A density functional theory study on the mechanism of dimethyl ether carbonylation over heteropolyacids catalyst

Abstract

Dimethyl ether (DME) carbonylation is considered as a key step for a promising route to produce ethanol from syngas. Heteropolyacids (HPAs) are proved to be efficient catalysts for DME carbonylation. In this work, the reaction mechanism of DME carbonylation was studied theoretically by using density functional theory calculations on two typical HPA models (HPW, HSiW). The whole process consists of three stages: DME dissociative adsorption, insertion of CO into methoxyl group and formation of product methyl acetate. The activation barriers of all possible elementary steps, especially two possible paths for CO insertion were calculated to obtain the most favorable reaction mechanism and rate-limiting step. Furthermore, the effect of the acid strength of Brønsted acid sites on reactivity was studied by comparing the activation barriers over HPW and HSiW with different acid strength, which was determined by calculating the deprotonation energy, Mulliken population analyses and adsorption energies of pyridine.

Key words： dimethyl ether; carbonylation; mechanism; heteropolyacids; density functional theory

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant No. 21325626) and the Program of Introducing Talents of Discipline to Universities (No. B06006).

References

1 Alexander E F, Richard J P, Brian T T, Andrew D J, Michael O H, Daniel M K. Ethanol can contribute to energy and environmental goals. Science, 2006, 311(5760): 506–508

2 Li L Y, Wang Q Y, Liu H C, Sun T T, Fan D, Yang M, Tian P, Liu Z M. Preparation of spherical mordenite zeolite assemblies with excellent catalytic performance for dimethyl ether carbonylation. ACS Applied Materials & Interfaces, 2018, 10(38): 32239–32246

3 Wei Q H, Yang G H, Gao X H, Tan L, Ai P P, Zhang P P, Lu P, Yoneyama Y, Tsubaki N. A facile ethanol fuel synthesis from dimethyl ether and syngas over tandem combination of Cu-doped H-ZSM-35 with Cu-Zn-Al catalyst. Chemical Engineering Journal, 2017, 316: 832–841

4 Volkova G G, Plyasova L M, Salanov A N, Kustova G N, Yurieva T M, Likholobov V A. Heterogeneous catalysts for halide-free carbonylation of dimethyl ether. Catalysis Letters, 2002, 80(3-4): 175–179

5 Volkova G G, Plyasova L M, Shkuratova L N, Budneva A A, Paukshtis E A, Timofeeva M N, Likholobov V A. Solid superacids for halide-free carbonylation of dimethyl ether to methyl acetate. Studies in Surface Science and Catalysis, 2004, 147(04): 403–408

6 Luzgin M V, Kazantsev M S, Wang W, Stepanov A G. Reactivity of methoxy species toward CO on keggin 12-H₃PW₁₂O₄₀: a study with solid state NMR. Journal of Physical Chemistry C, 2009, 113(45): 19639–19644

7 Luzgin M V, Kazantsev M S, Volkova G G, Wang W, Stepanov A G. Carbonylation of dimethyl ether on solid Rh-promoted Cs-salt of keggin 12-H₃PW₁₂O₄₀: a solid-state NMR study of the reaction mechanism. Journal of Catalysis, 2011, 277(1): 72–79

8 Luzgin M V, Kazantsev M S, Volkova G G, Stepanov A G. Solid-state NMR study of the kinetics and mechanism of dimethyl ether carbonylation on cesium salt of 12-tungstophosphoric acid modified with Ag, Pt and Rh. Journal of Catalysis, 2013, 308: 250–257

9 Boronat M, Martinez-Sanchez C, Law D, Corma A. Enzyme-like specificity in zeolites: a unique site position in mordenite for selective carbonylation of methanol and dimethyl ether with CO. Journal of the American Chemical Society, 2008, 130(48): 16316–16323

10 Li B J, Xu J, Han B, Wang X M, Qi G D, Zhang Z F, Wang C, Deng F. Insight into dimethyl ether carbonylation reaction over mordenite zeolite from in-situ solid-state NMR spectroscopy. Journal of Physical Chemistry C, 2013, 117(11): 5840–5847

11 Alsalme A M, Wiper P V, Khimyak Y Z, Kozhevnikova E F, Kozhevnikov I V. Solid acid catalysts based on 12H₃PW₁₂O₄₀ heteropoly acid: acid and catalytic properties at a gassolid interface. Journal of Catalysis, 2010, 276(1): 181–189

12 Li Y, Huang S Y, Cheng Z Z, Wang S P, Ge Q F, Ma X B. Synergy between Cu and Brønsted acid sites in carbonylation of dimethyl ether over Cu/HMOR. Journal of Catalysis, 2018, 365: 440–449

13 Li Y, Sun Q, Huang S Y, Cheng Z Z, Cai K, Lv J, Ma X B. Dimethyl ether carbonylation over pyridinemodified MOR: enhanced stability influenced by acidity. Catalysis Today, 2018, 311: 81–88

14 Lee K Y, Lee S W, Ihm S K. Acid strength control in MFI zeolite for the methanolto-hydrocarbons (MTH) reaction. Industrial & Engineering Chemistry Research, 2014, 53(24): 10072–10079

15 Opalka S M, Zhu T L. Influence of the Si/Al ratio and al distribution on the H-ZSM-5 lattice and brønsted acid site characteristics. Microporous and Mesoporous Materials, 2016, 222: 256–270

16 Meloni D, Laforge S, Martin D, Guisnet M, Rombi E, Solinas V. Acidic and catalytic properties of H-MCM-22 zeolites: 1. Characterization of the acidity by pyridine adsorption. Applied Catalysis A, General, 2001, 215(1): 55–66

17 Shen H B, Li Y, Huang S Y, Cai K, Cheng Z Z, Lv J, Ma X B. The carbonylation of dimethyl ether catalyzed by supported heteropoly acids: the role of Brønsted acid properties. Catalysis Today, 2019, 330: 117–123

18 Cai K, Huang S Y, Li Y, Cheng Z Z, Lv J, Ma X B. Influence of acid strength on the reactivity of dimethyl ether carbonylation over H-MOR. ACS Sustainable Chemistry & Engineering, 2018, 7(2): 2027–2034

19 Delley B. Hardness conserving semilocal pseudopotentials. Physical Review. B, 2002, 66(15): 155125

20 Janik M J, Campbell K A, Bardin B B, Davis R J, Neurock M. A computational and experimental study of anhydrous phosphotungstic acid and its interaction with water molecules. Applied Catalysis A, General, 2003, 256(1–2): 51–68

21 Zhang H L, Zheng A M, Yu H G, Li S L, Lu X, Deng F. Formation, location and photocatalytic reactivity of methoxy species on keggin 12-H₃PW₁₂O₄₀: a joint solid-state NMR spectroscopy and DFT calculation study. Journal of Physical Chemistry C, 2008, 112(40): 15765–15770

22 Janik M J, Macht J, Iglesia E, Neurock M. Correlating acid properties and catalytic function a first-principles analysis of alcohol. Journal of Physical Chemistry C, 2009, 113: 1872–1885

23 Carr R T, Neurock M, Iglesia E. Catalytic consequences of acid strength in the conversion of methanol to dimethyl ether. Journal of Catalysis, 2011, 278(1): 78–93

24 Yang J, Janik M J, Ma D, Zheng A M, Zhang M J, Neurock M, Davis R J, Ye C H, Deng F. Location, acid strength and mobility of the acidic protons in keggin 12-H₃PW₁₂O₄₀ a combined solid-state NMR spectroscopy and DFT quantum chemical calculation study. Journal of the American Chemical Society, 2005, 127: 18274–18280

25 Macht J, Janik M J, Neurock M, Iglesia E. Catalytic consequences of composition in polyoxometalate clusters with keggin structure. Angewandte Chemie International Edition in English, 2007, 46(41): 7864–7868

26 Yuan S P, Wang J G, Li Y W, Jiao H. Density functional investigations into the siting of Fe and the acidic properties of isomorphously substituted mordenite by B, Al, Ga and Fe. Journal of Molecular Structure THEOCHEM, 2004, 674(1): 267–274

27 Brändle M, Sauer J. Acidity differences between inorganic solids induced by their framework structure. A combined quantum mechanics/molecular mechanics ab initio study on zeolites. Journal of the American Chemical Society, 1998, 120(7): 1556–1570

28 Kazantsev M S, Luzgin M V, Stepanov A G. Carbonylation of dimethyl ether with CO on solid 12-tungstophosphoric acid: in situ magic angle spinning nmr monitoring of the reaction kinetics. Journal of Physical Chemistry C, 2013, 117(21): 11168–11175

29 Cheung P, Bhan A, Sunley G J, Iglesia E. Selective carbonylation of dimethyl ether to methyl acetate catalyzed by acidic zeolites. Angewandte Chemie International Edition in English, 2006, 45(10): 1617–1620

30 Cheung P, Bhan A, Sunley G, Law D, Iglesia E. Site requirements and elementary steps in dimethyl ether carbonylation catalyzed by acidic zeolites. Journal of Catalysis, 2007, 245(1): 110–123

31 Rasmussen D B, Christensen J M, Temel B, Studt F, Moses P G, Rossmeisl J, Riisager A, Jensen A D. Ketene as a reaction intermediate in the carbonylation of dimethyl ether to methyl acetate over mordenite. Angewandte Chemie International Edition in English, 2015, 54(25): 7261–7264

32 Cheng Z Z, Huang S Y, Li Y, Lv J, Cai K, Ma X B. Deactivation kinetics for the carbonylation of dimethyl ether to methyl acetate on H-MOR. Industrial & Engineering Chemistry Research, 2017, 56(46): 13618–13627