Concerted Hydrosilylation Catalysis by Silica-Immobilized Cyclic Carbonates and Surface Silanols.

Developing a method for creating a novel catalysis of organic molecules is essential because of the growing interest in organocatalysis. In this study, we found that cyclic carbonates immobilized on a nonporous or mesoporous silica support showed catalytic activity for hydrosilylation, which was not observed for the free cyclic carbonates, silica supports, or their physical mixture. Analysis of the effects of linker lengths and pore sizes on the catalytic activity and carbonate C=O stretching frequency revealed that the proximity of carbonates and surface silanols was crucial for synergistic hydrosilylation catalysis. A carbonate and silanol concertedly activated the silane and aldehyde for efficient hydride transfer. Density functional theory calculations on a model reaction system demonstrated that both the carbonate and silanol contributed to the stabilization of the transition state of hydride transfer, which resulted in a reasonable barrier height of 16.8 kcal mol-1. Furthermore, SiO2/carbonate(C4) enabled the hydrosilylation of an aldehyde with an amino group without catalyst poisoning, owing to the weak acidity of surface silanols, in sharp contrast to previously developed acid catalysts. This study demonstrates that immobilization on a solid support can convert inactive organic molecules into active and heterogeneous organocatalysts.

Facile formation of barium titanium oxyhydride on a titanium hydride surface as an ammonia synthesis catalyst.

Oxyhydrides are promising compounds as supports for ammonia synthesis catalysts because they suppress hydrogen poisoning on the catalyst surface and enhance the ammonia synthesis activity. Herein, we developed a facile method for preparing BaTiO2.5H0.5, a perovskite oxyhydride, on a TiH2 surface via the conventional wet impregnation method using TiH2 and Ba hydroxide. Scanning electron microscopy and high-angle annular dark-field scanning transmission electron microscopy observations revealed that BaTiO2.5H0.5 crystallized as nanoparticles of ca. 100-200 nm on the TiH2 surface. The Ru-loaded catalyst Ru/BaTiO2.5H0.5-TiH2 exhibited 2.46 times higher ammonia synthesis activity (3.05 mmol-NH3 g-1 h-1 at 400 °C) than the benchmark Ru catalyst Ru-Cs/MgO (1.24 mmol-NH3 g-1 h-1 at 400 °C) because of the suppression of hydrogen poisoning. The analysis of reaction orders showed that the effect of suppressing hydrogen poisoning on Ru/BaTiO2.5H0.5-TiH2 was equivalent to that of the reported Ru/BaTiO2.5H0.5 catalyst, thus supporting the formation of BaTiO2.5H0.5 perovskite oxyhydride. This study demonstrated that the selection of appropriate raw materials facilitates the formation of BaTiO2.5H0.5 oxyhydride nanoparticles on the TiH2 surface using the conventional synthesis method.

Method for evaluating the performance of catalytic reactions using renewable-energy-derived materials.

Hydrogen produced by electrolysis using electricity derived from renewable energy sources has a fluctuating supply. However, conventional catalyst evaluation methods cannot evaluate catalyst synthesis assuming a fluctuating feedstock. This paper investigates a simple screening method for catalysts that can be used for renewable energy by using a combination of three catalyst evaluation methods: Light-off Performance, equilibrium achievement degree, and maximum ammonia concentration. We examined the combination of evaluation methods and trends for each element, and finally concluded that a three-axis graph combining the three is the easiest graph to obtain the information necessary for catalyst screening intuitively rather than quantitatively.

Rhodium-Iodide Complex on a Catalytically Active SiO2 Surface for One-Pot Hydrosilylation-CO2 Cycloaddition.

In this study, a novel Rh-iodide complex was synthesized through a surface reaction between an immobilized Rh cyclooctadiene complex and alkylammonium iodide (N+ I- ) on SiO2 . In the presence of ammonium cations, the SiO2 -supported Rh-iodide complex could be effectively used for the one-pot synthesis of various silylcarbonate derivatives starting from epoxy olefins, hydrosilanes, and CO2 . The maximum turnover numbers (TONs) for the hydrosilylation reaction and the CO2 cycloaddition were 7600 (Rh) and 130 (N+ I- ), respectively. The catalyst exhibited much higher performance for hydrosilylation than solely the Rh complex on SiO2 . The mechanism of the Rh-catalyzed hydrosilylation reaction and the local structure of Rh, which is affected by the co-immobilized N+ I- , were investigated by using Rh and I K-edge XAFS and XPS. Analysis of the XAFS profiles indicated the presence of a Rh-I bond. The Rh unit was in its electron-rich state. Curve-fitting analysis of the Rh K-edge EXAFS profiles suggests dissociation of the cycloocta-1,5-diene (COD) ligand from the Rh center. Results from spectroscopic and kinetic analyses revealed that the high activity of the catalyst (during hydrosilylation) could be attributed to a decrease in steric hindrance and the electron-rich state of the Rh. The decrease in the steric hindrance could be attributed to the absence of COD, and the electron-rich state promoted the oxidative addition of Si-H. To the best of our knowledge, this is the first example of a one-pot silylcarbonate synthesis as well as a determination of a novel surface Rh-iodide complex and its catalysis.

CO2 conversion to formamide using a fluoride catalyst and metallic silicon as a reducing agent.

Metallic silicon could be an inexpensive, alternative reducing agent for CO2 functionalization compared to conventionally used hydrogen or hydrosilanes. Here, metallic silicon recovered from solar panel production is used as a reducing agent for formamide synthesis. Various amines are converted to their corresponding amides with CO2 and H2O via an Si-H intermediate species in the presence of a catalytic amount of tetrabutylammonium fluoride. The reaction system exhibits a wide substrate scope for formamide synthesis. Spectroscopic analysis, including in situ Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), N2 adsorption/desorption analyses, and isotopic experiments reveal that the fluoride catalyst effectively oxidizes Si atoms on both surface and interior of the powdered silicon particles. The solid recovered after catalysis contained mesopores with a high surface area. This unique behavior of the fluoride catalyst in the presence of metallic silicon may be extendable to other reductive reactions, including those with complex substrates. Therefore, this study presents a potential strategy for the efficient utilization of abundant resources.

Dehydrogenative Coupling of Alkanes and Benzene Enhanced by Slurry-Phase Interparticle Hydrogen Transfer.

The dehydrogenative coupling reaction of alkanes and benzene has attracted attention as a method of direct conversion of alkanes to raw materials for useful chemical products. Here, we report the first combined catalyst system composed of hydrotalcite-supported palladium and solid acid aluminum-exchanged montmorillonite for the direct alkylation of benzene promoted by slurry-phase interparticle hydrogen transfer at 150 °C. The combination of the two catalytic particles showed excellent activity and achieved the maximum benzene conversion of 21% and target product selectivity of 84% in the reaction of n-heptane and benzene. Our results, thus, provide a feasible strategy to design efficient liquid-phase reaction systems employing simple physical mixing of two catalytic particles.

The effect of a ruthenium precursor on the low-temperature ammonia synthesis activity over Ru/CeO2.

Catalysts supported on CeO2 were prepared using various Ru precursors. The H2-TPR profile of the catalyst was obtained beginning at -70 °C for the first time, and a previously unreported reduction peak was observed at approximately 50 °C. The lower peak temperature was associated with a higher ammonia synthesis activity.

A Resin-Supported Formate Catalyst for the Transformative Reduction of Carbon Dioxide with Hydrosilanes.

A heterogeneous formate anion catalyst for the transformative reduction of carbon dioxide (CO2 ) based on a polystyrene and divinylbenzene copolymer modified with alkylammonium formate was prepared from a widely available anion exchange resin. The catalyst preparation was easy and the characterization was carried out by using elemental analysis, Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and solid-state 13 C cross-polarization/magic-angle spinning nuclear magnetic resonance (13 C CP/MAS NMR) spectroscopy. The catalyst displayed good catalytic activity for the direct reduction of CO2 with hydrosilanes, tunably yielding silylformate or methoxysilane products depending on the hydrosilanes used. The catalyst was also active for the reductive insertion of CO2 into both primary and secondary amines. The catalytic activity of the resin-supported formate can be predicted from the FTIR spectra of the catalyst, probably because of the difference in the ionic interaction strength between the supported alkylammonium cations and formate anions. The ion pair density is thought to influence the catalytic activity, as shown by the elemental and solid-state 13 C NMR analyses.

Direct Alkylation of Benzene at Lower Temperatures in the Liquid Phase: Catalysis by Montmorillonites as Noble-Metal-Free Solid Acids.

Alkylated benzenes are widely used as raw materials for the production of a variety of chemical compounds. Conventionally, they are obtained by the Friedel-Crafts reaction between alkyl halides and benzene. In this study, the synthesis of halogen-free alkylated benzenes was made possible by the direct alkylation of benzene with alkanes using montmorillonites as noble-metal-free solid acid catalysts. The direct alkylation of benzene with n-heptane was performed at 150 °C. Aluminum-exchanged montmorillonite showed the highest yield of the target C-7 alkylated products (Ph-C7) compared with other homogeneous and heterogeneous acid catalysts: 1.8 % conversion of benzene with 58 % selectivity in 16 h. The montmorillonite catalyst system was applied to other linear and cyclic alkanes to give the corresponding alkylated products with good selectivities.

Organic bases catalyze the synthesis of urea from ammonium salts derived from recovered environmental ammonia.

Ammonia from sewage and livestock manure is a major environmental pollutant. To consume environmental ammonia, we investigated the organic base-catalyzed synthesis of urea. 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) catalyzes the conversion of ammonium carbamate to urea in 35% yield at 100 °C. Moreover, DBU also converts other ammonium salts into urea. A mechanism that involves nucleophilic attack of ammonia following ion exchange is proposed.

Multifunctional Catalytic Surface Design for Concerted Acceleration of One-Pot Hydrosilylation-CO2 Cycloaddition.

Silica-supported Rh-ammonium iodide catalyst showed high performance for hydrosilylation-CO2 cycloaddition reaction sequences. The catalyst was prepared by surface grafting of Rh and the silane-coupling reaction of the ammonium iodide moiety. The acceleration of each catalytic reaction was realized due to the concerted catalysis between Rh species, immobilized organic functions, and surface Si-OH groups. As a result, good to excellent yields of silyl carbonates were obtained from epoxyolefins, hydrosilanes, and CO2 under mild reaction conditions.

Development of an Iridium-Based Catalyst for High-Pressure Evolution of Hydrogen from Formic Acid.

A highly efficient and recyclable Ir catalyst bearing a 4,7-dihydroxy-1,10-phenanthroline ligand was developed for the evolution of high-pressure H2 gas (>100 MPa), and a large amount of atmospheric pressure H2 gas (>120 L), over a long term (3.5 months). The reaction proceeds through the dehydrogenation of highly concentrated aqueous formic acid (FA, 40 vol %, 10 mol L-1 ) at 80 °C using 1 µmol of catalyst, and a turnover number (TON) of 5 000 000 was calculated. The Ir catalyst precipitated after the reaction owing to its pH-dependent solubility in water, and 94 mol % was recovered by filtration. Thus, it can be treated and recycled like a heterogeneous catalyst. The catalyst was successfully recycled over 10 times for highpressure FA dehydrogenation at 22 MPa without any treatment or purification.

CO2 Hydrogenation Catalyzed by Iridium Complexes with a Proton-Responsive Ligand.

The catalytic cycle for the production of formic acid by CO2 hydrogenation and the reverse reaction have received renewed attention because they are viewed as offering a viable scheme for hydrogen storage and release. In this Forum Article, CO2 hydrogenation catalyzed by iridium complexes bearing sophisticated N^N-bidentate ligands is reported. We describe how a ligand containing hydroxy groups as proton-responsive substituents enhances the catalytic performance by an electronic effect of the oxyanions and a pendent-base effect through secondary coordination sphere interactions. In particular, [(Cp*IrCl)2(TH2BPM)]Cl2 (Cp* = pentamethylcyclopentadienyl; TH2BPM = 4,4',6,6'-tetrahydroxy-2,2'-bipyrimidine) enormously promotes the catalytic hydrogenation of CO2 in basic water by these synergistic effects under atmospheric pressure and at room temperature. Additionally, newly designed complexes with azole-type ligands were applied to CO2 hydrogenation. The catalytic efficiencies of the azole-type complexes were much higher than that of the unsubstituted bipyridine complex [Cp*Ir(bpy)(OH2)]SO4. Furthermore, the introduction of one or more hydroxy groups into ligands such as 2-pyrazolyl-6-hydroxypyridine, 2-pyrazolyl-4,6-dihydroxypyrimidine, and 4-pyrazolyl-2,6-dihydroxypyrimidine enhanced the catalytic activity. It is clear that the incorporation of additional electron-donating functionalities into proton-responsive azole-type ligands is effective for promoting further enhanced hydrogenation of CO2.

Formic acid dehydrogenation with bioinspired iridium complexes: a kinetic isotope effect study and mechanistic insight.

Highly efficient hydrogen generation from dehydrogenation of formic acid is achieved by using bioinspired iridium complexes that have hydroxyl groups at the ortho positions of the bipyridine or bipyrimidine ligand (i.e., OH in the second coordination sphere of the metal center). In particular, [Ir(Cp*)(TH4BPM)(H2 O)]SO4 (TH4BPM: 2,2',6,6'-tetrahydroxyl-4,4'-bipyrimidine; Cp*: pentamethylcyclopentadienyl) has a high turnover frequency of 39 500 h(-1) at 80 °C in a 1 M aqueous solution of HCO2 H/HCO2 Na and produces hydrogen and carbon dioxide without carbon monoxide contamination. The deuterium kinetic isotope effect study clearly indicates a different rate-determining step for complexes with hydroxyl groups at different positions of the ligands. The rate-limiting step is ß-hydrogen elimination from the iridium-formate intermediate for complexes with hydroxyl groups at ortho positions, owing to a proton relay (i.e., pendent-base effect), which lowers the energy barrier of hydrogen generation. In contrast, the reaction of iridium hydride with a proton to liberate hydrogen is demonstrated to be the rate-determining step for complexes that do not have hydroxyl groups at the ortho positions.

Preparation of catalytically active, covalent α-polylysine-enzyme conjugates via UV/vis-quantifiable bis-aryl hydrazone bond formation.

Covalent UV/vis-quantifiable bis-aryl hydrazone bond formation was investigated for the preparation of conjugates between α-poly-d-lysine (PDL) and either α-chymotrypsin (α-CT) or horseradish peroxidase (HRP). PDL and the enzymes were first modified via free amino groups with the linking reagents succinimidyl 6-hydrazinonicotinate acetone hydrazone (S-HyNic, at pH 7.6) and succinimidyl 4-formylbenzoate (S-4FB, at pH 7.2), respectively. The modified PDL and enzymes were then conjugated at pH 4.7, whereby polymer chains carrying several enzymes were obtained. Kinetics of the bis-aryl hydrazone bond formation was investigated spectrophotometrically at 354 nm. Retention of the enzymatic activity after conjugate formation was confirmed by using the substrates N-succinimidyl-l-Ala-l-Ala-l-Pro-l-Phe-p-nitroanilide (for α-CT) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS, for HRP). Thus, not only a mild and efficient preparation and convenient quantification of a conjugate between the polycationic α-polylysine and enzymes could be shown, but also the complete preservation of the enzymatic activity.

An upside down view of cholesterol's condensing effect: does surface occupancy play a role?

The condensing action of cholesterol has been compared with that of a structural isomer having its hydroxyl group located at the C-25 position (i.e., 25-OH'), that is, an isomer favoring an "upside down" orientation in lipid membranes. Surface pressure-area isotherms of mixed monolayers made from 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC)/cholesterol and DMPC/25-OH' have established that 25-OH' has a weaker condensing effect than cholesterol. Nearest-neighbor recognition measurements in liposomes made from 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) have also shown that 25-OH' has a weaker condensing effect in the physiologically relevant fluid bilayer state. These findings provide support for surface occupancy playing a role in the condensing action of cholesterol.

Simultaneous anomalous reflection and quartz-crystal microbalance measurements of protein bindings on a gold surface.

Protein bindings onto a gold surface were detected simultaneously by QCM (delta F(water)) and anomalous reflection (deltaR) of gold on the same surface in aqueous solutions; the obtained delta F(water)/deltaR values correlated with surface areas and viscosity of proteins.