Boosting Urea Electrosynthesis via Asymmetric Oxygen Vacancies in Zn‐Doped Fe <sub>2</sub> O <sub>3</sub> Catalysts
Abstract
Abstract Urea electrosynthesis from CO 2 and nitrate (NO 3 − ) provides an attractive pathway for storing renewable electricity and substituting traditional energy‐intensive urea synthesis technology. However, the kinetics mismatching between CO 2 reduction and NO 3 − reduction, as well as the difficulty of C─N coupling, are major challenges in urea electrosynthesis. Herein, we first calculated the free energy of *CO, *OCNO, and *NOH formation over defect‐rich Fe 2 O 3 catalysts with different metal dopants, which showed that Zn dopant was a promising candidate. Based on the theoretical study, we developed Zn‐doped defect‐rich Fe 2 O 3 catalysts (Zn–Fe 2 O 3 /O V ) containing asymmetric Zn–O V –Fe sites. It exhibited an outstanding urea faradaic efficiency of 62.4% and the remarkable recycling stability. The production rate of urea was as high as 7.48 mg h −1 mg cat −1 , which is higher than most of the reported works to date. Detailed control experiments and in situ spectroscopy analyses identified *OCNO as a crucial intermediate for C─N coupling. The Zn–Fe 2 O 3 /O V catalyst with asymmetric Zn–O V –Fe sites showed enhanced *CO coverage and promoted *OCNO formation, leading to high efficiency toward urea production.
Article Details
Authors (15)
Xinning Song
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Xiangyuan Jin
Beijing National Laboratory for Molecular Sciences Key Laboratory of Colloid and Interface and Thermodynamics Center for Carbon Neutral Chemistry Institute of Chemistry Chinese Academy of Sciences Beijing 100190 China
Tianhui Chen
Shoujie Liu
School of Materials Science and Engineering Anhui University Hefei P. R. China
Xiaodong Ma
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Xingxing Tan
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Ruhan Wang
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Libing Zhang
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Xing Tong
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Centre for Excellence in Molecular Sciences, Centre for Carbon Neutral Chemistry
Ziwei Zhao
Xinchen Kang
Institute of Chemistry, Chinese Academy of Sciences , , ,
Qinggong Zhu
Institute of Chemistry, Chinese Academy of Sciences , , ,
Qingli Qian
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Xiaofu Sun
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry
Buxing Han
Institute of Chemistry, Chinese Academy of Sciences , , ,