Sunlight-driven and gram-scale vanillin production via Mn-defected γ-MnO2 catalyst in aqueous environment.

The production of vanillin from biomass offers a sustainable route for synthesizing daily-use chemicals. However, achieving sunlight-driven vanillin synthesis through H2O activation in an aqueous environment poses challenges due to the high barrier of H2O dissociation. In this study, we have successfully developed an efficient approach for gram-scale vanillin synthesis in an aqueous reaction, employing Mn-defected γ-MnO2 as a photocatalyst at room temperature. Density functional theory calculations reveal that the presence of defective Mn species (Mn3+) significantly enhances the adsorption of vanillyl alcohol and H2O onto the surface of the γ-MnO2 catalyst. Hydroxyl radical (˙OH) species are formed through H2O activation with the assistance of sunlight, playing a pivotal role as oxygen-reactive species in the oxidation of vanillyl alcohol into vanillin. The Mn-defected γ-MnO2 catalyst exhibits exceptional performance, achieving up to 93.4% conversion of vanillyl alcohol and 95.7% selectivity of vanillin under sunlight. Notably, even in a laboratory setting during the daytime, the Mn-defected γ-MnO2 catalyst demonstrates significantly higher catalytic performance compared to the dark environment. This work presents a highly effective and promising strategy for low-cost and environmentally benign vanillin synthesis.

Spontaneous generation of singlet oxygen on microemulsion-derived manganese oxides with rich oxygen vacancies for efficient aerobic oxidation.

Developing innovative catalysts for efficiently activating O2 into singlet oxygen (1O2) is a cutting-edge field with the potential to revolutionize green chemical synthesis. Despite its potential, practical implementation remains a significant challenge. In this study, we design a series of nitrogen (N)-doped manganese oxides (Ny-MnO2, where y represents the molar amount of the N precursor used) nanocatalysts using compartmentalized-microemulsion crystallization followed by post-calcination. These nanocatalysts demonstrate the remarkable ability to directly produce 1O2 at room temperature without the external fields. By strategically incorporating defect engineering and interstitial N, the concentration of surface oxygen atoms (Os) in the vicinity of oxygen vacancy (Ov) reaches 51.1% for the N55-MnO2 nanocatalyst. This feature allows the nanocatalyst to expose a substantial number of Ov and interstitial N sites on the surface of N55-MnO2, facilitating effective chemisorption and activation of O2. Verified through electron paramagnetic resonance spectroscopy and reactive oxygen species trapping experiments, the spontaneous generation of 1O2, even in the absence of light, underscores its crucial role in aerobic oxidation. Density functional theory calculations reveal that an increased Ov content and N doping significantly reduce the adsorption energy, thereby promoting chemisorption and excitation of O2. Consequently, the optimized N55-MnO2 nanocatalyst enables room-temperature aerobic oxidation of alcohols with a yield surpassing 99%, representing a 6.7-fold activity enhancement compared to ε-MnO2 without N-doping. Furthermore, N55-MnO2 demonstrates exceptional recyclability for the aerobic oxidative conversion of benzyl alcohol over ten cycles. This study introduces an approach to spontaneously activate O2 for the green synthesis of fine chemicals.

The Effect of Ni-ZSM-5 Catalysts on Catalytic Pyrolysis and Hydro-Pyrolysis of Biomass.

With the demand of energy and re-utilization of wastes, the renewable lignocellulosic biomass, has attracted increasing and significant attention for alleviating the growing energy crisis and environment problems. As main components of lignocellulosic biomass, lignin, cellulose, and hemicellulose are connected by hydrogen bond to form a compact skeleton structure, resulting the trenchant condition of biomass pyrolysis. Also, pyrolysis products of above three main constituents contain a large amount of oxygenates that cause low heating value, high corrosiveness, high viscosity, and instability. Meanwhile, zeolites are of considerable significance to the conversion of lignocellulosic biomass to desirable chemical products on account of fine shape selectivity and moderate acid sites and strength. Among numerous zeolites, ZSM-5-based catalysts have been most extensively studied, and the acidity and porosity of ZSM-5 can be tuned by changing the content of Si or Al in zeolite. Beyond that, doping of other metal elements, such as Mn, Co, Ni, Ga, Ce, Pt, into ZSM-5 is also an efficient way to regulate the strength and density of acid sites in zeolite precisely. This review focused on the recent investigation of Ni-modified microporous ZSM-5 used in catalytic pyrolysis of lignin and cellulose. The application of metal-modified hierarchical ZSM-5 is also covered.

Solvothermal Synthesis of Humic Acid-Supported CeO2 Nanosheets Composite as High Performance Adsorbent for Congo Red Removal.

Surface properties and structures of materials are essential for their adsorption of pollutants in water. Humic acids (HA)-supported CeO2 nanosheet composites are synthesised by solvothermal method. The size of CeO2 nanosheets are approximately 100-500 nm. The obtained composite exhibits superior adsorption ability for Congo Red (CR) in water, which can be attributed to its unique structure and highly dispersed CeO2 nanosheet. The composite's adsorption behaviour of CR follows a pseudo-second-order mode and Langmuir adsorption model well, and the maximum adsorptive capacity for CR achieves 260 mg g-1. The presence of CeO2 nanosheets enhances surface area and enriches the mesoporous structure of the composites, thereby promoting CR adsorption capacity.

Fast and highly efficient SO2 capture by TMG immobilized on hierarchical micro-meso-macroporous AlPO-5/cordierite honeycomb ceramic materials.

SO2 capacity of the obtained TMG-AlPO-5/cordierite honeycomb ceramic (CHC) adsorbent was measured to be 1.13 mol per mol TMG. More importantly, compared with literature reported supported ionic liquids, it is featured by a significantly improved adsorption rate (t0.9 reduced from >30 min to ∼0.1 min) and negligible pressure drop.

Indented Cu2MoS4 nanosheets with enhanced electrocatalytic and photocatalytic activities realized through edge engineering.

Edges often play a role as active centers for catalytic reactions in some nanomaterials. Therefore it is highly desirable to enhance catalytic activity of a material through modulating the microstructure of the edges. However, the study associated with edge engineering is less investigated and still at its preliminary stage. Here we report that Cu2MoS4 nanosheets with indented edges can be fabricated through a simple chemical etching route at room temperature, using Cu2MoS4 nanosheets with flat ones as sacrifice templates. Taking the electrocatalytic hydrogen evolution reaction (HER), photocatalytic degradation of rhodamine B (RhB) and conversion of benzyl alcohol as examples, the catalytic activity of Cu2MoS4 indented nanosheets (INSs) obtained through edge engineering was comparatively studied with those of Cu2MoS4 flat nanosheets (FNSs) without any modification. The photocatalytic tests revealed that the catalytic active sites of Cu2MoS4 nanosheets were associated with their edges rather than basal planes. Cu2MoS4 INSs were endowed with larger electrochemically active surface area (ECSA), more active edges and better hydrophilicity through the edge engineering. As a result, the as-fabricated Cu2MoS4 INSs exhibited an excellent HER activity with a small Tafel slope of 77 mV dec(-1), which is among the best records for Cu2MoS4 catalysts. The present work demonstrated the validity of adjusting catalytic activity of the material through edge engineering and provided a new strategy for designing and developing highly efficient catalysts.

Superhydrophobic and superoleophilic polydimethylsiloxane-coated cotton for oil-water separation process: An evidence of the relationship between its loading capacity and oil absorption ability.

Developing functional porous materials with highly efficient oil-water separation ability are of great importance due to the global scale of severe water pollution arising from oil spillage and chemical leakage. A solution immersion process was used to fabricate polydimethylsiloxane (PDMS)-coated cotton, which exhibited superhydrophobic and superoleophilic properties. The water contact angle of ∼ 157° and mass of ∼ 1.49 g were retained after 1000 compression cycles, indicating that the PDMS was strongly attached to the cotton fibres. The PDMS-coated cotton absorbed various oils and organic solvents with high selectivity, high absorption capacity (up to 7080 wt.%), and good recyclability (exceeding 500 cycles). Notably, the loading capacity of the PDMS-coated cotton against water exhibited a similar trend to its oil absorption capacity. These findings will further the application of superhydrophobic and superoleophilic porous materials in oil/water separation.

A transition-metal-free, one-pot procedure for the synthesis of α,ß-epoxy ketones by oxidative coupling of alkenes and aldehydes via base catalysis.

A new strategy for the synthesis of epoxides is presented. This process allows the direct synthesis of epoxides from alkenes and aldehydes through C-H functionalization and C-C/C-O bond formation.

Oil/water separation performances of superhydrophobic and superoleophilic sponges.

Superhydrophobic and superoleophilic sponges were fabricated by immersion in an ethanol solution of octadecyltrichlorosilane. The resulting coating strongly adheres to the sponges after curing at 45 °C for 24 h. Absorption capacities of 42-68 times the polymerized octadecylsiloxane sponge weight were obtained for toluene, light petroleum, and methylsilicone oil. These adsorption capacities were maintained after 50 cycles.

Fabrication of microcavity-array superhydrophobic surfaces using an improved template method.

We fabricated the first superhydrophobic (SH) surface with microcavities, using a simple process. The process included an improved template method (ITM) for constructing the SH surface with cavities, using taro leaves as a pattern mask, and a dip-coating method for modifying the SH surface. The results obtained using the ITM are significantly better than those achieved using traditional template methods. In addition, the water-repellence of the microcavities surface was significantly enhanced by decorating with a layer of polymerized n-octadecylsiloxane nanosheets.

Extraordinarily high activity in the hydrodesulfurization of 4,6-dimethyldibenzothiophene over Pd supported on mesoporous zeolite Y.

Design and preparation of highly active hydrodesulfurization (HDS) catalysts is very important for the removal of air pollution. Herein, we report an extraordinarily active HDS catalyst, which is synthesized by loading of Pd on mesoporous zeolite Y (Pd/HY-M). The mesoporous zeolite Y is successfully synthesized using a water glass containing N,N-dimethyl-N-octadecyl-N-(3-triethoxysilylpropyl) ammonium [(C(2)H(5)O)(3)SiC(3)H(6)N(CH(3))(2)C(18)H(37)](+) cation as a mesoscale template. Compared with mesoporous Beta and ZSM-5 supported Pd catalysts (80.0% and 73.4% for Pd/HBeta-M and Pd/HZSM-5-M, respectively) as well as commercial catalyst of γ-Al(2)O(3) supported Pd catalyst (31.4%), Pd/HY-M catalyst exhibited very high activity in HDS of 4,6-dimethyldibenzothiophene (4,6-DM-DBT, 97.3%). The higher activity of Pd/HY-M than that of Pd/HBeta-M and Pd/HZSM-5-M is assigned to the larger micropore size of zeolite Y compared to that of Beta and ZSM-5. Theoretical simulation and adsorption experimental data show that 4,6-DM-DBT has difficulty entering the micropores of ZSM-5 and Beta zeolites, but the micropores of Y zeolite are accessible.

Facile preparation of superhydrophobic biomimetic surface based on octadecyltrichlorosilane and silica nanoparticles.

The present paper describes the simple and low-cost process for the production of a superhydrophobic surface with micronano hierarchical structure from the chemisorptions of SiO(2) nanoparticles onto polymerized n-octadecylsilane. The process was carried out under ambient conditions without the use of expensive equipment. The as-prepared micronano-binary films exhibited a very high contact angle of 179.9 degrees and a low contact hysteresis of 2.5 degrees . On the basis of the results of the characterization techniques, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and contact angle (CA) measurements, a formation mechnism of the superhydrophobic micronano structure was proposed. Drop impact experiments on the modified-glass substrate showed that the as-prepared films possess a high-impalement threshold.

Formation of superhydrophobic polymerized n-octadecylsiloxane nanosheets.

Superhydrophobic nanosheet assemblies of polymerized n-octadecylsiloxane (PODS) were obtained on glass using n-octadecyltricholorsilane (OTS) as a starting material and acetone as the extracting agent. The coating layers were characterized by infrared spectroscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, and contact angle measurements. It was shown that the PODS nanosheets consist of stacks of bilayered polysilsequioxane of OTS in a head-to-head arrangement. The relative humidity of the environment was found to control the self-assembly and eventually the morphology of the final coating. A coating-formation mechanism was proposed to describe the formation of OTS nanosheets on the basis of quick OTS hydrolysis, fast self-assembly, and slow polycondensation (i.e., after OTS hydrolysis, nanosheets can be formed only when the self-assembly process proceeds at a faster rate than polycondensation, which implies critical controlling factors in the formation of well-ordered OTS self-assembled monolayers (SAMs)).