Effects of phosphine ligands in nickel-catalyzed decarbonylation reactions of lactone.

Due to the ubiquity of carbonyl compounds and the abundance of nickel on the earth, nickel-catalyzed decarbonylation has garnered increasing attention in recent years. This type of reaction has seen significant developments in various aspects; however, certain challenges concerning reactivity, selectivity, and transformation efficiency remain pressing and demand urgent resolution. In this study, we employed DFT calculations to investigate the mechanism of nickel-catalyzed decarbonylation reactions involving lactones, as well as the effects of phosphine ligands. Mechanically, Ni(0) first activates the C(acyl)-O bond of the lactone, followed by a decarbonylation step, and ultimately results in reductive elimination under carbonyl coordination to yield the product. Through a comprehensive examination of the electronic and steric effects of the phosphine ligands, we deduced that the electronic effect of the ligand plays a dominant role in the decarbonylation reaction. By enhancing the electron-withdrawing ability of the ligand, the energy barrier of the entire reaction can be significantly reduced. The obtained insights should be valuable for understanding the detailed mechanism and the role of phosphine ligands in nickel catalysis. Moreover, they offer crucial clues for the rational design of more efficient catalytic reactions.

Zeolite nanosheets for catalysis.

Zeolites with well-defined micropores have been widely used as heterogeneous catalysts in the fields of petroleum refining, fine chemicals, and environment protection. However, the sole micropores in the zeolite structures usually impose diffusion constraints, which would greatly influence their catalytic performances. Therefore, it is highly desirable to shorten the diffusion pathway of zeolites and thus eliminate the diffusion constraints. One of the efficient methods is to synthesize zeolite nanosheets, which has become a hot topic in the past decades. In this tutorial review, the recent progresses in the synthesis of zeolite nanosheets and their relevant catalysis are briefly discussed. Various strategies for the synthesis of zeolite nanosheets are summarized including delamination, templated crystallization, additive-assisted synthesis, seed-directed synthesis, and gaseous expansion synthesis. In addition, the catalytic reactions of zeolite nanosheets with acidic and metal sites are also outlined. This tutorial review should be significant for the design and preparation of highly efficient zeolite catalysts.

Co-Cu nanoparticles uniformly embedded in the intra-crystalline mesoporous Silicalite-1 for catalytic ammonia borane hydrolysis.

Zeolite-encaged metal nanoparticles (NPs) catalysts are emerging as a new frontier owing to their superior ability to stabilize the structure and catalytic performance in the thermal and environmental catalytic reaction. However, the pore size below 2 nm of the conventional zeolites usually limits the accessibility of metal active sites. Herein, Co-Cu NPs of about 2.5-3.5 nm were uniformly encapsulated in the intracrystalline mesoporous Silicalite-1 (S-1) through alkali-treatment ligand-assisted strategy. The obtained sample (termed CoxCu1-x@HS-1) exhibited efficient activity and stability in the ammonia borane hydrolysis with the highest TOF value of 21.46 molH2·molMe-1·min-1. UV-vis DRS spectra indicated that intracrystalline mesopores have greatly improved the openness and accessibility of the active sites, thus improving their catalytic performance. The introduction of Cu regulates the electronic properties of Co, further increasing hydrogen production activity. This research creates new prospects to design other high-performance hierarchical porous zeolite-confined metal/metal oxide catalysts.

Highly Antibacterial and Self-Healing Janus Fabric for Effective Body Moisture/Thermal Management and Durable Waterproof.

Despite the development of many functional fabrics, they are unable to meet practical needs due to their monolithic functions and low durability. Therefore, a multifunctional waterborne polyurethane nanodroplet containing disulfide bonds (WSPU) was synthesized using a simple and environmentally friendly approach. The functional WSPU nanodroplet coating endowed fabrics with a variety of properties, including exceptional hydrophobicity, antibacterial properties, self-healing at room temperature, directional transport, etc. The functionalized fabric demonstrated durable mechanical and chemical stabilities due to the combined effects of disulfide bond reconstruction and hydrophobic chain migration. It exhibited the ability to regain its hydrophobic properties at room temperature after 50 friction cycles were performed without requiring external stimulation. Furthermore, the fabric maintained a water contact angle above 140°, even after being subjected to washing, boiling, and immersion in acid and alkali solutions. In addition, as a result of the fabric's Janus-like wettability, it performed various functions in accordance with varying weather conditions, in terms of wearing comfort and breathability. In hot weather or during exercise, the Janus fabric with the hydrophilic side facing outward enhances the process of sweat-directed perspiration, resulting in a notable cooling effect. On rainy days, the Janus fabric, when positioned with the hydrophobic side facing outward, exhibited excellent waterproof performance. This study presents an opportunity to explore the development of multifunctional fabrics through the combined effects of several functions.

Synthesis of Low Cost Titanium Silicalite-1 Zeolite for Highly Efficient Propylene Epoxidation.

Developing an effective and low-cost system to synthesize titanium silicalite-1 (TS-1) zeolite is desirable for a range of industrial applications. To date, the poor catalytic activity of the synthesized zeolite due to the low amount of framework titanium and large crystal size is the main obstacle limiting the widespread application of this material. Moreover, a large amount of wastewater is often produced by the existing synthesis process. Herein, a green and sustainable route for synthesizing small-crystal TS-1 with a high fraction of framework Ti was demonstrated via a seed-assisted method using a tetrapropylammonium bromide (TPABr)-ethanolamine hydrothermal system. The influence of the synthesis conditions on the physicochemical properties and catalytic activities of TS-1 was investigated. With the assistance of nanosized S-1 seeds, the incorporation of Ti into the framework of TS-1 was promoted, and the crystallization rate was effectively accelerated. After alkaline etching, the obtained hierarchical TS-1 had higher catalytic activity towards propylene epoxidation with an extremely high turnover frequency of 1,650 h-1. Furthermore, the mother liquid during the hydrothermal reaction could be reused for the next synthesis procedure. Consequently, utilization ratios of both ethanolamine and TPABr exceeding 95% were achieved by recycling the mother liquid. This low-cost approach for reducing wastewater could be easily scaled up to provide a promising synthesis method for the industrial production of TS-1 and other topological zeolites.

Clean Synthesis of Ti-MWW by Utilizing the Recycled Mother Liquor.

This article introduces a clean and efficient method for the synthesis of Ti-MWW by utilizing the recycled mother liquor. The effects of titanium and silicon sources on the synthesis of Ti-MWW and the recycling of the mother liquor are discussed in detail. Precipitated silica prepared with Na2SiO3 and CO2 was selected as the silicon source, and TiCl3 was selected as the titanium source. The mother liquor was recycled five times, and the obtained samples showed good catalytic activity in cyclohexanone ammoximation. This work can be conducive to reducing the influence on the environment and economizing on materials for the industrial production of Ti-MWW.

The Clean Synthesis of Small-Particle TS-1 with High-Content Framework Ti by Using NH4HCO3 and Suspended Seeds as an Assistant.

The synthesis of a TS-1 zeolite with high-content framework Ti and small particles has been developed by adding NH4HCO3 and suspended seeds as an assistant. With the addition of NH4HCO3, the Hofmann decomposition of the tetrapropylammonium cation (TPA+) decreased, and the framework Ti content of the zeolite increased first and then decreased while the particle became larger. With the assistance of suspended seeds, the TS-1 synthesized under a low-alkalinity system possesses small particle size and high-content framework Ti, and it shows the best catalytic activity among the prepared catalysts. Because the decomposition of TPA+ decreased, the mother liquid could be reused in the next run of preparation. Even though the recycled mother liquid was reused five times, all obtained TS-1 samples exhibited similar catalytic performances in propylene epoxidation. This work provides an efficient process for preparing TS-1 with good catalytic performance and reduces the discharge of the waste liquid.

Fabrication of Microspheres by Nano-TS-1 Crystals via a Spray-Forming Process: From Screening to Scale-up.

The spray-forming process of the nano-titanium silicalite (TS-1) zeolite was investigated and optimized in the lab in order to obtain materials with microsphere morphology and superior catalytic activity in cyclohexanone ammoximation on the industrial scale. The effects of spray-forming parameters, such as the state of the TS-1 raw material, load ratio, solid content, binder content, and calcination temperature, on the physicochemical and catalytic properties of TS-1 microspheres were investigated in detail. It was interesting to find that the shape of the spray-forming sample formed by wet powders was more intact than the sample formed by dried powders. Furthermore, the spray-forming process was successfully scaled up to a large spray device (LGZ-1000) according to the similarity principle of load ratio, and the shape of the TS-1 microspheres was as perfect as the spray-forming samples in the lab. The similarity principle of the load ratio for the spray-forming of titanium silicate was established and verified for the first time. The spray-forming TS-1 microspheres produced in the industry were used in cyclohexanone ammoximation, and ketone conversion and oxime selectivity were as high as 99.9 and 99.4%, respectively.

Seed-assisted synthesis of TS-1 crystals containing Al with high catalytic performances in cyclohexanone ammoximation.

In this study, titanium silicalite (TS-1) crystals containing Al were synthesized using aluminosilicate MFI zeolites as seeds in a tetrapropylammonium bromide (TPAB)-ethanolamine (EA) system. The TS-1 containing Al possessed large size, large L b value and higher catalytic activity in cyclohexanone ammoximation. Larger L b value would endow the TS-1 crystals with better mechanical strength and erosion resistance. The introduction of an Al atom into the TS-1 crystals resulted in the production of more acid sites and a bit strong Brönsted acid sites; these acid sites were more favorable to the catalytic performances in cyclohexanone ammoximation.