3D Oxide-Derived Ru Catalyst for Ultra-Efficient Hydrogenation of Levulinic Acid to γ-Valerolactone.

γ-valerolactone (GVL) is a key value-added chemical catalytically produced from levulinic acid (LA), an important biomass derivative platform chemical. Here an ultra-efficient 3D Ru catalyst generated by in situ reduction of RuZnOx nanoboxes is reported; the catalyst features a well-defined structure of highly dispersed in situ oxide-derived Ru (IOD-Ru) clusters (≈1 nm in size) spatially confined within the 3D nanocages with rich mesopores, which guarantees a maximized atom utilization with a high exposure of Ru active sites as well as a 3D accessibility for substrate molecules. The IOD-Ru exhibits ultrahigh performance for the hydrogenation of LA into GVL with a record-breaking turnover frequency (TOF) up to 59400 h-1 , 14 times higher than that of the ex situ reduction of RuZnOx nanoboxes catalyst. Structural characterizations and theoretical calculations collectively indicate that the defect-rich and coordination-unsaturated IOD-Ru sites can boost the activation of the carbonyl group in LA with a significantly lowered energy barrier of hydrogenation.

A Comparative Study of Electrochemical Reduction of Levulinic Acid on Various Electrodes in Organic Solvents.

Studies on the electrochemical hydrogenation (ECH) of levulinic acid (LA) to valeric acid (VA) or γ-valerolactone (GVL) have mainly focused on the electrochemical reduction of LA in acidic aqueous solutions. However, the narrow range of applied potentials has hindered understanding of some mechanistic aspects of LA electrochemical conversion. Earlier, we discovered that employing proton-deficient non-aqueous reaction media provides more comprehensive insights into the mechanism of LA electrochemical reduction. Here, we conducted further investigations into the LA electroreduction process using cyclic voltammetry in various organic solvents on a Pt electrode and on various electrode materials in acetonitrile, both with and without the addition of proton donors. The products of the ECH processes were identified using HPLC. The solvent nature, the presence of proton donors, the electrode material, and the applied potential strongly influence the LA electroreduction process. This study reveals that LA, in the presence proton donors, can undergo electrochemical reduction through different pathways, depending on the difference (ΔE1/2) between the reduction half-wave potential of protons and LA on a certain electrode. When the difference is large, the LA reduction is incomplete and the formation of GVL is observed. Under the close reduction potentials of protons and LA, LA can be completely reduced to VA.

Catalytic Conversion of Levulinic Acid into 2-Methyltetrahydrofuran: A Review.

Biomass-derived furanics play a pivotal role in chemical industries, with 2-methyltetrahydrofuran (2-MTHF), a hydrogenated product of levulinic acid (LA), being particularly significant. 2-MTHF finds valuable applications in the fuel, polymer, and chemical sectors, serving as a key component in P-series biofuel and acknowledged as a renewable solvent for various chemical processes. Numerous research groups have explored catalytic systems to efficiently and selectively convert LA to 2-MTHF, using diverse metal-supported catalysts in different solvents under batch or continuous process conditions. This comprehensive review delves into the impact of metal-supported catalysts, encompassing co-metals and co-catalysts, on the synthesis of 2-MTHF from LA. The article also elucidates the influence of different reaction parameters, such as temperature, type and quantity of hydrogen source, and time. Furthermore, the review provides insights into reaction mechanisms for all documented catalytic systems.

Zirconium Phosphate-Pillared Zeolite MCM-36 for Green Production of γ-Valerolactone from Levulinic Acid via Catalytic Transfer Hydrogenation.

γ-valerolactone (GVL), derived from biomass, is a crucial platform compound for biofuel synthesis and various industrial applications. Current methods for synthesizing GVL involve expensive catalysts and high-pressure hydrogen, prompting the search for greener alternatives. This study focuses on a novel zirconium phosphate (ZrP)-pillared zeolite MCM-36 derivative catalyst for converting levulinic acid (LA) to GVL using alcohol as a hydrogen source. The incorporation of ZrP significantly contributes to mesoporosity and greatly enhances the acidity of the catalysts. Additionally, we employed 31P MAS NMR to comprehensively investigate the influence of phosphorus species on both the acidity and the catalytic conversion of LA to GVL. By adjusting the Zr-to-P ratios, we synthesized catalysts with enhanced acidity, achieving high conversion of LA and selectivity for GVL. The catalyst exhibited high recyclability, showing only minor deactivation over the course of five cycles. Furthermore, the catalyst was successfully applied to the one-pot conversion of furfural to GVL, showcasing its versatility in biomass conversion. This study highlights the potential of the MCM-ZrP1 catalyst for sustainable biomass conversion and offers insights for future research in renewable energy technologies.

Precursor-Driven Catalytic Performances of Al2O3-Supported Earth-Abundant Ni Catalysts in the Hydrogenation of Levulinic Acid and Hydroxymethylfurfural into Added-Value Chemicals.

It has been shown that the nature of the metal precursor and the thermal effects during calcination determine the physicochemical properties of the catalysts and their catalytic activity in the levulinic acid (LA) and 5-hydroxymethylfurfural (HMF) hydrogenation reactions. The endothermic effect during calcination of the inorganic nickel precursor promoted higher metal dispersion and stronger interaction with the alumina surface. In contrast, the exothermic effects during the calcination of organic nickel precursors resulted in smaller metal dispersion and lower interaction with the support surface. A clear relationship was found between the size of the metal crystallites and the yield of LA hydrogenation reaction. The smaller crystallites were more active in the LA hydrogenation reaction. In turn, the size of the metal particles and their nature of interaction with the surface of the alumina influence the hydrogenation pathways of the HMF.

Process optimization for enzymatic production of a valuable biomass-based ester from levulinic acid.

The enzymatic production of isoamyl levulinate via esterification of isoamyl alcohol (IA) and levulinic acid (LA), a biomass-based platform chemical with attractive properties, in a solvent system has been performed in this study. For such a purpose, a low-cost liquid lipase (Eversa® Transform 2.0) immobilized by physical adsorption via hydrophobic interactions (mechanism of interfacial activation) on mesoporous poly(styrenene-divinylbenzene) (PSty-DVB) beads was used as heterogeneous biocatalyst. It was prepared at low ionic strength (5 mmol.L-1 buffer sodium acetate pH 5.0) and 25 â„ƒ using an initial protein loading of 40 mg.g-1 of support. Maximum protein loading of 31.2 ± 2.8 mg.g-1 of support and an immobilization yield of 83% was achieved. The influence of relevant factors (biocatalyst concentration and reaction temperature) on ester production was investigated using a central composite rotatable design (CCRD). Maximum acid conversion percentage of 65% was achieved after 12 h of reaction at 40 °C, 20% of mass of heterogeneous biocatalyst per mass of reaction mixture (20% m.m-1), and LA:IA molar ratio of 1:1.5 in a methyl isobutyl ketone (MIBK) medium. The biocatalyst retained around of 30% of its initial activity after five consecutive esterification batches under optimal experimental conditions. The proposed experimental procedure can be considered as an acceptable green process (EcoScale score of 66.5), in addition to the fact that a new strategy is proposed to sustainably produce a valuable industrial ester (isoamyl levulinate) from biomass-based materials using an immobilized and low-cost commercial lipase as catalyst.

The Role of Copper in the Hydrogenation of Furfural and Levulinic Acid.

Currently, there is a great interest in the development of sustainable and green technologies for production of biofuels and chemicals. In this sense, much attention is being paid to lignocellulosic biomass as feedstock, as alternative to fossil-based resources, inasmuch as its fractions can be transformed into value-added chemicals. Two important platform molecules derived from lignocellulosic sugars are furfural and levulinic acid, which can be transformed into a large spectrum of chemicals, by hydrogenation, oxidation, or condensation, with applications as solvents, agrochemicals, fragrances, pharmaceuticals, among others. However, in many cases, noble metal-based catalysts, scarce and expensive, are used. Therefore, an important effort is performed to search the most abundant, readily available, and cheap transition-metal-based catalysts. Among these, copper-based catalysts have been proposed, and the present review deals with the hydrogenation of furfural and levulinic acid, with Cu-based catalysts, into several relevant chemicals: furfuryl alcohol, 2-methylfuran, and cyclopentanone from FUR, and γ-valerolactone and 2-methyltetrahydrofuran from LA. Special emphasis has been placed on catalytic processes used (gas- and liquid-phase, catalytic transfer hydrogenation), under heterogeneous catalysis. Moreover, the effect of addition of other metal to Cu-based catalysts has been considered, as well as the issue related to catalyst stability in reusing studies.

Challenges and Opportunities in the Catalytic Synthesis of Diphenolic Acid and Evaluation of Its Application Potential.

Diphenolic acid, or 4,4-bis(4-hydroxyphenyl)pentanoic acid, represents one of the potentially most interesting bio-products obtainable from the levulinic acid supply-chain. It represents a valuable candidate for the replacement of bisphenol A, which is strongly questioned for its toxicological issues. Diphenolic acid synthesis involves the condensation reaction between phenol and levulinic acid and requires the presence of a Brønsted acid as a catalyst. In this review, the state of the art related to the catalytic issues of its synthesis have been critically discussed, with particular attention to the heterogeneous systems, the reference benchmark being represented by the homogeneous acids. The main opportunities in the field of heterogeneous catalysis are deeply discussed, as well as the bottlenecks to be overcome to facilitate diphenolic acid production on an industrial scale. The regioselectivity of the reaction is a critical point because only the p,p'-isomer is of industrial interest; thus, several strategies aiming at the improvement of the selectivity towards this isomer are considered. The future potential of adopting alkyl levulinates, instead of levulinic acid, as starting materials for the synthesis of new classes of biopolymers, such as new epoxy and phenolic resins and polycarbonates, is also briefly considered.

Ni-Cu and Ni-Co-Modified Fly Ash Zeolite Catalysts for Hydrodeoxygenation of Levulinic Acid to γ-Valerolactone.

Monometallic (Ni, Co, Cu) and bimetallic (Ni-Co, Ni-Cu) 10-20 wt.% metal containing catalysts supported on fly ash zeolite were prepared by post-synthesis impregnation method. The catalysts were characterized by X-ray powder diffraction, N2 physisorption, XPS and H2-TPR methods. Finely dispersed metal oxides and mixed oxides were detected after the decomposition of the impregnating salt on the relevant zeolite support. Via reduction intermetallic, NiCo and NiCu phases were identified in the bimetallic catalysts. The catalysts were studied in hydrodeoxygenation of lignocellulosic biomass-derived levulinic acid to γ-valerolactone (GVL) in a batch system by water as a solvent. Bimetallic, 10 wt.% Ni, and 10 wt.% Cu or Co containing fly ash zeolite catalysts showed higher catalytic activity than monometallic ones. Their selectivity to GVL reached 70-85% at about 100% conversion. The hydrogenation activity of catalysts was found to be stronger compared to their hydration ability; therefore, the reaction proceeds through formation of 4-hydroxy pentanoic acid as the only intermediate compound.

A review on biomass-derived levulinic acid for application in drug synthesis.

Levulinic acid (LEV) has been identified as a key building block chemical produced entirely from biomass. Its derivatives can be used to synthesize a variety of value-added chemicals, such as 2-butanone, 2-methyltetrahydrofuran, and so on. LEV has carbonyl and carboxyl functional groups, which makes it flexible, diverse, and unique during drug synthesis. It also reduces the cost of drug synthesis and makes the reaction cleaner and, not the least, has untapped potential in the field of medicine. This article reviews the application of LEV in cancer treatment, medical materials, and other medical fields. Overall, LEV can be used in the following ways: (1) Used as a raw material to directly synthesize drugs; (2) Used to synthesize related derivatives, which can be more specifically used in drug synthesis, and derivatives can achieve the corresponding release of drugs, such as paclitaxel (PTX)- LEV, polymer-betulinic acid (BA)-LEV after amidation; (3) It can modify chemical reagents or act as linkers to connect pharmaceutical reagents with carriers to form pharmaceutical intermediates, a pharmaceutical intermediate skeleton, and so on. (4) It can acylate and esterify to form: acetylpropionate and levulinyl, the indole, pyridazine, and other medicinally active functional groups can be synthesized by a long chain, which can reduce the cost of drug synthesis and simplify the tedious synthesis steps. (5) To form the protective group of levulinic acid, the hydroxyl or carboxyl position is first protected, and then the protective group is removed after the corresponding reaction, in order to participate in drug synthesis.

A Catalyst and Solvent Free Route for the Synthesis of N-Substituted Pyrrolidones from Levulinic Acid.

An efficient, metal-free, catalyst-free and solvent-free methodology for the reductive amination of levulinic acid with different anilines has been developed using HBpin as the reducing reagent. This protocol offers an excellent method to avoid solvents and added catalysts on the synthesis of different kinds of N-substituted pyrrolidones under metal free conditions. It is also the first report for the synthesis of different pyrrolidones by solvent-free as well as catalyst-free methods. The proposed mechanism for the formation of pyrrolidone has been supported by DFT calculations and control experiments.

Eco-conception of Highly Salt-Tolerant Alkyl Ether Carboxylate Hydrotropes with a Glyceryl Spacer.

New alkyl ether carboxylates with a glyceryl spacer instead of ethylene glycol units have been synthesised using environmentally friendly methodology. A cascade synthesis of acetalisation and hydrogenolysis was developed to obtain products containing an alkyl chain linked to a glycerol unit bearing a polar carboxylate head. These products were methylated by using trimethyl phosphate to observe the influence of a free or methoxylated alcohol on the physicochemical properties. Finally, saponification gave the carboxylate anionic group of the new hydrotropes. Studying the amphiphilicity, the tolerance to sodium and calcium ions, and the solubilising power of these bio-based ionic/nonionic hydrotropes has shown that they exhibit significantly improved application properties compared to similar petro-based hydrotropes.

Nitrogen-doped graphene supported Ni as an efficient and stable catalyst for levulinic acid hydrogenation.

Transforming levulinic acid (LA) toγ-valerolactone (GVL) is a significant route for converting biomass into valuable chemicals. The development of an efficient and robust heterogeneous catalyst for this reaction has aroused great interest. In this work, nitrogen-doped graphene (NG) supported nickel (Ni) based heterogeneous catalyst with excellent activities was successfully synthesized. The Ni/NG catalyst shows outstanding performance for hydrogenation of LA to GVL at a relatively low temperature of 140 °C, which is superior to most of reported heterogeneous catalysts. Further investigations indicate Ni nanoparticles are the active sites and the NG also plays an indispensable role. The catalytic performance is highly depended on the crystallinity, particles sizes and electronic structure of Ni in Ni/NG catalyst, which can be optimized by nitrogen doping. This work affords a new route for designing robust and excellent heterogeneous catalysts by doping method to optimize the support.

Effect of levulinic acid on production of polyhydroxyalkanoates from food waste by Haloferax mediterranei.

Polyhydroxyalkanoates (PHA), especially poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is considered as the most suitable candidate to replace petrochemical plastics. However, the high production cost and the composition of the monomers in the copolymer are the major constraints in production. The 3-hydroxyvalerate (3HV) rich copolymers are ideal for various applications due to their lower melting points, improved elasticity, and ductility. Haloferax mediterranei is a suitable microorganism for the production of biopolymer PHBV from biowaste. Nevertheless, the potential of H. mediterranei cultivated on food waste as sustainable substrate and levulinic acid as an inducer has not been explored for PHBV production. This study aims at the valorization of food waste as low-cost substrate and evaluation of effect of levulinic acid in the production and composition of PHBV using H. mediterranei. Shake-flask fermentations using different concentrations of salt, glucose and levulinic acid were first performed to optimize the cultivation conditions. The highest growth of the halophile was observed at salt concentration of 15% and glucose of concentration 10 g/L. Under optimized growth conditions, H. mediterranei was cultivated for PHBV production in fed-batch bioreactor with pulse fed levulinic acid. The maximum biomass of 3.19 ± 0.66 g/L was achieved after 140 h of cultivation with 3 g/L of levulinic acid. A decrease in H. mediterranei growth was noticed with the increase in levulinic acid concentration in the range of 3-10 g/L. The overall yield of PHBV at 3, 5, 7 and 10 g/L of levulinic acid were 18.23%, 56.70%, 31.54%, 21.29%, respectively. The optimum concentration of 5 g/L of levulinic acid was found to produce the maximum yield of 56.70% PHBV with 18.55 mol% 3HV content. A correlation between levulinic acid concentrations and PHBV production established in this study can serve as an important reference for future large-scale production.

Ru@hyperbranched Polymer for Hydrogenation of Levulinic Acid to Gamma-Valerolactone: The Role of the Catalyst Support.

Hydrogenation of levulinic acid (LA) obtained from cellulose biomass is a promising path for production of γ-valerolactone (GVL)-a component of biofuel. In this work, we developed Ru nanoparticle containing nanocomposites based on hyperbranched pyridylphenylene polymer, serving as multiligand and stabilizing matrix. The functionalization of the nanocomposite with sulfuric acid significantly enhances the activity of the catalyst in the selective hydrogenation of LA to GVL and allows the reaction to proceed under mild reaction conditions (100 °C, 2 MPa of H2) in water and low catalyst loading (0.016 mol.%) with a quantitative yield of GVL and selectivity up to 100%. The catalysts were successfully reused four times without a significant loss of activity. A comprehensive physicochemical characterization of the catalysts allowed us to assess structure-property relationships and to uncover an important role of the polymeric support in the efficient GVL synthesis.

On the Development of Phenol-Formaldehyde Resins Using a New Type of Lignin Extracted from Pine Wood with a Levulinic-Acid Based Solvent.

Resole resins have many applications, especially for foam production. However, the use of phenol, a key ingredient in resoles, has serious environmental and economic disadvantages. In this work, lignin extracted from pine wood using a "green" solvent, levulinic acid, was used to partially replace the non-sustainable phenol. The physicochemical properties of this novel resin were compared with resins composed of different types of commercial lignins. All resins were optimized to keep their free formaldehyde content below 1 wt%, by carefully adjusting the pH of the mixture. Substitution of phenol with lignin generally increases the viscosity of the resins, which is further increased with the lignin mass fraction. The addition of lignin decreases the kinetics of gelification of the resin. The type and amount of lignin also affect the thermal stability of the resins. It was possible to obtain resins with higher thermal stability than the standard phenol-formaldehyde resins without lignin. This work provides new insights regarding the development of lignin-based resoles as a very promising sustainable alternative to petrol-based resins.

Development of Ultrasound-Assisted Extraction to Produce Skin-Whitening and Anti-Wrinkle Substances from Safflower Seed.

In this study, ultrasound-assisted extraction (UAE) was applied to extract bioactive substances with skin-whitening, anti-wrinkle, and antioxidant effects from safflower seeds, and the extraction conditions were optimized by a central composite design. The independent variables, including extraction time (5.0~55.0 min), extraction temperature (26.0~94.0 °C), and ethanol concentration (0.0~100%), were optimized to increase tyrosinase activity inhibitory (TAI), collagenase activity inhibitory (CAI), and radical scavenging activity (RSA), which are indicators of skin-whitening, anti-wrinkle, and antioxidant effects. An extraction time of 26.4 min, extraction temperature of 52.1 °C, and ethanol concentration of 50.7% were found to be optimum conditions of UAE, under which TAI, CAI, and RSA were 53.3%, 91.5%, and 27.7%, respectively. The extract produced by UAE was analyzed by LC-MS/MS, and maleic acid and levulinic acid were identified as the main substances. Therefore, UAE is evaluated as an effective process to extract skin-whitening, anti-wrinkle, and antioxidant substances from safflower seeds at lower temperatures and shorter extraction times compared to the conventional extraction methods. Overall, safflower seeds extract can be used as a material for value-added cosmetics, including maleic acid and levulinic acid, which have bioactive functions.

Hydrodeoxygenation of Levulinic Acid to γ-Valerolactone over Mesoporous Silica-Supported Cu-Ni Composite Catalysts.

Monometallic (Cu, Ni) and bimetallic (Cu-Ni) catalysts supported on KIT-6 based mesoporous silica/zeolite composites were prepared using the wet impregnation method. The catalysts were characterized using X-ray powder diffraction, N2 physisorption, SEM, solid state NMR and H2-TPR methods. Finely dispersed NiO and CuO were detected after the decomposition of impregnating salt on the silica carrier. The formation of small fractions of ionic Ni2+ and/or Cu2+ species, interacting strongly with the silica supports, was found. The catalysts were studied in the gas-phase upgrading of lignocellulosic biomass-derived levulinic acid (LA) to γ-valerolactone (GVL). The bimetallic, CuNi-KIT-6 catalyst showed 100% LA conversion at 250 °C and atmospheric pressure. The high LA conversion and GVL yield can be attributed to the high specific surface area and finely dispersed Cu-Ni species in the catalyst. Furthermore, the catalyst also exhibited high stability after 24 h of reaction time with a GVL yield above 80% without any significant change in metal dispersion.

Proton-Promoted Nickel-Catalyzed Asymmetric Hydrogenation of Aliphatic Ketoacids.

A robust and highly active homogeneous chiral nickel-phosphine complex for the asymmetric hydrogenation of aliphatic γ- and δ-ketoacids has been discovered. The hydrogenation could proceed smoothly in the presence of 0.0133 mol% catalyst loading (S/C=7500). The coordination chemistry and catalytic behavior of Ni(OTf)2 with (S,S)-Ph-BPE were explored by 1 H NMR and HRMS. The mechanistic studies revealed that a proton promoted the activation of the substrate C=O bond and controlled the stereoselectivity through hydrogen bonds. A series of chiral γ- and δ-alkyl substituted lactones were obtained in high yields with excellent enantioselectivities (up to 98 % yield and 99 % ee). In addition, this catalytic system also demonstrated that levulinic acid produced from a biomass feedstock was converted into chiral γ-valerolactone without loss of ee value.

Atomic Pyridinic Nitrogen Sites Promoting Levulinic Acid Hydrogenations over Double-Shelled Hollow Ru/C Nanoreactors.

Nitrogen-doped nanocarbons are widely used as supports for metal-heterogeneous catalytic conversions. When nitrogen-doped nanocarbon supports are used to disperse metallic nanoparticles (MNPs), the nitrogen dopant can enhance MNPs electron density to reach higher catalytic activity and promote MNPs stability through anchoring effects. However, the precise identification of active nitrogen species between N-dopants and reactants is rarely reported. Herein, a proof-of-concept study on the active N species for levulinic acid hydrogenation is reported. A double-shell structured carbon catalyst (DSC) is designed with selectively locating ultrafine Ru NPs only on inner carbon shell, specifically, different N species on the external carbon shell. Through the design of such a nanostructure, it is demonstrated that the alkaline pyridinic N species on the outer shell serves as an anchor point for the spontaneous binding of the acidic reactant. The pyridinic N content can be modulated from 7.4 to 29.2 mg gcat-1 by selecting different precursors. Finally, the Ru-DSC-CTS (using chitosan as the precursor) catalyst achieves a 99% conversion of levulinic acid under 70 °C and 4 MPa hydrogen pressure for 1 h. This work sheds light on the design of nanoreactors at the atomic scale and investigates heterogeneous catalysis at the molecular level.