A series of cyclodextrin polymers (CDPs) were synthesized and they were used for removing different sulfides by molecular recognition. Different CDPs showed a higher desulfurization efficiency for sulfides with an aromatic ring structure than those with an aliphatic chain structure. For different cyclodextrin polymers, β-CDP has a more suitable cavity size for removing DBT. Moreover, it has a good synergetic effect of adjacent cyclodextrin cavities and good electronic interactions with DBT. For these reasons, β-CDP showed the best desulfurization performance, in particular it has good performance for deep desulfurization by forming inclusion complexes and excellent selectivity for removing DBT. Meanwhile, the β-CDP showed good regeneration performance. Various characterization measurements were used to characterize the β-CDP before and after desulfurization of DBT, the results of which showed that it had advantages of wide application temperature range and good structure stability before and after desulfurization. Finally, a molecular recognition mechanism for removing sulfides efficiently was proposed.

•The amorphous NiP/Hβ catalyst was prepared and used for n-hexane isomerization.•The sample shows higher catalytic activity than commercial platinum-based catalyst.•The catalyst shows high resistance to different sulfur compounds and water.•The acid property of catalyst surface is related to the NiP loadings.The amorphous NiP nanoparticles were synthesized and a novel amorphous NiP/Hβ catalyst was prepared successfully further. Due to the superior surface property of amorphous NiP/Hβ catalyst, it exhibited good catalytic application for n-hexane isomerization. The catalytic activity of amorphous NiP/Hβ catalyst was close to that of the prepared Pt/Hβ sample, and better than that of commercial catalyst and crystalline Ni2P/Hβ catalyst. What's more, the amorphous NiP/Hβ catalyst shows high resistance to different sulfur compounds and water on account of its unique surface property.The effect of loading amounts on surface property and catalytic performance was investigated, and the structure-function relationship among them was studied ulteriorly. The results demonstrate that loading amounts have effect on textural property and surface acid property, which further affect the catalytic performance. The 10 wt.% NiP/Hβ sample has appropriate pore structure and acid property with uniformly dispersed NiP nanoparticles on surface, which is helpful for providing suitable synergistic effect. The effects of reaction conditions on surface reactions and the mechanism for n-hexane isomerization were investigated further. Based on these results, the amorphous NiP/Hβ catalyst with superior surface property probably pavesa way to overcome the drawbacks of traditional noble metal catalyst, which shows good catalytic application prospects.

MCM-41 was selectively functionalized with CuO on the external surface and Cu2+ coordinated by organosilanes on the internal surface. The production of CuO and removal of template were achieved in one step, which is convenient and a save of energy. Results of transmission electron microscopy indicate the presence of CuO on outer surface of MCM-41. The successful grafting of organosilanes was confirmed by 13C and 29Si nuclear magnetic resonance. The prepared M(CuO)N(Cu) shows more comprehensive desulfurization performance due to the simultaneous and independent incorporation of CuO and copper ions. Dimethyl sulfide and dimethyl disulfide are selectively adsorbed on external surface of M(CuO)N(Cu), while tert-butyl mercaptan can be adsorbed on both external and internal surface of M(CuO)N(Cu).

Novel metal-free tetra-(3-phenyprop-2-allyloxy) phthalocyanine (TPAO-Pc) was synthesized and characterized by nuclear magnetic resonance spectrum (1H NMR), MALDI-TOF MS, Fourier-transform infrared (FT-IR) and UV-Visible absorption (UV-Vis) spectra. The effects of concentrations and solvents on the properties of self-assembly were investigated via absorption and fluorescence spectra, transmission electron microscopy (TEM). TPAO-Pc was stable in most organic solvents, such as toluene, acetone and dimethylsulfoxide (DMSO). However, the TPAO-Pc exhibited the tendency of forming “face-to-face” stacking mode self-assemblies (H-aggregate) in DMSO–water and acetone–water mixed solutions. Self-assembly of the TPAO-Pc was also demonstrated by fluorescence spectra. The TEM images displayed the core–shell nanospheres and dendritic nanostructure of TPAO-Pc formed in the DMSO–water and acetone–water mixed solutions, respectively. The mechanism of the self-assemblies growth was proposed on the basis of the experimental results. The morphology of the TPAO-Pc self-assemblies was related with the selected solvent conditions and the aggregation time. H-bond, π–π interaction may be the main driving force for the formation of core–shell nanospheres and dendritic nanostructure.

Two novel metal-free phthalocyanines have been designed and synthesized, namely tetra{[1H-benzo(d)imidazol-2-yl]thiol}phthalocyanine (TBIT-Pc) and tetra{[benzo(d)thiazol-2-yl]thiol}phthalocyanine (TBTT-Pc). These two compounds showed similar structures, while imidazolyl-NH in the substitutes of TBIT-Pc could form more hydrogen bonds. TBIT-Pc and TBTT-Pc were fully characterized by elemental analysis, 1H NMR, MALDI-TOF MS, FT-IR and the UV-Vis absorption spectrum. The self-assembly properties of TBIT-Pc and TBTT-Pc were comparatively studied. TBIT-Pc and TBTT-Pc were present as monomers in DMF in the concentration range of 9.04–20.3 μM. Depending mainly on the intermolecular hydrogen bonding (N–H⋯N) between benzimidazole substitutes, “head-to-tail” J-aggregates of TBIT-Pc were formed in DMSO, while there was no aggregation of TBTT-Pc in the same solvent. “Face-to-face” H-aggregates of TBIT-Pc and TBTT-Pc were formed with the addition of water to the solutions of DMSO, and the degree of aggregation increased with the introduction of H-bonds (N–H⋯N) in the benzimidazole substitutes of TBIT-Pc. The atomic force microscope (AFM) image and dynamic light scattering (DLS) displayed the formation of well-defined nanoparticles with a diameter of ca. 30 ± 15 nm with J-type aggregation of TBIT-Pc. And the dendritic nanostructures with H-aggregates of TBIT-Pc and TBTT-Pc with different size were observed from transmission electron microscopy (TEM) images. The possible mechanism of the effect of H-bonds on the formation of J-aggregates of TBIT-Pc and the H-aggregation of TBIT-Pc and TBTT-Pc was also discussed. In the formation process of aggregates, H-bonds and π–π interaction may be the dominant factors. In addition, the nanostructures fabricated from TBIT-Pc and TBTT-Pc showed good semiconducting properties revealed by current–voltage measurements.

Cu-incorporated MCM-41 was prepared by the direct synthesis method. The Cu-incorporated MCM-41 was then organically functionalized by grafting of organosilanes followed by the complexation of copper ions. The results of powder X-ray diffraction, Fourier transform infrared, and temperature-programmed reduction suggest the incorporation of Cu into the framework of MCM-41 during the direct synthesis process. The mesostructure of prepared samples is preserved after functionalization. The sulfur capacities for tert-butyl mercaptan, dimethyl sulfide, and dimethyl disulfide decrease in the same order (40)Cu–M > (40)Cu–M–N–Cu. The (40)Cu–M synthesized through the direct synthesis method also shows better desulfurization performance than M–Cu prepared by the incipient wetness impregnation method. This is attributed to the incorporated Cu species in the framework and well-dispersed CuO species of (40)Cu–M.

A relatively green, efficient and economical synthetic route for the one-step solid-phase synthesis of sulfonated cobalt phthalocyanine from sulfonated phthalic anhydride mixture was studied, and could solve the serious problems of waste acid pollution and the low utilization of materials in the direct sulfonation of phthalocyanine. The optimal reaction conditions were using a phthalic anhydride mixture with a sulfonation degree of 60% as the raw material, a ratio of urea to PA–SPA mixture of 4:1, a ratio of cobalt chloride to PA–SPA mixture of 1:4, ammonium molybdate (1 wt%) as catalyst, and carrying out the reaction at 260 °C for 3 hours. Under these optimal conditions, a yield of 52.9% can be achieved. Through sweetening experimental studies, the synthesized sulfonated cobalt(II) phthalocyanine had better sweetening performance than the industrial catalysts, in both the liquid–liquid sweetening and fixed bed sweetening experiments. A sweetening rate of 93% can be achieved in 20 min with the synthesized catalyst in a fixed bed.

A series of organically–inorganically functionalized MCM-41 compounds have been prepared with 3-aminopropyltrimethoxysilane (APTMS) as the organic component and CuO and/or Cu(NO3)2 as the inorganic component. The textural properties of functionalized MCM-41 were characterized by powder X-ray diffraction (XRD), nitrogen adsorption–desorption, and transmission electron microscopy (TEM). The results indicate that the hexagonally ordered structure of MCM-41 remained intact after functionalization. The presence of grafted organosilanes was confirmed by Fourier transform infrared (FTIR) spectra, 13C nuclear magnetic resonance (13C CP-MAS NMR), and 29Si nuclear magnetic resonance (29Si MAS NMR). All adsorbents showed similar desulfurization performances for different sulfur compounds in the order tert-butyl mercaptan (TBM) > dimethyl sulfide (DMS) > dimethyl disulfide (DMDS), which is due to the poor reactivities and polarities of DMS and DMDS. MCM-41-NH2-Cu functionalized with Cu2+ as the active sites is the most efficient adsorbent for the removal of TBM. The desulfurization mechanism was discussed based on the experimental results and X-ray photoelectron spectroscopy (XPS) characterization. The results show that CuO plays a more dominant role than Cu2+ for the removal of DMS and DMDS.

The effect of H2S contents on the transformation of 1-hexene with hydrogen over NiMoS/γ-Al2O3 catalyst was investigated. Inhibition of H2S on both hydrogenation and isomerization reactions of olefin has been demonstrated. And the promotion effect of H2S on the formation of C6 thiols and C12 thioethers has also been observed. It was found out that there was only one type of active site on the NiMoS/γ-Al2O3 for reactions which include hydrogenation reaction, isomerization reaction and sulfides formation reaction, and the formation reactions of sulfides were superior to both hydrogenation and isomerization reactions. The reaction network for the conversion of 1-hexene in the presence of H2S was proposed.

Based on the principle of biomimetic catalysis, β-cyclodextrin was applied to the acetalation reaction as a facile and efficient catalyst, and the synthesis was environmentally friendly with atomic economy. The influencing factors of the acetalation reaction e.g. the reaction time, the volume of water-carrying agent, the molar ratio of catalyst to benzaldehyde and the molar ratio of glycol to benzaldehyde had been studied. The yield of benzaldehyde glycol acetal would reach a maximum of 81.3% under the conditions approached. Six of other acetals were also synthesized. Moreover, a plausible reaction mechanism for the formation of acetal had been proposed.Download full-size image