Boosting CO2 reduction on Fe-N-C with sulfur incorporation: Synergistic electronic and structural engineering

Pan, Fuping; Li, Boyang; Sarnello, Erik; Hwang, Sooyeon; Gang, Yang; Feng, Xuhui; Xiang, Xianmei; Adli, Nadia Mohd; Li, Tao; Su, Dong; Wu, Gang; Wang, Guofeng; Li, Ying

doi:10.1016/j.nanoen.2019.104384

Title: Boosting CO₂ reduction on Fe-N-C with sulfur incorporation: Synergistic electronic and structural engineering

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Abstract

Developing earth-abundant efficient catalysts for CO₂ reduction reaction (CO₂RR) is of paramount importance for electrochemical conversion of CO₂ into value-added products. Despite numerous studies on iron and nitrogen codoped carbon (Fe-N-C) catalysts, grand challenges exist due to limited performance and understanding of catalytic mechanisms. This study reports a general strategy to boost electrocatalytic CO₂RR activity of Fe-N-C with the incorporation of S atoms to engineer carbon support structure and electronic properties of active Fe-N sites simultaneously via a copolymer-assisted synthetic approach. The employment of N,S comonomers significantly increases the numbers of micropores and surface area, enabling dense atomic Fe-N and enhanced utilization efficiency. We report the first-principles calculations reveal that S modulation upraises the Fermi energy of Fe 3d and increases charge density on Fe atoms of Fe-N₄, thereby enhancing intrinsic catalytic reactivity and selectivity for CO₂ reduction by strengthening the binding interaction between the Fe site and key COOH* intermediate. These integrated structural and electronic merits endow Fe-NS-C with outstanding activity (e.g., CO Faradaic efficiency of 98% at an overpotential of 490 mV) and stability (without deactivation in 30 h), ranking it one of the most active Fe-N-C reported to date. The finding offers an innovative design strategy tomore »« less

Authors:

Pan, Fuping ^[1]; Li, Boyang ^[2]; Sarnello, Erik ^[3]; Hwang, Sooyeon ^[4]; Gang, Yang ^[1]; Feng, Xuhui ^[1]; Xiang, Xianmei ^[1]; Adli, Nadia Mohd ^[5]; Li, Tao ^[6]; Su, Dong ^[4]; Wu, Gang ^[5]; Wang, Guofeng ^[2]; Li, Ying ^[1]

Texas A & M Univ., College Station, TX (United States)
Univ. of Pittsburgh, PA (United States)
Northern Illinois Univ., DeKalb, IL (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Univ. at Buffalo, NY (United States)
Northern Illinois Univ., DeKalb, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)

Publication Date:: Fri Dec 06 00:00:00 EST 2019

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Northern Illinois University

OSTI Identifier:: 1615906

Alternate Identifier(s):: OSTI ID: 1604622; OSTI ID: 1694278

Report Number(s):: BNL-213731-2020-JAAM
Journal ID: ISSN 2211-2855; 159482

Grant/Contract Number:: AC02-06CH11357; SC0012704; ACI-1053575

Resource Type:: Accepted Manuscript

Journal Name:: Nano Energy

Additional Journal Information:: Journal Volume: 68; Journal Issue: C; Journal ID: ISSN 2211-2855

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CO2 reduction; Fe-N-C; density functional theory; electrocatalysis; sulfur engineering; 25 ENERGY STORAGE

Citation Formats


                    Pan, Fuping, Li, Boyang, Sarnello, Erik, Hwang, Sooyeon, Gang, Yang, Feng, Xuhui, Xiang, Xianmei, Adli, Nadia Mohd, Li, Tao, Su, Dong, Wu, Gang, Wang, Guofeng, and Li, Ying. Boosting CO2 reduction on Fe-N-C with sulfur incorporation: Synergistic electronic and structural engineering.  United States: N. p., 2019. 
Web.  doi:10.1016/j.nanoen.2019.104384.

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                    Pan, Fuping, Li, Boyang, Sarnello, Erik, Hwang, Sooyeon, Gang, Yang, Feng, Xuhui, Xiang, Xianmei, Adli, Nadia Mohd, Li, Tao, Su, Dong, Wu, Gang, Wang, Guofeng, & Li, Ying. Boosting CO2 reduction on Fe-N-C with sulfur incorporation: Synergistic electronic and structural engineering.  United States.  https://doi.org/10.1016/j.nanoen.2019.104384

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                    Pan, Fuping, Li, Boyang, Sarnello, Erik, Hwang, Sooyeon, Gang, Yang, Feng, Xuhui, Xiang, Xianmei, Adli, Nadia Mohd, Li, Tao, Su, Dong, Wu, Gang, Wang, Guofeng, and Li, Ying. Fri .  
"Boosting CO2 reduction on Fe-N-C with sulfur incorporation: Synergistic electronic and structural engineering".  United States.  https://doi.org/10.1016/j.nanoen.2019.104384.  https://www.osti.gov/servlets/purl/1615906.

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@article{osti_1615906,

  title        = {Boosting CO2 reduction on Fe-N-C with sulfur incorporation: Synergistic electronic and structural engineering},

  author       = {Pan, Fuping and Li, Boyang and Sarnello, Erik and Hwang, Sooyeon and Gang, Yang and Feng, Xuhui and Xiang, Xianmei and Adli, Nadia Mohd and Li, Tao and Su, Dong and Wu, Gang and Wang, Guofeng and Li, Ying},

  abstractNote = {Developing earth-abundant efficient catalysts for CO2 reduction reaction (CO2RR) is of paramount importance for electrochemical conversion of CO2 into value-added products. Despite numerous studies on iron and nitrogen codoped carbon (Fe-N-C) catalysts, grand challenges exist due to limited performance and understanding of catalytic mechanisms. This study reports a general strategy to boost electrocatalytic CO2RR activity of Fe-N-C with the incorporation of S atoms to engineer carbon support structure and electronic properties of active Fe-N sites simultaneously via a copolymer-assisted synthetic approach. The employment of N,S comonomers significantly increases the numbers of micropores and surface area, enabling dense atomic Fe-N and enhanced utilization efficiency. We report the first-principles calculations reveal that S modulation upraises the Fermi energy of Fe 3d and increases charge density on Fe atoms of Fe-N4, thereby enhancing intrinsic catalytic reactivity and selectivity for CO2 reduction by strengthening the binding interaction between the Fe site and key COOH* intermediate. These integrated structural and electronic merits endow Fe-NS-C with outstanding activity (e.g., CO Faradaic efficiency of 98% at an overpotential of 490 mV) and stability (without deactivation in 30 h), ranking it one of the most active Fe-N-C reported to date. The finding offers an innovative design strategy to enable the design of advanced catalysts for CO2 conversion.},

  doi          = {10.1016/j.nanoen.2019.104384},

  journal      = {Nano Energy},

  number       = C,

  volume       = 68,

  place        = {United States},

  year         = {Fri Dec 06 00:00:00 EST 2019},

  month        = {Fri Dec 06 00:00:00 EST 2019}

}

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Title: Boosting CO2 reduction on Fe-N-C with sulfur incorporation: Synergistic electronic and structural engineering

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Title: Boosting CO₂ reduction on Fe-N-C with sulfur incorporation: Synergistic electronic and structural engineering