Pd₄S/SiO₂: A Sulfur-Tolerant Palladium Catalyst for Catalytic Complete Oxidation of Methane

Sulfur species (e.g. H2S or SO2) are the natural enemies of most metal catalysts, especiallypalladium catalysts. The previously reported methods of improving sulfur-tolerance were toeffectively defer the deactivation of palladium catalysts, but could not prevent PdO and carrierinteraction between sulfur species. In this report, novel sulfur-tolerant SiO2 supported Pd4Scatalysts (5 wt. % Pd loading) were prepared by H2S−H2 aqueous bubble method and applied tocatalytic complete oxidation of methane. The catalysts were characterization by X-ray diffraction,Transmission electron microscopy, X-ray photoelectron Spectroscopy, temperature-programmedoxidation, and temperature-programmed desorption techniques under identical conditions. Thestructural characterization revealed that Pd4S and metallic Pd0 were found on the surface of freshlyprepared catalysts. However, Pd4S remained stable while most of metallic Pd0 was converted toPdO during the oxidation reaction. When coexisting with PdO, Pd4S not only protected PdO fromsulfur poisoning, but also determined the catalytic activity. Moreover, the content of Pd4S could beadjusted by changing H2S concentration of H2S−H2 mixture. When H2S concentration was 7 %, thePd4S/SiO2 catalyst was effective in converting 96% of methane at the 400 °C and also exhibitedlong-term stability in the presence of 200 ppm H2S. A Pd4S/SiO2 catalyst that possesses excellentsulfur-tolerance, oxidation stability, and catalytic activity has been developed for catalyticcomplete oxidation of methane

In Situ Incorporation of Diamino Silane Group into Waterborne Polyurethane for Enhancing Surface Hydrophobicity of Coating

A series of waterborne polyurethanes (WPU) with crosslinked siloxane were obtained through introducing 3-(2-aminoethylamino)propyldimethoxymethylsilane (APTS) into WPU by in situ polymerization. The properties of WPU modified by APTS were studied through a variety of experimental methods. The water contact angle of the WPU coating surface increased from 64° to 86°, and the water resistance reduced to 3.90% when 3 wt% APTS was added, which improved the coating surface hydrophobicity. Firstly, Fourier transform infrared (FT-IR) and 1H-NMR spectra demonstrated the successful incorporation of APTS to polyurethanes and completed the hydrolytic condensation reaction-generated Si−O−Si crosslinking structure. Furthermore, the surface energy of the membrane was reduced when the crosslinking structure migrated and enriched on the surface of film. Besides, the crosslinking structure was abundant, and the distribution of siloxane in WPU was more uniform

Effects of Basic Promoters on the Catalytic Performance of Cu/SiO2 in the Hydrogenation of Dimethyl Maleate

Continuous hydrogenation of dimethyl maleate (DMM) toγ-butyrolactone (GBL), 1,4-butanediol (BDO) and tetrahydrofuran (THF) is a promising process in industry. In this study, Cu-M/SiO2 catalysts modified by basic promoters (M = Mg, Ca, Sr, Ba, La) were prepared, and characterized by physical adsorption of N2, in situ XRD, H2-TPR, CO2-TPD. With the addition of basic promoters, the basicity of Cu-M/SiO2 catalysts was improved. The particle size of CuO on Cu-M/SiO2 catalyst was increased after modified by Mg, Ca, Sr, Ba. However, the CuO particle was decreased on the Cu-La/SiO2 catalyst. The series of Cu-M/SiO2 catalyst was applied to the hydrogenation of DMM. The addition of basic promoters increased the selectivity of GBL during the hydrogenation for the basic promoters improved the dehydrogenation of BDO to GBL in alkaline sites. Furthermore, Cu-La/SiO2 presented a higher activity in the hydrogenation of DMM, due to its higher dispersion of Cu

In Vitro and in Vivo Anticancer Activity of Aconitine on Melanoma Cell Line B16

The anti-tumor effect of aconitine in melanoma cell line B16 has been studied in this paper. We found that B16 cells showed significantly reduced growth rates and increased apoptotic effects in the presence of aconitine. Furthermore, aconitine inhibited the PI3K/AKT and MAPK/ERK1/2 signaling pathways, thus regulating the levels of protein and mRNA of PCNA and apoptotic related signaling molecules. Above all, we found that aconitine showed an anti-melanoma effect in suppressing tumor growth in vivo. In conclusion, we show that aconitine may be a useful anticancer drug in the future

Heterogeneous Catalytic Synthesis of 2-Methylbenzimidazole from 2-Nitroaniline and Ethanol Over Mg Modified Cu-Pd/γ-Al2O3

The direct synthesis of benzimidazoles from 2-nitroaniline and ethanol over Cu-Pd/γ-Al2O3 catalysts has the advantages of requiring easily available starting materials, having high efficiency, and a simple procedure. The modification by Mg of the Cu-Pd/γ-Al2O3 catalyst could improve the catalytic activity significantly. The addition of Mg to the Cu-Pd/γ-Al2O3 catalyst could maintain and promote the formation of CuPd alloy active sites. Meanwhile, the basicity of the support was enhanced appropriately by Mg, which generated more basic sites (Al-Oδ−) to accelerate the dehydrogenation of alcohol and increased the rate of the whole coupled reaction. The 2-nitroaniline was completely converted over Cu-Pd/(Mg)γ-Al2O3 after reacting for six hours, and the yield of 2-methylbenzimidazole was 98.8%. The results of this work provide a simple method to develop a more efficient catalyst for the “alcohol-dehydrogenation, hydrogen transfer and hydrogenation” coupled reaction system

Study of the “Oxidation-Complexation” Coordination Composite Ionic Liquid System for Dissolving Precious Metals

The extraction of precious metals is of significant importance for recycling valuable precious metal resources, however, most of the current methods for extraction are inefficient, energy-intensive, or environmentally unfriendly. Herein, we report a new chemical dissolution system for precious metals employing the trichloroisocyanuric acid (TCCA) as an oxidant and tributyl monomethyl ammonium chloride (N4441Cl) as a complexant. The leaching yield was achieving 100 wt% for the metals of Au, Pd, Cu, and Ag at 25 °C, and the average dissolution rate of gold was reaching 375 mg/h, 107.1 times higher than that of traditional cyanide method. Based on the analysis of UV-Vis and XPS results, a possible reaction mechanism was proposed: the precious metals were probably oxidized by TCCA, then the formed precious metal ions coordinate with N4441Cl strongly to promote the dissolution process. Applied to gold dissolution from ores, waste electronic and electrical equipment (WEEE) and waste catalysts, the leaching yield of the TCCA-N4441Cl coordinative composite reached 97, 100, and 100 wt%, respectively, demonstrating that this method is not only efficient and environmentally friendly, but also with great adaptability and high potential for real applications

Synthesis of Hierarchical Porous Ti-ZSM-5: A High Active Catalyst for Benzene Alkylation with Methanol

The major challenge in the production of xylene from benzene alkylation with methanol is to avoid the side reaction of methanol with olefins, and this leads to the low utilization efficiency of methanol and the generation of byproduct ethylbenzene. Hierarchical porous Ti-ZSM-5 with appropriate acidity was achieved by substituting part of Al by Ti in the synthesis process, which exhibited the high utilization efficiency of methanol and high suppression of the ethylbenzene formation by the efficient suppression of methanol to olefins

Highly Active AuCu-Based Catalysts for Acetylene Hydrochlorination Prepared Using Organic Aqua Regia

Development of a sustainable process for designing and synthesising an active and stable catalyst for hydrochlorination of acetylene is challenging, yet crucial, for industrial vinyl chloride monomer (VCM) production. Herein, direct synthesis of bimetallic AuCu catalysts using organic aqua regia (OAR) preparation methods was investigated. In comparison with conventional aqua regia (AR), bimetallic AuCu catalysts synthesised from OAR exhibit enhanced activity and stability. After careful characterisation of the catalyst samples using X-ray diffraction patterns (XRD), Scanning transmission electron microscopy (STEM), X-ray photoelectron spectroscopy (XPS), and Temperature-programmed desorption (TPD), this observation was justified for the following reasons: 1) the existence of sulphur and nitrogen atoms stabilised the cationic Au active sites, and 2) OAR helped to sustain the function of the Cu promotor by stabilising it. Advanced understanding on the importance of promoter stability has unveiled new perspectives for this research area

Construction of ionic liquid-Pd/C based bifunction catalysts for the synthesis of UV-P

Adding light stabilizers to polymeric materials can inhibit or delay the light aging effect and improve the light resistance of materials. 2-(2′-Hydroxy-5′-methylphenyl) benzotriazole (UV-P), as a typical benzotriazole ultraviolet absorber, is widely used in various polymer synthetic materials and products owning to its outstanding oil resistance, color change resistance and low volatility. Currently, it is of great theoretical and practical significance to develop an environmentally friendly method to produce UV-P. Here, we introduce ionic liquids, tetra-butyl ammonium hydroxide, into the palladium-based catalyst, design a “transfer hydrogenation site - alkaline site” duel active center system, and investigate the physical and chemical properties and possible mechanism of this bifunction catalyst system. Such heterogeneous catalytic transfer hydrogenation method can remain 100% conversion and 93.86% selectivity. This bifunction catalyst also shows an outstanding stability when it was used for ten times, proving a green and efficient transfer hydrogenation method for the synthesis of UV-P

Preparation and Catalytic Performance of Metal-Rich Pd Phosphides for the Solvent-Free Selective Hydrogenation of Chloronitrobenzene

A facile synthesis method of palladium phosphide supported on the activated carbon was developed. The effects of Pd precursors for phosphatization, phosphatization temperature, and the ratio of hypophosphite/Pd on the generation of palladium phosphide were investigated, and a generation mechanism of the Pd3P crystal structure is proposed. The results demonstrate that only PdO, rather than Pd or PdCl2, can transform into Pd phosphide without damage to the activated carbon. The penetration of P into the Pd particle can dramatically improve the dispersion of Pd species particles on the activated carbon. The generation of Pd phosphide greatly depends on the phosphatization temperature and the ratio of hypophosphite/Pd. An intact Pd3P crystal structure was obtained when the ratio of hypophosphite/Pd reached 32 and the phosphatization temperature was above 400 °C. The Pd3P supported on the activated carbon exhibited superior catalytic performance in terms of the hydrogenation of halonitrobenzenes to haloanilines because it had few L acids and B acids sites and could not generate deficient-electron active hydrogen atoms as electrophiles