Abstract
Excessive amounts of oxy-functional groups in unprocessed bio-oil vitiate its quality as fuel; therefore, it has to be channelized to upgrading processes, and catalytic hydrodeoxygenation is one of the most suitable routes for the upgrading of crude bio-oil. In this computational work, catalytic hydrodeoxygenation (HDO) of guaiacol, which is an important phenolic compound of crude bio-oil, has been carried out using density functional theory (DFT) over a Pd(111) catalyst. The Pd(111) catalyst surface does not endorse direct eliminations of functional groups of guaiacol; however, it is found to perform excellently in stepwise dehydrogenation reactions of oxy-functionals of guaiacol according to present DFT results. The catechol product, formed through dehydrogenation of the methoxy group, followed by elimination of CH2 and association of the hydrogen atom, has been identified as one of the major products. The overall reaction rate is controlled by scission of CH2 from 2-methylene-oxy-phenol with an activation energy demand of 23.06 kcal mol–1. Further, the kinetic analysis of each reaction step involved in HDO of guaiacol over the Pd(111) catalyst surface has also been carried out at atmospheric pressure and at a wide range of temperatures from 473 to 673 K, with temperature intervals of 50 K. In the kinetic analysis part, various kinetic parameters, such as forward and reverse reaction rate constants, Arrhenius constants, and equilibrium rate constants, are reported. The kinetic modeling of the dominating reaction steps has revealed that even a lower temperature of 473 K provides a favorable reaction environment; and the temperature increment further improves the reaction favorability.
Similar content being viewed by others
References
Klass DL (2004) Biomass for renewable energy and fuels. Encycl Energy 1:193–212
Saidi M, Samimi F, Karimipourfard D et al (2014) Upgrading of lignin-derived bio-oils by catalytic hydrodeoxygenation. Energy Environ Sci 7:103–129. https://doi.org/10.1039/C3EE43081B
Nimmanwudipong T, Aydin C, Lu J et al (2012) Selective hydrodeoxygenation of guaiacol catalyzed by platinum supported on magnesium oxide. Catal Lett 142:1190–1196. https://doi.org/10.1007/s10562-012-0884-3
Lee CR, Yoon JS, Suh Y-W et al (2012) Catalytic roles of metals and supports on hydrodeoxygenation of lignin monomer guaiacol. Catal Commun 17:54–58. https://doi.org/10.1016/j.catcom.2011.10.011
Gao D, Schweitzer C, Hwang HT, Varma A (2014) Conversion of guaiacol on noble metal catalysts: reaction performance and deactivation studies. Ind Eng Chem Res 53:18658–18667. https://doi.org/10.1021/ie500495z
Sun J, Karim AM, Zhang H et al (2013) Carbon-supported bimetallic Pd-Fe catalysts for vapor-phase hydrodeoxygenation of guaiacol. J Catal 306:47–57. https://doi.org/10.1016/j.jcat.2013.05.020
Mu W, Ben H, Du X et al (2014) Noble metal catalyzed aqueous phase hydrogenation and hydrodeoxygenation of lignin-derived pyrolysis oil and related model compounds. Bioresour Technol 173:6–10. https://doi.org/10.1016/j.biortech.2014.09.067
Chang J, Danuthai T, Dewiyanti S et al (2013) Hydrodeoxygenation of guaiacol over carbon-supported metal catalysts. ChemCatChem 5:3041–3049. https://doi.org/10.1002/cctc.201300096
Shafaghat H, Sirous Rezaei P, Daud WMAW (2015) Catalytic hydrogenation of phenol, cresol and guaiacol over physically mixed catalysts of Pd/C and zeolite solid acids. RSC Adv 5:33990–33998. https://doi.org/10.1039/c5ra00367a
Boonyasuwat S, Omotoso T, Resasco DE, Crossley SP (2013) Conversion of guaiacol over supported Ru catalysts. Catal Lett 143:783–791. https://doi.org/10.1007/s10562-013-1033-3
Aqsha A, Katta L, Mahinpey N (2015) Catalytic hydrodeoxygenation of guaiacol as lignin model component using Ni-Mo/TiO 2 and Ni-V/TiO 2 catalysts. Catal Lett 145:1351–1363. https://doi.org/10.1007/s10562-015-1530-7
Ma R, Cui K, Yang L et al (2015) Selective catalytic conversion of guaiacol to phenols over a molybdenum carbide catalyst. Chem Commun 51:10299–10301. https://doi.org/10.1039/C5CC01900A
Bykova MV, Ermakov DY, Kaichev VV et al (2012) Ni-based sol-gel catalysts as promising systems for crude bio-oil upgrading: guaiacol hydrodeoxygenation study. Appl Catal B Environ 113–114:296–307. https://doi.org/10.1016/j.apcatb.2011.11.051
Olcese RN, Bettahar M, Petitjean D et al (2012) Gas-phase hydrodeoxygenation of guaiacol over Fe/SiO2 catalyst. Appl Catal B Environ 115–116:63–73. https://doi.org/10.1016/j.apcatb.2011.12.005
Gao D, Xiao Y, Varma A (2015) Guaiacol hydrodeoxygenation over platinum catalyst: reaction pathways and kinetics. Ind Eng Chem Res 54:10638–10644. https://doi.org/10.1021/acs.iecr.5b02940
Lee K, Gu GH, Mullen C et al (2015) Guaiacol hydrodeoxygenation mechanism on Pt(111): insights from density functional theory and linear free energy relations. ChemSusChem 8:315–322. https://doi.org/10.1002/cssc.201402940
Lu J, Behtash S, Mamun O, Heyden A (2015) Theoretical investigation of the reaction mechanism of the guaiacol hydrogenation over a Pt(111) catalyst. ACS Catal 5:2423–2435. https://doi.org/10.1021/cs5016244
Chiu C, Genest A, Borgna A, Rösch N (2014) Hydrodeoxygenation of guaiacol over Ru(0001): a DFT study. ACS Catal 4:4178–4188. https://doi.org/10.1021/cs500911j
Lu J, Behtash S, Mamun O, Heyden A (2015) Theoretical investigation of the reaction mechanism of the hydrodeoxygenation of guaiacol over a Ru (0001) model surface. J Catal 321:39–50. https://doi.org/10.1021/cs5016244
Verma AM, Kishore N (2016) DFT analyses of reaction pathways and temperature effects on various guaiacol conversion reactions in gas phase environment. ChemistrySelect 1:6196–6205. https://doi.org/10.1002/slct.201601139
Liu C, Zhang Y, Huang X (2014) Study of guaiacol pyrolysis mechanism based on density function theory. Fuel Process Technol 123:159–165. https://doi.org/10.1016/j.fuproc.2014.01.002
Huang J, Li X, Wu D et al (2013) Theoretical studies on pyrolysis mechanism of guaiacol as lignin model compound. J Renew Sustain Energy 5:043112–043117. https://doi.org/10.1063/1.4816497
Verma AM, Kishore N (2017) DFT study on gas-phase hydrodeoxygenation of guaiacol by various reaction schemes. Mol Simul 43:141–153. https://doi.org/10.1080/08927022.2016.1239825
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Petersson GA, Nakatsuji H, Li X, Caricato M, Marenich AV, Bloino J, Janesko BG, Gomperts R, Mennucci B, Hratchian HP, Ortiz JV, Izmaylov AF, Sonnenberg JL, Williams-Young D, Ding F, Lipparini F, Egidi F, Goings J, Peng B, Petrone A, Henderson T, Ranasinghe D, Zakrzewski VG, Gao J, Rega N, Zheng G, Liang W, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Throssell K, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark MJ, Heyd JJ, Brothers EN, Kudin KN, Staroverov VN, Keith TA, Kobayashi R, Normand J, Raghavachari K, Rendell A P, Burant JC, Iyengar SS, Tomasi J, Cossi M, Millam JM, Klene M, Adamo C, Cammi R, Ochterski JW, Martin RL, Morokuma K, Farkas O, Foresman JB, Fox DJ (2009) Gaussian 09, revision B.01. Gaussian Inc, Wallingford
Dennington R, Keith T, Millam J (2009) GaussView, version 5. Semichem Inc., Shawnee Mission
Hohenberg P, Kohn W (1964) Inhomogeneous electron gas. Phys Rev 136:B864–B871. https://doi.org/10.1103/PhysRevB.7.1912
Kohn W, Sham L (1965) Self-consistent equations including exchange and correlation effects. Phys Rev 385:A1133–A1138. https://doi.org/10.1103/PhysRev.140.A1133
Becke AD (1988) Density-functional exchange-energy approximation with correct asymptotic behavior. Phys Rev A 38:3098–3100. https://doi.org/10.1103/PhysRevA.38.3098
Perdew JP, Wang Y (1992) Accurate and simple analytic representation of the electron-gas correlation energy. Phys Rev B 45:13244–13249
Hay PJ, Wadt WR (1985) Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg. J Chem Phys 82:270–283. https://doi.org/10.1063/1.448799
McLean AD, Chandler GS (1980) Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18. J Chem Phys 72:5639–5648. https://doi.org/10.1063/1.438980
Hratchian HP, Schlegel HB (2004) Accurate reaction paths using a Hessian based predictor-corrector integrator. J Chem Phys 120:9918–9924. https://doi.org/10.1063/1.1724823
Carneiro J de M, Cruz MT de M (2008) Density functional theory study of the adsorption of formaldehyde on Pd4 and on Pd4/γ-Al2O3 clusters. J Phys Chem A 112:8929–8937. https://doi.org/10.1021/jp801591z
Verma AM, Kishore N (2017) Molecular simulations of palladium catalysed hydrodeoxygenation of 2-hydroxybenzaldehyde using density functional theory. Phys Chem Chem Phys 19:25582–25597. https://doi.org/10.1039/C7CP05113A
Eyring H (1935) The activated complex in chemical reactions. J Chem Phys 3:107–115. https://doi.org/10.1063/1.1749604
Carneiro WDM, Aranda DAG, Bu M (2007) Density functional theory study of benzene adsorption on small Pd and Pt clusters. J Phys Chem C 111:11068–11076. https://doi.org/10.1021/jp072572c
Orita H, Itoh N (2004) Simulation of phenol formation from benzene with a Pd membrane reactor: ab initio periodic density functional study. Appl Catal A Gen 258:17–23. https://doi.org/10.1016/j.apcata.2003.08.001
Li G, Han J, Wang H et al (2015) Role of dissociation of phenol in its selective hydrogenation on Pt(111) and Pd(111). ACS Catal 5:2009–2016. https://doi.org/10.1021/cs501805y
de Souza PM, Rabelo-Neto RC, Borges LEP et al (2017) Hydrodeoxygenation of phenol over Pd catalysts. Effect of support on reaction mechanism and catalyst deactivation. ACS Catal 7:2058–2073. https://doi.org/10.1021/acscatal.6b02022
Rubeš M, He J, Nachtigall P, Bludsk֝y O (2016) Direct hydrodeoxygenation of phenol over carbon-supported Ru catalysts: a computational study. J Mol Catal A Chem 423:300–307. https://doi.org/10.1016/j.molcata.2016.07.007
Acknowledgments
Authors gratefully acknowledge the financial support (sanction no. 34/20/17/2016-BRNS) received from Board of Research in Nuclear Sciences (India) for this work.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
ESM 1
(DOCX 727 kb)
Rights and permissions
About this article
Cite this article
Verma, A.M., Kishore, N. Molecular modeling approach to elucidate gas phase hydrodeoxygenation of guaiacol over a Pd(111) catalyst within DFT framework. J Mol Model 24, 254 (2018). https://doi.org/10.1007/s00894-018-3803-8
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00894-018-3803-8