Synthesis of Well-Ordered Mesoporous Aluminosilicates with High Aluminum Contents: The Challenge and the Promise.

SBA-15 has recently emerged as a potential material for the catalytic conversion of large molecules. Usually, SBA-15 has a low content of aluminum due to the conventional acidic synthesis medium. Although a few approaches have been adopted to prepare Al-SBA-15 with a high alumina content, it is still challenging to prepare well-ordered Al-SBA-15 with a high alumina content. Here, we demonstrate a facile synthesis process in neutral mediums for the grafting of Al into the framework of SBA-15. This approach relies mainly on the dissociation of Si-O-Si bonds and the polymerization of Si-O-Si/Al bonds promoted by sodium persulfate (SPS) in neutral mediums. In this way, well-ordered Al-SBA-15 with a high aluminum content and enhanced acidity was obtained. Results of X-ray fluorescence spectroscopy (XRF) showed an n(SiO2)/n(Al2O3) ratio of 13.7, much lower than that of the conventional sample (21.7) obtained in acidic medium. The characterization results indicated the presence of a well-ordered Al-containing mesophase with high hydrothermal stability. Notably, the Al content and the acidity of Al-SBA-15 can be tuned by changing the SPS amount.

Obtaining of Mesoporous Aluminosilicates with High Hydrothermal Stability by Composite Organic Templates: Utility and Mechanism.

We have reported the synthesis of mesoporous aluminosilicates (MAs) with high hydrothermal stability via assembly of basic characteristic structure units of typical microporous zeolite Y. In spite of this, high consumption of organic template and H2O remains a major obstacle to its industrial application. Herein, a facile and effective strategy called "composite templates" was employed to decrease significantly the amount of P123 and H2O. In this method, composite micelles of P123/poly(vinyl alcohol) (PVA) could be more easily dispersed in the solution due to the lowering of water's surface tension caused by the free hydroxyl groups of PVA. Moreover, the improved assembly ability of composite micelles in high concentration solution leads to the synthesis of hydrothermally stable MAs with 45% decrease of organic template P123 and 81% that of water amount. It was found that by the introduction of composite templates, the textural properties such as the surface area of materials, volume of pore, size of pore, and thickness were enlarged simultaneously. Meanwhile, this article presented an understanding into the assembly of composite micelles in the process of synthesis of MAs.

Distribution of Iron on FCC Catalyst and Its Effect on Catalyst Performance.

The effects of different iron contamination content on the formation of iron nodules and the performance of FCC catalysts have been studied by cyclic deactivation treatment using iron naphthenate. The catalysts were characterized by X-ray diffraction, N2 adsorption-desorption, and SEM. The catalysts' performance was evaluated by the Advanced Cracking Evaluation device. It has been found that there will be obvious nodulation on the catalyst when the iron concentration exceeds 7,400 µg/g. With the iron deposition from 53 µg/g to 11,690 µg/g, the crystal structure of zeolite will not be destroyed by iron. The surface area and pore volume of the catalyst decreased significantly; the surface area decreased from 125.3 m2/g to 91.0 m2/g, and the pore volume decreased from 0.21 cm3/g to 0.16 cm3/g. The studies also showed that the increase of iron deposition will lead to the decrease of catalytic reaction efficiency. With the iron deposition from 53 µg/g to 11,690 µg/g, the conversion decreased by 4.83%. Under the same 78 wt.% conversion, bottoms yield and coke yield increased by 2.15% and 1.31%, while gasoline yield and LCO yield decreased by 2.59% and 2.16%, respectively. The real state of the industrial iron contaminated equilibrium catalyst can be mimicked by using the cyclic deactivation method.

Diffusion and catalyst efficiency in hierarchical zeolite catalysts.

The preparation of hierarchical zeolites with reduced diffusion limitation and enhanced catalyst efficiency has become a vital focus in the field of zeolites and porous materials chemistry within the past decades. This review will focus on the diffusion and catalyst efficiency of hierarchical zeolites and industrial catalysts. The benefits of diffusion and catalyst efficiency at two levels of hierarchies (zeolitic component level and industrial catalyst level) from a chemical reaction engineering point of view will be analysed. At zeolitic component level, three types of mesopores based on the strategies applied toward enhancing the catalyst effectiveness factor are presented: (i) 'functional mesopores' (raising effective diffusivity); (ii) 'auxiliary mesopores' (decreasing diffusion length); and (iii) 'integrated mesopores' (a combination thereof). At industrial catalyst level, location and interconnectivity among the constitutive components are revealed. The hierarchical pore interconnectivity in multi-component zeolite based industrial catalysts is exemplified by fluid catalytic cracking and bi-functional hydroisomerization catalysts. The rational design of industrial zeolite catalysts at both hierarchical zeolitic component and catalyst body levels can be fully comprehended using the advanced in situ and/or operando spectroscopic, microscopic and diffraction techniques.

Solvent-Free Synthesis of Zeolites: Mechanism and Utility.

Zeolites have been extensively studied for years in different areas of chemical industry, such as shape selective catalysis, ion-exchange, and gas adsorption and separation. Generally, zeolites are prepared from solvothermal synthesis in the presence of a large amounts of solvents such as water and alcohols in sealed autoclaves under autogenous pressure. Water has been regarded as essential to synthesize zeolites for fast mass transfer of reactants, but it occupies a large space in autoclaves, which greatly reduces the yield of zeolite products. Furthermore, polluted wastes and relatively high pressure due to the presence of water solvent in the synthesis also leads to environmental and safety issues. Recently, inspired by great benefits of solvent-free synthesis, including the environmental concerns, energy consumption, safety, and economic cost, researchers continually challenge the rationale of the solvent and reconsider the age-old question "Do we actually need solvents at all in zeolite synthesis?" In this Account, we briefly summarize our efforts to rationally synthesize zeolites via a solvent-free route. Our research demonstrates that a series of silica, aluminosilicate, and aluminophosphate-based zeolites can be successfully prepared by mixing, grinding, and heating starting solid materials under solvent-free conditions. Combining an organotemplate-free synthesis with a solvent-free approach maximizes the advantages resulting in a more sustainable synthetic route, which avoids using toxic and costly organic templates and the formation of harmful gases by calcination of organic templates at high temperature. Furthermore, new insights into the solvent-free crystallization process of zeolites have been provided by modern techniques such as NMR and UV-Raman spectroscopy, which should be helpful in designing new zeolite structures and developing novel routes for synthesis of zeolites. The role of water and the vital intermediates during the crystallization of zeolites have been proposed and verified. In addition to a significant reduction in liquid wastes and a remarkable increase in zeolite yields, the solvent-free synthesis of zeolites exhibits more unprecedented benefits, including (i) the formation of hierarchical micro-, meso-, and macrostructures, which benefit the mass transfer in the reactions, (ii) rapid synthesis at higher temperatures, which greatly improve the space-time yields of zeolites, and (iii) construction of a novel catalytic system for encapsulation of metal nanoparticles and metal oxide particles within zeolite crystals synergistically combining the advantages of catalytic metal nanoparticles and metal oxide particles (high activity) and zeolites (shape selectivity). We believe that the concept of "solvent-free synthesis of zeolites" would open a door for deep understanding of zeolite crystallization and the design of efficient zeolitic catalysts.

Furfuralcohol Co-Polymerized Urea Formaldehyde Resin-derived N-Doped Microporous Carbon for CO2 Capture.

Carbon-based adsorbent is considered to be one of the most promising adsorbents for CO2 capture form flue gases. In this study, a series of N-doped microporous carbon materials were synthesized from low cost and widely available urea formaldehyde resin co-polymerized with furfuralcohol. These N-doped microporous carbons showed tunable surface area in the range of 416-2273 m(2) g(-1) with narrow pore size distribution within less than 1 nm and a high density of the basic N functional groups (2.93-13.92 %). Compared with the carbon obtained from urea resin, the addition of furfuralcohol apparently changed the surface chemical composition and pore size distribution, especially ultramicropores as can be deduced from the X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FT-IR), and pore size distribution measurements and led to remarkable improvement on CO2 adsorption capacity. At 1 atm, N-doped carbons activated at 600 °C with KOH/UFFC weight ratio of 2 (UFFA-2-600) showed the highest CO2 uptake of 3.76 and 1.57 mmol g(-1) at 25 and 75 °C, respectively.

Theoretical studies of the nitrogen containing compounds adsorption behavior on Na(I)Y and rare earth exchanged RE(III)Y zeolites.

In this work, the adsorption behavior of nitrogen containing compounds including NH3, pyridine, quinoline, and carbazole on Na(I)Y and rare earth exchanged La(III)Y, Pr(III)Y, Nd(III)Y zeolites was investigated by density functional theory (DFT) calculations. The calculation results demonstrate that rare earth exchanged zeolites have stronger adsorption ability for nitrogen containing compounds than Na(I)Y. Rare earth exchanged zeolites exhibit strongest interaction with quinoline while weakest with carbazole. Nd(III)Y zeolites are found to have strongest adsorption to all the studied nitrogen containing compounds. The analysis of the electronic total charge density and electron orbital overlaps show that nitrogen containing compounds interact with zeolites by π-electrons of the compounds and the exchanged metal atom. Mulliken charge population analysis also proves that adsorption energies are strongly dependent on the charge transfer between the nitrogen containing molecules and exchanged metal atom in the zeolites.

Tailoring acidity of HZSM-5 nanoparticles for methyl bromide dehydrobromination by Al and Mg incorporation.

Three kinds of HZSM-5 nanoparticles with different acidity were tailored by impregnating MgO or varying Si/Al ratios. Both the textural and acidic properties of the as-prepared nanoparticles were characterized by nitrogen adsorption-desorption measurements, X-ray diffraction (XRD), scanning electron microscopy (SEM), ammonia temperature-programmed desorption (NH3-TPD) and Fourier transform infrared spectroscopy (FTIR or Py-FTIR). It was found that the intensity of Lewis acid sites with weak strength was enhanced by impregnating MgO or reducing Al concentration, and such an enhancement could be explained by the formation of Mg(OH)(+) or charge unbalance of the MgO framework on the surface of HZSM-5 support. The effect of HZSM-5 nanoparticles' acidity on methyl bromide dehydrobromination as catalyst was evaluated. As the results, MgHZ-360 catalyst with the highest concentration of Lewis acid sites showed excellent stability, which maintained methyl bromide conversion of up 97% in a period of 400 h on stream. Coke characterization by BET measurements and TGA/DTA and GC/MS analysis revealed that polymethylated naphthalenes species were formed outside the channels of the catalyst with higher acid intensity and higher Brønsted acid concentration during the initial period of reaction, while graphitic carbon formed in the channels of catalyst with lower acid intensity and higher Lewis acid concentration during the stable stage.

A facile strategy to recycle template P123 from mesoporous aluminosilicates by ultrasonic extraction.

High synthesis cost of mesoporous aluminosilicates (MA) limits their practical application. Recycling of copolymer template employed in preparation of MA is an effective way to reduce the synthesis cost. An ultrasonic extraction strategy for recycling of organic template P123 in MAs is reported. Effects of different extraction parameters on P123 recovery are investigated and the optimum conditions are obtained. 75.0% P123 is recovered from MAs within 10 min by one-step ultrasonication. Characterizations indicated that the resulting P123-free MA (MA-U) exhibits excellent properties compared with that of calcined products. Moreover, recovered P123 can be employed to synthesize high hydrothermally stable MA. This investigation provides a facile strategy to recycle P123 from MA.

Unstable-Fe-site-induced formation of mesopores in microporous zeolite Y without using organic templates.

A novel organic template-free strategy for generating mesoporosity in Y zeolites is reported. It is revealed that Fe(3+) functioned as unstable sites in the Fe-NaY zeolite, which promotes deferrization-dealumination, leading to enhanced formation of intra-crystalline mesopores as well as desirable interconnectivity. The mesopore-enriched zeolite exhibits a remarkable ability in conversion of the bulky substrate.

Thiophenic compounds adsorption on Na(I)Y and rare earth exchanged Y zeolites: a density functional theory study.

We have theoretically investigated the adsorption of thiophene, benzothiophene, dibenzothiophene on Na(I)Y and rare earth exchanged La(III)Y, Ce(III)Y, Pr(III)Y Nd(III)Y zeolites by density functional theory calculations. The calculated results show that except benzothiophene adsorbed on Na(I)Y with a stand configuration, the stable adsorption structures of other thiophenic compounds on zeolites exhibit lying configurations. Adsorption energies of thiophenic compounds on the Na(I)Y are very low, and decrease with the increase of the number of benzene rings in thiophenic compounds. All rare earth exchanged zeolites exhibit strong interaction with thiophene. La(III)Y and Nd(III)Y zeolites are found to show enhanced adsorption energies to benzothiophene and Pr(III)Y zeolites are favorable for dibenzothiophene adsorption. The analysis of the electronic total charge density and electron orbital overlaps show that the thiophenic compounds interact with zeolites by π-electrons of thiophene ring and exchanged metal atom. Mulliken charge populations analysis reveals that adsorption energies are strongly dependent on the charge transfer of thiophenic molecule and exchanged metal atom.

Positively charged bulk Au particles as an efficient catalyst for oxidation of styrene with molecular oxygen.

Positively charged bulk Au particles with size of 20-150 nm were formed on amino-modified porous polydivinylbenzene (Au/PN), which showed superior catalytic performance and good recyclability in the aerobic oxidation of styrene.