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Title: Metal-Rich Transition Metal Diborides as Electrocatalysts for Hydrogen Evolution Reactions in a Wide Range of pH

Abstract

Solid solutions of HfB 2-ZrB 2 mixtures were prepared by high-energy ball milling of diboride and additive powders followed by spark plasma sintering (SPS). A mixture of stoichiometric 1:1 HfB 2-ZrB 2 borides was the base composition to which Hf, Zr, Ta, LaB 6 or Gd 2O 3 was added. Hf, Zr and Ta were added in order to bring the boron-to-metal ratio down to 1.86, rendering the boride as MeB 1.86. In the case of LaB 6 and Gd 2O 3, 1.8 mol% was added. Electroanalytical behavior of hydrogen evolution reactions was evaluated in 1 M H 2SO 4 and 1 M NaOH solutions. The LaB 6 additive material showed Tafel slopes of 125 and 90 mV/decade in acidic and alkaline solutions respectively. The Hf and Zr rich samples showed Tafel slopes of about 120 mV/decade in both electrolytes. The over potentials of hydrogen evolution reactions (at 10 mA/cm 2) in the alkaline solution were about 100 mV lower than those in acidic solution. The metal-rich diborides and addition of LaB 6 showed better hydrogen evolution reaction (HER) activities than the base 1:1 HfB 2-ZrB 2 stoichiometric diboride solid solution. Furthermore, the higher activity of metal-rich borides could bemore » attributed to the increased electron population at the d-orbitals of the metal shown by band structure modeling calculations using the Density Functional Theory approach.« less

Authors:
 [1];  [1];  [1]
  1. Univ. of Idaho, Moscow, ID (United States)
Publication Date:
Research Org.:
Univ. of Idaho, Moscow, ID (United States)
Sponsoring Org.:
USDOE Office of Fossil Energy (FE); USDOE National Energy Technology Laboratory (NETL)
OSTI Identifier:
1438824
Grant/Contract Number:  
FE0022988
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 163; Journal Issue: 13; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Band Structure; Diborides; Electrocatalyst; Hafnium; Hydrogen Evolution Reaction; Zirconium

Citation Formats

Sitler, Steven J., Raja, Krishnan S., and Charit, Indrajit. Metal-Rich Transition Metal Diborides as Electrocatalysts for Hydrogen Evolution Reactions in a Wide Range of pH. United States: N. p., 2016. Web. doi:10.1149/2.0201613jes.
Sitler, Steven J., Raja, Krishnan S., & Charit, Indrajit. Metal-Rich Transition Metal Diborides as Electrocatalysts for Hydrogen Evolution Reactions in a Wide Range of pH. United States. doi:10.1149/2.0201613jes.
Sitler, Steven J., Raja, Krishnan S., and Charit, Indrajit. Fri . "Metal-Rich Transition Metal Diborides as Electrocatalysts for Hydrogen Evolution Reactions in a Wide Range of pH". United States. doi:10.1149/2.0201613jes. https://www.osti.gov/servlets/purl/1438824.
@article{osti_1438824,
title = {Metal-Rich Transition Metal Diborides as Electrocatalysts for Hydrogen Evolution Reactions in a Wide Range of pH},
author = {Sitler, Steven J. and Raja, Krishnan S. and Charit, Indrajit},
abstractNote = {Solid solutions of HfB2-ZrB2 mixtures were prepared by high-energy ball milling of diboride and additive powders followed by spark plasma sintering (SPS). A mixture of stoichiometric 1:1 HfB2-ZrB2 borides was the base composition to which Hf, Zr, Ta, LaB6 or Gd2O3 was added. Hf, Zr and Ta were added in order to bring the boron-to-metal ratio down to 1.86, rendering the boride as MeB1.86. In the case of LaB6 and Gd2O3, 1.8 mol% was added. Electroanalytical behavior of hydrogen evolution reactions was evaluated in 1 M H2SO4 and 1 M NaOH solutions. The LaB6 additive material showed Tafel slopes of 125 and 90 mV/decade in acidic and alkaline solutions respectively. The Hf and Zr rich samples showed Tafel slopes of about 120 mV/decade in both electrolytes. The over potentials of hydrogen evolution reactions (at 10 mA/cm2) in the alkaline solution were about 100 mV lower than those in acidic solution. The metal-rich diborides and addition of LaB6 showed better hydrogen evolution reaction (HER) activities than the base 1:1 HfB2-ZrB2 stoichiometric diboride solid solution. Furthermore, the higher activity of metal-rich borides could be attributed to the increased electron population at the d-orbitals of the metal shown by band structure modeling calculations using the Density Functional Theory approach.},
doi = {10.1149/2.0201613jes},
journal = {Journal of the Electrochemical Society},
number = 13,
volume = 163,
place = {United States},
year = {2016},
month = {9}
}

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Works referenced in this record:

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