Understanding methane activation pathways on Zn-modified high-silica zeolites (ZSM-5, BEA) is of particular importance because of the possibility of methane involvement in coaromatization with higher alkanes on this type of zeolites. Herein, two samples of Zn-modified zeolite BEA containing exclusively either small zinc oxide clusters or isolated Zn 2+ cations have been synthesized and thoroughly characterized by a range of spectroscopic methods ( 1 H MAS NMR, DRIFTS, XPS, EXAFS, HRTEM) to show that only one of the Zn-species, either Zn 2+ cations or ZnO small clusters, exists in the void of zeolite pores. The ability of zinc sites of different nature to promote the activation of methane C−H bond with the zeolite Brønsted acid sites (BAS) has been examined in the reactions of methane H/D hydrogen exchange with BAS and the alkylation of benzene with methane. It has been found that both ZnO and Zn 2+ species promote the reaction of H/D exchange of methane with BAS. The rate of H/D exchange is higher by 2 and 3 orders of magnitude for the zeolite loaded with ZnO or Zn 2+ species, respectively, compared to pure acid-form zeolite H-BEA. So, the promoting effect of Zn 2+ cations is more profound than that of ZnO species for H/D exchange reaction. This implies that the synergistic effect of Zn-sites and BAS for C−H bond activation in methane is significantly higher for Zn 2+ cations compared to small ZnO clusters. It has been revealed, however, that only Zn 2+ cations promote the alkylation of benzene with methane, whereas ZnO species do not. The isolated Zn 2+ cations provide the formation of zinc-methyl species, which are further transformed to zinc-methoxy species. The latter is the key intermediate for the performance of the alkylation reaction. Hence, while both zinc oxide clusters and Zn 2+ cationic species are able to provide a synergistic effect for the activation of C−H bonds of methane displayed by the dramatic acceleration of H/D exchange reaction, only the Zn 2+ cationic species perform methane activation toward the alkylation of benzene with methane. This implies that only the Zn 2+ cations in Zn-modified zeolite can activate methane for the reaction of methane coaromatization with higher alkanes.

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With regard to possible involvement of zeolite Brønsted acid sites (BAS) in the activation of methane molecules for methane transformation to methanol, the effect of different Cu(II) species loaded in the zeolite on the kinetic parameters of the reaction of H/D hydrogen exchange of the alkane with BAS of Cu-modified ZSM-5 zeolites has been investigated with 1 H MAS NMR in situ at 533−563 K. It is found that the acceleration of the H/D exchange by 1 order of magnitude occurs for zeolite containingsites) compared to pure H-form zeolite. It is thus inferred that both Z 2 Cu(II) and Z 2 [Cu 3 (μ-O) 3 ] sites exhibit the promoting effect of copper on the activation of methane C−H bonds by BAS. Acceleration of the H/D exchange is rationalized by the change of the mechanism of the exchange accepted for the H-form zeolites for the mechanism that involves the formation of a transient molecular complex of methane with Cu(II) species, preceding the H/D exchange reaction. The formation of the complex of methane with both Z 2 Cu(II) and Z 2 [Cu 3 (μ-O) 3 ] sites is confirmed by DRIFTS. BASs with a higher strength than in H-ZSM-5, generated in the zeolite at copper loading, are concluded to not be responsible for the H/D exchange reaction acceleration.

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