源自水稻壳的高比表面纳米二氧化硅负载12-磷钨酸:一种高效纳米催化剂用于几种有机反应(英文)

Nano silica was prepared from rice husk with high surface area.X-ray diffraction(XRD) pattern showed that the amorphous form of silica was produced.Chemical composition of the nano silica was estimated by X-ray fluorescence spectroscopy and CHN analysis.The nano silica was used as a support for H3PW12O40.The nano silica and nano silica supported H3PW12O40 were characterized by inductively coupled plasma,XRD,transmission electron microscopy(TEM),N2 adsorption-desorption,and Fourier transform infrared spectroscopy.TEM images of nano silica as well as the supported catalyst displayed average size of 6 and 7 nm,respectively.The catalyst showed excellent activity in some important organic reactions including Biginelli,Hantzsch,Mannich,and Claisen-Schmidt reactions with good reusability.Catalytic activity of this nano catalyst is an improvement over the commercially available silica that is used to support H3PW12O40.     

Chitosan‐Silica Sulfate Nano Hybrid as a Novel and Highly Proficient Heterogeneous Nano Catalyst for Regioselective Ring Opening of Epoxides via Carboxylic Acids

The synthesis and characterization of chitosan‐silica sulfate nano hybrid (CSSNH ) as a novel and efficient heterogeneous nano catalyst involving acid‐base bifunctional activity is described. The catalytic potency and activity of this eco‐friendly catalyst was investigated in regioselective ring opening of epoxides with carboxylic acids to access structurally diverse 1,2‐diol mono‐esters in good to excellent yields. CSSNH catalyst was characterized using different microscopic and spectroscopic techniques encompassing scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, N₂ adsorption isotherm, and Fourier transform infrared spectroscopy. The green nature, cheapness, efficiency, ease of preparation, handling and reusability of this new catalyst makes this catalyst to be useful for green industrial processes.     

合成聚对苯二甲酸丙二醇酯负载型催化剂钛酸四丁酯/纳米二氧化硅的制备

以钛酸酯偶联剂(TMC-201)为改性剂,采用超声波分散方法对亲水性纳米二氧化硅(nano-SiO2)进行了表面改性。采用浸渍法将钛酯四丁酯(Ti(OC4H9)4)负载于表面改性的nano-SiO2上,制备了纳米级Ti(OC4H9)4/nano-SiO2负载型催化剂。考察了偶联剂用量、温度、时间对纳米SiO2表面改性的影响,研究了负载时间、负载温度和Ti(OC4H9)4用量对表面改性后纳米SiO2负载Ti(OC4H9)4的影响。结果表明,当TMC-201质量分数为35%、反应温度为90℃、反应时间为3.5 h时,纳米SiO2粒子表面接枝的偶联剂量最大;在室温下,负载48 h,Ti(OC4H9)4用量为表面改性纳米SiO2量的1/2时得到的Ti(OC4H9)4/nano-SiO2负载型催化剂负载Ti(OC4H9)4量最大;运用ICP-AES、FESEM等测试技术对修饰后的纳米SiO2及Ti(OC4H9)4/nano-SiO2负载型催化剂进行了表征;将Ti(OC4H9)4/nano-SiO2负载型催化剂用于聚对苯二甲酸丙二醇酯(PTT)聚酯合成的结果表明,与均相Ti(OC4H9)4催化剂相比,Ti(OC4H9)4/nano-SiO2负载型催化剂催化合成PTT聚酯过程中酯化时间177 min,与均相催化剂催化酯化时间相近,在缩聚2 h后得到PTT的特性粘度高达1.05,证明该负载型催化剂具有高的催化活性,既可催化酯化反应又可催化缩聚反应。     

Green synthesis and physical properties of crystalline silica engineering nanomaterial from rice husk (agriculture waste) at different annealing temperatures for its varied applications

Crystalline nano silica (SiO₂) was synthesized using a cost-effective eco-friendly method from agricultural waste material like rice husk. Polymer nanocomposite has been prepared using the sol-gel technique from crystalline nano silica using PVA as a polymer binder. Thermal analysis measurement is employed to investigate thermal stability. The XRD analysis shows the crystalline nature of silica is revealed to have characteristic peaks of SiO₂. The particle size was evaluated using Schererr's formula and found to be in the range of 21–31 nm. FTIR measurement shows the presence of O–Si–O (silane) bond formation. The PL measurement shows broad excitation prominently in the visible region. In the XRD pattern, a major peak of the Nanocomposite is observed at an angular position of 19.5° degree, which is more prominent than that of the PVA with the addition of 0.2 wt percent Nano silica to the PVA composite. SEM provides information on homogeneous distribution. This could be beneficial in terms of higher mechanical qualities as well as multifunctional properties. By hydrogen bonding, the PVA molecules are strongly linked to each SiO₂ nanoparticle as measured by FTIR. The stability of materials is confirmed by Zeta Potential and DLS. In the photoluminescence property of SiO₂-PVA crystalline Nano silica composite is excited using a radiation wavelength of 200 nm. The indirect bandgap was determined to be 4.28 eV which could be attributed to the 1100 °C annealing temperature. Such materials may be used as a semiconductor material obtained from a direct natural source, rice husk. Thus, in the present research structural, physical, and optical properties of crystalline nano silica and its polymer composite are explored, which leads us to prepare technological grads material from agricultural waste for varied applications including Agriculture to medical science.     

Replacement of Volatile Acetic Acid by Solid SiO2@COOH Silica (Nano)Beads for (Ep)Oxidation Using Mn and Fe Complexes Containing BPMEN Ligand

Mn and Fe BPMEN complexes showed excellent reactivity in catalytic oxidation with an excess of co-reagent (CH₃COOH). In the straight line of a cleaner catalytic system, volatile acetic acid was replaced by SiO₂ (nano)particles with two different sizes to which pending carboxylic functions were added (SiO₂@COOH). The SiO₂@COOH beads were obtained by the functionalization of SiO₂ with pending nitrile functions (SiO₂@CN) followed by CN hydrolysis. All complexes and silica beads were characterized by NMR, infrared, DLS, TEM, X-ray diffraction. The replacement of CH₃COOH by SiO₂@COOH (100 times less on molar ratio) has been evaluated for (ep)oxidation on several substrates (cyclooctene, cyclohexene, cyclohexanol) and discussed in terms of activity and green metrics.     

Online Solid-Phase Extraction of Cd(II), Cu(II), and Co(II) Using Covalently Attached Bis(salicylaldimine) to Silica Gel for Determination in Food and Water by Flame Atomic Absorption Spectrometry

In this study, a novel sorbent material bearing a bis(aldimine) group was designed and successfully synthesized by covalently bonding a 2-[N,N′-bis(salicylaldimine)]aminoethyl amine ligand to the silica gel surface that was characterized by carbon, hydrogen, and nitrogen elemental analysis, thermogravimetric analysis, and the Fourier transform infrared spectroscopy technique. The sorbent was used for the online solid-phase extraction (SPE) of Cd(II), Cu(II), and Co(II) ions for their determination at trace concentration levels by flame atomic absorption spectrometry. The effective factors for the online SPE such as the pH and the flow rate of the sample solution, and type, volume, and flow rate of eluent were investigated. The concentration levels of Cd(II), Cu(II), and Co(II) were measured in certified reference materials including Virginia tobacco leaves (CTA-VTL-2) and water-trace elements (NWTM-15.2) to validate this method. The metal levels in environmental water were determined by this method, and the values were checked by spiking and recovery experiments and independent analysis by inductively coupled plasma-mass spectrometry. The adsorption capacities of the sorbent were found to be 41.2, 31.6, and 25.6?mg/g for Cd(II), Cu(II), and Co(II), respectively. This method was also successfully used for the determination of Cd(II), Cu(II), and Co(II) concentrations in rice and molasses.     

Granulation of Nickel–Aluminum–Zirconium Complex Hydroxide Using Colloidal Silica for Adsorption of Chromium(VI) Ions from the Liquid Phase

We combined a nickel–aluminum–zirconium complex hydroxide (NAZ) with colloidal silica as a binder to prepare a granulated agent for adsorbing heavy metals from aqueous media. Three samples with different particle diameters were prepared to evaluate the effects on the properties: small (NAZ-S), medium (NAZ-M), and large (NAZ-L). We confirmed the granulation of the prepared samples at a binder content of 25%. NAZ-S had the largest specific surface area and number of hydroxyl groups, followed by NAZ-M and then NAZ-L. Regarding the adsorption capacity, NAZ-S adsorbed the most chromium(VI) ions followed by NAZ-M and then NAZ-L. The binding energy of Cr(2p) at 575–577 eV was detected after adsorption, and the effects of the temperature, contact time, and pH on the adsorption of chromium(VI) ions were evaluated. We identified the following adsorption mechanism: ion exchange with sulfate ions in the interlayer region of the NAZ samples. Finally, the chromium(VI) ions adsorbed by the NAZ samples were easily desorbed using a desorption solution. The results showed that NAZ offers great potential for the removal of chromium(VI) ions from aqueous solutions.     

Selective Pre-concentration and Solid Phase Extraction of Mercury（Ⅱ） from Natural Water by Silica Gel-loaded （E）-N-（1-Thien-2＇-ylethylidene）-1,2-phenylenediamine Phase

Silica gel-loaded （E）-N-（1-thien-2＇-ylethylidene）-1,2-phenylenediamine （TEPDA） phase was synthesized based on physical adsorption approaches. The stability of a chemically modified TEPDA especially in concentrated hydrochloric acid that was then used as a recycling and preconcentration reagent allowed the further uses of silica gel-loaded immobilized TEPDA phase. The application of this silica gel-loaded phase to sorption of a series of metal ions was performed by using different controlling factors such as the pH of the metal ion solution and the equilibration shaking time by the static technique. This difference was interpreted on the basis of selectivity incorporated in these sulfur containing silica gel-loaded TEPDA phases. Hg（Ⅱ） was found to exhibit the highest affinity towards extraction by these silica gel-loaded TEPDA phases. The pronounced selectivity was also confirmed by the determined distribution coefficients （Kd） of all the metal ions, showing the highest value reported for mercury（Ⅱ） extraction by the silica gel immobilized TEPDA phase. The potential applications of the silica gel immobilized TEPDA phase to selective extraction of mercury（Ⅱ） from aqueous solution were successfully accomplished and preconcentration of low concentration of Hg（Ⅱ） （30 pg·mL^-1） from natural tap water with a preconcentration factor of 200 for Hg（Ⅱ） off-line analysis was conducted by cold vapor atomic absorption analysis.