Oat husks,a byproduct of oat milling operations with limited economic value,present a promising feedstock for biorefinery processes due to their chemical composition.This study investigates the conversion of C5 carboh...Oat husks,a byproduct of oat milling operations with limited economic value,present a promising feedstock for biorefinery processes due to their chemical composition.This study investigates the conversion of C5 carbohydrates in oat husks into furfural through hydrothermal pretreatment using various phosphate-based catalysts,including H_(3)PO_(4),NH_(4)H_(2)PO_(4),NaH_(2)PO_(4),KH_(2)PO_(4),K_(2)HPO_(4) and K_(3)PO_(4) as catalyst.The catalysts’effectiveness in promoting furfural production was evaluated under identical hydrothermal conditions(treatment time for 60 min at a constant temperature of 170℃ and a catalyst amount).Continuous water steam was used to strip furfural from the reaction zone and minimize its degradation.Results indicated that H_(3)PO_(4) was the most effective catalyst,achieving a furfural yield of 13.99 wt.%,which corresponds to approximately 57%of the theoretical yield.NH4H2PO4 also showed moderate effectiveness,while sodium and potassium phosphate salts were significantly less effective.A scanning electron microscope analysis shows that catalysts with lower pH may disrupt the oat husks external layer thus providing a higher C5 carbohydrates conversion rate into furfural.The chemical complexity of oat husk contributes to side reactions between its carbohydrates and lignin during the hydrothermal treatment.This results in an increase in acid-insoluble lignin and inorganic matter in the oat husk lignocellulosic residue,which can reduce the effectiveness of further cellulose saccharification by enzymatic hydrolysis.展开更多
Transition-state shape selectivity plays a crucial role in catalytic systems where reactants and products exhibit comparable molecular dimensions,as it restricts the accessible configuration space of reaction intermed...Transition-state shape selectivity plays a crucial role in catalytic systems where reactants and products exhibit comparable molecular dimensions,as it restricts the accessible configuration space of reaction intermediates.Herein,we designed a Cu@MFI catalyst by encapsulating Cu active sites within the well-defined micropores of MFI zeolite through a pore confinement strategy.This architecture preserves the zeolite framework integrity while maintaining unhindered internal mass transport,thereby enabling precise spatial control over transition-state configurations.Employing furfural hydrogenation as a probe reaction,the metal-zeolite synergy in Cu@MFI endowed the catalyst with exceptional activity(100%furfural conversion)and quantitative selectivity(100%furfuryl alcohol)at 70℃,sustained across a broad temperature window.Mechanistic studies reveal that the transition-state shape selectivity effectively prevented H2O interaction with the furan ring,offering valuable insights for other reaction systems seeking to exploit shape selectivity for specific transformations.展开更多
Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O.Herein,a novel Al_(2)O_(3)/C-u hybrid catalyst,...Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O.Herein,a novel Al_(2)O_(3)/C-u hybrid catalyst,composed of N-modified dendritic carbon networks supporting Al_(2)O_(3)nanoparticles,was successfully prepared via carbonizing the freeze-dried gel from spontaneous cross-linking of alginate,Al3+and urea.The obtained carbon-supported Al_(2)O_(3)hybrid catalyst has a high ratio (31%) of Al species in pentahedral-coordinated state.The introduction of urea enhances the surface N content,the ratio of pyrrolic N,and specific surface area of catalyst,leading to improved adsorption capacity of C=O and the accessibility of active sites.In the furfural hydrogenation reaction with isopropyl alcohol as hydrogen donor,Al_(2)O_(3)/C-u catalyst achieved a 90%conversion of furfural with 98.0% selectivity to furfuryl alcohol,outperforming that of commercial γ-Al_(2)O_(3).Moreover,Al_(2)O_(3)/C-u demonstrates excellent catalytic stability in the recycling tests attributed to the synergistic effect of abundant weak Lewis acid sites and the anchoring effect of the carbon network on Al_(2)O_(3)nanoparticles.This work provides an innovative and facile strategy for fabrication of carbon-supported Al_(2)O_(3)hybrid catalysts with rich AlVspecies,serving as a high selective hydrogenation catalyst through MPV reaction route.展开更多
The electrocatalytic furfural oxidation reaction(FFOR)represents an economical and promising technology to replace conventional oxygen evolution reaction,enabling the co-production of high value chemicals and H_(2).Re...The electrocatalytic furfural oxidation reaction(FFOR)represents an economical and promising technology to replace conventional oxygen evolution reaction,enabling the co-production of high value chemicals and H_(2).Regulating the adsorption of furfural(FF)and OH^(-)species holds paramount importance in enhancing the overall performance.Herein,we have developed a unique CuO catalyst enriched with oxygen vacancies(O_(v)-CuO)resulting from the electrochemical reconstruction ofα-Cu_(2)S,which demonstrates exceptional FFOR performance,with a conversion of 95.3%,near-perfect selectivity and Faraday efficiency(FE)for furoic acid(FA)at 1.475 V vs.RHE.The study provides detailed comparison of the structural evolution of different sulfide precatalysts and their impact on FFOR.Furthermore,it delves into the structure-activity relationship through a combination of characterization and theoretical calculations.The O_(v)-CuO not only enhances OH^(-)adsorption,changes the rate-determining step,but also reduces the reaction energy barrier toward FFOR.Additionally,a much lower cell voltage is required to coproduce FA and hydrogen in the two-electrode co-electrolysis system.This work would provide valuable insights into the reaction mechanism of FFOR on Cu based catalysts and establish guidelines for designing defective electrocatalysts for biomass conversion.展开更多
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 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
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 state-of-the-art lithium-ion capacitors (LICs),consisting of high-capacity battery-type anode and high-rate capacitor-type cathode,can deliver high energy density and large power density when comparing with tradit...The state-of-the-art lithium-ion capacitors (LICs),consisting of high-capacity battery-type anode and high-rate capacitor-type cathode,can deliver high energy density and large power density when comparing with traditional supercapacitors and lithium-ion batteries,respectively.However,the ion kinetics mismatch between cathode and anode leads to unsatisfied cycling lifetime and anode degradation.Tremendous efforts have been devoted to solving the abovementioned issue.One promising strategy is altering high conductive hard carbon anode with excellent structural stability to match with activated carbon cathode,assembling dual-carbon LIC.In this contribution,one-pot in-situ expansion and heteroatom doping strategy was adopted to prepare sheet-like hard carbon,while activated carbon was obtained involving activation.Ammonium persulfate was used as expanding and doping agent simultaneously.While furfural residues (FR) were served as carbon precursor.The resulting hard carbon (FRNS-HC) and activated carbon (FRNS-AC)show excellent electrochemical performance as negative and positive electrodes in a lithium-ion battery (LIB).To be specific,374.2 m Ah g^(-1)and 123.1 m Ah g^(-1)can be achieved at 0.1 A g^(-1)and 5 A g^(-1)when FRNS-HC was tested as anode.When combined with a highly porous carbon cathode (S_(BET)=2961 m^(2)g^(-1)) synthesized from the same precursor,the LIC showed high specific energy of147.67 Wh kg^(-1)at approximately 199.93 W kg^(-1),and outstanding cycling life with negligible capacitance fading over 1000 cycles.This study could lead the way for the development of heteroatom-doped porous carbon nanomaterials applied to Li-based energy storage applications.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
Bimetallic CuCo catalysts with different Cu to Co ratios on N-doped porous carbon materials(N-C)were achieved using impregnation method and applied in the hydrogenation of furfural(FAL)to furfuryl alcohol(FOL).The hig...Bimetallic CuCo catalysts with different Cu to Co ratios on N-doped porous carbon materials(N-C)were achieved using impregnation method and applied in the hydrogenation of furfural(FAL)to furfuryl alcohol(FOL).The high hydrogenation activity of FAL over Cu_(1)Co_(1)/N-C was originated from the synergistic interactions of Cu and Co species,where Co^(0)and Cu^(0)simultaneously adsorb and activate H_(2),and Cu^(+) served as Lewis acid sites to activate C]O.Meanwhile,electrons transfer from Cu to Co promoted the formation of Cu^(+).In situ Fourier transform infrared spectroscopy analysis indicated that Cu_(1)Co_(1)/N-C adsorbed FAL with a tilted η^(1)-(O)configuration.The superior Cu_(1)Co_(1)/N-C showed excellent adsorbed ability towards H_(2) and FAL,but weak adsorption for FOL.Therefore,Cu_(1)Co_(1)/N-C possessed 93.1%FAL conversion and 99.0% FOL selectivity after 5 h reaction,which also exhibited satisfactory reusability in FAL hydrogenation for five cycles.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
Biomass-derived platform molecules,such as furfural,are abundant and renewable feedstock for valuable chemical production.It is critical to synthesize highly efficient photocatalysts for selective oxidation under visi...Biomass-derived platform molecules,such as furfural,are abundant and renewable feedstock for valuable chemical production.It is critical to synthesize highly efficient photocatalysts for selective oxidation under visible light.The Er@K-C_(3)N_(4)/UiO-66-NH_(2) catalyst was synthesized using a straight-forward hydrothermal technique,and exhibited exceptional efficiency in the photocatalytic oxidation of furfural to furoic acid.The catalyst was thoroughly characterized,confirming the effective adjustment of the band gap energy of Er@K-C_(3)N_(4)/UiO-66-NH_(2).Upon the optimized reaction conditions,the conversion rate of furfural reached 89.3%,with a corresponding yield of furoic acid at 79.8%.The primary reactive oxygen species was identified as·O_(2)^(-) from ESR spectra and scavenger tests.The incorporation of Er and K into the catalyst enhanced the photogenerated carriers transfer rate,hence increasing the separating efficiency of photogenerated electron-hole pairs.This study expands the potential applications of rare earth element doped g-C_(3)N_(4) in the photocatalytic selective oxidation of furfurans.展开更多
The transformation of biomasses from agro-industrial waste can significantly impact the production of green chemicals from sustainable resources.Pectin is a biopolymer present in lignocellulosic biomass as Orange Peel...The transformation of biomasses from agro-industrial waste can significantly impact the production of green chemicals from sustainable resources.Pectin is a biopolymer present in lignocellulosic biomass as Orange Peel Waste(OPW)and has possibilities for making platform compounds such as furfural for sustainable chemistry.In this work,we studied the transformation to furfural of OPW,pectins,and d-galacturonic acid(D-GalA),which is the main component(65 wt%)of pectin.We analyzed pectins with different degrees of esterification(45,60 and 95 DE)in a one-pot hydrolysis reaction system and studied the differences in depolymerization and dehydration of the carbohydrates.The results show that the production of furfural decreases as the DE value increases.Specifically,low DE values favor the formation of furfural since the decarboxylation reaction is favored over deesterification.Interestingly,the furfural concentration is dependent upon the polysaccharide composition of pentoses and uronic acid.The obtained concentrations of furfural(13 and 14 mmol/L),d-xylose(6.2 and 10 mmol/L),and L-arabinose(2.5 and 2.7 mmol/L)remained the same when the galacturonic acid was fed either as a polymer or a monomer under the same reaction conditions(0.01 M SA,90 min and 433 K).OPW is proposed as a feedstock in a biorefinery,in which on a per kg OPW dry basis,90 g of pectin and 15 g of furfural were produced in the most favorable case.We conclude that the co-production of pectin and furfural from OPW is economically feasible.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 the Latvian State Institute of Wood Chemistry Bioeconomic Research Grant No.09-24 titled“Selective Valorization of Lignocellulosic Biomass(SeVaLi)”.
文摘Oat husks,a byproduct of oat milling operations with limited economic value,present a promising feedstock for biorefinery processes due to their chemical composition.This study investigates the conversion of C5 carbohydrates in oat husks into furfural through hydrothermal pretreatment using various phosphate-based catalysts,including H_(3)PO_(4),NH_(4)H_(2)PO_(4),NaH_(2)PO_(4),KH_(2)PO_(4),K_(2)HPO_(4) and K_(3)PO_(4) as catalyst.The catalysts’effectiveness in promoting furfural production was evaluated under identical hydrothermal conditions(treatment time for 60 min at a constant temperature of 170℃ and a catalyst amount).Continuous water steam was used to strip furfural from the reaction zone and minimize its degradation.Results indicated that H_(3)PO_(4) was the most effective catalyst,achieving a furfural yield of 13.99 wt.%,which corresponds to approximately 57%of the theoretical yield.NH4H2PO4 also showed moderate effectiveness,while sodium and potassium phosphate salts were significantly less effective.A scanning electron microscope analysis shows that catalysts with lower pH may disrupt the oat husks external layer thus providing a higher C5 carbohydrates conversion rate into furfural.The chemical complexity of oat husk contributes to side reactions between its carbohydrates and lignin during the hydrothermal treatment.This results in an increase in acid-insoluble lignin and inorganic matter in the oat husk lignocellulosic residue,which can reduce the effectiveness of further cellulose saccharification by enzymatic hydrolysis.
文摘Transition-state shape selectivity plays a crucial role in catalytic systems where reactants and products exhibit comparable molecular dimensions,as it restricts the accessible configuration space of reaction intermediates.Herein,we designed a Cu@MFI catalyst by encapsulating Cu active sites within the well-defined micropores of MFI zeolite through a pore confinement strategy.This architecture preserves the zeolite framework integrity while maintaining unhindered internal mass transport,thereby enabling precise spatial control over transition-state configurations.Employing furfural hydrogenation as a probe reaction,the metal-zeolite synergy in Cu@MFI endowed the catalyst with exceptional activity(100%furfural conversion)and quantitative selectivity(100%furfuryl alcohol)at 70℃,sustained across a broad temperature window.Mechanistic studies reveal that the transition-state shape selectivity effectively prevented H2O interaction with the furan ring,offering valuable insights for other reaction systems seeking to exploit shape selectivity for specific transformations.
基金China Postdoctoral Science Foundation (2023M733451)Dalian Innovation Team in Key Areas(2020RT06)Engineering Research Center for Key Aromatic Compounds and LiaoNing Key Laboratory,Liaoning Provincial Natural Science Foundation (Doctoral Research Start-up Fund 2024-BSBA-37)。
文摘Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O.Herein,a novel Al_(2)O_(3)/C-u hybrid catalyst,composed of N-modified dendritic carbon networks supporting Al_(2)O_(3)nanoparticles,was successfully prepared via carbonizing the freeze-dried gel from spontaneous cross-linking of alginate,Al3+and urea.The obtained carbon-supported Al_(2)O_(3)hybrid catalyst has a high ratio (31%) of Al species in pentahedral-coordinated state.The introduction of urea enhances the surface N content,the ratio of pyrrolic N,and specific surface area of catalyst,leading to improved adsorption capacity of C=O and the accessibility of active sites.In the furfural hydrogenation reaction with isopropyl alcohol as hydrogen donor,Al_(2)O_(3)/C-u catalyst achieved a 90%conversion of furfural with 98.0% selectivity to furfuryl alcohol,outperforming that of commercial γ-Al_(2)O_(3).Moreover,Al_(2)O_(3)/C-u demonstrates excellent catalytic stability in the recycling tests attributed to the synergistic effect of abundant weak Lewis acid sites and the anchoring effect of the carbon network on Al_(2)O_(3)nanoparticles.This work provides an innovative and facile strategy for fabrication of carbon-supported Al_(2)O_(3)hybrid catalysts with rich AlVspecies,serving as a high selective hydrogenation catalyst through MPV reaction route.
基金supported by the Natural Science Foundation of Zhejiang Province(ZCLZ24B0301)the Lhasa Central Government Guiding Local Science and Technology Development Funds(No.LSKJ202458)the National Natural Science Foundation of China(No.22472150)。
文摘The electrocatalytic furfural oxidation reaction(FFOR)represents an economical and promising technology to replace conventional oxygen evolution reaction,enabling the co-production of high value chemicals and H_(2).Regulating the adsorption of furfural(FF)and OH^(-)species holds paramount importance in enhancing the overall performance.Herein,we have developed a unique CuO catalyst enriched with oxygen vacancies(O_(v)-CuO)resulting from the electrochemical reconstruction ofα-Cu_(2)S,which demonstrates exceptional FFOR performance,with a conversion of 95.3%,near-perfect selectivity and Faraday efficiency(FE)for furoic acid(FA)at 1.475 V vs.RHE.The study provides detailed comparison of the structural evolution of different sulfide precatalysts and their impact on FFOR.Furthermore,it delves into the structure-activity relationship through a combination of characterization and theoretical calculations.The O_(v)-CuO not only enhances OH^(-)adsorption,changes the rate-determining step,but also reduces the reaction energy barrier toward FFOR.Additionally,a much lower cell voltage is required to coproduce FA and hydrogen in the two-electrode co-electrolysis system.This work would provide valuable insights into the reaction mechanism of FFOR on Cu based catalysts and establish guidelines for designing defective electrocatalysts for biomass conversion.
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 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 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financially supported by the National Natural Science Foundation of China (22075308, 22209197)Natural Science Foundation of Shanxi Province (20210302 1224439, 202203021211002)Shanxi Province Science Foundation for Youths (No: SQ2019001)。
文摘The state-of-the-art lithium-ion capacitors (LICs),consisting of high-capacity battery-type anode and high-rate capacitor-type cathode,can deliver high energy density and large power density when comparing with traditional supercapacitors and lithium-ion batteries,respectively.However,the ion kinetics mismatch between cathode and anode leads to unsatisfied cycling lifetime and anode degradation.Tremendous efforts have been devoted to solving the abovementioned issue.One promising strategy is altering high conductive hard carbon anode with excellent structural stability to match with activated carbon cathode,assembling dual-carbon LIC.In this contribution,one-pot in-situ expansion and heteroatom doping strategy was adopted to prepare sheet-like hard carbon,while activated carbon was obtained involving activation.Ammonium persulfate was used as expanding and doping agent simultaneously.While furfural residues (FR) were served as carbon precursor.The resulting hard carbon (FRNS-HC) and activated carbon (FRNS-AC)show excellent electrochemical performance as negative and positive electrodes in a lithium-ion battery (LIB).To be specific,374.2 m Ah g^(-1)and 123.1 m Ah g^(-1)can be achieved at 0.1 A g^(-1)and 5 A g^(-1)when FRNS-HC was tested as anode.When combined with a highly porous carbon cathode (S_(BET)=2961 m^(2)g^(-1)) synthesized from the same precursor,the LIC showed high specific energy of147.67 Wh kg^(-1)at approximately 199.93 W kg^(-1),and outstanding cycling life with negligible capacitance fading over 1000 cycles.This study could lead the way for the development of heteroatom-doped porous carbon nanomaterials applied to Li-based energy storage applications.
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the National Natural Science Foundation of China (22108189, 22278286)Science Foundation for Distinguished Young Scholar of Shanxi Province(202303021223001)SINOPEC 122027
文摘Bimetallic CuCo catalysts with different Cu to Co ratios on N-doped porous carbon materials(N-C)were achieved using impregnation method and applied in the hydrogenation of furfural(FAL)to furfuryl alcohol(FOL).The high hydrogenation activity of FAL over Cu_(1)Co_(1)/N-C was originated from the synergistic interactions of Cu and Co species,where Co^(0)and Cu^(0)simultaneously adsorb and activate H_(2),and Cu^(+) served as Lewis acid sites to activate C]O.Meanwhile,electrons transfer from Cu to Co promoted the formation of Cu^(+).In situ Fourier transform infrared spectroscopy analysis indicated that Cu_(1)Co_(1)/N-C adsorbed FAL with a tilted η^(1)-(O)configuration.The superior Cu_(1)Co_(1)/N-C showed excellent adsorbed ability towards H_(2) and FAL,but weak adsorption for FOL.Therefore,Cu_(1)Co_(1)/N-C possessed 93.1%FAL conversion and 99.0% FOL selectivity after 5 h reaction,which also exhibited satisfactory reusability in FAL hydrogenation for five cycles.
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supported by Natural Science Foundation of Shandong Province(ZR2022MB049)National Natural Science Foundation of China(22078174)。
文摘Biomass-derived platform molecules,such as furfural,are abundant and renewable feedstock for valuable chemical production.It is critical to synthesize highly efficient photocatalysts for selective oxidation under visible light.The Er@K-C_(3)N_(4)/UiO-66-NH_(2) catalyst was synthesized using a straight-forward hydrothermal technique,and exhibited exceptional efficiency in the photocatalytic oxidation of furfural to furoic acid.The catalyst was thoroughly characterized,confirming the effective adjustment of the band gap energy of Er@K-C_(3)N_(4)/UiO-66-NH_(2).Upon the optimized reaction conditions,the conversion rate of furfural reached 89.3%,with a corresponding yield of furoic acid at 79.8%.The primary reactive oxygen species was identified as·O_(2)^(-) from ESR spectra and scavenger tests.The incorporation of Er and K into the catalyst enhanced the photogenerated carriers transfer rate,hence increasing the separating efficiency of photogenerated electron-hole pairs.This study expands the potential applications of rare earth element doped g-C_(3)N_(4) in the photocatalytic selective oxidation of furfurans.
基金supported by the project:“Obtención de biocombustibles y compuestos químicos de alto valor agregado a partir de biomasas de desecho ricas en pectina”,CONAHCYT agreement:CB 255527-2016the Fellowship with reference number:654271 from the Mexican Council for Science and Technology,CONAHCYT was assigned to Eva Estela Rivera Cedillo as PhD student.
文摘The transformation of biomasses from agro-industrial waste can significantly impact the production of green chemicals from sustainable resources.Pectin is a biopolymer present in lignocellulosic biomass as Orange Peel Waste(OPW)and has possibilities for making platform compounds such as furfural for sustainable chemistry.In this work,we studied the transformation to furfural of OPW,pectins,and d-galacturonic acid(D-GalA),which is the main component(65 wt%)of pectin.We analyzed pectins with different degrees of esterification(45,60 and 95 DE)in a one-pot hydrolysis reaction system and studied the differences in depolymerization and dehydration of the carbohydrates.The results show that the production of furfural decreases as the DE value increases.Specifically,low DE values favor the formation of furfural since the decarboxylation reaction is favored over deesterification.Interestingly,the furfural concentration is dependent upon the polysaccharide composition of pentoses and uronic acid.The obtained concentrations of furfural(13 and 14 mmol/L),d-xylose(6.2 and 10 mmol/L),and L-arabinose(2.5 and 2.7 mmol/L)remained the same when the galacturonic acid was fed either as a polymer or a monomer under the same reaction conditions(0.01 M SA,90 min and 433 K).OPW is proposed as a feedstock in a biorefinery,in which on a per kg OPW dry basis,90 g of pectin and 15 g of furfural were produced in the most favorable case.We conclude that the co-production of pectin and furfural from OPW is economically feasible.
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.
