DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Mechanistic Insights into Electrochemical Nitrogen Reduction Reaction on Vanadium Nitride Nanoparticles

Journal Article · · Journal of the American Chemical Society
ORCiD logo [1];  [1];  [1];  [1];  [2];  [3];  [3];  [2]; ORCiD logo [1]; ORCiD logo [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)

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

References (32)

Enhancing the rate of electrochemical nitrogen reduction reaction for ammonia synthesis under ambient conditions using hollow gold nanocages journal July 2018
A theoretical evaluation of possible transition metal electro-catalysts for N 2 reduction journal January 2012
Beyond fossil fuel–driven nitrogen transformations journal May 2018
Au Sub-Nanoclusters on TiO 2 toward Highly Efficient and Selective Electrocatalyst for N 2 Conversion to NH 3 at Ambient Conditions journal February 2017
Ammonia synthesis from N 2 and H 2 O using a lithium cycling electrification strategy at atmospheric pressure journal January 2017
Highly efficient electrochemical ammonia synthesis via nitrogen reduction reactions on a VN nanowire array under ambient conditions journal January 2018
Transition Metal Nitride Catalysts for Electrochemical Reduction of Nitrogen to Ammonia at Ambient Conditions journal January 2015
Ambient ammonia synthesis via palladium-catalyzed electrohydrogenation of dinitrogen at low overpotential journal May 2018
Mobility of heavy metals in sandy soil after application of composts produced from maize straw, sewage sludge and biochar journal March 2018
How a century of ammonia synthesis changed the world journal September 2008
Metal Nitride and Metal Carbide Nanoparticles by a Soft Urea Pathway journal November 2009
Solid-state electrochemical synthesis of ammonia: a review journal April 2011
Determination of the V2p XPS binding energies for different vanadium oxidation states (V5+ to V0+) journal April 2004
VN hollow spheres assembled from porous nanosheets for high-performance lithium storage and the oxygen reduction reaction journal January 2016
Oxidation of vanadium nitride and titanium nitride coatings journal February 2007
X-ray Absorption Near-Edge Structure (XANES) Spectroscopy journal January 2014
Electroreduction of N 2 to Ammonia at Ambient Conditions on Mononitrides of Zr, Nb, Cr, and V: A DFT Guide for Experiments journal December 2015
Computational Predictions of Catalytic Activity of Zincblende (110) Surfaces of Metal Nitrides for Electrochemical Ammonia Synthesis journal March 2017
Synthesis of ammonia directly from air and water at ambient temperature and pressure journal January 2013
The electric discharge and the production of nitric acid journal April 1909
Titanium nitride oxidation chemistry: An x‐ray photoelectron spectroscopy study journal October 1992
Electrochemical Nitrogen Reduction Reaction on Noble Metal Catalysts in Proton and Hydroxide Exchange Membrane Electrolyzers journal January 2017
Electrochemical Reduction of N 2 under Ambient Conditions for Artificial N 2 Fixation and Renewable Energy Storage Using N 2 /NH 3 Cycle journal November 2016
Electrochemical synthesis of ammonia at atmospheric pressure and low temperature in a solid polymer electrolyte cell journal January 2000
The Challenge of Electrochemical Ammonia Synthesis: A New Perspective on the Role of Nitrogen Scaling Relations journal June 2015
Ammonia synthesis at low temperatures journal March 2000
Ammonia Synthesis at Atmospheric Pressure journal October 1998
Favoring the unfavored: Selective electrochemical nitrogen fixation using a reticular chemistry approach journal March 2018
Effect of low-temperature biochar derived from pig manure and poultry litter on mobile and organic matter-bound forms of Cu, Cd, Pb and Zn in sandy soil journal July 2016
Electrochemical synthesis of ammonia via Mars-van Krevelen mechanism on the (111) facets of group III–VII transition metal mononitrides journal May 2017
Electrochemical reduction of aqueous nitrogen (N 2 ) at a low overpotential on (110)-oriented Mo nanofilm journal January 2017
Synthesis, Crystal Structure, and Magnetic Properties of a Vanadium Oxide Nitride with Pseudobrookite-type Structure journal October 2009

Cited By (71)

Ammonia Synthesis Under Ambient Conditions: Selective Electroreduction of Dinitrogen to Ammonia on Black Phosphorus Nanosheets journal January 2019
Ammonia Synthesis Under Ambient Conditions: Selective Electroreduction of Dinitrogen to Ammonia on Black Phosphorus Nanosheets journal January 2019
Unlocking the Potential of Disordered Rocksalts for Aqueous Zinc‐Ion Batteries 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 October 2019
Recent progress in electrocatalytic nitrogen reduction journal January 2019
The Crucial Role of Charge Accumulation and Spin Polarization in Activating Carbon‐Based Catalysts for Electrocatalytic Nitrogen Reduction journal March 2020
The Crucial Role of Charge Accumulation and Spin Polarization in Activating Carbon‐Based Catalysts for Electrocatalytic Nitrogen Reduction journal February 2020
Ambient electrochemical N 2 reduction to NH 3 under alkaline conditions enabled by a layered K 2 Ti 4 O 9 nanobelt journal January 2019
DyF 3 : An Efficient Electrocatalyst for N 2 Fixation to NH 3 under Ambient Conditions journal January 2020
Review on photocatalytic and electrocatalytic artificial nitrogen fixation for ammonia synthesis at mild conditions: Advances, challenges and perspectives journal May 2019
Quantification of Active Sites and Elucidation of the Reaction Mechanism of the Electrochemical Nitrogen Reduction Reaction on Vanadium Nitride journal September 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
Ti 3+ self-doped TiO 2−x nanowires for efficient electrocatalytic N 2 reduction to NH 3 journal January 2020
Selective Electrochemical Reduction of Nitrogen to Ammonia by Adjusting the Three-Phase Interface journal November 2019
High-yield production of few-layer boron nanosheets for efficient electrocatalytic N 2 reduction journal January 2019
Atomic Modulation, Structural Design, and Systematic Optimization for Efficient Electrochemical Nitrogen Reduction journal January 2020
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
Self-organized growth of flower-like SnS 2 and forest-like ZnS nanoarrays on nickel foam for synergistic superiority in electrochemical ammonia synthesis journal January 2019
High Efficiency Electrochemical Nitrogen Fixation Achieved with a Lower Pressure Reaction System by Changing the Chemical Equilibrium journal September 2019
Advanced Non‐metallic Catalysts for Electrochemical Nitrogen Reduction under Ambient Conditions journal July 2019
Carbon‐Nanoplated CoS@TiO 2 Nanofibrous Membrane: An Interface‐Engineered Heterojunction for High‐Efficiency Electrocatalytic Nitrogen Reduction journal December 2019
A Combined Theory‐Experiment Analysis of the Surface Species in Lithium‐Mediated NH 3 Electrosynthesis journal April 2020
Lithium-mediated ammonia synthesis from water and nitrogen: a membrane-free approach enabled by an immiscible aqueous/organic hybrid electrolyte system journal January 2019
Anomalous hydrogen evolution behavior in high-pH environment induced by locally generated hydronium ions journal October 2019
Photocatalytic and electrocatalytic approaches towards atmospheric nitrogen reduction to ammonia under ambient conditions journal April 2019
Glycerol oxidation assisted electrocatalytic nitrogen reduction: ammonia and glyceraldehyde co-production on bimetallic RhCu ultrathin nanoflake nanoaggregates journal January 2019
Potassium‐Ion‐Assisted Regeneration of Active Cyano Groups in Carbon Nitride Nanoribbons: Visible‐Light‐Driven Photocatalytic Nitrogen Reduction journal October 2019
Electrocatalytic N 2 -to-NH 3 conversion with high faradaic efficiency enabled using a Bi nanosheet array journal January 2019
Elementary kinetics of nitrogen electroreduction to ammonia on late transition metals journal January 2019
Aqueous electrocatalytic N 2 reduction for ambient NH 3 synthesis: recent advances in catalyst development and performance improvement journal January 2020
Synergistic Promotion of the Electrochemical Reduction of Nitrogen to Ammonia by Phosphorus and Potassium journal October 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
How to explore ambient electrocatalytic nitrogen reduction reliably and insightfully journal January 2019
Potassium‐Ion‐Assisted Regeneration of Active Cyano Groups in Carbon Nitride Nanoribbons: Visible‐Light‐Driven Photocatalytic Nitrogen Reduction journal November 2019
Co‐generation of Ammonia and H 2 from H 2 O Vapor and N 2 Using a Membrane Electrode Assembly text January 2020
Stable Confinement of Black Phosphorus Quantum Dots on Black Tin Oxide Nanotubes: A Robust, Double‐Active Electrocatalyst toward Efficient Nitrogen Fixation journal November 2019
Crystal‐Phase‐Engineered PdCu Electrocatalyst for Enhanced Ammonia Synthesis journal January 2020
Interface engineering in transition metal carbides for electrocatalytic hydrogen generation and nitrogen fixation journal January 2020
Carbon‐Nanoplated CoS@TiO 2 Nanofibrous Membrane: An Interface‐Engineered Heterojunction for High‐Efficiency Electrocatalytic Nitrogen Reduction journal November 2019
Crystal‐Phase‐Engineered PdCu Electrocatalyst for Enhanced Ammonia Synthesis journal February 2020
Experimental and theoretical understanding on electrochemical activation and inactivation processes of Nb 3 O 7 (OH) for ambient electrosynthesis of NH 3 journal January 2019
Is It Appropriate to Use the Nafion Membrane in Electrocatalytic N 2 Reduction? journal August 2019
Electrochemical Ammonia Synthesis and Ammonia Fuel Cells journal December 2018
A Combined Theory‐Experiment Analysis of the Surface Species in Lithium‐Mediated NH 3 Electrosynthesis journal January 2020
Unusual electrochemical N 2 reduction activity in an earth-abundant iron catalyst via phosphorous modulation journal January 2020
Greatly Enhanced Electrocatalytic N 2 Reduction on TiO 2 via V Doping journal May 2019
Ultrasmall V 8 C 7 nanoparticles embedded in conductive carbon for efficient electrocatalytic N 2 reduction toward ambient NH 3 production journal January 2019
A vanadium–nickel oxynitride layer for enhanced electrocatalytic nitrogen fixation in neutral media journal January 2020
Advances in Electrocatalytic N 2 Reduction—Strategies to Tackle the Selectivity Challenge journal October 2018
Plasma-engineered NiO nanosheets with enriched oxygen vacancies for enhanced electrocatalytic nitrogen fixation journal January 2020
Recent Progress on Electrocatalyst and Photocatalyst Design for Nitrogen Reduction journal October 2018
Ambient dinitrogen electrocatalytic reduction for ammonia synthesis journal January 2019
A pyrolysis–phosphorization approach to fabricate carbon nanotubes with embedded CoP nanoparticles for ambient electrosynthesis of ammonia journal January 2019
Recent Advanced Materials for Electrochemical and Photoelectrochemical Synthesis of Ammonia from Dinitrogen: One Step Closer to a Sustainable Energy Future journal September 2019
Oxygen vacancy-engineered Fe 2 O 3 nanocubes via a task-specific ionic liquid for electrocatalytic N 2 fixation journal January 2019
Ambient electrocatalytic nitrogen reduction on a MoO 2 /graphene hybrid: experimental and DFT studies journal January 2019
Anomalous hydrogen evolution behavior in high-pH environment induced by locally generated hydronium ions journal October 2019
Nitrogen‐Doped NiO Nanosheet Array for Boosted Electrocatalytic N 2 Reduction journal August 2019
Biomass Valorization via Paired Electrosynthesis Over Vanadium Nitride‐Based Electrocatalysts journal August 2019
Nitrogen Vacancies on 2D Layered W 2 N 3 : A Stable and Efficient Active Site for Nitrogen Reduction Reaction journal June 2019
Ambient electrohydrogenation of N 2 for NH 3 synthesis on non-metal boron phosphide nanoparticles: the critical role of P in boosting the catalytic activity journal January 2019
ZnO Quantum Dots Coupled with Graphene toward Electrocatalytic N 2 Reduction: Experimental and DFT Investigations journal August 2019
B 4 C nanosheets decorated with in situ -derived boron-doped graphene quantum dots for high-efficiency ambient N 2 fixation journal January 2019
Boron and nitrogen co-doped porous carbon nanofibers as metal-free electrocatalysts for highly efficient ammonia electrosynthesis journal January 2019
Electrochemical nitrogen fixation and utilization: theories, advanced catalyst materials and system design journal January 2019
High Efficiency Electrochemical Nitrogen Fixation Achieved with a Lower Pressure Reaction System by Changing the Chemical Equilibrium journal September 2019
Quantification of Active Sites and Elucidation of the Reaction Mechanism of the Electrochemical Nitrogen Reduction Reaction on Vanadium Nitride journal August 2019
Atomic Modulation, Structural Design, and Systematic Optimization for Efficient Electrochemical Nitrogen Reduction journal January 2020
Biomass-derived oxygen-doped hollow carbon microtubes for electrocatalytic N 2 -to-NH 3 fixation under ambient conditions journal January 2019
The doping and oxidation of 2D black and blue phosphorene: a new photocatalyst for nitrogen reduction driven by visible light journal January 2019