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Title: Colloidal silver diphosphide (AgP2) nanocrystals as low overpotential catalysts for CO2 reduction to tunable syngas

Abstract

Production of syngas with tunable CO/H2 ratio from renewable resources is an ideal way to provide a carbon-neutral feedstock for liquid fuel production. Ag is a benchmark electrocatalysts for CO2-to-CO conversion but high overpotential limits the efficiency. We synthesize AgP2 nanocrystals (NCs) with a greater than 3-fold reduction in overpotential for electrochemical CO2-to-CO reduction compared to Ag and greatly enhanced stability. Density functional theory calculations reveal a significant energy barrier decrease in the formate intermediate formation step. In situ X-ray absorption spectroscopy (XAS) shows that a maximum Faradaic efficiency is achieved at an average silver valence state of +1.08 in AgP2 NCs. A photocathode consisting of a n+p-Si wafer coated with ultrathin Al2O3 and AgP2 NCs achieves an onset potential of 0.2 V vs. RHE for CO production and a partial photocurrent density for CO at –0.11 V vs. RHE (j–0.11, CO) of –3.2 mA cm–2.

Authors:
 [1];  [2];  [1]; ORCiD logo [3]; ORCiD logo [1];  [1];  [4];  [1];  [5]; ORCiD logo [6];  [2]; ORCiD logo [1]
  1. Wake Forest Univ., Winston-Salem, NC (United States). Dept. of Chemistry
  2. Harbin Inst. of Technology (China). School of Materials Science and Engineering, Shenzhen Engineering Lab of Flexible Transparent Conductive Films
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  5. Univ. of Notre Dame, IN (United States). Dept. of Aerospace and Mechanical Engineering
  6. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC), Engineering & Technology; Wake Forest University; Shenzhen Bureau of Science, Technology and Innovation Commission
OSTI Identifier:
1624219
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Science & technology - other topics; Carbon capture and storage; Electrocatalysis; Heterogeneous catalysis; Nanoparticles

Citation Formats

Li, Hui, Wen, Peng, Itanze, Dominique S., Hood, Zachary D., Ma, Xiao, Kim, Michael, Adhikari, Shiba, Lu, Chang, Dun, Chaochao, Chi, Miaofang, Qiu, Yejun, and Geyer, Scott M. Colloidal silver diphosphide (AgP2) nanocrystals as low overpotential catalysts for CO2 reduction to tunable syngas. United States: N. p., 2019. Web. https://doi.org/10.1038/s41467-019-13388-8.
Li, Hui, Wen, Peng, Itanze, Dominique S., Hood, Zachary D., Ma, Xiao, Kim, Michael, Adhikari, Shiba, Lu, Chang, Dun, Chaochao, Chi, Miaofang, Qiu, Yejun, & Geyer, Scott M. Colloidal silver diphosphide (AgP2) nanocrystals as low overpotential catalysts for CO2 reduction to tunable syngas. United States. https://doi.org/10.1038/s41467-019-13388-8
Li, Hui, Wen, Peng, Itanze, Dominique S., Hood, Zachary D., Ma, Xiao, Kim, Michael, Adhikari, Shiba, Lu, Chang, Dun, Chaochao, Chi, Miaofang, Qiu, Yejun, and Geyer, Scott M. Mon . "Colloidal silver diphosphide (AgP2) nanocrystals as low overpotential catalysts for CO2 reduction to tunable syngas". United States. https://doi.org/10.1038/s41467-019-13388-8. https://www.osti.gov/servlets/purl/1624219.
@article{osti_1624219,
title = {Colloidal silver diphosphide (AgP2) nanocrystals as low overpotential catalysts for CO2 reduction to tunable syngas},
author = {Li, Hui and Wen, Peng and Itanze, Dominique S. and Hood, Zachary D. and Ma, Xiao and Kim, Michael and Adhikari, Shiba and Lu, Chang and Dun, Chaochao and Chi, Miaofang and Qiu, Yejun and Geyer, Scott M.},
abstractNote = {Production of syngas with tunable CO/H2 ratio from renewable resources is an ideal way to provide a carbon-neutral feedstock for liquid fuel production. Ag is a benchmark electrocatalysts for CO2-to-CO conversion but high overpotential limits the efficiency. We synthesize AgP2 nanocrystals (NCs) with a greater than 3-fold reduction in overpotential for electrochemical CO2-to-CO reduction compared to Ag and greatly enhanced stability. Density functional theory calculations reveal a significant energy barrier decrease in the formate intermediate formation step. In situ X-ray absorption spectroscopy (XAS) shows that a maximum Faradaic efficiency is achieved at an average silver valence state of +1.08 in AgP2 NCs. A photocathode consisting of a n+p-Si wafer coated with ultrathin Al2O3 and AgP2 NCs achieves an onset potential of 0.2 V vs. RHE for CO production and a partial photocurrent density for CO at –0.11 V vs. RHE (j–0.11, CO) of –3.2 mA cm–2.},
doi = {10.1038/s41467-019-13388-8},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {12}
}

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