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Nano Research 2023, 16(3): 3709-3718 https://doi.org/10.1007/s12274-022-4848-7
Research Article | Issue | Published: 13 September 2022

Low temperature one-pot synthesis of 1,1-diethoxyethane from ethanol on Bi/BiCeOx with strong metal–support interactions

Show Author's Information Zhe An,  Jiayu Liu,  Meng Cao,  Jian Zhang,  Yanru Zhu,  Hongyan Song,  Xu Xiang,  Jing He( )
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
Keywords:
strong metal–support interaction, ethanol conversion, 1,1-diethoxyethane, Biδ+-Ov-CeIII sites
Topics:
Catalysis Catalytic oxidation
Cite this article:
An Z, Liu J, Cao M, et al. Low temperature one-pot synthesis of 1,1-diethoxyethane from ethanol on Bi/BiCeOx with strong metal–support interactions. Nano Research, 2023, 16(3): 3709-3718. https://doi.org/10.1007/s12274-022-4848-7
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Abstract Full text Electronic supplementary material About this article

The direct conversion of ethanol to 1,1-diethoxyethane (DEE) through one-pot dehydrogenation-acetalization has attracted broad interest from both academia and industry. Based on thermodynamics, the oxidative dehydrogenation of alcohol to acetaldehyde requires high temperature to activate oxygen to realize the C–H cleavage, while the acetalization of acetaldehyde with ethanol is exothermic reversible reaction favorable at low temperature. The mismatching of the reaction condition for the two consecutive steps makes it a great challenge to achieve both high ethanol conversion and high DEE selectivity. This work reports a highly efficient bi-functional catalysis by Bi/BiCeOx for one-pot oxidative dehydrogenation-acetalization route from ethanol to DEE under 150 °C and ambient pressure, affording a selectivity of 98.5% ± 0.5% to DEE at an ethanol conversion of 87.0% ± 1.0%. An efficient tandem catalysis has been achieved on the interfacial Biδ+-Ov-CeIII sites in Bi/BiCeOx established by strong metal–support interaction, in which Biδ+-Ov- sites contribute to the oxidative dehydrogenation of ethanol at mild temperature, and -Ov-CeIII sites to the subsequent acetalization between the generated acetaldehyde and ethanol.


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About this article

Low temperature one-pot synthesis of 1,1-diethoxyethane from ethanol on Bi/BiCeOx with strong metal–support interactions

Show Author's information Zhe An, Jiayu Liu, Meng Cao, Jian Zhang, Yanru Zhu, Hongyan Song, Xu Xiang, Jing He( )
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Abstract

The direct conversion of ethanol to 1,1-diethoxyethane (DEE) through one-pot dehydrogenation-acetalization has attracted broad interest from both academia and industry. Based on thermodynamics, the oxidative dehydrogenation of alcohol to acetaldehyde requires high temperature to activate oxygen to realize the C–H cleavage, while the acetalization of acetaldehyde with ethanol is exothermic reversible reaction favorable at low temperature. The mismatching of the reaction condition for the two consecutive steps makes it a great challenge to achieve both high ethanol conversion and high DEE selectivity. This work reports a highly efficient bi-functional catalysis by Bi/BiCeOx for one-pot oxidative dehydrogenation-acetalization route from ethanol to DEE under 150 °C and ambient pressure, affording a selectivity of 98.5% ± 0.5% to DEE at an ethanol conversion of 87.0% ± 1.0%. An efficient tandem catalysis has been achieved on the interfacial Biδ+-Ov-CeIII sites in Bi/BiCeOx established by strong metal–support interaction, in which Biδ+-Ov- sites contribute to the oxidative dehydrogenation of ethanol at mild temperature, and -Ov-CeIII sites to the subsequent acetalization between the generated acetaldehyde and ethanol.

Keywords: strong metal–support interaction, ethanol conversion, 1,1-diethoxyethane, Biδ+-Ov-CeIII sites

References(61)

[1]

Silva, V. M. T. M.; Rodrigues, A. E. Novel process for diethylacetal synthesis. AIChE J. 2005, 51, 2752–2768.
DOI Google Scholar
[2]

Silva, V. M. T. M.; Rodrigues, A. E. Synthesis of diethylacetal: Thermodynamic and kinetic studies. Chem. Eng. Sci. 2001, 56, 1255–1263.
DOI Google Scholar
[3]

Nord, K. E.; Haupt, D. Reducing the emission of particles from a diesel engine by adding an oxygenate to the fuel. Environ. Sci. Technol. 2005, 39, 6260–6265.
DOI Google Scholar
[4]

Yin, K.; Chao, Y. G.; Lv, F.; Tao, L.; Zhang, W. Y.; Lu, S. Y.; Li, M. G.; Zhang, Q. H.; Gu, L.; Li, H. B. et al. One nanometer PtIr nanowires as high-efficiency bifunctional catalysts for electrosynthesis of ethanol into high value-added multicarbon compound coupled with hydrogen production. J. Am. Chem. Soc. 2021, 143, 10822–10827.
DOI Google Scholar
[5]

Zhou, P.; Zhang, Q. H.; Chao, Y. G.; Wang, L.; Li, Y. J.; Chen, H.; Gu, L.; Guo S. J. Partially reduced Pd single atoms on CdS nanorods enable photocatalytic reforming of ethanol into high value-added multicarbon compound. Chem 2021, 7, 1033–1049.
DOI Google Scholar
[6]
Distillers Co Yeast Ltd; Bramwyche, P. L.; Mugdan, M.; Stanley, H. M. Improvements in or relating to the manufacture of diethyl acetal. GB Patent 625131A, September 18, 1949.
[7]

Capeletti, M. R.; Balzano, L.; de la Puente, G.; Laborde, M.; Sedran, U. Synthesis of acetal (1,1-diethoxyethane) from ethanol and acetaldehyde over acidic catalysts. Appl. Catal. A: Gen. 2000, 198, L1–L4.
DOI Google Scholar
[8]

Silva, V. M. T. M.; Rodrigues, A. E. Dynamics of a fixed-bed adsorptive reactor for synthesis of diethylacetal. AIChE J. 2002, 48, 625–634.
DOI Google Scholar
[9]

Gaspar, A. B.; Esteves, A. M. L.; Mendes, F. M. T.; Barbosa, F. G.; Appel, L. G. Chemicals from ethanol—The ethyl acetate one-pot synthesis. Appl. Catal. A: Gen. 2009, 363, 109–114.
DOI Google Scholar
[10]

Chakraborty, S.; Piszel, P. E.; Hayes, C. E.; Baker, R. T.; Jones W. D. Highly selective formation of n-butanol from ethanol through the Guerbet process: A tandem catalytic approach. J. Am. Chem. Soc. 2015, 137, 14264–14267.
DOI Google Scholar
[11]

Liu, H. C.; Iglesia, E. Selective oxidation of methanol and ethanol on supported ruthenium oxide clusters at low temperatures. J. Phys. Chem. B 2005, 109, 2155–2163.
DOI Google Scholar
[12]

Bueno, A. C.; Gonçalves, J. A.; Gusevskaya, E. V. Palladium-catalyzed oxidation of primary alcohols: Highly selective direct synthesis of acetals. Appl. Catal. A: Gen. 2007, 329, 1–6.
DOI Google Scholar
[13]

Thavornprasert, K. A.; de la Goublaye de Ménorval, B.; Capron, M.; Gornay, J.; Jalowiecki-Duhamel, L.; Sécordel, X.; Cristol, S.; Dubois, J. L.; Dumeignil, F. Selective oxidation of ethanol towards a highly valuable product over industrial and model catalysts. Biofuels 2012, 3, 25–34.
DOI Google Scholar
[14]

He, X. H.; Liu, H. C. Efficient synthesis of 1,1-diethoxyethane via sequential ethanol reactions on silica-supported copper and H-Y zeolite catalysts. Catal. Today 2014, 233, 133–139.
DOI Google Scholar
[15]

Liu, H. C.; Iglesia, E. Selective one-step synthesis of dimethoxymethane via methanol or dimethyl ether oxidation on H3+nVnMo12−nPO40 keggin structures. J. Phys. Chem. B 2003, 107, 10840–10847.
DOI Google Scholar
[16]

Kolah, A. K.; Mahajani, S. M.; Sharma, M. M. Acetalization of formaldehyde with methanol in batch and continuous reactive distillation columns. Ind. Eng. Chem. Res. 1996, 35, 3707–3720.
DOI Google Scholar
[17]

Ding, J.; Huang, L.; Ji, G. J.; Zeng, Y. W.; Chen, Z. X.; Eddings, E. G.; Fan, M. H.; Zhong, Q.; Kung, H. H. Modification of catalytic properties of hollandite manganese oxide by Ag intercalation for oxidative acetalization of ethanol to diethoxyethane. ACS Catal. 2021, 11, 5347–5357.
DOI Google Scholar
[18]

Zhang, H. X.; Zhang, W. Q.; Zhao, M.; Yang, P. J.; Zhu, Z. P. A site-holding effect of TiO2 surface hydroxyl in the photocatalytic direct synthesis of 1,1-diethoxyethane from ethanol. Chem. Commun. 2017, 53, 1518–1521.
DOI Google Scholar
[19]

Zhang, H. X.; Wu, Y. P.; Li, L.; Zhu, Z. P. Photocatalytic direct conversion of ethanol to 1,1- diethoxyethane over noble-metal-loaded TiO2 nanotubes and nanorods. Chem. Sus. Chem. 2015, 8, 1226–1231.
DOI Google Scholar
[20]

Chao, Y. G.; Zhang, W. Q.; Wu, X. M.; Gong, N. N.; Bi, Z. H.; Li, Y. Q.; Zheng, J. F.; Zhu, Z. P.; Tan, Y. S. Visible-light direct conversion of ethanol to 1,1-diethoxyethane and hydrogen over a non-precious metal photocatalyst. Chem.—Eur. J. 2019, 25, 189–194.
DOI Google Scholar
[21]

Xiao, Y.; Wang, Y.; Varma, A. Low-temperature selective oxidation of methanol over Pt-Bi bimetallic catalysts. J. Catal. 2018, 363, 144–153.
DOI Google Scholar
[22]

Besson, M.; Gallezot, P. Selective oxidation of alcohols and aldehydes on metal catalysts. Catal. Today 2000, 57, 127–141.
DOI Google Scholar
[23]

Xiao, Y.; Greeley, J.; Varma, A.; Zhao, Z. J.; Xiao, G. M. An experimental and theoretical study of glycerol oxidation to 1, 3-dihydroxyacetone over bimetallic Pt-Bi catalysts. AIChE J. 2017, 63, 705–715.
DOI Google Scholar
[24]

Zhao, S.; Dai, Z.; Guo, W. J.; Chen, F. X.; Liu, Y. L.; Chen, R. Highly selective oxidation of glycerol over Bi/Bi3.64Mo0.36O6.55 heterostructure:Dual reaction pathways induced by photogenerated 1O2 and holes. Appl. Catal. B: Environ. 2019, 244, 206–214.
DOI Google Scholar
[25]

Pearson, R. G. Hard and soft acids and bases. J. Am. Chem. Soc. 1963, 85, 3533–3539.
DOI Google Scholar
[26]

Tateiwa, J. I.; Horiuchi, H.; Uemura, S. Ce3+-exchanged montmorillonite (Ce3+-mont) as a useful substrate-selective acetalization catalyst. J. Org. Chem. 1995, 60, 4039–4043.
DOI Google Scholar
[27]

Idriss, H.; Diagne, C.; Hindermann, J. P.; Kiennemann, A.; Barteau, M. A. Reactions of acetaldehyde on CeO2 and CeO2-supported catalysts. J. Catal. 1995, 155, 219–237.
DOI Google Scholar
[28]

Calaza, F. C.; Xu, Y.; Mullins, D. R.; Overbury, S. H. Oxygen vacancy-assisted coupling and enolization of acetaldehyde on CeO2 (111). J. Am. Chem. Soc. 2012, 134, 18034–18045.
DOI Google Scholar
[29]

Millange, F.; Walton, R. I.; O’Hare, D. Time-resolved in-situ X-ray diffraction study of the liquid-phase reconstruction of Mg-Al-carbonate hydrotalcite-like compounds. J. Mater. Chem. 2000, 10, 1713–1720.
DOI Google Scholar
[30]

Fornasari, G.; Gazzano, M.; Matteuzzi, D.; Trifirò, F.; Vaccari, A. Structure and reactivity of high-surface-area Ni/Mg/Al mixed oxides. Appl. Clay Sci. 1995, 10, 69–82.
DOI Google Scholar
[31]

Mai, H. X.; Sun, L. D.; Zhang, Y. W.; Si, R.; Feng, W.; Zhang, H. P.; Liu, H. C.; Yan, C. H. Shape-selective synthesis and oxygen storage behavior of ceria nanopolyhedra, nanorods, and nanocubes. J. Phys. Chem. B 2005, 109, 24380–24385.
DOI Google Scholar
[32]

Sood, S.; Umar, A.; Mehta, S. K.; Kansal, S. K. α-Bi2O3 nanorods: An efficient sunlight active photocatalyst for degradation of Rhodamine B and 2,4,6-trichlorophenol. Ceram. Int. 2015, 41, 3355–3364.
DOI Google Scholar
[33]

Shannon, R. D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Cryst. 1976, A32, 751–767.
DOI Google Scholar
[34]

Li, G. S.; Mao, Y. C.; Li, L. P.; Feng, S. H.; Wang, M. Q.; Yao, X. Solid solubility and transport properties of nanocrystalline (CeO2)1−x(BiO1.5)x by hydrothermal conditions. Chem. Mater. 1999, 11, 1259–1266.
DOI Google Scholar
[35]

Lou, Y.; Wang, L.; Zhao, Z. Y.; Zhang, Y. H.; Zhang, Z. G.; Lu, G. Z.; Guo, Y.; Guo, Y. L. Low-temperature CO oxidation over Co3O4-based catalysts: Significant promoting effect of Bi2O3 on Co3O4 catalyst. Appl. Catal. B: Environ. 2014, 146, 43–49.
DOI Google Scholar
[36]

Grabchenko, M. V.; Mamontov, G. V.; Zaikovskii, V. I.; La Parola, V.; Liotta, L. F.; Vodyankina, O. V. The role of metal–support interaction in Ag/CeO2 catalysts for CO and soot oxidation. Appl. Catal. B: Environ. 2020, 260, 118148.
DOI Google Scholar
[37]

Aneggi, E.; Wiater, D.; de Leitenburg, C.; Llorca, J.; Trovarelli, A. Shape-dependent activity of ceria in soot combustion. ACS Catal. 2014, 4, 172–181.
DOI Google Scholar
[38]

Tauster, S. J.; Fung, S. C.; Baker, R. T. K.; Horsley, J. A. Strong interactions in supported-metal catalysts. Science 1981, 211, 1121–1125.
DOI Google Scholar
[39]

van Deelen, T. W.; Mejía, C. H.; de Jong, K. P. Control of metal–support interactions in heterogeneous catalysts to enhance activity and selectivity. Nat. Catal. 2019, 2, 955–970.
DOI Google Scholar
[40]

Ro, I.; Resasco, J.; Christopher, P. Approaches for understanding and controlling interfacial effects in oxide-supported metal catalysts. ACS Catal. 2018, 8, 7368–7387.
DOI Google Scholar
[41]

Morgan, W. E.; Stec, W. J.; Van Wazer, J. R. Inner-orbital binding-energy shifts of antimony and bismuth compounds. Inorg. Chem. 1973, 12, 953–955.
DOI Google Scholar
[42]

Zhang, Q.; Zhou, Y.; Wang, F.; Dong, F.; Li, W.; Li, H. M.; Patzke, G. R. From semiconductors to semimetals: Bismuth as a photocatalyst for NO oxidation in air. J. Mater. Chem. A 2014, 2, 11065–11072.
DOI Google Scholar
[43]

Zhao, Z. W.; Zhang, W. D.; Lv, X. S.; Sun, Y. J.; Dong, F.; Zhang, Y. X. Noble metal-free Bi nanoparticles supported on TiO2 with plasmon-enhanced visible light photocatalytic air purification. Environ. Sci.: Nano 2016, 3, 1306–1317.
DOI Google Scholar
[44]

Lai, M.; Zhao, J.; Chen, Q. C.; Feng, S. J.; Bai, Y. J.; Li, Y. X.; Wang, C. Y. Photocatalytic toluene degradation over Bi-decorated TiO2: Promoted O2 supply to catalyst’s surface by metallic Bi. Catal. Today 2019, 335, 372–380.
DOI Google Scholar
[45]

Zhang, X. Y.; Yang, P. F.; Liu, Y. N.; Pan, J. H.; Li, D. Q.; Wang, B.; Feng, J. T. Support morphology effect on the selective oxidation of glycerol over AuPt/CeO2 catalysts. J. Catal. 2020, 385, 146–159.
DOI Google Scholar
[46]

Liu, M. H.; Wu, X. D.; Liu, S.; Gao, Y. X.; Chen, Z.; Ma, Y.; Ran, R.; Weng, D. Study of Ag/CeO2 catalysts for naphthalene oxidation: Balancing the oxygen availability and oxygen regeneration capacity. Appl. Catal. B: Environ. 2017, 219, 231–240.
DOI Google Scholar
[47]

Zhang, X.; Wang, D. K.; Jing, M. Z.; Liu, J.; Zhao, Z.; Xu, G. H.; Song, W. Y.; Wei, Y. C.; Sun, Y. Q. Ordered mesoporous CeO2-supported Ag as an effective catalyst for carboxylative coupling reaction using CO2. ChemCatChem 2019, 11, 2089–2098.
DOI Google Scholar
[48]

Liu, S.; Wu, X. D.; Liu, W.; Chen, W. M.; Ran, R.; Li, M.; Weng, D. Soot oxidation over CeO2 and Ag/CeO2: Factors determining the catalyst activity and stability during reaction. J. Catal. 2016, 337, 188–198.
DOI Google Scholar
[49]

Binet, C.; Daturi, M.; Lavalley, J. C. IR study of polycrystalline ceria properties in oxidised and reduced states. Catal. Today 1999, 50, 207–225.
DOI Google Scholar
[50]

Aliotta, C.; Liotta, L. F.; La Parola, V.; Martorana, A.; Muccillo, E. N. S.; Muccillo, R.; Deganello, F. Ceria-based electrolytes prepared by solution combustion synthesis: The role of fuel on the materials properties. Appl. Catal. B: Environ. 2016, 197, 14–22.
DOI Google Scholar
[51]

Hu, Z.; Liu, X. F.; Meng, D. M.; Guo, Y.; Guo, Y. L.; Lu, G. Z. Effect of ceria crystal plane on the physicochemical and catalytic properties of Pd/ceria for CO and propane oxidation. ACS Catal. 2016, 6, 2265–2279.
DOI Google Scholar
[52]

Kang, D. J.; Yu, X. L.; Ge, M. F. Morphology-dependent properties and adsorption performance of CeO2 for fluoride removal. Chem. Eng. J. 2017, 330, 36–43.
DOI Google Scholar
[53]

Hao, Q.; Wang, R. T.; Lu, H. J.; Xie, C. A.; Ao, W. H.; Chen, D. M.; Ma, C.; Yao, W. Q.; Zhu, Y. F. One-pot synthesis of C/Bi/Bi2O3 composite with enhanced photocatalytic activity. Appl. Catal. B: Environ. 2017, 219, 63–72.
DOI Google Scholar
[54]

Hardcastle, F. D.; Wachs, I. E. The molecular structure of bismuth oxide by Raman spectroscopy. J. Solid State Chem. 1992, 97, 319–331.
DOI Google Scholar
[55]

Lu, Y. F.; Huang, Y.; Zhang, Y. F.; Cao, J. J.; Li, H. W.; Bian, C.; Lee, S. C. Oxygen vacancy engineering of Bi2O3/Bi2O2CO3 heterojunctions: Implications of the interfacial charge transfer, NO adsorption and removal. Appl. Catal. B: Environ. 2018, 231, 357–367.
DOI Google Scholar
[56]

Emeis, C. A. Determination of integrated molar extinction coefficients for infrared absorption bands of pyridine adsorbed on solid acid catalysts. J. Catal. 1993, 141, 347–354.
DOI Google Scholar
[57]

Zaki, M. I.; Hasan, M. A.; Al-Sagheer, F. A.; Pasupulety L. In situ FTIR spectra of pyridine adsorbed on SiO2-Al2O3, TiO2, ZrO2 and CeO2: General considerations for the identification of acid sites on surfaces of finely divided metal oxides. Colloids Surf. A: Physicochem. Eng. Aspects 2001, 190, 261–274.
DOI Google Scholar
[58]

Mann, A. K. P.; Wu, Z. L.; Calaza, F. C.; Overbury, S. H. Adsorption and reaction of acetaldehyde on shape-controlled CeO2 nanocrystals: Elucidation of structure–function relationships. ACS Catal. 2014, 4, 2437–2448.
DOI Google Scholar
[59]

Ochoa, J. V.; Trevisanut, C.; Millet, J. M. M.; Busca, G.; Cavani, F. In situ DRIFTS-MS study of the anaerobic oxidation of ethanol over spinel mixed oxides. J. Phys. Chem. C 2013, 117, 23908–23918.
DOI Google Scholar
[60]

Llorca, J.; Homs, N.; de la Piscina, P. R. In situ DRIFT-mass spectrometry study of the ethanol steam-reforming reaction over carbonyl-derived Co/ZnO catalysts. J. Catal. 2004, 227, 556–560.
DOI Google Scholar
[61]

Taifan, W. E.; Yan, G. X.; Baltrusaitis, J. Surface chemistry of MgO/SiO2 catalyst during the ethanol catalytic conversion to 1,3-butadiene: In-situ DRIFTS and DFT study. Catal. Sci. Technol. 2017, 7, 4648–4668.
DOI Google Scholar
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Publication history
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Acknowledgements

Publication history

Received: 26 May 2022
Revised: 14 July 2022
Accepted: 02 August 2022
Published: 13 September 2022
Issue date: March 2023

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

Financial support from the National Natural Science Foundation of China (Nos. 22138001 and 21521005) and the National Key R&D Program of China (No. 2017YFA0206804) is acknowledged. We thank the support of Beijing Engineering Center for Hierarchical Catalysts.

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