Renewable resources based polymers provides a sustainable alternative to petroleum derived polymeric materials.As a part of our series on synthesis of vanillin based renewable polymers,we report the synthesis of poly(...Renewable resources based polymers provides a sustainable alternative to petroleum derived polymeric materials.As a part of our series on synthesis of vanillin based renewable polymers,we report the synthesis of poly(hydrovanilloin-furfural)[poly(HVL-Fur)]and poly(hydrovanilloin–5-hydromethylfurfural)[poly(HVL-5-HMF)].Vanillin was dimerized to a mixtures of meso/DL-hydrovanilloins with 94%meso product by electrochemical reductive coupling in aqueous sodium hydroxide using lead electrodes in quantitative yield.Then sodium hydroxide catalyzed condensation of hydrovanilloin with furfural in water at 80℃for 72 h was used to synthesize poly(HVL-Fur)with Mw=8600 g mol^(−1),PDI=1.28 in 78%yield.Similarly,condensation of hydrovanilloin with 5-hydroxymethylfurfural at 80℃for 48 h produced poly(HVL-5-HMF)with Mw=12,100 g mol−1,PDI=1.27 in 68%yield.poly(HVL-Fur)and poly(HVL-5-HMF)showed similar Tg values of 59℃and 60℃,respectively;whereas melting behaviors are dissimilar with Tm 171℃–173℃and 148℃–182℃,respectively.展开更多
The fructose-to-furfural transformation is facing major challenges in the selectivity and high efficiency. Herein, we have developed a simple and effective approach for the selective conversion of fructose to furfural...The fructose-to-furfural transformation is facing major challenges in the selectivity and high efficiency. Herein, we have developed a simple and effective approach for the selective conversion of fructose to furfural using Hβ zeolite modified by organic acids for dealuminization to regulate its textural and acidic properties. It was found that citric acid-dealuminized Hβ zeolite possessed high specific surface areas, wide channels and high Brønsted acid amount, which facilitated the selective conversion of fructose to furfural with a maximum yield of 76.2% at433 K for 1 h in the γ-butyrolactone(GBL)-H_(2)O system, as well as the concomitant formation of 83.0% formic acid. The^(13)C-isotope labelling experiments and the mechanism revealed that the selective cleavage of C1–C2 or C5–C6 bond on fructose was firstly occurred to form pentose or C5 intermediate by weak Brønsted acid, which was then dehydrated to furfural by strong Brønsted acid. Also this dealuminized Hβ catalyst showed the great recycling performance and was active for the conversion of glucose and mannose.展开更多
The electrocatalytic oxidation of biomass-derived furfural(FF)feedstocks into 2-furoic acid(FA)holds immense industrial potential in optics,cosmetics,polymers,and food.Herein,we fabricated Co O/Ni O/nickel foam(NF)and...The electrocatalytic oxidation of biomass-derived furfural(FF)feedstocks into 2-furoic acid(FA)holds immense industrial potential in optics,cosmetics,polymers,and food.Herein,we fabricated Co O/Ni O/nickel foam(NF)and Cu_(2)O/Ni O/NF electrodes via in situ pulsed laser irradiation in liquids(PLIL)for the bifunctional electrocatalysis of oxygen evolution reaction(OER)and furfural oxidation reaction(FOR),respectively.Simultaneous oxidation of NF surface to NiO and deposition of CoO and/or Cu_(2)O on NF during PLIL offer distinct advantages for enhancing both the OER and FOR.CoO/NiO/NF electrocatalyst provides a consistently low overpotential of~359 m V(OER)at 10 m A/cm^(2),achieving the maximum FA yield(~16.37 m M)with 61.5%selectivity,79.5%carbon balance,and a remarkable Faradaic efficiency of~90.1%during 2 h of FOR at 1.43 V(vs.reversible hydrogen electrode).Mechanistic pathway via in situ electrochemical-Raman spectroscopy on CoO/NiO/NF reveals the involvement of phase transition intermediates(NiOOH and CoOOH)as surface-active centers during electrochemical oxidation.The carbonyl carbon in FF is attacked by hydroxyl groups to form unstable hydrates that subsequently undergo further oxidation to yield FA products.This method holds promise for large-scale applications,enabling simultaneous production of renewable building materials and fuel.展开更多
Optimizing the intrinsic activity of non-noble metal by precisely tailoring electronic structure offers an appealing way to construct cost-effective catalysts for selective biomass valorization.Herein,we reported a P-...Optimizing the intrinsic activity of non-noble metal by precisely tailoring electronic structure offers an appealing way to construct cost-effective catalysts for selective biomass valorization.Herein,we reported a P-doping bifunctional catalyst(Ni-P/mSiO_(2))that achieved 96.6%yield for the hydrogenation rearrangement of furfural to cyclopentanone at mild conditions(1 MPaH_(2),150°C).The turnover frequency of Ni-P/mSiO_(2)was 411.9 h^(-1),which was 3.2-fold than that of Ni/mSiO_(2)(127.2 h^(-1)).Detailed characterizations and differential charge density calculations revealed that the electron-deficient Niδ+species were generated by the electron transfer from Ni to P,which promoted the ring rearrangement reaction.Density functional theory calculations illustrated that the presence of P atoms endowed furfural tilted adsorb on the Ni surface by the C=O group and facilitated the desorption of cyclopentanone.This work unraveled the connection between the localized electronic structures and the catalytic properties,so as to provide a promising reference for designing advanced catalysts for biomass valorization.展开更多
Gasification of furfural residue with coal can realize its efficient and clean utilization.But the high alkali metal content in furfural slag is easy to cause the corrosion of gasifier refractory.Two gasification coal...Gasification of furfural residue with coal can realize its efficient and clean utilization.But the high alkali metal content in furfural slag is easy to cause the corrosion of gasifier refractory.Two gasification coals with different silica alumina ratio and a furfural residue were selected in the study.The effects of furfural residue additions on corrosion of silica brick,corundum brick,high alumina brick and mullite brick were investigated by using XRD,SEM-EDS and Factsage Software,and the corrosion mechanism was analyzed.With increasing furfural residue addition,the permeability of the slags to high-aluminium-bearing refractories first decreases and then increases,while the permeability on silica brick shows a slight decrease trend.Leucite(KAlSi_(2)O_(6))with high-melting temperature is generated from the reaction of K_(2)O and SiO_(2)in slag with Al_(2)O_(3)in refractories after furfural residue is added,which hinders the infiltration of slag in refractories.Kaliophilite(KAlSiO_(4))of low-melting point is formed when K_(2)O content increases,and this contributes to the infiltration of slag in refractories.The acid-base reaction between slag and silica brick is distinctly occurred,more slag reacts with SiO_(2)in the silicon brick,resulting in a decrease in the amount of slag infiltrating into the silicon brick as furfural residue is added.The corrosion of silica brick is mainly caused by the acid-base reaction,while the corrosion of three alumina based refractory bricks of corundum,mullite and high alumina brick is determined by slag infiltration.A linear correlation between the percolation rate and slag viscosity is established,the slag permeability increases with decreasing viscosity,resulting in stronger permeability for the high Si/Al ratio slag with lower viscosity.展开更多
Acetic acid and furfural are known as prevalent inhibitors deriving from pretreatment during lignocellulosic ethanol production.They negatively impact cell growth,glucose uptake and ethanol biosynthesis of Saccharomyc...Acetic acid and furfural are known as prevalent inhibitors deriving from pretreatment during lignocellulosic ethanol production.They negatively impact cell growth,glucose uptake and ethanol biosynthesis of Saccharomyces cerevisiae strains.Development of industrial S.cerevisiae strains with high tolerance towards these inhibitors is thus critical for efficient lignocellulosic ethanol production.In this study,the acetic acid or furfural tolerance of different S.cerevisiae strains could be significantly enhanced after adaptive evolution via serial cultivation for 40 generations under stress conditions.The acetic acid-based adaptive strain SPSC01-TA9 produced 30.5 g·L^(-1)ethanol with a yield of 0.46 g·g^(-1)in the presence of 9 g·L^(-1)acetic acid,while the acetic acid/furfural-based adaptive strain SPSC01-TAF94 produced more ethanol of 36.2 g·L^(-1)with increased yield up to 0.49 g·g^(-1)in the presence of both 9 g·L^(-1)acetic acid and 4 g·L^(-1)furfural.Significant improvements were also observed during non-detoxified corn stover hydrolysate culture by SPSC01-TAF94,which achieved ethanol production and yield of 29.1 g·L^(-1)and 0.49 g·g^(-1),respectively,the growth and fermentation efficiency of acetic acid/furfural-based adaptive strain in hydrolysate was 95%higher than those of wildtype strains,indicating the acetic acid-and furfural-based adaptive evolution strategy could be an effective approach for improving lignocellulosic ethanol production.The adapted strains developed in this study with enhanced tolerance against acetic acid and furfural could be potentially contribute to economically feasible and sustainable lignocellulosic biorefinery.展开更多
Implementing a new energy-saving electrochemical synthesis system with high commercial value is a strategy of the sustainable development for upgrading the bulk chemicals preparation technology in the future.Here,we r...Implementing a new energy-saving electrochemical synthesis system with high commercial value is a strategy of the sustainable development for upgrading the bulk chemicals preparation technology in the future.Here,we report a multiple redox-mediated linear paired electrolysis system,combining the hydrogen peroxide mediated cathode process with the I2 mediated anode process,and realize the conversion of furfural to furoic acid in both side of the dividedflow cell simultaneously.By reasonably controlling the cathode potential,the undesired water splitting reaction and furfural reduction side reactions are avoided.Under the galvanostatic electrolysis,the two-mediated electrode processes have good compatibility,which reduce the energy consumption by about 22%while improving the electronic efficiency by about 125%.This system provides a green electrochemical synthesis route with commercial prospects.展开更多
Here,furfural oxidation was performed to replace the kinetically sluggish O_(2)evolution reaction(OER).Pt-Co_(3)O_(4)nanospheres were developed via pulsed laser ablation in liquid(PLAL)in a single step for the paired ...Here,furfural oxidation was performed to replace the kinetically sluggish O_(2)evolution reaction(OER).Pt-Co_(3)O_(4)nanospheres were developed via pulsed laser ablation in liquid(PLAL)in a single step for the paired electrocatalysis of an H_(2)evolution reaction(HER)and furfural oxidation reaction(FOR).The FOR afforded a high furfural conversion(44.2%)with a major product of 2-furoic acid after a 2-h electrolysis at 1.55 V versus reversible hydrogen electrode in a 1.0-M KOH/50-mM furfural electrolyte.The Pt-Co_(3)O_(4)electrode exhibited a small overpotential of 290 mV at 10 mA cm^(-2).As an anode and cathode in an electrolyzer system,the Pt-Co_(3)O_(4)electrocatalyst required only a small applied cell voltage of~1.83 V to deliver 10 mA cm^(-2),compared with that of the pure water electrolyzer(OER||HER,~1.99 V).This study simultaneously realized the integrated production of energy-saving H_(2)fuel at the cathode and 2-furoic acid at the anode.展开更多
Selective reductive amination of carbonyl compounds with high activity is very essential for the chemical and pharmaceutical industry,but scarcely successful paradigm was reported via efficient photocatalytic reaction...Selective reductive amination of carbonyl compounds with high activity is very essential for the chemical and pharmaceutical industry,but scarcely successful paradigm was reported via efficient photocatalytic reactions.Herein,the ultrasmall Ru nanoclusters(~0.9 nm)were successfully fabricated over P25 support with positive charged Ru^(δ+)species at the interface.A new route was developed to achieve the furfural(FAL)to furfurylamine(FAM)by coupling the light-driven reductive amination and hydrogen transfer of ethanol over this type catalyst.Strikingly,the photocatalytic activity and selectivity are strongly dependent on the particle size and electronic structure of Ruthenium.The Ru^(δ+)species at the interface promote the formation of active imine intermediates;moreover,the Ru nanoclusters facilitate the separation efficiency of electrons and holes as well as accelerate the further hydrogenation of imine intermediates to product primary amines.In contrast Ru particles in larger nanometer size facilitate the formation of the furfuryl alcohol and excessive hydrogenation products.In addition,the coupling byproducts can be effectively inhibited via the construction of sub-nanocluster.This study offers a new path to produce the primary amines from biomass-derived carbonyl compounds over hybrid semiconductor/metal-clusters photocatalyst via light-driven tandem catalytic process.展开更多
Hydrodeoxygenation of furfural(FF)into 2-methylfuran(MF)is a significant biomass utilization route.However,designing efficient and stable non-noble metal catalyst is still a huge challenge.Herein,we reported the N,O c...Hydrodeoxygenation of furfural(FF)into 2-methylfuran(MF)is a significant biomass utilization route.However,designing efficient and stable non-noble metal catalyst is still a huge challenge.Herein,we reported the N,O co-doped carbon anchored with Co nanoparticles(Co-SFB)synthesized by employing the organic ligands with the target heteroatoms.Raman,electron paramagnetic resonance(EPR),electrochemical impedance spectroscopy(EIS),and X-ray photoelectron spectroscopy(XPS)characterizations showed that the co-doping of N and O heteroatoms in the carbon support endows Co-SFB with enriched lone pair electrons,fast electron transfer ability,and strong metal-support interaction.These electronic properties resulted in strong FF adsorption as well as lower apparent reaction activation energy.At last,the obtained N,O co-doped Co/C catalyst showed excellent catalytic activity(nearly 100 mol%FF conversion and 94.6 mol%MF yield)and stability for in-situ dehydrogenation of FF into MF.This N,O co-doping strategy for the synthesis of highly efficient catalytic materials with controllable electronic state will provide an excellent opportunity to better understand the structure-function relationship.展开更多
Hemicellulose and lignin are not reasonably utilized during the dissolved pulp preparation process.This work aimed to propose a process for the co-production of dissolving pulp,furfural,and lignin from eucalyptus.High...Hemicellulose and lignin are not reasonably utilized during the dissolved pulp preparation process.This work aimed to propose a process for the co-production of dissolving pulp,furfural,and lignin from eucalyptus.High-grade dissolving pulp was prepared from eucalyptus using a combination of extremely low acid(ELA)pretreatment,Kraft cooking,and elementary chlorine-free(ECF)bleaching.The obtained pre-hydrolysate was catalytic conversion into furfural in a biphasic system,and lignin during Kraft cooking and ECF was recovered.The process condition was discussed as well as the mass flow direction.The results showed that ELA pretreatment could effectively remove 80.1%hemicellulose.Compared with traditional hydrothermal pretreatment,the ELA pretreatment significantly increased the xylose yield from 5.05 to 14.18 g/L at 170℃ for 2 h,which had practical significance for furfural production.The 82.7%furfural yield and 82.9%furfural selectivity were obtained from xylose-rich pre-hydrolysate using NaCl as a phase modifier in a biphasic system with 4-methyl-2-pentanone(MIBK)as an organic phase by ion exchange resin catalysts at 190℃ for 2 h.Subsequently,the pretreated eucalyptus was subjected to Kraft cooking,and the optimal alkali amount was 14%.Then,the Kraft pulp was bleached using the O-D1-EP-D_(2) sequence,and dissolving pulp was obtained with an ISO brightness of 86.0%,viscosity of 463 mL/g,andα-cellulose content of 95.4%.The Kraft lignin which has a potential application was investigated by 2D-HSQC NMR and 31P NMR.The results showed that the S/G ratio of Kraft lignin was 1.93,and the content of phenolic hydroxyl groups was 2.53 mmol/g.Moreover,based on the above proposed process,30.5 g dissolving pulp,5.5 g furfural,and 21.2 g lignin per 100 g eucalyptus chips(oven dry)were produced.This research will provide new catalysis and pulping technical routes for dissolving pulp,furfural,and Kraft lignin products,which are in great demand in the chemical industry.展开更多
Furfuryl ethers have been considered to be a promising fuel additive.One step reduction etherification of furfural over supported Pd catalysts provides a facile way for the preparation of furfuryl ether.However,the pr...Furfuryl ethers have been considered to be a promising fuel additive.One step reduction etherification of furfural over supported Pd catalysts provides a facile way for the preparation of furfuryl ether.However,the preparation of a reusable Pd catalyst for reductive etherification remains to be a great challenge.In this study,a series of Si O_(2)supported Pd catalysts with particle size ranging from 2.2 nm to 28 nm were prepared.Their textural properties and catalytic performance in furfural reductive etherification have been systematically studied.The results herein shed light on the particle size effect on the competition between hydrogenation/hydrogenolysis of C=O in furfural over Pd surface.We found out that Pd nanoparticles larger than 3 nm are preferred for one step reductive etherification.Based on this finding,we prepared a Pd/ZSM-5 bifunctional catalyst comprising Pd nanoparticles larger than 3 nm and decreased acidity in presence of amino organosilane,which served as a bifunctional catalyst succeeding in one-pot synthesis of ether via reductive-etherification and direct-etherification.This strategy showed significant advantage in efficiently converting furfuryl acohol,a major side-product,into ether,while suppressing the undesired side-reactions.展开更多
A cost-effective and sustainable noble-metal free catalyst system based on ubiquitously available Mn-Cu bimetallic oxides was served as efficient catalysts for furfural selective oxidation to furancarboxylic acid(FA)....A cost-effective and sustainable noble-metal free catalyst system based on ubiquitously available Mn-Cu bimetallic oxides was served as efficient catalysts for furfural selective oxidation to furancarboxylic acid(FA). Interestingly, Mn_(2)Cu_(1)O_(x)exhibited an excellent furfural conversion of 99% with quantitative selectivity toward FA. Especially, we demonstrate the significant weakening of the Mn-O bonds with the incorporation of CuO into the Mn-Cu oxides, resulting in an improved OLreactivity of Mn_(2)Cu_(1)O_(x), which brings about a higher catalytic activity for furfural oxidation. More importantly, Mn_(2)Cu_(1)O_(x)could exhibit YFA>90% over 5 cycles of reusability test. Through this study, the relationship between the morphology, surface chemistry, and catalytic activity of Mn-Cu bimetallic oxides are elucidated, providing a simple and environmentally friendly catalytic strategy and scientific basis for the development of Mn-Cu bimetallic oxides bioderived molecular aerobic oxidation materials.展开更多
Conventional chemical oxidation of aldehydes such as furfural to corresponding acids by molecular oxygen usually needs high pressure to increase the solubility of oxygen in aqueous phase,while electrochemical oxidatio...Conventional chemical oxidation of aldehydes such as furfural to corresponding acids by molecular oxygen usually needs high pressure to increase the solubility of oxygen in aqueous phase,while electrochemical oxidation needs input of external electric energy.Herein,we developed a liquid flow fuel cell(LFFC)system to achieve oxidation of furfural in anode for furoic acid production with co-production of hydrogen gas.By controlling the electron transfer in cathode for reduction of oxygen,efficient generation of electricity or production of H_(2)O_(2)were achieved.Metal oxides especially Ag_(2)O have been screened as the efficient catalyst to promote the oxidation of aldehydes,while liquid redox couples were used for promoting the kinetics of oxygen reduction.A novel alkaline-acidic asymmetric design was also used for anolyte and catholyte,respectively,to promote the efficiency of electron transfer.Such an LFFC system achieves efficient conversion of chemical energy of aldehyde oxidation to electric energy and makes full use the transferred electrons for high-value added products without input of external energy.With(VO_(2))_(2)SO_(4)as the electron carrier in catholyte for four-electron reduction of oxygen,the peak output power density(Pmax)at room temperature reached 261 mW/cm^(2)with furoic acid and H_(2)yields of 90%and 0.10 mol/mol furfural,respectively.With anthraquinone-2-sulfonate(AQS)as the cathodic electron carrier,Pmaxof 60 mW/cm^(2)and furoic acid,H_(2)and H_(2)O_(2)yields of 0.88,0.15 and 0.41 mol/mol furfural were achieved,respectively.A new reaction mechanism on furfural oxidation on Ag_(2)O anode was proposed,referring to one-electron and two-electron reaction pathways depending on the fate of adsorbed hydrogen atom transferred from furfural aldehyde group.展开更多
Here,CuO nanorods fabricated via pulsed laser ablation in liquids were decorated with Ir,Pd,and Ru NPs(loading~7 wt%) through pulsed laser irradiation in the liquids process.The resulting NPs-decorated CuO nanorods we...Here,CuO nanorods fabricated via pulsed laser ablation in liquids were decorated with Ir,Pd,and Ru NPs(loading~7 wt%) through pulsed laser irradiation in the liquids process.The resulting NPs-decorated CuO nanorods were characterized spectroscopically and employed as multifunctional electrocatalysts in OER,HER,and the furfural oxidation reactions(FOR).Ir-CuO nanorods afford the lowest overpotential of~345 mV(HER) and 414 mV(OER) at 10 mA cm^(-2),provide the highest 2-furoic acid yield(~10.85 mM) with 64.9% selectivity,and the best Faradaic efficiency~72.7% in 2 h of FOR at 1.58 V(vs.RHE).In situ electrochemical-Raman analysis of the Ir-CuO detects the formation of the crucial intermediates,such as Cu(Ⅲ)-oxide,Cu(OH)_(2),and Ir_x(OH)_y,on the electrode-electrolyte surface,which act as a promoter for HER and OER.The Ir-CuO ‖ Ir-CuO in a coupled HER and FOR-electrolyzer operates at~200 mV lower voltage,compared with the conventional electrolyzer and embodies the dual advantage of energy-saving H_(2) and 2-furoic acid production.展开更多
Hydrogenative rearrangement of biomas s-derived furfurals(furfural and 5-hydroxymethyl furfural) to C_(5) cyclic compounds(such as cyclopentanones and cyclopentanols) offers an expedient reaction route for acquiring O...Hydrogenative rearrangement of biomas s-derived furfurals(furfural and 5-hydroxymethyl furfural) to C_(5) cyclic compounds(such as cyclopentanones and cyclopentanols) offers an expedient reaction route for acquiring O-containing value-added chemicals thereby replacing the traditional petroleum-based approaches.The scope for developing efficient bifunctional catalysts and establishing mild reaction conditions for upgrading furfurals to cyclic compounds has stimulated immense deliberation in recent years.Extensive efforts have been made toward developing catalysts for multiple tandem conversions,including those with various metals and supports.In this scientific review,we aim to summarize the research progress on the synergistic effect of the metal-acid sites,including simple metal-supported acidic supports,adjacent metal acid sites-supported catalysts,and in situ H_(2)-modified bifunctional catalysts.Distinctively,the catalytic performance,catalytic mechanism,and future challenges for the hydrogenative rearrangement are elaborated in detail.The methods highlighted in this review promote the development of C_(5) cyclic compound synthesis and provide insights to regulate bifunctional catalysis for other applications.展开更多
The reductive transformation of furfural (FAL) into furfuryl alcohol (FOL) is an attractive route for the use of renewable bio‐sources but it suffers from the heavy use of H2. We describe here a highly efficient ...The reductive transformation of furfural (FAL) into furfuryl alcohol (FOL) is an attractive route for the use of renewable bio‐sources but it suffers from the heavy use of H2. We describe here a highly efficient reduction protocol for converting aqueous FAL to FOL. A single phase rutile TiO2 support with a gold catalyst (Au/TiO2‐R) that used CO/H2O as the hydrogen source catalyze this reduction efficiently under mild conditions. By eliminating the consumption of fossil fuel‐derived H2, our pro‐cess has the benefit afforded by using CO as a convenient and cost competitive reducing reagent.展开更多
Photocatalytic hydrogenation of furfural offers an ideal method for selective biomass upgrading into value-added chemicals or fuel additives under mild conditions. However, it is still challenging to control the produ...Photocatalytic hydrogenation of furfural offers an ideal method for selective biomass upgrading into value-added chemicals or fuel additives under mild conditions. However, it is still challenging to control the product selectivity due to side reactions of functional groups and reactive radical intermediates.Herein, photocatalytic transfer hydrogenation of furfural was studied using the TiO_(2)-based photocatalysts with alcohols as both the solvent and hydrogen donor. Ultralow loading metal supported on TiO_(2),together with adding a small amount of water in the system, were demonstrated to greatly increase the selectivity of furfuryl alcohol product. Electron paramagnetic resonance(EPR), ultraviolet-visible spectroscopy(UV-Vis) and photoluminescence(PL) measurements gave evidence that ultralow loading Pt or Pd on TiO_(2)increase the oxygen vacancy concentration and the photogenerated charge separation efficiency, which accelerates the photocatalytic reduction of furfural. In situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS) and mechanistic studies confirmed that photogenerated holes and electrons are active species, with dissociatively adsorbed methanol being directly oxidized by holes,furfural hydrogenated by protons and electrons and H_(2)O modifying the intermediate diffusion which contributes to high selectivity of furfuryl alcohol. This work demonstrates a simple approach to design photocatalysts and tune product selectivity in biomass valorization.展开更多
From both fundamental and practical perspectives, the production of chemicals from biomass re-sources using high-efficiency non-precious metal catalysts is important. However, many processes require addition of stoic...From both fundamental and practical perspectives, the production of chemicals from biomass re-sources using high-efficiency non-precious metal catalysts is important. However, many processes require addition of stoichiometric or excess quantities of base, which leads to high energy consump-tion, leaching problems, and side reactions. In this study, we investigated the high-efficiency oxida-tive esterification of furfural to methylfuroate by molecular oxygen with a Co-N-C/MgO catalyst. The catalyst was prepared by direct pyrolysis of a cobalt(Ⅱ) phenanthroline complex on MgO at 800℃ under N2 atmosphere. From furfural, 93.0% conversion and 98.5% selectivity toward methylfuroate were achieved under 0.5 MPa O2 with reaction at 100 ℃ for 12 h without a basic additive. The con-version and selectivity were much higher than those obtained with cobalt catalysts produced by pyrolysis of a cobalt(Ⅱ) phenanthroline complex on activated carbon or typical basic supports, in-cluding NaX, NaY, and CaO. X-ray photoelectron spectroscopy, X-ray diffraction, transmission elec-tron microscopy, and experimental results revealed that the high efficiency of Co-N-C/MgO for pro-duction of methylfuroate was closely related to the cobalt-nitrogen-doped carbon species and its catalytic ability in hydrogen abstraction. In contrast, Co-N-C(HCl) that synthesized by removing MgO with HCl from Co-N-C/MgO, as the catalyst produced mainly an acetal as a condensation prod-uct, and chloride ions had a negative effect on the oxidative esterification. Although the catalytic performance of the cobalt-nitrogen-doped carbon species was greatly affected by HCl treatment, it could be recovered to a great extent by addition of MgO. Moreover, changes in the oxygen pressure hardly affected the oxidative esterification of furfural with Co-N-C/MgO. This study not only pro-vides an effective approach to prepare methylfuroate, but also for designing high-performance non-precious metal catalysts for the oxidative esterification of biomass-derived compounds.展开更多
基金funded by United States National Science Foundation(NSF)Grant HRD-1036593USDA-NIFA Grant 12684238:Award No.2020-65209-31474United States Department of Energy Grant DE-SC0023345.
文摘Renewable resources based polymers provides a sustainable alternative to petroleum derived polymeric materials.As a part of our series on synthesis of vanillin based renewable polymers,we report the synthesis of poly(hydrovanilloin-furfural)[poly(HVL-Fur)]and poly(hydrovanilloin–5-hydromethylfurfural)[poly(HVL-5-HMF)].Vanillin was dimerized to a mixtures of meso/DL-hydrovanilloins with 94%meso product by electrochemical reductive coupling in aqueous sodium hydroxide using lead electrodes in quantitative yield.Then sodium hydroxide catalyzed condensation of hydrovanilloin with furfural in water at 80℃for 72 h was used to synthesize poly(HVL-Fur)with Mw=8600 g mol^(−1),PDI=1.28 in 78%yield.Similarly,condensation of hydrovanilloin with 5-hydroxymethylfurfural at 80℃for 48 h produced poly(HVL-5-HMF)with Mw=12,100 g mol−1,PDI=1.27 in 68%yield.poly(HVL-Fur)and poly(HVL-5-HMF)showed similar Tg values of 59℃and 60℃,respectively;whereas melting behaviors are dissimilar with Tm 171℃–173℃and 148℃–182℃,respectively.
基金supported by Program for National Natural Science Foundation of China(Nos.22178135,21978104 and 22278419)the National Key Research and Development Program of China(No.2021YFC2101601)。
文摘The fructose-to-furfural transformation is facing major challenges in the selectivity and high efficiency. Herein, we have developed a simple and effective approach for the selective conversion of fructose to furfural using Hβ zeolite modified by organic acids for dealuminization to regulate its textural and acidic properties. It was found that citric acid-dealuminized Hβ zeolite possessed high specific surface areas, wide channels and high Brønsted acid amount, which facilitated the selective conversion of fructose to furfural with a maximum yield of 76.2% at433 K for 1 h in the γ-butyrolactone(GBL)-H_(2)O system, as well as the concomitant formation of 83.0% formic acid. The^(13)C-isotope labelling experiments and the mechanism revealed that the selective cleavage of C1–C2 or C5–C6 bond on fructose was firstly occurred to form pentose or C5 intermediate by weak Brønsted acid, which was then dehydrated to furfural by strong Brønsted acid. Also this dealuminized Hβ catalyst showed the great recycling performance and was active for the conversion of glucose and mannose.
基金supported by the Korea Basic Science Institute(National research Facilities and Equipment Center)grant funded by the Ministry of Education(2019R1A6C1010042,2021R1A6C103A427)the financial support from the National Research Foundation of Korea(NRF)(2022R1A2C2010686,2022R1A4A3033528,2021R1I1A1A01060380,2021R1C1C2010726,2019H1D3A1A01071209)。
文摘The electrocatalytic oxidation of biomass-derived furfural(FF)feedstocks into 2-furoic acid(FA)holds immense industrial potential in optics,cosmetics,polymers,and food.Herein,we fabricated Co O/Ni O/nickel foam(NF)and Cu_(2)O/Ni O/NF electrodes via in situ pulsed laser irradiation in liquids(PLIL)for the bifunctional electrocatalysis of oxygen evolution reaction(OER)and furfural oxidation reaction(FOR),respectively.Simultaneous oxidation of NF surface to NiO and deposition of CoO and/or Cu_(2)O on NF during PLIL offer distinct advantages for enhancing both the OER and FOR.CoO/NiO/NF electrocatalyst provides a consistently low overpotential of~359 m V(OER)at 10 m A/cm^(2),achieving the maximum FA yield(~16.37 m M)with 61.5%selectivity,79.5%carbon balance,and a remarkable Faradaic efficiency of~90.1%during 2 h of FOR at 1.43 V(vs.reversible hydrogen electrode).Mechanistic pathway via in situ electrochemical-Raman spectroscopy on CoO/NiO/NF reveals the involvement of phase transition intermediates(NiOOH and CoOOH)as surface-active centers during electrochemical oxidation.The carbonyl carbon in FF is attacked by hydroxyl groups to form unstable hydrates that subsequently undergo further oxidation to yield FA products.This method holds promise for large-scale applications,enabling simultaneous production of renewable building materials and fuel.
基金supported by the National Key R&D Program of China(2023YFD1701504)the 2115 Talent Development Program of China Agricultural University Fund(1011-00109018)the Beijing Innovation Team of the Modern Agricultural Research System(BAIC08-2023-FQ02)。
文摘Optimizing the intrinsic activity of non-noble metal by precisely tailoring electronic structure offers an appealing way to construct cost-effective catalysts for selective biomass valorization.Herein,we reported a P-doping bifunctional catalyst(Ni-P/mSiO_(2))that achieved 96.6%yield for the hydrogenation rearrangement of furfural to cyclopentanone at mild conditions(1 MPaH_(2),150°C).The turnover frequency of Ni-P/mSiO_(2)was 411.9 h^(-1),which was 3.2-fold than that of Ni/mSiO_(2)(127.2 h^(-1)).Detailed characterizations and differential charge density calculations revealed that the electron-deficient Niδ+species were generated by the electron transfer from Ni to P,which promoted the ring rearrangement reaction.Density functional theory calculations illustrated that the presence of P atoms endowed furfural tilted adsorb on the Ni surface by the C=O group and facilitated the desorption of cyclopentanone.This work unraveled the connection between the localized electronic structures and the catalytic properties,so as to provide a promising reference for designing advanced catalysts for biomass valorization.
基金Shandong Province Natural Science Foundation,China(ZR2020KB014,ZR2022QB206)the National Natural Science Foundation of China(22178001)+1 种基金Anhui Provincial Natural Science Foundation(2308085Y19)Research Project for Outstanding Youth of Department of Education of Anhui Province(2022AH030045).
文摘Gasification of furfural residue with coal can realize its efficient and clean utilization.But the high alkali metal content in furfural slag is easy to cause the corrosion of gasifier refractory.Two gasification coals with different silica alumina ratio and a furfural residue were selected in the study.The effects of furfural residue additions on corrosion of silica brick,corundum brick,high alumina brick and mullite brick were investigated by using XRD,SEM-EDS and Factsage Software,and the corrosion mechanism was analyzed.With increasing furfural residue addition,the permeability of the slags to high-aluminium-bearing refractories first decreases and then increases,while the permeability on silica brick shows a slight decrease trend.Leucite(KAlSi_(2)O_(6))with high-melting temperature is generated from the reaction of K_(2)O and SiO_(2)in slag with Al_(2)O_(3)in refractories after furfural residue is added,which hinders the infiltration of slag in refractories.Kaliophilite(KAlSiO_(4))of low-melting point is formed when K_(2)O content increases,and this contributes to the infiltration of slag in refractories.The acid-base reaction between slag and silica brick is distinctly occurred,more slag reacts with SiO_(2)in the silicon brick,resulting in a decrease in the amount of slag infiltrating into the silicon brick as furfural residue is added.The corrosion of silica brick is mainly caused by the acid-base reaction,while the corrosion of three alumina based refractory bricks of corundum,mullite and high alumina brick is determined by slag infiltration.A linear correlation between the percolation rate and slag viscosity is established,the slag permeability increases with decreasing viscosity,resulting in stronger permeability for the high Si/Al ratio slag with lower viscosity.
基金supported by the National Key Research and Development Program of China(2021YFC2101303)the National Natural Science Foundation of China(U22A20424 and 22378048)+6 种基金the Major Scientific and Technological Projects of Sinopecthe Dalian Technology Talents Project for Distinguished Young Scholars(2021RJ03)the Yunnan Provincial Rural Energy Engineering Key Laboratory(2022KF003)the National Natural Science Foundation of Liaoning Province(2023-MS-110)the Liaoning Revitalization Talents Program(XLYC2202049)the Fundamental Research Funds for the Central Universities(DUT22LK22)the CAS Key Laboratory of Renewable Energy,Guangzhou Institute of Energy Conversion(E229kf0401)。
文摘Acetic acid and furfural are known as prevalent inhibitors deriving from pretreatment during lignocellulosic ethanol production.They negatively impact cell growth,glucose uptake and ethanol biosynthesis of Saccharomyces cerevisiae strains.Development of industrial S.cerevisiae strains with high tolerance towards these inhibitors is thus critical for efficient lignocellulosic ethanol production.In this study,the acetic acid or furfural tolerance of different S.cerevisiae strains could be significantly enhanced after adaptive evolution via serial cultivation for 40 generations under stress conditions.The acetic acid-based adaptive strain SPSC01-TA9 produced 30.5 g·L^(-1)ethanol with a yield of 0.46 g·g^(-1)in the presence of 9 g·L^(-1)acetic acid,while the acetic acid/furfural-based adaptive strain SPSC01-TAF94 produced more ethanol of 36.2 g·L^(-1)with increased yield up to 0.49 g·g^(-1)in the presence of both 9 g·L^(-1)acetic acid and 4 g·L^(-1)furfural.Significant improvements were also observed during non-detoxified corn stover hydrolysate culture by SPSC01-TAF94,which achieved ethanol production and yield of 29.1 g·L^(-1)and 0.49 g·g^(-1),respectively,the growth and fermentation efficiency of acetic acid/furfural-based adaptive strain in hydrolysate was 95%higher than those of wildtype strains,indicating the acetic acid-and furfural-based adaptive evolution strategy could be an effective approach for improving lignocellulosic ethanol production.The adapted strains developed in this study with enhanced tolerance against acetic acid and furfural could be potentially contribute to economically feasible and sustainable lignocellulosic biorefinery.
基金This study is supported by the National Key Research and Development Program of China(2017YFB0307500).
文摘Implementing a new energy-saving electrochemical synthesis system with high commercial value is a strategy of the sustainable development for upgrading the bulk chemicals preparation technology in the future.Here,we report a multiple redox-mediated linear paired electrolysis system,combining the hydrogen peroxide mediated cathode process with the I2 mediated anode process,and realize the conversion of furfural to furoic acid in both side of the dividedflow cell simultaneously.By reasonably controlling the cathode potential,the undesired water splitting reaction and furfural reduction side reactions are avoided.Under the galvanostatic electrolysis,the two-mediated electrode processes have good compatibility,which reduce the energy consumption by about 22%while improving the electronic efficiency by about 125%.This system provides a green electrochemical synthesis route with commercial prospects.
基金supported by Korea Basic Science Institute(National research Facilities and Equipment Center)grant funded by the Ministry of Education(Nos.2019R1A6C1010042 and 2021R1A6C103A427)the financial support from National Research Foundation of Korea(NRF),(2022R1A2C2010686,2022R1A4A3033528,2019H1D3A1A01071209,and 2021R1I1A1A01060380)
文摘Here,furfural oxidation was performed to replace the kinetically sluggish O_(2)evolution reaction(OER).Pt-Co_(3)O_(4)nanospheres were developed via pulsed laser ablation in liquid(PLAL)in a single step for the paired electrocatalysis of an H_(2)evolution reaction(HER)and furfural oxidation reaction(FOR).The FOR afforded a high furfural conversion(44.2%)with a major product of 2-furoic acid after a 2-h electrolysis at 1.55 V versus reversible hydrogen electrode in a 1.0-M KOH/50-mM furfural electrolyte.The Pt-Co_(3)O_(4)electrode exhibited a small overpotential of 290 mV at 10 mA cm^(-2).As an anode and cathode in an electrolyzer system,the Pt-Co_(3)O_(4)electrocatalyst required only a small applied cell voltage of~1.83 V to deliver 10 mA cm^(-2),compared with that of the pure water electrolyzer(OER||HER,~1.99 V).This study simultaneously realized the integrated production of energy-saving H_(2)fuel at the cathode and 2-furoic acid at the anode.
基金financially supported by the National Natural Science Foundation of China(202102007,21978147 and 21935001)the Fundamental Research Funds for the Central Universities(buctrc202112)。
文摘Selective reductive amination of carbonyl compounds with high activity is very essential for the chemical and pharmaceutical industry,but scarcely successful paradigm was reported via efficient photocatalytic reactions.Herein,the ultrasmall Ru nanoclusters(~0.9 nm)were successfully fabricated over P25 support with positive charged Ru^(δ+)species at the interface.A new route was developed to achieve the furfural(FAL)to furfurylamine(FAM)by coupling the light-driven reductive amination and hydrogen transfer of ethanol over this type catalyst.Strikingly,the photocatalytic activity and selectivity are strongly dependent on the particle size and electronic structure of Ruthenium.The Ru^(δ+)species at the interface promote the formation of active imine intermediates;moreover,the Ru nanoclusters facilitate the separation efficiency of electrons and holes as well as accelerate the further hydrogenation of imine intermediates to product primary amines.In contrast Ru particles in larger nanometer size facilitate the formation of the furfuryl alcohol and excessive hydrogenation products.In addition,the coupling byproducts can be effectively inhibited via the construction of sub-nanocluster.This study offers a new path to produce the primary amines from biomass-derived carbonyl compounds over hybrid semiconductor/metal-clusters photocatalyst via light-driven tandem catalytic process.
基金supported by the National Key R&D Program of China(2021YFC2103704)the National Natural Science Foundation of China(22022812,21978259)+1 种基金Key R&D Program of Zhejiang(2022C01208)Institute of Zhejiang University-Quzhou S&T Planed Projects(IZQ2021KJ1001)。
文摘Hydrodeoxygenation of furfural(FF)into 2-methylfuran(MF)is a significant biomass utilization route.However,designing efficient and stable non-noble metal catalyst is still a huge challenge.Herein,we reported the N,O co-doped carbon anchored with Co nanoparticles(Co-SFB)synthesized by employing the organic ligands with the target heteroatoms.Raman,electron paramagnetic resonance(EPR),electrochemical impedance spectroscopy(EIS),and X-ray photoelectron spectroscopy(XPS)characterizations showed that the co-doping of N and O heteroatoms in the carbon support endows Co-SFB with enriched lone pair electrons,fast electron transfer ability,and strong metal-support interaction.These electronic properties resulted in strong FF adsorption as well as lower apparent reaction activation energy.At last,the obtained N,O co-doped Co/C catalyst showed excellent catalytic activity(nearly 100 mol%FF conversion and 94.6 mol%MF yield)and stability for in-situ dehydrogenation of FF into MF.This N,O co-doping strategy for the synthesis of highly efficient catalytic materials with controllable electronic state will provide an excellent opportunity to better understand the structure-function relationship.
基金This research was funded by the National Natural Science Foundation of China(No.21978104)the Program for the National Key Research and Development Program of China(No.2021YFC2101601).
文摘Hemicellulose and lignin are not reasonably utilized during the dissolved pulp preparation process.This work aimed to propose a process for the co-production of dissolving pulp,furfural,and lignin from eucalyptus.High-grade dissolving pulp was prepared from eucalyptus using a combination of extremely low acid(ELA)pretreatment,Kraft cooking,and elementary chlorine-free(ECF)bleaching.The obtained pre-hydrolysate was catalytic conversion into furfural in a biphasic system,and lignin during Kraft cooking and ECF was recovered.The process condition was discussed as well as the mass flow direction.The results showed that ELA pretreatment could effectively remove 80.1%hemicellulose.Compared with traditional hydrothermal pretreatment,the ELA pretreatment significantly increased the xylose yield from 5.05 to 14.18 g/L at 170℃ for 2 h,which had practical significance for furfural production.The 82.7%furfural yield and 82.9%furfural selectivity were obtained from xylose-rich pre-hydrolysate using NaCl as a phase modifier in a biphasic system with 4-methyl-2-pentanone(MIBK)as an organic phase by ion exchange resin catalysts at 190℃ for 2 h.Subsequently,the pretreated eucalyptus was subjected to Kraft cooking,and the optimal alkali amount was 14%.Then,the Kraft pulp was bleached using the O-D1-EP-D_(2) sequence,and dissolving pulp was obtained with an ISO brightness of 86.0%,viscosity of 463 mL/g,andα-cellulose content of 95.4%.The Kraft lignin which has a potential application was investigated by 2D-HSQC NMR and 31P NMR.The results showed that the S/G ratio of Kraft lignin was 1.93,and the content of phenolic hydroxyl groups was 2.53 mmol/g.Moreover,based on the above proposed process,30.5 g dissolving pulp,5.5 g furfural,and 21.2 g lignin per 100 g eucalyptus chips(oven dry)were produced.This research will provide new catalysis and pulping technical routes for dissolving pulp,furfural,and Kraft lignin products,which are in great demand in the chemical industry.
基金financial support from the National Natural Science Foundation of China(21773067)the Open Research fund of Shanghai Key Laboratory of Green Chemistry and Chemical Processes。
文摘Furfuryl ethers have been considered to be a promising fuel additive.One step reduction etherification of furfural over supported Pd catalysts provides a facile way for the preparation of furfuryl ether.However,the preparation of a reusable Pd catalyst for reductive etherification remains to be a great challenge.In this study,a series of Si O_(2)supported Pd catalysts with particle size ranging from 2.2 nm to 28 nm were prepared.Their textural properties and catalytic performance in furfural reductive etherification have been systematically studied.The results herein shed light on the particle size effect on the competition between hydrogenation/hydrogenolysis of C=O in furfural over Pd surface.We found out that Pd nanoparticles larger than 3 nm are preferred for one step reductive etherification.Based on this finding,we prepared a Pd/ZSM-5 bifunctional catalyst comprising Pd nanoparticles larger than 3 nm and decreased acidity in presence of amino organosilane,which served as a bifunctional catalyst succeeding in one-pot synthesis of ether via reductive-etherification and direct-etherification.This strategy showed significant advantage in efficiently converting furfuryl acohol,a major side-product,into ether,while suppressing the undesired side-reactions.
基金supported by the National Natural Science Fund of China (Nos. 21978246 and 21776234)。
文摘A cost-effective and sustainable noble-metal free catalyst system based on ubiquitously available Mn-Cu bimetallic oxides was served as efficient catalysts for furfural selective oxidation to furancarboxylic acid(FA). Interestingly, Mn_(2)Cu_(1)O_(x)exhibited an excellent furfural conversion of 99% with quantitative selectivity toward FA. Especially, we demonstrate the significant weakening of the Mn-O bonds with the incorporation of CuO into the Mn-Cu oxides, resulting in an improved OLreactivity of Mn_(2)Cu_(1)O_(x), which brings about a higher catalytic activity for furfural oxidation. More importantly, Mn_(2)Cu_(1)O_(x)could exhibit YFA>90% over 5 cycles of reusability test. Through this study, the relationship between the morphology, surface chemistry, and catalytic activity of Mn-Cu bimetallic oxides are elucidated, providing a simple and environmentally friendly catalytic strategy and scientific basis for the development of Mn-Cu bimetallic oxides bioderived molecular aerobic oxidation materials.
基金supported by the National Natural Science Foundation of China(No.2187817622178197)。
文摘Conventional chemical oxidation of aldehydes such as furfural to corresponding acids by molecular oxygen usually needs high pressure to increase the solubility of oxygen in aqueous phase,while electrochemical oxidation needs input of external electric energy.Herein,we developed a liquid flow fuel cell(LFFC)system to achieve oxidation of furfural in anode for furoic acid production with co-production of hydrogen gas.By controlling the electron transfer in cathode for reduction of oxygen,efficient generation of electricity or production of H_(2)O_(2)were achieved.Metal oxides especially Ag_(2)O have been screened as the efficient catalyst to promote the oxidation of aldehydes,while liquid redox couples were used for promoting the kinetics of oxygen reduction.A novel alkaline-acidic asymmetric design was also used for anolyte and catholyte,respectively,to promote the efficiency of electron transfer.Such an LFFC system achieves efficient conversion of chemical energy of aldehyde oxidation to electric energy and makes full use the transferred electrons for high-value added products without input of external energy.With(VO_(2))_(2)SO_(4)as the electron carrier in catholyte for four-electron reduction of oxygen,the peak output power density(Pmax)at room temperature reached 261 mW/cm^(2)with furoic acid and H_(2)yields of 90%and 0.10 mol/mol furfural,respectively.With anthraquinone-2-sulfonate(AQS)as the cathodic electron carrier,Pmaxof 60 mW/cm^(2)and furoic acid,H_(2)and H_(2)O_(2)yields of 0.88,0.15 and 0.41 mol/mol furfural were achieved,respectively.A new reaction mechanism on furfural oxidation on Ag_(2)O anode was proposed,referring to one-electron and two-electron reaction pathways depending on the fate of adsorbed hydrogen atom transferred from furfural aldehyde group.
基金supported by the Korea Basic Science Institute (National research Facilities and Equipment Center) grant funded by the Ministry of Education. (2019R1A6C1010042, 2021R1A6C103A427)the financial support from the National Research Foundation of Korea (NRF), (2022R1A2C2010686, 2022R1A4A3033528, 2021R1I1A1A01060380, 2019H1D3A1A01071209)。
文摘Here,CuO nanorods fabricated via pulsed laser ablation in liquids were decorated with Ir,Pd,and Ru NPs(loading~7 wt%) through pulsed laser irradiation in the liquids process.The resulting NPs-decorated CuO nanorods were characterized spectroscopically and employed as multifunctional electrocatalysts in OER,HER,and the furfural oxidation reactions(FOR).Ir-CuO nanorods afford the lowest overpotential of~345 mV(HER) and 414 mV(OER) at 10 mA cm^(-2),provide the highest 2-furoic acid yield(~10.85 mM) with 64.9% selectivity,and the best Faradaic efficiency~72.7% in 2 h of FOR at 1.58 V(vs.RHE).In situ electrochemical-Raman analysis of the Ir-CuO detects the formation of the crucial intermediates,such as Cu(Ⅲ)-oxide,Cu(OH)_(2),and Ir_x(OH)_y,on the electrode-electrolyte surface,which act as a promoter for HER and OER.The Ir-CuO ‖ Ir-CuO in a coupled HER and FOR-electrolyzer operates at~200 mV lower voltage,compared with the conventional electrolyzer and embodies the dual advantage of energy-saving H_(2) and 2-furoic acid production.
基金support from the National Natural Science Foundation of China (Nos. 22178158, 52162014 and 22065024)Science and Technology Project of Education Department of Jiangxi Province (No. GJJ2200402)+3 种基金Jiangxi Provincial Natural Science Foundation (No. 20224BAB213023)the Outstanding Youth Science Fund Project of Jiangxi Province (No. 20224ACB213008)the Jiangxi Provincial Double Thousand Talents Plan-Youth Program (No. S2021GDQN0947)Natural Science Foundation of Chongqing (No. 2023NSCQ-MSX0052)
文摘Hydrogenative rearrangement of biomas s-derived furfurals(furfural and 5-hydroxymethyl furfural) to C_(5) cyclic compounds(such as cyclopentanones and cyclopentanols) offers an expedient reaction route for acquiring O-containing value-added chemicals thereby replacing the traditional petroleum-based approaches.The scope for developing efficient bifunctional catalysts and establishing mild reaction conditions for upgrading furfurals to cyclic compounds has stimulated immense deliberation in recent years.Extensive efforts have been made toward developing catalysts for multiple tandem conversions,including those with various metals and supports.In this scientific review,we aim to summarize the research progress on the synergistic effect of the metal-acid sites,including simple metal-supported acidic supports,adjacent metal acid sites-supported catalysts,and in situ H_(2)-modified bifunctional catalysts.Distinctively,the catalytic performance,catalytic mechanism,and future challenges for the hydrogenative rearrangement are elaborated in detail.The methods highlighted in this review promote the development of C_(5) cyclic compound synthesis and provide insights to regulate bifunctional catalysis for other applications.
基金supported by the National Natural Science Foundation of China (21273044, 21473035, 91545108)the Research Fund for the Doctoral Program of Higher Education (2012007000011)+2 种基金SINOPEC (X514005)Science & Technology Commission of Shanghai Municipality (08DZ2270500)the Open Project of State Key Laboratory of Chemical Engineering (SKL-ChE-15C02)~~
文摘The reductive transformation of furfural (FAL) into furfuryl alcohol (FOL) is an attractive route for the use of renewable bio‐sources but it suffers from the heavy use of H2. We describe here a highly efficient reduction protocol for converting aqueous FAL to FOL. A single phase rutile TiO2 support with a gold catalyst (Au/TiO2‐R) that used CO/H2O as the hydrogen source catalyze this reduction efficiently under mild conditions. By eliminating the consumption of fossil fuel‐derived H2, our pro‐cess has the benefit afforded by using CO as a convenient and cost competitive reducing reagent.
基金supported by the Ministry of Science and Technology of the People’s Republic of China, China (2018YFE0118100)the National Natural Science Foundation of China, China (21905275, 22025206, 21721004, 21991090)+5 种基金the Liaoning Revitalization Talents Program, China (XLYC2002012)the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy, China (Grant. YLU-DNL Fund 2021019)the CAS-NSTDA Joint Research Project, China (GJHZ2075)Dalian Institute of Chemical Physics, CAS, China (Grant: DICP I202131)the Science and Technology Commission of Shanghai Municipality, China (19DZ2271100)support of the Liaoning Key Laboratory of Biomass Conversion for Energy and Material。
文摘Photocatalytic hydrogenation of furfural offers an ideal method for selective biomass upgrading into value-added chemicals or fuel additives under mild conditions. However, it is still challenging to control the product selectivity due to side reactions of functional groups and reactive radical intermediates.Herein, photocatalytic transfer hydrogenation of furfural was studied using the TiO_(2)-based photocatalysts with alcohols as both the solvent and hydrogen donor. Ultralow loading metal supported on TiO_(2),together with adding a small amount of water in the system, were demonstrated to greatly increase the selectivity of furfuryl alcohol product. Electron paramagnetic resonance(EPR), ultraviolet-visible spectroscopy(UV-Vis) and photoluminescence(PL) measurements gave evidence that ultralow loading Pt or Pd on TiO_(2)increase the oxygen vacancy concentration and the photogenerated charge separation efficiency, which accelerates the photocatalytic reduction of furfural. In situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS) and mechanistic studies confirmed that photogenerated holes and electrons are active species, with dissociatively adsorbed methanol being directly oxidized by holes,furfural hydrogenated by protons and electrons and H_(2)O modifying the intermediate diffusion which contributes to high selectivity of furfuryl alcohol. This work demonstrates a simple approach to design photocatalysts and tune product selectivity in biomass valorization.
基金the National Basic Research Program of China,the National Natural Science Foundation of China,the Key Research Program of the Chinese Academy of Sciences,the Creative Foundation of President of Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences
基金supported by the National Natural Science Foundation of China(21233008,21643013,21690084)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020300)the Youth Innovation Promotion Association CAS(2013121)~~
文摘From both fundamental and practical perspectives, the production of chemicals from biomass re-sources using high-efficiency non-precious metal catalysts is important. However, many processes require addition of stoichiometric or excess quantities of base, which leads to high energy consump-tion, leaching problems, and side reactions. In this study, we investigated the high-efficiency oxida-tive esterification of furfural to methylfuroate by molecular oxygen with a Co-N-C/MgO catalyst. The catalyst was prepared by direct pyrolysis of a cobalt(Ⅱ) phenanthroline complex on MgO at 800℃ under N2 atmosphere. From furfural, 93.0% conversion and 98.5% selectivity toward methylfuroate were achieved under 0.5 MPa O2 with reaction at 100 ℃ for 12 h without a basic additive. The con-version and selectivity were much higher than those obtained with cobalt catalysts produced by pyrolysis of a cobalt(Ⅱ) phenanthroline complex on activated carbon or typical basic supports, in-cluding NaX, NaY, and CaO. X-ray photoelectron spectroscopy, X-ray diffraction, transmission elec-tron microscopy, and experimental results revealed that the high efficiency of Co-N-C/MgO for pro-duction of methylfuroate was closely related to the cobalt-nitrogen-doped carbon species and its catalytic ability in hydrogen abstraction. In contrast, Co-N-C(HCl) that synthesized by removing MgO with HCl from Co-N-C/MgO, as the catalyst produced mainly an acetal as a condensation prod-uct, and chloride ions had a negative effect on the oxidative esterification. Although the catalytic performance of the cobalt-nitrogen-doped carbon species was greatly affected by HCl treatment, it could be recovered to a great extent by addition of MgO. Moreover, changes in the oxygen pressure hardly affected the oxidative esterification of furfural with Co-N-C/MgO. This study not only pro-vides an effective approach to prepare methylfuroate, but also for designing high-performance non-precious metal catalysts for the oxidative esterification of biomass-derived compounds.