Electrodeposited 3D hierarchical NiFe microflowers assembled from nanosheets robust for the selective electrooxidation of furfuryl alcohol

A robust and green strategy for the selective upgrading of biomass-derived platform chemicals towards highly valuable products is important for the sustainable development.Herein,the efficient electrocatalytic oxidation of biomass-derived furfuryl alcohol(FFA)into furoic acid(FurAc)catalyzed by the electrodeposited non-precious NiFe microflowers was successfully reached under the low temperature and ambient pressure.The 3D hierarchical NiFe microflowers assembled from ultrathin nanosheets were controllably synthesized by the electrodeposition method and uniformly grown on carbon fiber paper(CFP).Electrochemical analysis confirmed that NiFe nanosheets more preferred in the selective oxidation of FFA(FFAOR)than oxygen evolution reaction(OER).The linear sweep voltammetry(LSV)in FFAOR displayed a clear decrease towards lower potential,resulting in 30 mV reduction of overpotential at 20 mA cm^(-2) compared with that of OER.The optimal catalyst Ni_(1)Fe_(2) nanosheets exhibited the highest selectivity of FurAc(94.0%)and 81.4%conversion of FFA within 3 h.Besides,the influence of various reaction parameters on FFAOR was then explored in details.After that,the reaction pathway was investigated and rationally proposed.The outstanding performance for FFAOR can be ascribed to the unique structure of 3D flower-like NiFe nanosheets and oxygen vacancies,resulting in large exposure of active sites,faster electron transfer and enhanced adsorption of reactants.Our findings highlight a facile and convenient mean with a promising green future,which is promising for processing of various biomass-derived platform chemicals into value-added products.

Modification of Wood by Tannin-Furfuryl Alcohol Resins-Effect on Dimensional Stability,Mechanical Properties and Decay Durability

Furfurylation is a well-known wood modification technology.This paper studied the effect of tannin addition on the wood furfurylation.Three kinds of dicarboxylic acids,adipic acid,succinic acid,and tartaric acid,as well as glyoxal as a comparing agent,were used to catalyse the polymerisation of furanic or tannin-furanic solutions during wood modification.Impregnation of furanic or tannin-furanic solution at a certain concentration into the wood followed with curing at 103℃for a specific duration was performed for the wood modification.Different properties of the modified woods like dimensional stability,resistance of treatment to leaching,mechanical properties,decay durability against white-rot(Coriolus versicolor,Pycnoporus sanguineus)and brown-rot(Coniophora puteana)as well as their chemical and anatomical characteristics were evaluated.Results revealed that the partial substitution of FA by the tannins improved the fixation of the chemicals impregnated in wood.Further,dimensional stability,leaching resistance,Brinell hardness,modulus of elasticity/modulus of rupture,and decay durability properties of the furfurylated wood were also improved in the presence of tannins.Scanning electron microscopy revealed the deposition of the polymer in the wood lumen cells and in the wood cell walls.

Selective hydrogenolysis of biomass-derived furfuryl alcohol into 1,2- and 1,5-pentanediol over highly dispersed Cu-Al_2O_3 catalysts

Cu nanoparticles supported on a variety of oxide supports, including SiO2, TiO2, ZrO2, Al2O3, MgO and ZnO, were investigated for the hydrogenolysis of biomass‐derived furfuryl alcohol to1,2‐pentanediol and 1,5‐pentanediol. A Cu‐Al2O3 catalyst with 10 wt% Cu loading prepared by a co‐precipitation method exhibited the best performance in terms of producing pentanediols compared with the other materials. This catalyst generated an 85.8% conversion and a 70.3% combined selectivity for the target pentanediols at 413 K and 8 MPa H2 over an 8‐h reaction. The catalyst could also be recycled over repeated reaction trials without any significant decrease in productivity. Characterizations with X‐ray diffraction, NH3/CO2‐temperature programmed desorption, N2 adsorption,transmission electron microscopy and N2 O chemisorption demonstrated that intimate and effective interactions between Cu particles and the acidic Al2O3 support in this material greatly enhanced its activity and selectivity. The promotion of the hydrogenolysis reaction was found to be especially sensitive to the Cu particle size, and the catalyst with Cu particles 1.9 to 2.4 nm in size showed the highest turnover frequency during the synthesis of pentanediols.

Selective hydrogenolysis of furfuryl alcohol to 1,5-and 1,2-pentanediol over Cu-LaCoO_3 catalysts with balanced Cu^O-CoO sites

Selective hydrogenolysis of biomass‐derived furfuryl alcohol(FFA)to 1,5‐and 1,2‐pentanediol(PeD)was conducted over Cu‐LaCoO3 catalysts with different Cu loadings;the catalysts were derived from perovskite structures prepared by a one‐step citrate complexing method.The catalytic performances of the Cu‐LaCoO3 catalysts were found to depend on the Cu loading and pretreatment conditions.The catalyst with 10 wt%Cu loading exhibited the best catalytic performance after prereduction in 5%H2‐95%N2,achieving a high FFA conversion of 100%and selectivity of 55.5%for 1,5‐pentanediol(40.3%)and 1,2‐pentanediol(15.2%)at 413 K and 6 MPa H2.This catalyst could be reused four times without a loss of FFA conversion but it resulted in a slight decrease in pentanediol selectivity.Correlation between the structural changes in the catalysts at different states and the simultaneous variation in the catalytic performance revealed that cooperative catalysis between Cu0 and CoO promoted the hydrogenolysis of FFA to PeDs,especially to 1,5‐PeD,while Co0 promoted the hydrogenation of FFA to tetrahydrofurfuryl alcohol(THFA).Therefore,it is suggested that a synergetic effect between balanced Cu0 and CoO sites plays a critical role in achieving a high yield of PeDs with a high 1,5‐/1,2‐pentanediol selectivity ratio during FFA hydrogenolysis.

One-pot cascade conversion of xylose to furfuryl alcohol over a bifunctional Cu/SBA-15-SO3H catalyst

The conversion of hemicellulose-derived xylose to furfuryl alcohol is a practical procedure for producing value-added chemicals from biomass.In this study,a bifunctional Cu/SBA-15-SO3 H catalyst was employed for the one-pot catalytic conversion of xylose to furfuryl alcohol with a yield of up to 62.6% at the optimized conditions of 140℃,4 MPa,and for 6 h in a biphasic water/n-butanol solvent.A high reaction temperature resulted in further hydrogenation to 2-methyl furan,while a high hydrogen pressure led to a side hydrogenation reaction to xylitol.The biphasic solvent allowed xylose solvation as well as furfuryl product extraction.The acidic-SO3 H sites and Cu sites co-existed,maintained a balance,and cooperatively catalyzed the cascade conversion.Excessive acidic sites and large pores could promote the xylose conversion,although a low furfuryl alcohol yield was obtained.This catalytic system could be potentially applied to the one-pot synthesis of furfuryl alcohol from hemicellulose-derived xylose.

Low-cost synthesis of nanoaggregate SAPO-34 and its application in the catalytic alcoholysis of furfuryl alcohol

Silicoaluminophosphate-34(SAPO-34) molecular sieves have important applications in the petrochemical industry as a result of their shape selectivity and suitable acidity. In this work, nanoaggregate SAPO-34 with a large external surface area was obtained by dissolving pseudoboehmite and tetraethylorthosilicate in an aqueous solution of tetraethylammonium hydroxide and subsequently adding phosphoric acid. After hydrolysis in an alkaline solution, the aluminum and silicon precursors exist as Al(OH)4-and SiO2(OH)-, respectively;this is beneficial for rapid nucleation and the formation of nanoaggregates in the following crystallization process. Additionally, to study the effect of the external surface area and pore size on the catalytic performance of different SAPO-34 structures, the alcoholysis of furfuryl alcohol to ethyl levulinate(EL) was chosen as a model reaction. In a comparison with the traditional cube-like SAPO-34, nanoaggregate SAPO-34 generated a higher yield of 74.1% of EL, whereas that with cube-like SAPO-34 was only 19.9%. Moreover, the stability was remarkably enhanced for nanoaggregate SAPO-34. The greater external surface area and larger number of external surface acid sites are helpful in improving the catalytic performance and avoiding coke deposition.

Emission of BTEX and PAHs from molding sands with furan cold setting resins containing different contents of free furfuryl alcohol during production of cast iron

At present, furan resin is the largest selling no-bake system of moulding sands. The most commonly used furan no-bake binders(FNB) are condensation products of furfuryl alcohol(FA) urea, formaldehyde and phenol. They are generally cured by exposure to organic sulfonic acids. FNB provide excellent mold and core strength, cure rapidly and allow the sand to be reclaimed at fairly high yields, generally 75%-80%, especially in applications where due allowance is made for the need to keep total sulfur content below 0.1%. However, due to probable carcinogenic properties of furfuryl alcohol, the EU Directive limits the content of this substance(in a monomer form in resin) to 25%. The classification of furfuryl alcohol and the resulting furan resin products has changed from "harmful" to "toxic by inhalation". The aim of this study was to determine the effect of free furfuryl alcohol content in the resin on the emission of harmful substances from the BTEX(Benzene Toluene Ethylbenzene & Xylene) and PAHs(polycyclic aromatic hydrocarbon) group exposed to high temperature and how it affects the emissions allowance of reclaimed sand in the matrix. Three resins from a leading manufacturer were examined, which contain a free furfuryl alcohol content of 71%-72%, about 50% and < 25%, respectively. The hardener for each resin was 65% aqueous solution of paratoluenesulfonic acid. Tests were carried out in semi-industrial conditions where liquid cast-iron was poured into sample sand mold at 1,350 °C. The matrix of the studied sands was reclaimed in the amount of 0, 50%, 100%, respectively.With the increase of free furfuryl alcohol content, the volume of evolved gases decreased. For all resins the main component from the BTEX group dominating in the emitted gases was benzene; however toluene also appeared in the amount of a few percentages. In contrast, ethylbenzene and xylenes occurred only in the gases emitted from resin-bonded sands with the largest furfuryl alcohol content. The increase in the share of reclaimed sands resulted in very significant increase in the volume of gas generated and participation of benzene in these gases. In terms of emission of compounds from the PAHs group virtually for all resins, the total content of these substances was comparable(within the limits of error). The main components were: fluoranthene, pyrene and benzo(a) anthracene.

Substitute materials of furfuryl alcohol in furan resin used for foundry and their technical properties

Based on a special synthesis process of furan resin,the furfuryl alcohol(FA),the main component of typical no-bake furan resins is substituted by ethanol and xylitol mother liquor which is relatively low price and chemically active.Through orthogonal test,the optimal amount of xylitol liquor,ethanol and modifier has been determined.Finally,the test results on technical properties show that the performance can meet the production requirement well,which indicate a success in this substituting attempt.

Effects of TiO_(2) Support and Cobalt Addition of Ni/TiO_(2) Catalyst in Selective Hydrogenation of Furfural to Furfuryl Alcohol

An effect of phase compositions(rutile,Rut and anatase,Ant)of TiO_(2)supports on the selective hydrogenation of furfural to furfuryl alcohol was investigated.The 15%wt Ni/TiO_(2)catalysts were prepared by incipient impregnation method.The result showed that Ni supported on anatase-rutile mixed phase TiO_(2)(91%Rut and 9%Ant,A2)provided the highest furfuryl alcohol yield at 43.8%due to the relatively strong Ni-TiO_(2)interaction,its appropriate crystallite sizes,and high average pore sizes.Furthermore,the effect of cobalt as a promoter on Ni/TiO_(2)-A2 catalysts was studied.The result showed that the Ni-Co/TiO_(2)-A2 catalysts exhibited poorer catalyst performances compared to the monometallic Ni/TiO_(2),probably because addition of cobalt can lower the reduction temperatures of Ni/TiO_(2)and weaken the metal-support interaction.

Preparation of an Abrasive Grinding Wheel Based on Tannin Resin Cross- Linked by Furfuryl Alcohol, Urea and Glyoxal

Simple bio-based abrasive grinding wheel based on thermosetting resin matrix was developed starting with condensed tannin and furfuryl alcohol,which are mainly derived from forest and agricultural products like tree barks,wheat and crops.Fourier transform infrared spectra(FTIR)signified the acidic conditions are quiet efficient for the reaction of furfuryl alcohol,urea and glyoxal all together and the-CH_(2)-NH-and-CH_(2)-O-CH(OH)-groups are predominating in cross-linking of the tannin-furfuryl alcohol-urea-glyoxal(TFUG)resin.The strengthening contribution of the tannin was also confirmed by the preservation of its distinct crystallinity using X-ray diffraction(XRD).Differential scanning calorimetry(DSC)and thermogravimetric analysis(TGA)ensured that TFUG resin can be cured at low temperature and offer higher heat resistance compared with phenol-formaldehyde(PF)resin.The high hardness and excellent compressive strength revealed by the corresponding investigations such as Brinell hardness,compression resistance,and grinding tests suggested a strong abrasive ability using the new grinding wheel compared with lab-made grinding wheel based on PF resin.This could be ascribed to the absence of cracks and low content of formed holes as confirmed using scanning electron microscopy(SEM)and balanced reaction conditions that leads to network structure with regular local reinforcements and homogeneous crosslink density.

Highly efficient catalytic valorization of biomass-derived hexoses and furfuryl alcohol in the presence of polymer-based catalysts

The catalytic transformation of furfuryl alcohol and hexose into value-added chemicals have been investigated with a series of polymer-based catalysts including poly(styrenesulfonic acid)(PSS),graphite oxide-doped poly(styrenesulfonic acid)(PSS-GO),and graphite-doped poly(-styrenesulfonic acid)(PSS-C).It is found that the selective conversion of furfuryl alcohol to methyl levulinate(MLE)was successfully performed with PSS as the catalyst,in which a 96.4%yield is attained in methanol solvent.Moreover,the efficient dehydration of D-fructose to produce 5-hydroxymethylfurfural(HMF)has also been achieved using PSS-GO as the catalyst,where a 76.5%yield of HMF was obtained in Nmethylpyrrodinone solvent.The effects of reaction temperature,time and solvent were investigated.Furthermore,the used catalysts have been respectively characterized by XRD,TG,FTIR,SEM and TEM techniques to reveal the physical properties and structures of these polymeric catalytic materials.

DFT Study of Poly Furfuryl Alcohol-Rhodamine B Blend

A theoretical study of poly furfuryle alcohol (PFA), rhodamine B (Rh B) dye and their blends (PFA-Rh B) is carried out by using the density functional theory (DFT). Electronic states and opto-electronic properties are investigated. The electronic states indicate that the oligomers of FA are insulators and Rh B is a wide band gap semiconductor. Their blends have a narrow band gap of about 0.75 eV. The optoelectronic properties are studied using TDDFT, which indicates that the chain length of poly furfuryl alcohol is an effective parameter to control both energies and intensities of absorption in which longer chain causes absorption with high intensity within long wavelength. A single broad baned of electron excitations is more like 8-oligomer-RhB case, which centers at wavelengths about 599 nm and 625 nm. This band of absorption covers the whole visible region of spectrum.

Predication of Selective Ring-opening Hydrogenolysis for Furfuryl Alcohol to Produce Pentanediol over Dual-atom Catalysts

Selective activation of C-O bond is of fundamental importance in the precise conversion of oxygenates into value-added compounds in an atom-economic and sustainable manner, and meanwhile, the structurally well-defined dual-atoms catalysts (DACs) have been scarcely investigated in this field. In this study, a series of transition metal DACs anchored on nitrogen-doped graphene (TM2/NC, TM=Pt, Ir, Rh, Pd, Ru, Co, Ni and Cu) was constructed to make a comprehensive investigation of their selectivity in the hydrogenative transformation of furfuryl alcohol (FAL), an important biomass platform molecule, to 1,2-pentanediol (1,2-PeD) via selective cleavage of furanic C5-O bond, by density functional theory (DFT) calculations and microkinetic modeling. We found that Ir2/NC demonstrated a high selectivity for the cleavage of furanic C5-O bond to produce 1,2-PeD, while the production of THFAL or 1,5-pentanediol (1,5-PeD) on other TM2/NC catalysts are more favorable. Furthermore, we found that the selective C-O bond cleavage of FAL furan ring is affected by the orbital overlap between the d-orbitals of the anchored metal atoms and the p-orbitals of the adsorbed C atom in FAL, suggesting that the selectivity of the C-O bond cleavage is inextricably related with the electronic property of the anchored metals.

Biobased Furfurylated Poplar Wood for Flame-Retardant Modification with Boric Acid and Ammonium Dihydrogen Phosphate

Furfurylated wood exhibits excellent dimensional stability and corrosion resistance,making it a promising material for constructing buildings,but it is highly flammable.Herein,flame-retardant furfurylated poplar wood was produced via a two-step process utilizing boric acid(BA)and ammonium dihydrogen phosphate(ADP)as flame-retardant components,and biomass-derived furfuryl alcohol(FA)as a modifier.The acidity of BA and ADP allowed them to catalyze the polymerization of FA,which formed a cross-linked network that immobilized BA and ADP inside the wood.The addition of BA/ADP substantially delayed the time to ignition from 10 to 385 s and reduced the total heat release and total smoke release by 58.75%and 77.31%,respectively.Analysis of the pyrolysis process showed that the decomposition products of BA and ADP protected the underlying furfurylated wood and diluted combustible gases.This method significantly improved the fire retardancy and smokeless properties of furfurylated wood,providing promising prospects for its application as an engineering material.

Hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol on NiB/SiO_(2) amorphous alloy catalyst

NiB/SiO2 amorphous alloy catalyst was prepared by power electroless plating method and characterized by induction coupled plasma(ICP),Brunauer–Emmett–Teller method(BET),transmission electron microscope(TEM)and X-ray diffraction(XRD)techniques.The catalytic perfor-mance of NiB/SiO2 was investigated for the hydrogenation of furfuryl alcohol(FA)to tetrahydrofurfuryl alcohol(THFA).The effects of operational conditions,such as reaction tem-perature,pressure,and stirring rate were carefully studied.The proper conditions were determined as the following:pressure 2.0 MPa,temperature 120°C and stirring rate 550 r/min.A typical result with FA conversion of 99%and THFA selectivity of 100%was obtained under such conditions,which was close to that over Raney Ni.

Catalytic transfer hydrogenation of biomass-derived furfural to furfuryl alcohol with formic acid as hydrogen donor over CuCs-MCM catalyst

Catalytic transfer hydroge nation(CTH)of furfural(FF)to furfu ryl alcohol(FFA)has received great intere st in recent years.He rein,Cu-Cs bimetallic supported catalyst,CuCs(2)-MCM,was developed for the CTH of FF to FFA using formic as hydrogen donor.CuCs(2)-MCM achieved a 99.6%FFA yield at an optimized reaction conditions of 170℃,1 h.Cu species in CuCs(2)-MCM had dual functions in catalytically decomposing formic acid to generate hydrogen and hydrogenating FF to FFA.The doping of Cs made the size of Cu particles smaller and improved the dispersion of the Cu active sites.Impo rtantly,the Cs species played a favorable role in enhancing the hydrogenation activity as a promoter by adjusting the surface acidity of Cu species to an appropriate level.Correlation analysis showed that surface acidity is the primary factor to affect the catalytic activity of CuCs(2)-MCM.

Hierarchical ZnIn2S4 microspheres as photocatalyst for boosting the selective biohydrogenation of furfural into furfuryl alcohol under visible light irradiation

Photocatalyst-enzyme coupling process for visible light driven biotransformation holds promise in producing solar chemicals.In this work,aiming to produce furfuryl alcohol,the important bulk chemical that is typically derived from renewable lignocellulose,a highly selective furfural hydrogenation process is proposed by coordinating the alcohol dehydrogenase with the ZnIn2S4 assistant reduced form of nicotinamide adenine dinucleotid(NADH)regeneration.Results indicated that under visible light irradiation,the hierarchical ZnIn2S4 microspheres exhibited excellent holes and electrons separating efficiency,affording to high NADH regeneration(yield of 90.2±3.28%).When adopting the photo-biocoupled reduction process in furfural transformation,a furfuryl alcohol yield of 79.4±1.95%was achieved under the optimized conditions.The photocatalyst-enzyme coupling process also showed good stability,exceeding 70%of catalytic activity was reserved after reusing the catalysts for 10 cycles.The novel photo-biocoupled system showed promising in extending to the highly selective hydrogenation of other biochemicals from lignocelluloses.

Study on the condensation and crosslinking reactions of furfuryl alcohol and tris(2-hy-droxyethyl)isocyanurate by thermal methods

Condensation and crosslinking reactions of furfuryl alcohol(FA)and FA with tris(2-hydro- xyethyl)isocyanurate(THEIC)are studied by means of DSC,TG,TBA,NMR and elemental analysis. Four exothermic peaks are observed on the DSC curves of thermal condensation of FA and FA with THEIC in the presence of sulfuric acid.The peaks Ⅰ,Ⅱ(50—80℃),Ⅲ(110—130℃)and Ⅳ(150— 190℃)correspond to linear polycondensation of FA through head-to-tail condensation,head-to-head etherification,crosslinking dehydration reaction between methylene group and terminal hydroxy group of FA polymeric chain and to further crosslinking reaction at higher temperature,respectively.The reactivity of FA and THEIC increases sharply at 130—150℃ and THEIC is reacted completely at 150℃.Addition of THEIC raises the initial decomposition temperature of FA polymer by 60℃.

糠醇浸渍速生人工林木材的干燥特性研究

木材浸渍改性商业应用的主要技术难点之一是二次干燥速度慢、易开裂、易变形。本文以杨木和杉木为研究对象,使用浓度为30%和50%的糠醇水溶液对其进行浸渍改性,再以百度干燥法分析糠醇浸渍材的干燥特性,辅以干缩试验和剖面密度(VDP)试验探究干燥缺陷成因。结果表明:50%浓度浸渍材的干燥缺陷等级均大于30%浓度浸渍材,杨木浸渍材的等级均高于杉木浸渍材;杉木30%和50%浓度浸渍材百度干燥平均时间分别为24 h和29 h,而杨木30%和50%浓度浸渍材分别为20 h和30 h。浸渍材不同位置的干缩系数存在显著差异,浸渍后密度分布更加不均匀。杉木和杨木糠醇浸渍材二次干燥困难的主要原因为固化的糠醇堵塞了水分内部迁移通道,从而使干燥速度降低;糠醇分布不均匀导致干缩系数差异进一步加大,处理材易开裂、易变形。

Pt/CaO材料催化糠醇加氢制备戊二醇

通过浸渍法制备出一系列氧化钙负载铂金属催化材料,用于生物质基糠醇选择性加氢制备戊二醇研究。研究采用X射线衍射仪、扫描电子显微镜、CO_(2)-程序升温脱附、N2等温吸附-脱附、X射线光电子能谱、热重-差热分析法等一系列表征手段,对合成的催化剂样品物理化学性质进行了系统表征。实验结果表明,Pt/CaO-600催化剂表现出优异的催化活性,在4MPa氢压、210℃反应温度条件下,糠醇转化率为99.8%,1,2-戊二醇和1,5-戊二醇收率分别可达48.6%和21.5%。催化剂的优异性能可归因于作为载体的CaO提供了适宜的碱性位点,有利于糠醇开环反应的发生,进而提高了糠醇转化率与戊二醇选择性。同时,催化剂还表现出了优异的循环使用性能,经重复使用4次后,其催化糠醇转化率可达96.5%,1,2-戊二醇和1,5-戊二醇的收率分别为40.3%和17.0%。