Supported Ni (60 wt% Ni) catalysts were prepared and phosphided into corresponding Ni2P catalysts. They were used for the hydrogenation of furfural as well as for the probe reactions (the hydrogenation of furan and propanal). The results demonstrated that the acidic support promoted the adsorption and hydrogenation of furan ring and aldehyde group over the nickel sites while the basic support played the opposite role. The IR spectra demonstrated that the aldehyde group was more easily hydrogenated than the furan ring at room temperature, implying the sequential hydrogenation of furfural to furfuryl alcohol (FA) and then to tetrahydrofurfuryl alcohol (THFA) over Ni. The microcalorimetric studies revealed that both the aldehyde group and furan ring were strongly adsorbed on Ni so that the Ni catalysts were highly active to hydrogenate the two groups, i.e., the Ni catalysts favored the formation of THFA. On the other side, although the adsorption heats of aldehyde group were much lower on Ni2P than on Ni, the adsorption heats were significantly higher for aldehyde group than for furan ring on Ni2P, implying the high selectivity to FA on Ni2P.

High-surface-area supports SiO2, MgO, and MgSiO (MgO-SiO2) were prepared and used to support 2% Pd for the hydrogenation of imines. It was found that the basic surface of the catalysts constrained the decomposition of diisopropylimine (DIPI), resulting in the higher selectivity to diisopropylamine (DIPA) during the hydrogenation of DIPI. However, the basic surface also limited the conversion of DIPI over Pd. On the other hand, Pd/MgSiO possessed surface basicity that was not strong enough so that the catalyst remained highly active for the hydrogenation of imines, especially for the production of N-methylglucosamine (NMGA) from N-methylglucosimine (NMGI). In addition, the surface basicity enhanced the yield to NMGA and the stability of the MgSiO support in the organic amines. Thus, Pd/MgSiO exhibited significantly higher activity than Pd/MgO and higher selectivity and stability than Pd/SiO2 during the production of NMGA from NMGI.

Ru/MgO-Al2O3 catalysts (2-6 wt% Ru) were prepared by a two-step co-precipitation method and were found to be highly active and selective for the hydrogenation of aromatic amines to alicyclic amines. Hydrogenation of toluene in the presence of triethylamine (TEA) was used as a probe reaction to explain the obtained results. It was found that adsorption of toluene in the presence of TEA on Ru than on Co and Ni catalysts was significantly less inhibited and thus the conversion of toluene. Ru/MgO-Al2O3 was thus found to be significantly superior to the Ni/MgO-Al2O3 and Co/MgO-Al2O3 for the hydrogenation of aromatic amines to alicyclic amines.

Pd–Ru/SiO2 showed special surface chemical properties that were totally different from those of Pd/SiO2 and Ru/SiO2 and exhibited high activity and selectivity for the hydrogenation of benzoic acid to cyclohexanecarboxylic acid.

A 60％Co/Al2O3 catalyst was prepared by the co-precipitation method.It was then reduced by H2,sulfided by CS2 and phosphided by PPh3,respectively,to metallic Co,Co9S8 and cobalt phosphides(Co2P and CoP).It was found that the activities of these catalysts for the hydrodesulfurization(HDS)reactions followed the order of CoP/Al2O3＞Co2P/Al2O3＞Co9S8/Al2O3＞Co(metal)/Al2O3.In addition,the phases of CoP and Co9S8 were stable(did not change)during the HDS reactions,and CoP was significantly more active than Co9S8.On the other hand,Co2P could be converted into CoP and Co3S4 during the HDS reactions,and thus the Co2P/Al2O3 was less active than the CoP/Al2O3.The Co(metal)/Al2O3 could be sulfided when directly used for the HDS reactions with the formation of large particles of Co9S8(9 nm),which were significantly larger than those in the pre-sulfided Co9S8/Al2O3(5 nm).Thus the Co(metal)/Al2O3 was less active than the Co9S8/Al2O3 for the HDS reactions.

采用共沉淀法制备了高分散80％Ni/Al2O3催化剂,经350℃焙烧,得高分散NiO/Al2O3(NiO粒径～3 nm),将其以CS2硫化(310 ℃,4 h)或PPh3磷化(320 ℃,36 h),分别获得了高分散的硫化镍(Ni3S2和Ni3S4,5.8 nm)和Ni2P(7.0 nm),在二苯并噻吩(DBT)的加氢脱硫(HDS)反应中,Ni2P的活性远高于NiSx(360 ℃时DBT的转化率分别为100％和75％).若将NiSx用PPh3磷化,则NiSx全部转化为Ni2P(13.3 nm),其HDS活性远高于原来的Nisx且与直接磷化获得的Ni2P(7.0 nm)相当.反之,若将Ni2P用CS2硫化,则Ni2P物相不变,粒径也没有长大,表明Ni2P物相远比NiSx稳定,且其HDS活性高于直接磷化的Ni2P,表明其Ni2P表面可能生成了HDS活性更高的某种Ni-P-S物种.

The effects of solvents (n-hexane, isopropanol (IPA), tetrahydrofuran (THF) and methanol) on the hydrogenation of toluene over the Pd/SiO2 and Ru/SiO2 catalysts were studied. Microcalorimetric adsorption and IR spectroscopy were employed to understand the effects. It was found that n-hexane adsorbed weakly on the catalysts and thus affected less the hydrogenation of toluene, while THF and methanol adsorbed strongly on the catalysts and inhibited the activity of hydrogenation of toluene significantly. IPA also adsorbed strongly on the catalysts, but it exhibited a hydrogen transfer effect on the surfaces that promoted the conversion of toluene.

In this paper, we report on the rational design, synthesis, characterization, and application of eco-friendly hydroxyapatite/carbon (HAP/C) composites as effective sorbents for the simultaneous remediation of organicinorganic pollution in wastewaters. Carbon content in composites ranged from ca. 4 to ca. 20 wt%. Structural and morphological features of the composites were studied by N2 adsorption/desorption analyses, electron microscopy (TEM and HAADF-STEM/EDX) and X-ray powder diffraction (XRPD). These features were correlated with the composition and the exposure of surface functional groups. Surface acid-base groups were assessed by liquid-solid acid/base titrations and results depended on the composition ratio of the two components. Batch adsorption tests, performed with various initial concentrations of pollutant species and dosages, proved that composites merged the sorption properties of the two moieties, being able to simultaneously adsorb organic (methylene blue) and inorganic (Cu(II) and Ni(II)) pollutants. On the optimal carbonaceous scaffold content (ca. 8 wt% carbon), kinetic tests revealed that this composite could almost completely remove high concentrations of co-present pollutants, namely, Cu(II), Ni(II), (300 ppm) and methylene blue (250 ppm) in ca. 1 h, with sorbent dosage of 10 g L-1. In addition, leaching tests proved the permanent retention of the hazardous species on the composites.

Vanadium oxyphosphate (VPO) with a high surface area was synthesized in a mixed solvent of ionic liquid [Bmim]Br and water, using phosphorous acid to reduce V5+ to V4+ and as a partial phosphorus source, and V2O5 as the vanadium source. The effects of ionic liquids on the synthesis process were investigated in detail. Using pure water as the solvent, the product was a vanadium phosphate compound with large flakes. With the increase in the amount of ionic liquid, the size of the large flakes of vanadium phosphate gradually decreased, and the morphology was changed to spherical particles. When the proportion of ionic liquid was 80% or the ionic liquid was solely used as the solvent, the VPO showed completely spherical particle morphology, and the specific surface area was the highest. X-ray diffraction analysis showed that the crystal phase of VPO changed from vanadium (IV) hydrogenphosphate hemihydrate (VOHPO4·0.5H2O) to an amorphous state with an increase in ionic liquid ratio. All of the above results show that ionic liquids play an important role in the synthesis of VPO materials. After being calcined in an n-butane/air atmosphere, the precursors were transformed into the vanadium pyrophosphate phase. The active VPO catalysts were used in the selective oxidation of cyclohexanol, and the yield of cyclohexanone was 57.98% for the VPO-80 catalyst synthesized using the ionothermal method but only 21.41% for the VPO-W catalyst synthesized using a traditional hydrothermal method, which shows the advantage of ionic liquid synthesis for VPO catalysts. Vanadium oxyphosphate material with high surface area was synthesized in the mixed solvent of ionic liquid [Bmim]Br and water. Ionic liquid plays an important role in the morphology and properties of synthesized VPO materials. The active VPO catalysts were used in the selective oxidation of cyclohexanol, and the yield of cyclohexanone was 57.98% for VPO-80 catalyst synthesized by ionothermal method, but only 21.41% for VPO-W catalyst synthesized by traditional hydrothermal method, which exhibited the advantages of ionic liquid synthesis for VPO catalysts.

Nitrogen-containing mesoporous carbons (SNMC) were shaped by the drop ball method. A SNMC and a commercial coconut shell carbon (CSC) were oxidized by nitric acid to obtain the OSNMC and OCSC supports. Then, the Pd/OSNMC, Pd/SNMC, Pd/OCSC and Pd/CSC catalysts (5%wt) were prepared to study the effects of carboxyl group on the hydrogenation of C=C double bond. The results showed that both the doped N and surface O-containing functional groups increased the dispersion and surface electron density of supported Pd, leading to the increased heats for the adsorption of hexene and H2 and thus the increased intrinsic activity for the hydrogenation of hexene on Pd. The pre-adsorption of propionic acid (PA) significantly inhibited the adsorption of hexene and H2 and decreased the conversion of hexene on Pd. However, the surface O-containing functional groups inhibited the adsorption of carboxyl groups and offset the inhibition effect of carboxyl groups on the hydrogenation of hexene on Pd, while the doped N atoms played the opposite role. Thus, it is expected that the surface O-containing functional groups are beneficial to the hydrogenation of unsaturated fatty acids on Pd/C catalysts.

HZSM-5 is a widely used catalyst for the conversion of methanol to aromatics (MTA), but its single micropore system often results in severe diffusion limitations, leading to the decrease of reaction rate and the change of selectivity to aromatics, as well as affecting the carbon deposition and catalyst deactivation. Thus, an ingenious protective desiliconization method with a mixed solution of sodium hydroxide and tetrapropylammonium hydroxide as a desiliconization agent was developed to create hierarchical porous systems without destruction of the main structure of the molecular sieve. Such modification leads to the greatly increased mesoporous volume from 0.12 to 0.38 cm(3) g(-1), and only slightly decreased microporous volume from 0.12 to 0.09 cm(3) g(-1). However, the desiliconization sharply increases the acidity of the catalyst (from 0.248 to 0.341 mmol g(-1) for the strong acid sites), which may significantly affect the distribution of aromatics and accelerate the carbon deposition rate. Thus, the deposition of inert SiO2 on the catalyst surface is subsequently carried out to passivate the surface acidity and adjust the orifice of the catalyst. Accordingly, a hierarchical porous HZSM-5 molecular sieve catalyst (Si@Z5-Na + TP) with suitable acidity is precisely prepared, which exhibits the high selectivity to benzene, toluene and xylenes (BTX) with the excellent anticoking ability in the MTA reaction. The selectivity to BTX in aromatics (63.32%) and the carbon deposition rate (0.91 mg g(cat)(-1) h(-1)) over the Si@Z5-Na + TP catalyst are both much more superior than those over the parent HZSM-5 catalyst (47.5% and 2.23 mg g(cat)(-1) h(-1), respectively).

甲苯-甲醇侧链烷基化合成苯乙烯具有极高的工业应用前景和学术研究意义.我们介绍了甲苯与甲醇侧链烷基化反应制苯乙烯的课题背景,总结了改性X型分子筛、复合型分子筛、多孔碳和金属氧化物以及其它类型催化剂在甲苯-甲醇侧链烷基化反应中的应用状况,分析了其反应机理及甲醛深度分解的原因以及目前催化剂的不足,并提出了可能的改进方案.最后对该领域的今后研究重点进行了展望,为提升甲苯与甲醇侧链烷基化催化剂的活性、选择性及使用寿命等相关研究提供参考.

A highly dispersed Cu-O-Si composite oxide framework catalyst with high surface area (619 m2/g) and very small particle size (~3 nm) has been synthesized using an improved precipitation method, which showed high catalytic activity toward the hydrogenation of dimethyl oxalate (DMO) (99.9% conversion of DMO and 96.7% selectivity for ethylene glycol) even at low temperature (175 °C). In addition, its chemical stability was significantly enhanced due to the formation of a Cu-O-Si composite structure and the low reaction temperature, and the catalyst did not show any significant inactivation during the stability test over 140 h.

Ni/ZrO2–CeO2 catalysts with high loading of nickel have been prepared by coprecipitation method and employed to investigate the catalytic hydrodeoxygenation (HDO) performance of guaiacol. The mater...

The acidity of a mesoporous carbon has been enhanced and strengthened thanks to the formation of new oxygenated functionalities.

Mesoporous melamine formaldehyde resins (MMF) with high surface areas and large pore volumes and diameters were prepared without the use of a template. Conditions such as solvent, concentration, formaldehyde/melamine ratio and curing temperature and time on the pore parameters of synthesized MMF were investigated. The results showed that the sample (MMF9-120) synthesized in the solvent H2O/DMAc had the surface area higher than 1000 m(2)/g, pore diameter of about 22 nm and pore volume of about 3.5 cm(3)/g. It was found to be amphiphilic owing to the presence of amino, ether and alkyl groups on its surface, so that it adsorbed great amount of H2O and toluene. Due to the large pore diameter and volume, it also adsorbed great amount of tannic acid (MW = 1701) and bovine serum albumin (MW = 69 k) (850 and 1160 mg/g, respectively), indicating an excellent adsorbent for large molecules. In addition, it was thermally stable and when heated at 350 degrees C, the formed MMF9350 still possessed the high surface area (549 m(2)/g), which was expected to be a new resin support for catalysts, as compared to the traditional porous polystyrene resins which can only be used at temperatures below 120 degrees C.

Bisphenol F (BPF) is an important monomer and was usually prepared from phenol (Ph) and formaldehyde (FA) catalyzed by an acid. In this study, an acid resin–carbon composite (PP-170) was prepared for the synthesis of BPF from Ph and FA liberated through the decomposition of a polyoxymethylene dimethyl ether (PODE2). Characterization results showed that −SO3H and Ar–OH groups were successfully introduced into PP-170, and were mostly distributed in the inner pores. As compared with H3PO4 and H2SO4, the PP-170 had the higher turnover frequencies for the synthesis of BPF, as well as the higher selectivity to BPF (especially the 4,4-BPF). Thus, PP-170 seemed a good solid acid catalyst for the synthesis of BPF from Ph and PODE2. In addition, the catalyst could be easily regenerated by the simple calcination and then reused at least twice with almost the same activity.

Nickel phosphate (NiPO) nanofibers with high surface area (288 m(2)/g) were obtained from phosphoric acid and nickel nitrate in an ionic liquid ([Bmim]Br) via an ionothermal synthesis process at 150 degrees C. Heating the nano fibers under a H-2 atmosphere at 700 degrees C led to the formation of Ni2P nanorods, similar to 50 nm in diameter and 100-200 nm in length. The Ni2P nanorod catalyst exhibited a much higher turnover frequency in the hydrodesulfurization of dibenzothiophene than the previously reported Ni2P catalysts with nanoparticle, nanosheet or irregular block morphologies, which may be attributable to the morphology effect of the nanorods.

Highly dispersed and loaded (60 wt %) catalysts Co/MgAlO, Co/MgO, and Co/Al2O3 were prepared for the hydrogenation of toluene without and with triethylamine (TEA). It was found that while Al2O3 favored the dispersion of Co, MgO promoted the reduction of CoOx so that the Co/MgAlO exhibited the small Co particles (∼6.5 nm), high H2 uptake (363 μmol/g), and thus was highly active for the hydrogenation reaction without TEA (not only higher than the Co/Al2O3 and Co/MgO but also higher than the 60% Ni/MgAlO). In addition, the adsorption heat of TEA was significantly lower on the Co/MgAlO than on the Ni/MgAlO so that the reaction activity for the hydrogenation of toluene was significantly less affected by TEA on the Co/MgAlO than on the Ni/MgAlO. Thus, the Co/MgAlO can be expected to be better than the Ni/MgAlO for the synthesis of alicyclic amines from aromatic amines.

A series of SiO2-TiO2 binary oxides supported high loading Ni catalysts were prepared using the co-precipitation method and tested in guaiacol hydrodeoxygenation (HDO). The catalysts were characterized using N-2 adsorption-desorption, XRD, TEM, FT-IR, XPS, H-2-TPD, and NH3-TPD. The formation of Si-O-Ti bond in the SiO2-TiO2 binary oxides was verified by XPS, which can increase the total amount of acidic sites and enhance the interaction between metal Ni and TiO2. The oxygen defect sites of TiO2 were formed near the perimeter of the metal-support interface, leading to generation of Ni delta--O-v-Ti-3+ interface sites, which play the role of active centers to catalyze guaiacol HDO. These positive factors promoted HDO activity over Ni catalysts supported on binary oxides, compared to Ni loaded on single oxide supports. The selectivity of products indicates relatively high temperature and low H-2 pressure are beneficial for producing oxygen-free aromatics in HDO of guaiacol.