High-yielding one-pot synthesis of glucose from cellulose and pentoses/hexoses real biomass is achieved by using simple activated carbons 0.012% HCl in water. Ball-milling the carbon together created good physical contact between solid substrate catalyst before reaction, selectively drastically improving depolymerization rate to oligomers. Thus, our methodology overcomes a major obstacle this type namely, that collision limited. Mechanistic studies have suggested active sites are weakly...

This manuscript demonstrates the synthesis of selective Lewis-acid sites in a metal–organic framework (MOF) for glucose transformation to 5-hydroxymethylfurfural (HMF). These are synthesized via partial phosphate modification zirconia-cluster nodes MOF NU-1000, which titrates strong that would lead undesired side reactions. Our mechanistic study using isotope tracer analysis and kinetic effect measurements reveals an isomerization–dehydration mechanism mainly occurs on catalyst, where...

The synthesis of glucose from cellulose is a critical roadblock for establishing new sustainable cycle biorefinery to produce bio-based and environmentally-benign chemicals. We have previously demonstrated that the pre-treatment ball-milling solid catalyst (mix-milling) drastically improves yield oligosaccharides; however, effect this type has not been quantitatively evaluated. In study, we performed several model reactions found mix-milling method enhanced solid–solid reactions, such as...

Abstract Carbon‐based materials have attracted interest as high‐performance catalysts for the aqueous‐phase conversion of cellulose. The adsorption β‐glucans plays a crucial role in catalytic performance carbons, although primary driving force and details process remain unclear. This study demonstrates that occurs at hydrophobic sites on carbon surface hydrophilic groups are not involved. Analysis temperature dependence also reveals entropy change associated with is positive. Our results...

A combination of ethanol solvent and hydrotalcite (HT) with a Mg/Al ratio 3:1 was effective for the isomerization glucose to fructose in up 56% yield high selectivity 80%. The shifts equilibrium between fructose, which allows exceed upper limit enzymatic conducted water at modest temperatures (i.e., 50%). HT catalyst maintained such catalytic performance repeated use least three times via calcination subsequent reconstruction original layered structure by memory effect, operated an aqueous...

This review summarizes a variety of catalytic systems to achieve the selective hydrodeoxygenation potent biomass-derived platform chemicals with focus on features including performance, active sites, and mechanism.

A trade-off of activity–selectivity exists in primary C–O hydrogenolysis biomass-derived diols to secondary alcohols over bimetallic catalysts, especially the combination noble metal and early transition metallic state oxide state, respectively. Herein, high surface concentration boron nitride (BN)-supported metals addition Mo as third broke trade-off. High yields (>50%) were obtained with robust productivity up 25-fold based on Ir Ir–Fe0.13–Mo0.08/BN (Ir = 20 wt %, Fe/Ir 0.13, Mo/Ir 0.08)...

Abstract Chitin, a polymer of N ‐acetylglucosamine units with β‐1,4‐glycosidic linkages, is the most abundant marine biomass. Chitin monomers containing ‐acetyl groups are useful precursors to various fine chemicals and medicines. However, selective conversion robust chitin ‐acetylated currently requires large excess acid or long reaction time, which limits its application. We demonstrate fast catalytic transformation retention by combining mechanochemistry homogeneous catalysis....

We report the catalytic conversion of biomass-derived carbohydrates to methyl lactate using metal oxides. The combination Lewis acid–base sites on γ-Al2O3 is superior several amphoteric oxides for production from both dihydroxyacetone and glucose in methanol. successful by attributed high densities acid base functionalities that are essential promotion stepwise reaction, which consists isomerization, retro-aldol, dehydration reactions.

Olefin production from polyols via deoxydehydration (DODH) was carried out over Ag-modified CeO2 -supported heterogeneous Re catalysts with H2 as a reducing agent. Both high DODH activity and low hydrogenation ability for C=C bonds were observed in the reaction of erythritol, giving 1,3-butadiene yield up to 90 % under "solvent-free" conditions. This catalyst is applicable other substrates such methyl glycosides (methyl α-fucopyranoside: 91 product; β-ribofuranoside: 88 yield), which...

Synthesis of 2-imidazolidinone (EU) from ethylenediamine carbamate (EDA-CA), which was produced via chemical absorption CO2 in (EDA), with a fixed-bed flow reactor performed using CeO2 and EDA as heterogeneous catalyst reaction solvent, respectively. In the previously reported batch system for same reaction, yield EU low (62%) due to its sequential into N,N′-bis(2-aminoethyl)urea (LU) 38% liquid phase under optimized conditions at 413 K. stark contrast, enabled highly selective high-yielding...

Abstract Strong metal‐support interaction (SMSI) greatly improves the performances of various supported metal nanoparticle catalysts. Classical SMSI relies on oxide species with substoichiometric oxygen concentration, which prefers to retreat off in humid and oxidative atmospheres. A is reported oxygen‐saturated overlayers Au/TiO 2 catalyst achieved by steaming treatment, an opposite condition classical formation. Through a combination experimental theoretical methods, this study...

The reaction kinetics of deoxydehydration + hydrogenation (DODH HG; didehydroxylation) erythritol to butanediols and n-butane over the ReOx-Pd/CeO2 catalyst was investigated. Competitive adsorption polyols deactivation during DODH HG were necessary be considered in kinetics. order strength on surface >1,2-butanediol > water >1,4-butanediol monoalcohols. investigated with two models: time-dependent conversion-dependent ones. model better fitted both activities reused catalysts time-course...

We demonstrate adsorption and depolymerization of long-chain β-glu strands derived from cellulose, within the microporous confines a zeolite-templated carbon (ZTC) material. The ZTC adsorbs that have radius gyration several-fold larger than micropore diameter do so rapidly (less 2 min) in adsorbed coverages up to 80% mass. Principles supramolecular chemistry predict such occurs inside based on its size as host being nearly ideal for glucan guest. A comparative study partially etched...

Carbon materials bearing carboxylic acids and phenolic groups efficiently catalyze the hydrolysis of cellulose. In this work, we demonstrate that salicylic acid phthalic show higher activity than other substituted benzoic as models catalytic sites on carbons in cellobiose Notably, their turnover frequencies are larger those o-chlorobenzoic o-trifluoromethylbenzoic acid, despite lower strength. The high performance is not attributed to a reduction activation energy but an increase frequency...

Metal–organic framework material NU-1000 exhibits an unprecedented molecular recognition for simple carbohydrates.

A series of ceria-supported Fe catalysts with a trace amount noble-metal modification (NM–Fe/CeO2, NM = Pt, Ir, Pd, Rh, and Ru) were prepared by the co-impregnation method used for guaiacol hydrodeoxygenation (HDO) to phenolic compounds at 673 K atmospheric pressure. In absence H2O, addition noble metal improved initial activities but showed severer deactivation than Fe/CeO2. Conversely, water little effect on activity helped improve stability NM–Fe/CeO2. Among all tested NM–Fe/CeO2...

Characterization of Mo species on Rh metal particles in Rh–MoOx/C catalyst for C–O hydrogenolysis reactions was carried out with situ ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and density functional theory (DFT) calculations. The as-prepared sample high oxidation states Rh3+, Rh4+ Mo6+ reduced 0.2 Torr H2. All the most were to Rh0 Mo4+ during heating 570 K. thickness layers after reduction calculated by a numerical analysis based XPS intensity ratio uniform adlayer stacking...

Sugar alcohols can be converted to mono-alcohols in good yields over a Pt–WO_x/SiO₂ catalyst without C–C dissociation, and 1,4-butanediol 1,4-anhydroxylitol also produced with related systems.

Catalysts with high selectivity to cleave terminal OH groups of 1,2-alkanediol are vital extending the scope value-added products from biomass instead fossil fuels but have not yet been reported so far. In this study, 1,2-butanediol (1,2-BuD) hydrogenolysis was selected as a model reaction develop such regioselective catalyst. The 2-butanol (2-BuOH) over Ir/rutile TiO2 (Ir = 5 wt %) moderate (53%) initially rapidly decreased (39%) at longer time (72 h). Addition Fe enhanced both activity and...

Key reactions and possible biomass resources for the synthesis of industrially important unsaturated compounds are summarized.

Cerium oxide (CeO2) was recently reported to function as a highly active heterogeneous catalyst in the flow synthesis of 2-imidazolidinone (EU) without gas-phase CO2 from ethylenediamine carbamate (EDA-CA), latter which can be synthesized easily (EDA) and ambient CO2, an EDA solvent. However, deactivation due surface deposition polyurea-like compounds has remained grand challenge. In this study, attempt develop new catalysts with better stability than conventional CeO2 by tuning properties,...

Abstract Catalytic hydrogenolysis systems of C-O bonds in furan ring, tetrahydrofuran ring and tetrahydropyran biomass-derived cyclic compounds are reviewed. Furfural or its hydrogenation products (furfuryl alcohol tetrahydrofurfuryl alcohol) have been frequently used as substrates for this type reactions. Ring-opening furfuryl over metal catalysts combined with basic components gives a mixture 1,2-pentanediol, 1,5-pentanediol other by-products. The selectivity much depends on reaction...