Jordy Ramos-Yataco , Xinrui Zhang , Selim Alayoglu , Hien N. Pham , Abhaya K. Datye , Tobin J. Marks , Justin Notestein
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引用次数: 0
Abstract
Methane dehydroaromatization (MDA) is a promising approach for direct methane transformation to aromatics and hydrogen. The benchmark catalyst Mo/H-ZSM-5 struggles to find commercial adoption because of thermodynamically-limited yields and rapid coking on Brønsted acid and molybdenum carbide species, especially on zeolite external surfaces. Here, gas-phase atomic layer deposition (ALD) overcoats H-ZSM-5 external surfaces with SiO2 or Al2O3. NH3-TPD, HRTEM, and textural properties show that these overcoats exclusively passivate zeolite external surfaces. Under MDA conditions, SiO2 gives softer coke and increases cumulative benzene yields by 25 %, while Al2O3 strongly decreases yields. H2-TPR and UV–visible and Raman spectroscopy show how the overcoats redisperse the MoOx precatalysts, especially over multiple deactivation and isothermal oxidative regeneration cycles. Combined with 27Al-MAS NMR, MoOx redistribution and dealumination are seen as the causes of long-term deactivation over multiple regeneration cycles, and this process continues to occur regardless of the overcoat. Overall, the deposition of a small amount of silica on the outer surface of Mo/H-ZSM-5 reduces the formation of hard coke, which could be regenerated by milder methods such as hydrogen treatment.
期刊介绍:
Microporous and Mesoporous Materials covers novel and significant aspects of porous solids classified as either microporous (pore size up to 2 nm) or mesoporous (pore size 2 to 50 nm). The porosity should have a specific impact on the material properties or application. Typical examples are zeolites and zeolite-like materials, pillared materials, clathrasils and clathrates, carbon molecular sieves, ordered mesoporous materials, organic/inorganic porous hybrid materials, or porous metal oxides. Both natural and synthetic porous materials are within the scope of the journal.
Topics which are particularly of interest include:
All aspects of natural microporous and mesoporous solids
The synthesis of crystalline or amorphous porous materials
The physico-chemical characterization of microporous and mesoporous solids, especially spectroscopic and microscopic
The modification of microporous and mesoporous solids, for example by ion exchange or solid-state reactions
All topics related to diffusion of mobile species in the pores of microporous and mesoporous materials
Adsorption (and other separation techniques) using microporous or mesoporous adsorbents
Catalysis by microporous and mesoporous materials
Host/guest interactions
Theoretical chemistry and modelling of host/guest interactions
All topics related to the application of microporous and mesoporous materials in industrial catalysis, separation technology, environmental protection, electrochemistry, membranes, sensors, optical devices, etc.