Search

The biomass valorization is of great importance as an alternative for the production of transport fuels and fine chemicals. Furfural hydrogenation to furfuryl alcohol is a prevailing industrial route for the utilization of hemicellulose component of biomass. The toxicity of the chromium species in commercial copper chromite catalyst for furfuryl alcohol production motivates the development of efficient chromium-free catalyst. Thus, a highly efficient silica supported copper catalyst is developed in this study. The catalyst is prepared by freeze drying of a gel precursor that is synthesized by ammonia evaporation, followed by calcination and H2 reduction. The catalyst exhibits higher furfural hydrogenation activity than oven dried catalyst, commercial copper chromite catalyst and a plant supplied commercial silica supported copper catalyst. The catalyst also shows good stability. The superior performance of the freeze dried catalyst has resulted from its developed pore structure and higher amount of Cu0 as well as Cu+ active sites.

We report a facile atom assembly of heterometallic bi-/tri-atom clusters (Pt1,2Cu1) starting from mono-metallic atoms (Pt1) in a protective PDMS-PEG layer.

The PdII–Cl–CuI complex and HCl have evolved as catalytically active species from paired PdCl2–CuCl2/[BMim]Cl in catalytic hydrolysis of β-1,4-glycosidic bonds in cellulose.

Defective cobalt oxide hydrate nanosheets with abundant oxygen vacancies and high porosity were fabricated via room-temperature reductive treatments, and they performed well in the electrocatalytic oxidation reaction of 5-hydroxymethylfurfural.

1-Butanol is a potential bio-based fermentation product obtained from cellulosic biomass. As a value-added chemical, 2-ethyl-1-hexanol (2-EH) can be produced by Guerbet conversion from 1-butanol. This work reports the enhanced catalytic Guerbet reaction of 1-butanol to 2-EH by a series of Cp*Ir complexes (Cp*: 1,2,3,4,5-pentamethylcyclopenta-1,3-diene) coordinated to bipyridine-type ligands bearing an ortho-hydroxypyridine group with an electron-donating group and a Cl− anion. The catalytic activity of the Cp*Ir complex increased by increasing the electron density of the bipyridine ligand when functionalized with the para-NMe2 and ortho-hydroxypyridine groups. A record turnover number of 14047 was attained. A mechanistic study indicated that the steric effect of the ethyl group on the α-C of 2-ethylhexanal (2-EHA) and the conjugation effect of C=C–C=O in 2-ethylhex-2-enal (2-EEA) benefits the high selectivity of 2-EH from 1-butanol by inhibiting the cross-aldol reaction of 2-EHA and 2-EEA with butyraldehyde. Nuclear magnetic resonance study revealed the formation of a carbonyl group in the bipyridine-type ligand via the reaction of the Cp*Ir complex with KOH.

The rapid consumption of fossil resources and the grim environmental situation encourage the application of renewable and clean energy resources. Conversion of biomass, which is a kind of renewable, CO2 neutral as well as abundant reserves carbon containing resource, is significantly important. The production of fuels from biomass by means of gasification and Fischer-Tropsch synthesis is one of the most promising routes for industrial applications. The wax-free liquid fuels synthesis directly from H2-deficient syngas similar to bio-gas is highly advantageous for reducing investment and operating cost. Thus, the Mn-promoted meso-ZSM-5 supported cobalt catalyst was applied for the production of wax-free liquid fuels by catalytic H2-deficient syngas conversion in this study. The performance of the reaction was influenced obviously by Mn content. The cobalt dispersion increased with the addition of Mn, whereas the reduction degree decreased after Mn doping. Then, the balance between the dispersion and reduction degree led to the change in CO uptake followed a volcanic curve. The catalyst with moderate amount of Mn (1 wt%) had the suitable cobalt particle size and the maximum CO uptake. Thus, the highest CO conversion was obtained over Co-1Mn/meso-ZSM-5 catalyst thanks to its maximum exposed active sites. The appropriate amount of Mn addition also resulted in the decreasing of CH4 selectivity. The highest space time yield of liquid fuels was acquired over the Co-1Mn/meso-ZSM-5 catalyst from H2-deficient syngas conversion under the moderate conditions.

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 lignocellulosic biomass utilization is a feasible way to obtain alternative fuels and chemicals. Xylitol as an ideal sweetener is one of the top twelve value-added chemicals derived from biomass. Xylitol is also used in the pharmaceutical and cosmetics industries. Thus, the production of xylitol from biomass is significantly important. A silica supported nickel catalyst derived from nickel phyllosilicate for efficient aqueous phase xylose hydrogenation to xylitol was developed in this study. Higher xylose conversion was observed over the nickel phyllosilicate derived catalyst compared to nickel oxide derived nickel catalyst prepared by impregnation and commercial Raney Ni catalyst. The excellent xylitol selectivity (approximately 99 %) was also obtained over the nickel phyllosilicate derived catalyst. The differences in structure and property resulted from different preparation methods were investigated by means of XRF, N2 physisorption, XRD, FT-IR, H2-TPR, TEM as well as H2-TPD. The higher nickel dispersion of nickel phyllosilicate derived catalysts, which could be synthesized by ammonia evaporation and deposition-precipitation using Na2CO3 as precipitator, led to higher xylose conversion. In addition, the phyllosilicate derived nickel catalyst demonstrated outstanding stability. Consequently, phyllosilicate derived nickel catalyst is promising for the industrial application for the production of xylitol form xylose aqueous hydrogenation thanks to its higher activity and selectivity as well as good stability.

Although numerous efforts have been made in direct syngas conversion to higher alcohols via Fischer–Tropsch synthesis, the higher alcohols distribution remains a challenge. Here, we introduce alkaline earth metal oxide as promoter into activated carbon supported cobalt catalyst to tune distribution of higher alcohols. With the addition of Mg, the distribution of C2-5 alcohols increase from 41.2 to 75.8% accompanying with distribution of C6-18 alcohols decrease from 52.8 to 14.0%. Ba-promoted Co based catalyst (CoBa/AC) presents similar alcohols distribution to un-promoted catalyst, while the alcohol selectivity over CoBa/AC is higher than Co/AC. For promoted catalysts, the distribution of C6-18 alcohols increased in the order of Mg

Carbon–carbon (C–C) coupling is critically important in organic synthesis. Direct C–C coupling to replace two C–H bonds is preferred over coupling of two prefunctionalized C–intermediates but is sy...

An in situ generated AuIII catalyst is found to catalyze the direct oxidation of CH4 to C1 oxygenates in 1-ethylimidazolium bis-(trifluoromethylsulfonyl)amide ([Eim][NTf2]) at 90 °C. The formation ...

The electronic and structural differences of anatase TiO2 (TiO2-A) and rutile TiO2 (TiO2-R) supported Ni catalysts are studied to understand the distinctively different catalytic pathways in guaiacol hydrodeoxygenation over Ni/TiO2-A and Ni/TiO2-R catalysts. Temperature programmed reduction profiles of NiO/TiO2-A and NiO/TiO2-R reveal two types of metal–support interactions. NiO on TiO2-R requires much higher temperature to reduce than NiO on TiO2-A by hydrogen reduction. Surface TiO2-A is partially reduced together with NiO at low temperature driven by strong interaction between reduced Ni and the reducible TiO2-A surface. In situ X-ray photoelectron spectroscopy (XPS), high resolution TEM (HRTEM), and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy of adsorbed CO reveal two types of reduced Ni species on Ni/TiO2-A: Ni0 particles and atomically dispersed electron-rich Niδ− atoms. While Ni0 particles are formed only at high Ni loadings, they are fully encapsulated by an overlayer of partially reduced TiOx, making the surface of Ni particles totally inaccessible to CO and to reactants. The electron-rich Niδ− atoms are favorably formed at all Ni loadings on the TiO2-A surface and show only linearly adsorbed CO in the DRIFT spectra. Electron transfer from Ti and O on the TiO2-A surface to atomically dispersed Ni is indicated by the observation of dominant electron-rich Niδ− species in conjunction with Ti(4+δ)+ and O(2−δ)− on Ni/TiO2-A following H2 reduction. In contrast, the chemical states of metallic Ni0 and Ti4+ remain unchanged on Ni/TiO2-R after H2 reduction. The atomically dispersed Niδ− species, formed only on the Ni/TiO2-A surface, is proposed as the active site responsible for the selective hydrodeoxygenation of guaiacol to phenolics. In contrast, the metallic Ni0 particles formed on the Ni/TiO2-R surface catalyze the typical catalytic hydrogenation, preferentially saturating the aromatic ring.

We report a facile strategy for synthesizing uniform heterometallic bi/tri-atom clusters starting from mono-metallic atoms in the liquid phase. Specifically, Pt

Selectively producing chemicals from cellulosic carbohydrate pyrolysis in large quantities is challenging, especially anhydro-monosaccharides with double-ring, triple-ring, and furan/pyran structures. Formation of these sugar derivatives greatly improves when the pyranose ring opening is inhibited during pyrolysis, which is accomplished by chemically replacing the hydroxyl group at the anomeric carbon with an alkoxy group. A simpler ring-locking approach is required for scalable chemical production, however. In this work, we demonstrate that introducing Na2SO4 and H2SO4 to glucose pyrolysis significantly increases levoglucosan (LGA) formation, from a 6% yield to as high as 40% at 350 °C. With H2SO4 as the acid catalyst, Na+ acts to inhibit the ring opening. Glucose pyrolysis with different alkali metal cations (Li+, Na+, K+, Rb+ and Cs+) gives different reaction products, which can be explained largely by an ionic electronegativity effect. Weaker electronegativity promotes the formation of a ring-opened product such as 5-hydroxymethylfurfural (HMF), and stronger electronegativity increases the formation of sequential dehydration products like levoglucosenone (LGO). Sodium has the optimum ionic electronegativity for preferential association with the ring oxygen. The Na2SO4/H2SO4 combination improved LGA yields for all carbohydrate substrates tested (up to 70%), including lignocellulose. These findings highlight the potential of using alkali metal salts to produce anhydrosugars in high yields from cellulosic carbohydrate pyrolysis.

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.

The development of highly active and non-noble cocatalysts is crucial for sustainable hydrogen (H2) generation through photocatalytic water splitting. Herein, Cu3N nanocrystals (∼15 nm) have been first used as a cocatalyst coupled with CdS for efficient photocatalytic H2 evolution with a rate of ∼4512 μmol g−1 h−1, achieving a dramatic improvement of 851-fold compared to bare CdS. Mechanistic studies revealed that the appropriate d-band center of Cu3N (−1.875 eV) with promoted photogenerated charge carrier kinetics induced its intrinsic activity, as a result of the balance between the adsorption and desorption of H species.

Furfuryl alcohol, a vital intermediate for the production of foundry resins, fragrances, pharmaceuticals and pesticide, is produced by hydrogenation of furfural in gas phase or liquid phase. The furfuryl alcohol production in gas phase over silica supported copper catalyst is favored thanks to the environmental and technical advantages. The effect of preparation methods of silica supported copper catalysts on the structure and performance was investigated by means of ICP, N2 physisorption, ex-situ/in-situ XRD, in-situ XPS, FT-IR, H2-TPR, TEM, N2O titration, TG as well as furfural hydrogenation. The results indicated that the different catalyst synthesis strategies led to the diverse copper species in the calcined samples and disparate Cu0 surface area as well as different molar ratio of Cu+/(Cu+ + Cu0) in the fresh samples. The performance of impregnation derived sample was poorer than that of commercial CuCr-Strem catalyst. The catalysts prepared by deposition precipitation and ion exchange exhibited similar performance to the CuCr-Strem. The ammonia evaporation derived catalyst (Cu/SiO2-EA) showed superior performance in the activity, selectivity and stability among all the studied catalysts. The excellent performance was related to the highest surface area of Cu0, smallest copper particle size, large surface area and pore volume as well as appropriate higher Cu+/(Cu+ + Cu0) ratio. Furthermore, all the copper catalysts went through deactivation, which was caused by carbon deposition, during the reaction. Owing to the largest amount of Cu0 sites and large SBET, the Cu/SiO2-EA exhibited the slowest deactivation rate.

Mechanistic pathways of catalytic hydrodeoxygenation determine the portfolios of biomass-derived platform chemicals. Bifunctional catalysts involving active metals on acidic supports are known to c...

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.

The catalytic properties of physical mixtures of Ni particles (100–200 nm) with nanoparticles of anatase TiO2 (TiO2-A), ZrO2, Al2O3, rutile TiO2 (TiO2-R), and CeO2 were investigated for the hydrode...

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 P

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 P

Selective hydrocleavage of aromatic C O bond while preserving the aromatic ring is a desired catalytic process in hydrodeoxygenation (HDO) of biomass derived aromatic oxygenates to high value biochemicals. Guaiacol with typical methoxy and phenolic hydroxyl groups is a representative aromatic di-oxygenates of lignin fragments. Sub-nanometer sized silver, a poor hydrogenation metal catalyst, was found to initiate H2 dissociation and H spillover onto anatase TiO2 (TiO2-A) surface. The spillover hydrogen enhanced the partial reduction of TiO2-A surface at a substantially lowered temperature as compared to the reduction of TiO2-A by molecular H2. The reduction of TiO2-A surface by spillover hydrogen was enhanced at Ag loading as low as 0.01 wt% on TiO2-A. The ratio of spillover H to Ag was as high as 675 at Ag loading of 0.01 wt% and the ratio decreased with increasing Ag loading. We found that the yield of phenolic products was linearly correlated with the amount of spillover hydrogen that created oxygen vacancy (Ov) through partial reduction of TiO2-A surface. Methanol was formed as the main side-product, indicating that the direct hydrocleavage of aromatic C-OCH3 in guaiacol is favored over that of aromatic C-OH on the created site.

Knowledge of the interfacial structure of nanocomposite materials is a prerequisite for rational design of nanostructured photocatalysts. Herein, TiO2 and g-C3N4 2D/2D nanocomposites were fabricated from three distinct synthetic protocols (i.e., co-calcination, solvothermal treatment and charge-induced aggregation), showing different degrees of enhancement (1.4–6.1 fold) in the visible-light induced photocatalytic hydrogen evolution reaction compared to the simple physical mixture. We propose that the interfacial Ti–O–N covalent bonding promotes the charge carrier transfer and separation more effectively than the electrostatic interaction, thus accelerating the photocatalytic H2 production. Meanwhile, the exposed surface area of TiO2 in the composite needs to be enlarged for deposition of the co-catalyst. This research sheds light on the rational design of hybrid nanocomposites based on earth-abundant elements for photocatalysis.

A bubbling fluidized bed pyrolyzer was integrated with an in-situ honeycomb as a catalytic upgrading zone for the conversion of biomass to liquid fuels. In the upgrading zone, zeolite coated ceramic honeycomb (ZCCH) catalysts consisting of ZSM-5 (Si/Al = 25) were stacked and N2 or recycled non-condensable gas was used as a carrier gas. Ground corncob particles were fast pyrolyzed in the bubbling bed using fine sand particles as a heat carrier and the resulting pyrolysis vapors were passed on-line over the catalytic upgrading zone. The influence of carrier gas, temperature, and weight hourly space velocity (WHSV) of catalyst on the oil product properties, distribution and mass balance were studied. Using ZCCH effectively increased the hydrocarbon yield and the heating value of the dry oil, especially in the presence of the recycled noncondensable gas. Even a low usage of zeolite catalyst at WSHVof 180 h‒1 was effective in upgrading the pyrolysis oil and other light olefins. The highest hydrocarbon (⩾C2) and liquid aromatics yields reached to 14.23 and 4.17 wt-%, respectively. The undesirable products including light oxygenates, furans dramatically decreased in the presence of the ZCCH catalyst.

The synthesis of furan compounds by renewable carbohydrates has emerged as an important path toward biomass utilization. 5-Hydroxymethylfurfural (5-HMF) and furfural are two typical furan products from cellulosic and hemicellulosic materials, of which the primary components (hexoses and pentoses) undergo selective dehydration. It is worth noting that hemicellulose is rich in not only pentoses but also hexoses, indicating the feasibility of producing 5-HMF and furfural simultaneously. However, research on the production of 5-HMF from hemicellulose-derived hexoses remains lacking. Mannose, a major hexose component of hemicellulose, has been previously found to be a suitable feedstock for 5-HMF production in the presence of homogeneous catalysts, such as metal salts. In this work, Cr-, Al- and Sn/MCM-41 catalysts were prepared by a simple impregnation method and characterized. The conversion of mannose into 5-HMF was evaluated in dimethyl sulfoxide (DMSO) solvent. It was found that the as-synthesized Sn/MCM-41 catalyst showed a superior activity to Cr/MCM-41 and Al/MCM-41. Mannose could be effectively converted into 5-HMF with a yield of ∼45% and ∼88% conversion at 150 °C after 60 min, which were comparable to reported results over heterogeneous catalysts. The as-synthesized Sn/MCM-41 catalyst was also efficient for the conversion of glucose and fructose with reasonable 5-HMF yields. The Sn/MCM-41 catalyst could be reused for eight consecutive cycles without significant loss of catalytic activity.

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.

The rates of Bronsted-acid-catalyzed reactions of ethyl tert-butyl ether, tert-butanol, levoglucosan, 1,2-propanediol, fructose, cellobiose, and xylitol were measured in solvent mixtures of water with three polar aprotic cosolvents: γ-valerolactone; 1,4-dioxane; and tetrahydrofuran. As the water content of the solvent environment decreases, reactants with more hydroxyl groups have higher catalytic turnover rates for both hydrolysis and dehydration reactions. We present classical molecular dynamics simulations to explain these solvent effects in terms of three simulation-derived observables: (1) the extent of water enrichment in the local solvent domain of the reactant; (2) the average hydrogen bonding lifetime between water molecules and the reactant; and (3) the fraction of the reactant accessible surface area occupied by hydroxyl groups, all as a function of solvent composition. We develop a model, constituted by linear combinations of these three observables, that predicts experimentally determined rate constants as a function of solvent composition for the entire set of acid-catalyzed reactions.

The synthesis of pyrrolidinones from reductive amination of levulinic acid (LA) with primary amines is reported. Pyrrolidinones have various applications such as surfactants, pharmaceutical intermediates, dispersants, and solvents. The half-sandwich Cp*Ir complex (Cp* is 1,2,3,4,5-pentamethylcyclopenta-1,3-diene) coordinated by bipyridine ligand bearing both dimethylamino and ortho-hydroxyl groups showed high catalytic activity for the reductive amination of LA. A range of primary amines, such as aromatic and benzyl amines, were readily converted to corresponding pyrrolidinones in good yields.

A highly efficient activated carbon supported cobalt based catalyst for Fischer-Tropsch synthesis was constructed. The catalyst was prepared by incipient wetness co-impregnation. The obtained catalyst was activated by multistep activation processes, which was composed of reduction of calcined sample in H2, syngas treatment, carburization in CO, and re-reduction in H2 successively. The multistep activation processes derived catalyst (CoZr/AC-RSCR) demonstrated far higher CO conversion and lower CH4 selectivity than those of conventional H2 reduction derived catalyst (CoZr/AC-R). The excellent performance of CoZr/AC-RSCR catalyst resulted from its higher amount of exposed active sites and the dominant hexagonal closed-packed (hcp) metallic cobalt phases. Furthermore, the catalytic performance could be further improved by tuning the content of hcp metallic cobalt phase stacking using the proper and effective treatment conditions of the multistep activation method. Finally, extremely high productivity of the mixture of alcohols and hydrocarbons with carbon number larger than 5 (194.6 g/h·kg-cat.) was acquired over CoZr/AC catalyst.

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.

A new strategy is exploited toward dramatically increased carbon utilization efficiency of biomass fast pyrolysis by implementing co-upgrading of by-products (biochar and pyrolysis gas) of fast pyrolysis. Simultaneous autocatalytic conversion of biochar and pyrolysis gas is demonstrated using a fixed-bed reactor and an isothermal thermogravimetric analyzer. The reaction of corncob char with simulated pyrolysis gas reveals the feasibility of producing valuable CO and H2 under suitable reaction temperature (>800 °C). The reactivity of biochar and simulated pyrolysis gas increases with increasing potassium content. The raw corncob biochar exhibits high reactivity owing to its high indigenous potassium content. Furthermore, kinetic analysis demonstrates that the modified random pore model (MRPM) satisfactorily describes the reaction behavior of corncob biochar and CO2. The activation energy calculation verifies that the co-upgrading of raw corncob biochar and pyrolysis gas for the production of syngas is feasible at suitable temperature without further treatment.

Producing bio-intermediates from lignocellulosic biomass with minimal process steps has a far-reaching impact on the biofuel industry. We studied the metal chloride catalyzed aldol condensation of furfural with acetone under conditions compatible with the upstream polysaccharide conversions to furfurals. In situ far infrared spectroscopy (FIR) was applied to guide the screening of aldol condensation catalysts based on the distinguishing characteristics of metal chlorides in their coordination chemistries with carbonyl-containing compounds. NiCl2, CoCl2, CrCl3, VCl3, FeCl3, and CuCl2 were selected as the potential catalysts in this study. The FIR results further helped to rationalize the excellent catalytic performance of VCl3 in furfural condensation with acetone, with 94.7% yield of biofuel intermediates (C8, C13) in 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) solvent. Remarkably, addition of ethanol facilitated the acetal pathway of the condensation reaction, which dramatically increased the desired product selectivity over the furfural pathway. Most significantly, we demonstrate for the first time that VCl3 catalyzed aldol condensation in acidic medium is fully compatible with upstream polysaccharide hydrolysis to monosaccharide and the subsequent monosaccharide isomerization and dehydration to furfurals. Our preliminary results showed that a 44% yield of biofuel intermediates (C8, C13) can be obtained in one-pot conversion of xylose catalyzed by paired metal chlorides, CrCl2 and VCl3. A number of prior works have shown that the biofuel intermediates derived from the one-pot reaction of this work can be readily hydrogenated to biofuels.

Diketones are ubiquitous blocks for organic synthesis. This work shows a highly active catalyst for the production of diketone 1-hydroxyhexane-2,5-dione (HHD) by hydrogenation of 5-hydroxymethylfurfural (5-HMF), a biobased platform chemical. Half-sandwich Cp*Ir complexes with ortho-hydroxyl group functionalized bipyridine ligands were synthesized and found to exhibit remarkably high catalytic activity for this reaction in acidic water. The HHD formation rate was further increased when the bipyridine ligands of Cp*Ir complexes were modified by an electron-donating group. A bipyridine ligand with both dimethylamino and ortho-hydroxyl groups achieved a HHD formation turnover frequency (TOF) of 31 560 h–1 by H2 and a TOF of 6140 h–1 by formic acid, representing 180-fold and 3 000-fold over the activities of the best reported results, respectively.

Far infrared spectroscopy complements the application of mid-infrared, near-infrared spectroscopy with the advantage of capable of measuring these typical lower energy vibration modes accurately.

The production of furfuryl alcohol from furfural hydrogenation in gas phase is of great significance for the valorization of biomass. The existing catalyst for this transformation suffers from high cost and complex preparation process. Thus, a highly efficient copper catalyst was developed by a simple impregnation method using ethanolamine modified granular silica as carrier. The catalytic performance was related to the amount of ethanolamine used in modification. Highly dispersed copper with uniform particle size distribution was obtained from appropriate amount of ethanolamine modified granular silica. The ethanolamine modified granular silica (mass ratio between ethanolamine and silica was 3 in the initial modification mixture) supported copper catalyst exhibited the best performance in terms of catalyst lifetime thanks to its maximum amount of Cu0 sites and largest amount of Cu+ sites. A slow deactivation of the catalyst after extended time on stream evaluation is attributed to carbon deposition and slow copper sintering.

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., Synthesis of discrete reduced metal atoms weakly coordinated and stabilized in liquid media remains challenging. Here, the authors report the genesis of mononuclear electron deficient Pt1(0) in polydimethylsiloxane-polyethylene glycol aggregates, and its ultrahigh activity in olefin hydrosilylation with excellent terminal adducts selectivity.

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 streng...