Cleavage/cross-coupling strategy for converting β-O-4 linkage lignin model compounds into high valued benzyl amines via dual C–O bond cleavage

Lignin is the most recalcitrant of the three components of lignocellulosic biomass. The strength and stability of the linkages have long been a great challenge for the degradation and valorization of lignin biomass to obtain bio-fuels and commercial chemicals. Up to now, the selective cleavage of C–O linkages of lignin to afford chemicals contains only C, H and O atoms. Our group has developed a cleavage/crosscoupling strategy for converting 4-O-5 linkage lignin model compounds into high value-a...     

Catalytic transformation of cellulose and its derived carbohydrates into chemicals involving C–C bond cleavage

The catalytic transformation of cellulose, the major component of abundant and renewable lignocellulosic biomass, into building-block chemicals is a key to establishing sustainable chemical processes. Cellulose is a polymer of glucose and a lot research effort has been devoted to the conversion of cellulose to six-carbon platform compounds such as glucose and glucose derivatives through C–O bond activation. There also exist considerable studies on the catalytic cleavage of C–C bonds in biomass for the production of high-value chemicals, in particular polyols and organic acids such as ethylene glycol and lactic acid. This review article highlights recent advances in the development of new catalytic systems and new strategies for the selective cleavage of C–C bonds in cellulose and its derived carbohydrates under inert, reductive and oxidative atmospheres to produce C1–C5polyols and organic acids. The key factors that influence the catalytic performance will be clarified to provide insights for the design of more efficient catalysts for the transformation of cellulose with precise cleavage of C–C bonds to high-value chemicals. The reaction mechanisms will also be discussed to understand deeply how the selective cleavage of C–C bonds can be achieved in biomass.     

Boosted activity of Cu/SiO2 catalyst for furfural hydrogenation by freeze drying

The biomass valorization is of great importance as an alternative for the production of transport fuels and fine chemicals.Furfural hydrogenation to furfuryl alcohol is a prevailing industrial route for the utilization of hemicellulose component of biomass.The toxicity of the chromium species in commercial copper chromite catalyst for furfuryl alcohol production motivates the development of efficient chromium-free catalyst.Thus,a highly efficient silica supported copper catalyst is developed in ...     

Boosted activity of Cu/SiO2 catalyst for furfural hydrogenation by freeze drying

The biomass valorization is of great importance as an alternative for the production of transport fuels and fine chemicals.Furfural hydrogenation to furfuryl alcohol is a prevailing industrial route for the utilization of hemicellulose component of biomass.The toxicity of the chromium species in commercial copper chromite catalyst for furfuryl alcohol production motivates the development of efficient chromium-free catalyst.Thus,a highly efficient silica supported copper catalyst is developed in ...     

Microwave assisted liquefaction of wheat straw alkali lignin for the production of monophenolic compounds

The microwave assisted liquefaction process of wheat straw alkali lignin was investigated to obtain monophenolic compounds as the precursor of bio-fuel. It is found that the total yield of monophenolic compounds is significantly improved under microwave irradiation, reaching 15.77%under a relatively mild liquefaction condition of 10 wt% H2SO4 as the catalyst, 10 wt% phenol as the hydrogen-donor reagent at 120?C for40 min. Compared with conventional thermal liquefaction process, microwave irradiation promotes the cleavage of C–C bonds, which gives an extra 29% of Caryl–Cα bond cleavage, and increases the yield of monophenolic compounds from 0.92% to 13.61% under the same conditions.The excessive temperature and prolonged time under microwave irradiation will promote the recondensation of degraded lignin fragments, so the key to obtain high yield of monophenolic compounds is to avoid the recondensation reaction. The selected solid catalyst promotes the dissociation of methoxy groups, and the addition of phenol into liquefaction can only slightly improve the yield of monophencolic compounds.     

Catalytic conversion of cellulose-based biomass and glycerol to lactic acid

Catalytic transformation of cellulose into value-added chemicals is of great importance for utilization of renewable and abundant biomass. Due to the high oxygen content, cellulose serves as an ideal candidate for the production of oxygenates, in particular lactic acid which is a versatile building block in chemical industry. The efficient conversion of cellulose to lactic acid generally requires selective activation of specific C–O and C–C bonds, and therefore multifunctional catalysts that combine several key reactions including hydrolysis, isomerization and retro-aldol fragmentation are highly desirable. This review article highlights the recently developed catalytic systems and catalysts for the selective transformation of cellulose and cellulose-derived carbohydrates into lactic acid, lactates and/or its esters. Emphases will be put on the reaction mechanism and key factors that exert effects on the catalytic performances. In addition, the catalytic transformation of glycerol, a C_3 compound over-supplied from biodiesel industry, will also be surveyed. Recent advances in the development of new catalysts or strategies are analyzed and discussed to gain insight into the transformation of C_3 compound to lactic acid.     

Iron-catalyzed selective oxidation of 5-hydroxylmethylfurfural in air: A facile synthesis of 2,5-diformylfuran at room temperature

An iron(Ⅲ)-catalyzed selective oxidation of 5-HMF to 2,5-DFF in air at room temperature was developed.This approach gives 2,5-DFF with good selectivity and yields. Additionally, a two-step process was developed for the oxidation of 2,5-DFF to 2,5-FDCA at remarkably high substrate concentrations. This work demonstrates unequivocally the great potential of iron as a cheap and earth-abundant catalyst for the development of new protocols for the conversion of biomass to value-added chemicals.     

Catalytic performance of zinc-supported copper and nickel catalysts in the glycerol hydrogenolysis

Gas-phase catalytic conversion of glycerol to value added chemicals was investigated over zinc-supported copper and nickel catalysts.The addition of aluminum in the support was also investigated in glycerol conversion and the results indicate an increase in the acidity and adsorption capacity for both copper and nickel catalysts.HRTEM and XRD analysis revealed Ni Zn alloy formation in the Ni/ZnO catalyst.The XRD patterns of the prepared Zn Al mixed oxide catalysts show the presence of Gahanite phase(ZnAl_2O_4).In addition,H_2 chemisorption and TPR results suggest a strong metal-support interactions(SMSI)effect between Ni and Zn O particles.Bare supports Zn O and ZnAl(Zn/Al=0.5) were investigated in the glycerol conversion and they did not present activity.Copper supported on ZnO and ZnAl mixed oxide(Zn/Al=0.5)was active towards hydroxyacetone formation.Nickel was active in the hydrogenolysis of glycerol both for C–C and C–O bonds cleavage of glycerol producing CH_4.Strong metal-support interactions(SMSI)between Ni and ZnO has a remarkable suppression effect on the methanation activity during the glycerol conversion.     

第二届国际生物质催化炼制大会(CatBior 2013)专刊前言(英)

Today’s society is facing significant challenges from the depletion of oil reserves and the increase of CO₂ emissions.Biorefinery may provide a possible solution to this dilemma as it opens a new way to the sustainable production of fuels and chemicals from vast but nonfood renewable biomass.Catalysis is expected to be a chief player in pursuit of new biorefinery technologies,just as it has been in the oil-refinery industry.In order to provide an ideal forum to present and discuss the state-of-the-art of the catalytic technologies in biomass processing,the International Congress on Catalysis for Biorefineries（CatBior）was initiated in 2011 in Spain.The congress     

Transformations of N-arylpropiolamides to indoline-2,3-diones and acids via C≡C triple bond oxidative cleavage and C(sp^2)–H functionalization

A new palladium-catalyzed oxidative conversion of N-arylpropiolamides and H2O to various indoline-2,3-diones and acids through the C≡C triple bond cleavage and C(sp2)–H functionalization is described,which is promoted by a cooperative action of catalytic CuBr2,2,2,6,6-tetramethyl-1-piperidinyloxy(TEMPO)and O2.The method provides a practical tool for transformations of alkynes by means of a C–H functionalization strategy,which enables the formation of one C–C bond and multiple C–O bonds in a single reaction with high substrates compatibility and excellent functional group tolerance.     

Low temperature microwave-assisted vs conventional pyrolysis of various biomass feedstocks

A comparison between conventional pyrolysis and a novel developed low-temperature microwave-assisted pyrolysis methodology has been performed for the valorisation of a range of biomass feedstocks including waste residues.Microwave pyrolysis was found to efficiently deliver comparable evolution of bio-gases in the system as compared with conventional pyrolysis at significantly reduced temperatures(120 180 C vs 250 400 C).The gas obtained from microwave-assisted pyrolysis was found to contain CO 2,CH 4 and CO as major components as well as other related chemicals(e.g.acids,aldehydes,alkanes) which were obtained in different proportions depending on the selected feedstock.     

凝结相中功能性碳材料和碳纳米复合物催化转化生物质制备可再生化学品(英文)

The production of chemicals from lignocellulosic biomass provides opportunities to synthesize chemicals with new functionalities and grow a more sustainable chemical industry. However, new challenges emerge as research transitions from petrochemistry to biorenewable chemistry. Compared to petrochemisty, the selective conversion of biomass-derived carbohydrates requires most catalytic reactions to take place at low temperatures ( 300 °C) and in the condensed phase to prevent reactants and products from degrading. The stability of heterogeneous catalysts in liquid water above the normal boiling point represents one of the major challenges to overcome. Herein, we review some of the latest advances in the field with an emphasis on the role of carbon materials and carbon nanohybrids in addressing this challenge.     

Electrochemical performance of Klason lignin as a low-cost cathode-active material for primary lithium battery

A few classes of organic compounds are promising electrode-active materials due to their high power and energy densities,low cost,environmental friendliness,and functionality.In the present work,the possibility of using Klason lignin extracted from buckwheat husks as a cathode-active material for a primary lithium battery has been investigated for the first time.The reaction mechanism in the lithium/lignin electrochemical cell was suggested based on the deep galvanostatic discharge(up to 0.005 V) data and cyclic voltammetry results.The dependence of the electrochemical behavior of the Klason lignin on the milling degree was evaluated.The maximum specific capacity of the lignin is equal to 600 m Ah g-1at a discharge current density of 75 μA cm-2.Beneficial effect of the thermal treatment of the Klason lignin cathode at250°C on the cell performance was established.It was found that the discharge capacity of the cell increased by 30% in the range from 3.3 to0.9 V for the treated cathode material.These results demonstrate the prospects of using Klason lignin-based electrochemical cells as low-rate primary power sources.     

纤维素催化转化为高附加值化学品的研究进展

Currently,under huge pressure from energy demands and environmental problems,much attention is being paid to biomass conversion,which will play an important role in meeting the requirements for a sustainable society.As the most abundant biomass on earth, cellulose is usually used as the first research target for biomass conversion.In this review,the recalcitrant structure of cellulose is discussed and non-catalytic hydrolysis by hot-compressed water and catalytic hydrolysis using solid acids are then considered.We also review the catalytic conversion of cellulose into valuable chemicals including hexitols(sorbitol and mannitol),ethylene glycol,and related compounds using various heterogeneous catalysts.     

Direct and selective methanation of biomass via oxygenvacancy‐mediated catalysis

正Producing biofuels from renewable biomass resources is considered to be an effective way to reduce carbon emissions and is helpful for establishing sustainable society [1]. Bio‐methane (CH4) is a promising and available clean energy in the future owing to its properties such as high calorific values, low carbon emissions and full miscibility and interchangeability with natural gas or shale gas. Therefore, the production of me‐thane directly from waste biomass resources like straw is highly attractive. However, because of the robustness and vari‐ety of C–C bonds and C–O bonds existing in biomass molecules,it is very difficult to achieve high‐selective methanation of bio‐     

Photocatalytic transformation of selected biomass derivatives to value added chemicals and hydrogen fuel

Biomass is the most bountiful renewable carbon resource on earth. Photocatalytic transformation is a promising method to utilize biomass to obtain high-value-added chemicals and it has more obvious advantages compared with thermochemical and biological processes due to the milder operational conditions, fewer reagents and equipment. Semiconductor material is one of the most common kinds of heterogeneous biomass photocatalysts, which has the advantages of high selectivity, stable catalytic perfor...     

Synthesis ofa trimeric lignin model compound composed ofol-O-4 and β-O-4 linkages under microwave irradiation

A trimeric lignin model compound composed of α-O-4 and β-O-4 linkages was prepared by the microwave-assisted synthesis, which consisted of three steps： （a） the synthesis of 3-methoxy-4- benzyloxyacetophenone （2） from acetovanillone （1）, （b） the bromination of compound 2 to produce 3- methoxy-4-benzyloxy-α-bromoacetophenone （3）, and （c） followed by a nucleophilic substitution of compound （3） to obtain 3-methoxy-4-benzyloxy-α-（3-methoxy-4-（1-propenyl）phenol）-acetophenone （4）. The target product was characterized by MS, 1H NMR and 13C NMR spectroscopy. It was found that the trimeric compound synthesized can be used as a preferable lignin model compound because it contains guaiacyl structural unit （3-methoxy-4-hydroxy phenyl propane） linked by α-O-4 and β-O-4 linkages. In addition, under the conditions of microwave irradiation, the reaction time of each step is significantly reduced, and the selectivity of target product is greatly improved. The yields of each step and the overall sequence are 95.31%. 87.3%. 90.6% and 75.4% （95.31%× 87.3% × 90.6%）. respectively.     

Transformation of Biomass into Aromatics with Zeolite Catalysts

Biomass is a nature renewable resource which can be used for the production of high value chemicals and bio-fuels. In the present work, the transformation of sawdust into aromat- ics such as benzene, toluene and xylenes was investigated over a series of zeolite catalysts （NaZSM-5, HZSM-5, ReY and HY catalysts）. Among the tested catalysts, the HZSM-5 catalyst shows the highest activity for the production of aromatics. The yield and carbon selectivity of aromatics reached about 26.5% and 62.5C-mo1%, respectively over the HZSM-5 catalyst under the optimal condition of T=450 ℃, f（N2）=300 cm^3/min, and catalyst/lignin ratio of 2. The effects of the reaction conditions including temperature, gas flow rate, and catalyst/sawdust ratio on the production of aromatics were investigated in detail and the formation of aromatics from lignocellulosic biomass was also addressed.     

Conversion of CO2 to ethanol by using a metal-organic framework catalyst

<正>With the development of CO_2 capture technology, CO_2 can become an attractive C1 resource for synthesizing commodity chemicals. For example, direct conversion of CO_2 to ethanol is of interest, but this process is also quite challenging, because it requires both the formation of one C–C bond and the retention of one C–O bond [1]. A combination of dual active sites, one for methanol formation and one for C–C coupling has been widely investigated for such a conversion, but an unbalanced rate in the two steps frequently leads to the formation of either methanol or long-chain hydrocarbons [2].     

A 3D MIL-101@rGO composite as catalyst for efficient conversion of straw cellulose into valuable organic acid

Efficient conversion of straw cellulose to chemicals or fuels is an attracting topic today for the utilization of biomass to substitute for fossil resources. The development of catalysts is of vital importance.In this work, a composite catalyst metal-organic frameworks(MOFs) immobilized on three-dimensional reduced graphene oxide(3D-r GO) were synthesized by in situ growth of the MIL-101(Cr) within the 3Dr GO matrix. The supporting of 3D-r GO guaranteed the dispersion and acid site density of MI...