Elucidation of Active Sites in Aldol Condensation of Acetone over Single-Facet Dominant Anatase TiO2 (101) and (001) Catalysts

Lin, Fan; Wang, Huamin; Zhao, Yuntao; Fu, Jia; Mei, Donghai; Jaegers, Nicholas R.; Gao, Feng; Wang, Yong

doi:10.1021/jacsau.0c00028

Elucidation of Active Sites in Aldol Condensation of Acetone over Single-Facet Dominant Anatase TiO₂ (101) and (001) Catalysts

Journal Article · Tue Dec 15 00:00:00 EST 2020 · JACS Au

DOI:https://doi.org/10.1021/jacsau.0c00028· OSTI ID:1783813

Lin, Fan ^[1]; ^[1]; Zhao, Yuntao ^[1]; Fu, Jia ^[2]; ^[3]; ^[4]; ^[1]; ^[4]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Tiangong University, Tianjin (China)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Tiangong University, Tianjin (China)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)

Aldol condensations of carbonyl compounds for C–C bond formation are a very important class of reactions in organic synthesis and upgrading of biomass-derived feedstocks. However, the atomic level understanding of reaction mechanisms and structure-activity correlation on widely used transition metal oxide catalysts are limited due to the high degree of struc-tural heterogeneity of catalysts such as commercial TiO₂ powders. Here, we provide a deep understanding of the reaction mechanisms, kinetics, and structure–function relationships for vapor phase acetone aldol condensation through the con-trolled synthesis of two catalysts with high surface areas and clean, dominant facets, coupled with detailed characterization and kinetic studies that are further assisted by density functional theory (DFT) calculations. Temperature-dependent diffuse reflectance infrared Fourier transform spectroscopy showed the existence of abundant acetone bonded to surface hydroxyl groups (acetone-O_sH) and acetone bonded to Lewis acid sites (acetone-Ti_5c) on surface of both {101} and {001} facet dom-inant TiO₂. Intermolecular C–C coupling of enolate intermediate from acetone-Ti_5c and a vicinal acetone-O_sH is a kinetically relevant step, which is consistent with kinetic and isotopic studies and DFT calculations. The {001} facet showed a lower apparent activation energy (or higher reactivity) than the {101} facet. This is likely caused by the weaker Lewis acid and Brønsted base strengths of the {001} facet which favors the reprotonation–desorption of the coupled intermediate, making the C–C coupling step more exothermic on the {001} facet and resulting in an earlier transition state with a lower activation barrier. It is also possible that the {001} facet has a smoother surface configuration and less steric hindrance during intermo-lecular C–C bond formation than the {101} facet.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1783813

Report Number(s):: PNNL-SA--157855

Journal Information:: JACS Au, Journal Name: JACS Au Journal Issue: 1 Vol. 1; ISSN 2691-3704

Publisher:: ACS PublicationsCopyright Statement

Country of Publication:: United States

Language:: English

References (54)

Aqueous Phase Aldol Condensation of Formaldehyde and Acetone on Anatase TiO ₂ (101) Surface: A Theoretical Investigation Zhao, Yuntao; Zhu, Xinli; Wang, Hua ChemCatChem, Vol. 12, Issue 4 https://doi.org/10.1002/cctc.201901736	journal	December 2019
CarbonCarbon Bond Formation via Aldolization of Acetaldehyde on Single Crystal and Polycrystalline TiO2 Surfaces Idriss, H.; Kim, K. S.; Barteau, M. A. Journal of Catalysis, Vol. 139, Issue 1 https://doi.org/10.1006/jcat.1993.1012	journal	January 1993
Reactions of Acetaldehyde on CeO2 and CeO2-Supported Catalysts Idriss, H.; Diagne, C.; Hindermann, J. P. Journal of Catalysis, Vol. 155, Issue 2 https://doi.org/10.1006/jcat.1995.1205	journal	September 1995
Acetone and Acetaldehyde Oligomerization on TiO2 Surfaces Luo, Shengcheng; Falconer, John L. Journal of Catalysis, Vol. 185, Issue 2 https://doi.org/10.1006/jcat.1999.2511	journal	July 1999
Acetone adsorption on hydroxylated silica gel: Correlation of sorption isotherms and IR spectra Okunev, A. G.; Paukshtis, E. A.; Aristov, Y. I. Reaction Kinetics and Catalysis Letters, Vol. 65, Issue 1 https://doi.org/10.1007/BF02475330	journal	September 1998
Titanium oxide based catalysts - a review Matsuda, S.; Kato, A. Applied Catalysis, Vol. 8, Issue 2 https://doi.org/10.1016/0166-9834(83)80076-1	journal	November 1983
Structure and stability of the anatase TiO2 (101) and (001) surfaces Hengerer, R.; Bolliger, B.; Erbudak, M. Surface Science, Vol. 460, Issue 1-3 https://doi.org/10.1016/S0039-6028(00)00527-6	journal	July 2000
Adsorption and surface reactions of acetaldehyde on TiO2, CeO2 and Al2O3 Raskó, J.; Kiss, J. Applied Catalysis A: General, Vol. 287, Issue 2 https://doi.org/10.1016/j.apcata.2005.04.003	journal	June 2005
Liquid phase aldol condensation reactions with MgO–ZrO2 and shape-selective nitrogen-substituted NaY Shen, Wenqin; Tompsett, Geoffrey A.; Hammond, Karl D. Applied Catalysis A: General, Vol. 392, Issue 1-2 https://doi.org/10.1016/j.apcata.2010.10.023	journal	January 2011
Controllable self-aldol condensation of cyclopentanone over MgO-ZrO2 mixed oxides: Origin of activity & selectivity Liang, Decheng; Li, Guozhu; Liu, Yanhong Catalysis Communications, Vol. 81 https://doi.org/10.1016/j.catcom.2016.04.008	journal	June 2016
An overview of dehydration, aldol-condensation and hydrogenation processes for production of liquid alkanes from biomass-derived carbohydrates Chheda, Juben N.; Dumesic, James A. Catalysis Today, Vol. 123, Issue 1-4 https://doi.org/10.1016/j.cattod.2006.12.006	journal	May 2007
Theoretical study on the reaction mechanisms of the aldol-condensation of 5-hydroxymethylfurfural with acetone catalyzed by MgO and MgO+ Chen, Shu; Yang, Huaqing; Hu, Changwei Catalysis Today, Vol. 245 https://doi.org/10.1016/j.cattod.2014.05.004	journal	May 2015
Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach VandeVondele, Joost; Krack, Matthias; Mohamed, Fawzi Computer Physics Communications, Vol. 167, Issue 2 https://doi.org/10.1016/j.cpc.2004.12.014	journal	April 2005
Aldol condensation of citral with acetone on MgO and alkali-promoted MgO catalysts Díez, V. K.; Apesteguía, C. R.; Di Cosimo, J. I. Journal of Catalysis, Vol. 240, Issue 2 https://doi.org/10.1016/j.jcat.2006.04.003	journal	June 2006
IR spectral evidence of aldol condensation: Acetaldehyde adsorption over TiO2 surface Singh, Manishwar; Zhou, Nanjia; Paul, Dilip K. Journal of Catalysis, Vol. 260, Issue 2 https://doi.org/10.1016/j.jcat.2008.07.020	journal	December 2008
Condensation and esterification reactions of alkanals, alkanones, and alkanols on TiO2: Elementary steps, site requirements, and synergistic effects of bifunctional strategies Wang, Shuai; Goulas, Konstantinos; Iglesia, Enrique Journal of Catalysis, Vol. 340 https://doi.org/10.1016/j.jcat.2016.05.026	journal	August 2016
Aldol condensation among acetaldehyde and ethanol reactants on TiO2: Experimental evidence for the kinetically relevant nucleophilic attack of enolates Zhang, Hongbo; Ibrahim, Malek Y. S.; Flaherty, David W. Journal of Catalysis, Vol. 361 https://doi.org/10.1016/j.jcat.2018.02.030	journal	May 2018
Substituent Effects and Molecular Descriptors of Reactivity in Condensation and Esterification Reactions of Oxygenates on Acid–Base Pairs at TiO ₂ and ZrO ₂ Surfaces Wang, Shuai; Iglesia, Enrique The Journal of Physical Chemistry C, Vol. 120, Issue 38 https://doi.org/10.1021/acs.jpcc.6b07304	journal	September 2016
Real-Time Observation of Reconstruction Dynamics on TiO ₂ (001) Surface under Oxygen via an Environmental Transmission Electron Microscope Yuan, Wentao; Wang, Yong; Li, Hengbo Nano Letters, Vol. 16, Issue 1 https://doi.org/10.1021/acs.nanolett.5b03277	journal	December 2015
Aldol Condensation of Acetaldehyde over Titania, Hydroxyapatite, and Magnesia Young, Zachary D.; Hanspal, Sabra; Davis, Robert J. ACS Catalysis, Vol. 6, Issue 5 https://doi.org/10.1021/acscatal.6b00264	journal	April 2016
Performance of DFT+ U Approaches in the Study of Catalytic Materials Capdevila-Cortada, Marçal; Łodziana, Zbigniew; López, Núria ACS Catalysis, Vol. 6, Issue 12 https://doi.org/10.1021/acscatal.6b01907	journal	November 2016
TiO ₂ -Catalyzed n -Valeraldehyde Self-Condensation Reaction Mechanism and Kinetics Zhao, Lili; An, Hualiang; Zhao, Xinqiang ACS Catalysis, Vol. 7, Issue 7 https://doi.org/10.1021/acscatal.7b00432	journal	June 2017
Aldol Condensation of Cyclopentanone on Hydrophobized MgO. Promotional Role of Water and Changes in the Rate-Limiting Step upon Organosilane Functionalization Ngo, Duong T.; Tan, Qiaohua; Wang, Bin ACS Catalysis, Vol. 9, Issue 4 https://doi.org/10.1021/acscatal.8b05103	journal	February 2019
Single-Facet Dominant Anatase TiO ₂ (101) and (001) Model Catalysts to Elucidate the Active Sites for Alkanol Dehydration Lin, Fan; Chen, Yuan; Zhang, Lu ACS Catalysis, Vol. 10, Issue 7 https://doi.org/10.1021/acscatal.9b04654	journal	February 2020
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
Theoretical Studies on Anatase and Less Common TiO ₂ Phases: Bulk, Surfaces, and Nanomaterials De Angelis, Filippo; Di Valentin, Cristiana; Fantacci, Simona Chemical Reviews, Vol. 114, Issue 19 https://doi.org/10.1021/cr500055q	journal	May 2014
Heterogeneous Catalysts for the Guerbet Coupling of Alcohols Kozlowski, Joseph T.; Davis, Robert J. ACS Catalysis, Vol. 3, Issue 7 https://doi.org/10.1021/cs400292f	journal	June 2013
Recent Advances in Catalytic Conversion of Ethanol to Chemicals Sun, Junming; Wang, Yong ACS Catalysis, Vol. 4, Issue 4 https://doi.org/10.1021/cs4011343	journal	March 2014
Experimental and Theoretical Study of n -Butanal Self-Condensation over Ti Species Supported on Silica Hanna, David G.; Shylesh, Sankaranarayanapillai; Li, Yi-Pei ACS Catalysis, Vol. 4, Issue 9 https://doi.org/10.1021/cs500704b	journal	July 2014
FT-IR study of the adsorption and transformation of formaldehyde on oxide surfaces Busca, Guido; Lamotte, Jean; Lavalley, Jean Claude Journal of the American Chemical Society, Vol. 109, Issue 17 https://doi.org/10.1021/ja00251a025	journal	August 1987
A Correlation of Reaction Rates Hammond, George S. Journal of the American Chemical Society, Vol. 77, Issue 2 https://doi.org/10.1021/ja01607a027	journal	January 1955
Direct Conversion of Bio-ethanol to Isobutene on Nanosized Zn _x Zr _y O _z Mixed Oxides with Balanced Acid–Base Sites Sun, Junming; Zhu, Kake; Gao, Feng Journal of the American Chemical Society, Vol. 133, Issue 29 https://doi.org/10.1021/ja204235v	journal	July 2011
Highly Selective Formation of n -Butanol from Ethanol through the Guerbet Process: A Tandem Catalytic Approach Chakraborty, Sumit; Piszel, Paige E.; Hayes, Cassandra E. Journal of the American Chemical Society, Vol. 137, Issue 45 https://doi.org/10.1021/jacs.5b10257	journal	November 2015
Entropy-Driven High Reactivity of Formaldehyde in Nucleophilic Attack by Enolates on Oxide Surfaces Wang, Shuai; Iglesia, Enrique Journal of the American Chemical Society, Vol. 140, Issue 2 https://doi.org/10.1021/jacs.7b11749	journal	January 2018
Adsorption and Solar Light Decomposition of Acetone on Anatase TiO ₂ and Niobium Doped TiO ₂ Thin Films Mattsson, Andreas; Leideborg, Michael; Larsson, Karin The Journal of Physical Chemistry B, Vol. 110, Issue 3 https://doi.org/10.1021/jp055656z	journal	December 2005
Surface Reactions of Acetone on Al ₂ O ₃ , TiO ₂ , ZrO ₂ , and CeO ₂ : IR Spectroscopic Assessment of Impacts of the Surface Acid−Base Properties Zaki, M. I.; Hasan, M. A.; Pasupulety, L. Langmuir, Vol. 17, Issue 3 https://doi.org/10.1021/la000976p	journal	February 2001
An Infrared Spectroscopic Study of Acetone and Mesityl Oxide Adsorption on Acid Catalyst Panov, A.; Fripiat, J. J. Langmuir, Vol. 14, Issue 14 https://doi.org/10.1021/la971359c	journal	July 1998
Role of point defects on the reactivity of reconstructed anatase titanium dioxide (001) surface Wang, Yang; Sun, Huijuan; Tan, Shijing Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3214	journal	July 2013
Facet-dependent trapping and dynamics of excess electrons at anatase TiO2 surfaces and aqueous interfaces Selcuk, Sencer; Selloni, Annabella Nature Materials, Vol. 15, Issue 10 https://doi.org/10.1038/nmat4672	journal	June 2016
Review of catalytic systems and thermodynamics for the Guerbet condensation reaction and challenges for biomass valorization Gabriëls, Dries; Hernández, Willinton Yesid; Sels, Bert Catalysis Science & Technology, Vol. 5, Issue 8 https://doi.org/10.1039/C5CY00359H	journal	January 2015
Engineering a high energy surface of anatase TiO ₂ crystals towards enhanced performance for energy conversion and environmental applications Chen, Wei; Kuang, Qin; Wang, Qiuxiang RSC Advances, Vol. 5, Issue 26 https://doi.org/10.1039/C5RA00344J	journal	January 2015
A catalytic aldol condensation system enables one pot conversion of biomass saccharides to biofuel intermediates Li, Huixiang; Xu, Zhanwei; Yan, Peifang Green Chemistry, Vol. 19, Issue 7 https://doi.org/10.1039/C7GC00362E	journal	January 2017
All-electron ab-initio molecular dynamics Krack, Matthias; Parrinello, Michele Physical Chemistry Chemical Physics, Vol. 2, Issue 10 https://doi.org/10.1039/b001167n	journal	January 2000
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
In situ IR study of surface hydroxyl species of dehydrated TiO2: towards understanding pivotal surface processes of TiO2 photocatalytic oxidation of toluene Lin, Huaxiang; Long, Jinlin; Gu, Quan Physical Chemistry Chemical Physics, Vol. 14, Issue 26 https://doi.org/10.1039/c2cp40893g	journal	January 2012
Surface chemistry of titania (anatase) and titania-supported catalysts Hadjiivanov, Konstantin I.; Klissurski, Dimitar G. Chemical Society Reviews, Vol. 25, Issue 1 https://doi.org/10.1039/cs9962500061	journal	January 1996
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Separable dual-space Gaussian pseudopotentials Goedecker, S.; Teter, M.; Hutter, J. Physical Review B, Vol. 54, Issue 3 https://doi.org/10.1103/PhysRevB.54.1703	journal	July 1996
Relativistic separable dual-space Gaussian pseudopotentials from H to Rn Hartwigsen, C.; Goedecker, S.; Hutter, J. Physical Review B, Vol. 58, Issue 7 https://doi.org/10.1103/PhysRevB.58.3641	journal	August 1998
Surface structure of anatase TiO 2 ( 001 ) : Reconstruction, atomic steps, and domains Liang, Yong; Gan, Shupan; Chambers, Scott A. Physical Review B, Vol. 63, Issue 23 https://doi.org/10.1103/PhysRevB.63.235402	journal	May 2001
Electron transport via polaron hopping in bulk Ti O 2 : A density functional theory characterization Deskins, N. Aaron; Dupuis, Michel Physical Review B, Vol. 75, Issue 19 https://doi.org/10.1103/PhysRevB.75.195212	journal	May 2007
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
Structure Determination of the Two-Domain ( 1 × 4 ) Anatase TiO 2 ( 001 ) Surface Herman, G. S.; Sievers, M. R.; Gao, Y. Physical Review Letters, Vol. 84, Issue 15 https://doi.org/10.1103/PhysRevLett.84.3354	journal	April 2000
Visualizing H ₂ O molecules reacting at TiO ₂ active sites with transmission electron microscopy Yuan, Wentao; Zhu, Beien; Li, Xiao-Yan Science, Vol. 367, Issue 6476 https://doi.org/10.1126/science.aay2474	journal	January 2020

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Elucidation of Active Sites in Aldol Condensation of Acetone over Single-Facet Dominant Anatase TiO2 (101) and (001) Catalysts

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Elucidation of Active Sites in Aldol Condensation of Acetone over Single-Facet Dominant Anatase TiO₂ (101) and (001) Catalysts