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

Journal Article · Thu Jan 02 00:00:00 EST 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.9b11238· OSTI ID:1592083

Baddour, Frederick G.  ^[1]; Roberts, Emily J. ^[2]; To, Anh T. ^[1]; Wang, Lu  ^[2]; Habas, Susan E. ^[1]; Ruddy, Daniel A.  ^[1]; Bedford, Nicholas M.  ^[3]; Wright, Joshua ^[4]; Nash, Connor P. ^[1]; Schaidle, Joshua A.  ^[1]; Brutchey, Richard L.  ^[2]; Malmstadt, Noah  ^[2]

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

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.

• Research Organization: National Renewable Energy Lab. (NREL), Golden, CO (United States)
• Sponsoring Organization: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Bioenergy Technologies Office
• Grant/Contract Number: AC36-08GO28308; AC02-06CH11357
• OSTI ID: 1592083
• Report Number(s): NREL/JA-5100-75569
• Journal Information: Journal of the American Chemical Society, Vol. 142, Issue 2; ISSN 0002-7863
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: English

Related Subjects

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