Hydrogenolysis of methyl glycolate to ethanol over a Pt–Cu/SiO2 single-atom alloy catalyst: a further step from cellulose to ethanol

Cellulosic ethanol can be produced via a chemocatalytic approach in which cellulose is first converted into methyl glycolate (MG) in methanol using a W-based catalyst under an oxygen atmosphere, and the formed MG is then hydrogenated to ethanol over a supported copper catalyst. Aiming at enhancing the ethanol selectivity for this two-step approach, we developed a 0.1Pt–Cu/SiO2 single-atom alloy catalyst in the present study, where Pt was isolated as single atoms, and formed a Pt–Cu alloy phase. The characterizations of the catalyst via in situ XRD, FTIR, CO-adsorbed DRIFTS, N2O chemisorption, and XPS revealed that the introduction of 0.1 wt% Pt into the Cu/SiO2 catalyst resulted in an improvement in the Cu dispersion and an increase in the Cu+/Cu0 ratio. Moreover, Pt single atoms promoted the activation of hydrogen. As a consequence, the catalytic activity and selectivity of ethanol were enhanced; the maximum selectivity of ethanol (76.7%) was obtained at 503 K. Over 700 h on stream, the catalyst did not show any deactivation, demonstrating a promising stability.

[1]  Matthew T. Darby,et al.  Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C-H activation. , 2018, Nature chemistry.

[2]  M. Dusselier,et al.  Heterogeneous catalysis for bio-based polyester monomers from cellulosic biomass: advances, challenges and prospects , 2017 .

[3]  K. Gasem,et al.  Highly selective and stable Cu/SiO2 catalysts prepared with a green method for hydrogenation of diethyl oxalate into ethylene glycol , 2017 .

[4]  Shengping Wang,et al.  A Fe5C2 nanocatalyst for the preferential synthesis of ethanol via dimethyl oxalate hydrogenation. , 2017, Chemical communications.

[5]  Jifeng Pang,et al.  Chemocatalytic Conversion of Cellulosic Biomass to Methyl Glycolate, Ethylene Glycol, and Ethanol. , 2017, ChemSusChem.

[6]  Tao Zhang,et al.  Production of Primary Amines by Reductive Amination of Biomass-Derived Aldehydes/Ketones. , 2017, Angewandte Chemie.

[7]  Jifeng Pang,et al.  Selectivity Control for Cellulose to Diols: Dancing on Eggs , 2017 .

[8]  Xiaodong Wang,et al.  Performance of Cu-Alloyed Pd Single-Atom Catalyst for Semihydrogenation of Acetylene under Simulated Front-End Conditions , 2017 .

[9]  Natalie A. Wasio,et al.  Selective Formic Acid Dehydrogenation on Pt-Cu Single-Atom Alloys , 2017 .

[10]  Juan Zhang,et al.  Effect of Cu-doping on the structure and performance of molybdenum carbide catalyst for low-temperature hydrogenation of dimethyl oxalate to ethanol , 2017 .

[11]  M. Flytzani-Stephanopoulos,et al.  Tackling CO Poisoning with Single-Atom Alloy Catalysts. , 2016, Journal of the American Chemical Society.

[12]  Juan Zhang,et al.  Molybdenum carbide as an efficient catalyst for low-temperature hydrogenation of dimethyl oxalate. , 2016, Chemical communications.

[13]  Shengping Wang,et al.  Insight into the Balancing Effect of Active Cu Species for Hydrogenation of Carbon-Oxygen Bonds , 2015 .

[14]  E. Sykes,et al.  H2 Activation and Spillover on Catalytically Relevant Pt–Cu Single Atom Alloys , 2015 .

[15]  Xiao-hui Liu,et al.  Production of methyl levulinate from cellulose: selectivity and mechanism study , 2015 .

[16]  A. Suurnäkki,et al.  Enzymatic hydrolysis of lignocellulosic polysaccharides in the presence of ionic liquids , 2015 .

[17]  Chao Wen,et al.  Reaction temperature controlled selective hydrogenation of dimethyl oxalate to methyl glycolate and ethylene glycol over copper-hydroxyapatite catalysts , 2015 .

[18]  Tao Zhang,et al.  Kinetic study of retro‐aldol condensation of glucose to glycolaldehyde with ammonium metatungstate as the catalyst , 2014 .

[19]  K. Wu,et al.  Enzymatic breakdown of biomass: enzyme active sites, immobilization, and biofuel production , 2014 .

[20]  Yulei Zhu,et al.  Cu Nanoparticles Inlaid Mesoporous Al2O3 As a High-Performance Bifunctional Catalyst for Ethanol Synthesis via Dimethyl Oxalate Hydrogenation , 2014 .

[21]  Chao Wen,et al.  Highly selective one-pot continuous synthesis of 2-methoxyethanol via hydrogenation of dimethyl oxalate on Cu/ZrO2 catalysts with balanced acid sites , 2014 .

[22]  E. Sykes,et al.  Atomic Scale Surface Structure of Pt/Cu(111) Surface Alloys , 2014 .

[23]  Jianwei Zheng,et al.  Lanthanum Oxide-Modified Cu/SiO2 as a High-Performance Catalyst for Chemoselective Hydrogenation of Dimethyl Oxalate to Ethylene Glycol , 2013 .

[24]  Jamie H. D. Cate,et al.  Enhanced biofuel production through coupled acetic acid and xylose consumption by engineered yeast , 2013, Nature Communications.

[25]  Z. Cao,et al.  Chemical synthesis of lactic acid from cellulose catalysed by lead(II) ions in water , 2013, Nature Communications.

[26]  Yulei Zhu,et al.  Promoting effect of boron oxide on Cu/SiO2 catalyst for glycerol hydrogenolysis to 1,2-propanediol , 2013 .

[27]  Kangnian Fan,et al.  Enhanced catalytic performance for SiO2–TiO2 binary oxide supported Cu-based catalyst in the hydrogenation of dimethyloxalate , 2013 .

[28]  Tao Zhang,et al.  One-pot conversion of cellulose to ethylene glycol with multifunctional tungsten-based catalysts. , 2013, Accounts of chemical research.

[29]  Shengping Wang,et al.  Synthesis of ethanol via syngas on Cu/SiO2 catalysts with balanced Cu0-Cu+ sites. , 2012, Journal of the American Chemical Society.

[30]  Yue Liu,et al.  Tungsten trioxide promoted selective conversion of cellulose into propylene glycol and ethylene glycol on a ruthenium catalyst. , 2012, Angewandte Chemie.

[31]  Xiaofeng Yang,et al.  Single-atom catalysis of CO oxidation using Pt1/FeOx. , 2011, Nature chemistry.

[32]  P. He,et al.  Effect of boric oxide doping on the stability and activity of a Cu-SiO2 catalyst for vapor-phase hydrogenation of dimethyl oxalate to ethylene glycol , 2011 .

[33]  Jingguang G. Chen,et al.  Trend in the CC and CO bond hydrogenation of acrolein on Pt–M (M = Ni, Co, Cu) bimetallic surfaces , 2009 .

[34]  H. Xie,et al.  Hydrodechlorination of 1,2-dichloroethane catalyzed by dendrimer-derived Pt–Cu/SiO2 catalysts , 2008 .

[35]  Kangnian Fan,et al.  Cu/SiO2 catalysts prepared by the ammonia-evaporation method: Texture, structure, and catalytic performance in hydrogenation of dimethyl oxalate to ethylene glycol , 2008 .

[36]  M. Mavrikakis,et al.  A Cu/Pt near-surface alloy for water-gas shift catalysis. , 2007, Journal of the American Chemical Society.

[37]  David K. Johnson,et al.  Biomass Recalcitrance: Engineering Plants and Enzymes for Biofuels Production , 2007, Science.

[38]  D. Luebke,et al.  Hydrogen-Assisted 1,2-Dichloroethane Dechlorination Catalyzed by Pt−Cu/SiO2: Evidence for Different Functions of Pt and Cu Sites , 2003 .

[39]  C. Louis,et al.  Conditions of Formation of Copper Phyllosilicates in Silica-Supported Copper Catalysts Prepared by Selective Adsorption , 2002 .

[40]  V. Ponec.  Alloy catalysts: the concepts , 2001 .

[41]  C. Louis,et al.  Metal Particle Size in Silica-Supported Copper Catalysts. Influence of the Conditions of Preparation and of Thermal Pretreatments , 2000 .