Highly Efficient Iridium-Iron-Molybdenum Catalysts Condensed on Boron Nitride for Biomass-Derived Diols' Hydrogenolysis to Secondary Monoalcohols.

A trade-off of activity-selectivity exists in primary C-O hydrogenolysis of biomass-derived diols to secondary alcohols over bimetallic catalysts, especially the combination of noble metal and early transition metal in the metallic state and metal oxide state, respectively. Herein, the combination of high surface concentration of boron nitride (BN)-supported metals and the addition of Mo as third metal broke the trade-off. High yields (>50%) of secondary alcohols were obtained with robust productivity up to 25-fold based on Ir over Ir-Fe0.13-Mo0.08/BN (Ir = 20 wt %, Fe/Ir = 0.13, Mo/Ir = 0.08) than previously reported Ir-Fe catalysts. In contrast, simply increasing the loading amount of Ir-Fe catalysts or the addition of Mo species only enhanced the productivity by <2-4-fold. Various characterizations showed that large Ir loading enables the formation of condensed nanostructures (∼2 nm) on the BN support, which further alloy with Mo and Fe to form an face centred cubic (fcc)-type trimetallic alloy with surface enrichment of Fe. On the other hand, in Ir-Fe0.25-Mo0.08/BN with lower Ir (5 wt %) and lower Ir-based activity, the Mo species were rather bound on the support surface possibly as the MoBx state. These structures were formed by simple impregnation and reduction with H2 at the reaction temperature (453 K). The high activity of Ir-Fe0.13-Mo0.08/BN (20 wt % Ir) is derived from two aspects: (1) the formation of condensed nanostructures (∼2 nm) exposing more active sites and (2) alloying with Mo to modify the electronic state of Ir to enhance the H2 activation ability, as shown by the decreased Ea (82-84 → 67 kJ mol-1).

Formation of paired Ga sites in CHA-type zeolite frameworks via a transcription-induced method.

Paired Ga sites represented by the Ga-O-Si-O-Ga sequence were firstly formed intentionally in CHA-type zeolite frameworks via the transcription of pre-formed paired Ga species in a Ga-rich amorphous silica-gallia under seed-assisted hydrothermal conditions. Such paired Ga sites behaved as ion-exchange sites for capturing divalent cation, Co2+.

Direct Esterification of Alkylcarbamic Acids with Alcohols over CeO2 Catalyst.

Alkylcarbamic acids, which are easily produced via chemical absorption of CO2 into amines, have a great potential to be substrates for producing value-added chemicals. In this research, the esterification of various alkylcarbamic acids with alcohols into alkyl N-alkylcarbamates was demonstrated by using a heterogeneous catalyst as well as the corresponding amine additives. In the model reaction, the esterification of benzylcarbamic acid (BZA-CA) and methanol (MeOH), the target product of methyl N-benzylcarbamate was obtained in 64 % CO2 -based yield at 413 K in 12 h over a CeO2 catalyst, which also exhibited good reusability. In this catalytic system, the corresponding amine additive (i. e., benzylamine for BZA-CA) had the important role in the improvement of CO2 -moiety-based balance, allowing the precise kinetic study, in contrast to the cases without such additive. The detailed kinetic study on the target catalytic system and control systems suggested that BZA-CA underwent the esterification by MeOH directly. The current catalytic system using the combination of CeO2 catalyst and corresponding amine additive was also demonstrated to be applicable to the synthesis of alkyl N-alkylcarbamates from alkylcarbamic acids and alcohols with short, linear alkyl chains (≤C3 ).

Comparative Study between 2-Furonitrile and 2-Cyanopyridine as Dehydrants in Direct Synthesis of Dialkyl Carbonates from CO2 and Alcohols over Cerium Oxide Catalyst.

The shift of equilibrium by removing water with nitrile dehydrants is crucial for CeO2 -catalyzed synthesis of dialkyl carbonates from CO2 and alcohols. Two nitriles - 2-cyanopyridine and 2-furonitrile - were previously found as effective dehydrants, yet their detailed comparison as well as exploration of potential of 2-furonitrile remain insufficient. Herein, the performance of 2-cyanopyridine and 2-furonitrile was compared in the synthesis of various dialkyl carbonates. 2-furonitrile was found to be superior to 2-cyanopyridine in the synthesis of dialkyl carbonates from CO2 and bulky or long-chain (≥C3) alcohols. Namely, the yield of diisopropyl carbonate (up to 50 %) achieved using CeO2 and 2-furonitrile is comparable to or even higher than previously reported ones. Meanwhile, 2-cyanopyridine acted as a better dehydrant than 2-furonitrile in the synthesis of dimethyl carbonate and diethyl carbonate. The adsorption experiments and density functional theory calculations have indicated that the better performance of 2-furonitrile compared to 2-cyanopyridine in the synthesis of dialkyl carbonates from bulky or long-chain alcohols is due to the weaker interaction of 2-furonitrile with the CeO2 surface. Such weak interaction of 2-furonitrile offers a larger reaction field on the catalyst surface for both CO2 and alcohols.

Hydrodeoxygenation of Oxygen-Containing Aromatic Plastic Wastes to Liquid Organic Hydrogen Carriers.

To address the global plastic pollution issues and the challenges of hydrogen storage and transportation, we report a system, based on the hydrodeoxygenation (HDO) of oxygen-containing aromatic plastic wastes, from which organic hydrogen carriers (LOHCs) can be derived. We developed a catalytic system comprised of Ru-ReOx /SiO2 +HZSM-5 for direct HDO of polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyphenylene oxide (PPO), and their mixtures, to cycloalkanes as LOHCs, with high yields up to 99 %, under mild reaction conditions. The theoretical hydrogen storage capacity reaches ca. 5.74 wt%. The reaction pathway involves depolymerization of PC into C15 aromatics and C15 monophenols by direct hydrogenolysis of the C-O bond between the benzene ring and ester group, and subsequent parallel hydrogenation of C15 aromatics and HDO of C15 monophenols. HDO of cyclic alcohol is the rate-determining step. The active site is Ru metallic nanoparticles with partially covered ReOx species. The excellent performance is attributed to the synergetic effect of oxophilic ReOx species and Ru metallic sites for C-O hydrogenolysis and hydrogenation, and the promotion effect of HZSM-5 for dehydration of cyclic alcohol. The highly efficient and stable dehydrogenation of cycloalkanes over Pt/γ-Al2 O3 confirms that HDO products can act as LOHCs.

Hydrogenation of n-octanoic acid over the MoPt alloy of Mo-Pt/SiO2 catalyst under solvent-free conditions.

SiO2-Supported bimetallic Mo and Pt worked as an effective heterogeneous catalyst for hydrogenation of n-octanoic acid at a low temperature of 373 K in the absence of solvent, providing 78% yield of hydrogenated products (62% yield of 1-octanol and 32% yield of octyl octanoate). Based on the catalyst characterization, MoPt alloy (Mo/Pt = 1) was formed by high-temperature reduction and was proposed to be the active site for the reaction.

Porous nanographene formation on γ-alumina nanoparticles via transition-metal-free methane activation.

γ-Al2O3 nanoparticles promote pyrolytic carbon deposition of CH4 at temperatures higher than 800 °C to give single-walled nanoporous graphene (NPG) materials without the need for transition metals as reaction centers. To accelerate the development of efficient reactions for NPG synthesis, we have investigated early-stage CH4 activation for NPG formation on γ-Al2O3 nanoparticles via reaction kinetics and surface analysis. The formation of NPG was promoted at oxygen vacancies on (100) surfaces of γ-Al2O3 nanoparticles following surface activation by CH4. The kinetic analysis was well corroborated by a computational study using density functional theory. Surface defects generated as a result of surface activation by CH4 make it kinetically feasible to obtain single-layered NPG, demonstrating the importance of precise control of oxygen vacancies for carbon growth.

Deoxydehydration of Biomass-Derived Polyols Over Silver-Modified Ceria-Supported Rhenium Catalyst with Molecular Hydrogen.

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 a 1,3-butadiene yield of up to 90 % under "solvent-free" conditions. This catalyst is applicable to other substrates such as methyl glycosides (methyl α-fucopyranoside: 91 % yield of DODH product; methyl ß-ribofuranoside: 88 % yield), which were difficult to be converted to the DODH products over the DODH catalysts reported previously. ReOx -Ag/CeO2 was reused 3 times without a decrease of activity or selectivity after calcination as regeneration. Although the transmission electron microscopy energy-dispersive X-ray spectroscopy and X-ray absorption fine structure analyses showed that Re species were highly dispersed and Ag was present as metal particles with various sizes from well-dispersed species (<1 nm) to around 5 nm particles, the catalysts prepared from size-controlled Ag nanoparticles showed similar performance, indicating that the catalytic performance is insensitive to the Ag particle size.

CeO2-Catalyzed Synthesis of 2-Imidazolidinone from Ethylenediamine Carbamate.

CeO2 acted as an effective and reusable heterogeneous catalyst for the direct synthesis of 2-imidazolidinone from ethylenediamine carbamate (EDA-CA) without further addition of CO2 in the reaction system. 2-Propanol was the best solvent among the solvents tested from the viewpoint of selectivity to 2-imidazolidinone, and the use of an adequate amount of 2-propanol provided high conversion and selectivity for the reaction. This positive effect of 2-propanol on the catalytic reaction can be explained by the solubility of EDA-CA in 2-propanol under the reaction conditions and no formation of solvent-derived byproducts. This catalytic system using the combination of the CeO2 catalyst and the 2-propanol solvent provided 2-imidazolidinone in up to 83% yield on the EDA-CA basis at 413 K under Ar. The reaction conducted under Ar showed a higher reaction rate than that with pressured CO2, which clearly demonstrated the advantage of the catalytic system operated at low CO2 pressure or even without CO2.

Adsorption of Keggin-Type Polyoxometalates on Rh Metal Particles under Reductive Conditions.

The adsorption of POMs on Rh/SiO2 in water solvent under strongly reductive conditions was investigated. Aqueous solutions of α-Keggin type silicotungstate and silicovanadotungstates were mixed with Rh/SiO2 at 393-473 K under 1 MPa of H2. Monovanadium-substituted silicotungstate, α-SiVW11O405- (SiVW11), was more readily adsorbed than nonsubstituted silicotungstate, α-SiW12O404- (SiW12). After adsorption at 433 K, SiVW11 was desorbed from Rh/SiO2 by oxidation with Br2 water without change of the Keggin structure, as evidenced by 51V NMR. Trivanadium-substituted silicotungstate, α-1,2,3-SiV3W9O407-, was not stable, and the desorbed species from Rh/SiO2 by oxidation with Br2 did not maintain the Keggin structure. The very high temperature for adsorption (473 K) also led to the decomposition of the Keggin structure of SiVW11. An increase in the concentration of SiVW11 in the liquid phase gave a saturation of the amount of desorbable SiVW11, up to five SiVW11 anions per one Rh particle with a 3 nm size. The elemental analysis and W L3-edge extended X-ray absorption fine structure of Rh/SiO2 after the adsorption of SiVW11 showed that a part of SiVW11 was decomposed and irreversibly adsorbed as metallic W species incorporated into the surface of Rh metal particles. The amount of decomposed SiVW11 was almost the same as that of SiVW11 adsorbed as the original Keggin structure. The desorbable SiVW11 was probably bonded on the W atom incorporated on the Rh metal particles as the two-electron-reduced form (α-SiVIIIW11O407-).

Selective Hydrogenolysis of Erythritol over Ir-ReOx /Rutile-TiO2 Catalyst.

Partial hydrogenolysis of erythritol, which can be produced at large scale by fermentation, to 1,4-butanediol (1,4-BuD) is investigated with Ir-ReOx /SiO2 and Ir-ReOx /rutile-TiO2 catalysts. In addition to the higher conversion rate over Ir-ReOx /TiO2 than over Ir-ReOx /SiO2 , which has been also reported for glycerol hydrogenolysis, Ir-ReOx /TiO2 showed higher selectivity to 1,4-BuD than Ir-ReOx /SiO2 , especially at low conversion levels, leading to high 1,4-BuD productivity of 20 mmol1,4-BuD gIr -1 h-1 at 373 K (36 % conversion, 33 % selectivity). The productivity based on the noble metal amount is higher than those reported previously, although the maximum yield of 1,4-BuD (23 %) is not higher than the highest reported values. The reactions of various triols, diols and mono-ols are tested and the selectivity and the reaction rates are compared between catalysts and between substrates. The Ir-ReOx /TiO2 catalyst showed about twofold higher activity than Ir-ReOx /SiO2 in hydrogenolysis of the C-OH bond at the 2- or 3-positions in 1,2- and 1,3-diols, respectively, whereas the hydrogenolysis of C-OH at the 1-position is less promoted by the TiO2 support. Lowering the loading amount of Ir on TiO2 (from 4 wt % to 2 or 1 wt %) decreases the Ir-based activity and 1,4-BuD selectivity. Similarly, increasing the loading amount on SiO2 from 4 wt % to 20 wt % increases the Ir-based activity and 1,4-BuD selectivity, although they remain lower than those for TiO2 -supported catalyst with 4 wt % Ir. High metal loadings on the support seem to be important.

One-pot imine synthesis from methylarenes and anilines under air over heterogeneous Cu oxide-modified CeO2 catalyst.

Cu oxide-modified CeO2 (CuOx-CeO2) with 2 wt% Cu loading amount was the most effective and reusable heterogeneous catalyst for selective one-pot imine synthesis from methylarenes and anilines via direct oxidation of the sp3 C-H bond in the methylarenes with atmospheric air (0.1 MPa) as an oxidant.

Erythritol: Another C4 Platform Chemical in Biomass Refinery.

The potential of erythritol as a platform chemical in biomass refinery is discussed in terms of erythritol production and utilization. Regarding erythritol production, fermentation of sugar or starch has been already commercialized. The shift of the carbon source from glucose to inexpensive inedible waste glycerol is being investigated, which will decrease the price of erythritol. The carbon-based yield of erythritol from glycerol is comparable to or even higher than that from glucose. The metabolic pathway of erythritol biosynthesis has become clarified: erythrose-4-phosphate, which is one of the intermediates in the pentose phosphate pathway, is dephosphorylated and reduced to erythritol. The information about the metabolic pathway may give insights to improve the productivity by bleeding. Regarding erythritol utilization, chemical conversions of erythritol, especially deoxygenation, have been investigated in these days. Erythritol is easily dehydrated to 1,4-anhydroerythritol, which can be also used as the substrate for production of useful C4 chemicals. C-O hydrogenolysis and deoxydehydration using heterogeneous catalysts are effective reactions for erythritol/1,4-anhydroerythritol conversion.

Biobased Cycloolefin Polymers: Carvone-Derived Cyclic Conjugated Diene with Reactive exo-Methylene Group for Regioselective and Stereospecific Living Cationic Polymerization.

Carvone, a naturally abundant chiral cyclic α,ß-unsaturated carbonyl compound, was chemically transformed into cyclic exo-methylene conjugated dienes. The exo-methylene group had high reactivity in cationic polymerization and was efficiently polymerized in a controlled manner via regioselective 1,4-conjugated additions using initiating systems effective for living cationic polymerization of vinyl ethers. The obtained polymers with 1,3-cyclohexenyl units and tetra-substituted olefins in the main chain showed high glass transition temperatures over 110 °C. The chiral monomer underwent stereospecific polymerization to result in polymers with low solubility and weak packing of the rigid main chain in the lamellar layers. The racemic mixture resulted in soluble amorphous polymers, which were subsequently hydrogenated into cycloolefin polymers with enhanced thermal properties.

A nickel-iridium alloy as an efficient heterogeneous catalyst for hydrogenation of olefins.

Nickel and iridium supported on SiO2 (Ni-Ir/SiO2) acted as an effective and reusable heterogeneous catalyst for hydrogenation of olefins, and it showed higher activity and selectivity than the monometallic counterparts. The Ni-Ir/SiO2 catalyst has small Ni-Ir alloy and monometallic Ni particles, and the high catalytic performance can be attributed to the isolated Ni atom in the Ni-Ir alloys.

Preparation of Highly Active Monometallic Rhenium Catalysts for Selective Synthesis of 1,4-Butanediol from 1,4-Anhydroerythritol.

1,4-Butanediol can be produced from 1,4-anhydroerythritol through the co-catalysis of monometallic mixed catalysts (ReOx /CeO2 +ReOx /C) in the one-pot reduction with H2 . The highest yield of 1,4-butanediol was over 80 %, which is similar to the value obtained over ReOx -Au/CeO2 +ReOx /C catalysts. Mixed catalysts of CeO2 +ReOx /C showed almost the same performance, giving 89 % yield of 1,4-butanediol. The reactivity trends of possible intermediates suggest that the reaction mechanism over ReOx /CeO2 +ReOx /C is similar to that over ReOx -Au/CeO2 +ReOx /C: deoxydehydration (DODH) of 1,4-anhydroerythritol to 2,5-dihydrofuran over ReOx species on the CeO2 support with the promotion of H2 activation by ReOx /C, isomerization of 2,5-dihydrofuran to 2,3-dihydrofuran catalyzed by ReOx on the C support, hydration of 2,3-dihydrofuran catalyzed by C, and hydrogenation to 1,4-butanediol catalyzed by ReOx /C. The reaction order of conversion of 1,4-anhydroerythritol with respect to H2 pressure is almost zero and this indicates that the rate-determining step is the formation of 2,5-dihydrofuran from the coordinated substrate with reduced Re in the DODH step. The activity of ReOx /CeO2 +ReOx /C is higher than that of ReOx -Au/CeO2 +ReOx /C, which is probably related to the reducibility of ReOx /C and the mobility of the Re species between the supports. High-valent Re species such as Re7+ on the CeO2 and C supports are mobile in the solvent; however, low-valent Re species, including metallic Re species, have much lower mobility. Metallic Re and cationic low-valent Re species with high reducibility and low mobility can be present on the carbon support as a trigger for H2 activation and promoter of the reduction of Re species on CeO2 . The presence of noble metals such as Au can enhance the reducibility through the activation of H2 molecules on the noble metal and the formation of spilt-over hydrogen over noble metal/CeO2 , as indicated by H2 temperature-programmed reduction. The higher reducibility of ReOx -Au/CeO2 lowers the DODH activity of ReOx -Au/CeO2 +ReOx /C in comparison with ReOx /CeO2 +ReOx /C by restricting the movement of Re species from C to CeO2 .

Across the Board: Keiichi Tomishige.

In this series of articles, the board members of ChemSusChem discuss recent research articles that they consider of exceptional quality and importance for sustainability. This entry features Prof. K. Tomishige, who highlights the importance of the chemical conversion of monosaccharides and the future necessity for the development of heterogeneous catalysts.

CO2 Conversion with Alcohols and Amines into Carbonates, Ureas, and Carbamates over CeO2 Catalyst in the Presence and Absence of 2-Cyanopyridine.

Recent progress on the CeO2 catalyzed synthesis of organic carbonates, ureas, and carbamates from CO2 +alcohols, CO2 +amines, and CO2 +alcohols+amines, respectively, is reviewed. The reactions of CO2 with alcohols and amines are reversible ones and the degree of the equilibrium limitation of the synthesis reactions is strongly dependent on the properties of alcohols and amines as the substrates. When the equilibrium limitation of the reaction is serious, the equilibrium conversion of the substrate and the yield of the target product is very low, therefore, the shift of the equilibrium reaction to the product side by the removal of H2 O is essential in order to get the target product in high yield. One of the effective method of the H2 O removal from the related reaction systems is the combination with the hydration of 2-cyanopyridine to 2-picolinamide, which is also catalyzed by CeO2 .

Ring-opening polymerization of trimethylene carbonate to poly(trimethylene carbonate) diol over a heterogeneous high-temperature calcined CeO2 catalyst.

CeO2 calcined at 1273 K showed higher activity per surface area than other metal oxides in the ring-opening polymerization of trimethylene carbonate under neat conditions without any additives, providing metal-free and additive-free poly(trimethylene carbonate) diols with no ether bonds with high selectivity. It was demonstrated that CeO2 was a robust and reusable heterogeneous catalyst.

Selective hydrogenation of amides to alcohols in water solvent over a heterogeneous CeO2-supported Ru catalyst.

CeO2-supported Ru (Ru/CeO2) worked as an effective and reusable heterogeneous catalyst for the selective dissociation of the C-N bond in amides, particularly primary amides, with H2 in water solvent at low reaction temperature of 333 K, and high yields of the corresponding alcohols were obtained from primary amides.