Microwave-Mediated ammonia synthesis over Co2Mo3N catalysts at low pressures

Dutta, Biswanath; Wildfire, Christina; Shekhawat, Dushyant

doi:10.1016/j.cej.2024.152924

Microwave-Mediated ammonia synthesis over Co₂Mo₃N catalysts at low pressures

Journal Article · Fri Jun 07 00:00:00 EDT 2024 · Chemical Engineering Journal

DOI:https://doi.org/10.1016/j.cej.2024.152924· OSTI ID:2432333

^[1]; Wildfire, Christina ^[2]; Shekhawat, Dushyant ^[2]

National Energy Technology Laboratory (NETL), Pittsburgh, PA (United States); NETL Support Contractor, Pittsburgh, PA (United States)
National Energy Technology Laboratory (NETL), Morgantown, WV (United States)

The Haber-Bosch process for ammonia (NH₃) synthesis is a major contributor to greenhouse gas emissions and is responsible for > 2 % of the world’s energy consumption each year encouraging the need for alternative renewable-based options. Here, this study investigates an earth-abundant ternary metal nitride (i.e., Co₂Mo₃N) catalyst to develop a renewable-based NH₃ synthesis approach, utilizing an energy-efficient microwave-assisted route. Using a combination of spectroscopic and catalytic measurements coupled with surface analysis techniques, Co₂Mo₃N was evaluated as a stable and efficient NH₃ synthesis catalyst. Results presented here demonstrate NH₃ synthesis on Co₂Mo₃N at ~420 °C and ambient pressure yield ~0.7 mmolNH3.g_cat^-1.h^-1 and up to ~12 mmol_NH3.g_cat^-1.h^-1 at 28 bar under microwave irradiation. Co₂Mo₃N displayed an activation energy of ~72 kJ.mol^-1 and yielded NH₃ following first-order kinetics with respect to both H₂ and N₂. These studies illustrate the potential of using this catalyst for a sustainable, cost-effective, and environmentally friendly approach to producing NH₃.

View Accepted Manuscript (DOE)

Research Organization:: National Energy Technology Laboratory (NETL), Pittsburgh, PA, Morgantown, WV, and Albany, OR (United States)

Sponsoring Organization:: USDOE Office of Fossil Energy and Carbon Management (FECM); USDOE Advanced Research Projects Agency - Energy (ARPA-E)

OSTI ID:: 2432333

Journal Information:: Chemical Engineering Journal, Journal Name: Chemical Engineering Journal Vol. 494; ISSN 1385-8947

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (44)

Development and Recent Progress on Ammonia Synthesis Catalysts for Haber–Bosch Process Humphreys, John; Lan, Rong; Tao, Shanwen Advanced Energy and Sustainability Research, Vol. 2, Issue 1 https://doi.org/10.1002/aesr.202000043	journal	December 2020
Enhanced sulfur‐resistant methanation performance over MoO₃–ZrO₂ catalyst prepared by solution combustion method Ullah, Niamat; Qu, Jianglei; Li, Zhenhua Applied Organometallic Chemistry, Vol. 33, Issue 9 https://doi.org/10.1002/aoc.5022	journal	July 2019
ChemInform Abstract: The Simultaneous Powder X‐Ray and Neutron Diffraction Refinement of Two η‐Carbide Type Nitrides, Fe₃Mo₃N and Co₃Mo₃N, Prepared by Ammonolysis and by Plasma Nitridation of Oxide Precursors. Jackson, Shalawn K.; Layland, Ralph C.; zur Loye, Hans‐Conrad ChemInform, Vol. 30, Issue 50 https://doi.org/10.1002/chin.199950031	journal	December 1999
TPD and TPR Studies of Molybdenum Nitride Wei, Zhaobin; Xin, Qin; Grange, P. Journal of Catalysis, Vol. 168, Issue 2 https://doi.org/10.1006/jcat.1997.1641	journal	June 1997
Transient response study of NO reduction with H2 on Co4N/γ-Al2O3 catalyst Yao, Zhiwei; Zhang, Xiaohong Reaction Kinetics, Mechanisms and Catalysis, Vol. 109, Issue 2 https://doi.org/10.1007/s11144-013-0560-7	journal	March 2013
Effect of iron oxide precursor on the properties and ammonia synthesis activity of fused iron catalysts Jafari, Ali; Ebadi, Abbas; Sahebdelfar, Saeed Reaction Kinetics, Mechanisms and Catalysis, Vol. 126, Issue 1 https://doi.org/10.1007/s11144-018-1498-6	journal	November 2018
Electrochemical Synthesis of Ammonia Based on Co3Mo3N Catalyst and LiAlO2–(Li,Na,K)2CO3 Composite Electrolyte Amar, Ibrahim A.; Lan, Rong; Petit, Christophe T. G. Electrocatalysis, Vol. 6, Issue 3 https://doi.org/10.1007/s12678-014-0242-x	journal	December 2014
An XPS and TPR study of the reduction of promoted cobalt-kieselguhr Fischer-Tropsch catalysts Sexton, B. Journal of Catalysis, Vol. 97, Issue 2 https://doi.org/10.1016/0021-9517(86)90011-4	journal	February 1986
Electrochromic colour centres in amorphous tungsten trioxide thin films☆ Gabrusenoks, J.; Cikmach, P.; Lusis, A. Solid State Ionics, Vol. 14, Issue 1 https://doi.org/10.1016/0167-2738(84)90006-7	journal	September 1984
XPS study of as-prepared and reduced molybdenum oxides Choi, J. -G.; Thompson, L. T. Applied Surface Science, Vol. 93, Issue 2 https://doi.org/10.1016/0169-4332(95)00317-7	journal	February 1996
Facile synthesis of interstitial metal nitrides with the filled β-manganese structure Prior, Timothy J.; Battle, Peter D. Journal of Solid State Chemistry, Vol. 172, Issue 1 https://doi.org/10.1016/S0022-4596(02)00171-8	journal	April 2003
Valence band photoemission study of the TiMoN system Sanjinés, R.; Wiemer, C.; Almeida, J. Thin Solid Films, Vol. 290-291 https://doi.org/10.1016/S0040-6090(96)09082-7	journal	December 1996
Cobalt molybdenum bimetallic nitride catalysts for ammonia synthesis Kojima, Ryoichi; Aika, Ken-ichi Applied Catalysis A: General, Vol. 215, Issue 1-2 https://doi.org/10.1016/S0926-860X(01)00529-4	journal	July 2001
A novel fused iron catalyst for ammonia synthesis promoted with rare earth gangue Yu, Xiujin; Lin, Bingyu; Lin, Jianxin Journal of Rare Earths, Vol. 26, Issue 5 https://doi.org/10.1016/S1002-0721(08)60168-4	journal	October 2008
The role of preparation route upon the ambient pressure ammonia synthesis activity of Ni2Mo3N Bion, N.; Can, F.; Cook, J. Applied Catalysis A: General, Vol. 504 https://doi.org/10.1016/j.apcata.2014.10.030	journal	September 2015
Microwave-enhanced catalytic ammonia synthesis under moderate pressure and temperature Wang, Yuxin; Khan, Tuhin S.; Wildfire, Christina Catalysis Communications, Vol. 159 https://doi.org/10.1016/j.catcom.2021.106344	journal	November 2021
Microwave-assisted ammonia synthesis over Cs-Ru/CeO2 catalyst at ambient pressure: Effects of metal loading and support particle size Araia, Alazar; Wang, Yuxin; Robinson, Brandon Catalysis Communications, Vol. 170 https://doi.org/10.1016/j.catcom.2022.106491	journal	October 2022
Plasma N2-fixation: 1900–2014 Patil, B. S.; Wang, Q.; Hessel, V. Catalysis Today, Vol. 256 https://doi.org/10.1016/j.cattod.2015.05.005	journal	November 2015
Microwave-driven heterogeneous catalysis for activation of dinitrogen to ammonia under atmospheric pressure Hu, Jianli; Wildfire, Christina; Stiegman, Albert E. Chemical Engineering Journal, Vol. 397 https://doi.org/10.1016/j.cej.2020.125388	journal	October 2020
Exemplification of catalyst design for microwave selective heating and its application to efficient in situ catalyst synthesis Wang, Kaiyang; Dimitrakis, Georgios; Irvine, Derek J. Chemical Engineering and Processing: Process Intensification, Vol. 122 https://doi.org/10.1016/j.cep.2017.01.012	journal	December 2017
Co3Mo3N nanosheets arrays on nickel foam as highly efficient bifunctional electrocatalysts for overall urea electrolysis Tong, Rui; Xu, Miao; Huang, Haiming International Journal of Hydrogen Energy, Vol. 47, Issue 22 https://doi.org/10.1016/j.ijhydene.2022.01.181	journal	March 2022
Lowering reaction temperature: Electrochemical ammonia synthesis by coupling various electrolytes and catalysts Guo, Xinghua; Zhu, Yunpei; Ma, Tianyi Journal of Energy Chemistry, Vol. 26, Issue 6 https://doi.org/10.1016/j.jechem.2017.09.012	journal	November 2017
The influence of phase and morphology of molybdenum nitrides on ammonia synthesis activity and reduction characteristics Mckay, D.; Hargreaves, J. S. J.; Rico, J. L. Journal of Solid State Chemistry, Vol. 181, Issue 2 https://doi.org/10.1016/j.jssc.2007.12.001	journal	February 2008
Kinetics of ammonia synthesis over Ru/Pr2O3 Imamura, Kazuya; Miyahara, Shin-ichiro; Kawano, Yukiko Journal of the Taiwan Institute of Chemical Engineers, Vol. 105 https://doi.org/10.1016/j.jtice.2019.10.006	journal	December 2019
The enhancement of the magnetic properties of α-Fe2O3 nanocatalyst using an external magnetic field for the production of green ammonia Alqasem, Bilal; Yahya, Noorhana; Qureshi, Saima Materials Science and Engineering: B, Vol. 217 https://doi.org/10.1016/j.mseb.2016.12.002	journal	March 2017
Ammonia for power Valera-Medina, A.; Xiao, H.; Owen-Jones, M. Progress in Energy and Combustion Science, Vol. 69 https://doi.org/10.1016/j.pecs.2018.07.001	journal	November 2018
Designing Local Microwave Heating of Metal Nanoparticles/Metal Oxide Substrate Composites Ano, Taishi; Tsubaki, Shuntaro; Fujii, Satoshi The Journal of Physical Chemistry C, Vol. 125, Issue 43 https://doi.org/10.1021/acs.jpcc.1c06650	journal	October 2021
Low-T Mechanisms of Ammonia Synthesis on Co ₃ Mo ₃ N Zeinalipour-Yazdi, Constantinos D.; Hargreaves, Justin S. J.; Catlow, C. Richard A. The Journal of Physical Chemistry C, Vol. 122, Issue 11 https://doi.org/10.1021/acs.jpcc.7b12364	journal	January 2018
Enhancement of Ammonia Synthesis on a Co ₃ Mo ₃ N-Ag Electrocatalyst in a K-βAl ₂ O ₃ Solid Electrolyte Cell Díez-Ramírez, J.; Kyriakou, V.; Garagounis, I. ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 10 https://doi.org/10.1021/acssuschemeng.7b01618	journal	August 2017
Topotactic Nitrogen Transfer: Structural Transformation in Cobalt Molybdenum Nitrides Hunter, Stuart M.; Mckay, David; Smith, Ronald I. Chemistry of Materials, Vol. 22, Issue 9 https://doi.org/10.1021/cm100208a	journal	May 2010
Catalyst Design by Interpolation in the Periodic Table: Bimetallic Ammonia Synthesis Catalysts Jacobsen, Claus J. H.; Dahl, Søren; Clausen, Bjerne S. Journal of the American Chemical Society, Vol. 123, Issue 34 https://doi.org/10.1021/ja010963d	journal	August 2001
Ammonia Dissociation on Pt{100}, Pt{111}, and Pt{211}: A Comparative Density Functional Theory Study Offermans, W. K.; Jansen, A. P. J.; van Santen, R. A. The Journal of Physical Chemistry C, Vol. 111, Issue 47 https://doi.org/10.1021/jp073083f	journal	November 2007
Microwave-Specific Enhancement of the Carbon–Carbon Dioxide (Boudouard) Reaction Hunt, Jacob; Ferrari, Anthony; Lita, Adrian The Journal of Physical Chemistry C, Vol. 117, Issue 51, p. 26871-26880 https://doi.org/10.1021/jp4076965	journal	November 2013
Structure and Electronic Properties of Solid Acids Based on Tungsten Oxide Nanostructures Barton, David G.; Shtein, Max; Wilson, Ryan D. The Journal of Physical Chemistry B, Vol. 103, Issue 4 https://doi.org/10.1021/jp983555d	journal	January 1999
Boosting CO2 hydrogenation via size-dependent metal–support interactions in cobalt/ceria-based catalysts Parastaev, Alexander; Muravev, Valery; Huertas Osta, Elisabet Nature Catalysis, Vol. 3, Issue 6 https://doi.org/10.1038/s41929-020-0459-4	journal	May 2020
Kinetic evidence: the rate-determining step for ammonia synthesis over electride-supported Ru catalysts is no longer the nitrogen dissociation step Kobayashi, Yasukazu; Kitano, Masaaki; Kawamura, Shigeki Catalysis Science & Technology, Vol. 7, Issue 1 https://doi.org/10.1039/C6CY01962E	journal	January 2017
Bimetallic molybdenum nitride Co ₃ Mo ₃ N: a new promising catalyst for CO ₂ reforming of methane Fu, Xiaojuan; Su, Haiquan; Yin, Wenchao Catalysis Science & Technology, Vol. 7, Issue 8 https://doi.org/10.1039/C6CY02428A	journal	January 2017
Ammonia synthesis from nitrogen and water at intermediate temperatures and elevated pressures by using an electrochemical hydrogen-membrane reactor with supported Ru catalysts and phosphate electrolytes Imamura, Kanako; Kubota, Jun Sustainable Energy & Fuels, Vol. 3, Issue 6 https://doi.org/10.1039/C9SE00049F	journal	January 2019
Novel class of ammonia synthesis catalysts Jacobsen, Claus J. H. Chemical Communications, Issue 12 https://doi.org/10.1039/b002930k	journal	January 2000
Surface Science and Catalysis—Studies on the Mechanism of Ammonia Synthesis: The P. H. Emmett Award Address Ertl, G. Catalysis Reviews, Vol. 21, Issue 2 https://doi.org/10.1080/03602458008067533	journal	January 1980
Impact of organic capping layer on the magnetic anisotropy of ultrathin Co films Gladczuk, L.; Lasek, K.; Puzniak, R. Journal of Physics D: Applied Physics, Vol. 50, Issue 48 https://doi.org/10.1088/1361-6463/aa9308	journal	November 2017
Theoretical structure determination of γ − Al 2 O 3 Gutiérrez, Gonzalo; Taga, Adrian; Johansson, Börje Physical Review B, Vol. 65, Issue 1 https://doi.org/10.1103/PhysRevB.65.012101	journal	November 2001
Hydrogen Production From Water Electrolysis: Current Status and Future Trends Ursua, Alfredo; Gandia, Luis M.; Sanchis, Pablo Proceedings of the IEEE, Vol. 100, Issue 2 https://doi.org/10.1109/JPROC.2011.2156750	journal	February 2012
Non-Thermal Plasma for Process and Energy Intensification in Dry Reforming of Methane Abiev, Rufat Sh.; Sladkovskiy, Dmitry A.; Semikin, Kirill V. Catalysts, Vol. 10, Issue 11 https://doi.org/10.3390/catal10111358	journal	November 2020

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Microwave-Mediated ammonia synthesis over Co2Mo3N catalysts at low pressures

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Microwave-Mediated ammonia synthesis over Co₂Mo₃N catalysts at low pressures