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Title: Phosphorus-Rich Colloidal Cobalt Diphosphide (CoP 2) Nanocrystals for Electrochemical and Photoelectrochemical Hydrogen Evolution

Abstract

Developing earth-abundant and efficient electrocatalysts for photoelectrochemical water splitting is critical to realizing a high-performance solar-to-hydrogen energy conversion process. Here in this paper, phosphorus-rich colloidal cobalt diphosphide nanocrystals (CoP 2 NCs) are synthesized via hot injection. The CoP 2 NCs show a Pt-like hydrogen evolution reaction (HER) electrocatalytic activity in acidic solution with a small overpotential of 39 mV to achieve -10 mA cm -2 and a very low Tafel slope of 32 mV dec -1. Density functional theory (DFT) calculations reveal that the high P content both physically separates Co atoms to prevent H from over binding to multiple Co atoms, while simultaneously stabilizing H adsorbed to single Co atoms. The catalytic performance of the CoP 2 NCs is further demonstrated in a metal–insulator–semiconductor photoelectrochemical device consisting of bottom p-Si light absorber, atomic layer deposition Al–ZnO passivation layers, and the CoP 2 cocatalyst. The p-Si/AZO/TiO 2/CoP 2 photocathode shows a photocurrent density of -16.7 mA cm -2 at 0 V versus reversible hydrogen electrode (RHE) and an output photovoltage of 0.54 V. The high performance and stability are attributed to the junction between p-Si and AZO, the corrosion-resistance of the pinhole-free TiO 2 protective layer, and the fast HERmore » kinetics of the CoP 2 NCs.« less

Authors:
 [1];  [2];  [1];  [1]; ORCiD logo [3];  [1];  [4];  [2]; ORCiD logo [1]
  1. Wake Forest Univ., Winston‐Salem NC (United States). Dept. of Chemistry
  2. Harbin Inst. of Technology, Shenzhen (China). Shenzhen Engineering Lab. of Flexible Transparent Conductive Films, Dept. of Materials Science and Engineering
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  4. Soochow Univ. Suzhou, Jiangsu (China). Inst. of Functional Nano and Soft Materials (FUNSOM)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1511912
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Name: Advanced Materials; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Li, Hui, Wen, Peng, Itanze, Dominique S., Kim, Michael W., Adhikari, Shiba, Lu, Chang, Jiang, Lin, Qiu, Yejun, and Geyer, Scott M.. Phosphorus-Rich Colloidal Cobalt Diphosphide (CoP2) Nanocrystals for Electrochemical and Photoelectrochemical Hydrogen Evolution. United States: N. p., 2019. Web. doi:10.1002/adma.201900813.
Li, Hui, Wen, Peng, Itanze, Dominique S., Kim, Michael W., Adhikari, Shiba, Lu, Chang, Jiang, Lin, Qiu, Yejun, & Geyer, Scott M.. Phosphorus-Rich Colloidal Cobalt Diphosphide (CoP2) Nanocrystals for Electrochemical and Photoelectrochemical Hydrogen Evolution. United States. doi:10.1002/adma.201900813.
Li, Hui, Wen, Peng, Itanze, Dominique S., Kim, Michael W., Adhikari, Shiba, Lu, Chang, Jiang, Lin, Qiu, Yejun, and Geyer, Scott M.. Mon . "Phosphorus-Rich Colloidal Cobalt Diphosphide (CoP2) Nanocrystals for Electrochemical and Photoelectrochemical Hydrogen Evolution". United States. doi:10.1002/adma.201900813.
@article{osti_1511912,
title = {Phosphorus-Rich Colloidal Cobalt Diphosphide (CoP2) Nanocrystals for Electrochemical and Photoelectrochemical Hydrogen Evolution},
author = {Li, Hui and Wen, Peng and Itanze, Dominique S. and Kim, Michael W. and Adhikari, Shiba and Lu, Chang and Jiang, Lin and Qiu, Yejun and Geyer, Scott M.},
abstractNote = {Developing earth-abundant and efficient electrocatalysts for photoelectrochemical water splitting is critical to realizing a high-performance solar-to-hydrogen energy conversion process. Here in this paper, phosphorus-rich colloidal cobalt diphosphide nanocrystals (CoP2 NCs) are synthesized via hot injection. The CoP2 NCs show a Pt-like hydrogen evolution reaction (HER) electrocatalytic activity in acidic solution with a small overpotential of 39 mV to achieve -10 mA cm-2 and a very low Tafel slope of 32 mV dec-1. Density functional theory (DFT) calculations reveal that the high P content both physically separates Co atoms to prevent H from over binding to multiple Co atoms, while simultaneously stabilizing H adsorbed to single Co atoms. The catalytic performance of the CoP2 NCs is further demonstrated in a metal–insulator–semiconductor photoelectrochemical device consisting of bottom p-Si light absorber, atomic layer deposition Al–ZnO passivation layers, and the CoP2 cocatalyst. The p-Si/AZO/TiO2/CoP2 photocathode shows a photocurrent density of -16.7 mA cm-2 at 0 V versus reversible hydrogen electrode (RHE) and an output photovoltage of 0.54 V. The high performance and stability are attributed to the junction between p-Si and AZO, the corrosion-resistance of the pinhole-free TiO2 protective layer, and the fast HER kinetics of the CoP2 NCs.},
doi = {10.1002/adma.201900813},
journal = {Advanced Materials},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {5}
}

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