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

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)

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

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Bioenergy Technologies Office (EE-3B)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1274095

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

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

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (33)

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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
“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
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
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
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
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
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
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
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
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
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
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
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

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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
W ₂ C nanorods with various amounts of vacancy defects: determination of catalytic active sites in the hydrodeoxygenation of benzofuran Liu, Rong; Pang, Min; Chen, Xiaozhen Catalysis Science & Technology, Vol. 7, Issue 6 https://doi.org/10.1039/c6cy02702d	journal	January 2017
Advances in porous and nanoscale catalysts for viable biomass conversion Sudarsanam, Putla; Peeters, Elise; Makshina, Ekaterina V. Chemical Society Reviews, Vol. 48, Issue 8 https://doi.org/10.1039/c8cs00452h	journal	January 2019
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
Driving towards cost-competitive biofuels through catalytic fast pyrolysis by rethinking catalyst selection and reactor configuration Griffin, Michael B.; Iisa, Kristiina; Wang, Huamin Energy & Environmental Science, Vol. 11, Issue 10 https://doi.org/10.1039/c8ee01872c	journal	January 2018
Hydrodeoxygenation of biomass-derived oxygenates over metal carbides: from model surfaces to powder catalysts Lin, Zhexi; Chen, Rui; Qu, Zhenping Green Chemistry, Vol. 20, Issue 12 https://doi.org/10.1039/c8gc00239h	journal	January 2018
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

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