that sulfur vacancies at MoS2 edges are the active sites and the selective production of formate is enabled via a completely new water-mediated hydrogenation mechanism, in which surface OH* and H* species in dynamic equilibrium with water serve as moderate hydrogenating agents for CO2 with residual O* reduced by hydrogen. This study provides a new route for developing low-cost high-performance catalysts for CO2 hydrogenation to formate.
Conflict of interest
The authors declare no competing interests.
Open Research
Data Availability Statement
The data that support the findings of this study are available from the corresponding author upon reasonable request.
Supporting Information
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