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Research Article | Online first | Published: 23 March 2024

Acidic electroreduction CO2 to formic acid via interfacial modification of Bi nanoparticles at industrial-level current

Show Author's Information Tian Dong1,  Hongdong Li1( ),  Zhenhui Wang1,  Yanling Geng1,  Rui Chang1,  Xiaofeng Tian1,  Jianping Lai1,  Shouhua Feng1,  Lei Wang1,2( )
Key Laboratory of Eco-Chemical Engineering, International Science and Technology Cooperation Base of Eco-Chemical Engineering and Green Manufacturing, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
Shandong Engineering Research Center for Marine Environment Corrosion and Safety Protection, College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
Keywords:
electrolyte additive, acidic media, CO2 electrolysis, hydrophobic interfacial microenvironment, industrial-level current
Topics:
Electrocatalysis
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Dong T, Li H, Wang Z, et al. Acidic electroreduction CO2 to formic acid via interfacial modification of Bi nanoparticles at industrial-level current. Nano Research, 2024, https://doi.org/10.1007/s12274-024-6536-2
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Abstract Full text Electronic supplementary material About this article

Electrocatalytic CO2 reduction reaction (CO2RR) in acidic media is a promising approach to overcome the unavoidable formation of carbonates in alkaline or neutral electrolytes. However, the proton-rich environment near the catalyst surface favors hydrogen evolution reactions (HER), leading to lower energy efficiency of the desired products, especially in industrial-level current densities. Here, quaternary ammonium cationic surfactant (cetyltrimethylammonium bromide (CTAB)) was introduced into acidic electrolyte to modulate the interfacial microenvironment, which greatly enhanced CO2 electroreduction to formic acid (HCOOH) at the Bi/C nanoparticles electrode. Using a Bi/C nanoparticles electrode with CTAB added, constant production of formic acid was enabled with a cathodic energy efficiency of > 40% and maximum FEHCOOH (FE = Faradaic efficiency) of 86.2% at −400 mA·cm−2 over 24 h. Combined with in-situ attenuated total reflection Fourier transform infrared spectroscopy, the concentration of *OCHO intermediates significantly increased after CTAB modification, confirming that the hydrophobic interface microenvironment formed by dynamic adsorption of positively charged long alkyl chains on Bi/C nanoparticle electrodes inhibited HER and improved the selectivity of CO2RR to HCOOH.


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Electronic supplementary material
About this article

Acidic electroreduction CO2 to formic acid via interfacial modification of Bi nanoparticles at industrial-level current

Show Author's information Tian Dong1, Hongdong Li1( ), Zhenhui Wang1, Yanling Geng1, Rui Chang1, Xiaofeng Tian1, Jianping Lai1, Shouhua Feng1, Lei Wang1,2( )
Key Laboratory of Eco-Chemical Engineering, International Science and Technology Cooperation Base of Eco-Chemical Engineering and Green Manufacturing, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
Shandong Engineering Research Center for Marine Environment Corrosion and Safety Protection, College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

Abstract

Electrocatalytic CO2 reduction reaction (CO2RR) in acidic media is a promising approach to overcome the unavoidable formation of carbonates in alkaline or neutral electrolytes. However, the proton-rich environment near the catalyst surface favors hydrogen evolution reactions (HER), leading to lower energy efficiency of the desired products, especially in industrial-level current densities. Here, quaternary ammonium cationic surfactant (cetyltrimethylammonium bromide (CTAB)) was introduced into acidic electrolyte to modulate the interfacial microenvironment, which greatly enhanced CO2 electroreduction to formic acid (HCOOH) at the Bi/C nanoparticles electrode. Using a Bi/C nanoparticles electrode with CTAB added, constant production of formic acid was enabled with a cathodic energy efficiency of > 40% and maximum FEHCOOH (FE = Faradaic efficiency) of 86.2% at −400 mA·cm−2 over 24 h. Combined with in-situ attenuated total reflection Fourier transform infrared spectroscopy, the concentration of *OCHO intermediates significantly increased after CTAB modification, confirming that the hydrophobic interface microenvironment formed by dynamic adsorption of positively charged long alkyl chains on Bi/C nanoparticle electrodes inhibited HER and improved the selectivity of CO2RR to HCOOH.

Keywords: electrolyte additive, acidic media, CO2 electrolysis, hydrophobic interfacial microenvironment, industrial-level current

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Publication history
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Acknowledgements

Publication history

Received: 25 December 2023
Revised: 29 January 2024
Accepted: 30 January 2024
Published: 23 March 2024

Copyright

© Tsinghua University Press 2024

Acknowledgements

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 52072197, 22302108, 21971132, and 52272222), Youth Innovation and Technology Foundation of Shandong Higher Education Institutions, China (No. 2023KJ313), Outstanding Youth Foundation of Shandong Province, China (No. ZR2019JQ14), Major Scientific and Technological Innovation Project (No. 2019JZZY020405), Major Basic Research Program of Natural Science Foundation of Shandong Province (No. ZR2020ZD09), Natural Science Foundation of Qingdao (No. 23-2-1-12-zyyd-jch), and Qingdao Postdoctoral Researcher Applied Research Project (No. QDBSH20220202043).

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