FeMo sub-nanoclusters/single atoms for neutral ammonia electrosynthesis

Liu, Wei; Han, L.; Wang, H.-T.; Zhao, X.; Boscoboinik, Jorge A.; Liu, X.; Pao, C.-W.; Sun, Jiaqiang; Zhuo, L.; Luo, J.; Ren, J.; Pong, W.-F.; Xin, H.L.

doi:10.1016/j.nanoen.2020.105078

FeMo sub-nanoclusters/single atoms for neutral ammonia electrosynthesis

Journal Article · Thu Jul 09 00:00:00 EDT 2020 · Nano Energy

DOI:https://doi.org/10.1016/j.nanoen.2020.105078· OSTI ID:1756175

Liu, Wei ^[1]; Han, L. ^[2]; Wang, H.-T. ^[3]; Zhao, X. ^[4]; ^[5]; Liu, X. ^[1]; Pao, C.-W. ^[6]; Sun, Jiaqiang ^[7]; Zhuo, L. ^[8]; Luo, J. ^[1]; Ren, J. ^[9]; Pong, W.-F. ^[3]; Xin, H.L. ^[10]

Tianjin Univ. of Technology (China)
Tianjin Univ. of Technology (China); Univ. of California, Irvine, CA (United States)
Tamkang Univ. (China)
Tianjin Univ. (China)
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
National Synchrotron Radiation Research Center (Taiwan)
Chinese Academy of Sciences (CAS), Shanxi (China)
Xi'an Univ. of Technology (China)
Lanzhou Univ. of Technology (China)
Univ. of California, Irvine, CA (United States)

Electrochemical N₂ reduction reaction (NRR) has long been regarded as a promising process to generate NH₃ under ambient conditions. Therefore, developing cost-effective and high-performance non-noble-metal catalysts for NRR is highly desirable. Inspired by the biological nitrogenase structure, we here designed and synthesized a catalyst with iron-molybdenum sub-nanoclusters and single atoms on porous nitrogen-doped carbon (FeMo/NC). The catalyst features porous structure beneficial to active site exposure and accessibility to electrolyte as well as FeMo sub-nanoclusters and single atoms enabling to activate N₂ molecular. In situ near-ambient pressure X-ray photoelectron spectroscopy tests reveal that during the process from vacuum to nitrogen saturation, N₂ was close to, adsorbed on and interacted with Fe and Mo in FeMo/NC. The Fe and Mo through electron transfer play a key role in activating the N₂ molecules. Therefore, when tested for NRR, FeMo/NC achieves the maximum Faradaic efficiency (FE) of 11.8 ± 0.8% at -0.25 V and NH₃ yield rate of 26.5 ± 0.8 μg h^-1 mg_cat.^-1 at -0.3 V in neutral electrolyte. Moreover, the catalyst exhibits ignorable variations in the FE and a slight decrease in current density for 100,000 s. This work develops a non-precious bimetallic electrocatalyst with synergetic effect capability for efficient NH₃ production and provides a guideline for the design of efficient and robust catalysts with coexistence of sub-nanoclusters and single atoms.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1756175

Alternate ID(s):: OSTI ID: 1809800
OSTI ID: 1690156

Report Number(s):: BNL--220762-2020-JAAM

Journal Information:: Nano Energy, Journal Name: Nano Energy Vol. 77; ISSN 2211-2855

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (53)

Electrochemical Reduction of N ₂ under Ambient Conditions for Artificial N ₂ Fixation and Renewable Energy Storage Using N ₂ /NH ₃ Cycle Bao, Di; Zhang, Qi; Meng, Fan-Lu Advanced Materials, Vol. 29, Issue 3 https://doi.org/10.1002/adma.201604799	journal	November 2016
Au Sub-Nanoclusters on TiO ₂ toward Highly Efficient and Selective Electrocatalyst for N ₂ Conversion to NH ₃ at Ambient Conditions Shi, Miao-Miao; Bao, Di; Wulan, Ba-Ri Advanced Materials, Vol. 29, Issue 17 https://doi.org/10.1002/adma.201606550	journal	February 2017
Amorphizing of Au Nanoparticles by CeO _x -RGO Hybrid Support towards Highly Efficient Electrocatalyst for N ₂ Reduction under Ambient Conditions Li, Si-Jia; Bao, Di; Shi, Miao-Miao Advanced Materials, Vol. 29, Issue 33 https://doi.org/10.1002/adma.201700001	journal	July 2017
Fe Isolated Single Atoms on S, N Codoped Carbon by Copolymer Pyrolysis Strategy for Highly Efficient Oxygen Reduction Reaction Li, Qiheng; Chen, Wenxing; Xiao, Hai Advanced Materials, Vol. 30, Issue 25 https://doi.org/10.1002/adma.201800588	journal	May 2018
Molybdenum Carbide Nanodots Enable Efficient Electrocatalytic Nitrogen Fixation under Ambient Conditions Cheng, Hui; Ding, Liang-Xin; Chen, Gao-Feng Advanced Materials, Vol. 30, Issue 46 https://doi.org/10.1002/adma.201803694	journal	October 2018
Ammonia Detection Methods in Photocatalytic and Electrocatalytic Experiments: How to Improve the Reliability of NH ₃ Production Rates? Zhao, Yunxuan; Shi, Run; Bian, Xuanang Advanced Science, Vol. 6, Issue 8 https://doi.org/10.1002/advs.201802109	journal	February 2019
Anchoring PdCu Amorphous Nanocluster on Graphene for Electrochemical Reduction of N ₂ to NH ₃ under Ambient Conditions in Aqueous Solution Shi, Miao-Miao; Bao, Di; Li, Si-Jia Advanced Energy Materials, Vol. 8, Issue 21 https://doi.org/10.1002/aenm.201800124	journal	April 2018
Electrocatalytic Synthesis of Ammonia at Room Temperature and Atmospheric Pressure from Water and Nitrogen on a Carbon-Nanotube-Based Electrocatalyst Chen, Shiming; Perathoner, Siglinda; Ampelli, Claudio Angewandte Chemie International Edition, Vol. 56, Issue 10 https://doi.org/10.1002/anie.201609533	journal	January 2017
An Amorphous Noble-Metal-Free Electrocatalyst that Enables Nitrogen Fixation under Ambient Conditions Lv, Chade; Yan, Chunshuang; Chen, Gang Angewandte Chemie International Edition, Vol. 57, Issue 21 https://doi.org/10.1002/anie.201801538	journal	March 2018
Atomically Dispersed Molybdenum Catalysts for Efficient Ambient Nitrogen Fixation Han, Lili; Liu, Xijun; Chen, Jinping Angewandte Chemie International Edition, Vol. 58, Issue 8 https://doi.org/10.1002/anie.201811728	journal	January 2019
Front Cover: Single‐Atom Catalysts for the Electrocatalytic Reduction of Nitrogen to Ammonia under Ambient Conditions (Chem. Asian J. 17/2019) Qiu, Yuan; Peng, Xianyun; Lü, Fang Chemistry – An Asian Journal, Vol. 14, Issue 17 https://doi.org/10.1002/asia.201901100	journal	August 2019
Near ambient pressure XPS with a conventional X-ray source: NAP XPS with a conventional X-ray source Jürgensen, A.; Esser, N.; Hergenröder, R. Surface and Interface Analysis, Vol. 44, Issue 8 https://doi.org/10.1002/sia.4826	journal	January 2012
BN Pairs Enriched Defective Carbon Nanosheets for Ammonia Synthesis with High Efficiency Chen, Chen; Yan, Dafeng; Wang, Yu Small, Vol. 15, Issue 7 https://doi.org/10.1002/smll.201805029	journal	January 2019
Amorphous Sn/Crystalline SnS ₂ Nanosheets via In Situ Electrochemical Reduction Methodology for Highly Efficient Ambient N ₂ Fixation Li, Pengxiang; Fu, Wenzhi; Zhuang, Peiyuan Small, Vol. 15, Issue 40 https://doi.org/10.1002/smll.201902535	journal	August 2019
Aqueous electrocatalytic N2 reduction under ambient conditions Cao, Na; Zheng, Gengfeng Nano Research, Vol. 11, Issue 6 https://doi.org/10.1007/s12274-018-1987-y	journal	May 2018
Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials Yamashita, Toru; Hayes, Peter Applied Surface Science, Vol. 254, Issue 8 https://doi.org/10.1016/j.apsusc.2007.09.063	journal	February 2008
Reversible Nitrogen Fixation Based on a Rechargeable Lithium-Nitrogen Battery for Energy Storage Ma, Jin-Ling; Bao, Di; Shi, Miao-Miao Chem, Vol. 2, Issue 4 https://doi.org/10.1016/j.chempr.2017.03.016	journal	April 2017
Nickel doped cobalt - hollow nanoparticles as an efficient electrocatalyst for hydrogen evolution from neutral water Abdullah, Muhammad Imran; Hameed, Asima; Zhang, Ning International Journal of Hydrogen Energy, Vol. 44, Issue 29 https://doi.org/10.1016/j.ijhydene.2019.04.076	journal	June 2019
Self-supported NbSe2 nanosheet arrays for highly efficient ammonia electrosynthesis under ambient conditions Wang, Yong; Chen, Anran; Lai, Shuhua Journal of Catalysis, Vol. 381 https://doi.org/10.1016/j.jcat.2019.10.029	journal	January 2020
Metal-organic framework-derived nitrogen-doped highly disordered carbon for electrochemical ammonia synthesis using N2 and H2O in alkaline electrolytes Mukherjee, Shreya; Cullen, David A.; Karakalos, Stavros Nano Energy, Vol. 48 https://doi.org/10.1016/j.nanoen.2018.03.059	journal	June 2018
Enhancing the rate of electrochemical nitrogen reduction reaction for ammonia synthesis under ambient conditions using hollow gold nanocages Nazemi, Mohammadreza; Panikkanvalappil, Sajanlal R.; El-Sayed, Mostafa A. Nano Energy, Vol. 49 https://doi.org/10.1016/j.nanoen.2018.04.039	journal	July 2018
Nitrogen-coordinated single Fe sites for efficient electrocatalytic N2 fixation in neutral media Lü, Fang; Zhao, Shunzheng; Guo, Ruijie Nano Energy, Vol. 61 https://doi.org/10.1016/j.nanoen.2019.04.092	journal	July 2019
Facile Ammonia Synthesis from Electrocatalytic N ₂ Reduction under Ambient Conditions on N-Doped Porous Carbon Liu, Yanming; Su, Yan; Quan, Xie ACS Catalysis, Vol. 8, Issue 2 https://doi.org/10.1021/acscatal.7b02165	journal	January 2018
Ambient Electrochemical Ammonia Synthesis with High Selectivity on Fe/Fe Oxide Catalyst Hu, Lin; Khaniya, Asim; Wang, Jun ACS Catalysis, Vol. 8, Issue 10 https://doi.org/10.1021/acscatal.8b02585	journal	August 2018
Pomegranate-like N,P-Doped Mo ₂ C@C Nanospheres as Highly Active Electrocatalysts for Alkaline Hydrogen Evolution Chen, Yu-Yun; Zhang, Yun; Jiang, Wen-Jie ACS Nano, Vol. 10, Issue 9 https://doi.org/10.1021/acsnano.6b04725	journal	September 2016
High-Efficiency Electrosynthesis of Ammonia with High Selectivity under Ambient Conditions Enabled by VN Nanosheet Array Zhang, Rong; Zhang, Ya; Ren, Xiang ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 8 https://doi.org/10.1021/acssuschemeng.8b01261	journal	July 2018
Nitrogen Cycle Electrocatalysis Rosca, Victor; Duca, Matteo; de Groot, Matheus T. Chemical Reviews, Vol. 109, Issue 6 https://doi.org/10.1021/cr8003696	journal	June 2009
Mechanism of Molybdenum Nitrogenase Burgess, Barbara K.; Lowe, David J. Chemical Reviews, Vol. 96, Issue 7 https://doi.org/10.1021/cr950055x	journal	January 1996
Structural studies of the molybdenum site in the MoFe protein and its FeMo cofactor by EXAFS Conradson, Steven D.; Burgess, Barbara K.; Newton, William E. Journal of the American Chemical Society, Vol. 109, Issue 24 https://doi.org/10.1021/ja00258a042	journal	November 1987
Ammonia Electrosynthesis with High Selectivity under Ambient Conditions via a Li ⁺ Incorporation Strategy Chen, Gao-Feng; Cao, Xinrui; Wu, Shunqing Journal of the American Chemical Society, Vol. 139, Issue 29 https://doi.org/10.1021/jacs.7b04393	journal	July 2017
Single Mo Atom Supported on Defective Boron Nitride Monolayer as an Efficient Electrocatalyst for Nitrogen Fixation: A Computational Study Zhao, Jingxiang; Chen, Zhongfang Journal of the American Chemical Society, Vol. 139, Issue 36 https://doi.org/10.1021/jacs.7b05213	journal	August 2017
Metal (Hydr)oxides@Polymer Core–Shell Strategy to Metal Single-Atom Materials Zhang, Maolin; Wang, Yang-Gang; Chen, Wenxing Journal of the American Chemical Society, Vol. 139, Issue 32 https://doi.org/10.1021/jacs.7b05372	journal	August 2017
Edge-Site Engineering of Atomically Dispersed Fe–N ₄ by Selective C–N Bond Cleavage for Enhanced Oxygen Reduction Reaction Activities Jiang, Rui; Li, Li; Sheng, Tian Journal of the American Chemical Society, Vol. 140, Issue 37 https://doi.org/10.1021/jacs.8b07294	journal	August 2018
Catalytic reduction of molecular nitrogen in solutions Shilov, A. E. Russian Chemical Bulletin, Vol. 52, Issue 12 https://doi.org/10.1023/B:RUCB.0000019873.81002.60	journal	December 2003
Crystallographic structure and functional implications of the nitrogenase molybdenum–iron protein from Azotobacter vinelandii Kirn, Jongsun; Rees, D. C. Nature, Vol. 360, Issue 6404 https://doi.org/10.1038/360553a0	journal	December 1992
One electron at a time Chirik, Paul J. Nature Chemistry, Vol. 1, Issue 7 https://doi.org/10.1038/nchem.386	journal	October 2009
Coupled molybdenum carbide and reduced graphene oxide electrocatalysts for efficient hydrogen evolution Li, Ji-Sen; Wang, Yu; Liu, Chun-Hui Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11204	journal	April 2016
High-performance artificial nitrogen fixation at ambient conditions using a metal-free electrocatalyst Qiu, Weibin; Xie, Xiao-Ying; Qiu, Jianding Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-05758-5	journal	August 2018
A rigorous electrochemical ammonia synthesis protocol with quantitative isotope measurements Andersen, Suzanne Z.; Čolić, Viktor; Yang, Sungeun Nature, Vol. 570, Issue 7762 https://doi.org/10.1038/s41586-019-1260-x	journal	May 2019
Synthesis of ammonia directly from air and water at ambient temperature and pressure Lan, Rong; Irvine, John T. S.; Tao, Shanwen Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep01145	journal	January 2013
Galvanic deposition of Rh and Ru on randomly structured Ti felts for the electrochemical NH ₃ synthesis Kugler, Kurt; Luhn, Mareike; Schramm, Jean André Physical Chemistry Chemical Physics, Vol. 17, Issue 5 https://doi.org/10.1039/C4CP05501B	journal	January 2015
Challenges in reduction of dinitrogen by proton and electron transfer van der Ham, Cornelis J. M.; Koper, Marc T. M.; Hetterscheid, Dennis G. H. Chem. Soc. Rev., Vol. 43, Issue 15 https://doi.org/10.1039/C4CS00085D	journal	January 2014
Surfactant-free atomically ultrathin rhodium nanosheet nanoassemblies for efficient nitrogen electroreduction Liu, Hui-Min; Han, Shu-He; Zhao, Yue Journal of Materials Chemistry A, Vol. 6, Issue 7 https://doi.org/10.1039/C7TA10866D	journal	January 2018
Ag nanosheets for efficient electrocatalytic N ₂ fixation to NH ₃ under ambient conditions Huang, Hehan; Xia, Li; Shi, Xifeng Chemical Communications, Vol. 54, Issue 81 https://doi.org/10.1039/C8CC06365F	journal	January 2018
Ambient NH ₃ synthesis via electrochemical reduction of N ₂ over cubic sub-micron SnO ₂ particles Zhang, Ling; Ren, Xiang; Luo, Yonglan Chemical Communications, Vol. 54, Issue 92 https://doi.org/10.1039/C8CC06524A	journal	January 2018
Ambient N ₂ fixation to NH ₃ electrocatalyzed by a spinel Fe ₃ O ₄ nanorod Liu, Qin; Zhang, Xiaoxue; Zhang, Bing Nanoscale, Vol. 10, Issue 30 https://doi.org/10.1039/C8NR04524K	journal	January 2018
Atomically dispersed metal dimer species with selective catalytic activity for nitrogen electrochemical reduction Li, Yang; Zhang, Qi; Li, Can Journal of Materials Chemistry A, Vol. 7, Issue 39 https://doi.org/10.1039/C9TA07845B	journal	January 2019
Electrochemical synthesis of ammonia at atmospheric pressure and low temperature in a solid polymer electrolyte cell Kordali, V.; Kyriacou, G.; Lambrou, Ch. Chemical Communications, Issue 17 https://doi.org/10.1039/b004885m	journal	January 2000
Ammonia Synthesis from First-Principles Calculations Honkala, K. Science, Vol. 307, Issue 5709 https://doi.org/10.1126/science.1106435	journal	January 2005
Evidence for Interstitial Carbon in Nitrogenase FeMo Cofactor Spatzal, T.; Aksoyoglu, M.; Zhang, L. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1214025	journal	November 2011
Ammonia synthesis by N2 and steam electrolysis in molten hydroxide suspensions of nanoscale Fe2O3 Licht, S.; Cui, B.; Wang, B. Science, Vol. 345, Issue 6197 https://doi.org/10.1126/science.1254234	journal	August 2014
New recipe produces ammonia from air, water, and sunlight Service, R. F. Science, Vol. 345, Issue 6197 https://doi.org/10.1126/science.345.6197.610	journal	August 2014
Light-driven dinitrogen reduction catalyzed by a CdS:nitrogenase MoFe protein biohybrid Brown, K. A.; Harris, D. F.; Wilker, M. B. Science, Vol. 352, Issue 6284 https://doi.org/10.1126/science.aaf2091	journal	April 2016

Similar Records

Atomically Dispersed Molybdenum Catalysts for Efficient Ambient Nitrogen Fixation

Journal Article · Tue Dec 11 19:00:00 EST 2018 · Angewandte Chemie (International Edition) · OSTI ID:1498864

Modulating Single-Atom Palladium Sites with Copper for Enhanced Ambient Ammonia Electrosynthesis

Journal Article · Tue Sep 15 20:00:00 EDT 2020 · Angewandte Chemie · OSTI ID:1737412

Atomically Dispersed Molybdenum Catalysts for Efficient Ambient Nitrogen Fixation

Journal Article · Thu Jan 17 19:00:00 EST 2019 · Angewandte Chemie · OSTI ID:1786172

Related Subjects

77 NANOSCIENCE AND NANOTECHNOLOGY
Ammonia electrosynthesis
FeMo electrocatalyst
Neutral electrolyte
Nitrogen fixation
Single atom
Sub-nanocluster

FeMo sub-nanoclusters/single atoms for neutral ammonia electrosynthesis

Citation Formats

References (53)

Similar Records

Related Subjects