Non-oxidative ethanol dehydrogenation is a renewable source of acetaldehyde and hydrogen. The reaction is often catalyzed by supported copper catalysts with high selectivity. The activity and long-term stability depend on many factors, including particle size, choice of support, doping, etc. Herein, we present four different synthetic pathways to prepare Cu/SiO2 catalysts (∼2.5 wt % Cu) with varying copper distribution: hydrolytic sol-gel (sub-nanometer clusters), dry impregnation (A̅ = 3.4 nm; σ = 0.9 nm and particles up to 32 nm), strong electrostatic adsorption (A̅ = 3.1 nm; σ = 0.6 nm), and solvothermal hot injection followed by Cu particle deposition (A̅ = 4.0 nm; σ = 0.8 nm). All materials were characterized by ICP-OES, XPS, N2 physisorption, STEM-EDS, XRD, RFC N2O, and H2-TPR and tested in ethanol dehydrogenation from 185 to 325 °C. The sample prepared by hydrolytic sol-gel exhibited high Cu dispersion and, accordingly, the highest catalytic activity. Its acetaldehyde productivity (2.79 g g-1 h-1 at 255 °C) outperforms most of the Cu-based catalysts reported in the literature, but it lacks stability and tends to deactivate over time. On the other hand, the sample prepared by simple and cost-effective dry impregnation, despite having Cu particles of various sizes, was still highly active (2.42 g g-1 h-1 acetaldehyde at 255 °C). Importantly, it was the most stable sample out of the studied materials. The characterization of the spent catalyst confirmed its exceptional properties: it showed the lowest extent of both coking and particle sintering.

CEITEC Brno University of Technology Purkynova 123 CZ 61200 Brno Czech Republic

Consiglio Nazionale delle Ricerche Istituto di Scienze e Tecnologie Chimiche G Natta Via Golgi 19 20133 Milano Italy

Department of Chemistry Masaryk University Kotlarska 2 CZ 61137 Brno Czech Republic

Institute of Environmental Technology CEET VSB TUO 17 listopadu 2172 15 CZ 70800 Ostrava Czech Republic

Institute of Physics of Materials Academy of Sciences of the Czech Republic Zizkova 22 CZ 61662 Brno Czech Republic

Zobrazit více v PubMed

Veleva V.; Ellenbecker M. Indicators of Sustainable Production: Framework and Methodology. J. Cleaner Prod. 2001, 9, 519–549. 10.1016/S0959-6526(01)00010-5. DOI

Ueda W. Functions and Activities of Catalysis Research Center, Hokkaido University, for Catalysis Research Communities. Catal. Surv. Asia 2009, 13, 143–146. 10.1007/s10563-009-9073-9. DOI

Grison C.; Lock Toy Ki Y. Ecocatalysis, a New Vision of Green and Sustainable Chemistry. Curr. Opin. Green Sustainable Chem. 2021, 29, 100461 10.1016/j.cogsc.2021.100461. DOI

White W. C. Butadiene Production Process Overview. Chem.-Biol. Interact. 2007, 166, 10–14. 10.1016/j.cbi.2007.01.009. PubMed DOI

Cespi D.; Passarini F.; Vassura I.; Cavani F. Butadiene from Biomass, a Life Cycle Perspective to Address Sustainability in the Chemical Industry. Green Chem. 2016, 18, 1625–1638. 10.1039/C5GC02148K. DOI

Pomalaza G.; Capron M.; Ordomsky V.; Dumeignil F. Recent Breakthroughs in the Conversion of Ethanol to Butadiene. Catalysts 2016, 6, 203. 10.3390/catal6120203. DOI

Pomalaza G.; Arango Ponton P.; Capron M.; Dumeignil F. Ethanol-to-Butadiene: The Reaction and Its Catalysts. Catal. Sci. Technol. 2020, 10, 4860–4911. 10.1039/D0CY00784F. DOI

Shylesh S.; Gokhale A. A.; Scown C. D.; Kim D.; Ho C. R.; Bell A. T. From Sugars to Wheels: The Conversion of Ethanol to 1,3-Butadiene over Metal-Promoted Magnesia-Silicate Catalysts. ChemSusChem 2016, 9, 1462–1472. 10.1002/cssc.201600195. PubMed DOI

Jira R. Acetaldehyde from Ethylene-A Retrospective on the Discovery of the Wacker Process. Angew. Chem., Int. Ed. 2009, 48, 9034–9037. 10.1002/anie.200903992. PubMed DOI

Seifzadeh Haghighi S.; Rahimpour M. R.; Raeissi S.; Dehghani O. Investigation of Ethylene Production in Naphtha Thermal Cracking Plant in Presence of Steam and Carbon Dioxide. Chem. Eng. J. 2013, 228, 1158–1167. 10.1016/j.cej.2013.05.048. DOI

Fernandes R. A.; Jha A. K.; Kumar P. Recent Advances in Wacker Oxidation: From Conventional to Modern Variants and Applications. Catal. Sci. Technol. 2020, 10, 7448–7470. 10.1039/D0CY01820A. DOI

Lebedev Process . InComprehensive Organic Name Reactions and Reagents; John Wiley & Sons, Inc.: Hoboken, NJ, USA, NJ, USA, 2010.

Cheong J. L.; Shao Y.; Tan S. J. R.; Li X.; Zhang Y.; Lee S. S. Highly Active and Selective Zr/MCF Catalyst for Production of 1,3-Butadiene from Ethanol in a Dual Fixed Bed Reactor System. ACS Sustainable Chem. Eng. 2016, 4, 4887–4894. 10.1021/acssuschemeng.6b01193. DOI

Yuan E.; Ni P.; Xie J.; Jian P.; Hou X. Highly Efficient Dehydrogenation of 2,3-Butanediol Induced by Metal–Support Interface over Cu-SiO 2 Catalysts. ACS Sustainable Chem. Eng. 2020, 8, 15716–15731. 10.1021/acssuschemeng.0c05589. DOI

Hradsky D.; Machac P.; Skoda D.; Leonova L.; Sazama P.; Pastvova J.; Kaucky D.; Vsiansky D.; Moravec Z.; Styskalik A. Catalytic Performance of Micro-Mesoporous Zirconosilicates Prepared by Non-Hydrolytic Sol-Gel in Ethanol-Acetaldehyde Conversion to Butadiene and Related Reactions. Appl. Catal., A 2023, 652, 119037 10.1016/j.apcata.2023.119037. DOI

Angelici C.; Velthoen M. E. Z.; Weckhuysen B. M.; Bruijnincx P. C. A. Influence of Acid–Base Properties on the Lebedev Ethanol-to-Butadiene Process Catalyzed by SiO DOI

Kyriienko P. I.; Larina O. V.; Soloviev S. O.; Orlyk S. M.; Calers C.; Dzwigaj S. Ethanol Conversion into 1,3-Butadiene by the Lebedev Method over MTaSiBEA Zeolites (M = Ag, Cu, Zn). ACS Sustainable Chem. Eng. 2017, 5, 2075–2083. 10.1021/acssuschemeng.6b01728. DOI

Sun J.; Wang Y. Recent Advances in Catalytic Conversion of Ethanol to Chemicals. ACS Catal. 2014, 4, 1078–1090. 10.1021/cs4011343. DOI

Zhang H.; Tan H.-R.; Jaenicke S.; Chuah G.-K. Highly Efficient and Robust Cu Catalyst for Non-Oxidative Dehydrogenation of Ethanol to Acetaldehyde and Hydrogen. J. Catal. 2020, 389, 19–28. 10.1016/j.jcat.2020.05.018. DOI

Yu D.; Dai W.; Wu G.; Guan N.; Li L. Stabilizing Copper Species Using Zeolite for Ethanol Catalytic Dehydrogenation to Acetaldehyde. Chin. J. Catal. 2019, 40, 1375–1384. 10.1016/S1872-2067(19)63378-4. DOI

Ob-eye J.; Praserthdam P.; Jongsomjit B. Dehydrogenation of Ethanol to Acetaldehyde over Different Metals Supported on Carbon Catalysts. Catalysts 2019, 9, 66. 10.3390/catal9010066. DOI

Campisano I. S. P.; Rodella C. B.; Sousa Z. S. B.; Henriques C. A.; Teixeira da Silva V. Influence of Thermal Treatment Conditions on the Characteristics of Cu-Based Metal Oxides Derived from Hydrotalcite-like Compounds and Their Performance in Bio-Ethanol Dehydrogenation to Acetaldehyde. Catal. Today 2018, 306, 111–120. 10.1016/j.cattod.2017.03.017. DOI

Amokrane S.; Boualouache A.; Simon P.; Capron M.; Otmanine G.; Allam D.; Hocine S. Effect of Adding Transition Metals to Copper on the Dehydrogenation Reaction of Ethanol. Catal. Lett. 2021, 151, 2864–2883. 10.1007/s10562-020-03517-0. DOI

Church J. M.; Joshi H. K. Acetaldehyde by Dehydrogenation of Ethyl Alcohol. Ind. Eng. Chem. 1951, 43, 1804–1811. 10.1021/ie50500a035. DOI

Volanti D. P.; Sato A. G.; Orlandi M. O.; Bueno J. M. C.; Longo E.; Andrés J. Insight into Copper-Based Catalysts: Microwave-Assisted Morphosynthesis, In Situ Reduction Studies, and Dehydrogenation of Ethanol. ChemCatChem 2011, 3, 839–843. 10.1002/cctc.201000462. DOI

Wang Q. N.; Shi L.; Lu A. H. Highly Selective Copper Catalyst Supported on Mesoporous Carbon for the Dehydrogenation of Ethanol to Acetaldehyde. ChemCatChem 2015, 7, 2846–2852. 10.1002/cctc.201500501. DOI

Zhang P.; Wang Q. N.; Yang X.; Wang D.; Li W. C.; Zheng Y.; Chen M.; Lu A. H. A Highly Porous Carbon Support Rich in Graphitic-N Stabilizes Copper Nanocatalysts for Efficient Ethanol Dehydrogenation. ChemCatChem 2017, 9, 505–510. 10.1002/cctc.201601373. DOI

Cheng S. Q.; Weng X. F.; Wang Q. N.; Zhou B. C.; Li W. C.; Li M. R.; He L.; Wang D. Q.; Lu A. H. Defect-Rich BN-Supported Cu with Superior Dispersion for Ethanol Conversion to Aldehyde and Hydrogen. Chin. J. Catal. 2022, 43, 1092–1100. 10.1016/S1872-2067(21)63891-3. DOI

Freitas I. C.; Damyanova S.; Oliveira D. C.; Marques C. M. P.; Bueno J. M. C. Effect of Cu Content on the Surface and Catalytic Properties of Cu/ZrO2 Catalyst for Ethanol Dehydrogenation. J. Mol. Catal. A: Chem. 2014, 381, 26–37. 10.1016/j.molcata.2013.09.038. DOI

Fujita S.; Iwasa N.; Tani H.; Nomura W.; Arai M.; Takezawa N. Dehydrogenation Of Ethanol Over Cu / Zno Catalysts. React. Kinet. Catal. Lett. 2001, 73, 367–372. 10.1023/A:1014192214324. DOI

Yergaziyeva G. Y.; Dossumov K.; Mambetova M. M.; Strizhak P. Y.; Kurokawa H.; Baizhomartov B. Effect of Ni, La, and Ce Oxides on a Cu/Al DOI

Tu Y.-J.; Chen Y.-W. Effects of Alkali Metal Oxide Additives on Cu/SiO DOI

Li M.-Y.; Lu W.-D.; He L.; Schüth F.; Lu A.-H. Tailoring the Surface Structure of Silicon Carbide Support for Copper Catalyzed Ethanol Dehydrogenation. ChemCatChem 2019, 11, 481. 10.1002/cctc.201801742. DOI

Wong A.; Liu Q.; Griffin S.; Nicholls A.; Regalbuto J. R. Synthesis of Ultrasmall, Homogeneously Alloyed, Bimetallic Nanoparticles on Silica Supports. Science 2017, 358, 1427–1430. 10.1126/science.aao6538. PubMed DOI

Vykoukal V.; Halasta V.; Babiak M.; Bursik J.; Pinkas J. Morphology Control in AgCu Nanoalloy Synthesis by Molecular Cu(I) Precursors. Inorg. Chem. 2019, 58, 15246–15254. 10.1021/acs.inorgchem.9b02172. PubMed DOI

Sopousek J.; Vrestal J.; Pinkas J.; Broz P.; Bursik J.; Styskalik A.; Skoda D.; Zobac O.; Lee J. Cu-Ni Nanoalloy Phase Diagram - Prediction and Experiment. Calphad 2014, 45, 33–39. 10.1016/j.calphad.2013.11.004. DOI

Sopoušek J.; Pinkas J.; Brož P.; Buršík J.; Vykoukal V.; Škoda D.; Stýskalík A.; Zobač O.; Vřešt’ál J.; Hrdlička A.; Šimbera J. Ag-Cu Colloid Synthesis: Bimetallic Nanoparticle Characterisation and Thermal Treatment. J. Nanomater. 2014, 2014, 1. 10.1155/2014/638964. DOI

Wang Z.; Liu Q.; Yu J.; Wu T.; Wang G. Surface Structure and Catalytic Behavior of Silica-Supported Copper Catalysts Prepared by Impregnation and Sol–Gel Methods. Appl. Catal., A 2003, 239, 87–94. 10.1016/S0926-860X(02)00421-0. DOI

Makshina E. V.; Janssens W.; Sels B. F.; Jacobs P. A. Catalytic Study of the Conversion of Ethanol into 1,3-Butadiene. Catal. Today 2012, 198, 338–344. 10.1016/j.cattod.2012.05.031. DOI

Bhattacharyya S. K.; Avasthi B. N. One-Step Catalytic Conversion of Ethanol to Butadiene in a Fluidized Bed. Ind. Eng. Chem. Process Des. Dev. 1963, 2, 45–51. 10.1021/i260005a010. DOI

Angelici C.; Weckhuysen B. M.; Bruijnincx P. C. A. Chemocatalytic Conversion of Ethanol into Butadiene and Other Bulk Chemicals. ChemSusChem 2013, 6, 1595–1614. 10.1002/cssc.201300214. PubMed DOI

Dochain D. D.; Stýskalik A.; Debecker D. P. Ag- and Cu-Promoted Mesoporous Ta-SiO2 Catalysts Prepared by Non-Hydrolytic Sol-Gel for the Conversion of Ethanol to Butadiene. Catalysts 2019, 9, 920. 10.3390/catal9110920. DOI

Makshina E. V.; Dusselier M.; Janssens W.; Degrève J.; Jacobs P. A.; Sels B. F. Review of Old Chemistry and New Catalytic Advances in the On-Purpose Synthesis of Butadiene. Chem. Soc. Rev. 2014, 43, 7917–7953. 10.1039/C4CS00105B. PubMed DOI

Jiao L.; Regalbuto J. R. The Synthesis of Highly Dispersed Noble and Base Metals on Silica via Strong Electrostatic Adsorption: I. Amorphous Silica. J. Catal. 2008, 260, 329–341. 10.1016/j.jcat.2008.09.022. DOI

Schneider C. A.; Rasband W. S.; Eliceiri K. W. NIH Image to ImageJ: 25 Years of Image Analysis. Nat. Methods 2012, 9, 671–675. 10.1038/nmeth.2089. PubMed DOI PMC

Scotti N.; Finocchio E.; Evangelisti C.; Marelli M.; Psaro R.; Ravasio N.; Zaccheria F. Some Insight on the Structure/Activity Relationship of Metal Nanoparticles in Cu/SiO2 Catalysts. Chin. J. Catal. 2019, 40, 1788–1794. 10.1016/S1872-2067(19)63392-9. DOI

Scotti N.; Dangate M.; Gervasini A.; Evangelisti C.; Ravasio N.; Zaccheria F. Unraveling the Role of Low Coordination Sites in a Cu Metal Nanoparticle: A Step toward the Selective Synthesis of Second Generation Biofuels. ACS Catal. 2014, 4, 2818. 10.1021/cs500581a. DOI

Mori K.; Hara T.; Mizugaki T.; Ebitani K.; Kaneda K. Hydroxyapatite-Supported Palladium Nanoclusters: A Highly Active Heterogeneous Catalyst for Selective Oxidation of Alcohols by Use of Molecular Oxygen. J. Am. Chem. Soc. 2004, 126, 10657. 10.1021/ja0488683. PubMed DOI

Dvořák B.; Hudec A.; Pašek J. Measurements of Specific Copper Surface Area by a Pulse Chromatographic Technique. Collect. Czech. Chem. Commun. 1989, 54, 1514–1529. 10.1135/cccc19891514. DOI

Chinchen G. C.; Hay C. M.; Vandervell H. D.; Waugh K. C. The Measurement of Copper Surface Areas by Reactive Frontal Chromatography. J. Catal. 1987, 103, 79–86. 10.1016/0021-9517(87)90094-7. DOI

Kriesel J. W.; Sander M. S.; Tilley T. D. Block Copolymer-Assisted Synthesis of Mesoporous, Multicomponent Oxides by Nonhydrolytic, Thermolytic Decomposition of Molecular Precursors in Nonpolar Media. Chem. Mater. 2001, 13, 3554–3563. 10.1021/cm010068t. DOI

Guerreiro E. D.; Gorriz O. F.; Rivarola J. B.; Arrúa L. A. Characterization of Cu/SiO2 Catalysts Prepared by Ion Exchange for Methanol Dehydrogenation. Appl. Catal. A 1997, 165, 259–271. 10.1016/S0926-860X(97)00207-X. DOI

Kohler M. A.; Lee J. C.; Trimm D. L.; Cant N. W.; Wainwright M. S. Preparation of Cu/SiO2 Catalysts by the Ion-Exchange Technique. Appl. Catal. 1987, 31, 309–321. 10.1016/S0166-9834(00)80699-5. DOI

Zaccheria F.; Scotti N.; Marelli M.; Psaro R.; Ravasio N. Unravelling the Properties of Supported Copper Oxide: Can the Particle Size Induce Acidic Behaviour?. Dalton Trans. 2013, 42, 1319–1328. 10.1039/C2DT32454G. PubMed DOI

Wang K.-W.; Yeh C.-T. Temperature-Programmed Reduction Study on Carbon-Supported Platinum–Gold Alloy Catalysts. J. Colloid Interface Sci. 2008, 325, 203–206. 10.1016/j.jcis.2008.04.069. PubMed DOI

Sato A. G.; Volanti D. P.; de Freitas I. C.; Longo E.; Bueno J. M. C. Site-Selective Ethanol Conversion over Supported Copper Catalysts. Catal. Commun. 2012, 26, 122–126. 10.1016/j.catcom.2012.05.008. DOI

Wang Q.-N.; Shi L.; Li W.; Li W.-C.; Si R.; Schüth F.; Lu A.-H. Cu Supported on Thin Carbon Layer-Coated Porous SiO 2 for Efficient Ethanol Dehydrogenation. Catal. Sci. Technol. 2018, 8, 472–479. 10.1039/C7CY02057K. DOI

Copper Phosphinate Complexes as Molecular Precursors for Ethanol Dehydrogenation Catalysts