Hollow Zeolite Nanoreactor with Double Shells for Methanol Aromatization: Explicit Recognition on Catalytic Function of Inverse Elemental Zone and Shell-Cavity.

Core@shell catalyst composited of dual aluminosilicate zeolite can effectively regulate the distribution of acid sites to control hydrocarbon conversion process for the stable formation of target product. However, the diffusion restriction reduces the accessibility of inner active sites and affects synergy between core and shell. Herein, hollow ZSM-5 zeolite nanoreactor with inverse aluminum distribution and double shells are prepared and employed for methanol aromatization. It is demonstrated that the intershell cavity alleviated the steric hindrance from zeolites channel and provided more paths and pore entrance for guest molecule. Correspondingly, olefin intermediates generated from methanol over the external shell are easier to adsorb at internal acid sites for further reactions. Importantly, the diffusion of generated aromatic macromolecules to the external surface is also promoted, which slows down the formation of internal coke, and ensures the use of internal acid sites for aromatization. The aromatics selectivity of the nanoreactor remained at 8% after 154 h, while that of solid core@shell catalyst decreased to 2% after 75 h. This finding promises broader insight to improve internal active site utilization of core@shell catalyst at the diffusion level and can be great aid in the flexible design of multifunctional nanoreactors to enhance the relay efficiency.

Controllable Orientation Growth of ZSM-5 for Methanol to Hydrocarbon Conversion: Cooperative Effects of Seed Induction and Medium pH Control.

The growth orientation of ZSM-5 zeolites strongly affects product selectivity in methanol conversion reaction. Here, we proposed a versatile synthetic strategy by introducing seeds and controlling medium pH to achieve controllable orientation growth of ZSM-5. The systematic analysis of the crystallization process indicated that the introduction of seeds ensured successful crystallization in a quasi-neutral solution and the dissolution rate of seeds and aluminosilicate determined the growth orientation of ZSM-5. In the quasi-neutral solution, the slow dissolution of seeds and aluminosilicate enhanced growth advantages along the c axis. The ratio between the length of the c axis and b axis (Lc/Lb) of the obtained ZSM-5 at pH of 7 could reach 8.1, much higher than 1.8 obtained at pH of 11. No obvious impact of seed added amount on growth orientation was found, while with increasing seed crystal size, the obtained ZSM-5 showed preferred growth along the c axis. The Lc/Lb of the sample adding seeds with a size of 355 nm reached 7.9, much higher than 2.1 of the sample adding seeds with a size of 70 nm. The obtained ZSM-5 with specific growth orientation exhibited potential shape selectivity in methanol to aromatics and olefin reaction. This work opens new possibilities to tailor the orientation growth of ZSM-5 based on the seed-induced strategy under mild conditions.

Surface-Protection-Induced Controllable Restructuring of Pores and Acid Sites of the Nano-ZSM-5 Catalyst and Its Influence on the Catalytic Conversion of Methanol to Hydrocarbons.

Creating mesopores for the nano-ZSM-5 catalyst could further promote the diffusion of molecules in its micropores and improve the catalytic activity and stability. Inorganic alkali treatment of ZSM-5 usually removes internal silica for the existence of an aluminum distribution gradient and leads to a hollow structure. Herein, surface TPA+ adsorption-induced protective desilication and recrystallization successively occurred during hydrothermal treatment, and controllable mesopore fabrication was achieved. The evolution of mesopores and acid sites was characterized by N2 physisorption, XRD, XRF, TEM, NH3-TPD, Py-IR, 27Al MAS NMR, 29Si MAS NMR, and TG techniques. It was found that the TPAOH concentration influenced the formation of internal cavity and mesopores in the shell. Introducing TPABr into TPAOH solution increased the surface protection because of the increased TPA+ adsorption, and coated hollow ZSM-5 was obtained. The acidity was restructured during the above mesopore fabrication. High-concentration TPAOH solution promoted the insertion of destructive Al into the skeleton structure to form strong acid sites, and the catalytic lifetime was recovered and even obviously prolonged. This reflected the key role of strong acid sites on the catalytic performance. Applying hollow nano-ZSM-5 with a mesoporous shell and strong acidity increased the lifetime by 50% and the conversion capacity for liquid hydrocarbon by 20% compared to the parent sample.

Controllable integration of ultrasmall noble metal nanoparticles into mesoporous silica matrixes by a self-assembly method.

Noble metal nanoparticles smaller than 2 nm were immobilized inside the channels of mesoporous silica via a self-assembly method using cetyltrimethylammonium chloride as a structural directing agent. This general approach can be used for integration of various precious metals into mesoporous silica matrixes of ∼30 nm to achieve better matter utilisation and higher catalytic activity.