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; Resasco, Daniel E.

doi:10.1021/acscatal.8b05103

Aldol Condensation of Cyclopentanone on Hydrophobized MgO. Promotional Role of Water and Changes in the Rate-Limiting Step upon Organosilane Functionalization

Journal Article · Wed Feb 13 23:00:00 EST 2019 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.8b05103· OSTI ID:1529922

Ngo, Duong T. ^[1]; Tan, Qiaohua ^[1]; ^[1]; ^[1]

Univ. of Oklahoma, Norman, OK (United States)

Aldol condensation is a key C—C coupling reaction for upgrading of biomass-derived oxygenates to fuels and chemicals. In this work, we investigate the effects of added water on the condensation of cyclopentanone (CPO) on hydrophobized MgO catalysts. We have found that the role of water strongly depends on the degree of hydrophobic functionalization of the MgO surface. That is, on a nonfunctionalized (hydrophilic) high-surface-area MgO catalyst, the rate decreases with the addition of water, mostly due to active site blockage. By contrast, on MgO hydrophobized via silylation with octadecyltrichlorosilane (OTS), the rate actually increases with added water. A concomitant change in kinetics is observed from the pristine (hydrophilic) MgO to the hydrophobized sample. Specifically, on the hydrophilic sample, the reaction is first-order, as expected if the rate-limiting step is the formation of an enolate intermediate via α-H abstraction at a basic site, as widely reported in previous literature. By contrast, on the hydrophobized sample, the reaction becomes second-order, indicating a shift in rate-limiting step to the bimolecular C—C coupling. On pristine MgO, acid–base pairs are fully available on the surface, with the acid site polarizing the C=O group in the second cyclopentanone (electrophile) and making the attack by the enolate very favorable. It is proposed here that grafted OTS molecules interfere between active sites, making the adsorbate–adsorbate interaction on the surface less likely and reducing the rate of C—C coupling. Lastly, both isotope effect experiments and ab initio molecular dynamics simulations of cyclopentanone adsorption at the MgO/OTS interface further support this argument. Therefore, the promotional role of water seems to be the assistance of the C—C bond-forming step. It is proposed that, at low concentrations, water can help the second molecule (electrophile) be polarized from a remote Mg²⁺ site through a chain of H-bonded molecules.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0018284

OSTI ID:: 1529922

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 4 Vol. 9; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (55)

The Effect of Water on the Heterogeneously Catalyzed Selective Oxidation of Acrolein: An Isotope Study Petzold, Tina; Blickhan, Nina; Drochner, Alfons ChemCatChem, Vol. 6, Issue 7 https://doi.org/10.1002/cctc.201400099	journal	May 2014
Fine-Tuning the Acid-Base Properties of Boron-Doped Magnesium Oxide Catalyst for the Selective Aldol Condensation Pham, Tu N.; Zhang, Lu; Shi, Dachuan ChemCatChem, Vol. 8, Issue 23 https://doi.org/10.1002/cctc.201600953	journal	October 2016
Cyclopentanone as an Alternative Linking Reactant for Heterogeneously Catalyzed Furfural Aldol Condensation Cueto, Jennifer; Faba, Laura; Díaz, Eva ChemCatChem, Vol. 9, Issue 10 https://doi.org/10.1002/cctc.201601655	journal	April 2017
Enhancing the Acylation Activity of Acetic Acid by Formation of an Intermediate Aromatic Ester Duong, Nhung N.; Wang, Bin; Sooknoi, Tawan ChemSusChem, Vol. 10, Issue 13 https://doi.org/10.1002/cssc.201700394	journal	June 2017
A Systems-Level Roadmap for Biomass Thermal Fractionation and Catalytic Upgrading Strategies Herron, Jeffrey A.; Vann, Tyler; Duong, Nhung Energy Technology, Vol. 5, Issue 1 https://doi.org/10.1002/ente.201600147	journal	June 2016
Role of Water Vapor in the Partial Oxidation of Propene Saleh-Alhamed, Y. A.; Hudgins, R. R.; Silveston, P. L. Journal of Catalysis, Vol. 161, Issue 1 https://doi.org/10.1006/jcat.1996.0201	journal	June 1996
An Investigation of the Effects of Water on Rate and Selectivity for the Fischer–Tropsch Synthesis on Cobalt-Based Catalysts Krishnamoorthy, Sundaram; Tu, Mai; Ojeda, Manuel P. Journal of Catalysis, Vol. 211, Issue 2 https://doi.org/10.1006/jcat.2002.3749	journal	October 2002
Formation of Nickel, Cobalt, Copper, and Iron Aluminates fromα- andγ-Alumina-Supported Oxides: A Comparative Study Bolt, P. H.; Habraken, F. H. P. M.; Geus, J. W. Journal of Solid State Chemistry, Vol. 135, Issue 1 https://doi.org/10.1006/jssc.1997.7590	journal	January 1998
Fixed bed and slurry reactor studies of Fischer-Tropsch synthesis on precipitated iron catalyst Bukur, Dragomir B.; Patel, Snehal A.; Lang, Xiaosu Applied Catalysis, Vol. 61, Issue 1 https://doi.org/10.1016/S0166-9834(00)82154-5	journal	May 1990
Product distributions of the Fischer-Tropsch synthesis on precipitated iron catalysts Donnelly, Timothy J.; Satterfield, Charles N. Applied Catalysis, Vol. 52, Issue 1 https://doi.org/10.1016/S0166-9834(00)83375-8	journal	January 1989
The interaction of water with solid surfaces: fundamental aspects revisited Henderson, M. Surface Science Reports, Vol. 46, Issue 1-8 https://doi.org/10.1016/S0167-5729(01)00020-6	journal	May 2002
Oxidation of propane over V2O5–P2O5-based catalysts at relatively low temperatures Ai, Mamoru Catalysis Today, Vol. 42, Issue 3 https://doi.org/10.1016/S0920-5861(98)00105-9	journal	July 1998
Fischer–Tropsch synthesis: effect of water on the catalytic properties of a ruthenium promoted Co/TiO2 catalyst Li, Jinlin; Jacobs, Gary; Das, Tapan Applied Catalysis A: General, Vol. 233, Issue 1-2 https://doi.org/10.1016/S0926-860X(02)00194-1	journal	July 2002
The rate inhibiting effect of water as a product on reactions catalysed by cation exchange resins: formation of mesityl oxide from acetone as case study du Toit, Elizabeth; Nicol, Willie Applied Catalysis A: General, Vol. 277, Issue 1-2 https://doi.org/10.1016/j.apcata.2004.09.015	journal	December 2004
Evaluating strategies for catalytic upgrading of pyrolysis oil in liquid phase Pham, Tu Nguyet; Shi, Dachuan; Resasco, Daniel E. Applied Catalysis B: Environmental, Vol. 145 https://doi.org/10.1016/j.apcatb.2013.01.002	journal	February 2014
A comparative study of the catalytic oxidation of HCHO and CO over Mn0.75Co2.25O4 catalyst: The effect of moisture Wang, Yu; Zhu, Xiaobing; Crocker, Mark Applied Catalysis B: Environmental, Vol. 160-161 https://doi.org/10.1016/j.apcatb.2014.06.011	journal	November 2014
Improving stability of cyclopentanone aldol condensation MgO-based catalysts by surface hydrophobization with organosilanes Ngo, Duong T.; Sooknoi, Tawan; Resasco, Daniel E. Applied Catalysis B: Environmental, Vol. 237 https://doi.org/10.1016/j.apcatb.2018.06.044	journal	December 2018
CO/H2 adsorption on a Ru/Al2O3 model catalyst for Fischer Trospch: Effect of water concentration on the surface species Jiménez-Barrera, E.; Bazin, P.; Lopez-Cartes, C. Applied Catalysis B: Environmental, Vol. 237 https://doi.org/10.1016/j.apcatb.2018.06.053	journal	December 2018
Effect of water on hydrogenation of 1,3-butadiene over Au (111): A joint theoretical and experimental study Bu, Weida; Zhao, Liang; Zhang, Zhicheng Applied Surface Science, Vol. 289 https://doi.org/10.1016/j.apsusc.2013.10.038	journal	January 2014
The influence of water on the selective oxidation of acrolein to acrylic acid on Mo/V/W-mixed oxides Jekewitz, T.; Blickhan, N.; Endres, S. Catalysis Communications, Vol. 20 https://doi.org/10.1016/j.catcom.2011.12.022	journal	April 2012
Selective transformation of furfural to cyclopentanone Hronec, Milan; Fulajtarová, Katarina Catalysis Communications, Vol. 24 https://doi.org/10.1016/j.catcom.2012.03.020	journal	July 2012
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
Implementation of concepts derived from model compound studies in the separation and conversion of bio-oil to fuel Resasco, Daniel E.; Crossley, Steven P. Catalysis Today, Vol. 257 https://doi.org/10.1016/j.cattod.2014.06.037	journal	November 2015
On the support in cobalt Fischer–Tropsch synthesis—Emphasis on alumina and aluminates Rytter, Erling; Holmen, Anders Catalysis Today, Vol. 275 https://doi.org/10.1016/j.cattod.2015.11.042	journal	October 2016
DFT studies of the methanol decomposition mechanism on the H 2 O/Cu(110) and OH pre-adsorbed H 2 O/Cu(110) interfaces: Comparison with the clean Cu(110) surface Ren, Rui-Peng; Zhang, Yong-Chao; Liu, Shizhong International Journal of Hydrogen Energy, Vol. 41, Issue 4 https://doi.org/10.1016/j.ijhydene.2015.09.075	journal	January 2016
Complete low-barrier side-chain route for olefin formation during methanol conversion in H-SAPO-34 De Wispelaere, Kristof; Hemelsoet, Karen; Waroquier, Michel Journal of Catalysis, Vol. 305 https://doi.org/10.1016/j.jcat.2013.04.015	journal	September 2013
Silylated hydrophobic zeolites with enhanced tolerance to hot liquid water Zapata, Paula A.; Huang, Yi; Gonzalez-Borja, Miguel A. Journal of Catalysis, Vol. 308 https://doi.org/10.1016/j.jcat.2013.05.024	journal	December 2013
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
Liquid phase aldol condensation of cyclopentanone with valeraldehyde catalysed by oxynitrides possessing tuneable acid–base properties Hasni, Moez; Prado, Gwenola; Rouchaud, Jean Journal of Molecular Catalysis A: Chemical, Vol. 247, Issue 1-2 https://doi.org/10.1016/j.molcata.2005.11.023	journal	March 2006
Effects of Composition and Structure of Mg/Al Oxides on Their Activity and Selectivity for the Condensation of Methyl Ketones Shylesh, Sankaranarayanapillai; Kim, Daeyoup; Gokhale, Amit A. Industrial & Engineering Chemistry Research, Vol. 55, Issue 40 https://doi.org/10.1021/acs.iecr.6b03601	journal	September 2016
Water Interactions in Zeolite Catalysts and Their Hydrophobically Modified Analogues Chen, Kuizhi; Kelsey, Jarred; White, Jeffery L. ACS Catalysis, Vol. 5, Issue 12 https://doi.org/10.1021/acscatal.5b02040	journal	November 2015
Perspectives on the Effect of Water in Cobalt Fischer–Tropsch Synthesis Rytter, Erling; Holmen, Anders ACS Catalysis, Vol. 7, Issue 8 https://doi.org/10.1021/acscatal.7b01525	journal	July 2017
Organocatalytic Cross-Coupling of Biofuranics to Multifunctional Difuranic C ₁₁ Building Blocks Wilson, Jedediah; Chen, Eugene Y. -X. ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 9 https://doi.org/10.1021/acssuschemeng.6b01235	journal	August 2016
Enhanced Activity and Selectivity of Fischer–Tropsch Synthesis Catalysts in Water/Oil Emulsions Shi, Dachuan; Faria, Jimmy; Pham, Tu N. ACS Catalysis, Vol. 4, Issue 6 https://doi.org/10.1021/cs500040n	journal	April 2014
Zeolite Catalysis: Water Can Dramatically Increase or Suppress Alkane C–H Bond Activation Chen, Kuizhi; Damron, Joshua; Pearson, Carlie ACS Catalysis, Vol. 4, Issue 9 https://doi.org/10.1021/cs500858d	journal	August 2014
Overview of Applications of Biomass Fast Pyrolysis Oil Czernik, S.; Bridgwater, A. V. Energy & Fuels, Vol. 18, Issue 2, p. 590-598 https://doi.org/10.1021/ef034067u	journal	March 2004
Factors that Determine Zeolite Stability in Hot Liquid Water Zhang, Lu; Chen, Kuizhi; Chen, Banghao Journal of the American Chemical Society, Vol. 137, Issue 36 https://doi.org/10.1021/jacs.5b07398	journal	September 2015
Stability of Nanocrystals: Thermodynamic Analysis of Oxidation and Re-reduction of Cobalt in Water/Hydrogen Mixtures van Steen, Eric; Claeys, Michael; Dry, Mark E. The Journal of Physical Chemistry B, Vol. 109, Issue 8 https://doi.org/10.1021/jp045136o	journal	March 2005
Insights into the Preference of CO ₂ Formation from HCOOH Decomposition on Pd Surface: A Theoretical Study Zhang, Riguang; Liu, Hongyan; Wang, Baojun The Journal of Physical Chemistry C, Vol. 116, Issue 42 https://doi.org/10.1021/jp211900z	journal	October 2012
The Effect of Water on the CO Oxidation on Ag(111) and Au(111) Surfaces: A First-Principle Study Su, Hai-Yan; Yang, Ming-Mei; Bao, Xin-He The Journal of Physical Chemistry C, Vol. 112, Issue 44 https://doi.org/10.1021/jp803400p	journal	October 2008
Growth of Ultrasmooth Octadecyltrichlorosilane Self-Assembled Monolayers on SiO ₂ Wang, Yuliang; Lieberman, Marya Langmuir, Vol. 19, Issue 4 https://doi.org/10.1021/la020697x	journal	February 2003
What do we know about the acidity of solid acids? Gorte, R. J. Catalysis Letters, Vol. 62, Issue 1, p. 1-13 https://doi.org/10.1023/A:1019010013989	journal	January 1999
Distributed processes for biomass conversion could aid UN Sustainable Development Goals Resasco, Daniel E.; Wang, Bin; Sabatini, David Nature Catalysis, Vol. 1, Issue 10 https://doi.org/10.1038/s41929-018-0166-6	journal	October 2018
Role of water in metal catalyst performance for ketone hydrogenation: a joint experimental and theoretical study on levulinic acid conversion into gamma-valerolactone Michel, Carine; Zaffran, Jérémie; Ruppert, Agnieszka M. Chem. Commun., Vol. 50, Issue 83 https://doi.org/10.1039/C4CC04401K	journal	January 2014
Zeolite-catalysed C–C bond forming reactions for biomass conversion to fuels and chemicals Resasco, Daniel E.; Wang, Bin; Crossley, Steven Catalysis Science & Technology, Vol. 6, Issue 8 https://doi.org/10.1039/C5CY02271A	journal	January 2016
Efficient C–C coupling of bio-based furanics and carbonyl compounds to liquid hydrocarbon precursors over lignosulfonate derived acidic carbocatalysts Konwar, Lakhya Jyoti; Samikannu, Ajaikumar; Mäki-Arvela, Päivi Catalysis Science & Technology, Vol. 8, Issue 9 https://doi.org/10.1039/C7CY02601C	journal	January 2018
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
Synthesis of renewable high-density fuels using cyclopentanone derived from lignocellulose Yang, Jinfan; Li, Ning; Li, Guangyi Chemical Communications, Vol. 50, Issue 20 https://doi.org/10.1039/c3cc46588h	journal	January 2014
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
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
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 111, Issue 15 https://doi.org/10.1063/1.480097	journal	October 1999
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
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
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

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
C−C coupling
aldol condensation
cyclopentanone
magnesium oxide
rate-limiting steps
silane functionalization
water promotion
α-H abstraction

Aldol Condensation of Cyclopentanone on Hydrophobized MgO. Promotional Role of Water and Changes in the Rate-Limiting Step upon Organosilane Functionalization

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