Investigating the Nature of the Active Sites for the CO2 Reduction Reaction on Carbon-Based Electrocatalysts

Asset, Tristan; Garcia, Samuel T.; Herrera, Sergio; Andersen, Nalin; Chen, Yechuan; Peterson, Eric J.; Matanovic, Ivana; Artyushkova, Kateryna; Lee, Jack; Minteer, Shelley D.; Dai, Sheng; Pan, Xiaoqing; Chavan, Kanchan; Barton, Scott Calabrese; Atanassov, Plamen

doi:10.1021/acscatal.9b01513

Title: Investigating the Nature of the Active Sites for the CO₂ Reduction Reaction on Carbon-Based Electrocatalysts

Abstract

To achieve a better understanding of the CO₂ reduction reaction on carbon-based electrocatalysts, we synthesized a library of nitrogen-doped carbonaceous materials with atomically dispersed 3d transition metals and corresponding metal-free electrocatalysts. The sacrificial support method was used yielding catalyst materials of high dispersity and high graphitic content. The resulting electrocatalysts were impurity free, hence allowing a better understanding of the mechanism of CO₂ reduction. By combining the electrochemical results with density functional theory, we were able to separate the electrocatalysts into several categories, based on their CO₂ → COOH_ads free energy and their CO_ads binding strength. The “strong-CO binder” electrocatalysts (e.g., Cr, Mn and Fe–N–C) achieved a Faradaic efficiency up to 50% at –0.35 V vs. RHE (at pH = 7.5, in 0.1 M phosphate buffer). Such Faradaic efficiency was also achieved for a metal-free electrocatalyst, therefore showing the high activity of the metal-free, N-containing, moieties toward the CO₂ reduction reaction. Furthermore, this was confirmed by near ambient pressure X-ray photoelectron spectroscopy that confirmed pyridinic and hydrogenated (pyrrolic) nitrogen moieties act as preferential adsorption sites for the CO₂ on the Fe–N–C catalyst surface.

Authors:

Asset, Tristan ^[1]; Garcia, Samuel T. ^[2]; Herrera, Sergio ^[2]; Andersen, Nalin ^[2]; Chen, Yechuan ^[1]; Peterson, Eric J. ^[2];

^[3];

^[2]; Lee, Jack ^[4];

^[4];

^[1]; Pan, Xiaoqing ^[1]; Chavan, Kanchan ^[5];

^[5];

^[6]

Univ. of California, Irvine, CA (United States)
Univ. of New Mexico, Albuquerque, NM (United States)
Univ. of New Mexico, Albuquerque, NM (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Univ. of Utah, Salt Lake City, UT (United States)
Michigan State Univ., East Lansing, MI (United States)
Univ. of California, Irvine, CA (United States); Univ. of New Mexico, Albuquerque, NM (United States)

Publication Date:: Mon Jul 08 00:00:00 EDT 2019

Research Org.:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; U.S. Army; USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1601410

Report Number(s):: LA-UR-19-27597
Journal ID: ISSN 2155-5435

Grant/Contract Number:: AC52-06NA25396; AC02-05CH11231; 89233218CNA000001

Resource Type:: Accepted Manuscript

Journal Name:: ACS Catalysis

Additional Journal Information:: Journal Volume: 9; Journal Issue: 9; Journal ID: ISSN 2155-5435

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; : nitrogen-doped carbonaceous materials; transition metal−nitrogen−carbon catalysts; atomically dispersed transition-metal sites; CO2 reduction reaction; near ambient pressure X-ray photoelectron spectroscopy; density functional theory

Citation Formats


                    Asset, Tristan, Garcia, Samuel T., Herrera, Sergio, Andersen, Nalin, Chen, Yechuan, Peterson, Eric J., Matanovic, Ivana, Artyushkova, Kateryna, Lee, Jack, Minteer, Shelley D., Dai, Sheng, Pan, Xiaoqing, Chavan, Kanchan, Barton, Scott Calabrese, and Atanassov, Plamen. Investigating the Nature of the Active Sites for the CO2 Reduction Reaction on Carbon-Based Electrocatalysts.  United States: N. p., 2019. 
Web.  doi:10.1021/acscatal.9b01513.

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                    Asset, Tristan, Garcia, Samuel T., Herrera, Sergio, Andersen, Nalin, Chen, Yechuan, Peterson, Eric J., Matanovic, Ivana, Artyushkova, Kateryna, Lee, Jack, Minteer, Shelley D., Dai, Sheng, Pan, Xiaoqing, Chavan, Kanchan, Barton, Scott Calabrese, & Atanassov, Plamen. Investigating the Nature of the Active Sites for the CO2 Reduction Reaction on Carbon-Based Electrocatalysts.  United States.  https://doi.org/10.1021/acscatal.9b01513

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                    Asset, Tristan, Garcia, Samuel T., Herrera, Sergio, Andersen, Nalin, Chen, Yechuan, Peterson, Eric J., Matanovic, Ivana, Artyushkova, Kateryna, Lee, Jack, Minteer, Shelley D., Dai, Sheng, Pan, Xiaoqing, Chavan, Kanchan, Barton, Scott Calabrese, and Atanassov, Plamen. Mon .  
"Investigating the Nature of the Active Sites for the CO2 Reduction Reaction on Carbon-Based Electrocatalysts".  United States.  https://doi.org/10.1021/acscatal.9b01513.  https://www.osti.gov/servlets/purl/1601410.

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@article{osti_1601410,

  title        = {Investigating the Nature of the Active Sites for the CO2 Reduction Reaction on Carbon-Based Electrocatalysts},

  author       = {Asset, Tristan and Garcia, Samuel T. and Herrera, Sergio and Andersen, Nalin and Chen, Yechuan and Peterson, Eric J. and Matanovic, Ivana and Artyushkova, Kateryna and Lee, Jack and Minteer, Shelley D. and Dai, Sheng and Pan, Xiaoqing and Chavan, Kanchan and Barton, Scott Calabrese and Atanassov, Plamen},

  abstractNote = {To achieve a better understanding of the CO2 reduction reaction on carbon-based electrocatalysts, we synthesized a library of nitrogen-doped carbonaceous materials with atomically dispersed 3d transition metals and corresponding metal-free electrocatalysts. The sacrificial support method was used yielding catalyst materials of high dispersity and high graphitic content. The resulting electrocatalysts were impurity free, hence allowing a better understanding of the mechanism of CO2 reduction. By combining the electrochemical results with density functional theory, we were able to separate the electrocatalysts into several categories, based on their CO2 → COOHads free energy and their COads binding strength. The “strong-CO binder” electrocatalysts (e.g., Cr, Mn and Fe–N–C) achieved a Faradaic efficiency up to 50% at –0.35 V vs. RHE (at pH = 7.5, in 0.1 M phosphate buffer). Such Faradaic efficiency was also achieved for a metal-free electrocatalyst, therefore showing the high activity of the metal-free, N-containing, moieties toward the CO2 reduction reaction. Furthermore, this was confirmed by near ambient pressure X-ray photoelectron spectroscopy that confirmed pyridinic and hydrogenated (pyrrolic) nitrogen moieties act as preferential adsorption sites for the CO2 on the Fe–N–C catalyst surface.},

  doi          = {10.1021/acscatal.9b01513},

  journal      = {ACS Catalysis},

  number       = 9,

  volume       = 9,

  place        = {United States},

  year         = {Mon Jul 08 00:00:00 EDT 2019},

  month        = {Mon Jul 08 00:00:00 EDT 2019}

}

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https://doi.org/10.1021/acscatal.9b01513

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Cited by: 40 works

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Figures / Tables:

Figure 1: (a) DFT calculated free energy for CO₂ reduction to COOH_ads, CO_adsdesorption, and formation of HCO_ads from CO_adsfor the M-N-C electrocatalysts (the COOH_ads → CO_ads is always downhill and, therefore, not limiting). (b) schematic representation of the ‘low-spin’ M-N₄ orbital filling, along with the CO molecular orbitalmore »

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Title: Investigating the Nature of the Active Sites for the CO2 Reduction Reaction on Carbon-Based Electrocatalysts

Abstract

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Title: Investigating the Nature of the Active Sites for the CO₂ Reduction Reaction on Carbon-Based Electrocatalysts