Universal Formation of Single Atoms from Molten Salt for Facilitating Selective CO2 Reduction

Qi Hao; Cheng Zhen; Qi Tang; Jiazhi Wang; Peiyu Ma; Junxiu Wu; Tianyang Wang; Dongxue Liu; Linxuan Xie; Xiao Liu; M Danny Gu; Michael R Hoffmann; Gang Yu; Kai Liu; Jun Lu

doi:10.1002/adma.202406380

Universal Formation of Single Atoms from Molten Salt for Facilitating Selective CO₂ Reduction

Adv Mater. 2024 Aug;36(33):e2406380. doi: 10.1002/adma.202406380. Epub 2024 Jun 16.

Authors

Qi Hao^{1

2}, Cheng Zhen^{3

4}, Qi Tang^{5

6}, Jiazhi Wang⁷, Peiyu Ma⁸, Junxiu Wu⁹, Tianyang Wang², Dongxue Liu¹⁰, Linxuan Xie², Xiao Liu², M Danny Gu⁴, Michael R Hoffmann¹¹, Gang Yu¹², Kai Liu², Jun Lu⁹

Affiliations

¹ School of Materials Science & Engineering, Zhejiang University, Hangzhou, Zhejiang, 310027, China.
² School of Engineering, Westlake University, Hangzhou, Zhejiang, 310030, China.
³ Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen, 518055, China.
⁴ Eastern Institute for Advanced Study, Eastern Institute of Technology, Ningbo, Zhejiang, 315200, China.
⁵ State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin, 130022, China.
⁶ School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei, Anhui, 230026, China.
⁷ Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui, 230026, China.
⁸ Key Laboratory of Precision and Intelligent Chemistry, National Synchrotron Radiation Laboratory, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), University of Science and Technology of China, Hefei, Anhui, 230026, China.
⁹ College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, Zhejiang, 310027, China.
¹⁰ Key Laboratory of Automobile Materials Ministry of Education and College of Materials Science and Engineering, Jilin University, Changchun, Jilin, 130022, China.
¹¹ Department of Environmental Science and Engineering, California Institute of Technology, 1200 E California Blvd, Pasadena, CA, 91125, USA.
¹² Merging Contaminants Research Center, Beijing Normal University, Zhuhai, Guangdong, 519087, China.

PMID: 38857899
DOI: 10.1002/adma.202406380

Abstract

Clarifying the formation mechanism of single-atom sites guides the design of emerging single-atom catalysts (SACs) and facilitates the identification of the active sites at atomic scale. Herein, a molten-salt atomization strategy is developed for synthesizing zinc (Zn) SACs with temperature universality from 400 to 1000/1100 °C and an evolved coordination from Zn-N₂Cl₂ to Zn-N₄. The electrochemical tests and in situ attenuated total reflectance-surface-enhanced infrared absorption spectroscopy confirm that the Zn-N₄ atomic sites are active for electrochemical carbon dioxide (CO₂) conversion to carbon monoxide (CO). In a strongly acidic medium (0.2 m K₂SO₄, pH = 1), the Zn SAC formed at 1000 °C (Zn₁NC) containing Zn-N₄ sites enables highly selective CO₂ electroreduction to CO, with nearly 100% selectivity toward CO product in a wide current density range of 100-600 mA cm^-2. During a 50 h continuous electrolysis at the industrial current density of 200 mA cm^-2, Zn₁NC achieves Faradaic efficiencies greater than 95% for CO product. The work presents a temperature-universal formation of single-atom sites, which provides a novel platform for unraveling the active sites in Zn SACs for CO₂ electroreduction and extends the synthesis of SACs with controllable coordination sites.

Keywords: acidic CO2 electroreduction; coordination evolution; single‐atom anchoring; thermal‐controlled atomization.

Abstract

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