Highly Dispersed Pt Catalysts on Hierarchically Mesoporous Organosilica@Silica Nanoparticles with a Core-Shell Structure for Polycyclic Aromatic Hydrogenation.

Hydrogenation of naphthalene can effectively reduce the content of aromatics in oil and generate high-value products. A series of Pt-based aluminum-modified core-shell-structured hierarchically periodic mesoporous organosilica@mesoporous silica nanoparticles (Pt/Al-x-PMOs@MSNs) were successfully synthesized and tested for the hydrogenation properties, with preferable mass transfer of macromolecular reactants in the pores and increasing the total acidity of the catalysts. Moreover, the physicochemical properties of the core-shell-structured Pt-based catalysts were systematically analyzed using various characterization techniques. At 300 °C, the naphthalene conversion on the Pt/Al-10-PMOs@MSNs catalyst reached up to 100%, the selectivity of trans-decalin reached 83.9%, and the rate constants (k1, k2) and TOF were 13.2 × 10-6 mol·g-1·s-1, 1.7 × 10-7 mol·g-1·s-1, and 218.8 h-1, respectively. In the presence of sulfur, the naphthalene hydrogenation over the Pt/Al-10-PMOs@MSN catalyst first decreased to around 40% and then recovered to the original level, which originated from the synergistic effect of the texture and chemical properties over the Pt/Al-10-PMOs@MSNs with an excellent performance.

PdCu supported on dendritic mesoporous CexZr1-xO2 as superior catalysts to boost CO2 hydrogenation to methanol.

A dendritic PdCu/Ce0.3Zr0.7O2 (PdCu/CZ-3) catalyst with uniform spherical morphology was prepared for boosting the catalytic performance of CO2 hydrogenation to methanol (MeOH). The open dendritic pore channels and small particle sizes could reduce not only the diffuse resistance of reactants and products but also increase the accessibility between the active sites (PdCu and oxygen vacancy) and the reactants (H2 and CO2). More spillover hydrogen could be generated due to the highly dispersed PdCu active metals over the PdCu/CZ-3 catalyst. PdCu/CZ-3 can stimulate the generation of more Ce3+ cations, which is beneficial to produce more oxygen vacancies on the surface of the CZ-3 composite. Spillover hydrogen and oxygen vacancy could promote the formate and methoxy routes over PdCu/CZ-3, the primary intermediates producing MeOH. PdCu/CZ-3 displayed the highest CO2 conversions (25.5 %), highest MeOH yield (6.4 %), highest PdCu-TOFMeOH (7.7 h-1) and superior 100 h long-term stability than those of other PdCu/CexZr1-xO2 analogs and the reference PdCu/CeO2 and PdCu/ZrO2 catalysts. Density functional theory (DFT) calculations and in situ DRIFTS were performed to investigate the CO2 - MeOH hydrogenation mechanism.

A Brief Review on Solvent-Free Synthesis of Zeolites.

The traditional hydrothermal method to prepare zeolite will inevitably use a large amount of water as a solvent, which will lead to higher autogenous pressure, low efficiency, and wastewater pollution. The solvent-free method can be used to synthesize various types of zeolites by mechanical mixing, grinding, and heating of solid raw materials, which exhibits the apparent advantages of high yield, low pollution, and high efficiency. This review mainly introduces the development process of solvent-free synthesis, preparation of hierarchical zeolite, morphology control, synthesis mechanism and applications of solvent-free methods. It can be believed that solvent-free methods will become a research focus and have enormous industrial application potential.

Structural Screening and Design of Dendritic Micro-Mesoporous Composites for Efficient Hydrodesulfurization of Dibenzothiophene and 4,6-Dimethyldibenzothiophene.

Novel dendritic micro-mesoporous TS-1/dendritic mesoporous silica nanoparticle (DMSN) composites (TD) were assembled by TS-1 nanocrystals with ultrasmall particle size and strong acidity. TS-1 seeds and DMSNs were composited via the Ti-O-Si chemical bond, which stimulate the generation of Brønsted (B) and Lewis (L) acids. The spillover d-electrons produced by the Ti element of TS-1 seeds produced a spillover of d-electrons, which could interact with the surface of MoS2 phases, thereby reducing Mo-S interactions and create sulfur vacancies that are favorable for dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) hydrodesulfurization (HDS) reactions. The increased amount of B&L acid of NiMo/TD-2.0 with cetyltrimethylammonium bromide/sodium salicylate molar ratio of 2.0 played an important role in facilitating the hydrogenation (HYD) route of DBT HDS and the isomerization (ISO) route of 4,6-DMDBT HDS, which is more favorable for the reduction of steric hindrance of DBT and 4,6-DMDBT reactants in the HDS reaction process. The NiMo/TD-2.0 catalyst exhibited the highest turnover frequency (TOF) value and HDS reaction rate constant (kHDS) of DBT and 4,6-DMDBT due to its ultrasmall particle size, uniform spherical dendritic morphology, strong B&L acidity, and good stacking degree.

The Influence of Pore Structure and Acidity on the Hydrodesulfurization of Dibenzothiophene over NiMo-Supported Catalysts.

A series of mesoporous materials of SBA-16 were in situ incorporated into ZSM-5 crystallites via a two-step self-assemble method, and hydrodesulfurization (HDS) catalysts were prepared on the corresponding ZSM-5/SBA-16 (ZS) composites. The characterization results indicated that ZSM-5 nanoseeds were fabricated into the silica framework of the ZS composites, and the three-dimensional Im3m cubic structure of SBA-16 was retained simultaneously. In addition, the ZS series materials possessed open pores and large surfaces, which would facilitate the diffusion of reactants in the mesoporous channels. Moreover, the introduction of ZSM-5 seeds into composites could enhance the acidities of supports. As a result, the NiMo/ZS series catalysts exhibited high activities for DBT HDS processes. The NiMo/ZS-160 catalyst exhibited the highest catalytic efficiency (96.5%), which was apparently attributed to the synergistic contributions of the physicochemical properties of ZS supports and the dispersion states of active metals. Correspondingly, DBT HDS reactions over the NiMo/ZS series catalysts mainly proceeded via a hydrogenation desulfurization route that benefitted from the enhanced acidities especially the total Brønsted acid.

Ultrasmall Particle Sizes of Walnut-Like Mesoporous Silica Nanospheres with Unique Large Pores and Tunable Acidity for Hydrogenating Reaction.

The large particle sizes, inert frameworks, and small pore sizes of mesoporous silica nanoparticles greatly restrict their application in the acidic catalysis. The research reports a simple and versatile approach to synthesize walnut-like mesoporous silica nanospheres (WMSNs) with large tunable pores and small particle sizes by assembling with Beta seeds. The as-synthesized Beta-WMSNs composite materials possess ultrasmall particulate sizes (70 nm), large radial mesopores (≈30 nm), and excellent acidities (221.6 mmol g-1 ). Ni2 P active phase is supported on the surface of Beta-WMSNs composite materials, and it is found that the obtained composite spherical materials can reduce the Ni2 P particle sizes from 8.4 to 4.8 nm with the increasing amount of Beta seeds, which can provide high accessibilities of reactants to the active sites. Furthermore, the unique large pores and ultrasmall particle sizes of Beta-WMSNs samples facilitate the reduction of the diffusion resistance of reactants due to the short transporting length, thus the corresponding Ni2 P/Beta-WMSNs composite catalysts show the excellent hydrogenating activity compared to the pure Ni2 P/WMSNs catalyst.