Mechanistic Insights and Rational Design of Ca-Doped CeO2 Catalyst for Acetic Acid Ketonization

Zhou, Mingxia; Church, Aimee Lu; Cordon, Michael J.; Li, Chenyang; Hunt, Rodney Dale; Choi, Jae-Soon; Bai, Lei; Li, Zhenglong; Parks, James E.; Hu, Michael Z.; Curtiss, Larry A.; Assary, Rajeev S.

doi:10.1021/acssuschemeng.1c06675

Mechanistic Insights and Rational Design of Ca-Doped CeO₂ Catalyst for Acetic Acid Ketonization

Journal Article · Tue Aug 16 00:00:00 EDT 2022 · ACS Sustainable Chemistry & Engineering

DOI:https://doi.org/10.1021/acssuschemeng.1c06675· OSTI ID:1885393

^[1]; ^[2]; Cordon, Michael J. ^[2]; ^[1]; ^[2]; ^[3]; Bai, Lei ^[4]; ^[2]; ^[2]; ^[2]; ^[1]; ^[1]

Argonne National Lab. (ANL), Lemont, IL (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); LG Chem, Daejeon (Korea, Republic of)
West Virginia Univ., Morgantown, WV (United States)

Carboxylic acid ketonization has recently gained significant attention to produce biomass-derived hydrocarbon fuels as it not only removes the highly reactive carboxylic functional group but also increases the size of the carbon chain. In this work, Ca-doped CeO₂-based catalysts were investigated for acetic acid ketonization using a combined experimental and computational approach. Acetic acid conversion was performed across a range of temperatures including higher temperatures relevant to catalytic hot gas filtration (450 °C). Ca addition slightly decreases overall acetic acid ketonization reactivity yet stabilizes the catalyst at the higher temperatures necessary for catalytic hot gas filtration. From density functional theory calculations of the ketonization reaction mechanism, the C–C coupling and water formation steps are identified as two of the most energy-consuming steps on a CeO₂ surface with a proximal oxygen vacancy and the presence of a Ca dopant stabilizes the key intermediates. Calculations predict an optimal structure comprising three Ca ensembles to minimize the reaction free energies for C–C coupling and water formation steps. These findings provide a priori information to guide future experiments for ketonization catalyst design and development.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Laboratory Computing Resource Center (LCRC); Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; AC05-00OR22725

OSTI ID:: 1885393

Alternate ID(s):: OSTI ID: 1904179

Journal Information:: ACS Sustainable Chemistry & Engineering, Journal Name: ACS Sustainable Chemistry & Engineering Journal Issue: 34 Vol. 10; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (73)

Synergies between Bio- and Oil Refineries for the Production of Fuels from Biomass Huber, George W.; Corma, Avelino Angewandte Chemie International Edition, Vol. 46, Issue 38, p. 7184-7201 https://doi.org/10.1002/anie.200604504	journal	September 2007
Dehydration of 2-Octanol over Ca-doped CeO ₂ Catalysts Gnanamani, Muthu Kumaran; Jacobs, Gary; Shafer, Wilson D. ChemCatChem, Vol. 9, Issue 3 https://doi.org/10.1002/cctc.201601076	journal	January 2017
Ketonic Decarboxylation Reaction Mechanism: A Combined Experimental and DFT Study Pulido, Angeles; Oliver-Tomas, Borja; Renz, Michael ChemSusChem, Vol. 6, Issue 1 https://doi.org/10.1002/cssc.201200419	journal	November 2012
Ketonization of Carboxylic Acids by Decarboxylation: Mechanism and Scope Renz, Michael European Journal of Organic Chemistry, Vol. 2005, Issue 6 https://doi.org/10.1002/ejoc.200400546	journal	March 2005
Ueber s. g. gemischte Acetone Friedel, C. Annalen der Chemie und Pharmacie, Vol. 108, Issue 1 https://doi.org/10.1002/jlac.18581080124	journal	January 1858
Reactions of Carboxylic Acids on Oxides Pestman, R.; Koster, R. M.; Pieterse, J. A. Z. Journal of Catalysis, Vol. 168, Issue 2 https://doi.org/10.1006/jcat.1997.1623	journal	June 1997
Kinetics and Mechanism of Ketonization of Acetic Acid on Ru/TiO2 Catalyst Pham, Tu N.; Shi, Dachuan; Resasco, Daniel E. Topics in Catalysis, Vol. 57, Issue 6-9 https://doi.org/10.1007/s11244-013-0227-7	journal	November 2013
Generalized cluster description of multicomponent systems Sanchez, J. M.; Ducastelle, F.; Gratias, D. Physica A: Statistical Mechanics and its Applications, Vol. 128, Issue 1-2 https://doi.org/10.1016/0378-4371(84)90096-7	journal	November 1984
Ketones from monocarboxylic acids: Catalytic ketonization over oxide systems Gliński, M.; Kijeński, J.; Jakubowski, A. Applied Catalysis A: General, Vol. 128, Issue 2 https://doi.org/10.1016/0926-860X(95)00082-8	journal	August 1995
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Kinetics of catalyzed acid/acid and acid/aldehyde condensation reactions to non-symmetric ketones Hendren, Travis S.; Dooley, Kerry M. Catalysis Today, Vol. 85, Issue 2-4 https://doi.org/10.1016/S0920-5861(03)00399-7	journal	October 2003
Reaction of carboxylic acids on CeO2(111) and CeO2(100) Stubenrauch, J.; Brosha, E.; Vohs, J. M. Catalysis Today, Vol. 28, Issue 4 https://doi.org/10.1016/S0920-5861(96)00251-9	journal	September 1996
Cerium oxide-based catalysts for production of ketones by acid condensation Randery, S. Applied Catalysis A: General, Vol. 226, Issue 1-2 https://doi.org/10.1016/S0926-860X(01)00912-7	journal	March 2002
Oxide-catalyzed conversion of acetic acid into acetone: an FTIR spectroscopic investigation Hasan, M. A.; Zaki, M. I.; Pasupulety, L. Applied Catalysis A: General, Vol. 243, Issue 1 https://doi.org/10.1016/S0926-860X(02)00539-2	journal	March 2003
Surfaces of doped nanophase cerium oxide catalysts Palmqvist, A. E. C.; Wirde, M.; Gelius, U. Nanostructured Materials, Vol. 11, Issue 8 https://doi.org/10.1016/S0965-9773(00)00431-1	journal	November 1999
Ketones from acid condensation using supported CeO2 catalysts: Effect of additives Dooley, Kerry M.; Bhat, Arvind K.; Plaisance, Craig P. Applied Catalysis A: General, Vol. 320 https://doi.org/10.1016/j.apcata.2007.01.021	journal	March 2007
A review of catalytic upgrading of bio-oil to engine fuels Mortensen, P. M.; Grunwaldt, J.-D.; Jensen, P. A. Applied Catalysis A: General, Vol. 407, Issue 1-2, p. 1-19 https://doi.org/10.1016/j.apcata.2011.08.046	journal	November 2011
Reactivity and reaction intermediates for acetic acid adsorbed on CeO2(1 1 1) Calaza, Florencia C.; Chen, Tsung-Liang; Mullins, David R. Catalysis Today, Vol. 253 https://doi.org/10.1016/j.cattod.2015.03.033	journal	September 2015
Ketonization of oxygenated hydrocarbons on metal oxide based catalysts Kumar, Rawesh; Enjamuri, Nagasuresh; Shah, Sneha Catalysis Today, Vol. 302 https://doi.org/10.1016/j.cattod.2017.09.044	journal	March 2018
A fast and robust algorithm for Bader decomposition of charge density Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes Computational Materials Science, Vol. 36, Issue 3 https://doi.org/10.1016/j.commatsci.2005.04.010	journal	June 2006
Screw pyrolysis with integrated sequential hot gas filtration Tomasi Morgano, Marco; Leibold, Hans; Richter, Frank Journal of Analytical and Applied Pyrolysis, Vol. 113 https://doi.org/10.1016/j.jaap.2014.12.019	journal	May 2015
Ketonization of acetic acid on titania-functionalized silica monoliths Martinez, R. Journal of Catalysis, Vol. 222, Issue 2 https://doi.org/10.1016/j.jcat.2003.12.002	journal	March 2004
Catalytic coupling of carboxylic acids by ketonization as a processing step in biomass conversion Gaertner, Christian A.; Serrano-Ruiz, Juan Carlos; Braden, Drew J. Journal of Catalysis, Vol. 266, Issue 1, p. 71-78 https://doi.org/10.1016/j.jcat.2009.05.015	journal	August 2009
From the Sabatier principle to a predictive theory of transition-metal heterogeneous catalysis Medford, Andrew J.; Vojvodic, Aleksandra; Hummelshøj, Jens S. Journal of Catalysis, Vol. 328 https://doi.org/10.1016/j.jcat.2014.12.033	journal	August 2015
Selective ketonization of acetic acid over HZSM-5: The importance of acyl species and the influence of water Gumidyala, Abhishek; Sooknoi, Tawan; Crossley, Steven Journal of Catalysis, Vol. 340 https://doi.org/10.1016/j.jcat.2016.04.017	journal	August 2016
Acetic acid ketonization on tetragonal zirconia: Role of surface reduction Tosoni, Sergio; Pacchioni, Gianfranco Journal of Catalysis, Vol. 344 https://doi.org/10.1016/j.jcat.2016.10.002	journal	December 2016
Experimental and theoretical assessment of the mechanism and site requirements for ketonization of carboxylic acids on oxides Wang, Shuai; Iglesia, Enrique Journal of Catalysis, Vol. 345 https://doi.org/10.1016/j.jcat.2016.11.006	journal	January 2017
Insights into the improvement effect of Fe doping into the CeO2 catalyst for vapor phase ketonization of carboxylic acids Lu, Feipeng; Jiang, BinBo; Wang, Jingdai Molecular Catalysis, Vol. 444 https://doi.org/10.1016/j.mcat.2017.05.022	journal	January 2018
Ketonization of carboxylic acids over CeO2-based composite oxides Nagashima, Osamu; Sato, Satoshi; Takahashi, Ryoji Journal of Molecular Catalysis A: Chemical, Vol. 227, Issue 1-2 https://doi.org/10.1016/j.molcata.2004.10.042	journal	March 2005
Oxygen nonstoichiometry of nanosized ceria powder Kim, Sangtae; Merkle, Rotraut; Maier, Joachim Surface Science, Vol. 549, Issue 3 https://doi.org/10.1016/j.susc.2003.12.002	journal	February 2004
The electronic structure of oxygen vacancy defects at the low index surfaces of ceria Nolan, Michael; Parker, Stephen C.; Watson, Graeme W. Surface Science, Vol. 595, Issue 1-3 https://doi.org/10.1016/j.susc.2005.08.015	journal	December 2005
Understanding the Secondary Reactions of Flash Pyrolysis Vapors inside a Hot Gas Filtration Unit Ruiz, Miguel; Martin, Eric; Blin, Joël Energy & Fuels, Vol. 31, Issue 12 https://doi.org/10.1021/acs.energyfuels.7b02923	journal	December 2017
Density Functional Theory Study of the Formaldehyde Catalytic Oxidation Mechanism on a Au-Doped CeO₂(111) Surface Jing, Meizan; Song, Weiyu; Chen, Lulu The Journal of Physical Chemistry C, Vol. 122, Issue 1 https://doi.org/10.1021/acs.jpcc.7b09276	journal	December 2017
Ni-Doping Effects on Oxygen Removal from an Orthorhombic Mo ₂ C (001) Surface: A Density Functional Theory Study Zhou, Mingxia; Cheng, Lei; Choi, Jae-Soon The Journal of Physical Chemistry C, Vol. 122, Issue 3 https://doi.org/10.1021/acs.jpcc.7b09870	journal	January 2018
Effect of Ni Dopant on Furan Activation over Mo ₂ C Surface: Insights from First-Principles-Based Microkinetic Modeling Zhou, Mingxia; Doan, Hieu A.; Curtiss, Larry A. The Journal of Physical Chemistry C, Vol. 124, Issue 10 https://doi.org/10.1021/acs.jpcc.9b10126	journal	February 2020
Enhanced Hydrothermal Stability and Catalytic Activity of La _x Zr _y O _z Mixed Oxides for the Ketonization of Acetic Acid in the Aqueous Condensed Phase Lopez-Ruiz, Juan A.; Cooper, Alan R.; Li, Guosheng ACS Catalysis, Vol. 7, Issue 10 https://doi.org/10.1021/acscatal.7b01071	journal	August 2017
Aqueous-Phase Acetic Acid Ketonization over Monoclinic Zirconia Cai, Qiuxia; Lopez-Ruiz, Juan A.; Cooper, Alan R. ACS Catalysis, Vol. 8, Issue 1 https://doi.org/10.1021/acscatal.7b03298	journal	December 2017
Carbon Promoted ZrO ₂ Catalysts for Aqueous-Phase Ketonization of Acetic Acid Wu, Kejing; Yang, Mingde; Pu, Weihua ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 4 https://doi.org/10.1021/acssuschemeng.7b00226	journal	March 2017
Catalytic Hot-Gas Filtration with a Supported Heteropolyacid Catalyst for Preconditioning Biomass Pyrolysis Vapors Peterson, Braden; Engtrakul, Chaiwat; Wilson, A. Nolan ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 17 https://doi.org/10.1021/acssuschemeng.9b03188	journal	August 2019
Reduction Process in CeO ₂ −MO and CeO ₂ −M ₂ O ₃ Mixed Oxides: A Computer Simulation Study Balducci, Gabriele; Islam, M. Saiful; Kašpar, Jan Chemistry of Materials, Vol. 15, Issue 20 https://doi.org/10.1021/cm021289h	journal	October 2003
Concentration of Ce ³⁺ and Oxygen Vacancies in Cerium Oxide Nanoparticles Dutta, P.; Pal, S.; Seehra, M. S. Chemistry of Materials, Vol. 18, Issue 21 https://doi.org/10.1021/cm061580n	journal	October 2006
Highly Enhanced Concentration and Stability of Reactive Ce ³⁺ on Doped CeO ₂ Surface Revealed In Operando Chueh, William C.; McDaniel, Anthony H.; Grass, Michael E. Chemistry of Materials, Vol. 24, Issue 10 https://doi.org/10.1021/cm300574v	journal	May 2012
Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering Huber, George W.; Iborra, Sara; Corma, Avelino Chemical Reviews, Vol. 106, Issue 9, p. 4044-4098 https://doi.org/10.1021/cr068360d	journal	September 2006
Catalysis by Doped Oxides McFarland, Eric W.; Metiu, Horia Chemical Reviews, Vol. 113, Issue 6 https://doi.org/10.1021/cr300418s	journal	December 2012
Insights into the Ceria-Catalyzed Ketonization Reaction for Biofuels Applications Snell, Ryan W.; Shanks, Brent H. ACS Catalysis, Vol. 3, Issue 4 https://doi.org/10.1021/cs400003n	journal	February 2013
Ketonization of Carboxylic Acids: Mechanisms, Catalysts, and Implications for Biomass Conversion Pham, Tu N.; Sooknoi, Tawan; Crossley, Steven P. ACS Catalysis, Vol. 3, Issue 11 https://doi.org/10.1021/cs400501h	journal	October 2013
Ketonization of Carboxylic Acids in Biomass Conversion over TiO ₂ and ZrO ₂ Surfaces: A DFT Perspective Pacchioni, Gianfranco ACS Catalysis, Vol. 4, Issue 9 https://doi.org/10.1021/cs500791w	journal	July 2014
Bio-oil Stabilization and Upgrading by Hot Gas Filtration Baldwin, Robert M.; Feik, Calvin J. Energy & Fuels, Vol. 27, Issue 6 https://doi.org/10.1021/ef400177t	journal	May 2013
Ketonization Reactions of Carboxylic Acids and Esters over Ceria−Zirconia as Biomass-Upgrading Processes Gaertner, Christian A.; Serrano-Ruiz, Juan Carlos; Braden, Drew J. Industrial & Engineering Chemistry Research, Vol. 49, Issue 13 https://doi.org/10.1021/ie1004338	journal	July 2010
Hydrogen Cycle on CeO ₂ (111) Surfaces: Density Functional Theory Calculations Watkins, Matthew B.; Foster, Adam S.; Shluger, Alexander L. The Journal of Physical Chemistry C, Vol. 111, Issue 42 https://doi.org/10.1021/jp071715s	journal	October 2007
In Situ Characterization of Ceria Oxidation States in High-Temperature Electrochemical Cells with Ambient Pressure XPS DeCaluwe, Steven C.; Grass, Michael E.; Zhang, Chunjuan The Journal of Physical Chemistry C, Vol. 114, Issue 46 https://doi.org/10.1021/jp107694z	journal	November 2010
Catalytic conversion of biomass to biofuels Alonso, David Martin; Bond, Jesse Q.; Dumesic, James A. Green Chemistry, Vol. 12, Issue 9, p. 1493-1513 https://doi.org/10.1039/C004654J	journal	January 2010
Conversion of biomass to selected chemical products Gallezot, Pierre Chem. Soc. Rev., Vol. 41, Issue 4 https://doi.org/10.1039/C1CS15147A	journal	January 2012
Catalytic role of vacancy diffusion in ceria supported atomic gold catalyst Han, Zhong-Kang; Wang, Yang-Gang; Gao, Yi Chemical Communications, Vol. 53, Issue 65 https://doi.org/10.1039/C7CC04440B	journal	January 2017
Promotional effect of Ti doping on the ketonization of acetic acid over a CeO ₂ catalyst Lu, Feipeng; Jiang, BinBo; Wang, Jingdai RSC Advances, Vol. 7, Issue 36 https://doi.org/10.1039/C7RA00521K	journal	January 2017
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22 https://doi.org/10.1063/1.1323224	journal	December 2000
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Heteroatom doping effects on interaction of H₂O and CeO₂ (111) surfaces studied using density functional theory: Key roles of ionic radius and dispersion Murakami, Kota; Ogo, Shuhei; Ishikawa, Atsushi The Journal of Chemical Physics, Vol. 152, Issue 1 https://doi.org/10.1063/1.5138670	journal	January 2020
A grid-based Bader analysis algorithm without lattice bias Tang, W.; Sanville, E.; Henkelman, G. Journal of Physics: Condensed Matter, Vol. 21, Issue 8 https://doi.org/10.1088/0953-8984/21/8/084204	journal	January 2009
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium Kresse, G.; Hafner, J. Physical Review B, Vol. 49, Issue 20, p. 14251-14269 https://doi.org/10.1103/PhysRevB.49.14251	journal	May 1994
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
Linear response approach to the calculation of the effective interaction parameters in the LDA + U method Cococcioni, Matteo; de Gironcoli, Stefano Physical Review B, Vol. 71, Issue 3 https://doi.org/10.1103/PhysRevB.71.035105	journal	January 2005
Taming multiple valency with density functionals: A case study of defective ceria Fabris, Stefano; de Gironcoli, Stefano; Baroni, Stefano Physical Review B, Vol. 71, Issue 4 https://doi.org/10.1103/PhysRevB.71.041102	journal	January 2005
Efficient generation of generalized Monkhorst-Pack grids through the use of informatics Wisesa, Pandu; McGill, Kyle A.; Mueller, Tim Physical Review B, Vol. 93, Issue 15 https://doi.org/10.1103/PhysRevB.93.155109	journal	April 2016
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Structural Relaxation Made Simple Bitzek, Erik; Koskinen, Pekka; Gähler, Franz Physical Review Letters, Vol. 97, Issue 17 https://doi.org/10.1103/PhysRevLett.97.170201	journal	October 2006
Acetic Acid/Propionic Acid Conversion on Metal Doped Molybdenum Carbide Catalyst Beads for Catalytic Hot Gas Filtration Lu, Mi; Lepore, Andrew; Choi, Jae-Soon Catalysts, Vol. 8, Issue 12 https://doi.org/10.3390/catal8120643	journal	December 2018
Rapid Generation of Optimal Generalized Monkhorst-Pack Grids Wang, Yunzhe; Wisesa, Pandu; Balasubramanian, Adarsh arXiv https://doi.org/10.48550/arXiv.1907.13610	text	January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Mechanistic Insights and Rational Design of Ca-Doped CeO2 Catalyst for Acetic Acid Ketonization

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Mechanistic Insights and Rational Design of Ca-Doped CeO₂ Catalyst for Acetic Acid Ketonization