The hydrogen storage properties and catalytic mechanism of FeCl-doped LiAlHwere investigated in minute details. LiAlH-2 mol% FeClsamples start to release hydrogen at 76 °C, which is 64 °C lower than that of ...The hydrogen storage properties and catalytic mechanism of FeCl-doped LiAlHwere investigated in minute details. LiAlH-2 mol% FeClsamples start to release hydrogen at 76 °C, which is 64 °C lower than that of as-received LiAlH. Isothermal desorption measurements show that the 2 mol% FeCl-doped sample releases 7.0 wt% of hydrogen within 17 min at 250 °C. At lower temperatures of 110 °C and 80 °C, the sample can release 4.4 wt% and 3 wt% of hydrogen, respectively. The apparent activation energy of LiAlH-2 mol% FeClsamples for R2 is 105.02 k J/mol, which is 67 k J/mol lower than that of pure LiAlH. The reaction between LiAlHand FeClduring ball milling was found by analyzing the X-ray diffraction results,and Fe-Al particles formed in-situ from the reaction act as the real catalyst for the dehydrogenation of LiAlH.展开更多
Selective and durable fixed‐bed catalysts are highly desirable for developing eco‐efficient HPPO(hydrogen peroxide propylene oxide)process.The powder titanosilicate catalysts must be shaped before being applied in i...Selective and durable fixed‐bed catalysts are highly desirable for developing eco‐efficient HPPO(hydrogen peroxide propylene oxide)process.The powder titanosilicate catalysts must be shaped before being applied in industrial processes.As the essential additives for preparing formed catalysts,binders are usually the catalytically inert components,but they would cover the surface and pore mouth of zeolite,thereby declining the accessibility of active sites.By recrystallizing the binder(silica)/Ti‐MWW extrudates with the assistance of dual organic structure‐directing agents,the silica binder was converted into MWW zeolite phase to form a structured binder‐free Ti‐MWW zeolite with Si‐rich shell,which enhanced the diffusion efficiency and maintained the mechanical strength.Meanwhile,due to the partial dissolution of Si in the Ti‐MWW matrix,abundant silanol nests formed and part of framework TiO4 species were transferred into open TiO_(6)ones,improving the accumulation and activation ability of H_(2)O_(2)inside the monolith.Successive piperidine treatment and fluoridation of the binder‐free Ti‐MWW further enhanced the H_(2)O_(2)activation and oxygen transfer ability of the active Ti sites,and stabilized the Ti‐OOH intermediate through hydrogen bond formed between the end H in Ti‐OOH and the adjacent Si‐F species,thus achieving a more efficient epoxidation process.Additionally,the side reaction of PO hydrolysis was inhibited because the modification effectively quenched numerous Si‐OH groups.The lifetime of the modified binder‐free Ti‐MWW catalyst was 2400 h with the H_(2)O_(2)conversion and PO selectivity both above 99.5%.展开更多
基金supported by Tianjin Natural Science Foundation 09JCZDJC24800
文摘The hydrogen storage properties and catalytic mechanism of FeCl-doped LiAlHwere investigated in minute details. LiAlH-2 mol% FeClsamples start to release hydrogen at 76 °C, which is 64 °C lower than that of as-received LiAlH. Isothermal desorption measurements show that the 2 mol% FeCl-doped sample releases 7.0 wt% of hydrogen within 17 min at 250 °C. At lower temperatures of 110 °C and 80 °C, the sample can release 4.4 wt% and 3 wt% of hydrogen, respectively. The apparent activation energy of LiAlH-2 mol% FeClsamples for R2 is 105.02 k J/mol, which is 67 k J/mol lower than that of pure LiAlH. The reaction between LiAlHand FeClduring ball milling was found by analyzing the X-ray diffraction results,and Fe-Al particles formed in-situ from the reaction act as the real catalyst for the dehydrogenation of LiAlH.
文摘Selective and durable fixed‐bed catalysts are highly desirable for developing eco‐efficient HPPO(hydrogen peroxide propylene oxide)process.The powder titanosilicate catalysts must be shaped before being applied in industrial processes.As the essential additives for preparing formed catalysts,binders are usually the catalytically inert components,but they would cover the surface and pore mouth of zeolite,thereby declining the accessibility of active sites.By recrystallizing the binder(silica)/Ti‐MWW extrudates with the assistance of dual organic structure‐directing agents,the silica binder was converted into MWW zeolite phase to form a structured binder‐free Ti‐MWW zeolite with Si‐rich shell,which enhanced the diffusion efficiency and maintained the mechanical strength.Meanwhile,due to the partial dissolution of Si in the Ti‐MWW matrix,abundant silanol nests formed and part of framework TiO4 species were transferred into open TiO_(6)ones,improving the accumulation and activation ability of H_(2)O_(2)inside the monolith.Successive piperidine treatment and fluoridation of the binder‐free Ti‐MWW further enhanced the H_(2)O_(2)activation and oxygen transfer ability of the active Ti sites,and stabilized the Ti‐OOH intermediate through hydrogen bond formed between the end H in Ti‐OOH and the adjacent Si‐F species,thus achieving a more efficient epoxidation process.Additionally,the side reaction of PO hydrolysis was inhibited because the modification effectively quenched numerous Si‐OH groups.The lifetime of the modified binder‐free Ti‐MWW catalyst was 2400 h with the H_(2)O_(2)conversion and PO selectivity both above 99.5%.
