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Supplementary Materials for original manuscript submitted for publication in special issue of International Journal of Quantum Chemistry Carbonates in zeolites: formation, properties, reactivity Andrey A. Rybakov*a, Ilya, A. Bryukhanovb, Alexander V. Larina, Georgy M. Zhidomirova, c a Department of Chemistry, Moscow State University, Leninskie Gory, Moscow, GSP-2, Russia 119992; bDepartment of Mechanics and Mathematics, Moscow State University, Leninskie Gory, Moscow, GSP-2, 119992 Russia; cBoreskov Institute of Catalysis, SB RAS, Novosibirsk, 630090, Russia Ph. 7-495-939-3952, Fax 7-495-932-8846 TOTAL PAGES 8 TABLE 1 FIGURE 1 *) corresponding author: [email protected] S1. Water influence on Cu-carbonate formation Regarding the easiness of CH4 oxidation over CuOXCu moieties [S1-S4], one can propose that CO oxidation to CO2 should not be a limiting stage. Then the Cu-carbonate formation via the reactions between CO2 and CuOXCu moieties can be tested similarly to the route from EA oxide MeOXMe clusters [S5-S6], X = 1 - 2. The Part 3.2 justifies the application of the DFT tools relative to our cluster models containing CuOXCu moieties, X = 1 - 2, which can react to produce the carbonates. We can now check: 1) the activation energy of carbonate formation due to the reaction between CO2 and CuOCu species and 2) how the reaction of carbonate formation will depend on the presence of water. A reaction cycle will have additional attraction if the reaction will not require a high temperature treatment for full dehydration. The reaction of CO2 and CuOCu-8R(2Al) without water presents a first problem at the step of the reagents optimization. We have optimized a metastable structure (-3489.990800 a.u. in Table S1, Fig. S1a) which is less stable than the separated reagents (at infinity) (-3489.998780 a.u. in Table S1) and respective transition state (TS) (Fig. S1b). The Cu-O distance for the closest O atom of CO2 is 2.498 Å, the latter is tilt relative to one of the cations with a minor deformation (O-C-O = 177.6°, |C-O| = 1.163 and 1.177 Å). While using the metastable structure as reagents for the search of the TS geometry with QST3 method [S7], we have obtained the TS geometry (Fig. S1b) with required frequency of 268i cm-1 which is more stable than the structure (Fig. S1a) but less stable than separated reagents (Table 8). If one use the energy of the separated reagents as the estimation of the reagent energy, then the activation barrier for the CuCO3Cu formation can be conventionally evaluated Ea < 2.36 kcal/mol without water. This small barrier shows quick trapping of CO2 by CuOCu at room temperature. This activation energy rises only up to 5.18 kcal/mol if one water molecule is coordinated to the Cu cation of CuOCu-8R(2Al) which is not linked to CO2 (Fig. S1f). Such structure with non-dissociated water (Fig. S1f) remains more stable (as much as by 18.09 kcal/mol) than possible hydrocarbonate (HO)CuНCO3Cu(8R) (Fig. S1g). We did not succeed to find the TS geometry for its transformation into (H2O)CuCO3Cu(8R) using cluster approach. Once looking for a stable configuration for dissociated water with proton at the O atom of the 8R ring we observed the easy recombination of water and thus obtained more symmetric and more stable carbonate geometry together with water (Fig. S1j) than the asymmetric one (Fig. S1f) achieved via the reaction of CuOCu with CO2 (Fig. S1c, f) whose configuration does not depends on the presence of adsorbed water. In the terms of (Eq. 1) asymmetry parameter, this more symmetric carbonate possesses of 0.083 Å (Fig. S1j) instead of 0.243 Å for asymmetric one. In order to evaluate respective band splitting (BS) one could address to Fig. 1 of ref. [S8] (or Fig. 4 from ref. [S9]) where the fitted linear approximation BS() at the B3LYP/6-31G* level is depicted by dotted line. Then = 0.083 Å corresponds to the BS value around of 220-230 cm-1 from the Figure 1 of ref. [S8] that is in good agreement with experimental BS values of 226 cm-1 [S10] or 221 cm-1 [S11]. It signifies that the carbonate (Fig. S1j) suits very well to the spectroscopic data about the observed species which exists along the DMC formation reaction in CuY [S10-S11]1. Moreover, carbonate is stable in a reaction with water. We have observed a moderate reactivity of the CuOCu-8R(2Al) cluster relative to the water. Its heat of adsorption takes 21.1 kcal/mol without the zero point energy (ZPE) variation. This heat value is in the usual range for the heats of water adsorption at the zeolites with transition metal cations [S12]. The minor shift of the ZPE can be evaluated from the ZPE variation upon adsorption in similar systems, i.e., less than 0.4 and 0.6 kcal/mol at Mg2+ и Ca2+ forms, respectively [S13-S13]. The non-dissociated state is favored for water in the Cu8R(2Al) cluster with a recombination barrier of 2.3 kcal/mol and imaginary frequency of 1228i cm-1 (Fig. S1k). In this respect the Cu+2 resembles the EA cations [S13-S13]. However, this more symmetric form slightly varies upon the loss of water (not shown) achieving = 0.079 Å being less stable than the asymmetric one (-3490.027523 a.u. in Table 8) by 1.2 kcal/mol. 1 References [S1] J. S. Woertink, P. J. Smeets, M. H. Groothaert, M. A. Vance, B. F. Sels, R. A. Schoonheydt, E. I. Solomon, Proc. Natl. Acad. Sci. U. S. A., 2009, 106, 18908–13. [S2] P. J. Smeets, M. H. Groothaert, R. A. Schoonheydt, Catal. Today, 2005, 110, 303–309. [S3] M. H. Groothaert, P. J. Smeets, B. F. Sels, P. A. Jacobs, R. A. Schoonheydt, J. Am. Chem. Soc., 2005, 127, 1394–5. [S4] P. Vanelderen, R. G. Hadt, P. J. Smeets, E. I. Solomon, R. A. Schoonheydt, B. F. Sels, J. Catal., 2011, 284, 157–164. [S5] G. M. Zhidomirov, A. A. Shubin, A.V. Larin, S.I. Malykhin, A. A. Rybakov, Molecular models of active sites of zeolite catalysts; J. Leszczynski and M.K. Shukla, Eds.; Practical Aspects of Computational Chemistry I. An Overview of the Last Two Decades and Current Trends, Springer Science+Business Media B.V., 2012, XV, p. 579-644. [S6] G. M. Zhidomirov, A. V. Larin, D. N. Trubnikov, D. P. Vercauteren, J. Phys. Chem. C, 2009, 113, 8258–8265. [S7] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian 09, Revision A.1, Gaussian, Inc., Wallingford CT, 2009. [S8] A. V. Larin, I. A. Bryukhanov, A. A. Rybakov, V. L. Kovalev, D. P. Vercauteren, Microporous Mesoporous Mater., 2013, 173, 15–21. [S9] A. V. Larin, Microporous Mesoporous Mater., 2014, 200, 35–45. [S10] J. Engeldinger, M. Richter, U. Bentrup, Phys. Chem. Chem. Phys., 2012, 14, 2183. [S11] J. Engeldinger, C. Domke, M. Richter, U. Bentrup, Appl. Catal. A Gen., 2010, 382, 303– 311. [S12] B.V. Romanovsky, K.V.Topchieva, L.V. Stolyarova, A.M. Alekseev, Kinet. Katal., 1970, 11, 1525−1530. [S13] A. V. Larin, A. A. Rybakov, G. M. Zhidomirov, J. Phys. Chem. C, 2012, 116, 2399–2410. [S14] A. A. Rybakov, A. V. Larin, G. M. Zhidomirov, Inorg. Chem., 2012, 51, 12165–12175. Table S1. The energies (U, kcal/mol) of the formation steps (a.u.) of copper carbonate in the cluster Z = 8R(2Al) with and without water and activation energy (Ea, kcal/mol). The barriers for TS are shown in Figure S1. Activation energy or heat of the reactions (given in Fig. S1) are shown in brackets for TS or products, respectively. System -U, a.u. Figure <Cu2O-Z + CO2> <3489.990800> S1a Isolated Cu2O-Z and CO2 3489.998780 b) TS (Ea = <2.4> ) 3489.995014 S1b 3490.029590 S1c Cu2CO3 – Z (U = -24.3) а) (H2O)Cu2O-Z + CO2 3566.439243 S1d TS (Ea = 5.2) 3566.430990 S1e 3566.470210 S1f (H2O)Cu2CO3 – Z (U = -19.4) (HO)CuНCO3Cu-Z 3566.441374 S1g (HO)Cu-O(H)-Cu-Z + CO2 3566.443558 S1h TS (Ea = 15.7)a) 3566.418523 S1i (H2O)Cu2CO3 – Z 3566.475126 S1j Cu2CO3 – Z 3490.027523 (HO)Cu – HZ 3106.462957 TS (Ea = 2.3) 3106.459254 S1k (H2O)Cu – Z 3106.476524 H2O 76.407024 CO2 188.577570 Cu2O– Z 3301.421210 а) the reagents are (HO)Cu-O(H)-Cu-Z + CO2 (Fig. S1h), while the product is Cu2CO3 – Z + H2O (see the text); b) relative to the energy of isolated Cu2O-Z + CO2 species Figure caption Figure S1. Local geometries of (a, d, h) reagents, (b, e, i, k) transition states, (c, f, g, j) products of the reactions between the Cu28R(2Al) cluster and CO2 or/and H2O optimized at the B3LYP/631G* level. Only transition state (k) for H2O dissociation is shown. The arrows connect three steps of three reactions (reagent transition state product, two of them possess a common product (f)). More data about the structures are collected in Table 8. The atomic colors are given in blue, red, yellow, magenta, and grey for Cu, O, Si, Al, and H, respectively. Figure S1 a) b) Ea < 2.4 c) d) e) Ea = 5.2 f) g) h) i) Ea = 15.7 j) k) Ea = 2.3