Biomass-derived Furfuryl Alcohol Research Articles

Upcycling CO2 and bio-derived furan into degradable plastic monomer via coupling of photocatalysis and thermocatalysis

Coupling of CO2 with biomass-derived molecules into degradable plastic monomer provides a promising strategy to address the increasing problems of carbon recycle and carbon neutrality. Herein, we develop a sustainable route to produce 6-hydroxycaproate (6-HMC) by coupling photocatalytic carboxylation of biomass-derived furfuryl alcohol with CO2 to 2-furanacetic acid (FA), and the thermocatalytic hydrogenolysis of methyl 2-tetrahydrofuranyl acetate (MTFA) derived from FA, wherein Pd/CeO2 exhibit the highest productivity of 6-HMC (505 mmol6-HMC mmol-1metal h−1), much higher than its counterparts of precious- and non-precious-metal catalysts. Moreover, Pd/CeO2 also presents good stability for 6 recycles without remarkable decrease in 6-HMC yield. Systematic experiments and computational studies suggest that higher concentration of oxygen vacancies and strong metal-support interactions account for enhanced catalytic performance of Pd/CeO2. The work employs CO2 and lignocellulosic-derived platform molecule as feedstocks to produce valuable degradable plastic monomer, providing a promising route to access pure-CO2 originated high-carbon oxygen-containing compounds.

Highly selective oxidation of biomass-derived alcohols and aromatic alcohols to aldehydes over Ti3C2-TiO2 nanocomposites under visible light

Ti3C2Tx is a two-dimensional (2D) material belonging to the MXenes family. It has a unique combination of functional features that make it appropriate for a wide range of fascinating applications, including supercapacitors, batteries, strain sensors, photocatalysis, and more. In this study, we report a synthesis of Ti3C2-TiO2 nanocomposites with tight interfacial contact that has been successfully fabricated by in situ development of TiO2 nanoparticles (NPs) on the surface of Ti3C2Tx nanosheets (NSs) via a simple and cost-effective hydrothermal process. The catalysts are well characterized by various sophisticated techniques, including X-ray photoelectron spectroscopy (XPS), photoluminescence (PL), Brunauer-Emmett-Teller (BET), CHI660E electrochemical workstation, and HRTEM. The photocatalytic performance of pure Ti3C2Tx, Ti3C2-TiO2 (MT1), and Ti3C2-TiO2 (MT5) nanocomposites was evaluated by highly selective photo-oxidation of biomass-derived furfuryl alcohol (FA), cinnamyl alcohol, vanillin alcohol, and various aromatic alcohols to the corresponding aldehyde with >99% selectivity for all the alcohol substrates under visible light (385–740 nm). Photocatalytic oxidation results revealed that Ti3C2-TiO2 (MT5) has superior photocatalytic activity than Ti3C2-TiO2 (MT1) and pure Ti3C2Tx NSs. The exceptional photocatalytic activity was attributed to the composite's unique morphology and characteristics.

Robust biocatalyst for the green continuous flow synthesis of esters from biomass-derived furfuryl alcohol and C8–C18 carboxylic acids

A sustainable method suitable for industrial-scale continuous flow synthesis of esters from biomass-derived furfuryl alcohol (FA) and C8–C18 carboxylic acids was developed.

Hydrogenolysis of furfuryl alcohol over CuCeMgAl mixed metal oxide catalysts derived from layered double hydroxides

LDH-derived CuCeMgAl mixed metal oxide catalysts were synthesized. Ce addition promoted Cu dispersion and improved catalyst basicity, resulting in high activity in furfuryl alcohol hydrogenolysis and high selectivity toward 1,2-pentanediol.

Continuous production of 1,2-pentanediol from furfuryl alcohol over highly stable bimetallic Ni–Sn alloy catalysts

A bimetallic NiSn/ZnO catalyst converts biomass-derived furfuryl alcohol into 1,2-PDO continuously, yielding 91.0% over 400 hours.

Introduction of NiSO4 to Ni/SiO2 catalyst in hydrogenation of furfuryl alcohol: Tailoring metallic nickel sites to switch major product from tetrahydrofurfuryl alcohol to cyclopentanone

Nickel-based catalysts are widely used in hydrogenation of varied types of organics. However, the nickel catalyst, like Ni/SiO2, lacks selectivity for hydrogenation of C=C and C=O. This is undesirable in some scenarios, such as conversion of biomass-derived furfuryl alcohol (FA) to cyclopentanone (CPO), a fine chemical, in which the C=C in furan ring of FA needs to be retained. In this study, introduction of sulfur species to Ni/SiO2 catalyst via loading NiSO4 was adopted to inhibit hydrogenation of furan ring in FA, aiming to achieve conversion of FA to CPO via ring-opening route. The results indicated that NiSO4 was reduced to NixSy, which further reacted with metallic Ni, forming Ni3S2 species and introducing the acidic sites with high-strength. The co-existence of NixSy and metallic Ni species effectively hindered hydrogenation of furan ring in FA, reducing tetrahydrofurfuryl alcohol (THFA) yield from 97% over Ni/SiO2 to 0 over the NiSx/SiO2 catalysts and shifting the major product to CPO. Nonetheless, the enhanced acidic sites along with the introduction of NiSO4 catalyzed polymerization of reaction intermediates, competing with the production of CPO. The acidic sites, however, facilitated hydrogenolysis of vanillyl alcohol to selectively produce (yield: 94.3%) in hydrogenation of vanillin. Characterization of hydrogenation of FA with in-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) technique suggested the oxygen-containing functionalities in FA, instead of furan ring, could strongly adsorb on the NiS10/SiO2 catalyst, enhancing rearrangement reaction to form CPO while suppressing hydrogenation of the furan ring.

Boosting cathodic hydrogen evolution with furfuryl alcohol oxidation as the anodic half-reaction for hybrid water splitting

Both anode feedstock and integrated electrodes are highly significant for the development of hybrid water electrolysis technology. Herein, biomass-derived furfuryl alcohol is selected as the anode feedstock, mainly because it contains no base-labile group (e.g., -CHO) and does not spontaneously undergo a Cannizzaro-type transformation under alkaline conditions. Bimetallic hydroxide nanowire arrays with nickel foam as the substrate (denoted Cu2Co(OH)x/NF) are designed and readily prepared via a microwave-assisted heating method. Then, Cu2Co(OH)x/NF is used as an integrated electrode for electrocatalytic furfuryl alcohol oxidation to value-added furoic acid with enhanced hydrogen production in 1.0 M NaOH. The input potential is reduced by approximately 219 mV when the oxygen evolution reaction is replaced by furfuryl alcohol oxidation to drive a current density of 10 mA cm−2. Moreover, the as-obtained electrode can be recycled several times without an obvious decline in carboxylate yield or Faradaic efficiency.

Performance improvement of poplar wood based on the synergies of furfurylation and polyethylene glycol impregnation

Abstract Fast-growing wood usually exhibits dimensional instability and inferior mechanical strength, which severely obstructs its wide application. To improve the dimensional stability and mechanical strength, biomass-derived furfuryl alcohol combined with polyethylene glycol (PEG) was vacuum-impregnated into wood hierarchical structures, causing cell wall bulking and porosity reduction. Furfural resin and PEG distributed in cell lumina, cell walls and middle lamella regions indicated by analyses of scanning electron microscope and fourier transform infrared spectroscopy. Wood porosity was generally reduced and the specific surface area decreased by over 65% analyzed by the nitrogen absorption. Consequently, wood hydrophobicity and dimensional stability were highly improved, and the water absorption and volumetric change decreased by over 55% and 78%. The flexural strength and modulus elasticity were improved by over 49% and 46%. Furfural resin helped the fixation of PEG in wood and significantly reduced PEG leaching. PEG with flexible linear molecular structure formed interpenetrating polymer network in wood hierarchical structures with furfural resin and reduced self-crosslinking of furfural resin. Accordingly, the impact toughness of compound modified wood increased by 39% compared with solely furfurylated wood. This study provided efficient and sustainable concepts to facilitate better industrialized application of wood furfurylation and improve service value of fast-growing wood.

Nano-H-ZSM-5 with Short b-Axis Channels as a Highly Efficient Catalyst for the Synthesis of Ethyl Levulinate from Furfuryl Alcohol

For the ethanolysis of biomass-derived furfuryl alcohol (FA) to value-added ethyl levulinate (EL), the development of an efficient solid acid catalyst is very important for industrial application with high FA concentration. Herein, a H-ZSM-5 catalyst with nano b-axis channels (NB-H-ZSM-5) was synthesized and used for the conversion of FA. Detailed catalyst characterization proved that the NB-H-ZSM-5 catalysts (Si/Al = 25∼125) with ∼70 nm b-axis channels were successfully prepared. The NB-H-ZSM-5 catalyst with Si/Al = 75 showed the highest activity. Its structural characteristics allowed for fast diffusion of reactants and products and full utilization of active sites, which endowed it with higher activity compared to commercial H-ZSM-5 (C-H-ZSM-5). Its moderate acidity effectively inhibited the polymerization of FA even at a high FA concentration of 20 wt %. The spent catalyst was easily regenerated by coke burn-off to give a good recyclability. Furthermore, based on the proposed reaction network, a method of physically mixing the NB-H-ZSM-5 (75) catalyst with a small amount of Amberlyst-15 was proposed to further increase the EL yield from 64.7 to 82.1% at an FA concentration of 6 wt %.

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 Ni1Fe2 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.

Selective conversion of biomass-derived furfuryl alcohol into n-butyl levulinate over sulfonic acid functionalized TiO2 nanotubes

Sulfonic acid functionalized titanate nanotubes were prepared by the sulphonation reaction of hydrothermally synthesized TiO2 nanotubes (TNTs) using chlorosulfonic acid as the sulfating agent. The as-prepared catalysts were characterized by fourier transform infrared (FT-IR) spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX), X-ray diffraction (XRD) analysis, thermogravimetry-differential thermal gravimetry (TG-DTG) and X-ray photoelectron spectroscopy (XPS) techniques. The characterization results revealed that the catalysts retained the tubular structure of the TNTs and possessed a large number of active sulfonic acid sites. The catalytic performance of the catalysts for the synthesis of n-butyl levulinate was investigated via the alcoholysis of biomass-derived furfuryl alcohol under atmospheric pressure. The effects of the reaction factors such as the catalyst dosage, reaction time, and temperature on the alcoholysis of the furfuryl alcohol were systematically studied. Under mild conditions, about 79.9% yield of n-butyl levulinate was achieved. In addition, the catalysts showed a stable catalytic performance after four consecutive cycles. Furthermore, no leaching of the active species was observed during the hot filtration testing, which can be attributed to the covalently linked –SO3H groups on the TNTs surface. In addition, the opened tubular nanostructure of the catalyst and the introduced strong Brønsted acid sites exhibited synergistic effects, which facilitated the selective conversion of the furfuryl alcohol to butyl levulinate.

Double-metal cyanide as an acid and hydrogenation catalyst for the highly selective ring-rearrangement of biomass-derived furfuryl alcohol to cyclopentenone compounds

Herein, novel green synthetic routes to 4-hydroxy-2-cyclopentenone (HCP) and 2-cyclopentenone (CPE) from biomass-derived furfuryl alcohol via double-metal cyanide catalysis are proposed.

Efficient valorization of biomass-derived furfuryl alcohol to butyl levulinate using a facile lignin-based carbonaceous acid

The preparation and application of biorenewable carbon-based catalyst are attracting increasingly attention in the field of green and sustainable chemistry. Here, a facile and low-cost lignosulfonate-based carbonaceous solid acid (LSS) was availably prepared via directly sulfonating lignosulfonate that was from sulfite pulping industry, and used to catalyze biomass-derived furfuryl alcohol to yield versatile butyl levulinate. The fabrication and properties of LSS were highly sensitive to the sulfonation conditions (i.e., lignosulfonate-to-H2SO4 ratio and temperature). The physicochemical properties of the as-prepared LSS were well characterized using BET surface area, acid–base titration, SEM, XRD, FT-IR, XPS, and TGA techniques. The LSS contained –SO3H, –COOH and phenolic –OH groups and was ideal to perform the reaction of furfuryl alcohol with n-butanol to obtain butyl levulinate in yield higher than 95% at 110 °C for 8 h with catalyst dosage of 15 g/L. Meanwhile, the catalyst deactivated increasingly with a recycle number that was attributed to the adsorption of formed polymeric by-products on the active catalyst sites, and the slightly deactivated catalyst after plain sulfonation treatment was found to remain active with an almost unchanged product yield in consecutive cycles. This work highlights an economic, eco-friendly, sustainable and promising protocol for catalytic upgrading of bio-based compounds.

Selective hydrogenolysis of furfuryl alcohol to 1,5- and 1,2-pentanediol over Cu-LaCoO3 catalysts with balanced Cu0-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.

Kaolinite Catalyst for the Production of a Biodiesel-Based Compound from Biomass-Derived Furfuryl Alcohol

We report herein that pristine kaolinite was used to produce furanic ethers from furfuryl alcohol (FFA) with high catalytic performance (95% conversion and 96% selectivity). Kaolinite, supplied commercially and prepared without any treatment, was characterized by XRD, NH3-TPD, surface area analysis, and FT-IR spectroscopies. The result showed that the Lewis and Bronsted acid sites played a crucial role in the formation of furanic ether. The reusability tests showed that kaolinite was stable until the fifth consecutive run.

In Situ Polymerization of Furfuryl Alcohol with Ammonium Dihydrogen Phosphate in Poplar Wood for Improved Dimensional Stability and Flame Retardancy

Fast-growing plantation wood normally possesses some undesirable intrinsic properties, such as dimensional instability, inferior mechanical strength, and flammability, limiting its usage as an engineering material. Herein, we report a green and facile approach for upgrading the low-quality poplar wood via a combined treatment with biomass-derived furfuryl alcohol (FA) and ammonium dihydrogen phosphate (ADP) acting as a flame-retardant additive. Wood/PFA/ADP composites were prepared by impregnation of the FA precursor solutions into the wood matrix, followed by in situ polymerization upon heating to form a hydrophobic FA resin/ADP network within the wood scaffold. In-depth scanning electron microscopy coupled with enregy-dispersive X-ray spectroscopy (SEM-EDX) and confocal laser scanning microscopy (CLSM) analyses reveal the wide distribution of the FA resin/ADP complexes inside the cell walls and also in the cell lumens. The incorporation of hydrophobic FA resin into wood results in reduced water uptake a...

A waste-minimized protocol for copper-catalyzed Ullmann-type reaction in a biomass derived furfuryl alcohol/water azeotrope

We report the use of biomass-derived furfuryl alcohol as an effective bidentate ligand able to promote the Ullmann-type copper-catalyzed coupling of aryl halides with heteroaromatic or aliphatic amines.

HPW anchored Meso‐HZ‐5, a novel catalyst for selective synthesis of ethyl levulinate biofuel by alcoholysis of biomass‐derived furfuryl alcohol

Ethanolysis of biomass derived furfuryl alcohol (FA) produces ethyl levulinate (EL), a biofuel additive and precursor for γ‐valerolactone synthesis. The present study is devoted to develop an efficient and an environmentally benign catalytic system for one‐pot conversion of FA to EL biofuel, by revealing an insight of the catalytic mechanism. The catalytic activity of H‐ZSM‐5, Meso‐HZ‐5 (desilicated H‐ZSM‐5) and different percentage H3PW12O40(HPW) anchored to Meso‐HZ‐5 catalysts have been evaluated for the FA ethanolysis.As per our knowledge, this is the first research reporting the application of HPW anchored to Meso‐HZ‐5 catalysts for the conversion of FA into EL in biomass utilization. These catalysts were synthesized and characterized by Powder X‐ray diffraction (XRD), N2 physisorption and temperature programmed NH3 desorption (TPAD). Products of FA ethanolysis viz., 4,5,5‐triethoxypentan‐2‐one (TEP), ethoxy‐methyl‐ furan (EMF), diethyl ether (DEE), EL were identified by Gas Chromatography‐Mass Spectroscopy (GC‐MS) and quantified by flame ionization detector (GC‐FID). The physicochemical properties of catalysts were found to correlate to the product distribution matrix.Moreover, influences of several process parameters such as catalyst amount, reactant molar ratio, temperature and time on the extent of FA ethanolysis were systematically investigated. Under optimized conditions, 15% (w/w) HPW/Meso‐HZ‐5 exhibited a remarkable catalytic performance with complete FA conversion (100%) along with 97% yield of EL, these activity values are superior than the previously reported studies. The present study provides an insight of the catalytic mechanism along with a potential environmental benign and the economic catalyst for the efficient synthesis of EL biofuel from the biomass‐derived FA. © 2017 American Institute of Chemical Engineers Environ Prog, 37: 1736–1742, 2018

Revaluation of biomass-derived furfuryl alcohol derivatives for the synthesis of carbocyclic nucleoside phosphonate analogues.

The racemic synthesis of new carbocyclic nucleoside methylphosphonate analogues bearing purine bases (adenine and guanine) was accomplished using bio-sourced furfuryl alcohol derivatives. All compounds were prepared using a Mitsunobu coupling between the heterocyclic base and an appropriate carbocyclic precursor. After deprotection, the compounds were evaluated for their activity against a large number of viruses. However, none of them showed significant antiviral activity or cytotoxicity.

Catalytic Upgrading of Biomass-Derived Furfuryl Alcohol to Butyl Levulinate Biofuel over Common Metal Salts

Levulinate ester has been identified as a promising renewable fuel additive and platform chemical. Here, the use of a wide range of common metal salts as acid catalysts for catalytic upgrading of biomass-derived furfuryl alcohol to butyl levulinate was explored by conventional heating. Both alkali and alkaline earth metal chlorides did not lead effectively to the conversion of furfuryl alcohol, while several transition metal chlorides (CrCl3, FeCl3, and CuCl2) and AlCl3 exhibited catalytic activity for the synthesis of butyl levulinate. For their sulfates (Cr(III), Fe(III), Cu(II), and Al(III)), the catalytic activity was low. The reaction performance was correlated with the Brønsted acidity of the reaction system derived from the hydrolysis/alcoholysis of cations, but was more dependent on the Lewis acidity from the metal salts. Among these investigated metal salts, CuCl2 was found to be uniquely effective, leading to the conversion of furfuryl alcohol to butyl levulinate with an optimized yield of 95%. Moreover, CuCl2 could be recovered efficiently from the resulting reaction mixture and remained with almost unchanged catalytic activity in multiple recycling runs.