Abstract
Using DFT+U calculations with inclusion of van-der-Waals (vdW) forces, we studied CO2 activation and the initial steps of CO2 hydrogenation over Cu10 and Ru10 clusters supported on the TiO2 anatase (101) surface. CO2 is readily adsorbed and activated on the Ru cluster where direct CO2 dissociation proceeds with a barrier of 0.8 eV. When H atoms are co-adsorbed on the Ru cluster, H-addition to CO2 becomes preferred, as the best Ru sites for CO2 dissociation are blocked. A H atom is added to the CO2 molecule with formation of a formate [HCOO] species and an activation barrier of 1.2 eV. On Cu10/TiO2, only weak adsorption modes of the CO2 molecule are found, whereas H2 readily adsorbs on the Cu cluster. A reduction of the titania support does not significantly change this picture. Therefore, the only viable pathway for the CO2 hydrogenation over Cu10/TiO2 is the addition of a pre-adsorbed H atom to CO2 coming from the gas phase. This corresponds to an Eley–Rideal mechanism for the H-association to CO2. The work shows the importance to consider the hydrogen coverage on the metal cluster as an important variable in modeling the CO2 hydrogenation reaction.
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Su X, Xu J, Liang B, Duan H, Hou B, Huang Y (2016) Catalytic carbon dioxide hydrogenation to methane: a review of recent studies. J Energy Chem 25:1–13
Behrens M (2015) Chemical hydrogen storage by methanol: Challenges for the catalytic methanol synthesis from CO2. Recycl Catal 2:78–86
Luntz AC, Nilsson A, Pettersson LGM, Nørskov JK (2008) Chemical bonding at surfaces and interfaces. Elsevier, Amsterdam
Agnelli M, Kolb M, Mirodatos C (1994) CO hydrogenation on a nickel catalyst: 1. Kinetics and modeling of a low-temperature sintering process. J Catal 148:9–21
Xu J, Su X, Duan H et al (2016) Influence of pretreatment temperature on catalytic performance of rutile TiO2-supported ruthenium catalyst in CO2 methanation. J Catal 333:227–237
Gupta NM, Kamble VS, Kartha VB, Iyer RM, Thampi KR, Gratzel M (1994) FTIR spectroscopic study of the interaction of CO2 and CO2 + H2 over partially oxidized Ru/TiO2 catalyst. J Catal 146:173–184
Garbarino G, Bellotti D, Riani P, Magistri L, Busca G (2015) Methanation of carbon dioxide on Ru/Al2O3 and Ni/Al2O3 catalysts at atmospheric pressure: Catalysts activation, behaviour and stability. Int J Hydrog Energy 40:9171–9182
Abe T, Tanizawa M, Watanabe K, Taguchi A (2009) CO2 methanation property of Ru nanoparticle-loaded TiO2 prepared by a polygonal barrel-sputtering method. Energy Environ Sci 2:315–321
Eckle S, Anfang H-G, Behm RJ (2011) Reaction intermediates and side products in the methanation of CO and CO2 over supported Ru catalysts in H2-rich reformate gases. J Phys Chem C 115:1361–1367
Gao J, Liu Q, Gu F, Liu B, Zhong Z, Su F (2015) Recent advances in methanation catalysts for the production of synthetic natural gas. RSC Adv 5:22759–22776
Studt F, Behrens M, Kunkes EL et al (2015) The mechanism of CO and CO2 hydrogenation to methanol over Cu-based catalysts. ChemCatChem 7:1105–1111
Kunkes EL, Studt F, Abild-Pedersen F, Schlögl R, Behrens M (2015) Hydrogenation of CO2 and CO to methanol on Cu/ZnO/Al2O3: is there a common intermediate or not? J Catal 328:43–48
Behrens M, Studt F, Kasatkin I et al (2012) The active site of methanol synthesis over Cu/ZnO/Al2O3 industrial catalysts. Science 336:893
Bando KK, Sayama K, Kusama H, Okabe K, Arakawa H (1997) In-situ FT-IR study on CO2 hydrogenation over Cu catalysts supported on SiO2, Al2O3, and TiO2. Appl Catal A 165:391–409
Chen HYT, Tosoni S, Pacchioni G (2015) Adsorption of ruthenium atoms and clusters on anatase TiO2 and tetragonal ZrO2 (101) surfaces: a comparative DFT study. J Phys Chem C 119:10856–10868
Kresse G, Hafner J (1993) Ab initio molecular dynamics for liquid metals. Phys Rev B 47:558
Kresse G, Hafner J (1994) Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium. Phys Rev B 49:1425
Kresse G, Furthmüller J (1996) Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput Mater Sci 6(1):15
Kresse G, Furthmüller J (1996) Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B 54:11169
Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys Rev Lett 77:3865
Perdew JP, Burke K, Ernzerhof M (1997) Erratum: generalized gradient approximation made simple. Phys Rev Lett 78:1396
Blöchl PE (1994) Projector augmented-wave method. Phys Rev B 50:17953
Kresse G, Joubert J (1999) From ultrasoft pseudopotentials to the projector augmented-wave method. Phys Rev B 59:1758
Dudarev SL, Botton GA, Savrasov SY, Humphreys CJ, Sutton AP (1998) Electron-energy-loss spectra and the structural stability of nickel oxide: an LSDA + U study. Phys Rev B 57:1505
Hu Z, Metiu H (2011) Choice of U for DFT + U calculations for titanium oxides. J Phys Chem C 115:5841
Finazzi E, Di Valentin C, Pacchioni G, Selloni A (2008) Excess electron states in reduced bulk anatase TiO2: comparison of standard GGA, GGA + U, and hybrid DFT calculations. J Chem Phys 129:154113
Davidson E (1983) Methods in computational molecular physics. Plenum, New York
Monkhorst HJ, Pack JD (1976) Special points for Brillouin-zone integrations. Phys Rev B 13:5188
Djerdj I, Tonejc AM (2006) Structural investigations of nanocrystalline TiO2 samples. J Alloys Compd 413:159–174
Bredow T, Giordano L, Cinquini F, Pacchioni G (2004) Electronic properties of rutile TiO2 ultrathin films: Odd-even oscillations with the number of layers. Phys Rev B 70:035419
Grimme S (2006) Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J Comp Chem 27:1787
Tosoni S, Sauer J (2010) Accurate quantum chemical energies for the interaction of hydrocarbons with oxide surfaces: CH4/MgO(001). Phys Chem Chem Phys 12:14330–14340
Bader RFW (1991) A quantum theory of molecular structure and its applications. Chem Rev 91:893–928
Chen HYT, Tosoni S, Pacchioni G (2015) Hydrogen adsorption, dissociation, and spillover on Ru10 clusters supported on anatase TiO2 and tetragonal ZrO2 (101) surfaces. ACS Catal 5:5486
Ruiz Puigdollers A, Schlexer P, Pacchioni G (2015) Gold and silver clusters on TiO2 and ZrO2 (101) surfaces: role of dispersion forces. J Phys Chem C 119:15381–15389
Akamaru S, Shimazaki T, Kubo M, Abe T (2014) Density functional theory analysis of methanation reaction of CO2 on Ru nanoparticle supported on TiO2(101). Appl Catal A 470:405–411
Islam MM, Calatayud M, Pacchioni G (2011) Hydrogen adsorption and diffusion on the anatase TiO2 (101) surface: a first-principles investigation. J Phys Chem C 115:6809–6814
Dahl S, Logadottir A, Egeberg RC, Larsen JH, Chorkendorff I, Törnqvist E, Nørskov JK (1999) Role of steps in N2 activation on Ru (0001). Phys Rev Lett 83:1814
Schlexer P, Ruiz Puigdollers A, Pacchioni G (2015) Tuning the charge state of Ag and Au atoms and clusters deposited on oxide surfaces by doping: a DFT study of the adsorption properties of nitrogen-and niobium-doped TiO2 and ZrO2. Phys Chem Chem Phys 17:22342
Liu C, Yang B, Tyo E et al (2015) Carbon dioxide conversion to methanol over size-selected Cu4 clusters at low pressures. J Am Chem Soc 137:8676–8679
Schott V, Oberhofer H, Birkner A et al (2013) Chemical activity of thin oxide layers: strong interactions with the support yield a new thin-film phase of ZnO. Angew Chem Int Ed 52:11925
Acknowledgements
Financial support from the European Marie Curie Project CATSENSE (Grant Agreement No. 607417) is gratefully acknowledged. We also thank support from the Italian MIUR through the PRIN Project 2015K7FZLH SMARTNESS “Solar driven chemistry: new materials for photo- and electro-catalysis” and the Regione Lombardia and Italian CINECA supercomputing centre via the LISA joint initiative.
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Schlexer, P., Chen, HY.T. & Pacchioni, G. CO2 Activation and Hydrogenation: A Comparative DFT Study of Ru10/TiO2 and Cu10/TiO2 Model Catalysts. Catal Lett 147, 1871–1881 (2017). https://doi.org/10.1007/s10562-017-2098-1
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DOI: https://doi.org/10.1007/s10562-017-2098-1