Plasma-Assisted Surface Nitridation of Proton Intercalatable WO3 for Efficient Electrocatalytic Ammonia Synthesis

Zhang, Zhiyuan; Kondratowicz, Christopher; Smith, Jacob; Kucheryavy, Pavel; Ouyang, Junjie; Xu, Yijie; Desmet, Elizabeth; Kurdziel, Sophia; Tang, Eddie; Adeleke, Micheal; Lele, Aditya Dilip; Martirez, John Mark; Chi, Miaofang; Ju, Yiguang; He, Huixin

doi:10.1021/acsenergylett.5c01034

Plasma-Assisted Surface Nitridation of Proton Intercalatable WO₃ for Efficient Electrocatalytic Ammonia Synthesis

Journal Article · Sun Jun 22 00:00:00 EDT 2025 · ACS Energy Letters

DOI:https://doi.org/10.1021/acsenergylett.5c01034· OSTI ID:2586641

^[1]; Kondratowicz, Christopher ^[2]; Smith, Jacob ^[3]; Kucheryavy, Pavel ^[1]; ^[1]; ^[2]; Desmet, Elizabeth ^[2]; Kurdziel, Sophia ^[4]; ^[2]; Adeleke, Micheal ^[5]; Lele, Aditya Dilip ^[6]; ^[4]; Chi, Miaofang ^[7]; Ju, Yiguang ^[8]; He, Huixin ^[1]

Rutgers University, Newark, NJ (United States)
Princeton University, NJ (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Princeton Plasma Physics Laboratory (PPPL), Princeton, NJ (United States)
Rutgers University, Newark, NJ (United States); Science Park High School, Newark, NJ (United States)
Rowan University, Glassboro, NJ (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Duke University, Durham, NC (United States)
Princeton University, NJ (United States); Princeton Plasma Physics Laboratory (PPPL), Princeton, NJ (United States)

Electrocatalytic nitrogen reduction (eNRR) offers a green pathway for the production of NH₃ from N₂ and H₂O under ambient conditions. Transition metal oxynitrides (TMO_xN_y) are among the most promising catalysts but face challenges in achieving a high yield and faradaic efficiency (FE). This work develops a hybrid WO_xN_y/WO₃ catalyst with a unique heterogeneous interfacial complexion (HIC) structure. This design enables in situ generation and delivery of highly active hydrogen atoms (H*) in acidic electrolytes, promoting nitrogen hydrogenation and the formation of nitrogen vacancies (Nv) on the WO_xN_y surface. This significantly enhances the selectivity of eNRR for NH₃ synthesis while suppressing the hydrogen evolution reaction (HER). A simple two-step fabrication process─microwave hydrothermal growth followed by plasma-assisted surface nitridation─was developed to fabricate the designed catalyst electrode, achieving an NH₃ yield of 3.2 × 10^–10 mol·cm^–2·s^–1 with 40.1% FE, outperforming most TMN/TMO_xN_y electrocatalysts. Multiple control experiments confirm that the eNRR follows an HIC-enhanced Mars–van Krevelen (MvK) mechanism.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Princeton Plasma Physics Laboratory (PPPL), Princeton, NJ (United States); Princeton University, NJ (United States); Rutgers University, Newark, NJ (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Fusion Energy Sciences (FES)

Grant/Contract Number:: AC02-09CH11466; SC0025371

OSTI ID:: 2586641

Alternate ID(s):: OSTI ID: 2571373

Journal Information:: ACS Energy Letters, Journal Name: ACS Energy Letters Journal Issue: 7 Vol. 10; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (61)

Nitrogen Vacancies on 2D Layered W ₂ N ₃ : A Stable and Efficient Active Site for Nitrogen Reduction Reaction Jin, Huanyu; Li, Laiquan; Liu, Xin Advanced Materials https://doi.org/10.1002/adma.201902709	journal	June 2019
Electrochemical and Chemical Instability of Vanadium Nitride in the Synthesis of Ammonia Directly from Nitrogen Manjunatha, Revanasiddappa; Karajić, Aleksandar; Teller, Hanan ChemCatChem, Vol. 12, Issue 2 https://doi.org/10.1002/cctc.201901558	journal	October 2019
Recent Progress in Electrochemical Nitrogen Reduction on Transition Metal Nitrides Yang, Xiaoju; Xu, Bingjun; Chen, Jingguang G. ChemSusChem, Vol. 16, Issue 5 https://doi.org/10.1002/cssc.202201715	journal	January 2023
Plasma‐Assisted Sustainable Nitrogen‐to‐Ammonia Fixation: Mixed‐phase, Synergistic Processes and Mechanisms Qu, Zhongping; Zhou, Renwu; Sun, Jing ChemSusChem, Vol. 17, Issue 6 https://doi.org/10.1002/cssc.202300783	journal	December 2023
Sustainable Ammonia Synthesis from Nitrogen and Water by One‐Step Plasma Catalysis Zhang, Tianqi; Zhou, Renwu; Zhang, Shuai ENERGY & ENVIRONMENTAL MATERIALS, Vol. 6, Issue 2 https://doi.org/10.1002/eem2.12344	journal	April 2022
Complexion: A new concept for kinetic engineering in materials science Dillon, Shen J.; Tang, Ming; Carter, W. Craig Acta Materialia, Vol. 55, Issue 18 https://doi.org/10.1016/j.actamat.2007.07.029	journal	October 2007
Electrochemical synthesis of ammonia via Mars-van Krevelen mechanism on the (111) facets of group III–VII transition metal mononitrides Abghoui, Younes; Skúlason, Egill Catalysis Today, Vol. 286 https://doi.org/10.1016/j.cattod.2016.06.009	journal	May 2017
Nanostructured transition metal nitrides for energy storage and fuel cells Dong, Shanmu; Chen, Xiao; Zhang, Xiaoying Coordination Chemistry Reviews, Vol. 257, Issue 13-14 https://doi.org/10.1016/j.ccr.2012.12.012	journal	July 2013
Plasma-etching enhanced titanium oxynitride active phase with high oxygen content for ambient electrosynthesis of ammonia Kang, Shenghong; Wang, Jialu; Zhang, Shengbo Electrochemistry Communications, Vol. 100 https://doi.org/10.1016/j.elecom.2019.01.028	journal	March 2019
Tungsten nitride nanorods array grown on carbon cloth as an efficient hydrogen evolution cathode at all pH values Shi, Jinle; Pu, Zonghua; Liu, Qian Electrochimica Acta, Vol. 154 https://doi.org/10.1016/j.electacta.2014.12.096	journal	February 2015
Electrochemical performance engineering of tungsten oxynitride by a nitrogen controlling synthesis method for a binder-free supercapacitor electrode Kiafiroozkoohi, Narjess Sadat; Ghorbani, Shaban Reza; Arabi, Hadi Journal of Energy Storage, Vol. 97 https://doi.org/10.1016/j.est.2024.112956	journal	September 2024
Exploring nitrogen reduction reaction mechanisms in electrocatalytic ammonia synthesis: A comprehensive review Shetty, Abhishek Umesh; Sankannavar, Ravi Journal of Energy Chemistry, Vol. 92 https://doi.org/10.1016/j.jechem.2024.01.024	journal	May 2024
Electrocatalytic Nitrogen Reduction at Low Temperature Deng, Jiao; Iñiguez, Jesus A.; Liu, Chong Joule, Vol. 2, Issue 5 https://doi.org/10.1016/j.joule.2018.04.014	journal	May 2018
Design principles for transition metal nitride stability and ammonia generation in acid Peng, Jiayu; Giner-Sanz, Juan J.; Giordano, Livia Joule, Vol. 7, Issue 1 https://doi.org/10.1016/j.joule.2022.11.011	journal	January 2023
Achieving Decentralized, Electrified, and Decarbonized Ammonia Production Fernández, Carlos A.; Chapman, Oliver; Brown, Marilyn A. Environmental Science & Technology, Vol. 58, Issue 16 https://doi.org/10.1021/acs.est.3c10751	journal	April 2024
Metal Oxynitrides for the Electrocatalytic Reduction of Nitrogen to Ammonia Young, Samuel D.; Ceballos, Bianca M.; Banerjee, Amitava The Journal of Physical Chemistry C, Vol. 126, Issue 31 https://doi.org/10.1021/acs.jpcc.2c02816	journal	August 2022
Computational Predictions of Catalytic Activity of Zincblende (110) Surfaces of Metal Nitrides for Electrochemical Ammonia Synthesis Abghoui, Younes; Skúlason, Egill The Journal of Physical Chemistry C, Vol. 121, Issue 11 https://doi.org/10.1021/acs.jpcc.7b00196	journal	March 2017
Elucidation of the Active Phase and Deactivation Mechanisms of Chromium Nitride in the Electrochemical Nitrogen Reduction Reaction Nash, Jared; Yang, Xuan; Anibal, Jacob The Journal of Physical Chemistry C, Vol. 123, Issue 39 https://doi.org/10.1021/acs.jpcc.9b05436	journal	September 2019
Hierarchical Nanostructured WO ₃ with Biomimetic Proton Channels and Mixed Ionic-Electronic Conductivity for Electrochemical Energy Storage Chen, Zheng; Peng, Yiting; Liu, Fang Nano Letters, Vol. 15, Issue 10 https://doi.org/10.1021/acs.nanolett.5b02642	journal	September 2015
Electrocatalytic Reduction of Nitrogen to Ammonia: the Roles of Lattice O and N in Reduction at Vanadium Oxynitride Surfaces Osonkie, Adaeze; Ganesan, Ashwin; Chukwunenye, Precious ACS Applied Materials & Interfaces, Vol. 14, Issue 1 https://doi.org/10.1021/acsami.1c16104	journal	December 2021
Enhancement of Electrochemical Nitrogen Reduction Activity and Suppression of Hydrogen Evolution Reaction for Transition Metal Oxide Catalysts: The Role of Proton Intercalation and Heteroatom Doping Li, Qingdong; Kucukosman, Oguz Kaan; Ma, Qingquan ACS Catalysis, Vol. 14, Issue 11 https://doi.org/10.1021/acscatal.4c00223	journal	May 2024
Electroreduction of N ₂ to Ammonia at Ambient Conditions on Mononitrides of Zr, Nb, Cr, and V: A DFT Guide for Experiments Abghoui, Younes; Garden, Anna L.; Howalt, Jakob G. ACS Catalysis, Vol. 6, Issue 2 https://doi.org/10.1021/acscatal.5b01918	journal	December 2015
The Colors of Ammonia Hatzell, Marta C. ACS Energy Letters, Vol. 9, Issue 6 https://doi.org/10.1021/acsenergylett.4c01391	journal	June 2024
Electrochemical Ammonia Synthesis: The Energy Efficiency Challenge Zhou, Yuanyuan; Fu, Xianbiao; Chorkendorff, Ib ACS Energy Letters, Vol. 10, Issue 1 https://doi.org/10.1021/acsenergylett.4c02954	journal	December 2024
Electrochemical Dinitrogen Reduction to Ammonia by Mo ₂ N: Catalysis or Decomposition? Hu, Bo; Hu, Maowei; Seefeldt, Lance ACS Energy Letters, Vol. 4, Issue 5 https://doi.org/10.1021/acsenergylett.9b00648	journal	April 2019
Understanding the Electrocatalytic Interface for Ambient Ammonia Synthesis Hu, Lin; Xing, Zhuo; Feng, Xiaofeng ACS Energy Letters, Vol. 5, Issue 2 https://doi.org/10.1021/acsenergylett.9b02679	journal	January 2020
Tungsten Nitride/Tungsten Oxide Nanosheets for Enhanced Oxynitride Intermediate Adsorption and Hydrogenation in Nitrate Electroreduction to Ammonia Huang, Zhencong; Yang, Baopeng; Zhou, Yulong ACS Nano, Vol. 17, Issue 24 https://doi.org/10.1021/acsnano.3c07734	journal	December 2023
Critical Assessment of the Electrocatalytic Activity of Vanadium and Niobium Nitrides toward Dinitrogen Reduction to Ammonia Du, Hoang-Long; Gengenbach, Thomas R.; Hodgetts, Rebecca ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 7 https://doi.org/10.1021/acssuschemeng.8b06163	journal	February 2019
Contribution of Nitrogen Vacancies to Ammonia Synthesis over Metal Nitride Catalysts Ye, Tian-Nan; Park, Sang-Won; Lu, Yangfan Journal of the American Chemical Society, Vol. 142, Issue 33 https://doi.org/10.1021/jacs.0c06624	journal	August 2020
The Sensitivity of Metal Oxide Electrocatalysis to Bulk Hydrogen Intercalation: Hydrogen Evolution on Tungsten Oxide Miu, Evan V.; McKone, James R.; Mpourmpakis, Giannis Journal of the American Chemical Society, Vol. 144, Issue 14 https://doi.org/10.1021/jacs.2c00825	journal	March 2022
Hydrogen Radical-Induced Electrocatalytic N₂ Reduction at a Low Potential Feng, Xueting; Liu, Jiyuan; Chen, Long Journal of the American Chemical Society, Vol. 145, Issue 18 https://doi.org/10.1021/jacs.3c01319	journal	April 2023
Graphdiyne Enabled Nitrogen Vacancy Formation in Copper Nitride for Efficient Ammonia Synthesis Zhang, Zixuan; Feng, Xueting; Zhang, Zedong Journal of the American Chemical Society, Vol. 146, Issue 21 https://doi.org/10.1021/jacs.4c04985	journal	May 2024
Mechanistic Insights into Electrochemical Nitrogen Reduction Reaction on Vanadium Nitride Nanoparticles Yang, Xuan; Nash, Jared; Anibal, Jacob Journal of the American Chemical Society, Vol. 140, Issue 41 https://doi.org/10.1021/jacs.8b08379	journal	September 2018
Mixed Electron–Proton Conductors Enable Spatial Separation of Bond Activation and Charge Transfer in Electrocatalysis Yan, Bing; Bisbey, Ryan P.; Alabugin, Alexander Journal of the American Chemical Society, Vol. 141, Issue 28 https://doi.org/10.1021/jacs.9b03327	journal	June 2019
New Mechanism for N ₂ Reduction: The Essential Role of Surface Hydrogenation Ling, Chongyi; Zhang, Yehui; Li, Qiang Journal of the American Chemical Society, Vol. 141, Issue 45 https://doi.org/10.1021/jacs.9b09232	journal	October 2019
Production Mechanisms of NH and NH₂ Radicals in N₂−H₂ Plasmas van Helden, J. H.; van den Oever, P. J.; Kessels, W. M. M. The Journal of Physical Chemistry A, Vol. 111, Issue 45 https://doi.org/10.1021/jp0727650	journal	October 2007
Noble metal-comparable SERS enhancement from semiconducting metal oxides by making oxygen vacancies Cong, Shan; Yuan, Yinyin; Chen, Zhigang Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8800	journal	July 2015
Nitrogen-plasma treated hafnium oxyhydroxide as an efficient acid-stable electrocatalyst for hydrogen evolution and oxidation reactions Yang, Xiaofang; Zhao, Fang; Yeh, Yao-Wen Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09162-5	journal	April 2019
Identification and elimination of false positives in electrochemical nitrogen reduction studies Choi, Jaecheol; Suryanto, Bryan H. R.; Wang, Dabin Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-19130-z	journal	November 2020
Reversible hydrogen spillover in Ru-WO3-x enhances hydrogen evolution activity in neutral pH water splitting Chen, Jiadong; Chen, Chunhong; Qin, Minkai Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-33007-3	journal	September 2022
Vacancy-enabled N2 activation for ammonia synthesis on an Ni-loaded catalyst Ye, Tian-Nan; Park, Sang-Won; Lu, Yangfan Nature, Vol. 583, Issue 7816 https://doi.org/10.1038/s41586-020-2464-9	journal	July 2020
Ti2N nitride MXene evokes the Mars-van Krevelen mechanism to achieve high selectivity for nitrogen reduction reaction Johnson, Denis; Hunter, Brock; Christie, Jevaun Scientific Reports, Vol. 12, Issue 1 https://doi.org/10.1038/s41598-021-04640-7	journal	January 2022
Overcoming ammonia synthesis scaling relations with plasma-enabled catalysis Mehta, Prateek; Barboun, Patrick; Herrera, Francisco A. Nature Catalysis, Vol. 1, Issue 4 https://doi.org/10.1038/s41929-018-0045-1	journal	April 2018
Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia Suryanto, Bryan H. R.; Du, Hoang-Long; Wang, Dabin Nature Catalysis, Vol. 2, Issue 4 https://doi.org/10.1038/s41929-019-0252-4	journal	March 2019
Methods for nitrogen activation by reduction and oxidation Iriawan, Haldrian; Andersen, Suzanne Z.; Zhang, Xilun Nature Reviews Methods Primers, Vol. 1, Issue 1 https://doi.org/10.1038/s43586-021-00053-y	journal	August 2021
Highly mobile and reactive state of hydrogen in metal oxide semiconductors at room temperature Chen, Wan Ping; He, Ke Feng; Wang, Yu Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep03149	journal	November 2013
Current and future role of Haber–Bosch ammonia in a carbon-free energy landscape Smith, Collin; Hill, Alfred K.; Torrente-Murciano, Laura Energy & Environmental Science, Vol. 13, Issue 2 https://doi.org/10.1039/C9EE02873K	journal	January 2020
Photothermally assisted photocatalytic conversion of CO ₂ –H ₂ O into fuels over a WN–WO ₃ Z-scheme heterostructure Liu, Dali; Xu, You; Sun, Mengyao Journal of Materials Chemistry A, Vol. 8, Issue 3 https://doi.org/10.1039/C9TA10629D	journal	January 2020
A vanadium–nickel oxynitride layer for enhanced electrocatalytic nitrogen fixation in neutral media Chang, Bin; Deng, Lequan; Wang, Shouzhi Journal of Materials Chemistry A, Vol. 8, Issue 1 https://doi.org/10.1039/C9TA11378A	journal	January 2020
A hybrid plasma electrocatalytic process for sustainable ammonia production Sun, Jing; Alam, David; Daiyan, Rahman Energy & Environmental Science, Vol. 14, Issue 2 https://doi.org/10.1039/D0EE03769A	journal	January 2021
Transition metal oxynitride catalysts for electrochemical reduction of nitrogen to ammonia Ologunagba, Damilola; Kattel, Shyam Materials Advances, Vol. 2, Issue 4 https://doi.org/10.1039/D0MA00849D	journal	January 2021
Insights on cold plasma ammonia synthesis and decomposition using alkaline earth metal-based perovskites Gorky, Fnu; Lucero, Jolie M.; Crawford, James M. Catalysis Science & Technology https://doi.org/10.1039/D1CY00729G	journal	January 2021
Self-limiting nitrogen/hydrogen plasma radical chemistry in plasma-enhanced atomic layer deposition of cobalt Liu, Ji; Lu, Hongliang; Zhang, David Wei Nanoscale, Vol. 14, Issue 12 https://doi.org/10.1039/D1NR05568B	journal	January 2022
Strategies to activate inert nitrogen molecules for efficient ammonia electrosynthesis: current status, challenges, and perspectives Ren, Yongwen; Yu, Chang; Tan, Xinyi Energy & Environmental Science, Vol. 15, Issue 7 https://doi.org/10.1039/D2EE00358A	journal	January 2022
Interfacial electron-engineered tungsten oxynitride interconnected rhodium layer for highly efficient all-pH-value hydrogen production Zhang, Ben; Zheng, Yijuan; Xing, Zhenyu Journal of Materials Chemistry A, Vol. 12, Issue 8 https://doi.org/10.1039/D3TA06856K	journal	January 2024
*H migration-assisted MvK mechanism for efficient electrochemical NH₃ synthesis over TM–TiNO Cui, Luyao; Sun, Zijun; Wang, Yawen Physical Chemistry Chemical Physics, Vol. 26, Issue 21 https://doi.org/10.1039/D4CP01207K	journal	January 2024
Facile growth of aligned WO3 nanorods on FTO substrate for enhanced photoanodic water oxidation activity Kalanur, Shankara Sharanappa; Hwang, Yun Jeong; Chae, Sang Youn Journal of Materials Chemistry A, Vol. 1, Issue 10 https://doi.org/10.1039/c3ta01175e	journal	January 2013
High-performance energy-storage devices based on WO3 nanowire arrays/carbon cloth integrated electrodes Gao, Lina; Wang, Xianfu; Xie, Zhong Journal of Materials Chemistry A, Vol. 1, Issue 24 https://doi.org/10.1039/c3ta10831g	journal	January 2013
Enhancing Hydrogen Evolution Activity in Water Splitting by Tailoring Li+-Ni(OH)2-Pt Interfaces Subbaraman, R.; Tripkovic, D.; Strmcnik, D. Science, Vol. 334, Issue 6060 https://doi.org/10.1126/science.1211934	journal	December 2011
Plasma Assisted Combustion and Chemical Processing Ju, Yiguang; Starikovskiy, Andrey https://doi.org/10.1201/9781003203063	book	January 2025
The Effect of Electrolytes on the Kinetics of the Hydrogen Evolution Reaction Gebremariam, Goitom K.; Jovanović, Aleksandar Z.; Pašti, Igor A. Hydrogen, Vol. 4, Issue 4 https://doi.org/10.3390/hydrogen4040049	journal	October 2023

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