Bilirubin adsorption on amine/methyl bifunctionalized SBA-15 with platelet morphology

To remove bilirubin from human plasma, amine/methyl bifunctionalized SBA-15 materials were directly synthesized from the co-condensation of 3-aminopropylmethyldiethoxysilane and tetraethoxysilane with an amphiphilic block copolymer P123 as template. XRD, N(2) sorption analysis, FTIR and (29)Si MAS NMR were used to identify their well-ordered mesostructure and the grafting of amine and methyl groups on the surface of as-synthesized materials. Both SEM and TEM indicated that the bifunctionalized SBA-15 possessed platelet morphology. This might be attributed to the charge repulsion brought by protonated amine groups and the diminution of hydroxyl groups on the end of silicate-micelles, which passivated the end-to-end anchoring of silicate-micelles along the longitudinal axis. Such a material was investigated as the adsorbent for selective bilirubin removal from human plasma, which showed a high bilirubin clearance of 51.4% within 1.5 h with a little amount of albumin adsorption. The results of hemolysis assay suggested that the bifunctionalized SBA-15 caused serious hemolysis of red blood cells. However, in practical application, plasma separation technique could avoid direct contact between the adsorbent and red blood cells. The further hemeolysis assay proved that the plasma after contacting with the bifunctionalized SBA-15 could not lead to the hemolysis of red blood cells. Thus, the bifunctionalized SBA-15 is expected to be a potential candidate as a clinical hemoperfusion material.     

VOx/SBA-15催化剂上甲苯气相部分氧化

采用等体积浸渍法制备了不同负载量的VOx/SBA-15催化剂。UV-Vis和H2-TPR等表征结果表明,在较低钒负载量下,钒物种的分散程度较高,主要以孤立的VO4 3－以及少量聚合体V－O－V形式存在;钒负载量较高时会有大量的聚合体V－O－V甚至晶相V2O5出现,而且,催化剂的酸性随着钒物种的高度分散而降低。甲苯气相部分氧化反应结果表明,随着钒负载量的提高,苯甲醛的选择性先升后降,CO、CO2等选择性逐渐提高。这是由于催化剂存在大量的聚合体V－O－V和晶相V2O5时,聚集态钒物种表面较多的酸量促使苯甲醛深度氧化。在相同钒负载量下,催化剂VOx/SBA-15的钒物种分散状态优于VOx/MCM-41和VOx/SiO2,从而使得催化剂VOx/SBA-15呈现较高的苯甲醛选择性。     

原位还原法制备Ag/SBA-15及其对CO的催化氧化

以原位还原的方法一步合成了Ag/SBA-15复合催化剂,通过粉末XRD、TEM、ICP-AES和低温氮气吸附-脱附等手段对样品进行了表征.考察了不同催化剂对CO催化活性的影响,结果表明当金属纳米的尺寸大小为6~8nm左右,银的含量为6.86%时(Ag/SBA-15-3)的催化活性最高,在120℃时就可使CO完全氧化,可以重复使用,在100%的转化温度时保持200min转化率仍不降低.     

Propane/propylene separation by selective olefin adsorption on Cu/SBA-15 mesoporous silica

Samples of mesoporous silica, SBA-15, were prepared under hydrothermal conditions and Cu cations were incorporated into the framework by two different impregnation techniques. The corresponding adsorption/desorption isotherms of propylene, propane, and N₂ were measured to evaluate the material's effectiveness in the separation of propane/propylene mixtures. Adsorption uptake of propylene increased and that of propane decreased in Cu containing samples as compared to the uptakes observed in undoped SBA-15 samples. It was demonstrated that the presence of Cu atoms in the adsorbent lattice led to a greater selectivity towards propylene. Furthermore, the highest level of Cu(I) were obtained in samples prepared by equilibrium impregnation, which in turn improved the olefin/paraffin uptake ratio. Under some working conditions, the amount of propylene adsorbed in selected samples is totally reversible while propane uptake was negligible.     

Ni2P/SBA-15催化剂的结构及加氢脱硫性能

以硝酸镍为镍源,磷酸氢二铵为磷源,介孔分子筛SBA-15为载体,用共浸渍法制备了含磷化镍前驱体的样品,然后在氢气流中采用程序升温还原法,制备了Ni2P质量分数为5%-40%的Ni2P/SBA-15催化剂.用X射线衍射(XRD)、N2吸附脱附、透射电子显微镜(TEM)、傅立叶变换红外光谱(FTIR)等分析测试技术对催化剂的结构进行了表征,以噻吩和二苯并噻吩(DBT)为模型化合物,在微型同定床反应器上对催化剂的加氧脱硫(HDS)性能进行了评价.结果表明,Ni2P/SBA-15催化剂中SBA-15的介孔结构依然存在,活性组分Ni2P具有良好的分散性,但随Ni2P含量的增加,催化剂的比表面积、孔容和孔径均有明显减小.当反应温度为320℃时,Ni2P含量为15%-25%(w)的催化剂就具有很好的加氢脱硫催化性能;反应温度在360℃以上时,所有催化剂都具有优异的深度脱硫催化性能.Ni2P/SBA-15催化剂对二苯并噻吩的加氢脱硫(HDS)主要以直接脱硫机理(DDS)进行.     

Synthesis and characterization of P4VP/SBA-15 composite by in situ polymerization

Abstract  

Poly(4-vinylpyridine)/SBA-15 (P4VP/SBA-15) composites with various amounts of SBA-15 were prepared and characterized. The physical and chemical properties of P4VP/SBA-15 were investigated by XRD, BET, FT-IR, TGA, and SEM techniques. The catalytic performance of each material was determined for the Knoevenagel condensation reaction between carbonyl compounds and ethyl cyanoacetate in the presence of water as a solvent. The effects of reaction temperature, the amount of catalyst, amount of support, solvent, and the amount of benzoyl peroxide during the synthesis of P4VP/SBA-15 were investigated, as well as the recyclability of the heterogeneous composite. The catalyst used for this synthetically useful transformation showed a considerable level of reusability as well as very good activity. This reaction occurred rapidly when water was used as a solvent, so we assume it to be a green reaction.     

CO oxidation catalyzed by Ag/SBA-15 catalysts: Influence of the hydrothermal treatment

Four types of SBA-15 were prepared with different times and temperatures of treatment in order to obtain a range of micropore sizes. CO oxidation was used as a probe reaction in order to evaluate the nature of the active species when SBA-15s were doped with ca 10% Ag deposited from an AgNO₃ solution and calcined or reduced at 350 °C. The texture (TEM, nitrogen physisorption), structure (XRD) and reducibility (TPR) of the various catalysts (Ag/SBA-15) were studied and compared to those of a catalyst prepared by deposition of silver on fumed silica as a reference. These catalysts differ initially by the nature of silica and by pore sizes. In CO oxidation, pre-reduced catalysts are more active than pre-oxidised ones. This has to do with two phenomena, i.e. sintering, which produces large inactive silver particles, and formation of active silver species in the form of small Ag₂O particles.     

Study on the adsorption of lanthanum ion imprinted on SBA-15/Y

The lanthanum ion imprinted polymer (La-IIP/SBA-15/Y) was successfully synthesized by the surface ion imprinting method. Using La-IIP/SBA-15/Y as the adsorbent to adsorb lanthanum ions, the overall empirical conditions were optimized, and the best exploratory conditions were finally found. The pH of the solution was 2; the adsorption equilibrium was reached in 60 min and the saturated adsorption capacity was 562.95 mg/g La-IIP/SBA-15/Y adsorbed gadolinium ions in the study of its adsorption process and found that it conforms to the Langmuir isotherm adsorption model, and the adsorption reaction is a spontaneous reaction, and it also conforms to the quasi-second-order kinetic model. The selectivity of the adsorbent was explored experimentally, and the results showed that La-IIP/SBA-15/Y has good selectivity, and experimental elution and regeneration performance. The best elution effect is 2 mol/L hydrochloric acid. La-IIP/SBA-15/Y has good stability and can be reused.     

Cationic dye adsorption by poly(N-isopropylacrylamide/maleic acid) copolymeric hydrogels prepared by gamma rays

N-isopropylacrylamide/maleic acid hydrogels containing different quantities of maleic acid have been synthesized with γ-radiation. The hydrogels were used in experiments on swelling, diffusion and adsorption of a cationic dye methylene blue. The diffusion of MB into the hydrogels was found to be the non-Fickian type. The factors influencing adsorption capacity of the hydrogel such as gel composition, and irradiation dose were systematically investigated. The equilibrium data for dye adsorption was better described by the Freundlich isotherm than Langmuir isotherm model. The kinetic studies showed that the pseudo-second-order kinetic model fits better than the data obtained from pseudo-first-order model.     

Structure sensitivity of vibrational spectra of mesoporous silica SBA-15 and Pt/SBA-15

The vibrational properties of mesoporous silica (SBA-15) were investigated by deep ultraviolet (UV) Raman and infrared spectroscopies with and without the presence of platinum nanoparticles in the mesopores that were incorporated by sonication. Raman and IR spectral line assignments were made by comparison to amorphous silicas. This procedure permitted identification of vibrations of longitudinal (LO) and transverse (TO) optical lattice modes, the presence of Si-OH, and vibrational modes associated with the presence of three-, four-, and six-membered siloxane rings. Hydraulic pressing of the mesoporous silica with pressure in the range 3-7 tons cm(-2) destroys the X-ray diffraction pattern and strongly decreases the Raman peak (D2) associated with three-membered rings at the surface. In the presence of platinum nanoparticles in the silica mesopores, a peak attributed to a Pt-O stretching vibration appears at between 530 and 580 cm(-1) in the UV-Raman spectrum, which can be used to monitor the presence of the platinum particles and their interaction with the support. The D2 feature in the UV-Raman spectra also decreases with increasing Pt loading, which is attributed to interactions of the Pt nanoparticles with the silica surface.     

Preparation,characterization and hydrodesulfurization performances of Co-Ni_2P/SBA-15 catalysts

A series of Co-Ni2P/SBA-15 catalysts with various Co contents, Ni2P contents and P/Ni molar ratios were prepared by impregnating nickel nitrate, diammonium hydrogen phosphate, and then cobalt nitrate into SBA-15 support followed by temperature-programmed reduction in a H2 flow. The catalyst structure was characterized by X-ray diffraction(XRD), high resolution-transmission electron microscopy(HR-TEM)and N2adsorption-desorption techniques and their catalytic performance of the hydrodesulfurization(HDS) of dibenzothiophene(DBT) was evaluated. The effects of Co contents, Ni2 P contents and P/Ni molar ratios on the catalyst structure and HDS of DBT over the Co-Ni2P/SBA-15 catalyst were investigated. The results indicated that the mesoporous structure was mainly maintained and the nickel phosphides were well dispersed in all of the characterized catalysts. The 4Co-25Ni2P/SBA-15(P/Ni = 0.8) catalyst with the Co and Ni2 P contents of 4 wt% and25 wt%, respectively, and the P/Ni molar ratio of 0.8 showed the highest catalytic performance for HDS of DBT. Under the reaction conditions of 380?C and 3.0 MPa, the DBT conversion can reach 99.62%. The HDS of DBT proceeded mainly via the direct desulfurization(DDS)pathway with biphenyl(BP) as the dominant product on all of the catalysts and the BP selectivity was slightly enhanced after the introduction of Co promoters.     

Structural and sorption properties of carbon replicas obtained by matrix carbonization of organic precursors in SBA-15 and KIT-6

We have carried out a comparative study of matrix carbonization of some organic precursors (sucrose, polydivinylbenzene, polyphenol-formaldehyde, polyacrylonitrile, acetonitrile) in SBA-15 and KIT-6 silica mesoporous molecular sieves. We have shown that carbon mesoporous molecular sieves of the CMK-8 type, obtained in KIT-6 mesopores, have better adsorption characteristics due to the features of the three-dimensional cubic structure, the larger pore volume and thickness of the walls of the framework. The maximum micropore volume is observed in CMK-3 and CMK-8, obtained by carbonization of polyphenol-formaldehyde and polydivinylbenzene, while the greatest specific surface area is observed on carbonization of sucrose, where the maximum hydrogen adsorption capacity is achieved at a level of ∼1.4 wt.% (77 K, 1 atm). We show that the mesopore surface coverage by hydrogen in carbon mesoporous molecular sieves increases as the degree of graphitization increases.     

CO and NO adsorption on VO x /SBA-15 catalysts: an FT-IR spectroscopic study

The adsorption of CO and NO over VO _x -SBA-15 mesoporous materials with different vanadium content was investigated by FT-IR spectroscopy. Vanadium complexes were reduced in situ by hydrogen atmosphere at 450 °C for 3 h. Spectra of reduced samples show increasing in intensity of silanol groups, caused by dissociation of V–O(Si) bonds and formation of new H–O(Si) bonds. Reduction occurs with formation of water. The band corresponds to overtone of V=O stretching modes decreases in intensity because of oxygen withdrawing from V=O species. Presence of V⁴⁺ and V³⁺ species was observed. Inspection of CO adsorbed IR spectra evidenced existence at least two different type of V³⁺–CO complexes on the silica surface differing in both stretching frequencies and complex stabilities. We did not found principal difference between spectra of absorbed CO at ?196 °C on the samples with different concentration of vanadium, probably because of relative low degree of reduction. As well as heterogeneity of surface V³⁺ and V⁴⁺ species was evidenced by adsorption of NO. Both V³⁺ and V⁴⁺ ions possess two effective coordinative vacancies and as a result can adsorb two NO molecules forming dinitrosyls. A part of V³⁺ cations forms only mononitrosyls characterize by band at 1724 cm^?1. Results obtained after NO adsorption reveal existence of three different kinds of vanadium species. Probably two of them are isolated and associated vanadium sites. The third type of vanadium has different surrounding than other two types. It was demonstrated that NO is a better probe than CO for testing the oxidation and coordination state of reduced vanadium species.     

Mo-Ni2P/SBA-15催化剂的制备、表征及加氢脱硫催化性能

以介孔分子筛SBA-15 为载体, 通过分步浸渍硝酸镍、磷酸氢二铵、钼酸铵, 然后在H₂气流下程序升温还原(H₂-TPR), 制备了一系列不同Mo 含量的Mo-Ni₂P/SBA-15 催化剂. 采用X 射线衍射(XRD)、氮气吸脱附(BET)、透射电子显微镜(TEM)和X射线光电子能谱(XPS)对催化剂的结构进行了表征, 评价了催化剂对二苯并噻吩(DBT)的加氢脱硫(HDS)活性. 结果表明, Mo-Ni₂P/SBA-15 催化剂仍然保留有介孔结构, 催化剂的物相主要是Ni₂P. 催化剂表面的Ni 以Ni^δ+和Ni²⁺形式存在; P以P^δ-和P⁵⁺形式存在; Mo以Mo^δ+和Mo⁶⁺形式存在. Mo能促进催化性能的提高, 其中Mo含量为1% (w, 质量分数)的Mo-Ni₂P/SBA-15 催化剂具有最好的二苯并噻吩加氢脱硫催化活性, 在反应温度为380 ℃, 反应压力为3.0 MPa的条件下, 二苯并噻吩的转化率可达99.03%, 所有考察的Mo-Ni₂P/SBA-15都以直接加氢脱硫(DDS)途径为主.     

Selective adsorption of 2,4-dinitrophenol on molecularly imprinted nanocomposites of mesoporous silica SBA-15/polyaniline

Surface imprinting and adoption of a nano-sized physical form are two effective approaches to overcome the template transfer difficulty within molecularly imprinted polymers (MIPs). This work is an attempt to conquer the problem of template transfer difficulty within MIPs by using a nano-reactor as a substrate for the reaction between the monomer and the template. Negatively charged hexagonal nano-channels of SBA-15 can act as a support for attachment of positively charged aniline monomers and the 2,4-dinitrophenol (2,4-DNP) template. The imprinted and non-imprinted SBA-15/polyaniline nanocomposites were characterized by Fourier transform infrared (FT-IR), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and nitrogen adsorption-desorption isotherms. The results showed that the synthesized polymer possessed a highly ordered mesoporous structure. The distribution coefficient values of 2,4-DNP, K(d (2,4-DNP)), were estimated as 301.4 ± 2.3 and 101.2 ± 1.0 mL g(-1) for imprinted and non-imprinted polymers (NIP), respectively. The MIP-solid-phase extraction (SPE) process was optimized by evaluating the type of washing solvent and the composition and volume of the eluting solvent. The prepared MIP was used as a selective sorbent for SPE of 2,4-DNP in the presence of phenolic compounds in tap and sea water. The experimental results indicated that the MIP-SPE and NIP-SPE column yielded recoveries higher than 96% and 38%, respectively. The R.S.D. values were also lower than 3.2% and 4.6% for MIP-SPE and NIP-SPE, respectively.     

Ce/SBA-15复合材料的合成与表征

借助水热法,在酸性条件下直接加入合成系统前驱盐(硝酸铈),通过蒸发得到复合物,然后进行煅烧,制备了Ce/SBA-15复合材料。利用X-射线粉末衍射和扫描电镜表征,结果显示此材料呈现二维六角密堆积结构,合成材料中含有铈的氧化物晶体相。样品的形貌与SBA-15介孔材料的形貌基本相似。     

Yolk-shell nanostructural Ni_2P/C composites as the high performance electrocatalysts toward urea oxidation

Highly active and low-cost catalytic electrodes for urea oxidation reaction(UOR) are always crucial for exploration of urea fuel cells.Herein,novel york-shell-structural Ni_2P/C na nosphere hybrids(Ni_2P/C-YS)are rationally constructed via a hydrothermal method and subsequent phosphidation treatment under different temperature ranging from 250℃ to 450℃ for UOR applications.In the in-situ constructed hollow york-shell structure,the coupling of conductive carbon materials and active Ni_2P allows numerous interfaces facilitating the electron transfer and thereby accelerating the catalytic kinetics.The results demonstrate that Ni_2P/C-YS-350 nanocomposite can boost the UOR process with a low potential of 1.366 V vs.RHE at a current density of 50 mA/cm~2 in alkaline electrolyte and afford the superior durability with negligible potential decay after 23 h.This study presents that the carbon coated Ni_2P hybrid with the optimized crystallinities and hollow york-shell configurations can be a promising candidate for application in urea fuel cells.     

一步法制备钛负载介孔材料及其对CO2的吸附

以增溶了二氯二茂钛的P123胶束为模板,采用一步法得到了钛掺杂介孔材料Ti-SBA-15．FTIR、XRD、BET等测试结果显示Ti-SBA-15仍保持规整的孔道结构特征,样品经焙烧后茂环分解留下钛负载于介孔表面．对样品吸附CO2的测定结果表明,钛的负载有利于CO2的吸附,在N2气氛下焙烧的样品对C02的吸附性能显著提高,其中Ti-SBA-15（550-0．5-N2）对C02的最大吸附量为1．44mmolg^（-1）,钛在介孔材料中的存在形态对CO2吸附性能起决定性作用．     

预处理条件对Ag/SBA-15催化剂上甲苯催化氧化反应性能的影响

甲苯是一种典型的挥发性有机污染物.近年来,催化氧化法是一种广泛使用并具有开发潜力的有效去除挥发性有机污染物的方法,而贵金属催化剂一直是首选.介孔二氧化硅材料SBA-15具有规则孔道和较高的比表面积因而在催化领域中具有较大的应用潜力.本课题组已对一系列的SBA-15负载的纳米银催化剂的制备和低温催化氧化性能进行了研究,本文则通过研究不同预处理处理气氛对Ag/SBA-15催化剂结构以及甲苯催化氧化性能的系统研究,获得纳米银催化剂结构与甲苯催化氧化性能间的构效关系,对新催化剂的结构优化以及甲苯催化净化的低温催化剂开发具有重要的科学意义.研究表明,处理气氛明显影响了银物种和氧物种的状态,进而影响了催化剂的催化活性,先氧气(500℃)后氢气(300℃)处理的O500-H300催化剂对甲苯的反应活性明显优于在500℃氧气处理样品O500及氢气处理样品H500.由X-射线衍射和O2-程序升温脱附(TPD)可知,氧气500 oC处理使催化剂上形成大颗粒银粒子和氧化银粒子,以及大量次表层氧物种.氢气处理使催化剂形成较大的银粒子,由于未经过氧气处理,该催化剂上并没有次表层氧的生成.先氧气处理再氢气处理后催化剂上形成高分散的小粒径银粒子以及次表层氧物种,这表明低温氢气处理可以降低银粒子的尺寸并使催化剂上的银粒子得到再分散,同时不会影响次表层氧物种的形成.从催化剂的甲苯吸附和TPD实验中看出,大尺寸银粒子对甲苯具有较强的吸附性能,从而有利于甲苯在低温的催化氧化,但是在高温反应中没有优势;小尺寸银粒子虽然对甲苯的吸附能力不强,但是对分子氧有较好的吸附作用,进而增强自身与甲苯的相互作用,而且也促进了分子氧的活化,预处理中形成的次表层氧有效增强了甲苯和银粒子的相互作用,因此,先氧气后氢气处理的O500-H300样品在反应中显示出最好的甲苯催化活性.     

Deep desulfurization by selective adsorption of dibenzothiophenes on Ag+/SBA-15 and Ag+/SiO2

Silver (Ag+) salts adsorbed on amorphous silica or mesoporous SBA-15 extract dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-Me2DBT) from simulated, hydrotreated petroleum feedstocks.