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

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

doi:10.1021/acsenergylett.5c01034

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

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

electron Microscopy and Microanalysis

Research output: Contribution to journal › Article › peer-review

11 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	3349-3358
Number of pages	10
Journal	ACS Energy Letters
Volume	10
Issue number	7
DOIs	https://doi.org/10.1021/acsenergylett.5c01034
State	Published - Jul 11 2025

Funding

The collaborative effort of this study is supported by the US National Science Foundation (Award#: 2428523). HH would also like to acknowledge the support of Rutgers Research Council. YJ would like to acknowledge the support from the DOE Plasma-Enhanced H2 Production (PEHPr) Energy Earthshot Research Center (EERC) at Princeton Plasma Physics Laboratory under contract DEAC0209CH11466 for plasma reactors and DOE FES DE-SC0025371 grant for diagnostics. Microscopy was partially conducted at the Center for Nanophase Materials Science, Oak Ridge National Laboratory, supported by the U.S. Department of Energy, Office of Science, and in part at the Analytical Instrumentation Facility (AIF) at NCSU, which is supported by the State of North Carolina and the National Science Foundation (award number ECCS-2025064). Participation of Princeton Plasma Physics Laboratory, a national laboratory operated by Princeton University for the U.S. Department of Energy under Prime Contract No. DE-AC02-09CH11466, is made possible via the Strategic Partnership Projects program. The collaborative effort of this study is supported by the US National Science Foundation (Award#: 2428523). HH would also like to acknowledge the support of Rutgers Research Council. YJ would like to acknowledge the support from the DOE Plasma-Enhanced H Production (PEHPr) Energy Earthshot Research Center (EERC) at Princeton Plasma Physics Laboratory under contract DEAC0209CH11466 for plasma reactors and DOE FES DE-SC0025371 grant for diagnostics. Microscopy was partially conducted at the Center for Nanophase Materials Science, Oak Ridge National Laboratory, supported by the U.S. Department of Energy, Office of Science, and in part at the Analytical Instrumentation Facility (AIF) at NCSU, which is supported by the State of North Carolina and the National Science Foundation (award number ECCS-2025064). Participation of Princeton Plasma Physics Laboratory, a national laboratory operated by Princeton University for the U.S. Department of Energy under Prime Contract No. DE-AC02-09CH11466, is made possible via the Strategic Partnership Projects program. 2

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10.1021/acsenergylett.5c01034

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Zhang, Z., Kondratowicz, C., Smith, J., Kucheryavy, P., Ouyang, J., Xu, Y., Desmet, E., Kurdziel, S., Tang, E., Adeleke, M., Lele, A. D., Martirez, J. M., Chi, M., Ju, Y., & He, H. (2025). Plasma-Assisted Surface Nitridation of Proton Intercalatable WO₃ for Efficient Electrocatalytic Ammonia Synthesis. ACS Energy Letters, 10(7), 3349-3358. https://doi.org/10.1021/acsenergylett.5c01034

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title = "Plasma-Assisted Surface Nitridation of Proton Intercalatable WO3 for Efficient Electrocatalytic Ammonia Synthesis",

abstract = "Electrocatalytic nitrogen reduction (eNRR) offers a green pathway for the production of NH3 from N2 and H2O under ambient conditions. Transition metal oxynitrides (TMOxNy) are among the most promising catalysts but face challenges in achieving a high yield and faradaic efficiency (FE). This work develops a hybrid WOxNy/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 WOxNy 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/TMOxNy electrocatalysts. Multiple control experiments confirm that the eNRR follows an HIC-enhanced Mars-van Krevelen (MvK) mechanism.",

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

note = "Publisher Copyright: {\textcopyright} 2025 American Chemical Society.",

year = "2025",

month = jul,

day = "11",

doi = "10.1021/acsenergylett.5c01034",

language = "English",

volume = "10",

pages = "3349--3358",

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Zhang, Z, Kondratowicz, C, Smith, J, Kucheryavy, P, Ouyang, J, Xu, Y, Desmet, E, Kurdziel, S, Tang, E, Adeleke, M, Lele, AD, Martirez, JM, Chi, M, Ju, Y & He, H 2025, 'Plasma-Assisted Surface Nitridation of Proton Intercalatable WO₃ for Efficient Electrocatalytic Ammonia Synthesis', ACS Energy Letters, vol. 10, no. 7, pp. 3349-3358. https://doi.org/10.1021/acsenergylett.5c01034

TY - JOUR

T1 - Plasma-Assisted Surface Nitridation of Proton Intercalatable WO3 for Efficient Electrocatalytic Ammonia Synthesis

AU - Zhang, Zhiyuan

AU - Kondratowicz, Christopher

AU - Smith, Jacob

AU - Kucheryavy, Pavel

AU - Ouyang, Junjie

AU - Xu, Yijie

AU - Desmet, Elizabeth

AU - Kurdziel, Sophia

AU - Tang, Eddie

AU - Adeleke, Micheal

AU - Lele, Aditya Dilip

AU - Martirez, John Mark

AU - Chi, Miaofang

AU - Ju, Yiguang

AU - He, Huixin

PY - 2025/7/11

Y1 - 2025/7/11

N2 - Electrocatalytic nitrogen reduction (eNRR) offers a green pathway for the production of NH3 from N2 and H2O under ambient conditions. Transition metal oxynitrides (TMOxNy) are among the most promising catalysts but face challenges in achieving a high yield and faradaic efficiency (FE). This work develops a hybrid WOxNy/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 WOxNy 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/TMOxNy electrocatalysts. Multiple control experiments confirm that the eNRR follows an HIC-enhanced Mars-van Krevelen (MvK) mechanism.

AB - Electrocatalytic nitrogen reduction (eNRR) offers a green pathway for the production of NH3 from N2 and H2O under ambient conditions. Transition metal oxynitrides (TMOxNy) are among the most promising catalysts but face challenges in achieving a high yield and faradaic efficiency (FE). This work develops a hybrid WOxNy/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 WOxNy 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/TMOxNy electrocatalysts. Multiple control experiments confirm that the eNRR follows an HIC-enhanced Mars-van Krevelen (MvK) mechanism.

UR - https://www.scopus.com/pages/publications/105008977008

U2 - 10.1021/acsenergylett.5c01034

DO - 10.1021/acsenergylett.5c01034

M3 - Article

AN - SCOPUS:105008977008

SN - 2380-8195

VL - 10

SP - 3349

EP - 3358

JO - ACS Energy Letters

JF - ACS Energy Letters

IS - 7

ER -

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

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