scholarly journals Application of microwave radiation in the grafting of acidic sites on SBA-15 type material

Author(s):  
Maciej Trejda ◽  
Magdalena Drobnik ◽  
Ardian Nurwita

AbstractMesoporous silica of SBA-15 type was modified for the first time with 3-(trihydroxysiyl)-1-propanesulfonic acid (TPS) by post-synthesis modification involving microwave or conventional heating in order to generate the Brønsted acidic centers on the material surface. The samples structure and composition were examined by low temperature N2 adsorption/desorption, XRD, HRTEM, elemental and thermal analyses. The surface properties were evaluated by esterification of acetic acid with n-hexanol used as the test reaction. A much higher efficiency of TPS species incorporation was reached with the application of microwave radiation for 1 h than conventional modification for 24 h. It was found that the structure of mesoporous support was preserved after modification using both methods applied in this study. Materials obtained with the use of microwave radiation showed a superior catalytic activity and high stability.


Materials ◽  
2021 ◽  
Vol 14 (16) ◽  
pp. 4465
Author(s):  
Michał Zieliński ◽  
Monika Kot ◽  
Mariusz Pietrowski ◽  
Robert Wojcieszak ◽  
Jolanta Kowalska-Kuś ◽  
...  

This paper investigates the catalytic properties of the iridium catalysts supported on modified silicalite-1. Post-synthesis modification of silicalite-1, with solutions of ammonium compounds (NH4F and NH4OH), appeared to be an efficient method to generate the acidic sites in starting support. The modification of support led not only to changes in its acidity but also its porosity—formation of additional micro- and mesopores. The novel materials were used as supports for iridium. The iridium catalysts (1 wt.% Ir) were characterized by N2 adsorption/desorption measurements, temperature-programmed reduction with hydrogen (TPR-H2), H2 chemisorption, transmission electron microscopy (TEM), temperature-programmed desorption of ammonia (TPD-NH3), X-ray photoelectron spectroscopy (XPS) and tested in the hydrogenation of toluene reaction. The catalytic activity of iridium supported on silicalite-1 treated with NH4OH (higher porosity of support, better dispersion of active phase) was much higher than that of Ir supported on unmodified and modified with NH4F silicalite-1.



Catalysts ◽  
2020 ◽  
Vol 10 (2) ◽  
pp. 246 ◽  
Author(s):  
Vincenzo Palma ◽  
Daniela Barba ◽  
Marta Cortese ◽  
Marco Martino ◽  
Simona Renda ◽  
...  

Since the late 1980s, the scientific community has been attracted to microwave energy as an alternative method of heating, due to the advantages that this technology offers over conventional heating technologies. In fact, differently from these, the microwave heating mechanism is a volumetric process in which heat is generated within the material itself, and, consequently, it can be very rapid and selective. In this way, the microwave-susceptible material can absorb the energy embodied in the microwaves. Application of the microwave heating technique to a chemical process can lead to both a reduction in processing time as well as an increase in the production rate, which is obtained by enhancing the chemical reactions and results in energy saving. The synthesis and sintering of materials by means of microwave radiation has been used for more than 20 years, while, future challenges will be, among others, the development of processes that achieve lower greenhouse gas (e.g., CO2) emissions and discover novel energy-saving catalyzed reactions. A natural choice in such efforts would be the combination of catalysis and microwave radiation. The main aim of this review is to give an overview of microwave applications in the heterogeneous catalysis, including the preparation of catalysts, as well as explore some selected microwave assisted catalytic reactions. The review is divided into three principal topics: (i) introduction to microwave chemistry and microwave materials processing; (ii) description of the loss mechanisms and microwave-specific effects in heterogeneous catalysis; and (iii) applications of microwaves in some selected chemical processes, including the preparation of heterogeneous catalysts.



Catalysts ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 488
Author(s):  
Katarzyna Stawicka ◽  
Maciej Trejda ◽  
Maria Ziolek

Niobium containing SBA-15 was prepared by two methods: impregnation with different amounts of ammonium niobate(V) oxalate (Nb-15/SBA-15 and Nb-25/SBA-15 containing 15 wt.% and 25 wt.% of Nb, respectively) and mixing of mesoporous silica with Nb2O5 followed by heating at 500 °C (Nb2O5/SBA-15). The use of these two procedures allowed obtaining materials with different textural/surface properties determined by N2 adsorption/desorption isotherms, XRD, UV-Vis, pyridine, and NO adsorption combined with FTIR spectroscopy. Nb2O5/SBA-15 contained exclusively crystalline Nb2O5 on the SBA-15 surface, whereas the materials prepared by impregnation had both metal oxide and niobium incorporated into the silica matrix. The niobium species localized in silica framework generated Brønsted (BAS) and Lewis (LAS) acid sites. The inclusion of niobium into SBA-15 skeleton was crucial for the achievement of high catalytic performance. The strongest BAS were on Nb-25/SBA-15, whereas the highest concentration of BAS and LAS was on Nb-15/SBA-15 surface. Nb2O5/SBA-15 material possessed only weak LAS and BAS. The presence of the strongest BAS (Nb-25/SBA-15) resulted in the highest dehydration activity, whereas a high concentration of BAS was unfavorable. Silylation of niobium catalysts prepared by impregnation reduced the number of acidic sites and significantly increased acrolein yield and selectivity (from ca. 43% selectivity for Nb-25/SBA-15 to ca. 61% for silylated sample). This was accompanied by a considerable decrease in coke formation (from 47% selectivity for Nb-25/SBA-15 to 27% for silylated material).



2005 ◽  
Vol 20 (10) ◽  
pp. 2682-2690 ◽  
Author(s):  
Yufang Zhu ◽  
Weihua Shen ◽  
Xiaoping Dong ◽  
Jianlin Shi

A stable mesoporous multilamellar silica vesicle (MSV) was developed with a gallery pore size of about 14.0 nm. A simulative enzyme, hemoglobin (Hb), was immobilized on this newly developed MSV and a conventional mesoporous silica material SBA-15. The structures and the immobilization of Hb on the mesoporous supports were characterized with x-ray diffraction, transmission electron microscopy, N2 adsorption-desorption isotherms, Fourier transform infrared, ultraviolet-visible spectroscopy, and so forth. MSV is a promising support for immobilizing Hb due to its large pore size and high Hb immobilization capacity (up to 522 mg/g) compared to SBA-15 (236 mg/g). Less than 5% Hb was leached from Hb/MSV at pH 6.0. The activity study indicated that the immobilized Hb retained most peroxidase activity compared to free Hb. Thermal stability of the immobilized Hb was improved by the proctetive environment of MSV and SBA-15. Such an Hb-mesoporous support with high Hb immobilization capacity, high activity, and enhanced thermal stability will be attractive for practical applications.



Catalysts ◽  
2019 ◽  
Vol 9 (1) ◽  
pp. 44
Author(s):  
Cui Ouyang ◽  
Yingxia Li ◽  
Jianwei Li

The oxidation of benzene to phenol (BTOP) with N2O as the oxidant has been studied with a variety of Fe/ZSM-5 catalysts. The literature has conclusively proven that Fe2+ sites are the active sites. However, some studies have suggested that the Lewis acidic sites (LAS) are responsible for the generation of the active chemisorbed oxygen. Nevertheless, there is no clear relationship between the LAS and the N2O selectivity to phenol. In an effort to elucidate the effects of LAS on BTOP with various ZSM-5 catalysts, we investigated the initial N2O selectivity to phenol. Here we show that the initial N2O selectivity to phenol is negative with the amount of LAS over a certain range. The catalyst H-ZSM-5-ST (H-ZSM-5 treated with water vapor) showed a remarkable initial N2O selectivity to phenol as high as 95.9% with a 0.021 mmol g−1 LAS concentration on the surface of the catalyst, while the Fe/ZSM-5 catalyst demonstrated the lowest initial N2O selectivity to phenol (11.7%) with the highest LAS concentration (0.137 mmol g−1). Another remarkable feature is that steaming was more effective than Fe ion exchange and high temperature calcining. The samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), N2-adsorption-desorption, UV-vis, NH3-TPD and pyridine Fourier transform infrared (FT-IR) techniques. Our results demonstrate how the concentration of LAS is likely to affect the initial N2O selectivity to phenol within a certain range (0.021–0.137 mmol g−1). This research has demonstrated the synergy between the active Fe2+ sites and LAS.



Author(s):  
Adriana Freites Aguilera ◽  
Pasi Tolvanen ◽  
Kari Eränen ◽  
Sébastien Leveneur ◽  
Tapio Salmi


2013 ◽  
Vol 291-294 ◽  
pp. 300-306 ◽  
Author(s):  
Hong Yuan ◽  
Qing Shu

Two cesium phosphotungstate-derived solid acid catalysts (Cs2.5H0.5PW12 and Cs0.5H2.5PW12) were prepared. The resulting catalysts were characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), N2 adsorption and desorption isotherm and temperature programmed desorption of ammonia(NH3-TPD). The Cs2.5H0.5PW12 and Cs0.5H2.5PW12 were respectively used to catalyze the tranesterification of castor oil and methanol for the synthesis of biodiesel with the assistance of microwave. Results shown microwave radiation can greatly enhance the transesterification process when compared with conventional heating method. Cs2.5H0.5PW12 showed better catalyst performance than Cs0.5H2.5PW12. A maximum yield of 90% was obtained from the using of 30:1 molar ratio of methanol to castor oil and 15 wt % mass ratio of catalyst to castor oil at 343 K under microwave radiation after 4h.



2017 ◽  
Vol 319 ◽  
pp. 191-199 ◽  
Author(s):  
Zhongyu Yang ◽  
Honghong Yi ◽  
Xiaolong Tang ◽  
Shunzheng Zhao ◽  
Qingjun Yu ◽  
...  


2021 ◽  
Vol 259 ◽  
pp. 04001
Author(s):  
Zane Abelniece ◽  
Valdis Kampars ◽  
Helle-Mai Piirsoo ◽  
Aile Tamm

CuO on mesoporous silica catalyst was prepared with post synthesis impregnation method, and the effects of Al and Co promoters on CuO/SBA-15/kaolinite catalyst properties and CO2 hydrogenation were studied. The mixing technology with kaolinite clay (containing Al2O3) was used to obtain the granules and to enhance the CO2 conversion to methanol as a product. The performance of all catalysts for catalytic hydrogenation of CO2 was evaluated on a fixed-bed tubular micro-activity reactor at 20 bar and 250°C with H2/CO2 molar ratio 3:1. XRD analysis, N2 adsorption-desorption analysis and SEM-EDX analysis indicated that the mesoporous structure of SBA-15 remains after loading with CuO and promoters, and after mixing with kaolinite clay. Results were compared with results obtained with commercial CuO/Al2O3 catalyst, which showed high MeOH selectivity (78%) during CO2 hydrogenation reaction.



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