Atomic Molybdenum for Synthesis of Ammonia with 50% Faradic Efficiency

Zhang, Chenhao; Wang, Zhe; Lei, Jincheng; Ma, Lu; Yakobson, Boris I.; Tour, James M.

doi:10.1002/smll.202106327

Atomic Molybdenum for Synthesis of Ammonia with 50% Faradic Efficiency

Journal Article · Fri Mar 11 23:00:00 EST 2022 · Small

DOI:https://doi.org/10.1002/smll.202106327· OSTI ID:1889637

Zhang, Chenhao ^[1]; Wang, Zhe ^[1]; Lei, Jincheng ^[1]; Ma, Lu ^[2]; Yakobson, Boris I. ^[1]; ^[1]

Rice Univ., Houston, TX (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

The electrochemical dinitrogen (N₂) reduction reaction (NRR) under ambient conditions has gained significant interest as an environmentally friendly alternative to the traditional Haber–Bosch process for the synthesis of ammonia (NH₃). However, up to now, most of the reported NRR electrocatalysts with satisfactory catalytic activities have been hindered by the large overpotential in N₂ activation. The preparation of highly efficient Mo-based NRR electrocatalyst in acidic electrolytes under ambient conditions is demonstrated here, consisting of stabilized single Mo atoms anchored on holey nitrogen-doped graphene synthesized through a convenient potassium-salt-assisted activation method. At -0.05 V versus a reversible hydrogen electrode (RHE), an electrode consisting of the resultant electrocatalyst immobilized on carbon fiber paper can attain an exceptional Faradaic efficiency of 50.2% and a NH3 yield rate of 3.6 µg h^-1 mg_cat^-1 with low overpotentials. Density functional theory calculations further unveil that compared to the original graphene without holes, the edge coordinated Mo atoms and the existence of vacancies on holey graphene lower the overpotential of N₂ reduction, thereby promoting the NRR catalytic activity. Finally, this work could provide new guidelines for future designs in single-atom catalysis that would be beneficial to ambient N₂ fixation, and replacement of classical synthesis processes that are very energy-intensive.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); US Air Force Office of Scientific Research (AFOSR)

Grant/Contract Number:: SC0012704

OSTI ID:: 1889637

Alternate ID(s):: OSTI ID: 1854640

Report Number(s):: BNL-223488-2022-JAAM

Journal Information:: Small, Journal Name: Small Journal Issue: 15 Vol. 18; ISSN 1613-6810

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (41)

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
Electrochemical CO ₂ Reduction with Atomic Iron-Dispersed on Nitrogen-Doped Graphene Zhang, Chenhao; Yang, Shize; Wu, Jingjie Advanced Energy Materials, Vol. 8, Issue 19 https://doi.org/10.1002/aenm.201703487	journal	March 2018
A Review of Electrocatalytic Reduction of Dinitrogen to Ammonia under Ambient Conditions Cui, Xiaoyang; Tang, Cheng; Zhang, Qiang Advanced Energy Materials, Vol. 8, Issue 22 https://doi.org/10.1002/aenm.201800369	journal	May 2018
The Haber-Bosch Process Revisited: On the Real Structure and Stability of “Ammonia Iron” under Working Conditions Kandemir, Timur; Schuster, Manfred E.; Senyshyn, Anatoliy Angewandte Chemie International Edition, Vol. 52, Issue 48 https://doi.org/10.1002/anie.201305812	journal	October 2013
The Challenge of Electrochemical Ammonia Synthesis: A New Perspective on the Role of Nitrogen Scaling Relations Montoya, Joseph H.; Tsai, Charlie; Vojvodic, Aleksandra ChemSusChem, Vol. 8, Issue 13 https://doi.org/10.1002/cssc.201500322	journal	June 2015
Nitrogen Fixation by Ru Single-Atom Electrocatalytic Reduction Tao, Hengcong; Choi, Changhyeok; Ding, Liang-Xin Chem, Vol. 5, Issue 1 https://doi.org/10.1016/j.chempr.2018.10.007	journal	January 2019
Chemical forms of molybdenum ion in nitric acid solution studied using liquid-phase X-ray absorption fine structure, Ultraviolet–Visible absorption spectroscopy and first-principles calculations Watanabe, Shinta; Sato, Toshikazu; Nakaya, Masato Chemical Physics Letters, Vol. 723 https://doi.org/10.1016/j.cplett.2019.02.049	journal	May 2019
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
Spectrophotometric Method for Determination of Hydrazine Watt, G. W.; Chrisp, J. D. Analytical Chemistry, Vol. 24, Issue 12 https://doi.org/10.1021/ac60072a044	journal	December 1952
Spectrophotometric Determination of Ammonia as Indophenol Bolleter, W. T.; Bushman, C. J.; Tidwell, P. W. Analytical Chemistry, Vol. 33, Issue 4 https://doi.org/10.1021/ac60172a034	journal	April 1961
Chemical Synthesis of Single Atomic Site Catalysts Ji, Shufang; Chen, Yuanjun; Wang, Xiaolu Chemical Reviews, Vol. 120, Issue 21 https://doi.org/10.1021/acs.chemrev.9b00818	journal	April 2020
Single Molybdenum Atom Anchored on N-Doped Carbon as a Promising Electrocatalyst for Nitrogen Reduction into Ammonia at Ambient Conditions Ling, Chongyi; Bai, Xiaowan; Ouyang, Yixin The Journal of Physical Chemistry C, Vol. 122, Issue 29 https://doi.org/10.1021/acs.jpcc.8b05257	journal	July 2018
Electrochemical Nitrogen Reduction Reaction Performance of Single-Boron Catalysts Tuned by MXene Substrates Zheng, Shisheng; Li, Shunning; Mei, Zongwei The Journal of Physical Chemistry Letters, Vol. 10, Issue 22 https://doi.org/10.1021/acs.jpclett.9b02741	journal	October 2019
Electrochemical Ammonia Synthesis—The Selectivity Challenge Singh, Aayush R.; Rohr, Brian A.; Schwalbe, Jay A. ACS Catalysis, Vol. 7, Issue 1 https://doi.org/10.1021/acscatal.6b03035	journal	December 2016
The Use of Controls for Consistent and Accurate Measurements of Electrocatalytic Ammonia Synthesis from Dinitrogen Greenlee, Lauren F.; Renner, Julie N.; Foster, Shelby L. ACS Catalysis, Vol. 8, Issue 9 https://doi.org/10.1021/acscatal.8b02120	journal	July 2018
Rational Electrode–Electrolyte Design for Efficient Ammonia Electrosynthesis under Ambient Conditions Suryanto, Bryan H. R.; Kang, Colin S. M.; Wang, Dabin ACS Energy Letters, Vol. 3, Issue 6 https://doi.org/10.1021/acsenergylett.8b00487	journal	April 2018
Single-Atomic Ruthenium Catalytic Sites on Nitrogen-Doped Graphene for Oxygen Reduction Reaction in Acidic Medium Zhang, Chenhao; Sha, Junwei; Fei, Huilong ACS Nano, Vol. 11, Issue 7 https://doi.org/10.1021/acsnano.7b02148	journal	June 2017
Dinitrogen Coordination Chemistry: On the Biomimetic Borderlands MacKay, Bruce A.; Fryzuk, Michael D. Chemical Reviews, Vol. 104, Issue 2 https://doi.org/10.1021/cr020610c	journal	February 2004
Mechanism of Nitrogen Fixation by Nitrogenase: The Next Stage Hoffman, Brian M.; Lukoyanov, Dmitriy; Yang, Zhi-Yong Chemical Reviews, Vol. 114, Issue 8 https://doi.org/10.1021/cr400641x	journal	January 2014
Building Up a Picture of the Electrocatalytic Nitrogen Reduction Activity of Transition Metal Single-Atom Catalysts Liu, Xin; Jiao, Yan; Zheng, Yao Journal of the American Chemical Society, Vol. 141, Issue 24 https://doi.org/10.1021/jacs.9b03811	journal	April 2019
Tackling the Activity and Selectivity Challenges of Electrocatalysts toward the Nitrogen Reduction Reaction via Atomically Dispersed Biatom Catalysts Guo, Xiangyu; Gu, Jinxing; Lin, Shiru Journal of the American Chemical Society, Vol. 142, Issue 12 https://doi.org/10.1021/jacs.9b13349	journal	February 2020
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode Nørskov, J. K.; Rossmeisl, J.; Logadottir, A. The Journal of Physical Chemistry B, Vol. 108, Issue 46 https://doi.org/10.1021/jp047349j	journal	November 2004
Probing the Nature of Defects in Graphene by Raman Spectroscopy Eckmann, Axel; Felten, Alexandre; Mishchenko, Artem Nano Letters, Vol. 12, Issue 8 https://doi.org/10.1021/nl300901a	journal	July 2012
Carbon-based metal-free catalysts Liu, Xien; Dai, Liming Nature Reviews Materials, Vol. 1, Issue 11 https://doi.org/10.1038/natrevmats.2016.64	journal	September 2016
An Earth-system perspective of the global nitrogen cycle Gruber, Nicolas; Galloway, James N. Nature, Vol. 451, Issue 7176 https://doi.org/10.1038/nature06592	journal	January 2008
Atomic cobalt on nitrogen-doped graphene for hydrogen generation Fei, Huilong; Dong, Juncai; Arellano-Jiménez, M. Josefina Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9668	journal	October 2015
How a century of ammonia synthesis changed the world Erisman, Jan Willem; Sutton, Mark A.; Galloway, James Nature Geoscience, Vol. 1, Issue 10 https://doi.org/10.1038/ngeo325	journal	September 2008
Single-atom catalysts reveal the dinuclear characteristic of active sites in NO selective reduction with NH3 Qu, Weiye; Liu, Xiaona; Chen, Junxiao Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15261-5	journal	March 2020
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
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
A theoretical evaluation of possible transition metal electro-catalysts for N ₂ reduction Skúlason, Egill; Bligaard, Thomas; Gudmundsdóttir, Sigrídur Phys. Chem. Chem. Phys., Vol. 14, Issue 3 https://doi.org/10.1039/C1CP22271F	journal	January 2012
Nitrogenase bioelectrocatalysis: heterogeneous ammonia and hydrogen production by MoFe protein Milton, Ross D.; Abdellaoui, Sofiene; Khadka, Nimesh Energy & Environmental Science, Vol. 9, Issue 8 https://doi.org/10.1039/C6EE01432A	journal	January 2016
How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels Peterson, Andrew A.; Abild-Pedersen, Frank; Studt, Felix Energy & Environmental Science, Vol. 3, Issue 9 https://doi.org/10.1039/c0ee00071j	journal	January 2010
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Nitrogenase MoFe-Protein at 1.16 A Resolution: A Central Ligand in the FeMo-Cofactor Einsle, O. Science, Vol. 297, Issue 5587 https://doi.org/10.1126/science.1073877	journal	September 2002
Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center Yandulov, D. V. Science, Vol. 301, Issue 5629 https://doi.org/10.1126/science.1085326	journal	July 2003
N2 Reduction and Hydrogenation to Ammonia by a Molecular Iron-Potassium Complex Rodriguez, M. M.; Bill, E.; Brennessel, W. W. Science, Vol. 334, Issue 6057 https://doi.org/10.1126/science.1211906	journal	November 2011
Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts Guo, D.; Shibuya, R.; Akiba, C. Science, Vol. 351, Issue 6271 https://doi.org/10.1126/science.aad0832	journal	January 2016
Atomically dispersed Fe ³⁺ sites catalyze efficient CO ₂ electroreduction to CO Gu, Jun; Hsu, Chia-Shuo; Bai, Lichen Science, Vol. 364, Issue 6445 https://doi.org/10.1126/science.aaw7515	journal	June 2019

Similar Records

Prediction of Highly Selective Electrocatalytic Nitrogen Reduction at Low Overpotential on a Mo-Doped g-GaN Monolayer

Journal Article · Tue Oct 20 00:00:00 EDT 2020 · ACS Catalysis · OSTI ID:1808601

Ketjenblack-Supported and Unsupported ZrO₂–ZrN Nanoparticle Systems for Enabling Efficient Electrochemical Nitrogen Reduction to Ammonia

Journal Article · Wed Dec 25 23:00:00 EST 2024 · ACS Applied Materials and Interfaces · OSTI ID:2503910

Related Subjects

36 MATERIALS SCIENCE
atomic molybdenum
electrochemical N2 reduction reaction
holey graphene
nitrogen-doped graphene
single-atom catalysts

Atomic Molybdenum for Synthesis of Ammonia with 50% Faradic Efficiency

Citation Formats

References (41)

Similar Records

Related Subjects