Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: A comparative study of Bi, Sb, and BiSb for electrochemical nitrogen reduction leading to a new catalyst design strategy

Journal Article · · Journal of Materials Chemistry. A
DOI: https://doi.org/10.1039/d1ta05327b · OSTI ID:1851135
 [1];  [2];  [3];  [2]; ORCiD logo [3]; ORCiD logo [2]
  1. Univ. of Wisconsin, Madison, WI (United States); Hanyang Univ., Seoul (Korea, Republic of); OSTI
  2. Univ. of Wisconsin, Madison, WI (United States)
  3. Technion-Israel Institute of Technology, Haifa (Israel)
+ Show Author Affiliations

Recent studies identified Bi as one of the most promising non-noble metal elements that can promote the electrochemical N2 reduction reaction (ENRR) to produce NH3. The electronic features that make Bi a promising ENRR catalyst may also be owned by Sb that belongs to the same group as Bi. Thus, the ENRR properties of Bi, Sb, and a BiSb alloy were investigated comparatively to identify common characteristics that facilitate the ENRR. These catalysts were prepared as uniform coating layers on high surface area carbon felt electrodes, which could serve as both regular electrodes and pseudo-gas diffusion electrodes. The experimental results demonstrated that while Bi and Sb show comparable ENRR performances, the formation of a BiSb alloy distinctively increases the faradic efficiency for NH3 production. Additionally, the X-ray photoelectron spectroscopy results revealed that Bi in BiSb possesses a partial positive charge while Sb in BiSb possesses a partial negative charge, which can impact the way the catalyst surface interacts with the reactants and reaction intermediates of the ENRR and hydrogen evolution reaction (HER), the major competing reaction with the ENRR. Computational investigations including the Bader charge analysis and Gibbs free energy calculations for the elemental steps of the ENRR and HER provided an explanation of how the formation of a BiSb alloy can change the selectivity for the ENRR. The combined experimental and theoretical results and discussion contained in this study lead to a new strategy for designing efficient metal catalysts for the ENRR. Additionally, this study investigated how the use of gas phase and dissolved N2 affected the ENRR performances of the Bi, Sb, and BiSb catalysts.

Research Organization:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Nancy and Stephen Grand Technion Energy Program; Ministry of Science and Technology (MOST), Israel; European Cooperation in Science and Technology (COST); Korea Ministry of Science and Technology (MSIT); Hanyang University
Grant/Contract Number:
SC0008707
OSTI ID:
1851135
Journal Information:
Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 36 Vol. 9; ISSN 2050-7488
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (39)

A Review of Electrocatalytic Reduction of Dinitrogen to Ammonia under Ambient Conditions journal May 2018
Generating Defect‐Rich Bismuth for Enhancing the Rate of Nitrogen Electroreduction to Ammonia journal July 2019
Antimony‐Based Composites Loaded on Phosphorus‐Doped Carbon for Boosting Faradaic Efficiency of the Electrochemical Nitrogen Reduction Reaction journal September 2019
Lattice Parameter Study in the Bi1–xSbx Solid-solution System journal January 1982
The Challenge of Electrochemical Ammonia Synthesis: A New Perspective on the Role of Nitrogen Scaling Relations journal June 2015
XPS and AES study of antimony oxides journal October 1980
X-ray photoelectron spectra of antimony oxides journal November 1989
Characterisation of thin films of bismuth oxide by X-ray photoelectron spectroscopy journal January 1982
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Work function, electronegativity, and electrochemical behaviour of metals journal September 1972
A fast and robust algorithm for Bader decomposition of charge density journal June 2006
Recent progress in the electrochemical ammonia synthesis under ambient conditions journal September 2019
Spectrophotometric Method for Determination of Hydrazine journal December 1952
Catalytic Performance of Two-Dimensional Bismuth Tuned by Defect Engineering for Nitrogen Reduction Reaction journal August 2020
Single-Metal Atom Anchored on Boron Monolayer (β 12 ) as an Electrocatalyst for Nitrogen Reduction into Ammonia at Ambient Conditions: A First-Principles Study journal January 2019
Sulfur Atomically Doped Bismuth Nanobelt Driven by Electrochemical Self-Reconstruction for Boosted Electrocatalysis journal February 2020
Electrochemical Synthesis and Investigation of Stoichiometric, Phase - Pure CoSb 2 O 6 and MnSb 2 O 6 Electrodes for the Oxygen Evolution Reaction in Acidic Media journal June 2020
Electrochemical Ammonia Synthesis—The Selectivity Challenge journal December 2016
Two-Dimensional Mosaic Bismuth Nanosheets for Highly Selective Ambient Electrocatalytic Nitrogen Reduction journal February 2019
Gas-Diffusion Electrodes for Carbon Dioxide Reduction: A New Paradigm journal December 2018
Detonator of the population explosion journal July 1999
How a century of ammonia synthesis changed the world journal September 2008
A rigorous electrochemical ammonia synthesis protocol with quantitative isotope measurements journal May 2019
Promoting nitrogen electroreduction to ammonia with bismuth nanocrystals and potassium cations in water journal March 2019
Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia journal March 2019
A theoretical evaluation of possible transition metal electro-catalysts for N 2 reduction journal January 2012
Electrocatalytic N 2 -to-NH 3 conversion with high faradaic efficiency enabled using a Bi nanosheet array journal January 2019
Sb 2 S 3 nanoparticles anchored on SnO 2 nanofibers: a high-performance hybrid electrocatalyst toward ammonia synthesis under ambient conditions journal January 2019
Surface oxidized two-dimensional antimonene nanosheets for electrochemical ammonia synthesis under ambient conditions journal January 2020
Enabling electrochemical N 2 reduction to NH 3 in the low overpotential region using non-noble metal Bi electrodes via surface composition modification journal January 2020
Ammonia for hydrogen storage: challenges and opportunities journal January 2008
The Structure of Bismuth at Low Temperatures journal January 1960
Low Temperature Transport Properties of the Group V Semimetals journal January 1979
Inhomogeneous Electron Gas journal November 1964
Self-Consistent Equations Including Exchange and Correlation Effects journal November 1965
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Generalized Gradient Approximation Made Simple journal October 1996
Beyond fossil fuel–driven nitrogen transformations journal May 2018

Similar Records

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY