负载型酞菁钴(Ⅱ)光催化降解孔雀石绿的研究

采用光催化法研究了MCM-41-α-四(2-甲氧基乙氧基)酞菁钴(Ⅱ)催化剂对孔雀石绿降解速率的影响:在室温30℃中性环境下,研究了负载金属酞菁催化剂对4 mg/L孔雀石绿溶液的降解情况,同时研究了催化剂投加量、过氧化氢浓度对孔雀石绿降解的影响并探讨了光催化降解孔雀石绿的动力学规律.实验结果表明:制备的催化剂对孔雀石绿...     

Preparation of highly dispersed TiO2 in hydrophobic mesopores by simultaneous grafting and fluorinating

TiO₂ photocatalysts highly dispersed in the MCM-41 mesoporous silica material were synthesized using two different TiO₂ precursors of TiF₄ and (NH₄)₂TiO(C₂O₄)₂. The catalysts were characterized by X-ray diffraction (XRD), N₂ adsorption–desorption, transmission electron microscopy (TEM), UV–vis absorption, X-ray photoelectron spectroscopy (XPS), and Ti K-edge X-ray absorption fine structure (XAFS). The hydrophobic properties and catalytic activities of photocatalysts with different TiO₂ precursors and loading amount were examined by adsorption and degradation of iso-butanol diluted in water. The results showed that the TiO₂ loaded MCM-41 prepared from TiF₄ exhibited higher photocatalytic activity than from (NH₄)₂TiO(C₂O₄)₂. The fluorine-modified hydrophobic pore walls formed in the impregnation process using TiF₄ as well as highly dispersed TiO₂ nanoparticles play a crucial role for the high photocatalytic efficiency.     

Cobalt oxide nanoparticles on mesoporous MCM-41 and Al-MCM-41 by supercritical CO2 deposition

CoO and Co₃O₄ nanoparticles were uniformly dispersed inside mesoporous MCM-41 and Al-MCM-41 supports using supercritical CO₂ reactive deposition. This method represents a one-pot reproducible procedure that allows the dissolution of the organocobalt precursor and supports impregnation in supercritical CO₂ at 70 °C and 110 bar, followed by the precursor thermal decomposition into cobalt species at 200 °C and 160 bar. By the relative concentration of the cobalt precursor [cobalt (II) bis (η⁵-ciclopentadienil)], the load of cobalt nanoparticles was controlled and then determined by Inductively Coupled Plasma (ICP-OES). The synthesis of CoO and Co₃O₄ species inside the MCM-41 and Al-MCM-41 substrates was confirmed by X-ray Photoelectron (XPS) and Laser Raman Spectroscopies (LRS). By N₂ adsorption and Small Angle X-ray Scattering (SAXS), it was determined that the hexagonal arrangement as well as the surface area and pore size of the substrates changed after the addition of cobalt. By means of X-ray mapping from SEM images, a homogeneous distribution of cobalt nanoparticles was observed inside the mesopores when the cobalt loading was 1 wt.%. In addition, spherical cobalt nanoparticles of average diameter close to 20 nm were detected on the outer surface of MCM-41 and Al-MCM-41 supports when the cobalt content was higher. On the other hand, by Transmission Electron Microscopy (TEM), it was possible to measure the interplanar distance of the crystalline plane of the outer nanoparticles, which was later compared with the theoretical distance values which allowed identifying the CoO and Co₃O₄ phases.     

Hydrothermal synthesis, characterization, and photocatalytic performances of Cr incorporated, and Cr and Ti co-incorporated MCM-41 as visible light photocatalysts for water splitting

A series of Cr incorporated, and Cr and Ti co-incorporated MCM-41 photocatalysts were synthesized by hydrothermal method. X-ray diffraction (XRD), UV–vis diffuse reflectance spectra (UV–vis), Fourier transform infrared spectroscopy (FTIR), X-ray fluorescence analysis (XRF), N₂ adsorption–desorption isotherms and Raman spectra were used to investigate the effects of the incorporated elements on the structure of MCM-41. The experimental results for photocatalytic water splitting under visible light irradiation (λ > 430 nm) demonstrated that the photocatalytic activities of Cr-MCM-41 and Cr-Ti-MCM-41 catalysts for hydrogen production decreased with an increase in the amount of Cr incorporated. Compared with the Cr-MCM-41 which had the same amount of incorporated Cr, the Cr-Ti-MCM-41 exhibited much higher hydrogen evolution activities.     

Anchoring manganese acetylacetonate complex on MCM-41: Catalytic testing on limonene oxidation

This work reports the results of limonene oxidation in the liquid phase, over manganese acetylacetonate anchored onto MCM-41. Diluted t-butyl hydroperoxide is used as oxidant. Limonene oxide, carveol and carvone are formed, but the main product obtained is a polymer. The preservation of the MCM-41 channel system upon anchoring was checked by transmission electron microscopy (TEM), X-ray diffraction and nitrogen adsorption analysis. The complex anchoring was succeeded, since the catalyst could be used in four consecutive experiments. The maximum TOF values obtained for each run are similar and no significant metal complex leaching was observed (3% after the 4th run).     

UVA-LED assisted persulfate/nZVI and hydrogen peroxide/nZVI for degrading 4-chlorophenol in aqueous solutions

Photocatalytic degradation of 4-chlrophenol (4-CP) using UVA-LED assisted persulfate and hydrogen peroxide activated by the nZVI (Nano Zero Valent Iron) in a batch photocatalytic reactor was investigated. The reaction involved a lab-scale photoreactor irradiated with UVA-LED light emitted at 390 nm. The efficiency of the reaction was evaluted in terms of 4-CP degradation and mineralization degree at different pH of solution, initial concentrations of nZVI, persulfate, hydrogen peroxide and 4-CP. In UVA-LED/H₂O₂/nZVI process, complete degradation of 4-CP (>99%) and 75% mineralization was achieved at pH of 3, hydrogen peroxide concentration of 0.75 mM, nZVI dosage of 1mM and initial 4-CP concentration of 25mg/L at the reaction time of 30 min. The optimum conditions obtained for the best 4-CP degradation rate were at an initial concentration of 25mg/l, persulfate concentration of 1.5mM, nZVI dosage of 1mM, pH of 3 and reaction time of 120min for UVA-LED/persulfate/nZVI process. It was also observed that the 4-CP degradation rate is dependent on initial 4-CP concentrations for both processes. The pseudo-first-order kinetic constant at 25mg/L initial concentration of 4-CP was found to be 1.4×10^?1 and 3.8×10^?2 in UVA-LED/H₂O₂/nZVI and UVA-LED/persulfate/nZVI processes, respectively. Briefly, the UVA-LED/H₂O₂/nZVI process enhanced the degradation rate of 4-CP by 3.67-times in comparison to UVA-LED/persulfate/nZVI process at 30min contact time, which serves as a new and feasible approach for the degradation of 4-CP as well as other organic contaminants containing wastewater.     

Photocatalytic decomposition of 4-nitrophenol on Ti-containing MCM-41

A series of Ti-containing MCM-41 samples, such as Ti-MCM-41 with variable Si/Ti ratios and Cr–Ti-substituted TiO₂-loaded MCM-41 having different TiO₂ loading, were prepared and studied for the photocatalytic decomposition of 4-nitrophenol in UV and visible light. The samples were characterized using surface area measurement, XRD, FT-IR, and UV–vis DRS techniques. In the case of the Ti-MCM-41 samples with Si/Ti ratios higher than 20 which were found to have typical mesoporous structure, the framework incorporation of Ti into MCM-41 increased with decreasing Si/Ti ratio. On the contrary, the Ti-MCM-41 with lower Si/Ti ratio (Si/Ti = 10) shows low structural integrity and the formation of Ti-oxide species, leading to a considerable decrease in surface area. In the case of Cr–Ti-substituted TiO₂-loaded MCM-41 samples, significant absorption occurs in visible light and the absorption in both UV and visible region increases with increasing TiO₂ loading. However, when the amount of TiO₂ loaded on Cr–Ti-MCM-41 increased above 33 wt.%, the absorption in visible light increased slightly. Thus, it seems that, at higher TiO₂ loading, some TiO₂ particles are not closely bound to the wall of Cr–Ti-MCM-41. The photocatalytic activities of Ti-containing MCM-41 samples were strongly influenced by the amount of Ti. Under UV illumination, the highest photocatalytic activity for photocatalytic decomposition of 4-NP was observed for the Ti-MCM-41 having Si/Ti ratio of 20. Among various Ti-containing MCM-41 materials prepared in this work, only Cr–Ti-substituted TiO₂-loaded MCM-41 catalysts exhibited discernable photocatalytic activities in visible light, and their photocatalytic activities increased considerably with increasing TiO₂ loading up to 33 wt.%. Further increase in TiO₂ loading enhanced photocatalytic activity slightly.     

Covalent grafting of polyacrylamide onto mesoporous MCM-41 silica via free radical polymerization

MCM-41 mesoporous silicas were covalently modified with polyacrylamide (PAAm) by a novel grafting strategy. The effect of various parameters such as monomer concentration, reaction time, and temperature on the content of PAAm onto MCM-41 silicas were studied. Modified silicas were characterized by X-ray diffraction (XRD), infrared spectroscopy, FT-IR, thermogravimetric analysis, nitrogen adsorption–desorption analyses, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy which confirmed the grafting process. According to XRD, SEM and TEM results, PAAm-modified MCM-41 silica did not show changes in its morphology and mesostructure by comparing with pristine MCM-41. Nitrogen adsorption–desorption studies showed that the attaching of PAAm onto MCM-41 silica decreased the values of pore size, pore volume and surface area.     

Ag-BiVO4／MCM-41制备表征及光催化性能研究

采用浸渍法将Ag-BiVO4固载于MCM-41介孔分子筛上,制备了Ag-BiVOdMCM-41新型复合可见光催化荆,用IR、XRD、SEM等分析测试手段对其进行了结构和性能表征。分析表明：Ag-BiVO4光催化剂为单斜耜结构,复合光催化剂具有较大的比表面积。在λ〉400nm的可见光照射下,以降解亚甲基蓝溶液进行了光催化剂的光催化性能评价。实验结果表明,Ag—BiVO4/MCM-41具有高的可见光催化活性,且具备良好的吸附性能和高的光催化效率。     

The effect of the cobalt loading on the growth of single wall carbon nanotubes by CO disproportionation on Co-MCM-41 catalysts

Highly ordered MCM-41 mesoporous molecular sieves in which silicon was isomorphously substituted with 0.5-4 wt.% cobalt were synthesized using an alkyl template with a 16 carbon atoms alkyl chain length. These materials were used as catalysts for the synthesis of uniform diameter single wall carbon nanotubes (SWNT) by CO disproportionation (Boudouard reaction). The SWNT synthesis conditions were identical for all Co-MCM-41 samples, and consisted of pre-reduction of the Co-MCM-41 catalyst in hydrogen at 500 °C for 30 min followed by reaction with pure CO at 800 °C and 6 atm for 1 h (conditions previously optimized for 1 wt.% Co-MCM-41). The SWNT grown in the Co-MCM-41 catalysts were characterized by TGA, multi-excitation energy Raman spectroscopy and TEM. The state of the catalyst and the size of the metallic cobalt clusters formed in Co-MCM-41 during the SWNT synthesis were characterized by X-ray absorption spectroscopy. The mechanism controlling the diameter distribution of the SWNT produced is related to the size uniformity of the cobalt clusters nucleated in the Co-MCM-41 catalytic template: the SWNT growth selectivity and size uniformity is influenced by the cobalt concentration in the framework. If the cobalt is not initially strongly stabilized in the MCM-41 framework during template synthesis, the catalyst produces SWNT with a wider diameter distribution. Co-MCM-41 catalysts with up to 3 wt.% cobalt can be used to grow SWNT with a diameter distribution similar to that obtained with 1 wt.% Co-MCM-41, but at yields greater by a factor of approximately 2.4.     

Efficient degradation of <Emphasis Type="Italic">para</Emphasis>-chlorobenzoic acid in water by catalytic ozonation with La–Ce–MCM-41

La–Ce–MCM-41 was directly synthesized by a hydrothermal method and applied as heterogeneous catalyst for the ozonation process of para chlorobenzoic-acid (pCBA). La³⁺ and Ce³⁺ were successfully incorporated into the framework of MCM-41 and the formation of degradation products (p-chlorophenol, p-dihydroxybenzene, maleic acid and oxalic acid) were monitored qualitatively using gas chromatography–mass spectrometer and high performance liquid chromatography. Due to the synergy of bimetal and the fast degradation of accumulated intermediates, total organic carbon (TOC) removal efficiency was significantly improved (92 %) in La–Ce–MCM-41/O₃ process compared with ozonation (40 %) at identical reaction condition. The presence of tert-butanol (TBA) in La–Ce–MCM-41/O₃ process indicated that the oxidation of pCBA was mainly due to the function of hydroxyl radicals in the liquid bulk, and a plausible degradation pathway was proposed. TOC removal slightly decreased from 90 to 86 % after La–Ce–MCM-41 being re-utilized three times, which illustrated that La–Ce–MCM-41 was an efficient of promising catalyst for ozonation of pCBA.     

Isothermal template removal from MCM-41 in hydrogen flow

Thermal evacuation of template surfactant from MCM-41 in hydrogen atmosphere was investigated. Micelle templated silica was prepared using hexadecyltrimethylammonium bromide. The mechanism of template removal appears to be completely different in hydrogen as compared to calcination in air. It seems that moderate heating of as-synthesized MCM-41 (up to about 250 °C) in hydrogen stream for about 15 h is effective and simple method of template removal leaving no pure carbon residues on silica surface. Adsorption properties of partially evacuated MCM-41 samples were tested using gas chromatography. Products of template degradation were analyzed using GC–MS technique. The main products of template degradation at 250 °C in hydrogen flow are hexadecene and hexadecane-N,N-dimethylamine. Concentration of surface silanols for MCM-41 calcined and thermally treated in hydrogen flow was investigated by NMR technique.     

燃烧法制备二氧化钛催化剂的条件对其可见光催化性能的影响

Titania catalysts were synthesized by a solution combustion method （SCM）. Photodegradation of 4-chlorophenol （4-CP） using the synthesized catalysts was studied under both visible light （λ≥420nm） and sunlight irradiation. The effect of preparation conditions on photocatalytic activities of the synthesized catalysts was investigated. The optimal photocatalytic activity of the catalyst （denoted as A1 ） was obtained under the following synthesis conditions： ignition temperature of 350~C, fuel ratio （ φ） of 1 and calcination time of lh. The degradation and mineralization ratio of 4-CP were 78.2% and 53.7% respectively under visible light irradiation for 3h using catalyst A1. And the catalyst A1 also showed high photocatalytic activity under sunlight irradiation.     

MCM-41介孔材料的合成条件和特性对吸附镉离子的影响

以气相氧化硅为硅源,十六烷基三甲基溴化铵(cetyl trimethyl ammonium bromide,CTAB)为模板剂,分别在碱性[氢氧化钠(NaOH),四乙基氢氧化铵,tetraethyl ammonium hydroxide,(C2Hs)4NOH(TEAOH)]和酸性介质条件[盐酸(HCl)]T水热合成了MCM-41有序介孔材料MCM-41-N,MCM-41-T和MCM-41-H.用X射线衍射、氮气吸附-脱附等手段对比分析了合成的3种MCM-41介孔材料的物相、比表面积、孔径、孔体积等,发现酸性介质中合成的介孔材料的孔径最大.在此基础上,利用MCM-41介孔材料对比研究了处理含镉离子(Cd2 )废水的效果和机理,确定了不同介孔材料用量、不同初始pH值条件下MCM-41介孔材料对水中Cd2 的吸附率和吸附量.结果表明:介孔材料用量相同时,溶液pH值的增大有利于提高3种MCM-41介孔材料对水中Cd2 的处理效果.在pH值从7.0到8.0的过程中,其吸附率有1个突变,MCM-41-T的Cd2 吸附率从35.65%提高到62.15%;MCM-41-N的从38.80%提高到69.40%;MCM-41-H的从50.22%提高到73.47%.孔径最大的MCM-41-H对Cd2 的吸附效果最佳,最大吸附率为89.56%,最大吸附容量为8.57 mg/g.吸附溶液pH值的大小和介孔材料的孔径尺寸是决定吸附量大小的关键因素,因此,重点应通过优化合成工艺提高介孔材料的孔径.     

Synthesis of magnetically recyclable porous CoFe2O4/Rh composites with large BET surface area for enhanced photocatalytic degradation of organic pollutant

The organic pollutants in water have been a great environment challenges to human beings, and photocatalytic degradation is an effective method to solve this problem. In this paper, the Rh-loaded cobalt ferrite CoFe₂O₄ (CFO) nanoparticles have been successfully synthesized by in situ photodeposition of Rh nanoparticles onto the porous CFO particles as the photocatalysts. After incorporating Rh nanoparticles, the CFO/Rh composite has a higher specific surface area and is more efficient in charge separation than the bare CFO. The photocatalytic efficiency of decomposing Malachite Green (MG) is improved from 70% over the bare CFO to 97% over the optimized CFO/Rh in 60 min. The CFO/Rh sample also demonstrates its durability for the degradation of MG in 5 photocatalytic reaction cycles. Additionally, hydroxyl radicals (?OH) and superoxide radicals (?O₂^?) are proved to be the crucial reactive species during the photocatalytic degradation of MG with CFO/Rh, evidenced by the active species capture experiments. This work provides a useful approach to enhance the photocatalytic activity of semiconductors for degrading organic dyes.     

Synthesis and Characterization of Mesoporous Silica Functionalized with Calix[]arene Derivatives

This work reports a new method to covalently attach calix[4]arene derivatives onto MCM-41, using a diisocyanate as a linker. The modified mesoporous silicates were characterized by fourier transform infrared spectroscopy (FTIR), thermal analysis (TGA) and elemental analysis. The FTIR spectra and TGA analysis verified that the calix[4]arene derivates are covalently attached to the mesoporous silica. The preservation of the MCM-41 channel system was checked by X-ray diffraction and nitrogen adsorption analysis.     

Preparation of Cr–Ti Binary Oxide Anchored Mesoporous Silica by CVD Method and Their Photocatalytic Activities

Cr–Ti binary oxide anchored mesoporous silica (Cr–Ti/MCM-41) was prepared by stepwise CVD treatments of MCM-41 with TiCl₄ and CrO₂Cl₂. Cr–Ti/MCM-41 exhibited higher efficiency for the photocatalytic polymerization of ethylene as well as the oxidation of CO into CO₂ than those on single component Cr⁶⁺-oxide anchored MCM-41 under UV and visible light.     

Investigation of equilibrium and kinetic parameters of methylene blue adsorption onto MCM-41

Mesoporous MCM-41 was synthesized at room temperature using tetraethoxysilane (TEOS) with cetyltrimethylammonium bromide (CTAB) and employed as an effective adsorbent for the adsorption of methylene blue dye from aqueous solution. The as-synthesized MCM-41 was calcined at 250 and 550°C to study the relation between the surface area and pore volume with surfactant removal. The synthesized MCM-41 was characterized using thermo gravimetric analysis (TGA), X-ray diffraction (XRD) patterns, nitrogen adsorption/desorption isotherms and Fourier transform infrared (FT-IR) spectroscopy. The MCM-41 calcined at 550°C showed higher surface area (1,059 m² g^?1) with pore volume of 0.89 ml g^?1 and was used for the investigation of adsorption isotherms and kinetics. The experimental results indicated that the Freundlich and Redlich-Peterson models expressed the adsorption isotherm better than the Langmuir model. In addition, the influence of temperature and pH on adsorption was also investigated. The decrease in temperature or the increase in pH enhanced the adsorption of dye onto MCM-41. A maximum adsorption capacity of 1.5×10^?4 mol g^?1 was obtained at 30°C. The kinetic studies showed that the adsorption of dye on MCM-41 follows the pseudo-second-order kinetics.     

Synthesis, Characterization and Photocatalytic Activity of Titania Loaded Cd-MCM-41

Catalysts consisting of cadmium incorporated into MCM-41 mesoporous molecular sieves (Cd-MCM-41) with Si/Cd = 80 have been synthesized by the hydrothermal method using cadmium acetate as the source of cadmium. This was then loaded with titania via the sol-gel method to explore the photoactivity in UV light. These two materials were characterized by various physicochemical techniques such as N₂ physisorption, O₂ chemisorption, diffuse reflectance UV-vis, X-ray diffraction (XRD), Raman and X-ray photoelectron spectroscopy (XPS). The pore size of the Cd-MCM-41 was higher and the BET surface area was lower than those commonly found in our siliceous MCM-41. This is due to the partial pore breakage, as recorded by pore size distribution analysis. The oxygen chemisorption results shows that the dispersion of cadmium is quite high, and decreased after loading of titania. The XRD patterns of Cd-MCM-41 and 25%TiO₂/Cd-MCM-41 are similar to those of siliceous MCM-41; however, the intensity of the d ₁₀₀ peak is decreased and the unit-cell parameter increased with titania loading. Raman spectra could not detect any peaks, whereas peaks were detected at 144, 397, 518 and 641 cm_-1 with loading of titania, these peaks being associated with the anatase phase of titania. The surface composition and binding energy of the Cd 3d_5/2 peak for Cd-MCM-41 and 25%TiO₂/Cd-MCM-41 was analyzed by XPS and showed considerable infusion of cadmium ions on to the surface upon loading of titania. The Cd/Si surface atomic ratio measured by XPS increases 10 times with loading of titania on Cd-MCM-41, indicating that the two separate surface electronic levels such as Cd-O-Si and Cd-O-Ti were found for 25%TiO₂/Cd-MCM-41. The 25%TiO₂/Cd-MCM-41 showed higher activity than 25%TiO₂/MCM-41 for photocatalytic degradation of formic acid. The activity results are compared with the pure titania based on the transformation per site of Ti.     

Sonochemical assisted preparation of ZnS–ZnO/MCM-41 based on blast furnace slag and electric arc furnace dust for Cr (VI) photoreduction

Iron/steel making industry is a weed that produces large quantities of slag and dust. The objective of the present study was to develop a procedure for obtaining and characterizing photocatalysts derived from this waste for chromium remediation. The MCM-41 was synthesized via sodium silicate (Na₂SiO₃) derived from Blast Furnace Slag (BFS), and ZnO and ZnS were synthesized based on zinc extracted from Electric Arc Furnace Dust (EAFD). Subsequently, ZnO/ZnS were sono-chemically loaded on the MCM-41 and were tested for the Cr (IV) photoreduction. The resultant ZnO, ZnS, MCM-41, and composites were characterized by X-ray diffraction (XRD), Energy-dispersive X-ray spectroscopy (EDX), N2adsorption–desorption isotherms, Fourier-transform infrared (FT-IR) spectrometry, Dynamic Light scattering, and Transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). A regular hexagonal structure of typical mesoporous MCM-41 had been proven by small-angle XRD, HRTEM, and N2 adsorption–desorption. The photoreduction activity of ZnS–ZnO/MCM-41 nanocomposite has obvious efficiency compared to ZnO and ZnO/MCM-41, achieving a 94% photoreduction of Cr (VI) in 180 min under UV irradiation. The slight activity loss after 4 cycles (84.7%) reveals the good photoreduction properties of catalysts. Based on these results, ZnS–ZnO/MCM-41 composite material seems to be high efficiency, green, stable, environment, and economical alternative to be used as a photocatalyst for the reduction of Cr (VI).