Ammonia Electrosynthesis from Nitrate Using a Ruthenium–Copper Cocatalyst System: A Full Concentration Range Study

Hu, Qikun; Yang, Ke; Peng, Ouwen; Li, Minzhang; Ma, Lu; Huang, Songpeng; Du, Yonghua; Xu, Zong-Xiang; Wang, Qing; Chen, Zhongxin; Yang, Ming; Loh, Kian Ping

doi:10.1021/jacs.3c10516

Title: Ammonia Electrosynthesis from Nitrate Using a Ruthenium–Copper Cocatalyst System: A Full Concentration Range Study

Journal Article · 27 December 2023 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c10516 · OSTI ID:2432566

^[1]; Yang, Ke ^[2];

^[1]; Li, Minzhang ^[3]; Ma, Lu ^[4]; Huang, Songpeng ^[1]; Du, Yonghua ^[4];

^[3]; Wang, Qing ^[1];

^[5];

^[2];

^[1]

National Univ. of Singapore (Singapore)
Hong Kong Polytechnic University, Kowloon, Hong Kong (China)
Southern University of Science and Technology (SUSTech), Shenzhen (China)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
National Univ. of Singapore (Singapore); The Chinese University of Hong Kong, Shenzhen, Guangdong (Hong Kong)

Electrochemical synthesis of ammonia via the nitrate reduction reaction (NO3RR) has been intensively researched as an alternative to the traditional Haber–Bosch process. Most research focuses on the low concentration range representative of the nitrate level in wastewater, leaving the high concentration range, which exists in nuclear and fertilizer wastes, unexplored. The use of a concentrated electrolyte (≥1 M) for higher rate production is hampered by poor hydrogen transfer kinetics. Herein, we demonstrate that a cocatalytic system of Ru/Cu₂O catalyst enables NO3RR at 10.0 A in 1 M nitrate electrolyte in a 16 cm² flow electrolyzer, with 100% faradaic efficiency toward ammonia. Detailed mechanistic studies by deuterium labeling and operando Fourier transform infrared (FTIR) spectroscopy allow us to probe the hydrogen transfer rate and intermediate species on Ru/Cu₂O. Ab initio molecular dynamics (AIMD) simulations reveal that adsorbed hydroxide on Ru nanoparticles increases the density of the hydrogen-bonded water network near the Cu₂O surface, which promotes the hydrogen transfer rate. Finally, our work highlights the importance of engineering synergistic interactions in cocatalysts for addressing the kinetic bottleneck in electrosynthesis.

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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:: 2432566

Report Number(s):: BNL--225944-2024-JAAM

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 1 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (41)

Promoted Glycerol Oxidation Reaction in an Interface-Confined Hierarchically Structured Catalyst Chen, Zhongxin; Liu, Cuibo; Zhao, Xiaoxu Advanced Materials, Vol. 31, Issue 2 https://doi.org/10.1002/adma.201804763	journal	November 2018
Efficient Ammonia Electrosynthesis and Energy Conversion through a Zn‐Nitrate Battery by Iron Doping Engineered Nickel Phosphide Catalyst Zhang, Rong; Guo, Ying; Zhang, Shaoce Advanced Energy Materials, Vol. 12, Issue 13 https://doi.org/10.1002/aenm.202103872	journal	February 2022
Unveiling the Activity Origin of a Copper‐based Electrocatalyst for Selective Nitrate Reduction to Ammonia Wang, Yuting; Zhou, Wei; Jia, Ranran Angewandte Chemie International Edition, Vol. 59, Issue 13 https://doi.org/10.1002/anie.201915992	journal	March 2020
Challenges and Strategies for High‐Energy Aqueous Electrolyte Rechargeable Batteries Zhang, Huang; Liu, Xu; Li, Huihua Angewandte Chemie International Edition, Vol. 60, Issue 2 https://doi.org/10.1002/anie.202004433	journal	July 2020
Electrochemical Nitric Oxide Reduction on Metal Surfaces Wan, Hao; Bagger, Alexander; Rossmeisl, Jan Angewandte Chemie International Edition, Vol. 60, Issue 40 https://doi.org/10.1002/anie.202108575	journal	August 2021
Electrolyte Engineering Toward High‐Voltage Aqueous Energy Storage Devices Tan, Jianfeng; Liu, Jinping ENERGY & ENVIRONMENTAL MATERIALS, Vol. 4, Issue 3 https://doi.org/10.1002/eem2.12125	journal	October 2020
Restoring the Nitrogen Cycle by Electrochemical Reduction of Nitrate: Progress and Prospects Zeng, Yachao; Priest, Cameron; Wang, Guofeng Small Methods, Vol. 4, Issue 12 https://doi.org/10.1002/smtd.202000672	journal	September 2020
An FT-IR study of the adsorption and oxidation of N-containing compounds over Fe2O3-TiO2 SCR catalysts Larrubia, M. Angeles; Ramis, Gianguido; Busca, Guido Applied Catalysis B: Environmental, Vol. 30, Issue 1-2 https://doi.org/10.1016/S0926-3373(00)00220-4	journal	February 2001
Denitrification of high strength nitrate waste Dhamole, Pradip B.; Nair, Rashmi R.; D’Souza, Stanislaus F. Bioresource Technology, Vol. 98, Issue 2 https://doi.org/10.1016/j.biortech.2006.01.019	journal	January 2007
Recent advances in non-noble metal electrocatalysts for nitrate reduction Zhang, Xi; Wang, Yuting; Liu, Cuibo Chemical Engineering Journal, Vol. 403 https://doi.org/10.1016/j.cej.2020.126269	journal	January 2021
Increasing electrocatalytic nitrate reduction activity by controlling adsorption through PtRu alloying Wang, Zixuan; Young, Samuel D.; Goldsmith, Bryan R. Journal of Catalysis, Vol. 395 https://doi.org/10.1016/j.jcat.2020.12.031	journal	March 2021
New insight on electroreduction of nitrate to ammonia driven by oxygen vacancies-induced strong interface interactions Yin, Haibo; Zhao, Xiaoguang; Xiong, Shangchao Journal of Catalysis, Vol. 406 https://doi.org/10.1016/j.jcat.2021.12.031	journal	February 2022
The pitfalls in electrocatalytic nitrogen reduction for ammonia synthesis Liu, Huimin; Guijarro, Néstor; Luo, Jingshan Journal of Energy Chemistry, Vol. 61 https://doi.org/10.1016/j.jechem.2021.01.039	journal	October 2021
The influence of nitrate concentration and acidity on the electrocatalytic reduction of nitrate on platinum de Groot, M. T.; Koper, M. T. M. Journal of Electroanalytical Chemistry, Vol. 562, Issue 1 https://doi.org/10.1016/j.jelechem.2003.08.011	journal	January 2004
Hydroxylamine electrochemistry at polycrystalline platinum in acidic media: a voltammetric, DEMS and FTIR study Rosca, Victor; Beltramo, Guillermo L.; Koper, Marc T. M. Journal of Electroanalytical Chemistry, Vol. 566, Issue 1 https://doi.org/10.1016/j.jelechem.2003.11.011	journal	May 2004
Electrocatalytic Nitrate Reduction for Sustainable Ammonia Production van Langevelde, Phebe H.; Katsounaros, Ioannis; Koper, Marc T. M. Joule, Vol. 5, Issue 2 https://doi.org/10.1016/j.joule.2020.12.025	journal	February 2021
Engineering Single Atom Catalysts for Flow Production: From Catalyst Design to Reactor Understandings Chen, Zhongxin; Liu, Jia; Loh, Kian Ping Accounts of Materials Research, Vol. 4, Issue 1 https://doi.org/10.1021/accountsmr.2c00183	journal	December 2022
Pseudoconcentrated Electrolyte with High Ionic Conductivity and Stability Enables High-Voltage Lithium-Ion Battery Chemistry Ma, Guoqiang; Wang, Li; He, Xiangming ACS Applied Energy Materials https://doi.org/10.1021/acsaem.8b01020	journal	September 2018
Selective Electrocatalytic Reduction of Nitrate to Ammonia with Nickel Phosphide Yao, Qiufang; Chen, Jiabin; Xiao, Shaoze ACS Applied Materials & Interfaces, Vol. 13, Issue 26 https://doi.org/10.1021/acsami.0c22338	journal	June 2021
Studies of Contact and Solvent-Separated Ion Pairs of Carbanions. I. Effect of Temperature, Counterion, and Solvent Esch, T. E. Hogen-; Smid, J. Journal of the American Chemical Society, Vol. 88, Issue 2 https://doi.org/10.1021/ja00954a024	journal	January 1966
Efficient Ammonia Electrosynthesis from Nitrate on Strained Ruthenium Nanoclusters Li, Jie; Zhan, Guangming; Yang, Jianhua Journal of the American Chemical Society, Vol. 142, Issue 15 https://doi.org/10.1021/jacs.0c00418	journal	March 2020
Interface confined hydrogen evolution reaction in zero valent metal nanoparticles-intercalated molybdenum disulfide Chen, Zhongxin; Leng, Kai; Zhao, Xiaoxu Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14548	journal	February 2017
Selective electrochemical reduction of nitric oxide to hydroxylamine by atomically dispersed iron catalyst Kim, Dong Hyun; Ringe, Stefan; Kim, Haesol Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-22147-7	journal	March 2021
Electrochemical ammonia synthesis via nitrate reduction on Fe single atom catalyst Wu, Zhen-Yu; Karamad, Mohammadreza; Yong, Xue Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23115-x	journal	May 2021
Solvent-free microwave synthesis of ultra-small Ru-Mo2C@CNT with strong metal-support interaction for industrial hydrogen evolution Wu, Xueke; Wang, Zuochao; Zhang, Dan Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-24322-2	journal	June 2021
Addressing the quantitative conversion bottleneck in single-atom catalysis Chen, Zhongxin; Song, Jingting; Zhang, Rongrong Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-30551-w	journal	May 2022
Active hydrogen boosts electrochemical nitrate reduction to ammonia Fan, Kui; Xie, Wenfu; Li, Jinze Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-35664-w	journal	December 2022
Electrochemical reduction of nitrate to ammonia via direct eight-electron transfer using a copper–molecular solid catalyst Chen, Gao-Feng; Yuan, Yifei; Jiang, Haifeng Nature Energy, Vol. 5, Issue 8 https://doi.org/10.1038/s41560-020-0654-1	journal	July 2020
Efficient conversion of low-concentration nitrate sources into ammonia on a Ru-dispersed Cu nanowire electrocatalyst Chen, Feng-Yang; Wu, Zhen-Yu; Gupta, Srishti Nature Nanotechnology, Vol. 17, Issue 7 https://doi.org/10.1038/s41565-022-01121-4	journal	May 2022
The role of ruthenium in improving the kinetics of hydrogen oxidation and evolution reactions of platinum Zhu, Shangqian; Qin, Xueping; Xiao, Fei Nature Catalysis, Vol. 4, Issue 8 https://doi.org/10.1038/s41929-021-00663-5	journal	August 2021
Hydrogen bond network connectivity in the electric double layer dominates the kinetic pH effect in hydrogen electrocatalysis on Pt Li, Peng; Jiang, Yaling; Hu, Youcheng Nature Catalysis, Vol. 5, Issue 10 https://doi.org/10.1038/s41929-022-00846-8	journal	September 2022
Ultralow overpotential nitrate reduction to ammonia via a three-step relay mechanism Han, Shuhe; Li, Hongjiao; Li, Tieliang Nature Catalysis, Vol. 6, Issue 5 https://doi.org/10.1038/s41929-023-00951-2	journal	April 2023
Recent discoveries in the reaction mechanism of heterogeneous electrocatalytic nitrate reduction Wang, Zixuan; Richards, Danielle; Singh, Nirala Catalysis Science & Technology, Vol. 11, Issue 3 https://doi.org/10.1039/D0CY02025G	journal	January 2021
Nitrate electroreduction: mechanism insight, in situ characterization, performance evaluation, and challenges Wang, Yuting; Wang, Changhong; Li, Mengyang Chemical Society Reviews, Vol. 50, Issue 12 https://doi.org/10.1039/D1CS00116G	journal	January 2021
A single-site iron catalyst with preoccupied active centers that achieves selective ammonia electrosynthesis from nitrate Li, Panpan; Jin, Zhaoyu; Fang, Zhiwei Energy & Environmental Science, Vol. 14, Issue 6 https://doi.org/10.1039/D1EE00545F	journal	January 2021
Nitrate reduction to ammonium: from CuO defect engineering to waste NO_x-to-NH₃economic feasibility Daiyan, Rahman; Tran-Phu, Thanh; Kumar, Priyank Energy & Environmental Science, Vol. 14, Issue 6 https://doi.org/10.1039/D1EE00594D	journal	January 2021
Pd doping-weakened intermediate adsorption to promote electrocatalytic nitrate reduction on TiO₂ nanoarrays for ammonia production and energy supply with zinc–nitrate batteries Guo, Ying; Zhang, Rong; Zhang, Shaoce Energy & Environmental Science, Vol. 14, Issue 7 https://doi.org/10.1039/D1EE00806D	journal	January 2021
Reaction intermediate-mediated electrocatalyst synthesis favors specified facet and defect exposure for efficient nitrate–ammonia conversion Hu, Qi; Qin, Yongjie; Wang, Xiaodeng Energy & Environmental Science, Vol. 14, Issue 9 https://doi.org/10.1039/D1EE01731D	journal	January 2021
Solar-driven electrochemical synthesis of ammonia using nitrate with 11% solar-to-fuel efficiency at ambient conditions Kani, Nishithan C.; Gauthier, Joseph A.; Prajapati, Aditya Energy & Environmental Science, Vol. 14, Issue 12 https://doi.org/10.1039/D1EE01879E	journal	January 2021
Powering denitrification: the perspectives of electrocatalytic nitrate reduction Duca, Matteo; Koper, Marc T. M. Energy & Environmental Science, Vol. 5, Issue 12 https://doi.org/10.1039/c2ee23062c	journal	January 2012
A review of nitrate reduction using inorganic materials Zhu, Ivan; Getting, Tom Environmental Technology Reviews, Vol. 1, Issue 1 https://doi.org/10.1080/09593330.2012.706646	journal	November 2012

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Title: Ammonia Electrosynthesis from Nitrate Using a Ruthenium–Copper Cocatalyst System: A Full Concentration Range Study

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