Template-Guided Regioselective Encaging of Platinum Single Atoms into Y Zeolite: Enhanced Selectivity in Semihydrogenation and Resistance to Poisoning.

It is challenging to establish single metal atoms with a uniform coordination environment at targeted sites of a zeolite. In this study, single platinum atoms were selectively encaged in the six-membered rings of sodalite (SOD) cages within Y zeolite using a template-guiding strategy. During the in situ synthesis process, template molecules were designed to occupy supercages and thereby force coordinated platinum species into SOD cages. Subsequent control of the post-treatment conditions yielded the Y zeolite with selectively encaged single platinum atoms, denoted Pt@Y-SOD. The Pt@Y-SOD catalyst had good stability and excellent catalytic selectivity in the semihydrogenation reaction, and it exhibited interesting thiophene and carbon monoxide resistance in this transformation because interactions with these poisons are weakened by the configuration of the encaged single platinum atoms.

Highly Efficient Hydroisomerization of Endo-Tetrahydrodicyclopentadiene to Exo-Tetrahydrodicyclopentadiene over Pt/HY.

The fast deactivation caused by serious formation of coke is a major challenge in catalytic isomerization of endo-tetrahydrodicyclopentadiene (endo-THDCPD) into exo-tetrahydrodicyclopentadiene (exo-THDCPD) over the HY zeolite. In order to suppress the coke formation for the isomerization process, the conventional HY zeolite was modified with Pt at 0.3 wt %. Then, the hydroisomerization of endo-THDCPD into exo-THDCPD was evaluated over a fixed-bed reactor. The catalytic stability of Pt/HY was greatly enhanced in comparison to that of the HY zeolite. The Pt/HY catalyst provided 97% endo-THDCPD conversion and 96% selectivity for exo-THDCPD without deactivation after 100 h. Moreover, the formation mechanism of coke on the HY zeolite during the isomerization process was proposed based on the results of the coke analysis. It was indicated that the coke was generated from the oligomerization and condensation of olefin species, which originated from the ß-scission reaction or hydride transfer reaction of intermediates. The lower coke formation over Pt/HY was attributed to the lower amount of coke precursors, which could be hydrogenated by activated H2 over Pt sites. Therefore, Pt on Pt/HY and H2 were two crucial factors in efficiently enhancing the catalytic stability of the HY zeolite for this isomerization reaction.

Selectivity Control on Hydrogenation of Substituted Nitroarenes through End-On Adsorption of Reactants in Zeolite-Encapsulated Platinum Nanoparticles.

Platinum nanoparticles encapsulated into zeolite Y (Pt@Y catalyst) exhibit excellent catalytic selectivity in the hydrogenation of substituted nitroarenes to form the corresponding aromatic amines, even after complete conversion. With the hydrogenation of p-chloronitrobenzene as a model, the role of zeolite encapsulation toward perfect selectivity can be attributed to constraint of the substrate adsorbed on the platinum surface in an end-on conformation. This conformation results in the activation of only one adsorbed group, with little influence on the other one in the molecule. Owing to a much lower apparent activation energy of Pt@Y for the hydrogenation of a separately adsorbed nitro group than that of the adsorbed chloro group, the Pt@Y catalyst can prevent hydrodechlorination of p-chloronitrobenzene under mild conditions. Moreover, such a conformation results in a reduced adsorption energy of target p-chloroaniline on the platinum surface; thus suppressing the reactivity of hydrodechlorination of p-chloroaniline to circumvent further C-Cl bond breakage.

Protective desilication of highly siliceous H-ZSM-5 by sole tetraethylammonium hydroxide for the methanol to propylene (MTP) reaction.

Protective desilication of highly siliceous H-ZSM-5 was effectively realized by dissolution and recrystallization in tetraethylammonium hydroxide (TEAOH) solution. With better balance between dissolution of OH- and recrystallization of TEA+, intracrystalline mesopores could be generated by selective dissolution of Si by the drilling effects of TEAOH on the micropores, and then Si species in the mother liquor near the external surface could be recrystallized into ZSM-5 shell. With a significantly reduced diffusion length provided by the intracrystalline mesopores, TEAOH-treated samples exhibited longer lifetime and higher propylene selectivity than the parent H-ZSM-5 zeolite. The mediumly-treated T-16 h sample possessed the longest MTP lifetime of 140 h, 5.6 times that of the parent H-ZSM-5 zeolite. Furthermore, the coke content and adsorbed methyl benzene species on the T-16 h sample were heavier than those on the parent H-ZSM-5 sample, which were related to the intracrystalline mesopore structure.