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Title: 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
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)
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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)
Grant/Contract Number:
SC0012704
OSTI ID:
1484883
Report Number(s):
BNL-209653-2018-JAAM
Journal Information:
Journal of the American Chemical Society, Vol. 140, Issue 41; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 332 works
Citation information provided by
Web of Science

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Cited By (69)

Recent progress in electrocatalytic nitrogen reduction journal January 2019
Biomass-derived oxygen-doped hollow carbon microtubes for electrocatalytic N 2 -to-NH 3 fixation under ambient conditions journal January 2019
The Crucial Role of Charge Accumulation and Spin Polarization in Activating Carbon‐Based Catalysts for Electrocatalytic Nitrogen Reduction journal February 2020
High Efficiency Electrochemical Nitrogen Fixation Achieved with a Lower Pressure Reaction System by Changing the Chemical Equilibrium 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
Ammonia Synthesis Under Ambient Conditions: Selective Electroreduction of Dinitrogen to Ammonia on Black Phosphorus Nanosheets journal January 2019
Unusual electrochemical N 2 reduction activity in an earth-abundant iron catalyst via phosphorous modulation journal January 2020
Carbon‐Nanoplated CoS@TiO 2 Nanofibrous Membrane: An Interface‐Engineered Heterojunction for High‐Efficiency Electrocatalytic Nitrogen Reduction journal December 2019
Elementary kinetics of nitrogen electroreduction to ammonia on late transition metals journal January 2019
Oxygen vacancy-engineered Fe 2 O 3 nanocubes via a task-specific ionic liquid for electrocatalytic N 2 fixation journal January 2019
ZnO Quantum Dots Coupled with Graphene toward Electrocatalytic N 2 Reduction: Experimental and DFT Investigations journal August 2019
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
DyF 3 : An Efficient Electrocatalyst for N 2 Fixation to NH 3 under Ambient Conditions journal January 2020
Oxygen Doping Induced by Nitrogen Vacancies in Nb 4 N 5 Enables Highly Selective CO 2 Reduction journal November 2019
Biomass Valorization via Paired Electrosynthesis Over Vanadium Nitride‐Based Electrocatalysts journal August 2019
A Combined Theory‐Experiment Analysis of the Surface Species in Lithium‐Mediated NH 3 Electrosynthesis journal January 2020
Ti 3+ self-doped TiO 2−x nanowires for efficient electrocatalytic N 2 reduction to NH 3 journal January 2020
Nitrogen Vacancies on 2D Layered W 2 N 3 : A Stable and Efficient Active Site for Nitrogen Reduction Reaction journal June 2019
Advanced Non‐metallic Catalysts for Electrochemical Nitrogen Reduction under Ambient Conditions journal July 2019
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
Photocatalytic and electrocatalytic approaches towards atmospheric nitrogen reduction to ammonia under ambient conditions journal April 2019
Unlocking the Potential of Disordered Rocksalts for Aqueous Zinc‐Ion Batteries journal September 2019
Crystal‐Phase‐Engineered PdCu Electrocatalyst for Enhanced Ammonia Synthesis journal January 2020
Ambient electrocatalytic nitrogen reduction on a MoO 2 /graphene hybrid: experimental and DFT studies journal January 2019
Potassium‐Ion‐Assisted Regeneration of Active Cyano Groups in Carbon Nitride Nanoribbons: Visible‐Light‐Driven Photocatalytic Nitrogen Reduction journal November 2019
Anomalous hydrogen evolution behavior in high-pH environment induced by locally generated hydronium ions journal October 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
A pyrolysis–phosphorization approach to fabricate carbon nanotubes with embedded CoP nanoparticles for ambient electrosynthesis of ammonia journal January 2019
Glycerol oxidation assisted electrocatalytic nitrogen reduction: ammonia and glyceraldehyde co-production on bimetallic RhCu ultrathin nanoflake nanoaggregates journal January 2019
Synergistic Promotion of the Electrochemical Reduction of Nitrogen to Ammonia by Phosphorus and Potassium journal October 2019
Recent Progress on Electrocatalyst and Photocatalyst Design for Nitrogen Reduction journal October 2018
Electrocatalytic N 2 -to-NH 3 conversion with high faradaic efficiency enabled using a Bi nanosheet array journal January 2019
Aqueous electrocatalytic N 2 reduction for ambient NH 3 synthesis: recent advances in catalyst development and performance improvement journal January 2020
Interface engineering in transition metal carbides for electrocatalytic hydrogen generation and nitrogen fixation journal January 2020
Co‐generation of Ammonia and H 2 from H 2 O Vapor and N 2 Using a Membrane Electrode Assembly text January 2020
Atomic Modulation, Structural Design, and Systematic Optimization for Efficient Electrochemical Nitrogen Reduction journal January 2020
Selective Electrochemical Reduction of Nitrogen to Ammonia by Adjusting the Three-Phase Interface journal November 2019
Plasma-engineered NiO nanosheets with enriched oxygen vacancies for enhanced electrocatalytic nitrogen fixation journal January 2020
Crystal‐Phase‐Engineered PdCu Electrocatalyst for Enhanced Ammonia Synthesis journal February 2020
Nitrogen‐Doped NiO Nanosheet Array for Boosted Electrocatalytic N 2 Reduction journal August 2019
Greatly Enhanced Electrocatalytic N 2 Reduction on TiO 2 via V Doping journal May 2019
Carbon‐Nanoplated CoS@TiO 2 Nanofibrous Membrane: An Interface‐Engineered Heterojunction for High‐Efficiency Electrocatalytic Nitrogen Reduction journal November 2019
Electrochemical nitrogen fixation and utilization: theories, advanced catalyst materials and system design journal January 2019
Is It Appropriate to Use the Nafion Membrane in Electrocatalytic N 2 Reduction? journal August 2019
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
Boron and nitrogen co-doped porous carbon nanofibers as metal-free electrocatalysts for highly efficient ammonia electrosynthesis journal January 2019
A vanadium–nickel oxynitride layer for enhanced electrocatalytic nitrogen fixation in neutral media journal January 2020
Ambient dinitrogen electrocatalytic reduction for ammonia synthesis journal January 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
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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
Co‐generation of Ammonia and H 2 from H 2 O Vapor and N 2 Using a Membrane Electrode Assembly journal January 2020
Ammonia Synthesis Under Ambient Conditions: Selective Electroreduction of Dinitrogen to Ammonia on Black Phosphorus Nanosheets journal January 2019
A Combined Theory‐Experiment Analysis of the Surface Species in Lithium‐Mediated NH 3 Electrosynthesis journal April 2020

Figures / Tables (27)

Figure S1-1(p. 8)figure Figure S1-1
Table S1-1(p. 9)table Table S1-1
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Figure S1-8(p. 16)figure Figure S1-8
Figure S2-1(p. 19)figure Figure S2-1
Figure S2-2(p. 20)figure Figure S2-2
Figure S2-3(p. 21)figure Figure S2-3
Table S2-1(p. 22)table Table S2-1
Figure S3-1(p. 24)figure Figure S3-1
Figure S3-2(p. 25)figure Figure S3-2
Table S4-1(p. 27)table Table S4-1
Table S4-2(p. 28)table Table S4-2
Figure S4-1(p. 29)figure Figure S4-1
Figure S4-2(p. 30)figure Figure S4-2
Figure S4-3(p. 31)figure Figure S4-3
Figure S4-4(p. 32)figure Figure S4-4
Figure S4-5(p. 33)figure Figure S4-5
Figure S5-1(p. 34)figure Figure S5-1
Figure S5-2(p. 35)figure Figure S5-2
Table S6-1(p. 36)table Table S6-1
Table S6-2(p. 37)table Table S6-2
Table S7-1(p. 40)table Table S7-1

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