An open-framework zinc-cobalt phosphate CoZnPO4-V with 16-ring extra-large-pore channels has been obtained in the presence of chain-type polyamines as the structure directing agent (SDA). Its large single crystal suit...An open-framework zinc-cobalt phosphate CoZnPO4-V with 16-ring extra-large-pore channels has been obtained in the presence of chain-type polyamines as the structure directing agent (SDA). Its large single crystal suited for structure refinement has been prepared with the assistance of small organic amines. Single-crystal X-ray diffraction analysis has shown that CoZnPO4-V is a novel metal phosphate. It crystallizes in monoclinic space group P21/c (No. 14), with a = 31.936(3) , b = 8.3775(7) , c = 15.7874(13) , α = γ = 90°, β = 97.0530(10)°, V = 4191.8(6) 3, and Z = 4 with R1 = 0.0455,wR2 = 0.0869. Its three-dimensional framework can be considered as stacking from two-dimensional nets and one-dimensional units as linkers. Between the stacking nets and linkers are located extra-large channels with 16-ring apertures.展开更多
The hydration of alkyne represents the most straightforward and simplest route toward the synthesis of ketone. Herein, Brønsted acidic zeolites are explored as potential catalysts for the liquid-phase phenylacety...The hydration of alkyne represents the most straightforward and simplest route toward the synthesis of ketone. Herein, Brønsted acidic zeolites are explored as potential catalysts for the liquid-phase phenylacetylene hydration. The topology structure and Si/Al ratio are disclosed to be key factors controlling the catalytic activity of zeolites. Typically, H-MFI zeolite with a Si/Al molar ratio of 13 exhibits the highest catalytic activity, with turnover frequency of 6.0 h-1 at 363 K. Besides, H-MFI zeolite shows good catalytic stability and recyclability in the reaction of phenylacetylene hydration, and the substrate scope can be simply extended to other soluble aromatic alkynes. The reaction mechanism of phenylacetylene hydration is investigated by means of kinetic and spectroscopic analyses. The Markovnikov electrophilic addition of phenylacetylene by hydrated protons is established as the rate-determining step, followed by deprotonation and enol isomerization to derive acetophenone product.展开更多
基金Supported by the National Natural Science Foundation of China (Grant No. 20873069)973 Project (Grant No. 2009CB623502)
文摘An open-framework zinc-cobalt phosphate CoZnPO4-V with 16-ring extra-large-pore channels has been obtained in the presence of chain-type polyamines as the structure directing agent (SDA). Its large single crystal suited for structure refinement has been prepared with the assistance of small organic amines. Single-crystal X-ray diffraction analysis has shown that CoZnPO4-V is a novel metal phosphate. It crystallizes in monoclinic space group P21/c (No. 14), with a = 31.936(3) , b = 8.3775(7) , c = 15.7874(13) , α = γ = 90°, β = 97.0530(10)°, V = 4191.8(6) 3, and Z = 4 with R1 = 0.0455,wR2 = 0.0869. Its three-dimensional framework can be considered as stacking from two-dimensional nets and one-dimensional units as linkers. Between the stacking nets and linkers are located extra-large channels with 16-ring apertures.
基金This work was supported by the National Natural Science Foundation of China(No.22025203)the Municipal Natural Science Fund of Tianjin,China(No.18JCJQJC47400).
文摘The hydration of alkyne represents the most straightforward and simplest route toward the synthesis of ketone. Herein, Brønsted acidic zeolites are explored as potential catalysts for the liquid-phase phenylacetylene hydration. The topology structure and Si/Al ratio are disclosed to be key factors controlling the catalytic activity of zeolites. Typically, H-MFI zeolite with a Si/Al molar ratio of 13 exhibits the highest catalytic activity, with turnover frequency of 6.0 h-1 at 363 K. Besides, H-MFI zeolite shows good catalytic stability and recyclability in the reaction of phenylacetylene hydration, and the substrate scope can be simply extended to other soluble aromatic alkynes. The reaction mechanism of phenylacetylene hydration is investigated by means of kinetic and spectroscopic analyses. The Markovnikov electrophilic addition of phenylacetylene by hydrated protons is established as the rate-determining step, followed by deprotonation and enol isomerization to derive acetophenone product.
