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The incorporation of metal heteroatoms into zeolites is an effective modification strategy for enhancing their catalytic performance. Herein, for the first time we report a generalized methodology for inserting metal heteroatoms (such as Sn, Fe, Zn, and Co) into the layered zeolite precursor RUB-36 via interlayer expansion by using the corresponding metal acetylacetate salt. Through this generalized methodology, Sn-JHP-1, Fe-JHP-1, Zn-JHP-1 and Co-JHP-1 zeolites could be successfully prepared by the reaction of RUB-36 and corresponding metal acetylacetate salt at 180 °C for 24 h in the presence of HCl solution. As a typical example, Sn-JHP-1 and calcined Sn-JHP-1 (Sn-JHP-2) zeolite is well characterized by the X-ray diffraction (XRD), diffuse reflectance ultraviolet-visible (UV-Vis), inductively coupled plasma (ICP), N2 sorption, temperature-programmed-desorption of ammonia (NH3-TPD) and X-ray photoelectron spectroscopy (XPS) techniques, which confirm the expansion of adjacent interlayers and thus the incorporation of isolated Sn sites within the zeolite structure. Notably, the obtained Sn-JHP-2 zeolite sample shows enhanced catalytic performance in the conversion of glucose to levulinic acid (LA) reaction.

Preparation of aluminosilicate ferrierite (FER) zeolite nanosheets with controllable thickness in the presence of a sole organic ammonium is attractive, but still challenging. In this report, with the employment of N,N-diethyl-cis-2,6-dimethylpiperidinium (DMP) as both a structure directing agent and crystal growth inhibitor, aluminosilicate FER zeolite nanosheets, with a variety of crystal thicknesses, ranging from 6 to 200 nm, are successfully synthesized under hydrothermal conditions. Very interestingly, the amount of DMP in the starting gel is the key factor for crystal thickness control of aluminosilicate FER zeolite nanosheets. The obtained FER products, with different thicknesses, are well characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), N2 sorption, thermogravimetric analysis (TG), inductively coupled plasma (ICP), and magic angle spinning nuclear magnetic resonance (MAS NMR) techniques. This simple strategy might provide a novel avenue for the synthesis of other zeolite nanosheets with controllable thickness.

High silica chabazite zeolite (CHA) is very important for selective catalytic reduction of NOx with ammonia (NH3-SCR), but its synthesis is time-consuming under conventional hydrothermal conditions (160 °C for 90–120 h). Herein, we report a novel strategy for highly efficient synthesis of CHA zeolite by means of fast crystallization at high temperatures in the absence of water solvent (240 °C for 1.5 h). X-ray diffraction, N2-adsorption isotherms, inductively coupled plasma, scanning electron microscopy, 29Si and 27Al MAS NMR, as well as thermogravimetry-differential thermal analysis suggest that the samples have high quality. This concept significantly enhances the space-time yields (STY) for CHA zeolite prepared from high-temperature synthesis in the absence of water solvent (almost two orders of magnitude higher than those of conventional hydrothermal synthesis). Moreover, compared with hydrothermal synthesis, the samples obtained from fast crystallization at higher temperatures (Si/Al = 12, 2.0% Cu loading) shows enhanced catalytic performance at 350–550 °C in NH3-SCR.

Given the numerous industrial applications of zeolites as adsorbents, catalysts, and ion-exchangers, the development of new zeolite structures is highly desired to expand their practical applications. Currently, a general route to develop new zeolite structures is to use interlayer expansion agents to connect layered silicates. In this review, we briefly summarize the novel zeolite structures constructed from the lamellar precursor zeolites MWW, RUB-36, PREFER, Nu-6(1), COK-5, and PLS-1 via interlayer expansion. The contents of the summary contain detailed experiments, physicochemical characterizations, possible expansion mechanisms, and catalytic properties. In addition, the insertion of metal heteroatoms (such as Ti, Fe, Sn) into the layered zeolite precursor through interlayer expansion, which could be helpful to modify the catalytic function, is discussed.

The strong metal–support interactions (SMSI) are well-known but crucial for preparation of supported metal nanoparticle catalysts, which generally occur by reduction and oxidation under harsh conditions. Here, we delineate the example of constructing SMSI without reduction and oxidation, where the key is to employ a hydroxide-to-oxide support transformation. The covering of Au nanoparticles by oxides, electronic interaction, and changes in CO adsorption tests of the catalyst are identical to those of the classic SMSI. Owing to the SMSI with oxide barriers on the Au nanoparticles, the supported Au catalysts are sintering-resistant at high temperatures, which benefit long-life reactions, outperforming the conventional supported catalysts.

The synthesis of organic nitriles without using toxic cyanides is in great demand but challenging to make. Here we report an environmentally benign and cost-efficient synthesis of nitriles from the direct oxidative cyanation of primary carbon-hydrogen bonds with easily available molecular oxygen and urea. The key to this success is to design and synthesize manganese oxide catalysts fixed inside zeolite crystals, forming a manganese oxide catalyst with zeolite sheath (MnOx@S-1), which exhibits high selectivity for producing nitriles by efficiently facilitating the oxidative cyanation reaction and hindering the side hydration reaction. The work delineates a sustainable strategy for synthesizing nitriles while avoiding conventional toxic cyanide, which might open a new avenue for selective transformation of carbon-hydrogen bonds., Sustainable strategies for nitrile synthesis are needed. Here, the authors report an environmentally benign, selective heterogeneous catalyst for the synthesis of nitriles by the oxidative cyanation of carbon and hydrogen (C-H) bonds, which comprises nanoscale manganese oxide catalysts fixed inside a zeolite crystal.

Enhancing the yield of alkyl lactate from sugars is in great demand but challengeable to accomplish. Here we report a facile but efficient route to make this by employing a hierarchical and Sn-cont...

Large crystalline particles of ZSM-5 zeolites (S-ZSM-5) have been successfully synthesized by adjusting crystallization time and Si/Al ratios in the starting solid mixtures in the absence of water solvent. Catalytic tests in the methanol-to-olefins (MTO) reaction show that these S-ZSM-5 zeolites obtained from the solvent-free route exhibit superior catalytic properties including excellent propylene selectivity and extraordinarily long life in the MTO reaction. Particularly, when the crystallization time is 30 h and the Si/Al ratio in the starting solid mixture is adjusted at 150 under the solvent-free conditions, the S-ZSM-5-30h-150 catalyst with the large particle sizes (10–20 μm) gives propylene selectivity as high as 50.0% and catalyst life as long as 9 h, which are much better than those (propylene selectivity at 38.9% and catalyst life of 3 h) of the conventional ZSM-5 zeolite with smaller crystals (ca. 5 μm) synthesized from the hydrothermal route. High-resolution TEM images of these S-ZSM-5 zeolite...

As a class of important catalysts and adsorbents, zeolites are normally prepared through hydrothermal synthesis, whereby a relatively long crystallization time and use of a large amount water solvent strongly hinder the enhancement of zeolite space-time yields (STYs), which is a critical factor for the industrial manufacturing. To overcome this limitation, herein we report a novel strategy for highly efficient zeolite synthesis by means of fast crystallization at high temperatures (200–240 °C) in the absence of water solvent. This concept significantly enhances the crystallization rates and allows drastic reduction of the time required for crystallization of the zeolite frameworks such as the crystallization of MFI from 12–24 h at 180 °C to 0.5 h at 240 °C and RUB-36 from 14 days at 140 °C to 1.5 days at 200 °C. Together with much better utilization of the reactor volume, the space-time yields (STYs) for zeolites prepared from high-temperature synthesis in the absence of water solvent can be remarkably increased. The STYs of MFI and RUB-36 are as high as 11 000 and 178 kg m−3 per day, which are almost two orders of magnitude higher than those of conventional hydrothermal synthesis. This novel synthesis method should be applicable for synthesizing a wide variety of zeolite structures and bears the potential for highly efficient zeolite synthesis on an industrial scale.

As a C1 feedstock, CO2 has the potential to be uniquely highly economical in both a chemical and a financial sense. Porous materials bearing particular binding and active sites that can capture and convert CO2 simultaneously are promising candidates for CO2 utilization. In this work, a bipyridine-constructed polymer featuring a high surface area, a hierarchical porous structure, and excellent stability was synthesized through free-radical polymerization. After metalation, the resultant catalysts exhibited superior activities in comparison with those of their homogeneous counterparts in the cycloaddition of CO2 to epoxides. The high performance of the heterogeneous catalysts originates from cooperative effects between the CO2 -philic polymer and the embedded metal species. In addition, the catalysts showed excellent stabilities and are readily recyclable; thus, they are promising for practical utilization for the conversion of CO2 into value-added chemicals.

Aluminosilicate SSZ-39 zeolite shows the excellent catalytic performance in selective catalytic reduction of NOx with NH3 (NH3-SCR) reaction, but their synthesis is still not efficient due to the use of a large amount of water as a solvent under hydrothermal condition. Herein, for the first time, we report a solvent-free synthesis of aluminosilicate SSZ-39 zeolite without addition of water in the presence of N,N-dimethyl-3,5-dimethylpiperidine (DMDMP) cation as an organic structure-directing agent. Various characterizations, including powder X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetry-differential thermal analysis (TG-DTA), N2 sorption, inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis, solid nuclear magnetic resonance (NMR) and NH3-temperature-programmed desorption (NH3-TPD), show that the aluminosilicate SSZ-39 zeolite displays high crystallinity, uniform sheet-like morphology, large surface area, four-coordinated aluminum species, strong acidic sites and excellent hydrothermal stability. Compared with the conventional synthesis for aluminosilicate SSZ-39 zeolite, the solvent-free synthesis of aluminosilicate SSZ-39 zeolite has the obvious advantages such as high product yield, simple synthesis procedures, and the reduction of pollutants. More importantly, the copper-exchanged aluminosilicate SSZ-39 zeolite shows the good catalytic performance in NH3-SCR reaction, which is fully comparable with that of the Cu-SSZ-39 zeolite synthesized under hydrothermal condition from the reported literature.

We have successfully synthesized a porphyrin based porous organic polymer (POP-TPP) from free-radical polymerization of tetrastyrylporphyrin monomer under solvothermal conditions. Besides high surface area (1200 m(2)/g) and high thermal stability, the obtained polymer features open metal chelating sites, and thus the catalytic activities of metalloporphyrins can be reasonably adjusted by introducing various metal ions. After metalation with Co3+, Zn2+, and Mg2+, the Co/POP-TPP, Zn/POP-TPP, and Mg/POP-TPP as heterogeneous catalysts are very active for cycloaddition of epoxides with CO2 to cyclic carbonates at ambient conditions with n-Bu4NBr as a nucleophilic additive. Particularly, under the relatively low CO2 concentration (15% in volume), the activity of heterogeneous Co/POP-TPP catalyst is even higher than that of the corresponding homogeneous Co/TPP catalyst. More importantly, there is no activity loss even if the Co/POP-TPP is recycled for 18 times. The excellent catalytic activity and superior recyclability of the obtained catalysts indicate that the porphyrin based porous organic polymer is a promising candidate for construction of efficient heterogeneous catalysts in the future. (C) 2016 Elsevier Inc. All rights reserved.

Catalytic combustion over zeolite supported platinum catalysts is regarded as one of the efficient methods for removal of volatile organic compounds (VOCs). In this work, we show a preparation of Pt loaded mesoporous ZSM-5 zeolite (Pt/Meso-ZSM-5) with various cations. The sample N 2 sorption isotherms and TEM image show abundant mesoporosity existing in the zeolite crystals. The catalytic toluene combustion tests show that the Pt/Meso-ZSM-5 catalysts have higher activities than conventional ZSM-5 supported Pt catalysts (Pt/ZSM-5), which is related to their difference in the concentration of active sites Pt 0 and the rate of mass transfer. Particularly, after reduction with hydrogen at 300 °C, the Pt nanoparticles supported on Meso-ZSM-5 with K + and Cs + cations (Pt-R/Meso-KZSM-5 and Pt-R/Meso-CsZSM-5) exhibit much higher activities than those on Meso-ZSM-5 with Na + and H + cations, which is well consistent with their order of the Pt 0 concentration. For example, Pt-R/Meso-KZSM-5 gives the temperature for conversion of 98% toluene ( T 98 ) at only 175 °C, while Pt-R/Meso-HZSM-5 shows the T 98 at 190 °C. More importantly, Pt-R/Meso-KZSM-5 has a long life, and its activity cannot be influenced by the water and CO 2 . These features are critically important for practical applications of these catalysts in the future.

Ni-P alloy coatings with a phosphorus content of 11.65 wt% were deposited by electroless plating. The as-plated nano-amorphous Ni-P alloy coatings were heated in air for 1 h at 200–500 °C. By using an atomic force microscope and the x-ray diffraction method, the nanocrystalline morphology and the crystallization phase identification of the coatings were studied. The corrosion behavior of the coatings in the 3.5 wt% NaCl solution was analyzed using polarization curves and impedance spectroscopy. It was observed that the corrosion behavior of the coatings was affected by the change in the nanocrystalline structure; during the heat treatment, the nanocrystalline structure of the coating alloy undergoes sequential changes from amorphous → the adjustment of amorphous → precipitated phase → crystalline. Meanwhile, the corrosion behavior of the coating alloy has also changed from uniform corrosion controlled by charge transfer → uniform corrosion controlled by diffusion → grain boundary corrosion. The Ni phase and the Ni3P phase developed a compact and dense nanocrystal layer on the surface of the coating alloy, in which the best performance by the corrosion resistant coating can be found.

The layered silicate COK-5 has been used for an interlayer expansion reaction with dichlorodimethylsilane (DCDMS) at 180 °C to interconnect neighboring layers, yielding a new and crystalline microporous framework. The samples containing the methyl functional groups in the as-made form and having OH groups in the calcined form were designed as COE-5 and calcined COE-5. These samples were characterized with X-ray diffraction (XRD), N 2 sorption isotherms, inductively coupled plasma optical emission spectrometry (ICP-OES), infrared spectroscopy (IR), high-resolution transmission electron micrograph (HRTEM), thermogravimetry-differential thermal analysis (TG-DTA), and 29 Si and 13 C solid-state magic-angle spinning nuclear magnetic resonance (MAS NMR), as well as the contact angle techniques. XRD patterns and HRTEM images suggest that the sample interlayer spacing has been expanded by nearly 0.5 A. The N 2 sorption isotherms of the materials show the BET surface areas are 165 m 2 /g for COE-5 and 340 m 2 /g for calcined COE-5. 29 Si and 13 C MAS NMR as well as IR spectroscopy confirm the insertion of the linker group -Si(CH 3 ) 2 - connecting neighboring layers. Interestingly, calcined COE-5 shows enhanced catalytic performance in the acetalisation of glycerol with acetone to produce solketal, compared with COK-5.

In the interlayer expansion of the layered zeolite precursor COK-5, a Sn, salt, bis(2,4-pentanedionate)-dichlorotin [Sn(acac) 2 Cl 2 ], instead of a silylating agent was used to link the layers at 180 °C. The obtained material, which is designed as Sn-COE-5, shows a shift of the first XRD reflection, which is very similar to that of COK-5 interlayer expanded with dichlorodimethylsilane (DCDMS), indicating an increase in interlayer distance. X-ray diffraction (XRD), N 2 sorption isotherms, inductively coupled plasma (ICP), and X-ray photoelectron spectroscopy (XPS) support the incorporation of isolated Sn sites in the sample. In the conversion of glucose to levulinic acid, Sn-COE-5 exhibits much higher activity than COK-5, which is due to the presence of Lewis acidic sites in the Sn-COE-5.

A glass carbon electrode was modified by the nickel form of an aluminum-rich beta-SDS zeolite synthesized from an organotemplate-free and seed-directed route. Catalytic tests in the electro-oxidation of methanol show that this modified electrode exhibits improved catalytic activity, compared with the electrode modified conventional nickel form of beta zeolite.

The removal of volatile organic compounds is an important aspect of sustainability and environmental protection. Catalytic oxidation is one of the most efficient routes to achieve this. The K+ form of an aluminium-rich Beta zeolite-supported Pt nanoparticle (2.2 nm) [Pt/KBeta-seed-directed synthesis (SDS)] catalyst is very active for the low-temperature catalytic removal of toluene and results in full conversion at a much lower temperature than a conventional KBeta-supported Pt nanoparticle (Pt/KBeta-TEA) catalyst. The higher activity of the Pt/KBeta-SDS catalyst compared with the Pt/KBeta-TEA catalyst is related to the advantages of the higher K+ content and fewer terminal silanol defects in the KBeta-SDS catalyst than in the KBeta-TEA catalyst. The higher K+ content is helpful for the formation of more Pt0 species, and both the higher K+ content and the lower number of terminal silanol defects are favourable for the adsorption of toluene, as evidenced by XPS and the toluene-TPD profiles. More importantly, the Pt/KBeta-SDS catalyst shows very stable activities in the presence of H2O and CO2 in the feed gases. The combination of this extraordinary activity and excellent stability in the catalytic removal of toluene over the Pt/KBeta-SDS catalyst are important for future environment protection.

SAPO-11 nanosheets with partially filled micropores (N-SAPO-11) and a thickness of 10–20 nm were synthesized using polyhexamethylene biguanide hydrochloride (PHMB) as a mesoporogen and di-n-propylamine (DPA) as a microporous template. After Pt loading (0.5 wt%), the Pt/N-SAPO-11 catalyst exhibits higher selectivity for the isomers and lower selectivity for cracking products than conventional Pt/SAPO-11 catalysts in the hydroisomerization of n-dodecane.

We reported selective hydrogenolysis of carbon–oxygen species over a CeO2-supported Au–Pt alloy catalyst (Au–Pt/CeO2) using biomass-derived formic acid as the hydrogen source. The success of this reaction is reasonably attributed to the high efficiency of Au–Pt/CeO2 in the tandem steps of formic acid dehydrogenation and carbon–oxygen species hydrodeoxygenation.

Development of sustainable routes for synthesizing aluminophosphate-based zeolites are very important because of their wide applications. As a typical sustainable route, solvent-free synthesis of zeolites not only decreases polluted wastes but also increases product yields. Systematic solvent-free syntheses of hierarchically porous aluminophosphate-based zeolites with AEL and AFI structures is presented. XRD patterns and SEM images show that these samples have high crystallinity. N2 sorption isotherm tests show that these samples are hierarchically porous, and their surface areas are comparable with those of corresponding zeolites from hydrothermal route. Chosen as an example, catalytic oxidation of ethylbenzene with O2 shows that cobalt substituted APO-11 from the solvent-free route (S-CoAPO-11) is more active than conventional CoAPO-11 from hydrothermal route owing to the sample hierarchical porosity.

A series of ZSM-5 zeolite with various cations (H+, Na+, K+, and Cs+) and Si/Al ratios (60, 100, 300, and ∞) supported 0.5 % Pt have been prepared and tested in the combustion of toluene. It is found that Pt/KZSM-5-100 catalyst exhibits excellently high catalytic activity, negligible inhibition effect of H2O, and long catalyst life. 0.5 %Pt/KZSM-5-100 catalyst exhibits superior performance in combustion of VOCs, which would be potentially important for environmental protection.

The development of the sustainable synthesis of zeolites has become a very hot topic in recent years. Herein, we report a sustainable route for synthesizing all-silica SOD zeolite under solvent-free conditions. The method of solvent-free synthesis includes mixing, grinding, and heating raw solids. The all-silica SOD zeolite obtained was well characterized by multiple measurement techniques (XRD, SEM, IR, thermogravimetric-differential thermal analysis (TG-DTA), and magic angel spinning nuclear magnetic resonance (MAS NMR)). The crystallization process of all-silica SOD zeolite was also investigated in detail by XRD, SEM, UV-Raman, and MAS NMR techniques. In addition, the effects of the crystallization compositions, including the molar ratios of Na2O/SiO2 and ethylene glycol/SiO2, on the synthesis of the pure all-silica SOD zeolite were investigated at different temperatures.

A solvent-free route is developed for synthesizing titanosilicate zeolites with good crystallinity, uniform crystals, high surface area, and tetrahedral Ti species in the framework. Catalytic tests show that S-TS-1 exhibits almost the same catalytic activity in hexane oxidation with H2O2 as that of conventional TS-1 synthesized by a hydrothermal route.

Size-controllable Pt nanoparticles ranging from 1.3 to 2.3 nm were successfully loaded onto ZSM-5 (Pt-x/ZSM-5, where x is the mean diameter of the Pt nanoparticles). Catalytic tests in complete oxidation of toluene as a model for VOC removal show that Pt-1.9/ZSM-5 has the highest activity, due to a balance of Pt dispersion and Pt(0) proportion.

Development of sustainable routes for synthesis of zeolites is very important because of wide applications of zeolites at large scale in the fields of catalysis, adsorption, and separation. Here we report a novel and generalized route for synthesis of zeolites in the presence of NH4F from grinding the anhydrous starting solid materials and heating at 140-240 °C. Accordingly, zeolites of MFI, BEA*, EUO, and TON structures have been successfully synthesized. The presence of F(-) drives the crystallization of these zeolites from amorphous phase. Compared with conventional hydrothermal synthesis, the synthesis in this work not only simplifies the synthesis process but also significantly enhances the zeolite yields. These features should be potentially of great importance for industrial production of zeolites at large scale in the future.