Tuning the Selectivity of Catalytic Nitrile Hydrogenation with Phase-Controlled Co Nanoparticles Prepared by Hydrosilane-Assisted Method.

Cobalt (Co) is a promising candidate to replace noble metals in the hydrogenation process, which is widely employed in the chemical industry. Although the catalytic performance for this reaction has been considered to be significantly dependent on the Co crystal phase, no satisfactory systematic studies have been conducted, because it is difficult to synthesize metal nanoparticles that have different crystalline structures with similar sizes. Here we report a new method for the synthesis of cobalt nanoparticles using hydrosilane as a reducing agent (hydrosilane-assisted method). This new method uses 1,3-butanediol and propylene glycol to successfully prepare fcc and hcp cobalt nanoparticles, respectively. These two types of Co nanoparticles have similar sizes and surface areas. The hcp Co nanoparticles exhibit higher catalytic performance than fcc nanoparticles for the hydrogenation of benzonitrile under mild conditions. The present hcp Co catalyst is also effective for highly selective benzyl amine production from benzonitrile without ammonia addition, whereas many catalytic systems require ammonia addition for selective benzyl amine production. Mechanistic studies revealed that the fast formation of the primary amine and the prevention of condensation and secondary amine hydrogenation promote selective benzonitrile hydrogenation for benzylamine over hcp Co nanoparticles.

Synthesis and Aerobic Oxidation Catalysis of Mesoporous Todorokite-Type Manganese Oxide Nanoparticles by Crystallization of Precursors.

The pursuit of a high surface area while maintaining high catalytic performance remains a challenge due to a trade-off relationship between these two features in some cases. In this study, mesoporous todorokite-type manganese oxide (OMS-1) nanoparticles with high specific surface areas were synthesized in one step by a new synthesis approach involving crystallization (i.e., solid-state transformation) of a precursor produced by a redox reaction between MnO4- and Mn2+ reagents. The use of a low-crystallinity precursor with small particles is essential to achieve this solid-state transformation into OMS-1 nanoparticles. The specific surface area reached up to ca. 250 m2 g-1, which is much larger than those (13-185 m2 g-1) for Mg-OMS-1 synthesized by previously reported methods including multistep synthesis or dissolution/precipitation processes. Despite ultrasmall nanoparticles, a linear correlation between the catalytic reaction rates of OMS-1 and the surface areas was observed without a trade-off relationship between particle size and catalytic performance. These OMS-1 nanoparticles exhibited the highest catalytic activity among the Mn-based catalysts tested for the oxidation of benzyl alcohol and thioanisole with molecular oxygen (O2) as the sole oxidant, including highly active ß-MnO2 nanoparticles. The present OMS-1 nanomaterial could also act as a recyclable heterogeneous catalyst for the aerobic oxidation of various aromatic alcohols and sulfides under mild reaction conditions. The mechanistic studies showed that alcohol oxidation proceeds with oxygen species caused by the solid, and the high surface area of OMS-1 significantly contributes to an enhancement of the catalytic activity for aerobic oxidation.

Effect of MnO2 Crystal Structure on Aerobic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid.

Aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) as a bioplastics monomer is efficiently promoted by a simple system based on a nonprecious-metal catalyst of MnO2 and NaHCO3. Kinetic studies indicate that the oxidation of 5-formyl-2-furancarboxylic acid (FFCA) to FDCA is the slowest step for the aerobic oxidation of HMF to FDCA over activated MnO2. We demonstrate through combined computational and experimental studies that HMF oxidation to FDCA is largely dependent on the MnO2 crystal structure. Density functional theory (DFT) calculations reveal that vacancy formation energies at the planar oxygen sites in α- and γ-MnO2 are higher than those at the bent oxygen sites. ß- and λ-MnO2 consist of only planar and bent oxygen sites, respectively, with lower vacancy formation energies. Consequently, ß- and λ-MnO2 are likely to be good candidates as oxidation catalysts. On the other hand, experimental studies reveal that the reaction rates per surface area for the slowest step (FFCA oxidation to FDCA) decrease in the order of ß-MnO2 > λ-MnO2 > γ-MnO2 ≈ α-MnO2 > δ-MnO2 > ε-MnO2; the catalytic activity of ß-MnO2 exceeds that of the previously reported activated MnO2 by three times. The order is in good agreement not only with the DFT calculation results, but also with the reduction rates per surface area determined by the H2-temperature-programmed reduction measurements for MnO2 catalysts. The successful synthesis of high-surface-area ß-MnO2 significantly improves the catalytic activity for the aerobic oxidation of HMF to FDCA.

Electronic Effect of Ruthenium Nanoparticles on Efficient Reductive Amination of Carbonyl Compounds.

Highly selective synthesis of primary amines over heterogeneous catalysts is still a challenge for the chemical industry. Ruthenium nanoparticles supported on Nb2O5 act as a highly selective and reusable heterogeneous catalyst for the low-temperature reductive amination of various carbonyl compounds that contain reduction-sensitive functional groups such as heterocycles and halogens with NH3 and H2 and prevent the formation of secondary amines and undesired hydrogenated byproducts. The selective catalysis of these materials is likely attributable to the weak electron-donating capability of Ru particles on the Nb2O5 surface. The combination of this catalyst and homogeneous Ru systems was used to synthesize 2,5-bis(aminomethyl)furan, a monomer for aramid production, from 5-(hydroxymethyl)furfural without a complex mixture of imine byproducts.

Preparation of Mesoporous Basic Oxides through Assembly of Monodispersed Mg-Al Layered Double Hydroxide Nanoparticles.

Mesoporous basic Mg-Al mixed metal oxides (MMOs) with a high surface area and large pore size have been prepared through the assembly of monodispersed layered double hydroxide nanoparticles (LDHNPs) with block copolymer templates. The particle sizes of the LDHNPs were mainly controlled by varying the concentration of tris(hydroxymethyl)aminomethane (THAM), which was used as a surface stabilizing agent. LDHNPs and micelles of a block copolymer (Pluronic F127) were assembled to form a composite. The composites were calcined to transform them into mesoporous MMOs and to remove the templates. The Brunauer-Emmett-Teller surface areas, mesopore sizes, and pore volumes increased as a result of using the templates. Moreover, the pore sizes of the mesoporous MMOs could be controlled by using LDHNPs of different sizes. The mesoporous MMOs prepared from the LDHNPs showed much higher catalytic activity than a conventional MMO catalyst for the Knövenagel condensation of ethyl cyanoacetate with benzaldehyde. The mesoporous MMO catalyst prepared using the smallest LDHNPs, about 12 nm in size, showed the highest activity. Therefore, the use of monodispersed LDHNPs and templates is effective for preparing highly active mesoporous solid base catalysts.

Photoassist-phosphorylated TiO2 as a catalyst for direct formation of 5-(hydroxymethyl)furfural from glucose.

Photo-assisted phosphorylation of an anatase TiO2 catalyst was examined to improve its catalytic performance for the direct production of 5-(hydroxymethyl)furfural (HMF), a versatile chemical platform, from glucose. In phosphorylation based on simple esterification between phosphoric acid and surface OH groups on anatase TiO2 with water-tolerant Lewis acid sites, the density of phosphates immobilized on TiO2 is limited to 2 phosphates nm-2, which limits selective HMF production. Phosphorylation of the TiO2 surface under fluorescent light irradiation increases the surface phosphate density to 50%, which is higher than the conventional limit, thus preventing the adsorption of hydrophilic glucose molecules on TiO2 and resulting in a more selective HMF production over photoassist-phosphorylated TiO2.

Recent progress in the development of solid catalysts for biomass conversion into high value-added chemicals.

In recent decades, the substitution of non-renewable fossil resources by renewable biomass as a sustainable feedstock has been extensively investigated for the manufacture of high value-added products such as biofuels, commodity chemicals, and new bio-based materials such as bioplastics. Numerous solid catalyst systems for the effective conversion of biomass feedstocks into value-added chemicals and fuels have been developed. Solid catalysts are classified into four main groups with respect to their structures and substrate activation properties: (a) micro- and mesoporous materials, (b) metal oxides, (c) supported metal catalysts, and (d) sulfonated polymers. This review article focuses on the activation of substrates and/or reagents on the basis of groups (a)-(d), and the corresponding reaction mechanisms. In addition, recent progress in chemocatalytic processes for the production of five industrially important products (5-hydroxymethylfurfural, lactic acid, glyceraldehyde, 1,3-dihydroxyacetone, and furan-2,5-dicarboxylic acid) as bio-based plastic monomers and their intermediates is comprehensively summarized.

Synthesis of α-Dawson-type silicotungstate [α-Si2W18O62]8- and protonation and deprotonation inside the aperture through intramolecular hydrogen bonds.

The design of structurally well-defined anionic molecular metal-oxygen clusters, polyoxometalates (POMs), leads to inorganic receptors with unique and tunable properties. Herein, an α-Dawson-type silicotungstate, TBA8[α-Si2W18O62]⋅3 H2O (II) that possesses a -8 charge was successfully synthesized by dimerization of a trivacant lacunary α-Keggin-type silicotungstate TBA4H6[α-SiW9O34]⋅2 H2O (I) in an organic solvent. POM II could be reversibly protonated (in the presence of acid) and deprotonated (in the presence of base) inside the aperture by means of intramolecular hydrogen bonds with retention of the POM structure. In contrast, the aperture of phosphorus-centered POM TBA6[α-P2W18O62]⋅H2O (III) was not protonated inside the aperture. The density functional theory (DFT) calculations revealed that the basicities and charges of internal µ3-oxygen atoms were increased by changing the central heteroatoms from P(5+) to Si(4+), thereby supporting the protonation of II. Additionally, II showed much higher catalytic performance for the Knoevenagel condensation of ethyl cyanoacetate with benzaldehyde than I and III.

A basic germanodecatungstate with a -7 charge: efficient chemoselective acylation of primary alcohols.

The synthesis of highly negatively charged polyoxometalates with electrically and structurally controlled uniform basic sites can lead to the unique base catalysis. In this work, a γ-Keggin germanodecatungstate, [γ-HGeW10O36](7-) (A), having a -7 charge was, for the first time, successfully synthesized by the reaction of [γ-H2GeW10O36](6-) with one equivalent of [(n-C4H9)4N]OH under non-aqueous conditions. The activities of germanodecatungstates for base-catalyzed reactions dramatically increased with increase in the number negative charges from -6 to -7. In the presence of A, various combinations of acylating agents and primary alcohols including those with acid-sensitive functional groups chemoselectively gave the desired acylated products in high yields even under the stoichiometric conditions.

Synthesis and structural characterization of inorganic-organic-inorganic hybrids of dipalladium-substituted γ-Keggin silicodecatungstates.

Three inorganic-organic-inorganic hybrids of dipalladium-substituted γ-Keggin silicodecatungstates with organic linkers of different lengths, TBA8[{(γ-H2SiW10O36Pd2)(O2C(CH2)nCO2)}2] (n = 1 (II), 3 (III), and 5 (IV), TBA = [(n-C4H9)4N](+)), were synthesized by exchange of the acetate ligands in TBA4[γ-H2SiW10O36Pd2(OAc)2] (ITBA) with malonic, glutaric, and pimelic acids, respectively. The X-ray crystallographic analysis of II, IIIA (IIIA: III with DCE, DCE = 1,2-dichloroethane), and IVA (IVA: IV with 10DCE) revealed that the anion parts of II, IIIA, and IVA were inorganic-organic-inorganic hybrids composed of two dipalladium-substituted γ-Keggin silicodecatungstates connected by two dicarboxylate ligands. In the crystal structure of IVA, 10 DCE molecules per polyanion were present in the vicinity of polyanions. Compound IVB (IVB: IV with 0.2DCE) was obtained by the evacuation of IVA. The DCE sorption-desorption isotherms of IVB showed that the amount of DCE sorbed was saturated at 10.5 mol mol(-1), of which the amount was close to that (10 mol mol(-1)) of crystallographically assigned DCE molecules. In the DCE sorption-desorption isotherms, a low-pressure hysteresis was observed probably because of hydrogen-bonding interaction between DCE molecules and polyanions. The powder X-ray diffraction (XRD) pattern of IVA changed with decrease in the relative DCE vapor pressure to form IVC (IVC: IV with 0.7DCE) at P/P0 = 0.0. The in situ powder XRD study showed reversible structure transformation between IVA and IVC driven by the sorption-desorption of DCE.

Nanosized Ti-Based Perovskite Oxides as Acid-Base Bifunctional Catalysts for Cyanosilylation of Carbonyl Compounds.

The development of effective solid acid-base bifunctional catalysts remains a challenge because of the difficulty associated with designing and controlling their active sites. In the present study, highly pure perovskite oxide nanoparticles with d0-transition-metal cations such as Ti4+, Zr4+, and Nb5+ as B-site elements were successfully synthesized by a sol-gel method using dicarboxylic acids. Moreover, the specific surface area of SrTiO3 was increased to 46 m2 g-1 by a simple procedure of changing the atmosphere from N2 to air during calcination of an amorphous precursor. The resultant SrTiO3 nanoparticles showed the highest catalytic activity for the cyanosilylation of acetophenone with trimethylsilyl cyanide (TMSCN) among the tested catalysts not subjected to a thermal pretreatment. Various aromatic and aliphatic carbonyl compounds were efficiently converted to the corresponding cyanohydrin silyl ethers in good-to-excellent yields. The present system was applicable to a larger-scale reaction of acetophenone with TMSCN (10 mmol scale), in which 2.06 g of the analytically pure corresponding product was isolated. In this case, the reaction rate was 8.4 mmol g-1 min-1, which is the highest rate among those reported for heterogeneous catalyst systems that do not involve a pretreatment. Mechanistic studies, including studies of the catalyst effect, Fourier transform infrared spectroscopy, and temperature-programmed desorption measurements using probe molecules such as pyridine, acetophenone, CO2, and CHCl3, and the poisoning effect of pyridine and acetic acid toward the cyanosilylation, revealed that moderate-strength acid and base sites present in moderate amounts on SrTiO3 most likely enable SrTiO3 to act as a bifunctional acid-base solid catalyst through cooperative activation of carbonyl compounds and TMSCN. This bifunctional catalysis through SrTiO3 resulted in high catalytic performance even without a heat pretreatment, in sharp contrast to the performance of basic MgO and acidic TiO2 catalysts.

Air-Stable Ni Catalysts Prepared by Liquid-Phase Reduction Using Hydrosilanes for Reactions with Hydrogen.

The liquid-phase reduction method for the preparation of metal nanoparticles (NPs) by the reduction of metal salts or metal complexes in a solvent with a reducing agent is widely used to prepare Ni NPs that exhibit high catalytic activity in various organic transformations. Intensive research has been conducted on control of the morphology and size of Ni NPs by the addition of polymers and long-chain compounds as protective agents; however, these agents typically cause a decrease in catalytic activity. Here, we report on the preparation of Ni NPs using hydrosilane (Ni-Si) as a reducing agent and a size-controlling agent. The substituents on silicon can control not only the size but also the crystal phase of the Ni NPs. The prepared Ni NPs exhibited high catalytic performance for the hydrogenation of unsaturated compounds, aromatics, and heteroaromatics to give the corresponding hydrogenated products in high yields. The unique feature of Ni catalysts prepared by the hydrosilane-assisted method is that the catalysts can be handled under air as opposed to conventional Ni catalysts such as Raney Ni. Characterization studies indicated that the surface hydroxide was reduced under the catalytic reaction conditions with H2 at around 100 °C and with the assistance of organosilicon compounds deposited on the catalyst surface. The hydrosilane-assisted method presented here could be applied to the preparation of supported Ni catalysts (Ni-Si/support). The interaction between the Ni NPs and a metal oxide support enabled the direct amination of alcohols with ammonia to afford the primary amine selectively.

A redox-active inorganic crown ether based on a polyoxometalate capsule.

Cation-uptake has been long researched as an important topic in materials science. Herein we focus on a molecular crystal composed of a charge-neutral polyoxometalate (POM) capsule [MoVI72FeIII30O252(H2O)102(CH3CO2)15]3+ encapsulating a Keggin-type phosphododecamolybdate anion [α-PMoVI12O40]3-. Cation-coupled electron-transfer reaction occurs by treating the molecular crystal in an aqueous solution containing CsCl and ascorbic acid as a reducing reagent. Specifically, multiple Cs+ ions and electrons are captured in crown-ether-like pores {MoVI3FeIII3O6}, which exist on the surface of the POM capsule, and Mo atoms, respectively. The locations of Cs+ ions and electrons are revealed by single-crystal X-ray diffraction and density functional theory studies. Highly selective Cs+ ion uptake is observed from an aqueous solution containing various alkali metal ions. Cs+ ions can be released from the crown-ether-like pores by the addition of aqueous chlorine as an oxidizing reagent. These results show that the POM capsule functions as an unprecedented "redox-active inorganic crown ether", clearly distinguished from the non-redox-active organic counterpart.

Palladium(II) containing γ-Keggin silicodecatungstate that efficiently catalyzes hydration of nitriles.

A mixture of Pd(OAc)(2) and TBA(4)[γ-SiW(10)O(34)(H(2)O)(2)] (TBA-SiW10, TBA = [(n-C(4)H(9))(4)N](+)) showed high catalytic activities for hydration of various kinds of structurally diverse nitriles including aromatic, aliphatic, heteroaromatic, and double bond-containing ones. For hydration of 3-cyanopyridine, the turnover frequency was 860 h(-1), and the turnover number reached up to 670. A dipalladium-substituted γ-Keggin silicodecatungstate, [γ-H(2)SiW(10)O(36)Pd(2)(OAc)(2)](4-) (I), was successfully synthesized by the reaction of [γ-SiW(10)O(34)(H(2)O)(2)](4-) with Pd(OAc)(2) in a mixed solvent of acetone and water. The crystal structure of I was a monomeric, dipalladium-substituted, γ-Keggin silicodecatungstate with bidentate acetate ligands. Compound I showed similar activities and selectivities to those of a simple mixture of Pd(OAc)(2) and TBA-SiW10. The kinetic, mechanistic, and density functional theory calculation studies show that the dipalladium site plays an important role in the present hydration, and the nucleophilic attack of a hydroxide or water to the nitrile carbon atom is included in the rate-determining step.

Efficient [WO4](2-)-catalyzed chemical fixation of carbon dioxide with 2-aminobenzonitriles to quinazoline-2,4(1H,3H)-diones.

A simple monomeric tungstate, TBA(2)[WO(4)] (I, TBA = tetra-n-butylammonium), could act as an efficient homogeneous catalyst for chemical fixation of CO(2) with 2-aminobenzonitriles to quinazoline-2,4(1H,3H)-diones. Various kinds of structurally diverse 2-aminobenzonitriles could be converted into the corresponding quinazoline-2,4(1H,3H)-diones in high yields at atmospheric pressure of CO(2). Reactions of inactive 2-amino-4-chlorobenzonitrile and 2-amino-5-nitrobenzonitrile at 2 MPa of CO(2) also selectively proceeded. The present system was applicable to a g-scale reaction of 2-amino-5-fluorobenzonitrile (10 mmol scale) with CO(2) and 1.69 g of analytically pure quinazoline-2,4(1H,3H)-dione could be isolated. In this case, the turnover number reached up to 938 and the value was the highest among those reported for base-mediated systems so far. NMR spectroscopies showed formation of the corresponding carbamic acid through the simultaneous activation of both 2-aminobenzonitirile and CO(2) by I. Kinetic and computational studies revealed that I plays an important role in conversion of the carbamic acid into the product.

Reversible deprotonation and protonation behaviors of a tetra-protonated γ-Keggin silicodecatungstate.

The potentiometric titration of a γ-Keggin tetra-protonated silicodecatungstate, [γ-SiW(10)O(34)(H(2)O)(2)](4-) (H(4)·I), with TBAOH (TBA = [(n-C(4)H(9))(4)N](+)) showed inflection points at 2 and 3 equiv of TBAOH. The (1)H, (29)Si, and (183)W NMR data suggested that the in situ formation of tri-, doubly-, and monoprotonated silicodecatungstates, [γ-SiW(10)O(34)(OH)(OH(2))](5-) (H(3)·I), [γ-SiW(10)O(34)(OH)(2)](6-) (H(2)·I), and [γ-SiW(10)O(35)(OH)](7-) (H·I), with C(1), C(2v), and C(2) symmetries, respectively. Single crystals of TBA(6)·H(2)·I suitable for the X-ray structure analysis were successfully obtained and the anion part was a monomeric γ-Keggin divacant silicodecatungstate with two protonated bridging oxygen atoms. Compounds H(3)·I, H(2)·I, and H·I were reversibly monoprotonated to form H(4)·I, H(3)·I, and H(2)·I, respectively.

Strategic design and refinement of Lewis acid-base catalysis by rare-earth-metal-containing polyoxometalates.

Efficient polyoxometalate (POM)-based Lewis acid-base catalysts of the rare-earth-metal-containing POMs (TBA(6)RE-POM, RE = Y(3+), Nd(3+), Eu(3+), Gd(3+), Tb(3+), or Dy(3+)) were designed and synthesized by reactions of TBA(4)H(4)[γ-SiW(10)O(36)] (TBA = tetra-n-butylammonium) with RE(acac)(3) (acac = acetylacetonato). TBA(6)RE-POM consisted of two silicotungstate units pillared by two rare-earth-metal cations. Nucleophilic oxygen-enriched surfaces of negatively charged POMs and the incorporated rare-earth-metal cations could work as Lewis bases and Lewis acids, respectively. Consequently, cyanosilylation of carbonyl compounds with trimethylsilyl cyanide ((TMS)CN) was efficiently promoted in the presence of the rare-earth-metal-containing POMs via the simultaneous activation of coupling partners on the same POM molecules. POMs with larger metal cations showed higher catalytic activities for cyanosilylation because of the higher activation ability of C═O bonds (higher Lewis acidities) and sterically less hindered Lewis acid sites. Among the POM catalysts examined, the neodymium-containing POM showed remarkable catalytic performance for cyanosilylation of various kinds of structurally diverse ketones and aldehydes, giving the corresponding cyanohydrin trimethylsilyl ethers in high yields (13 substrates, 94-99%). In particular, the turnover frequency (714,000 h(-1)) and the turnover number (23,800) for the cyanosilylation of n-hexanal were of the highest level among those of previously reported catalysts.

Chemo- and regioselective direct hydroxylation of arenes with hydrogen peroxide catalyzed by a divanadium-substituted phosphotungstate.

Peroxide in, phenol out: The catalyst [γ-PW(10)O(38)V(2)(µ-OH)(2)](3-) showed high activity in the hydroxylation of various aromatic compounds with aqueous H(2)O(2). The system was regioselective, producing para-phenols from monosubstituted benzene derivatives. Furthermore, alkylarenes with reactive side-chain C sp 3-H bonds could be chemoselectively hydroxylated without significant formation of side-chain oxygenated products.