Boosting CO2 Electroreduction over a Covalent Organic Framework in the Presence of Oxygen
Hui Guo
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002 Fujian, Fuzhou, P. R. China
University of Chinese Academy of Sciences, 100049 Beijing, P. R. China
These authors contributed equally to this work.
Contribution: Data curation (lead), Writing - original draft (lead)
Search for more papers by this authorDr. Duan-Hui Si
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002 Fujian, Fuzhou, P. R. China
These authors contributed equally to this work.
Search for more papers by this authorHong-Jing Zhu
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002 Fujian, Fuzhou, P. R. China
University of Chinese Academy of Sciences, 100049 Beijing, P. R. China
Search for more papers by this authorZi-Ao Chen
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002 Fujian, Fuzhou, P. R. China
University of Chinese Academy of Sciences, 100049 Beijing, P. R. China
Search for more papers by this authorProf. Rong Cao
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002 Fujian, Fuzhou, P. R. China
Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, 350108 Fuzhou, Fujian, P. R. China
University of Chinese Academy of Sciences, 100049 Beijing, P. R. China
Search for more papers by this authorCorresponding Author
Prof. Yuan-Biao Huang
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002 Fujian, Fuzhou, P. R. China
Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, 350108 Fuzhou, Fujian, P. R. China
University of Chinese Academy of Sciences, 100049 Beijing, P. R. China
Search for more papers by this authorHui Guo
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002 Fujian, Fuzhou, P. R. China
University of Chinese Academy of Sciences, 100049 Beijing, P. R. China
These authors contributed equally to this work.
Contribution: Data curation (lead), Writing - original draft (lead)
Search for more papers by this authorDr. Duan-Hui Si
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002 Fujian, Fuzhou, P. R. China
These authors contributed equally to this work.
Search for more papers by this authorHong-Jing Zhu
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002 Fujian, Fuzhou, P. R. China
University of Chinese Academy of Sciences, 100049 Beijing, P. R. China
Search for more papers by this authorZi-Ao Chen
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002 Fujian, Fuzhou, P. R. China
University of Chinese Academy of Sciences, 100049 Beijing, P. R. China
Search for more papers by this authorProf. Rong Cao
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002 Fujian, Fuzhou, P. R. China
Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, 350108 Fuzhou, Fujian, P. R. China
University of Chinese Academy of Sciences, 100049 Beijing, P. R. China
Search for more papers by this authorCorresponding Author
Prof. Yuan-Biao Huang
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, 350002 Fujian, Fuzhou, P. R. China
Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, 350108 Fuzhou, Fujian, P. R. China
University of Chinese Academy of Sciences, 100049 Beijing, P. R. China
Search for more papers by this authorAbstract
Herein, we propose an oxygen-containing species coordination strategy to boost CO2 electroreduction in the presence of O2. A two-dimensional (2D) conjugated metal-covalent organic framework (MCOF), denoted as NiPc-Salen(Co)2-COF that is composed of the Ni-phthalocyanine (NiPc) unit with well-defined Ni−N4−O sites and the salen(Co)2 moiety with binuclear Co−N2O2 sites, is developed and synthesized for enhancing the CO2RR under aerobic condition. In the presence of O2, one of the Co sites in the NiPc-Salen(Co)2-COF that coordinated with the intermediate of *OOH from ORR could decrease the energy barrier of the activation of CO2 molecules and stabilize the key intermediate *COOH of the CO2RR over the adjacent Co center. Besides, the oxygen species axially coordinated Ni−N4−O sites can favor in reducing the energy barrier of the intermediate *COOH formation for the CO2RR. Thus, NiPc-Salen(Co)2-COF exhibits high oxygen-tolerant CO2RR performance and achieves outstanding CO Faradaic efficiency (FECO) of 97.2 % at −1.0 V vs. the reversible hydrogen electrode (RHE) and a high CO partial current density of 40.3 mA cm−2 at −1.1 V in the presence of 0.5 % O2, which is superior to that in pure CO2 feed gas (FECO=94.8 %, jCO=19.9 mA cm−2). Notably, the NiPc-Salen(Co)2-COF achieves an industrial-level current density of 128.3 mA cm−2 in the flow-cell reactor with 0.5 % O2 at −0.8 V, which is higher than that in pure CO2 atmosphere (jCO=104.8 mA cm−2). It is worth noting that an excellent FECO of 86.8 % is still achieved in the presence of 5 % O2 at −1.0 V. This work provides an effective strategy to enable the CO2RR under O2 atmosphere by utilizing the *OOH intermediates of ORR to boost CO2 electroreduction.
Conflict of interests
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available from the corresponding author upon reasonable request.
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