An Exceptionally Mild and Scalable Solution-Phase Synthesis of Molybdenum Carbide Nanoparticles for Thermocatalytic CO2 Hydrogenation

Baddour, Frederick G.; Roberts, Emily J.; To, Anh T.; Wang, Lu; Habas, Susan E.; Ruddy, Daniel A.; Bedford, Nicholas M.; Wright, Joshua; Nash, Connor P.; Schaidle, Joshua A.; Brutchey, Richard L.; Malmstadt, Noah

doi:10.1021/jacs.9b11238

Title: An Exceptionally Mild and Scalable Solution-Phase Synthesis of Molybdenum Carbide Nanoparticles for Thermocatalytic CO₂ Hydrogenation

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Abstract

Transition metal carbides (TMCs) have demonstrated outstanding potential for utilization in a wide range of catalytic applications because of their inherent multifunctionality and tunable composition. However, the harsh conditions required to prepare these materials have limited the scope of synthetic control over their physical properties. The development of low-temperature, carburization-free routes to prepare TMCs would unlock the versatility of this class of materials, enhance our understanding of their physical properties, and enable their cost-effective production at industrial scales. Here in this paper, we report an exceptionally mild and scalable solution-phase synthesis route to phase-pure molybdenum carbide (α-MoC_1-x) nanoparticles (NPs) in a continuous flow millifluidic reactor. We exploit the thermolytic decomposition of Mo(CO)₆ in the presence of a surface-stabilizing ligand and a high boiling point solvent to yield MoC_1-x NPs that are colloidally stable and resistant to bulk oxidation in air. To demonstrate the utility of this synthetic route to prepare catalytically active TMC NPs, we evaluated the thermochemical CO₂ hydrogenation performance of α-MoC_1-x NPs dispersed on an inert carbon support. The α-MoC_1-x/C catalyst exhibited a 2-fold increase in both activity on a per-site basis and selectivity to C₂₊ products as compared to the bulk α-MoC_1-x analogue.

Authors:

^[1]; Roberts, Emily J. ^[2]; To, Anh T. ^[1];

^[2]; Habas, Susan E. ^[1];

^[1];

^[3]; Wright, Joshua ^[4]; Nash, Connor P. ^[1];

^[1];

^[2];

^[2]

National Renewable Energy Lab. (NREL), Golden, CO (United States). National Bioenergy Center
Univ. of Southern California, Los Angeles, CA (United States)
Univ. of New South Wales, Sydney, NSW (Australia)
Illinois Inst. of Technology, Chicago, IL (United States)

Publication Date:: Thu Jan 02 00:00:00 EST 2020

Research Org.:: National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office

OSTI Identifier:: 1592083

Report Number(s):: NREL/JA-5100-75569
Journal ID: ISSN 0002-7863

Grant/Contract Number:: AC36-08GO28308; AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 142; Journal Issue: 2; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; transition metal carbides; catalysis; nanoparticles; CCTPL

Citation Formats


                    Baddour, Frederick G., Roberts, Emily J., To, Anh T., Wang, Lu, Habas, Susan E., Ruddy, Daniel A., Bedford, Nicholas M., Wright, Joshua, Nash, Connor P., Schaidle, Joshua A., Brutchey, Richard L., and Malmstadt, Noah. An Exceptionally Mild and Scalable Solution-Phase Synthesis of Molybdenum Carbide Nanoparticles for Thermocatalytic CO2 Hydrogenation.  United States: N. p., 2020. 
Web.  doi:10.1021/jacs.9b11238.

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                    Baddour, Frederick G., Roberts, Emily J., To, Anh T., Wang, Lu, Habas, Susan E., Ruddy, Daniel A., Bedford, Nicholas M., Wright, Joshua, Nash, Connor P., Schaidle, Joshua A., Brutchey, Richard L., & Malmstadt, Noah. An Exceptionally Mild and Scalable Solution-Phase Synthesis of Molybdenum Carbide Nanoparticles for Thermocatalytic CO2 Hydrogenation.  United States.  https://doi.org/10.1021/jacs.9b11238

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                    Baddour, Frederick G., Roberts, Emily J., To, Anh T., Wang, Lu, Habas, Susan E., Ruddy, Daniel A., Bedford, Nicholas M., Wright, Joshua, Nash, Connor P., Schaidle, Joshua A., Brutchey, Richard L., and Malmstadt, Noah. Thu .  
"An Exceptionally Mild and Scalable Solution-Phase Synthesis of Molybdenum Carbide Nanoparticles for Thermocatalytic CO2 Hydrogenation".  United States.  https://doi.org/10.1021/jacs.9b11238.  https://www.osti.gov/servlets/purl/1592083.

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@article{osti_1592083,

  title        = {An Exceptionally Mild and Scalable Solution-Phase Synthesis of Molybdenum Carbide Nanoparticles for Thermocatalytic CO2 Hydrogenation},

  author       = {Baddour, Frederick G. and Roberts, Emily J. and To, Anh T. and Wang, Lu and Habas, Susan E. and Ruddy, Daniel A. and Bedford, Nicholas M. and Wright, Joshua and Nash, Connor P. and Schaidle, Joshua A. and Brutchey, Richard L. and Malmstadt, Noah},

  abstractNote = {Transition metal carbides (TMCs) have demonstrated outstanding potential for utilization in a wide range of catalytic applications because of their inherent multifunctionality and tunable composition. However, the harsh conditions required to prepare these materials have limited the scope of synthetic control over their physical properties. The development of low-temperature, carburization-free routes to prepare TMCs would unlock the versatility of this class of materials, enhance our understanding of their physical properties, and enable their cost-effective production at industrial scales. Here in this paper, we report an exceptionally mild and scalable solution-phase synthesis route to phase-pure molybdenum carbide (α-MoC1-x) nanoparticles (NPs) in a continuous flow millifluidic reactor. We exploit the thermolytic decomposition of Mo(CO)6 in the presence of a surface-stabilizing ligand and a high boiling point solvent to yield MoC1-x NPs that are colloidally stable and resistant to bulk oxidation in air. To demonstrate the utility of this synthetic route to prepare catalytically active TMC NPs, we evaluated the thermochemical CO2 hydrogenation performance of α-MoC1-x NPs dispersed on an inert carbon support. The α-MoC1-x/C catalyst exhibited a 2-fold increase in both activity on a per-site basis and selectivity to C2+ products as compared to the bulk α-MoC1-x analogue.},

  doi          = {10.1021/jacs.9b11238},

  journal      = {Journal of the American Chemical Society},

  number       = 2,

  volume       = 142,

  place        = {United States},

  year         = {Thu Jan 02 00:00:00 EST 2020},

  month        = {Thu Jan 02 00:00:00 EST 2020}

}

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Title: An Exceptionally Mild and Scalable Solution-Phase Synthesis of Molybdenum Carbide Nanoparticles for Thermocatalytic CO2 Hydrogenation

Abstract

Citation Formats

Title: An Exceptionally Mild and Scalable Solution-Phase Synthesis of Molybdenum Carbide Nanoparticles for Thermocatalytic CO₂ Hydrogenation