Understanding the Role of Base Species on Reversed Cu Catalyst in Ring Opening of Furan Compounds to 1, 2-Pentanediol.

The hydrogenation of biomass-derived furan compounds provides a sustainable pathway for the production of various valuable chemicals; product selectivity among multiple reaction pathways of furan compound hydrogenation is crucially dependent on catalytic sites; however controlling reaction pathways remains challenging due to the lack of identification and understanding of active sites. In this work we reveal the role of base sites in furfural selective hydrogenation through deliberately designed and synthesized reversed catalysts, basic metal oxides and hydroxide on Cu. It is demonstrated that base species greatly enhanced the selectivity of 1, 2-pentanediol (1, 2-PeD) from furfural, presenting a nearly fourfold increase of 1, 2-PeD: methyl furan ratio over the Cu based reverse catalysts. A combination of infrared spectroscopy and DFT calculations demonstrates the strong interaction between the C-O-C bond in furan ring and the catalyst surface in preferentially parallel adsorption mode in the presence of base species on Cu, thus facilitating the activation of C-O-C bond to produce 1, 2-PeD. This work provides a strategy of designing reversed catalyst to study the effect of promoters and reveals the role of base sites in the hydrogenation of biomass-derived furan compounds to diols.

Selective nucleophilic α-C alkylation of phenols with alcohols via Ti=Cα intermediate on anatase TiO2 surface.

C-C bond forming reaction by alkylation of aryl rings is a main pillar of chemistry in the production of broad portfolios of chemical products. The dominant mechanism proceeds via electrophilic substitution of secondary and tertiary carbocations over acid catalysts, forming multiple aryl alkylation products non-selectively through all secondary and tertiary carbons in the alkyl chains but producing little α-C alkylation products because primary carbocations are poorly stable. Herein, we report that anatase TiO2 (TiO2-A) catalyzes nucleophilic α-C alkylation of phenols with alcohols in high selectivity to simply linear alkylphenols. Experimental and computational studies reveal the formation of Ti=C- bond with the α-carbon of the alkyl group at oxygen vacancies of the TiO2-A surface. The subsequent α-C alkylation by selective substitution of phenol ortho-C-H bond is verified by deuterium exchanged substrate and DFT calculations.

Bi/trinuclear Pt1,2Cu cluster assembly from isolated metal atoms.

We report a facile strategy for synthesizing uniform heterometallic bi/tri-atom clusters starting from mono-metallic atoms in the liquid phase. Specifically, Pt1,2Cu bi/tri-atoms are prepared by reducing CuCl2 at preformed Pt1 atoms with ethanol inside a PDMS-PEG protective layer. The metal atoms in the Pt1,2Cu clusters are in reduced chemical states.

Enhanced lactic acid production from P2O5-pretreated biomass by domesticated Pediococcus pentosaceus without detoxification.

Expensive cellulase and complex detoxification procedures increase the cost of biomass lactic acid fermentation. Therefore, it is of great significance to develop a robust method to ferment lactic acid using biomass by avoiding cellulase and detoxification. This study demonstrates the advantage of combining mechanocatalytic P2O5 pre-treatment and strain domestication. We show that an enzyme-free mechanocatalytic saccharification process by combining mix-milling of P2O5 with biomass and successive hydrolysis produces a fermentable hydrolysate with much less inhibitory compounds than the hydrolysates obtained by conventional methods; only 5-HMF, furfural and acetic acid were detected in the biomass hydrolysate, and no phenolic inhibitors were detected. Pretreatment of biomass with P2O5 not only avoided cellulase, but also obtained less toxic hydrolysate. Furthermore, the Pediococcus pentosaceus strain gained superior inhibitor tolerance through domestication. It could tolerate 17.1 g/L acetic acid, 12.5 g/L 5-HMF, 11.9 g/L guaiacol and 11.5 g/L furfural and showed activity in decomposing furfural and 5-HMF for self-detoxification, allowing efficient lactic acid fermentation from biomass hydrolysate without detoxification. The lactic acid concentration and conversion rate fermented by domesticated bacteria were increased by 113.5% and 22.4%, respectively. In addition, the domesticated bacteria could utilize glucose and xylose simultaneously to produce lactic acid selectively. The combination of P2O5 pre-treatment and strain domestication to ferment lactic acid is applied to several biomass feedstocks, including corn stalk, corn stalk residue and rice husk residue. Lactic acid concentrations of 29.8 g/L, 31.1 g/L, and 46.2 g/L were produced from the hydrolysates of corn stalk, corn stalk residue and rice husk residue, respectively.

The effect of mix-milling with P2O5 on cellulose physicochemical properties responsible for increased glucose yield.

Breaking the recalcitrant structure of native crystalline cellulose is an energy demanding rate liming step in the production of glucose from cellulosic biomass. Mix-milling of lignocellulosic substrates (with P2O5) dramatically increased glucose yield. In this work, the changes of physicochemical characteristics (morphology, structure, degree of polymerization (DP), solubility) of cellulose during mix-milling (with P2O5) are correlated with glucose yield in the subsequent chemical hydrolysis process. The mix-milling enables highly efficient breakdown of cellulose I crystalline to smaller amorphous particles with low DP, which is recrystallized into cellulose II structure after water-wetting. As a result, the mix-milled cellulose (MMC) shows higher hydrolysis reactivity than that of single-milled cellulose (SMC). The results showed that small particle size, low DP, higher solubility and cellulose II content are correlated with the hydrolysis reactivity of cellulose.

Mechanistic understanding of humin formation in the conversion of glucose and fructose to 5-hydroxymethylfurfural in [BMIM]Cl ionic liquid.

Humin formation is one of the key issues that hinders economical 5-HMF production from hexose sugars such as glucose and fructose. In this work, the mechanism of humin formation in glucose/fructose conversion to HMF was studied in an ionic liquid system (1-butyl-3-methylimidazolium chloride, [BMIM]Cl) with CrCl3 as the catalyst. Elemental analysis, XRD, FT-IR, and TEM were applied to study the molecular structure and morphology of the solid humins. The possible intermediates to form solid humins were investigated by HPLC-MS. We synthesized furanic model compounds that mimic the experimentally identified humin intermediates to investigate the mechanism of humin growth at an early stage. The results showed that a furan compound bearing a hydroxymethyl and an electron-donating group was unstable due to three types of reactions: (1) bimolecular ether formation reactions; (2) intermolecular addition reaction; (3) furan ring opening reaction with water. The stability of a furan compound in [BMIM]Cl was increased when the hydroxymethyl group of a furan compound was protected by a methyl group, and the stability was further enhanced with an additional electron-withdrawing group (such as an aldehyde group) on the furan ring. Protecting the hydroxymethyl group of 5-HMF with a methyl group allows easy separation of the products from the [BMIM]Cl solvent through extraction.

Essential Quality Attributes of Tangible Bio-Oils from Catalytic Pyrolysis of Lignocellulosic Biomass.

This review covers the characteristics of pyrolysis and catalytic pyrolysis bio-oils by focusing on the fundamental factors that determine bio-oil upgradability. The abundant works on the subject of bio-oil production from lignocellulosic biomass were studied to establish the essential attributes of the bio-oils for assessment of the oil stability and upgradability. Bio-oils from catalytic pyrolysis processes relating to catalysts of different compositions and structures are discussed. A general relationship between the higher heating value and the oxygen content in the catalytic pyrolysis oils exists, but this relationship does not apply to the thermal pyrolysis oil. Reporting bio-oil yield is meaningful only when the oxygen content of the oil is measured because the pyrolytic oil stability is mainly determined by the oxygen content. Isoenergy plot that associates bio-oil yield with oxygen content is presented and discussed.

Genesis of electron deficient Pt1(0) in PDMS-PEG aggregates.

While numerous single atoms stabilized by support surfaces have been reported, the synthesis of in-situ reduced discrete metal atoms weakly coordinated and stabilized in liquid media is a more challenging goal. We report the genesis of mononuclear electron deficient Pt1(0) by reducing H2PtCl6 in liquid polydimethylsiloxane-polyethylene glycol (PDMS-PEG) (Pt1@PDMS-PEG). UV-Vis, far-IR, and X-ray photoelectron spectroscopies evidence the reduction of H2PtCl6. CO infrared, and 195Pt and 13C NMR spectroscopies provide strong evidence of Pt1(0), existing as a pseudo-octahedral structure of (R1OR2)2Pt(0)Cl2H2 (R1 and R2 are H, C, or Si groups accordingly). The weakly coordinated (R1OR2)2Pt(0)Cl2H2 structure and electron deficient Pt1(0) have been validated by comparing experimental and DFT calculated 195Pt NMR spectra. The H+ in protic state and the Cl- together resemble HCl as the weak coordination. Neutralization by a base causes the formation of Pt nanoparticles. The Pt1@PDMS-PEG shows ultrahigh activity in olefin hydrosilylation with excellent terminal adducts selectivity.

Structural Dependence and Spectroscopic Evidence of Methane Dissolution in Ionic Liquids.

High methane dissolution capacity in a liquid is important for methane storage and transformation. In this work, methane solubility in different ionic liquids (ILs) was studied and was found associated with IL's structural and physical properties. In imidazolium-based ILs, ILs containing C-F and long alkyl chain showed high methane solubility mainly due to lower surface tension and molar density. Reducing the surface tension of solvent by adding 0.16 mol of trimethyl-1-propanaminium iodide (FC-134) with respect to [Bmim][NTf2] increased methane solubility by 39.3%. In situ high-pressure attenuated total reflection Fourier transform infrared spectroscopic results indicated a reversible process of methane dissolution in the ILs. The antisymmetric C-H stretching band of dissolved methane in ILs showed highly prominent rotational-vibrational bands with high intensity and narrow half-peak width compared to gaseous methane. Induced interaction between methane and IL resulted in increased dipole variation strength and reduced methane molecular symmetry. The constant antisymmetric C-H stretching peak at 3016.85 cm-1 revealed an unconstrained methane rotation in the stable physical and chemical environment of IL. Methane insertion into the IL's intranetwork space needs activation energy to overcome the interaction of cation-anion network. Kinetic analysis of methane in [Bmim][NTf2] and [Bmim][HSO4] at different temperatures indicated that methane dissolution in these two ILs was a reversible first-order and very weak endothermic process and that methane dissolution required high activation energy in ILs with stronger cation-anion interaction.

Phosphorus pentoxide/metal chloride mediated efficient and facile catalytic conversion of fructose into 5-hydroxymethylfurfural.

Phosphorus pentoxide (P2O5)/metal chloride mixtures could significantly improve 5-HMF yield and selectivity for the catalytic conversion of fructose under mild conditions, whereas neither P2O5 nor tested metal chloride alone gave reasonable performances. A maximum 5-HMF yield of 75% with ∼85% selectivity could be achieved within 30 min at 80 °C.

Synthesis of Bis(hydroxylmethylfurfuryl)amine Monomers from 5-Hydroxymethylfurfural.

We report the synthesis of bis(hydroxylmethylfurfuryl)amine (BHMFA) from 5-hydroxymethylfurfural (5-HMF) by reacting 5-HMF with primary amines in the presence of homogeneous Ru(II) catalysts having sterically strained ligands. BHMFA is a group of furan-based monomers that offer great potential to form functional biopolymers with tunable properties. A range of primary amines, such as aliphatic and benzyl amines, are readily converted with 5-HMF to form the corresponding BHMFA in good yields. The reaction proceeds through reductive amination of 5-HMF with primary amine to form secondary amine, followed by reductive amination of 5-HMF with in situ generated secondary amine to produce BHMFA.

Lignocellulosic ethanol production by starch-base industrial yeast under PEG detoxification.

Cellulosic ethanol production from lignocellulosic biomass offers a sustainable solution for transition from fossil based fuels to renewable alternatives. However, a few long-standing technical challenges remain to be addressed in the development of an economically viable fermentation process from lignocellulose. Such challenges include the needs to improve yeast tolerance to toxic inhibitory compounds and to achieve high fermentation efficiency with minimum detoxification steps after a simple biomass pretreatment. Here we report an in-situ detoxification strategy by PEG exo-protection of an industrial dry yeast (starch-base). The exo-protected yeast cells displayed remarkably boosted vitality with high tolerance to toxic inhibitory compounds, and with largely improved ethanol productivity from crude hydrolysate derived from a pretreated lignocellulose. The PEG chemical exo-protection makes the industrial S. cerevisiae yeast directly applicable for the production of cellulosic ethanol with substantially improved productivity and yield, without of the need to use genetically modified microorganisms.

[CuCl(n)](2-n) ion-pair species in 1-ethyl-3-methylimidazolium chloride ionic liquid-water mixtures: ultraviolet-visible, X-ray absorption fine structure, and density functional theory characterization.

We studied the coordination environment about Cu(II) in a pure ionic liquid, 1-ethyl-3-methylimidazolium chloride ([EMIM]Cl), and in binary mixtures of this compound with water across the entire range of compositions, using a combination of X-ray absorption fine structure (XAFS), ultraviolet-visible (UV-vis) spectroscopy, and electronic structure calculations. Our results show a series of stages in the ion pairing of the divalent cation, Cu(II), including the contact ion pairing of Cu(2+) with multiple Cl(-) ligands to form various CuCl(n)((2-n)) polyanions, as well as the subsequent solvation and ion pairing of the polychlorometallate anion with the EMIM(+) cation. Ion-pair formation is strongly promoted in [EMIM]Cl by the low dielectric constant and by the extensive breakdown of the water hydrogen-bond network in [EMIM]Cl-water mixtures. The CuCl(4)(2-) species dominates in the [EMIM]Cl solvent, and calculations along with spectroscopy show that its geometry distorts to C(2) symmetry compared to D(2d) in the gas phase. These results are important in understanding catalysis and separation processes involving transition metals in ionic liquid systems.

Cleaving the ß--O--4 bonds of lignin model compounds in an acidic ionic liquid, 1-H-3-methylimidazolium chloride: an optional strategy for the degradation of lignin.

The hydrolysis of ß--O--4 bonds in two lignin model compounds was studied in an acidic ionic liquid, 1-H-3-methylimidazolium chloride. The ß--O--4 bonds of both guaiacylglycerol-ß-guaiacyl ether and veratrylglycerol-ß-guaiacyl ether underwent catalytic hydrolysis to produce guaiacol as the primary product with more than 70 % yield at 150 °C. Up to 32 wt % substrate concentration could be treated in the system without a decrease in guaiacol production. The ionic liquid could be reused without loss of activity in guaiacol production from both guaiacylglycerol-ß-guaiacyl ether and veratrylglycerol-ß-guaiacyl ether. A possible mechanism accounting for the guaiacol production is presented.

Metal chlorides in ionic liquid solvents convert sugars to 5-hydroxymethylfurfural.

Replacing petroleum feedstocks by biomass requires efficient methods to convert carbohydrates to a variety of chemical compounds. We report the catalytic conversion of sugars giving high yield to 5-hydroxymethylfurfural (HMF), a versatile intermediate. Metal halides in 1-alkyl-3-methylimidazolium chloride are catalysts, among which chromium (II) chloride is found to be uniquely effective, leading to the conversion of glucose to HMF with a yield near 70%. A wide range of metal halides is found to catalyze the conversion of fructose to HMF. Only a negligible amount of levulinic acid is formed in these reactions.

Inverse temperature-dependent pathway of cellulose decrystallization in trifluoroacetic acid.

An unusual inverse temperature-dependent pathway was observed during cellulose decrystallization in trifluoroacetic acid (TFA). Decreasing the TFA treatment temperature accelerated the cellulose decrystallization process. It took only 100 min to completely decrystallize cellulose at 0 degrees C in TFA, a result not achieved in 48 h at 25 degrees C in the same medium. There was neither cellulose esterification nor a change of cellulose macrofibril morphology by TFA treatment at 0 degrees C. Our IR data suggest that TFA molecules are present as cyclic dimers when they penetrate into crystalline cellulose regions, transforming crystalline cellulose to amorphous cellulose. On the other hand, the rate of TFA penetration into the cellulose matrix was greatly retarded at higher temperatures where monomeric TFA prevails. At elevated temperatures, esterification of TFA monomers on the external surface of crystalline cellulose, agglomeration of cellulose macrofibrils, as well as water released from the esterification reaction, inhibit the diffusion rate of TFA into the cellulose crystalline region and decrease the TFA swelling capability.