Synthesis of α-MoC1-x Nanoparticles with a Surface-Modified SBA-15 Hard Template: Determination of Structure-Function Relationships in Acetic Acid Deoxygenation

Baddour, Frederick G.; Nash, Connor P.; Schaidle, Joshua A.; Ruddy, Daniel A.

doi:10.1002/anie.201602878

Title: Synthesis of α-MoC_1-x Nanoparticles with a Surface-Modified SBA-15 Hard Template: Determination of Structure-Function Relationships in Acetic Acid Deoxygenation

Journal Article · Tue Jun 07 00:00:00 EDT 2016 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201602878· OSTI ID:1274095

Baddour, Frederick G. ^[1]; Nash, Connor P. ^[1]; Schaidle, Joshua A. ^[1]; Ruddy, Daniel A. ^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States). National Bioenergy Center

Surface modification of mesoporous SBA-15 silica generated a hydrophobic environment for a molybdenum diamine (Mo-diamine) precursor solution, enabling direct growth of isolated 1.9 ± 0.4 nm α-MoC_1-x nanoparticles (NPs) inside the pores of the support. The resulting NP catalysts are bifunctional, and compared to bulk α-MoC_1-x and β-Mo₂C, the NPs exhibit a greater acid-site:H-site ratio and a fraction of stronger acid sites. The greater acid-site:H-site ratio results in higher decarbonylation (DCO) selectivity during acetic acid hydrodeoxygenation (HDO) reactions, and the stronger acid sites lead to higher activity and ketonization (KET) selectivity at high temperatures. Lastly, the hard-templating synthetic method could be a versatile route toward carbide NPs of varying size, composition, and phase, on a range of mesoporous oxide supports.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

OSTI ID:: 1274095

Report Number(s):: NREL/JA-5100-66185

Journal Information:: Angewandte Chemie (International Edition), Vol. 55, Issue 31; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 34 works

Citation information provided by
Web of Science

References (28)

Chemical Titration and Transient Kinetic Studies of Site Requirements in Mo ₂ C-Catalyzed Vapor Phase Anisole Hydrodeoxygenation Lee, Wen-Sheng; Kumar, Anurag; Wang, Zhenshu ACS Catalysis, Vol. 5, Issue 7 https://doi.org/10.1021/acscatal.5b00713	journal	June 2015
Compounds of molybdenum and tungsten with high specific surface area Volpe, Leo; Boudart, M. Journal of Solid State Chemistry, Vol. 59, Issue 3 https://doi.org/10.1016/0022-4596(85)90302-0	journal	October 1985
Structure and site evolution of molybdenum carbide catalysts upon exposure to oxygen Sullivan, Mark M.; Held, Jacob T.; Bhan, Aditya Journal of Catalysis, Vol. 326 https://doi.org/10.1016/j.jcat.2015.03.011	journal	June 2015
Urea and Urea Nitrate Decomposition Pathways: A Quantum Chemistry Study Tokmakov, Igor V.; Alavi, Saman; Thompson, Donald L. The Journal of Physical Chemistry A, Vol. 110, Issue 8 https://doi.org/10.1021/jp0564647	journal	March 2006
Nanostructured materials for applications in heterogeneous catalysis Zaera, Francisco Chem. Soc. Rev., Vol. 42, Issue 7 https://doi.org/10.1039/c2cs35261c	journal	January 2013
A Facile Molecular Precursor Route to Metal Phosphide Nanoparticles and Their Evaluation as Hydrodeoxygenation Catalysts Habas, Susan E.; Baddour, Frederick G.; Ruddy, Daniel A. Chemistry of Materials, Vol. 27, Issue 22, p. 7580-7592 https://doi.org/10.1021/acs.chemmater.5b02140	journal	November 2015
Compounds of molybdenum and tungsten with high specific surface area Volpe, Leo; Boudart, M. Journal of Solid State Chemistry, Vol. 59, Issue 3 https://doi.org/10.1016/0022-4596(85)90301-9	journal	October 1985
Multiple Phases of Molybdenum Carbide as Electrocatalysts for the Hydrogen Evolution Reaction Wan, Cheng; Regmi, Yagya N.; Leonard, Brian M. Angewandte Chemie, Vol. 126, Issue 25 https://doi.org/10.1002/ange.201402998	journal	May 2014
Influence of Surface Modification of Ti−SBA15 Catalysts on the Epoxidation Mechanism for Cyclohexene with Aqueous Hydrogen Peroxide Brutchey, Richard L.; Ruddy, Daniel A.; Andersen, Lars K. Langmuir, Vol. 21, Issue 21 https://doi.org/10.1021/la051182j	journal	October 2005
Conceptual Process Design and Techno-Economic Assessment of Ex Situ Catalytic Fast Pyrolysis of Biomass: A Fixed Bed Reactor Implementation Scenario for Future Feasibility Dutta, Abhijit; Schaidle, Joshua A.; Humbird, David Topics in Catalysis, Vol. 59, Issue 1 https://doi.org/10.1007/s11244-015-0500-z	journal	October 2015
Growth of Gd2O3 nanoparticles inside mesoporous silica frameworks Ballem, Mohamed Ali; Söderlind, Fredrik; Nordblad, Per Microporous and Mesoporous Materials, Vol. 168 https://doi.org/10.1016/j.micromeso.2012.10.009	journal	March 2013
Silver nanoparticles synthesized from mesoporous Ag/SBA-15 composites Zhu, Weiping; Han, Yanchun; An, Lijia Microporous and Mesoporous Materials, Vol. 80, Issue 1-3 https://doi.org/10.1016/j.micromeso.2004.12.018	journal	May 2005
Thermal decomposition (pyrolysis) of urea in an open reaction vessel Schaber, Peter M.; Colson, James; Higgins, Steven Thermochimica Acta, Vol. 424, Issue 1-2 https://doi.org/10.1016/j.tca.2004.05.018	journal	December 2004
Selective vapor-phase hydrodeoxygenation of anisole to benzene on molybdenum carbide catalysts Lee, Wen-Sheng; Wang, Zhenshu; Wu, Ryan J. Journal of Catalysis, Vol. 319 https://doi.org/10.1016/j.jcat.2014.07.025	journal	November 2014
Crystal structure and morphology control of molybdenum carbide nanomaterials synthesized from an amine–metal oxide composite Wan, Cheng; Knight, Nicole A.; Leonard, Brian M. Chemical Communications, Vol. 49, Issue 88 https://doi.org/10.1039/c3cc46551a	journal	January 2013
Experimental and Computational Investigation of Acetic Acid Deoxygenation over Oxophilic Molybdenum Carbide: Surface Chemistry and Active Site Identity Schaidle, Joshua A.; Blackburn, Jeffrey; Farberow, Carrie A. ACS Catalysis, Vol. 6, Issue 2 https://doi.org/10.1021/acscatal.5b01930	journal	January 2016
Controlled synthesis of highly dispersed TiO2 nanoparticles using SBA-15 as hard template Zhao, Li; Yu, Jiaguo Journal of Colloid and Interface Science, Vol. 304, Issue 1 https://doi.org/10.1016/j.jcis.2006.08.042	journal	December 2006
Multiple Phases of Molybdenum Carbide as Electrocatalysts for the Hydrogen Evolution Reaction Wan, Cheng; Regmi, Yagya N.; Leonard, Brian M. Angewandte Chemie International Edition, Vol. 53, Issue 25 https://doi.org/10.1002/anie.201402998	journal	May 2014
Metal Nitride and Metal Carbide Nanoparticles by a Soft Urea Pathway Giordano, Cristina; Erpen, Christian; Yao, Weitang Chemistry of Materials, Vol. 21, Issue 21 https://doi.org/10.1021/cm9018953	journal	November 2009
Acetone condensation over molybdenum nitride and carbide catalysts Bej, S. K.; Thompson, L. T. Applied Catalysis A: General, Vol. 264, Issue 2 https://doi.org/10.1016/j.apcata.2003.12.051	journal	June 2004
“Nanocasting”: Using SBA-15 Silicas as Hard Templates to Obtain Ultrasmall Monodispersed γ-Fe ₂ O ₃ Nanoparticles Delahaye, E.; Escax, V.; El Hassan, N. The Journal of Physical Chemistry B, Vol. 110, Issue 51 https://doi.org/10.1021/jp0647075	journal	December 2006
Catalytic performances of platinum doped molybdenum carbide for simultaneous hydrodenitrogenation and hydrodesulfurization Lewandowski, M.; Szymańska-Kolasa, A.; Da Costa, P. Catalysis Today, Vol. 119, Issue 1-4 https://doi.org/10.1016/j.cattod.2006.08.062	journal	January 2007
Acetone Hydrodeoxygenation over Bifunctional Metallic–Acidic Molybdenum Carbide Catalysts Sullivan, Mark M.; Bhan, Aditya ACS Catalysis, Vol. 6, Issue 2 https://doi.org/10.1021/acscatal.5b02656	journal	January 2016
Synthesis of Mo and W Carbide and Nitride Nanoparticles via a Simple “Urea Glass” Route Giordano, Cristina; Erpen, Christian; Yao, Weitang Nano Letters, Vol. 8, Issue 12 https://doi.org/10.1021/nl8018593	journal	December 2008
Recent advances in heterogeneous catalysts for bio-oil upgrading via “ex situ catalytic fast pyrolysis”: catalyst development through the study of model compounds Ruddy, Daniel A.; Schaidle, Joshua A.; Ferrell III, Jack R. Green Chem., Vol. 16, Issue 2 https://doi.org/10.1039/C3GC41354C	journal	January 2014
Tungsten carbides as selective deoxygenation catalysts: experimental and computational studies of converting C3 oxygenates to propene Ren, Hui; Chen, Ying; Huang, Yulin Green Chem., Vol. 16, Issue 2 https://doi.org/10.1039/C3GC41256C	journal	January 2014
Preparation and catalytic properties of transition metal carbides and nitrides Oyama, S. T. Catalysis Today, Vol. 15, Issue 2 https://doi.org/10.1016/0920-5861(92)80175-M	journal	June 1992
Structure–performance relations of molybdenum- and tungsten carbide catalysts for deoxygenation Stellwagen, Daniel R.; Bitter, Johannes H. Green Chemistry, Vol. 17, Issue 1 https://doi.org/10.1039/C4GC01831A	journal	January 2015

Cited By (4)

Valorization of Biomass‐derived Small Oxygenates: Kinetics, Mechanisms and Site Requirements of H ₂ ‐involved Hydrogenation and Deoxygenation Pathways over Heterogeneous Catalysts Shi, Hui ChemCatChem, Vol. 11, Issue 7 https://doi.org/10.1002/cctc.201801828	journal	February 2019
Ultra-small Mo ₂ N on SBA-15 as a highly efficient promoter of low-loading Pd for catalytic hydrogenation Cheng, Xusheng; Wang, Dongxu; Liu, Jiancong Nanoscale, Vol. 10, Issue 47 https://doi.org/10.1039/c8nr06916f	journal	January 2018
Operando NAP-XPS unveils differences in MoO3 and Mo2C during hydrodeoxygenation Murugappan, Karthick; Anderson, Eric M.; Teschner, Detre Nature Catalysis, Vol. 1, Issue 12 https://doi.org/10.1038/s41929-018-0171-9	journal	November 2018
Synergistic effect of Mo–W carbides on selective hydrodeoxygenation of guaiacol to oxygen-free aromatic hydrocarbons Tran, Chi-Cong; Han, Yinglei; Garcia-Perez, Manuel Catalysis Science & Technology, Vol. 9, Issue 6 https://doi.org/10.1039/c8cy02184h	journal	January 2019

Similar Records

Compositional dependence of hydrodeoxygenation pathway selectivity for Ni _{2−
x} Rh _x P nanoparticle catalysts

Journal Article · Tue Aug 08 00:00:00 EDT 2023 · Journal of Materials Chemistry. A · OSTI ID:1274095

LiBretto, Nicole J.; Tacey, Sean A.; Zubair, Muhammad; +9 more

Assessing the Role of Interfacial and Metal Sites in Pt/TiO2-Catalyzed Acetic Acid Hydrodeoxygenation

Conference · Fri May 20 00:00:00 EDT 2022 · OSTI ID:1274095

Tacey, Sean A.; Farberow, Carrie A.

Phosphonic acid modifiers for enhancing selective hydrodeoxygenation over Pt catalysts: The role of the catalyst support

Journal Article · Tue Mar 26 00:00:00 EDT 2019 · Journal of Catalysis · OSTI ID:1274095

Coan, Patrick D.; Griffin, Michael B.; Ciesielski, Peter N.; +1 more

Related Subjects

09 BIOMASS FUELS
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
bifunctional catalysts
biomass conversion
hydrodeoxygenation
metal carbides
surface chemistry

Title: Synthesis of α-MoC1-x Nanoparticles with a Surface-Modified SBA-15 Hard Template: Determination of Structure-Function Relationships in Acetic Acid Deoxygenation

Citation Formats

References (28)

Cited By (4)

Similar Records

Related Subjects

Title: Synthesis of α-MoC_1-x Nanoparticles with a Surface-Modified SBA-15 Hard Template: Determination of Structure-Function Relationships in Acetic Acid Deoxygenation