Tailoring crystal planes and oxygen vacancies of ceria for enhanced catalytic performance of single-atom Ru in hydrogenative dearomatization of lignin-derived phenols

Abstract

Lignin-based guaiacol and its derivatives can be hydrogenated to synthesize 2-methoxycyclohexanols (2-MCHs), widely used in the pharmaceutical industry, while the efficient catalytic conversion of guaiacols into 2-MCHs is challenging due to the interference of the side reaction of C_Ar-OCH₃ bond cleavage. In this work, highly selective hydrogenation of various guaiacyl lignin-derived phenols to 2-MCHs (yields of 86%-97%) was realized over a single-atom Ru-based catalyst (Ru₁/o-CeO₂-ov) that preferentially exposes the CeO₂(111) plane and has abundant oxygen vacancies. Control experiments and mechanism studies expounded that Ru-O-Ce is the active site for hydrogenation of aromatic ring in guaiacols, and the exposed (111) plane and abundant oxygen vacancies of ceria can reduce the activation energy of aromatic ring hydrogenation, thereby enabling guaiacols to generate the corresponding hydrogenated products with high selectivity. Response surface optimization experiments indicated that temperature and time have relatively more significant effects on the 2-MCH yield. Moreover, the Ru₁/o-CeO₂-ov catalyst exhibited excellent reusability, and was extensively applicable to the hydrogenative dearomatization of different types of lignin-derived phenols, providing a unique solution for upgrading biomass feedstock into specific structural chemicals.

Keywords

Single-atom catalyst / lignin-derived phenols / oxygen vacancy / crystal plane control / aromatic ring hydrogenation

References

[1] Ashokkumar V,Jayashree S.Recent advances in lignocellulosic biomass for biofuels and value-added bioproducts - a critical review.Bioresour Technol2022;344:126195

[2] Pompei S,Schiller C,Kroutil W.Thiols act as methyl traps in the biocatalytic demethylation of guaiacol derivatives.Angew Chem Int Ed2021;60:16906-10 PMCID:PMC8361964

[3] Smet G, Bai X, Maes BUW. Selective C(aryl)-O bond cleavage in biorenewable phenolics.Chem Soc Rev2024;53:5489-551

[4] Zhao Y,Hu R.Water-assisted catalytic transfer hydrogenation of guaiacol to cyclohexanol over Ru/NiAl₂O₄.Chem Eng J2024;485:149934

[5] Wang B,Wu H,Liao Y.Synergy of heterogeneous Co/Ni dual atoms enabling selective C-O bond scission of lignin coupling with in-situ N-functionalization.J Energy Chem2024;92:16-25

[6] Smet G, Bai X, Mensch C, Sergeyev S, Evano G, Maes BUW. Selective nickel-catalyzed hydrodeacetoxylation of aryl acetates.Angew Chem Int Ed2022;61:e202201751

[7] Wu R,Yan J.Intermetallic synergy in platinum-cobalt electrocatalysts for selective C-O bond cleavage.Nat Catal2024;7:702-18

[8] Lang M.Toward value-added arenes from lignin-derived phenolic compounds via catalytic hydrodeoxygenation.ACS Sustainable Chem Eng2022;10:13208-43

[9] Zhang J,Wang Y.Recent advances in the selective catalytic hydrodeoxygenation of lignin-derived oxygenates to arenes.Green Chem2020;22:1072-98

[10] Lang M.Heterogeneous metal-based catalysts for cyclohexane synthesis from hydrodeoxygenation of lignin-derived phenolics.Fuel2023;344:128084

[11] Wong SS,Zhang J,Yan N.Downstream processing of lignin derived feedstock into end products.Chem Soc Rev2020;49:5510-60

[12] Winterton N.The green solvent: a critical perspective.Clean Technol Environ Policy2021;23:2499-522 PMCID:PMC8482956

[13] Marco-Contelles J,Anjum S.Naturally occurring cyclohexane epoxides: sources, biological activities, and synthesis.Chem Rev2004;104:2857-900

[14] Liu L,Zhang K.Selective conversion of cyclohexene to 2-methoxycyclohexanol over molybdenum oxide on beta zeolite.Ind Eng Chem Res2023;62:16207-14

[15] Feng J,Zhang Y.Research on synthesis and thermodynamic properties of 2-methoxycyclohexanol.J Therm Anal Calorim2018;131:2197-203

[16] Jiang Y,Hunger M,Baiker A.Comparative studies on the catalytic activity and structure of a Cu-MOF and its precursor for alcoholysis of cyclohexene oxide.Catal Sci Technol2015;5:897-902

[17] Obeso JL,Flores CV.Lewis acid-catalyzed ring-opening alcoholysis of cyclohexene oxide: the role of open metal sites in the Bi(III)‐based metal-organic framework SU-101.ChemCatChem2023;15:e202300471

[18] Abbasi KR,Zhang J,Alvarado R.Analyze the environmental sustainability factors of China: the role of fossil fuel energy and renewable energy.Renew Energy2022;187:390-402

[19] Zhou H,Sadow AD.Toward hydrogen economy: Selective guaiacol hydrogenolysis under ambient hydrogen pressure.Appl Catal B Environ2020;270:118890

[20] Nakagawa Y,Tamura M.Selective production of cyclohexanol and methanol from guaiacol over Ru catalyst combined with MgO.Green Chem2014;16:2197-203

[21] Hensley AJ,Shangguan J,Mcewen JS.Catalytic consequences of hydrogen addition events and solvent-adsorbate interactions during guaiacol-H₂ reactions at the H₂O-Ru(0001) interface.J Catal2021;395:467-82

[22] Wang B,Yan X,Wu H.Cooperative catalysis of Co single atoms and nanoparticles enables selective CAr-OCH₃ cleavage for sustainable production of lignin-based cyclohexanols.J Energy Chem2023;79:535-49

[23] Nania C,Gueci L,Duca D.DFT insights into competing mechanisms of guaiacol hydrodeoxygenation on a platinum cluster.Phys Chem Chem Phys2023;25:10460-71

[24] Zhang K,Wu H.Selective hydrodeoxygenation of aromatics to cyclohexanols over ru single atoms supported on CeO₂.J Am Chem Soc2022;144:20834-46

[25] Wang X,Wang S,Fan W.Ni nanoparticles entrapped in nickel phyllosilicate for selective hydrogenation of guaiacol to 2-methoxycyclohexanol.Appl Catal A Gen2018;568:231-41

[26] Yamaguchi A,Yamazaki K,Hiyoshi N.Stereoselective hydrogenation of guaiacol to cis-2-methoxycyclohexanol using supported rhodium catalysts in supercritical carbon dioxide.Catal Today2024;425:114356

[27] Kumar A,Bhaskar T.High surface area biochar from sargassum tenerrimum as potential catalyst support for selective phenol hydrogenation.Environ Res2020;186:109533

[28] Chen J,Tu T.Selective hydrogenation of phenols to cyclohexanols catalyzed by robust solid NHC-Rh coordination assemblies in water.Green Chem2023;25:7541-6

[29] Qian W,Qiao Y.Ru subnanoparticles on N-doped carbon layer coated SBA-15 as efficient Catalysts for arene hydrogenation.Appl Catal A Gen2019;585:117183

[30] Wang Q,Safonova OV.Tunable catalysis by reversible switching between Ru_(III) single sites and Ru₀ clusters in solid micelles.J Catal2023;426:336-44

[31] Wang A,Zhang T.Heterogeneous single-atom catalysis.Nat Rev Chem2018;2:65-81

[32] Li L,Lin X,Gong J.Theoretical insights into single-atom catalysts.Chem Soc Rev2020;49:8156-78

[33] Gong X,Han C,Mei X.Heterogeneous single-atom catalysts for energy process: recent progress, applications and challenges.Energy Mater2023;

[34] Wang W,Qiang Q.Catalytic refining lignin-derived monomers: seesaw effect between nanoparticle and single-atom Pt.Angew Chem Int Ed2024;63:e202404683

[35] Zhang L,Gao S.Atomically dispersed Co catalyst for efficient hydrodeoxygenation of lignin-derived species and hydrogenation of nitroaromatics.ACS Catal2020;10:8672-82

[36] Li J,Zhao Y.Lignin-tailored fabrication of Ni single atom catalyst with Ni-N₃ active site for efficient and selective catalytic transfer hydrogenation of lignin-derived aldehydes.Chem Eng J2024;496:154315

[37] Guo H,Chen Y.Mechanistic insights into hydrodeoxygenation of lignin derivatives over Ni single atoms supported on Mo₂C.ACS Catal2024;14:703-17

[38] Gao X,Liu Z,Wu Y.Hydrodeoxygenation of lignin-derived phenols into cycloalkanes by atomically dispersed Pt-polyoxometalate catalysts.Appl Catal B Environ Energy2024;352:124059

[39] Jiang F,Liu B.Insights into the influence of CeO₂ crystal facet on CO₂ hydrogenation to methanol over Pd/CeO₂ catalysts.ACS Catal2020;10:11493-509

[40] Li H,Zhao Z.The nature of loading-dependent reaction barriers over mixed RuO₂/TiO₂ catalysts.ACS Catal2018;8:5526-32

[41] Huang H,Wang X.Morphology effect of Ru/CeO₂ catalysts for the catalytic combustion of chlorobenzene.Appl Catal B Environ2014;158-159:96-105

[42] Campbell CT.Oxygen vacancies and catalysis on ceria surfaces.Science2005;309:713-4

[43] Vayssilov GN,Migani A.Support nanostructure boosts oxygen transfer to catalytically active platinum nanoparticles.Nat Mater2011;10:310-5

[44] Liu P,Liu W,Liu S.Oxidative redispersion-derived single-site Ru/CeO₂ catalysts with mobile Ru complexes trapped by surface hydroxyls instead of oxygen vacancies.ACS Catal2024;14:6028-44

[45] Zhao Z,Xue W.Solvent-mediated charge separation drives alternative hydrogenation path of furanics in liquid water.Nat Catal2019;2:431-6

[46] Arora SS.Kinetics of aromatics hydrogenation on HBEA.J Catal2020;383:24-32

[47] Jiang W,He Z.Highly selective hydrogenation of arenes over Rh nanoparticles immobilized on α-Al₂O₃ support at room temperature.Chem Eng Sci2023;270:118544

[48] Zhang Q,Gao P.PVP-NiB amorphous catalyst for selective hydrogenation of phenol and its derivatives.Chin J Catal2014;35:1793-9