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Mechanistic Insights into Electrochemical Nitrogen Reduction Reaction on Vanadium Nitride Nanoparticles

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.8b08379· OSTI ID:1484883
 [1];  [1];  [1];  [1];  [2];  [3];  [3];  [2];  [1];  [1]
  1. Univ. of Delaware, Newark, DE (United States). Center for Catalytic Science and Technology, Dept. of Chemical and Biomolecular Engineering
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division; Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
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Renewable production of ammonia, a building block for most fertilizers, via the electrochemical nitrogen reduction reaction (ENRR) is desirable; however, a selective electrocatalyst is lacking. Here we show that vanadium nitride (VN) nanoparticles are active, selective, and stable ENRR catalysts with an ENRR rate and a Faradaic efficiency (FE) of 3.3 × 10–10 mol s–1 cm–2 and 6.0% at -0.1 V within 1 h, respectively. ENRR with 15N2 as the feed produces both 14NH3 and 15NH3, which indicates that the reaction follows a Mars–van Krevelen mechanism. Ex situ X-ray photoelectron spectroscopy characterization of fresh and spent catalysts reveals that multiple vanadium oxide, oxynitride, and nitride species are present on the surface and identified VN0.7O0.45 as the active phase in the ENRR. Operando X-ray absorption spectroscopy and catalyst durability test results corroborate this hypothesis and indicate that the conversion of VN0.7O0.45 to the VN phase leads to catalyst deactivation. We hypothesize that only the surface N sites adjacent to a surface O are active in the ENRR. Finally, an ammonia production rate of 1.1 × 10–10 mol s–1 cm–2 can be maintained for 116 h, with a steady-state turnover number of 431.
Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0012704
OSTI ID:
1484883
Report Number(s):
BNL--209653-2018-JAAM
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 41 Vol. 140; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Nitrogen Vacancies on 2D Layered W 2 N 3 : A Stable and Efficient Active Site for Nitrogen Reduction Reaction journal June 2019
Unlocking the Potential of Disordered Rocksalts for Aqueous Zinc‐Ion Batteries journal September 2019
Recent Advanced Materials for Electrochemical and Photoelectrochemical Synthesis of Ammonia from Dinitrogen: One Step Closer to a Sustainable Energy Future journal September 2019
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Quantification of Active Sites and Elucidation of the Reaction Mechanism of the Electrochemical Nitrogen Reduction Reaction on Vanadium Nitride journal August 2019
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The Crucial Role of Charge Accumulation and Spin Polarization in Activating Carbon‐Based Catalysts for Electrocatalytic Nitrogen Reduction journal March 2020
Ammonia Synthesis Under Ambient Conditions: Selective Electroreduction of Dinitrogen to Ammonia on Black Phosphorus Nanosheets journal January 2019
Quantification of Active Sites and Elucidation of the Reaction Mechanism of the Electrochemical Nitrogen Reduction Reaction on Vanadium Nitride journal September 2019
Stable Confinement of Black Phosphorus Quantum Dots on Black Tin Oxide Nanotubes: A Robust, Double‐Active Electrocatalyst toward Efficient Nitrogen Fixation journal November 2019
Potassium‐Ion‐Assisted Regeneration of Active Cyano Groups in Carbon Nitride Nanoribbons: Visible‐Light‐Driven Photocatalytic Nitrogen Reduction journal November 2019
High Efficiency Electrochemical Nitrogen Fixation Achieved with a Lower Pressure Reaction System by Changing the Chemical Equilibrium journal September 2019
Carbon‐Nanoplated CoS@TiO 2 Nanofibrous Membrane: An Interface‐Engineered Heterojunction for High‐Efficiency Electrocatalytic Nitrogen Reduction journal December 2019
Crystal‐Phase‐Engineered PdCu Electrocatalyst for Enhanced Ammonia Synthesis journal February 2020
The Crucial Role of Charge Accumulation and Spin Polarization in Activating Carbon‐Based Catalysts for Electrocatalytic Nitrogen Reduction journal February 2020
DyF 3 : An Efficient Electrocatalyst for N 2 Fixation to NH 3 under Ambient Conditions journal January 2020
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Synergistic Promotion of the Electrochemical Reduction of Nitrogen to Ammonia by Phosphorus and Potassium journal October 2019
Overcoming Chemical Inertness under Ambient Conditions: A Critical View on Recent Developments in Ammonia Synthesis via Electrochemical N 2 Reduction by Asking Five Questions journal January 2020
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A Combined Theory‐Experiment Analysis of the Surface Species in Lithium‐Mediated NH 3 Electrosynthesis journal April 2020
Advanced Non‐metallic Catalysts for Electrochemical Nitrogen Reduction under Ambient Conditions journal July 2019
ZnO Quantum Dots Coupled with Graphene toward Electrocatalytic N 2 Reduction: Experimental and DFT Investigations journal August 2019
Co‐generation of Ammonia and H 2 from H 2 O Vapor and N 2 Using a Membrane Electrode Assembly journal January 2020
Oxygen Doping Induced by Nitrogen Vacancies in Nb 4 N 5 Enables Highly Selective CO 2 Reduction journal November 2019
Advances in Electrocatalytic N 2 Reduction—Strategies to Tackle the Selectivity Challenge journal October 2018
Recent Progress on Electrocatalyst and Photocatalyst Design for Nitrogen Reduction journal October 2018
Greatly Enhanced Electrocatalytic N 2 Reduction on TiO 2 via V Doping journal May 2019
Is It Appropriate to Use the Nafion Membrane in Electrocatalytic N 2 Reduction? journal August 2019
Review on photocatalytic and electrocatalytic artificial nitrogen fixation for ammonia synthesis at mild conditions: Advances, challenges and perspectives journal May 2019
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Electrocatalytic N 2 -to-NH 3 conversion with high faradaic efficiency enabled using a Bi nanosheet array journal January 2019
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Figures / Tables (27)

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