Selective Upcycling of Polyethylene over Ru/H-ZSM-5 Bifunctional Catalyst into High-Quality Liquid Fuel at Mild Conditions.

It has been known that plastics with undegradability and long half-times have caused serious environmental and ecological issues. Considering the devastating effects, the development of efficient plastic upcycling technologies with low energy consumption is absolutely imperative. Catalytic hydrogenolysis of single-use polyethylene over Ru-based catalysts to produce high-quality liquid fuel has been one of the current top priority strategies, but it is restricted by some tough challenges, such as the tendency towards methanation resulting from terminal C-C cleavage. Herein, we introduced Ru nanoparticles supported on hollow ZSM-5 zeolite (Ru/H-ZSM-5) for hydrocracking of high-density polyethylene (HDPE) under mild reaction conditions. The implication of experimental results is that the 1Ru/H-ZSM-5 (~1 wt % Ru) acted as an effective and reusable bifunctional catalyst providing higher conversion rate (82.53 %) and liquid fuel (C5-C21) yield (62.87 %). Detailed characterization demonstrated that the optimal performance in hydrocracking of PE could be attributed to the moderate acidity and appropriate positively charged Ru species resulting from the metal-zeolite interaction. This work proposes a promising catalyst for plastic upcycling and reveals its structure-performance relationship, which has guiding significance for catalyst design to improve the yield of high-value liquid fuels.

Small Pd nanoparticles supported in large pores of mesocellular foam: an excellent catalyst for racemization of amines.

Highly dispersed palladium nanoparticles (1-2 nm) supported in large-pore mesocellular foam (MCF; 29 nm) were synthesized. The Pd-nanocatalyst/MCF system was characterized by transmission electron microscopy (TEM), powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The performance of the Pd nanocatalyst obtained was examined for amine racemization. The Pd nanocatalyst showed higher activity and selectivity toward racemization of (S)-1-phenylethyl amine than any other amine racemization catalyst reported so far and it could be reused several times. Our data from TEM and XRD suggest a restructuring of the Pd nanocatalyst from amorphous to crystalline and an increase in Pd nanocatalyst size during the racemization reaction. This led to an unexpected increase of activity after the first use. The Pd nanocatalyst obtained can be integrated with other resolving processes of racemic organic compounds to increase the yield of chiral organic products.

An Overview of the Challenges and Progress of Synthesis, Characterization and Applications of Plugged SBA-15 Materials for Heterogeneous Catalysis.

A new generation of SBA-15, plugged SBA-15, was initially synthesized in 2002 using extra silica precursors (Si/organic template molar ratios ≈ 80-140) in the gel mixture. The plugged SBA-15 materials possess short cylinders (length ≈ 20-100 nm), which are connected to neighbors by constricted entrances (windows) through the central axis. The gas adsorption-desorption isotherms of plugged SBA-15 materials present unique hysteresis loop Type H5 classification identified by IUPAC in 2015, which is related to certain pore structures containing open and plugged mesopores. The plugged SBA-15 has been used to support various types of catalysts, including metal complexes, metal nanocatalysts, and active metals by the incorporation in their framework demonstrating excellent (enantio)selectivity, stability against coke, and thermal stability. The plugged SBA-15 materials bear the other unique properties of the ship-in-the-bottle synthesis of, e.g., metal complexes that confine homogeneous catalysts, which is not possible by conventional SBA-15 due to leaching. In this mini-review, the challenges and progress of the synthesis in controlling the plugging and incorporation of metals and organic moiety in their framework, characterizing the short mesochannel dimensions (window and length sizes) by several advanced techniques and applying plugged SBA-15 materials in heterogeneous catalysis for challenging reactions, has been discussed.

Crystallization of as-Mesocellular Silica Foam into Hierarchical TS-1 Zeolites by Conventional Hydrothermal and Dense-Gel Routes for Oxidation Reactions.

Crystallization of as-mesocellular silica foam (as-MCF) into TS-1 zeolites by conventional hydrothermal and dense-gel routes is reported. The TS-1 synthesized through the dense-gel route (TS-1-d) showed higher meso-macroporosity (0.311 vs 0.233 cm3/g), smaller particle size (130 vs 305 nm), and enhanced external surface area (86 vs 31 m2/g) than that synthesized under conventional hydrothermal conditions (TS-1-h). These might suggest that an organic template from as-MCF acted as mesoporogen in the dense-gel synthesis; however, segregation of the organic template and the synthesis mixture occurred in the conventional hydrothermal synthesis. The obtained TS-1 from the crystallization of as-MCF showed an enhanced framework Ti. The turnover frequencies (h-1) of TS-1-d toward hydroxylation of phenol and oxidation of dibenzothiophene (DBT) were 2 and 5 times, respectively, higher than those by TS-1-h. The DBT conversion by TS-1-d reached >99.0%, while it was only 63% by TS-1-h, suggesting the potential of TS-1-d for deep desulfurization of the fuels. Consequently, the crystallization of as-mesoporous materials through the dense-gel route is a promising approach to prepare TS-1 zeolites with smaller particle sizes and enhanced mesoporosity.

Production of dye-decolorizing peroxidase (rDyP) from complex substrates by repeated-batch and fed-batch cultures of recombinant Aspergillus oryzae.

We examined production levels of dye-decolorizing peroxidase (rDyP) by recombinant Aspergillus oryzae using wheat bran and rice bran powders in repeated-batch and fed-batch cultures. Similar average rDyP productivities were observed in repeated-batch cultures using wheat bran powder and rice bran powder. Average rDyP productivities in fed-batch cultures were slightly lower than those in repeated-batch cultures. The rDyP production was affected by the addition of K(2)HPO(4) in the repeated-batch and fed-batch cultures using wheat bran powder. All average rDyP productivities in this study were significantly higher than those for any other peroxidases previously reported.

Quantitative relationship between support porosity and the stability of pore-confined metal nanoparticles studied on CuZnO/SiO2 methanol synthesis catalysts.

Metal nanoparticle growth represents a major deactivation mechanism of supported catalysts and other functional nanomaterials, particularly those based on low melting-point metals. Here we investigate the impact of the support porous structure on the stability of CuZnO/SiO2 model methanol synthesis catalysts. A series of silica materials with ordered cagelike (SBA-16 mesostructure) and disordered (SiO2-gel) porosities and varying pore sizes were employed as catalyst supports. Nitric oxide moderated nitrate decomposition enabled the synthesis of catalytically active Cu nanoparticles (3-5 nm) exclusively inside the silica pores with short interparticle spacings. Under relevant reactive conditions, confinement of the Cu particles in cagelike silica pores notably enhances catalyst stability by limiting Cu particle growth as compared to catalysts deposited in SiO2-gel host materials with also 3D and highly interconnected though unconstrained porosity. For both pore morphologies, we find a direct relationship between catalyst stability and support porosity, provided the narrowest characteristic pore dimension is employed as a porosity descriptor. For cagelike porosities this corresponds to the size of the entrances to the nanocages. Our results point to nanoparticle diffusion and coalescence as a relevant growth mechanism under reactive conditions and underscore the significance of the narrowest pore constrictions to mitigate growth and improve catalyst stability. This finding contributes to the establishment of general and quantitative structure-stability relationships which are essential for the design of catalysts and related functional nanostructures with long lifetimes under operation conditions.

Significant changes in the transesterification activity of free and mesoporous-immobilized Rhizopus oryzae lipase in ionic liquids.

We examined the activity of free Rhizopus oryzae lipase (ROL) and ROL immobilized on mesoporous materials in transesterification reactions in various dialkylimidazolium-cation based ionic liquids. For free ROL, the highest activity (0.39 U/mg protein) was obtained in [OMIm][PF(6)] followed by that (0.28 U/mg protein) in [BMIm][PF(6)]. Specific activities of ROL immobilized on mesocellular foam (MCF) were only 0.47 and 0.43 U/mg protein in [OMIm][PF(6)] and [BMIm][PF(6)], respectively. However, the specific activities of ROL immobilized on octadecyl functionalized MCF (C(18)-MCF) increased significantly to 15.64 and 14.84 U/mg protein in [OMIm][PF(6)] and [BMIm][PF(6)], respectively. Consequently, ROL immobilized on C(18)-MCF is a promising biocatalyst for biotransformation reactions in ionic liquids.

Stable repeated-batch production of recombinant dye-decolorizing peroxidase (rDyP) from Aspergillus oryzae.

Recombinant Aspergillus oryzae expressing a dye-decolorizing peroxidase gene (dyp) was cultivated for repeated-batch production of recombinant dye-decolorizing peroxidase (rDyP) using maltose as a carbon source. High-level rDyP activity in limitation of carbon and nitrogen sources was maintained stably for 26 cycles of repeated 1-d batches of A. oryzae pellets without any additional pH control. Cultures maintained at 4 degrees C for 20 d resumed rDyP production following a single day of incubation. One liter filtrated crude rDyP containing 4600 U rDyP decolorized 5.07 g RBBR at the apparent decolorization rate of 17.7 mg l(-1) min(-1).