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Title: Colloidal Cobalt Phosphide Nanocrystals as Trifunctional Electrocatalysts for Overall Water Splitting Powered by a Zinc–Air Battery

Abstract

Highly efficient and stable electrocatalysts, particularly those that are capable of multifunctionality in the same electrolyte, are in high demand for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). In this paper, highly monodisperse CoP and Co 2P nanocrystals (NCs) are synthesized using a robust solution-phase method. The highly exposed (211) crystal plane and abundant surface phosphide atoms make the CoP NCs efficient catalysts toward ORR and HER, while metal-rich Co 2P NCs show higher OER performance owing to easier formation of plentiful Co 2P@COOH heterojunctions. Density functional theory calculation results indicate that the desorption of OH* from cobalt sites is the rate-limiting step for both CoP and Co 2P in ORR and that the high content of phosphide can lower the reaction barrier. A water electrolyzer constructed with a CoP NC cathode and a Co 2P NC anode can achieve a current density of 10 mA cm -2 at 1.56 V, comparable even to the noble metal-based Pt/C and RuO 2/C pair. Finally and furthermore, the CoP NCs are employed as an air cathode in a primary zinc–air battery, exhibiting a high power density of 62 mW cm -2 and good stability.

Authors:
 [1];  [2];  [3];  [1]; ORCiD logo [4];  [5];  [1];  [1];  [6];  [5];  [1];  [7];  [3]; ORCiD logo [1]
  1. Wake Forest Univ., Winston-Salem, NC (United States). Dept. of Chemistry
  2. IBM TJ Watson Research Center, Yorktown Heights, NY (United States). Physical Science Division
  3. Harbin Inst. of Technology, Shenzhen (China). Shenzhen Graduate School. Dept. of Materials Science and Engineering. Shenzhen Engineering Lab. of Flexible Transparent Conductive Films
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Material Science and Technology Division
  5. Wake Forest Univ., Winston-Salem, NC (United States). Dept. of Physics. Center for Nanotechnology and Molecular Materials
  6. Soochow Univ., Suzhou (China). Inst. of Functional Nano and Soft Materials
  7. High Point Univ., NC (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE; Wake Forest Univ. (United States); National Science Foundation (NSF)
OSTI Identifier:
1422608
Grant/Contract Number:  
AC05-00OR22725; CHE-1531698
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 9; 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; cobalt phosphide; density functional theory; overall water splitting; trifunctional electrocatalysts; zinc-air batteries

Citation Formats

Li, Hui, Li, Qi, Wen, Peng, Williams, Trey B., Adhikari, Shiba, Dun, Chaochao, Lu, Chang, Itanze, Dominique, Jiang, Lin, Carroll, David L., Donati, George L., Lundin, Pamela M., Qiu, Yejun, and Geyer, Scott M. Colloidal Cobalt Phosphide Nanocrystals as Trifunctional Electrocatalysts for Overall Water Splitting Powered by a Zinc–Air Battery. United States: N. p., 2018. Web. doi:10.1002/adma.201705796.
Li, Hui, Li, Qi, Wen, Peng, Williams, Trey B., Adhikari, Shiba, Dun, Chaochao, Lu, Chang, Itanze, Dominique, Jiang, Lin, Carroll, David L., Donati, George L., Lundin, Pamela M., Qiu, Yejun, & Geyer, Scott M. Colloidal Cobalt Phosphide Nanocrystals as Trifunctional Electrocatalysts for Overall Water Splitting Powered by a Zinc–Air Battery. United States. doi:10.1002/adma.201705796.
Li, Hui, Li, Qi, Wen, Peng, Williams, Trey B., Adhikari, Shiba, Dun, Chaochao, Lu, Chang, Itanze, Dominique, Jiang, Lin, Carroll, David L., Donati, George L., Lundin, Pamela M., Qiu, Yejun, and Geyer, Scott M. Mon . "Colloidal Cobalt Phosphide Nanocrystals as Trifunctional Electrocatalysts for Overall Water Splitting Powered by a Zinc–Air Battery". United States. doi:10.1002/adma.201705796. https://www.osti.gov/servlets/purl/1422608.
@article{osti_1422608,
title = {Colloidal Cobalt Phosphide Nanocrystals as Trifunctional Electrocatalysts for Overall Water Splitting Powered by a Zinc–Air Battery},
author = {Li, Hui and Li, Qi and Wen, Peng and Williams, Trey B. and Adhikari, Shiba and Dun, Chaochao and Lu, Chang and Itanze, Dominique and Jiang, Lin and Carroll, David L. and Donati, George L. and Lundin, Pamela M. and Qiu, Yejun and Geyer, Scott M.},
abstractNote = {Highly efficient and stable electrocatalysts, particularly those that are capable of multifunctionality in the same electrolyte, are in high demand for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). In this paper, highly monodisperse CoP and Co2P nanocrystals (NCs) are synthesized using a robust solution-phase method. The highly exposed (211) crystal plane and abundant surface phosphide atoms make the CoP NCs efficient catalysts toward ORR and HER, while metal-rich Co2P NCs show higher OER performance owing to easier formation of plentiful Co2P@COOH heterojunctions. Density functional theory calculation results indicate that the desorption of OH* from cobalt sites is the rate-limiting step for both CoP and Co2P in ORR and that the high content of phosphide can lower the reaction barrier. A water electrolyzer constructed with a CoP NC cathode and a Co2P NC anode can achieve a current density of 10 mA cm-2 at 1.56 V, comparable even to the noble metal-based Pt/C and RuO2/C pair. Finally and furthermore, the CoP NCs are employed as an air cathode in a primary zinc–air battery, exhibiting a high power density of 62 mW cm-2 and good stability.},
doi = {10.1002/adma.201705796},
journal = {Advanced Materials},
issn = {0935-9648},
number = 9,
volume = 30,
place = {United States},
year = {2018},
month = {1}
}

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    Works referencing / citing this record:

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