Mitigating the Poisoning Effect of Formate during CO2 Hydrogenation to Methanol over Co-Containing Dual-Atom Oxide Catalysts.

During the hydrogenation of CO2 to methanol over mixed-oxide catalysts, the strong adsorption of CO2 and formate poses a barrier for H2 dissociation, limiting methanol selectivity and productivity. Here we show that by using Co-containing dual-atom oxide catalysts, the poisoning effect can be countered by separating the site for H2 dissociation and the adsorption of intermediates. We synthesized a Co- and In-doped ZrO2 catalyst (Co-In-ZrO2) containing atomically dispersed Co and In species. Catalyst characterization showed that Co and In atoms were atomically dispersed and were in proximity to each other owing to a random distribution. During the CO2 hydrogenation reaction, the Co atom was responsible for the adsorption of CO2 and formate species, while the nearby In atoms promoted the hydrogenation of adsorbed intermediates. The cooperative effect increased the methanol selectivity to 86% over the dual-atom catalyst, and methanol productivity increased 2-fold in comparison to single-atom catalysts. This cooperative effect was extended to Co-Zn and Co-Ga doped ZrO2 catalysts. This work presents a different approach to designing mixed-oxide catalysts for CO2 hydrogenation based on the preferential adsorption of substrates and intermediates instead of promoting H2 dissociation to mitigate the poisonous effects of substrates and intermediates.

Mechanochemical Hydrolysis of Polysaccharide Biomass: Scope and Mechanistic Insights.

Mechanical forces can affect chemical reactions in a way that thermal reactions cannot do, which may have a variety of applications. In biomass conversion, the selective conversion of cellulose and chitin is a grand challenge because they are the top two most abundant resources and recalcitrant materials that are insoluble in common solvents. However, recent works have clarified that mechanical forces enable the depolymerization of these polysaccharides, leading to the selective production of corresponding monomers and oligomers. This article reviews the mechanochemical hydrolysis of cellulose and chitin, particularly focusing on the scope and mechanisms to show a landscape of this research field and future subjects. We introduce the background of mechanochemistry and biomass conversion, followed by recent progress on the mechanochemical hydrolysis of the polysaccharides. Afterwards, a considerable space is devoted to the mechanistic consideration on the mechanochemical reactions.

Induction of plant disease resistance by mixed oligosaccharide elicitors prepared from plant cell wall and crustacean shells.

Basal plant immune responses are activated by the recognition of conserved microbe-associated molecular patterns (MAMPs), or breakdown molecules released from the plants after damage by pathogen penetration, so-called damage-associated molecular patterns (DAMPs). While chitin-oligosaccharide (CHOS), a primary component of fungal cell walls, is most known as MAMP, plant cell wall-derived oligosaccharides, cello-oligosaccharides (COS) from cellulose, and xylo-oligosaccharide (XOS) from hemicellulose are representative DAMPs. In this study, elicitor activities of COS prepared from cotton linters, XOS prepared from corn cobs, and chitin-oligosaccharide (CHOS) from crustacean shells were comparatively investigated. In Arabidopsis, COS, XOS, or CHOS treatment triggered typical defense responses such as reactive oxygen species (ROS) production, phosphorylation of MAP kinases, callose deposition, and activation of the defense-related transcription factor WRKY33 promoter. When COS, XOS, and CHOS were used at concentrations with similar activity in inducing ROS production and callose depositions, CHOS was particularly potent in activating the MAPK kinases and WRKY33 promoters. Among the COS and XOS with different degrees of polymerization, cellotriose and xylotetraose showed the highest activity for the activation of WRKY33 promoter. Gene ontology enrichment analysis of RNAseq data revealed that simultaneous treatment of COS, XOS, and CHOS (oligo-mix) effectively activates plant disease resistance. In practice, treatment with the oligo-mix enhanced the resistance of tomato to powdery mildew, but plant growth was not inhibited but rather tended to be promoted, providing evidence that treatment with the oligo-mix has beneficial effects on improving disease resistance in plants, making them a promising class of compounds for practical application.

Catalytic conversion of chitin as a nitrogen-containing biomass.

The conversion of chitin enables the utilisation of naturally-fixed nitrogen in addition to carbon toward establishing a sustainable carbon and nitrogen cycle. Chitin is an abundant biomass, 100 Gt per year, but most chitin-containing waste is discarded due to its recalcitrant properties. This feature article summarises the challenges and our work on chitin conversion to N-acetylglucosamine and oligomers with fascinating applications. Afterwards, we introduce recent progress on the chemical transformation of N-acetylglucosamine, followed by a discussion of future perspectives based on current status and findings.

Selective Synthesis of Oligosaccharides by Mechanochemical Hydrolysis of Chitin over a Carbon-Based Catalyst.

Oligosaccharides possess fascinating functions that are applicable in a variety of fields, such as agriculture. However, the selective synthesis of oligosaccharides, especially chitin-oligosaccharides, has remained a challenge. Chitin-oligosaccharides activate the plant immune system, enabling crops to withstand pathogens without harmful agrichemicals. Here, we demonstrate the conversion of chitin to chitin-oligosaccharides using a carbon catalyst with weak acid sites and mechanical milling. The catalyst produces chitin-oligosaccharides with up to 94 % selectivity in good yields. Monte-Carlo simulations indicate that our system preferentially hydrolyzes larger chitin molecules over oligomers, thus providing the desired high selectivity. This unique kinetics is in contrast to the fact that typical catalytic systems rapidly hydrolyze oligomers to monomers. Unlike other materials carbons more strongly adsorb large polysaccharides than small oligomers, which is suitable for the selective synthesis of small oligosaccharides.

Effective Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran by an Acetal Protection Strategy.

An acetal protection strategy for 5-hydroxymethylfurfural (HMF) was used to obtain 2,5-diformyfuran (DFF) using concentrated HMF solutions and a γ-Al2 O3 -supported Ru catalyst (Ru/γ-Al2 O3 ). The HMF-acetal with 1,3-propanediol can be oxidized to DFF-acetal with a yield of 84.0 % at an HMF conversion of 94.2 % from a 50 wt % solution. In contrast, aerobic oxidation of nonprotected HMF using a 10 wt % solution afforded DFF only in a moderate yield (52.3 %). Kinetic studies indicated that the six-membered ring acetal group not only prevents side reactions but also accelerates aerobic oxidation of the -CH2 OH moiety to -CHO under retention of the acetal functionality. Organic deposits formed during the reaction explained the significant decrease in the activity of the Ru/γ-Al2 O3 catalyst, which could be recovered neither by washing in water or organic solvents, nor by a calcination-reduction treatment. Sonication of the used Ru/γ-Al2 O3 catalyst in an aqueous NaOH solution successfully removed the deposits and allowed reuse of the catalyst for at least four times without activity loss.

Impact of tensile and compressive forces on the hydrolysis of cellulose and chitin.

Mechanochemistry enables unique reaction pathways in comparison to conventional thermal reactions. Notably, it can achieve selective hydrolysis of cellulose and chitin, a set of abundant and recalcitrant biomass, by solvent-free ball-milling in the presence of acid catalysts. Although the merits of mechanochemistry for this reaction are known, the reaction mechanism is still unclear. Here, we show how the mechanical forces produced by ball-milling activate the glycosidic bonds of carbohydrate molecules towards hydrolysis. This work uses experimental and theoretical evaluations to clarify the mechanism. The experimental results reveal that the ball-mill accelerates the hydrolysis by mechanical forces rather than local heat. Meanwhile, the classical and quantum mechanics calculations indicate the subnano to nano Newton order of tensile and compressive forces that activate polysaccharide molecules in the ball-milling process. Although previous studies have taken into account only the stretching of the molecules, our results show that compressive forces are stronger and effective for the activation of glycosidic bonds. Accordingly, in addition to stretching, compression is crucial for the mechanocatalytic reaction. Our work connects the classical physics of ball-milling on a macro scale with molecular activation at a quantum level, which would help to understand and control mechanochemical reactions.

On the Electronic Structure Origin of Mechanochemically Induced Selectivity in Acid-Catalyzed Chitin Hydrolysis.

Recently, mechanical ball milling was applied to chitin depolymerization. The mechanical activation afforded higher selectivity toward glycosidic bond cleavage over amide bond breakage. Hence, the bioactive N-acetylglucosamine (GlcNAc) monomer was preferentially produced over glucosamine. In this regard, the force-dependent mechanochemical activation-deactivation process in the relaxed and pulled GlcNAc dimer undergoing deacetylation and depolymerization reactions was studied. For the relaxed case, the activation energies of the rate-determining steps (RDS) proved that the two reactions could occur simultaneously. Mechanical forces associated with ball milling were approximated with linear pulling and were introduced explicitly in the RDS of both reactions through force-modified potential energy surface (FMPES) formalism. In general, as the applied pulling force increases, the activation energy of the RDS of deacetylation shows no meaningful change, while that of depolymerization decreases. This result is consistent with the selectivity exhibited in the experiment. Energy and structural analyses for the depolymerization showed that the activation can be attributed to a significant change in the glycosidic dihedral at the reactant state. A lone pair of the neighboring pyranose ring O adopts a syn-periplanar conformation relative to the glycosidic bond. This promotes electron donation to the σ*-orbital of the glycosidic bond, leading to activation. Consequently, the Brønsted-Lowry basicity of the glycosidic oxygen also increases, which can facilitate acid catalysis.

Facile Preparation of 3-Acetamido-5-acetylfuran from N-Acetyl-d-glucosamine by using Commercially Available Aluminum Salts.

3-Acetamido-5-acetylfuran (3A5AF) is a promising intermediate obtained from chitin for the production of N-containing value-added chemicals. However, the synthetic method is complicated so far, which has limited further investigation using 3A5AF. Herein, a facile method was developed for synthesizing 3A5AF from N-acetyl-d-glucosamine (NAG), including a simple isolation procedure. A 30 % yield of 3A5AF was obtained by performing the dehydration of NAG in N,N-dimethylformamide (DMF) solvent in the presence of AlCl3 ⋅6 H2 O at a temperature as low as 120 °C by conventional heating for 30 min. This method tolerated a wide range of temperature and concentration of substrate, thus easily allowing scale-up of the reaction. The produced 3A5AF was isolated with 98 % purity by simple column chromatography. Additionally, a highly functionalized N-containing lactone was identified as a byproduct under these reaction conditions.

Metal cation-exchanged zeolites with the location, state, and size of metal species controlled.

Rh ion-exchanged MFI-type aluminosilicate zeolites with different Al distributions were prepared for controlling the location, state, and size of Rh species. The MFI-type aluminosilicate zeolite with the framework Al atoms predominantly located inside the channel intersections leads to the formation of relatively large Rh species, which were confirmed by ultraviolet-visible (UV-vis) and infrared (IR) spectroscopies. Moreover, this catalyst showed a high catalytic activity for the oxidative reforming reaction of methane.

Zeolite-supported ultra-small nickel as catalyst for selective oxidation of methane to syngas.

The development of simple catalysts with high performance in the selective oxidation of methane to syngas at low temperature has attracted much attention. Here we report a nickel-based solid catalyst for the oxidation of methane, synthesised by a facile impregnation method. Highly dispersed ultra-small NiO particles of 1.6 nm in size are successfully formed on the MOR-type zeolite. The zeolite-supported nickel catalyst gives continuously 97-98% methane conversion, 91-92% of CO yield with a H2/CO ratio of 2.0, and high durability without serious carbon deposition onto the catalyst at 973 K. DFT calculations demonstrate the effect of NiO particle size on the C-H dissociation process of CH4. A decrease in the NiO particle size enhances the production of oxygen originating from the NiO nanoparticles, which contributes to the oxidation of methane under a reductive environment, effectively producing syngas.

Synthesis of 5-hydroxymethylfurfural from highly concentrated aqueous fructose solutions using activated carbon.

An efficient and environmentally friendly system for producing 5-hydroxymethylfurfural (5-HMF) from fructose has been proposed. Substrate concentration is an important factor for practical application of the process; however, use of a high concentration of fructose has rarely been tested in the reaction because the conditions accelerate intermolecular side reactions to form adhesive humins. Humin byproducts stuck on reactor surfaces can make the production of 5-HMF on an industrial scale difficult. Therefore, developing a catalytic reaction system that can promote the synthesis of 5-HMF from highly concentrated fructose without causing adhesion of humins to reactors is needed. The present study demonstrated that activated carbons are promising materials for this system. Activated carbon catalyzed the conversion of fructose to 5-HMF without adhesion of humins to reactor vessels under practical conditions of high substrate concentration up to 73.2%. The catalytic activity was determined not only by the amount of surface weakly acidic oxygenated groups but also by the adsorption of fructose. In addition, strong adsorption of 5-HMF led to low selectivity of 5-HMF and the formation of adhesive humins. This is the first report to describe the synthesis of 5-HMF from solutions containing a fructose concentration greater than 70%.

Surface Modification of a Supported Pt Catalyst Using Ionic Liquids for Selective Hydrodeoxygenation of Phenols into Arenes under Mild Conditions.

The selective and efficient removal of oxygenated groups from lignin-derived phenols is a critical challenge to utilize lignin as a source for renewable aromatic chemicals. This report describes how surface modification of a zeolite-supported Pt catalyst using ionic liquids (ILs) remarkably increases selectivity for the hydrodeoxygenation (HDO) of phenols into arenes under mild reaction conditions using atmospheric pressure H2 . Unmodified Pt/H-ZSM-5 converts phenols into aliphatic species as the major products along with a slight amount of arenes (10 % selectivity). In contrast, the catalyst modified with an IL, 1-butyl-3-methylimidazolium triflate, keeps up to 76 % selectivity for arenes even at a nearly complete conversion of phenols. The IL on the surface of Pt catalyst may offer the adsorption of phenols in an edge-to-face manner onto the surface, thus accelerating the HDO without the ring hydrogenation.

Soluble Cello-Oligosaccharides Produced by Carbon-Catalyzed Hydrolysis of Cellulose.

Cello-oligosaccharides are biologically important molecules that can elicit a defensive immune response in plants and improve the health of animals. Cellulose, a polymer of glucose linked by ß-1,4-glycosidic bonds, is an ideal feedstock for synthesis of cello-oligosaccharides. However, cello-oligosaccharides rapidly degrade under the conditions used for cellulose hydrolysis. Here, cellulose was hydrolyzed over a carbon catalyst in a semi-flow reactor to achieve a high yield of cello-oligosaccharides (72 %). The excellent activity of the oxidized carbon catalyst, the adsorption of cellulose on the catalyst, and the high space velocity of products in the reactor were essential. Moreover, a method for quantification of individual cello-oligosaccharides was developed, which suggested a reduction in the rate of hydrolysis with a reduction in chain length.

Selective Sequestration of Aromatics from Aqueous Mixtures with Sugars by Hydrophobic Molecular Calixarene Cavities Grafted on Silica.

The separation of aromatic contaminants from sugar-aromatic aqueous mixtures is required in second-generation biorefineries because aromatic compounds deactivate (bio)catalysts typically involved in upgrading lignocellulosic biomass to fuels and chemicals. This separation remains challenging, however, because of the degree of molecular recognition needed to sequester dilute aromatic impurities from concentrated sugar streams. Herein, we demonstrate that hydrophobic cavities of p- tert-butylcalix[4]arene macrocycles grafted on amorphous silica (calix/SiO2) perform this separation selectively and efficiently by acting as selective molecular hosts that adsorb aromatic compounds (5-hydroxymethylfurfural, vanillin, and vanillic acid) while excluding monomeric sugar (glucose chosen as a prototypical model) in aqueous mixtures. By comparing calix/SiO2 to a range of organically modified SiO2 surfaces and other porous adsorbents, we demonstrate that the organization of hydrophobic functional groups within discrete nests consisting of calixarene cavities is crucial for facilitating the adsorption of aromatics. Density functional theory calculations of the host-guest complex indicate that adsorption is brought about by weak dispersive (van der Waals) interactions between tert-butyl upper-rim substituents in calixarene hosts and aromatic guests. Calix/SiO2 can be repeatedly reused, demonstrating its viability as an adsorbent within a continuous biorefining process. These calix/SiO2 adsorbents expand the palette of materials available for selective sugar-aromatic separations, which until now have been limited to pyrene-based sites of metal-organic framework NU-1000, and demonstrate that sites consisting of relatively simple hydrophobic tert-butyl substituents organized around a hemispherical molecular cavity provide a sufficient degree of molecular recognition for performing this separation selectively.

Aerobic Oxidation of 5-(Hydroxymethyl)furfural Cyclic Acetal Enables Selective Furan-2,5-dicarboxylic Acid Formation with CeO2 -Supported Gold Catalyst.

The utilization of 5-(hydroxymethyl)furfural (HMF) for the large-scale production of essential chemicals has been largely limited by the formation of solid humin as a byproduct, which prevents the operation of stepwise batch-type and continuous flow-type processes. The reaction of HMF with 1,3-propanediol produces an HMF acetal derivative that exhibits excellent thermal stability. Aerobic oxidation of the HMF acetal with a CeO2 -supported Au catalyst and Na2 CO3 in water gives a 90-95 % yield of furan 2,5-dicarboxylic acid, an increasingly important commodity chemical for the biorenewables industry, from concentrated solutions (10-20 wt %) without humin formation. The six-membered acetal ring suppresses thermal decomposition and self-polymerization of HMF in concentrated solutions. Kinetic studies supported by DFT calculations identify two crucial steps in the reaction mechanism, that is, the partial hydrolysis of the acetal into 5-formyl-2-furan carboxylic acid involving OH- and Lewis acid sites on CeO2 , and subsequent oxidative dehydrogenation of the in situ generated hemiacetal involving Au nanoparticles. These results represent a significant advance over the current state of the art, overcoming an inherent limitation of the oxidation of HMF to an important monomer for biopolymer production.

Cellulose Depolymerization over Heterogeneous Catalysts.

Cellulosic biomass is the largest source of renewable organic carbon on our planet. Cellulose accounts for 40-50 wt % of this lignocellulose, and it is a feedstock for industrially important chemicals and fuels. The first step in cellulose conversion involves its depolymerization to glucose or to its hydrogenated product sorbitol. The hydrolysis of cellulose to glucose by homogeneous mineral acids was the subject of research for almost a century. However, homogeneous acids have significant drawbacks and are neither economical nor environmentally friendly. In 2006, our group reported for the first time the ability of heterogeneous catalysts to depolymerize cellulose through hydrolytic hydrogenation to produce sorbitol. Later, we reported the hydrolysis of cellulose to glucose using carbon catalyst containing weakly acidic functional groups. Understanding the reaction between cellulose and heterogeneous catalyst is a challenge as the reaction occurs between a solid substrate and a solid catalyst. In this Account, we describe our efforts for the conversion of cellulose to sorbitol and glucose using heterogeneous catalysts. Sorbitol is produced by sequential hydrolysis and hydrogenation of cellulose in one pot. We reported sorbitol synthesis from cellulose in the presence of supported metal catalysts and H2 gas. The reducing environment of the reaction prevents byproduct formation, and harsh reaction conditions can be used to achieve sorbitol yield of up to 90%. Glucose is produced by acid catalyzed hydrolysis of cellulose, a more challenging reaction owing to the tendency of glucose to rapidly decompose in hot water. Sulfonated carbons were first reported as active catalysts for cellulose hydrolysis, but they were hydrothermally unstable under the reaction conditions. We found that carbon catalysts bearing weakly acidic functional groups such as hydroxyl and carboxylic acids are also active. Weakly acidic functional groups are hydrothermally stable, and a soluble sugar yield of 90% was achieved in a 20 min reaction. We clarified that the polycyclic aromatic surface of the carbon adsorbs cellulose molecules on its surface by CH-π and hydrophobic interactions driven by a positive change in entropy of the system. The adsorbed molecules are rapidly hydrolyzed by active sites containing vicinal functional groups that recognize the hydroxyl groups on cellulose to achieve a high frequency factor. This phenomenon is analogous to the hydrolysis of cellulose by enzymes that use CH-π and hydrophobic interactions along with weakly acidic carboxylic acid and carboxylate pair to catalyze the reaction. However, in comparison with enzymes, carbon catalyst is functional over a wide range of pH and temperatures. We also developed a continuous flow slurry process to demonstrate the feasibility for commercial application of carbon-catalyzed cellulose hydrolysis to glucose using inexpensive catalyst prepared by air oxidation. We believe that further efforts in this field should be directed toward eliminating roadblocks for the commercialization of cellulose conversion reactions.

Electrical Matching at Metal/Molecule Contacts for Efficient Heterogeneous Charge Transfer.

In a metal/molecule hybrid system, unavoidable electrical mismatch exists between metal continuum states and frontier molecular orbitals. This causes energy loss in the electron conduction across the metal/molecule interface. For efficient use of energy in a metal/molecule hybrid system, it is necessary to control interfacial electronic structures. Here we demonstrate that electrical matching between a gold substrate and π-conjugated molecular wires can be obtained by using monatomic foreign metal interlayers, which can change the degree of d-π* back-donation at metal/anchor contacts. This interfacial control leads to energy level alignment between the Fermi level of the metal electrode and conduction molecular orbitals, resulting in resonant electron conduction in the metal/molecule hybrid system. When this method is applied to molecule-modified electrocatalysts, the heterogeneous electrochemical reaction rate is considerably improved with significant suppression of energy loss at the internal electron conduction.

Insights into Supramolecular Sites Responsible for Complete Separation of Biomass-Derived Phenolics and Glucose in Metal-Organic Framework NU-1000.

The molecular origins of adsorption of lignin-derived phenolics to metal-organic framework NU-1000 are investigated from aqueous solution as well as in competitive mode with glucose present in the same aqueous mixture. A comparison of adsorption equilibrium constants (Kads) for phenolics functionalized with either carboxylic acid or aldehyde substituents demonstrated only a slight increase (less than a factor of 6) for the former according to both experiments and calculations. This small difference in Kads between aldehyde and carboxylic-acid substituted adsorbates is consistent with the pyrene unit of NU-1000 as the adsorption site, rather than the zirconia nodes, while at saturation coverage, the adsorption capacity suggests multiple guests per pyrene. Experimental standard free energies of adsorption directly correlated with the molecular size and electronic structure calculations confirmed this direct relationship, with the pyrene units as adsorption site. The underlying origins of this relationship are grounded in noncovalent π-π interactions as being responsible for adsorption, the same interactions present in the condensed phase of the phenolics, which to a large extent govern their heat of vaporization. Thus, NU-1000 acts as a preformed aromatic cavity for driving aromatic guest adsorption from aqueous solution and does so specifically without causing detectable glucose adsorption from aqueous solution, thereby achieving complete glucose-phenolics separations. The reusability of NU-1000 during an adsorption/desorption cycle was good, even with some of the phenolic compounds with greatest affinity not easiliy removed with water and ethanol washes at room temperature. A competitive adsorption experiment gave an upper bound for Kads for glucose of at most 0.18 M-1, which can be compared with Kads for the phenolics investigated here, which fell in the range of 443-42 639 M-1. The actual value of Kads for glucose may be much closer to zero given the lack of observed glucose uptake with NU-1000 as adsorbent.

Complete furanics-sugar separations with metal-organic framework NU-1000.

Metal-organic framework NU-1000 selectively adsorbs furanics, while completely excluding the adsorption of monomeric sugars from the same aqueous mixture. The highly refined degree of molecular recognition exhibited by NU-1000 is exemplified with it selectively adsorbing 5-hydroxymethylfurfural, even in the presence of up to a 300-fold excess of glucose in solution.