Synthesis and characterization of polyaniline/MCM-41 nanocomposites and their photocatalytic activity

The novel organic-inorganic nanocomposites were synthesized via in-situ polymerization of polyaniline (PANI) with mesoporous silica (MCM-41) for methylene blue (MB) dye degradation under visible light. The synthesized PANI/MCM-41 nanocomposites were characterized through Fourier transform infrared (FTIR), X-ray diffraction (XRD), Raman spectroscopy, field emission scanning electron microscopy (FESEM), and UV-visible studies. The structural and optical properties confirmed the interaction between PANI and MCM-41. The photocatalytic experiments showed that the MB dye was efficiently degraded by approximately 70% under light irradiation over the surface of the PANI/MCM-41 nanocomposites. The degradation might occur due to the efficient charge separation of the e(-)-h+ pairs at the interface of PANI and MCM-41 in the excited state under light irradiation.     

Gel-like properties of MCM-41 material and its transformation to MCM-50 in a caustic alkaline surround

MCM-41 material, prepared by sol–gel method, reveals gel-like properties in a caustic alkaline environment, i.e., 6 M potassium hydroxide (KOH) electrolyte. The gellation of MCM-41 starts at a KOH weight ratio of 40 wt.%. The structural change of the material is verified with X-Ray diffractograms and supported by observation using Scanning Electron Microscope (SEM). As the KOH weight ratio increases, the MCM-41 hexagonal arrays structure gradually transforms into MCM-50 lamellar structure before disappearing completely at 80 wt.% KOH. The MCM gel phase is further characterized by rotational viscometry and texture analysis. The gel phase shows shear thinning or pseudoplastic behavior and possesses homogeneous matrix structure.     

Preparation of highly dispersed tungsten oxide on MCM-41 via atomic layer deposition and its application to butanol dehydration

Highly dispersed tungsten oxide on MCM-41 was synthesized using a novel atomic layer deposition (ALD) method. BET, XRD, XPS, NH3-TPD, and pyridine-IR were used to study the physicochemical properties of the supported tungsten oxides. In this study, the maximum loading of tungsten oxide on MCM-41 that could be prepared using the modified ALD method was 27.0 wt%. It was confirmed that the textural properties of the mesoporous silica were maintained after tungsten oxide loading. The NH3-TPD and Py-IR results indicated that weak acid sites, mainly Lewis acid sites, were produced over the WO3/MCM-41 samples. Moreover, 2-butanol dehydration was performed to demonstrate the potential advantages of the WO3/MCM-41 catalysts. The WO3/MCM-41 catalyst with 27.0 wt% tungsten oxide loading showed the highest activity in the dehydration of 2-butanol, which was attributed to the highest overall number of acid sites among the WO3/MCM-41 catalysts. The highly dispersed tungsten oxide on MCM-41 prepared via ALD can be an effective catalyst for producing butenes through 2-butanol dehydration.     

MCM-41负载戊二酸锌催化剂催化CO2和环氧丙烷的共聚反应

制备了MCM-41负载戊二酸锌催化剂(ZnGA/MCM-41),并采用热重分析、红外光谱和X射线衍射对催化剂进行了表征。结果表明,ZnGA与载体间存在相互作用,ZnGA能以更小的粒径均匀分散到MCM-41的表面。实验研究表明,该催化剂对于CO2与环氧丙烷(PO)共聚反应显示出较高的催化效率,并得到高分子量的聚碳酸亚丙酯(PPC);通过调节负载量和催化剂的用量,最高催化效率达到了89.5g聚合物/g ZnGA;共聚产物的红外光谱和核磁数据表明,所得共聚产物具有接近完全交替(>97.4%)的碳酸酯结构。     

Controlled radical polymerization of vinyl acetate in presence of mesoporous silica supported TiCl4 heterogeneous catalyst

The heterogeneous TiCl₄ catalysts supported on mesoporous mobile composition of matter (MCM-41) and mesoporous silicone particles synthesized from block copolymer of PPG–PEG–PPG (SPB) complexed with dimethyl formamide (DMF) ligand were used in a controlled free radical reaction with benzoyl peroxide (BPO) initiator in bulk polymerization of vinyl acetate (VAc). In this polymerization process, mesoporous particle of SPB increased the reactivity of TiCl₄ catalyst with DMF ligand. The active site formed on the surface and the pores of the catalyst produced specific sequences of VAc on the chain with different thermal and microstructural properties and crystallinity.     

杂多酸固载催化剂的合成及窄分子量纤维素制备的研究

通过水热合成法制备MCM-41型介孔分子筛,采用浸渍法负载磷钨酸于MCM-41介孔分子筛中,煅烧得到新型HPW/MCM-41固载催化剂。利用傅里叶红外光谱(FT-IR)、X射线衍射(XRD)、热重分析(TG)和扫描电镜(SEM)对固载催化剂进行表征;考察催化剂对棉纤维催化降解反应的性能。结果表明,新型HPW/MCM-41固载催化剂即持有了磷钨酸的Keggin结构,同时又保持了分子筛的完整介孔结构,具有催化、筛分双重性能。棉纤维催化降解反应数据显示,磷钨酸负载量、反应温度、催化剂用量、液固比及停留时间均影响HPW/MCM-41降解纤维素的性能。在单因素实验最佳反应条件下,棉纤维素降解产物的分子量分布较为均匀,降解产物的产率较优。     

Spatial organization of peptide nanotubes for electrochemical devices

A novel biosensor for hydrogen peroxide was developed by combining the known properties of microperoxidase-11 (MP11) as an oxidation catalyst, and the interesting properties of diphenylalanine peptide nanotubes (PNTs) as a supporting matrix to allow a good bioelectrochemical interface. In this case, the synthesized MP11/PNTs were immobilized onto the ITO electrode surface via layer-by-layer (LBL) deposition, using poly(allylamine hydrochloride) (PAH) as positively charged polyelectrolyte layers. The PNTs provide a favorable microenvironment for MP11 to perform direct electron transfer to the electrode surface. The resulting electrodes showed a pair of well-defined redox peaks with formal potential at about −343 mV (versus SCE) in phosphate buffer solution (pH 7). The experimental results also demonstrated that the resulting biosensor exhibited good electrocatalytic activity to the reduction of H₂O₂ with a sensitivity of 9.43 μA cm⁻² mmol⁻¹ L, and a detection limit of 6 μmol L⁻¹ at the signal-to-noise ratio of 3. Moreover, we also observed that the peptides self-assembly can be influenced upon changing the pH of the solution. Alkaline solution appears to favor the packing of diphenylalanine nanotubes being closer than acidic or neutral conditions. The study proved that the combination of PNTs with MP11 is able to open new opportunities for the design of enzymatic biosensors with potential applications in practice.     

Chemical fluid deposition of monometallic and bimetallic nanoparticles on ordered mesoporous silica as hydrogenation catalysts

A simple and green method of depositing monometallic (Ru, Rh, Pd) and bimetallic nanoparticles (Ru-Rh, Ru-Pd and Rh-Pd) on an ordered mesoporous silica support (MCM-41) in supercritical carbon dioxide (scCO2) is described. Metal acetylacetonates were used in the experiments as CO2-soluble metal precursors. Suitable temperature and pressure conditions for synthesizing each kind of nanoparticles were applied in this study. The characterizations of these nanocomposites were performed by transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDS). The nanoparticles had average sizes varying from 2 nm to 8 nm. The Ru nanoparticles were clearly shown to be inside the mesopores of MCM-41 from the TEM image. These nanocomposites used as catalysts for hydrogenation was demonstrated. The efficiency of the scCO2 prepared Ru/MCM-41 catalyst was nearly 8 times than that of a Ru/MCM-41 catalyst prepared by conventional impregnation method.     

Facile synthesis of fully ordered L10-FePt nanoparticles with controlled Pt-shell thicknesses for electrocatalysis

We report a simple one-step approach for the synthesis of ～4 nm uniform and fully L10-ordered face-centered tetragonal (fct) FePt nanopartides (NPs) embedded in ～60 nm MCM-41 (fct-FePt NPs@MCM-41).We controlled the Pt-shell thickness of the fct-FePt NPs by treating the fct-FePt NPs@MCM-41 with acetic acid (HOAc) or hydrochloric acid (HC1) under sonication,thereby etching the surface Fe atoms of the NPs.The fct-FePt NPs deposited onto the carbon support (fct-FePt NP/C) were prepared by mixing the fct-FePt NPs@MCM-41 with carbon and subsequently removing the MCM-41 using NaOH.We also developed a facile method to synthesize acid-treated fct-FePt NP/C by using a HF solution for simultaneous surface-Fe etching and MCM-41 removal.We studied the effects of both surface-Fe etching and Pt-shell thickness on the electrocatalytic properties of fct-FePt NPs for the methanol oxidation reaction (MOR).Compared with the non-treated fct-FePt NP/C catalyst,the HOAc-treated and HCl-treated catalysts exhibit up to 34％ larger electrochemically active surface areas (ECASAs);in addition,the HCl-treated fct-FePt NP (with ～1.0 nm Pt shell)/C catalyst exhibits the highest specific activity.The HF-treated fct-FePt NP/C exhibits an ECASA almost 2 times larger than those of the other acid-treated fct-FePt NP/C catalysts and shows the highest mass activity (1,435 mA.mg~,2.3 times higher than that of the commercial Pt/C catalyst) and stability among the catalysts tested.Our findings demonstrate that the surface-Fe etching for the generation of the Pt shell on fct-FePt NPs and the Pt-shell thickness can be factors for optimizing the electrocatalysis of the MOR.     

Vapor-phase photo-oxidation of methanol over nano-size titanium dioxide clusters dispersed in MCM-41 host material part 2: catalytic properties and surface transient species

We report in this paper on the ultraviolet-assisted vapor-phase oxidation of methanol at room temperature, with the help of nano-size clusters of titanium dioxide dispersed in an MCM-41 silicate matrix. The surface species formed during the adsorption/oxidation of methanol and the transformation that they undergo as a result of ultraviolet irradiation were monitored using in-situ Fourier transform infrared and thermal desorption spectroscopy techniques. Parallel experiments conducted on TiO2/MCM, bulk titania, and pristine MCM-41 samples helped in identifying the individual role of titanium dioxide and host matrix in these processes. The photo-catalytic oxidation of methanol, at concentrations of 0.1 to 1.1 mol% in air, gave rise to formation of CO2 and H2O as products, for both the TiO2/MCM and bulk TiO2 samples. No such reaction occurred on titania-free MCM. Furthermore, the rate of reaction depended upon the TiO2 content of a sample and also on the concentration of methanol in reaction mixture. Thus, the rate of conversion increased progressively with the increase in TiO2 loading from 5 to 21 wt% in TiO2/MCM samples, particularly for the experiments with high concentration of methanol. For low methanol concentration (0.1 mol%) in air, the effect of titania content in MCM was very small. The specific activity (per g of titania) of a sample, on the other hand, showed an inverse relationship with the loading of titanium dioxide in a sample. Infrared and temperature-programmed desorption results revealed that the mode of CH3OH adsorption and the reactivity of the transient species formed during the oxidation process were independent of the size of dispersed titania particles. Thus, the particles of approximately 2-6 nm size, present in TiO2/MCM, exhibited a chemisorption behavior similar to that of the bulk titania. The results of the present study provide strong evidence that the hydroxyl groups, both on the host matrix and at the titania sites, participate independently in the formation of methoxyl groups and at the same time promote the heterogeneous photo-catalytic oxidation of methanol molecules via formation of transient formate groups. Our results also show that the effect of titania crystallite size in the photo-catalytic properties relate mainly to the larger surface area and hence to the enhanced number of chemisorption sites, rather than to the changes in electronic properties.     

磁性MCM-41分离回收RT培司废水中四甲基氢氧化铵的研究

硝基苯法合成RT培司(4-氨基二苯胺)的废水色度高、组分复杂、催化剂四甲基氢氧化铵(TMAOH)难以分离回收。提出采用磁性MCM-41对RT培司废水中有机副产物进行选择性吸附分离。制备的磁性MCM-41样品采用X射线衍射仪(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、N₂吸附-脱附和振动样品磁场计(VSM) 等手段进行表征。结果表明, 磁性MCM-41颗粒的粒径范围为200~300 nm, BET比表面积约为655.2 m²/g, 孔径分布为0.5~4 nm, 内核铁酸镍的存在使磁性MCM-41具有超顺磁性。吸附研究表明磁性MCM-41对RT培司废水中吩嗪、偶氮苯和苯胺等有机物具有良好吸附作用, 经5次吸附磁分离后, RT培司废水中四甲基氢氧化铵能够达到回用要求, 吸附后的磁性MCM-41在外加磁场下极易分离。     

Development and characterization of the composites based on mesoporous MCM-41 and polyethylene glycol and their properties

Novel MCM-41/polyethylene glycol composites have been synthesized using different ratios of MCM-41. The structure of the different composites was confirmed by using various characterization tools, including: thermal analyses (TGA and DTA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and field emission scanning electron microscopy (FE-SEM). The XRD and FT-IR results indicated that PEG interacts with MCM-41 via the formation of hydrogen bonds where no new phase was detected. The TGA analysis results demonstrated that the presence of MCM-41 practically affects the temperature of the main step of degradation. The DTA analysis demonstrated that an increase in the MCM-41 content up to 30 wt.% is accompanied by a continuous decrease in the melting point of PEG.     

Mesoporous silicates as nanoreactors for carbon nanotube production in the absence of transition metal catalysts

Carbon nanotubes were produced from either a template or the polymer-filled pore systems of mesoporous silicates of various structures and dimensions by heat treatment in the absence of air. Successful synthesis was done when the template molecules contained little or no oxygen. For SBA-15 material, where the structure-directing molecule used for synthesis of mesoporous silicate was polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, no carbon nanostructures were formed. A peculiar carbon nanostructure was generated from the template for pore expanded MCM-41. To demonstrate carbon nanotube formation from polymer in the mesoporous silicates, the mesopores of MCM-41, MCM-48, and SBA-15 silicates were filled with divinyl-benzene polymer and then graphitized at 1300 K. The polymer was successfully transformed into carbon nanotubes for the MCM class silicate but not the SBA-15 silicate.     

Elaboration of a new hydrogen peroxide biosensor using microperoxidase 8 (MP8) immobilized on a polypyrrole coated electrode

A novel strategy for elaborating a new biosensor for hydrogen peroxide has been developed by combining the known properties of microperoxidase 8 (MP8) as an oxidation catalyst, and the interesting properties of conducting polypyrrole as a supporting matrix to allow a good bioelectrochemical interface and a large dispersion of MP8 on the modified glassy carbon electrode.

MP8 was immobilized into the conducting polypyrrole by entrapment during the electrochemical polymerization, and the modified electrode was characterized both by electrochemical and FT-IR measurements. We demonstrated that MP8 could be immobilized into polypyrrole and could undergo an efficient electron transfer.

The obtained modified electrode showed a high catalytic activity toward H₂O₂ without the need for an electron mediator. A linear calibration curve was obtained by amperometric measurement at a potential of − 0.1 V/ECS for concentrations of H₂O₂ ranging from 1 to 10 μM. The detection limit obtained was 1 nM which constituted a real improvement, by about three orders of magnitude, when compared to the values reported for other systems using an electrochemical detection.     

MCM-41 填加量与偶联修饰对复合材料拉伸性能的影响

通过溶液共混法制备出MCM-41/ 环氧树脂、偶联修饰MCM-41/ 环氧树脂纳米复合材料。研究了填充MCM-41 介孔分子筛颗粒的偶联修饰以及不同的填充颗粒含量对分散性和复合材料拉伸性能的影响。结果表明: 在MCM-41/ 环氧树脂纳米复合材料中, MCM-41 仍保持着长程有序的孔道结构。修饰后的MCM-41 变成亲油性, 有利于增强颗粒与环氧树脂间的界面结合和纳米网络结构的形成, 使MCM-41 颗粒更能均匀分散在聚合物基体中, 提高复合材料的拉伸性能。修饰后的MCM-41 填加量为2.5 %(质量分数) 时, 拉伸强度达到最大值,比基体树脂提高99.2 % , 杨氏模量提高了110 %。      

In situ incorporation of nickel nanoparticles into the mesopores of MCM-41 by manipulation of solvent-solute interaction and its activity toward adsorptive desulfurization of gas oil

In this contribution, different amounts of nickel were incorporated into the mesopores of MCM-41 via an in situ approach. A hydrophobic nickel precursor was incorporated into the nanochannels of mesoporous silica by manipulation of solvent-solute interaction. The synthesized material was characterized using X-ray diffraction, nitrogen physisorption, temperature programmed reduction, and transmission electron microscopy. The results implicate the formation of MCM-41 with well-ordered hexagonal structure and establish also the presence of nickel nanoparticles inside the nanochannels of mesoporous silica. Adsorptive desulfurization of gas oil was conducted using the nickel-incorporated MCM-41 samples. The effects of nickel concentration, temperature of process and feed flow rate on the desulfurization process were examined. The MCM-41 containing 6 wt.% of nickel had both the highest breakthrough sulfur adsorption capacity and total sulfur adsorption capacity, which were 0.69 and 1.67 mg sulfur/g adsorbent, respectively. The breakthrough sulfur adsorption capacity was almost regained after reductive regeneration of spent adsorbent. The obtained results suggest that the method applied for the synthesis of Niy/MCM resulted in formation of well-dispersed, accessible and small nickel nanoparticles incorporated into the pores of MCM-41 which might be an advantage for adsorption of refractory sulfur compounds from low sulfur gas oil.     

纳米介孔MCM-41-M/偶联剂体系对天然橡胶性能的影响

制备了天然橡胶(NR)/MCM-41-M、NR/偶联剂化学改性纳米介孔MCM-41-M、NR/MCM-41-M/偶联剂复合材料,研究了不同含量的MCM-41-M、不同种类偶联剂对MCM 41-M的改性以及偶联剂的添加方式对NR复合材料性能的影响.结果表明;MCM-41-M在NR中有明显的补强作用,当代替3份炭黑时NR基复合材料的拉伸强度达到最大值,比纯NR提高了12.7%。与MCM-41-M和KH-570直接添加到NR中相比,MCM-41-M经偶联剂KH-570改性使拉伸强度提高了50%。将MCM-41-M用偶联剂KH 570改性后添加到NR中,使NR的玻璃化转变温度升高、玻璃化转变区的损耗角减小、储能模量提高到最大。     

Synthesis and characterization of mesoporous Si-MCM-41 materials and their application as solid acid catalysts in some esterification reactions

Mesoporous MCM-41 has been synthesized by sol–gel method at room temperature possessing good thermal stability, high surface area as well as retention of surface area at high temperature. The MCM-41 neutral framework has been modified and put to practical use by incorporating Al³⁺ in the siliceous MCM-41 framework and supporting 12-TPA (12-tungstophosphoric acid) onto MCM-41 by process of anchoring and calcination to induce Brønsted acidity in MCM-41 to yield Al-MCM-41 and 12TPA-MCM-41, respectively. The synthesized materials have been characterized for elemental analysis by ICP-AES, XRD, SEM, TEM, EDX, FT–IR and TGA. Surface area has been determined by BET method and pore size and pore size distribution determined by BJH method. Surface acidity has been evaluated by NH₃-TPD method. The potential use of Al-MCM-41 and 12TPA-MCM-41 as solid acid catalysts has been explored and compared by studying esterification as a model reaction wherein monoesters such as ethyl acetate (EA), propyl acetate (PA), butyl acetate (BA) and benzyl acetate (BzA) have been synthesized, optimizing several parameters such as catalyst amount, reaction time, reaction temperature and mole ratio of reagents.     

Organo-functionalized mesoporous supports for Jacobsen-type catalyst: Laponite versus MCM-41

In order to exploit the different textural properties of Laponite and MCM-41, specifically in terms of their external versus internal surface areas, in the covalent anchoring of a chiral Mn(III) salen complex, these materials were functionalized with 3-aminopropyltriethoxysilane (APTES), subsequently activated with sodium ethoxide, and finally used to anchor the Jacobsen catalyst derivative C1. All the materials were characterized by nitrogen elemental analysis, XPS, PXRD, nitrogen adsorption at −196 °C, FTIR and for those with the immobilized complex, they were additionally characterized by Mn AAS. The APTES anchored at the edges of the Laponite single crystals and inside the MCM-41 pores. Moreover, under the same preparative conditions, higher amount of APTES was anchored onto MCM-41 than onto Laponite, which is due to the higher surface area of MCM-41 compared to Laponite, as well as to its more exposed SiO₄ tetrahedra. Activation of the two organo-functionalized materials with sodium ethoxide originated anionic nitrogen groups as deduced by the increase of surface sodium content of these materials and N1s binding energy changes, but led to a small decrease in N bulk content as a result of some APTES leaching. Moreover, for MCM-41 some disruption of the silica framework occurred as a consequence of the basic treatment, as suggested by XPS, PXRD, and nitrogen adsorption study. The APTES functionalized Laponite and MCM-41 materials, as well as the activated analogs, were able to anchor C1 through axial coordination of the metal centre to the grafted surface nitrogen atoms. APTES functionalized MCM-41 presented similar complex content to Laponite analog, what points out for the fact that, at least for the bulky complex used in this work, there was no clear benefit in using a material of high internal area; for the ethoxide activated analogs, Laponite showed the highest complex content of all materials, but MCM-41 was able to anchor the lowest complex quantity, probably as a consequence of damaging effect caused by the basic treatment within its porous structure. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

硅烷修饰对环氧树脂/纳米介孔MCM-41复合材料性能的影响

用偶联剂将纳米介孔MCM-41粉体修饰后与环氧树脂溶液共混,制备出环氧树脂/MCM-41纳米复合材料.研究了偶联剂的含量和不同溶剂的修饰对纳米介孔MCM-41粉体分散性和复合材料力学性能的影响.结果表明,加入适量的偶联剂和在极性较小的介质中修饰,可制备出单分散的纳米介孔MCM-41颗粒增强的新型网络复合材料.偶联剂中的有机基团-(CH2)3-NH2不仅进入孔道、修饰了MCM-41的孔壁,而且使介孔分子筛保持了有序的孔道结构.环氧树脂高分子链与偶联修饰后的MCM-41颗粒的内、外表面以强烈的化学键结合,使MCM-41颗粒均匀分散在聚合物基体中,提高了材料的力学性能,其拉伸强度比基体树脂提高了69%,杨氏模量提高了90%.