The transfer hydrogenation of levulinic acid to γ-valerolactone over CuNiAl catalyst

Abstract

The catalytic performance of heterogeneous catalysts remains a great challenge for large-scale commercial applications under harsh reaction conditions. Herein, we designed a CuNiAl catalyst using a layered double hydroxides precursor, and the catalytic performances were evaluated in transfer hydrogenation of levulinic acid to γ-valerolactone with formic acid as a hydrogen donor. CuNiAl catalyst presented high activity and the improved stability compared to CuAl catalyst. The CuNi alloy formed in the CuNiAl catalyst could prevent Cu particles from partial oxidation, overgrowth and leaching under acidic reaction conditions. Moreover, the synergistic effects between Cu active sites and the surface acid-base on the surface were the key factors for producing γ-valerolactone with a high yield of 97.3% over the CuNiAl catalyst.

Keywords

CuNiAl catalyst / levulinic acid / CuNi alloy / γ-valerolactone / transfer hydrogenation / formic acid

References

[1] Chu S,Liu N.The path towards sustainable energy.Nat Mater2016;16:16-22

[2] Stamenkovic VR,Lopes PP.Energy and fuels from electrochemical interfaces.Nat Mater2016;16:57-69

[3] Manzer LE.Catalytic synthesis of α-methylene-γ-valerolactone: a biomass-derived acrylic monomer.Appl Catal A Gen2004;272:249-56

[4] Hengst K,Doronkin DE.Continuous synthesis of γ-valerolactone in a trickle-bed reactor over supported nickel catalysts.Ind Eng Chem Res2017;56:2680-9

[5] Fábos V,Horváth IT.Selective conversion of levulinic and formic acids to γ-valerolactone with the shvo catalyst.Organometallics2014;33:181-7

[6] Wettstein SG,Chong Y.Production of levulinic acid and gamma-valerolactone (GVL) from cellulose using GVL as a solvent in biphasic systems.Energy Environ Sci2012;5:8199

[7] Yan K,Jarvis C.Clean and selective production of γ-valerolactone from biomass-derived levulinic acid catalyzed by recyclable Pd nanoparticle catalyst.J Clean Prod2014;72:230-2

[8] Molleti J,Yadav GD.Novel synthesis of Ru/OMS catalyst by solvent-free method: Selective hydrogenation of levulinic acid to γ-valerolactone in aqueous medium and kinetic modelling.Chem Eng J2018;334:2488-99

[9] Siddiqui N,Goyal R.Study of γ-valerolactone production from hydrogenation of levulinic acid over nanostructured Pt-hydrotalcite catalysts at low temperature.Fuel2022;323:124272

[10] Li W,Lin H.Highly efficient hydrogenation of biomass-derived levulinic acid to γ-valerolactone catalyzed by iridium pincer complexes.Green Chem2012;14:2388

[11] Xu Q,Pan T.Supported copper catalysts for highly efficient hydrogenation of biomass-derived levulinic acid and γ-valerolactone.Green Chem2016;18:1287-94

[12] Hengne AM.Cu-ZrO₂ nanocomposite catalyst for selective hydrogenation of levulinic acid and its ester to γ-valerolactone.Green Chem2012;14:1064

[13] Upare PP,Hwang YK.Nickel-promoted copper-silica nanocomposite catalysts for hydrogenation of levulinic acid to lactones using formic acid as a hydrogen feeder.Appl Catal A Gen2015;491:127-35

[14] Yanase D,Sato F,Sato S.Vapor-phase hydrogenation of levulinic acid to γ-valerolactone over Cu-Ni alloy catalysts.Appl Catal A Gen2021;616:118093

[15] Yan K.Selective hydrogenation of furfural and levulinic acid to biofuels on the ecofriendly Cu-Fe catalyst.Fuel2014;115:101-8

[16] Belguendouz MN,Rapado P.Selective synthesis of γ-valerolactone from levulinic and formic acid over ZnAl mixed oxide.Chem Eng J2021;414:128902

[17] Dutta S,Tsang DC.Green synthesis of gamma-valerolactone (GVL) through hydrogenation of biomass-derived levulinic acid using non-noble metal catalysts: a critical review.Chem Eng J2019;372:992-1006

[18] Gu X,Jiang HL,Xu Q.Synergistic catalysis of metal-organic framework-immobilized Au-Pd nanoparticles in dehydrogenation of formic acid for chemical hydrogen storage.J Am Chem Soc2011;133:11822-5

[19] Grasemann M.Formic acid as a hydrogen source - recent developments and future trends.Energy Environ Sci2012;5:8171

[20] Singh AK,Kumar A.Hydrogen energy future with formic acid: a renewable chemical hydrogen storage system.Catal Sci Technol2016;6:12-40

[21] Soszka E,Jędrzejczyk M,Grams J.Chlorine influence on palladium doped nickel catalysts in levulinic acid hydrogenation with formic acid as hydrogen source.ACS Sustainable Chem Eng2018;6:14607-13

[22] Patel J.Solvent free hydrogenation of levulinic acid over in-situ generated Ni(0) stabilized by supported phosphomolybdic acid using formic acid as an internal hydrogen source.Renew Energy2022;201:190-201

[23] Zhou Z,Xu S.A CuNi alloy-carbon layer core-shell catalyst for highly efficient conversion of aqueous formaldehyde to hydrogen at room temperature.ACS Appl Mater Interfaces2021;13:37299-307

[24] Chen K,Wu CD.In situ generation and stabilization of accessible Cu/Cu₂O heterojunctions inside organic frameworks for highly efficient catalysis.Angew Chem Int Ed Engl2020;132:1941-7

[25] Zhang Y,Zhang J.Nanostructured Ni-MoCx: an efficient non-noble metal catalyst for the chemoselective hydrogenation of nitroaromatics.Nano Res2023;16:8919-28

[26] Ang ML,Cui Y,Kawi S.Bimetallic Ni-Cu alloy nanoparticles supported on silica for the water-gas shift reaction: activating surface hydroxyls via enhanced CO adsorption.Catal Sci Technol2016;6:3394-409

[27] Pang SH,Medlin JW.Synergistic effects of alloying and thiolate modification in furfural hydrogenation over Cu-based catalysts.J Phys Chem Lett2014;5:4110-4

[28] Srivastava S,Parikh J.Synergism studies on alumina-supported copper-nickel catalysts towards furfural and 5-hydroxymethylfurfural hydrogenation.J Mol Catal A Chem2017;426:244-56

[29] Osipova ES,Gutsul EI.Reactivity of heterobimetallic ion pairs in formic acid dehydrogenation.Organometallics2023;42:2651-60

[30] Ge H,Yang X.Computational design of cobalt catalysts for hydrogenation of carbon dioxide and dehydrogenation of formic acid.Inorg Chem2016;55:12179-84

[31] Bielinski EA,Zhang Y.Lewis acid-assisted formic acid dehydrogenation using a pincer-supported iron catalyst.J Am Chem Soc2014;136:10234-7

[32] Gong Z,Lin Y.Rational synthesis of ruthenium-based metallo-supramolecular polymers as heterogeneous catalysts for catalytic transfer hydrogenation of carbonyl compounds.Appl Catal B Environ2022;312:121383

[33] Lunkenbein T,Behrens M,Willinger MG.Formation of a ZnO overlayer in industrial Cu/ZnO/Al₂O₃ catalysts induced by strong metal-support interactions.Angew Chem Int Ed Engl2015;127:4627-31

[34] Xu M,Rao D.Insights into interfacial synergistic catalysis over Ni@TiO_2-x catalyst toward water-gas shift reaction.J Am Chem Soc2018;140:11241-51

[35] Ro I,Christopher P.Approaches for understanding and controlling interfacial effects in oxide-supported metal catalysts.ACS Catal2018;8:7368-87

[36] Wang L,Zhu Y.Strong metal-support interactions achieved by hydroxide-to-oxide support transformation for preparation of sinter-resistant gold nanoparticle catalysts.ACS Catal2017;7:7461-5

[37] Tang H,Wei J.Ultrastable hydroxyapatite/titanium-dioxide-supported gold nanocatalyst with strong metal-support interaction for carbon monoxide oxidation.Angew Chem Int Ed Engl2016;55:10606-11