Hydrogenations for olefinic double bonds catalyted by the Pd-Fe2O3/D3520 resin and Pd-Bi2O3/D3520 resin were reported. These catatysts were characterized by IR spectra and XPS methods. The XPS investigation indicated ...Hydrogenations for olefinic double bonds catalyted by the Pd-Fe2O3/D3520 resin and Pd-Bi2O3/D3520 resin were reported. These catatysts were characterized by IR spectra and XPS methods. The XPS investigation indicated that the-electron transfer from Fe atom in Fe2O3 to Pd, enhanced the hy-drogenation activity of the catalysts,and Bi2O3 drew electrons from Pd, leading to the lowering of the hydrogenation rate. When Pd/Bi atom ratio = 1, the hydrogenation was inhibited entirely. The IR spectra of resin 1)3520 showed no significant changes when Pd and the metallic oxides were supported on the polymer particles. That indicates that there are no obvious inter-actions between Pd (or metallic oxides) and supporter. Finally , a possible hydrogenation mechanism ,was also supposed.展开更多
The neodymium complexes with crosslinked polystyrene containing -CH2SH and -CH2SOCH3 groups, P-CH2SH . NdCl3 and P-CH2SOCH3. NdCl3, were prepared. P-CH2SH . NdCl3 shows no catalytic activity for butadiene polymerizati...The neodymium complexes with crosslinked polystyrene containing -CH2SH and -CH2SOCH3 groups, P-CH2SH . NdCl3 and P-CH2SOCH3. NdCl3, were prepared. P-CH2SH . NdCl3 shows no catalytic activity for butadiene polymerization, while P-CH2SOCH3. NdCl3 can catalyze the polymerization of butadiene. The content of cis-1,4-polybutadiene is more than 95%.展开更多
In the course of investigating the catalytic behavior of metal complexes for ring opening metathesis polymerization of cycloolefins, metathesis, hydroformylation and selective hydrogenation of olefins experimental res...In the course of investigating the catalytic behavior of metal complexes for ring opening metathesis polymerization of cycloolefins, metathesis, hydroformylation and selective hydrogenation of olefins experimental results time and again indicate the presence of effects of macromolecular supports - the utilization of macromolecular supports increases obviously the activity, selectivity, and stability of the catalysts and so as to increase the conversion of substrates, yields of reactions, properties of formed polymers and so on. Discussed these effects on the basis of the authors' experiments. (Author abstract) 18 Refs.展开更多
Fe_3O_4-PVDF membranes were prepared by blending of magnetic Fe_3O_4 powders with polyvinylidene fluoride to investigate whether those were usable or not in catalytic membrane reactors. Filtration performances and cat...Fe_3O_4-PVDF membranes were prepared by blending of magnetic Fe_3O_4 powders with polyvinylidene fluoride to investigate whether those were usable or not in catalytic membrane reactors. Filtration performances and catalytic activity of membranes in microwave conditions were measured in separate processes. Composite Fe_3O_4-PVDF membranes were characterized by TG-DTA, FTIR, XRD, SEM and contact angle techniques.Disappearing of α-phases at PVDF was observed with increasing amount of additives from XRD diffraction patterns. Decomposition of polymer fastened due to catalytic effect of Fe_3O_4. Finger-like structures and large number of small pores were observed at the SEM images. Those provided effective transportation of substrate among the active sites of catalyst. At the experiments conducted in batch reactor, 51%, 77%, 66% and 63% benzyl alcohol conversion were recorded for 2%, 4%, 6% and 8% Fe_3O_4-PVDF composite pieces respectively. Catalyst were separated magnetically and reused several times. On the other hand Fe_3O_4 blended PVDF membranes provided improved flux and BSA rejection compared with performance of bare PVDF membrane; 41.6% BSA rejection was obtained with 4% Fe_3O_4-PVDF whereas it was only 6.7% for PVDF. Fe_3O_4-PVDF composites performed high activity for the benzyl alcohol oxidation in batch reactor and also better filtration at filtration cell. These results promise to obtain practical and low cost membrane material for catalytic reactors usable in microwave support to get fast results.展开更多
Chloromethylated styrene-divinylbenzene copolymer beads with 8% crosslink were chemically modified by reaction with Ethylenediaminetetraaceticacid leading to the incorporation of nitrogen as ligating site on the surfa...Chloromethylated styrene-divinylbenzene copolymer beads with 8% crosslink were chemically modified by reaction with Ethylenediaminetetraaceticacid leading to the incorporation of nitrogen as ligating site on the surface of the polymer. The polymeric ligand on treatment with a solution of Copper chloride gave the corresponding metal complex. The polymer supported Cu(II) complex was characterized by elemental analyses, IR,GC-MS, scanning electron micrographs (SEM). The oxidation of various alcohols such as benzyl alcohol, 2-butanol, and 2-propanol was investigated using the supported metal complexes in presence of molecular oxygen as the oxidant. The swelling studies were done by using different solvents. Kinetic data indicate that the catalysts could be recycled without significant degradation of polymer matrix.展开更多
A silica gel supported cobalt（lI） Schiff base complex was synthesized and used for the oxidation of alkyl aromatics using molecular oxygen as an oxidant under atmosphere pressure. The catalyst shows a high conversio...A silica gel supported cobalt（lI） Schiff base complex was synthesized and used for the oxidation of alkyl aromatics using molecular oxygen as an oxidant under atmosphere pressure. The catalyst shows a high conversion of alkyl aromatics and selectivity to benzylic ketones, and could be reused at least 5 times without significant loss of catalytic activity.展开更多
采用表面反应改性法制备了ZrO2 SiO2(ZrSiO)表面复合物,用等体积浸渍法制备了ZrSiO负载的Ni Cu双金属催化剂,并用IR、TPD、TPSR和微反技术考察了CH4、H2O和O2在催化剂表面上的化学吸附及反应性能。结果表明,在Ni Cu ZrSiO催化剂上存在着...采用表面反应改性法制备了ZrO2 SiO2(ZrSiO)表面复合物,用等体积浸渍法制备了ZrSiO负载的Ni Cu双金属催化剂,并用IR、TPD、TPSR和微反技术考察了CH4、H2O和O2在催化剂表面上的化学吸附及反应性能。结果表明,在Ni Cu ZrSiO催化剂上存在着Ni Cu金属位,Lewis酸位Znn+和碱位Zr O-三类活性中心;CH4和H2O在金属位和Lewis酸位Znn+和碱位Zr O-的协同作用下可形成解离吸附态;CH4、H2O和O2在Ni Cu ZrSiO催化剂表面上的主要反应产物为H2和CO2,选择性均在95%以上。展开更多
文摘Hydrogenations for olefinic double bonds catalyted by the Pd-Fe2O3/D3520 resin and Pd-Bi2O3/D3520 resin were reported. These catatysts were characterized by IR spectra and XPS methods. The XPS investigation indicated that the-electron transfer from Fe atom in Fe2O3 to Pd, enhanced the hy-drogenation activity of the catalysts,and Bi2O3 drew electrons from Pd, leading to the lowering of the hydrogenation rate. When Pd/Bi atom ratio = 1, the hydrogenation was inhibited entirely. The IR spectra of resin 1)3520 showed no significant changes when Pd and the metallic oxides were supported on the polymer particles. That indicates that there are no obvious inter-actions between Pd (or metallic oxides) and supporter. Finally , a possible hydrogenation mechanism ,was also supposed.
文摘The neodymium complexes with crosslinked polystyrene containing -CH2SH and -CH2SOCH3 groups, P-CH2SH . NdCl3 and P-CH2SOCH3. NdCl3, were prepared. P-CH2SH . NdCl3 shows no catalytic activity for butadiene polymerization, while P-CH2SOCH3. NdCl3 can catalyze the polymerization of butadiene. The content of cis-1,4-polybutadiene is more than 95%.
基金The project was supported by the National Natural Science Foundation of China, "Macromolecular ligand effects of catalytic system for ring opening metathesis polymerization of dicydopentadiene" (Approval No. 29474160) & "Polymeric metal complex catalysts
文摘In the course of investigating the catalytic behavior of metal complexes for ring opening metathesis polymerization of cycloolefins, metathesis, hydroformylation and selective hydrogenation of olefins experimental results time and again indicate the presence of effects of macromolecular supports - the utilization of macromolecular supports increases obviously the activity, selectivity, and stability of the catalysts and so as to increase the conversion of substrates, yields of reactions, properties of formed polymers and so on. Discussed these effects on the basis of the authors' experiments. (Author abstract) 18 Refs.
文摘Fe_3O_4-PVDF membranes were prepared by blending of magnetic Fe_3O_4 powders with polyvinylidene fluoride to investigate whether those were usable or not in catalytic membrane reactors. Filtration performances and catalytic activity of membranes in microwave conditions were measured in separate processes. Composite Fe_3O_4-PVDF membranes were characterized by TG-DTA, FTIR, XRD, SEM and contact angle techniques.Disappearing of α-phases at PVDF was observed with increasing amount of additives from XRD diffraction patterns. Decomposition of polymer fastened due to catalytic effect of Fe_3O_4. Finger-like structures and large number of small pores were observed at the SEM images. Those provided effective transportation of substrate among the active sites of catalyst. At the experiments conducted in batch reactor, 51%, 77%, 66% and 63% benzyl alcohol conversion were recorded for 2%, 4%, 6% and 8% Fe_3O_4-PVDF composite pieces respectively. Catalyst were separated magnetically and reused several times. On the other hand Fe_3O_4 blended PVDF membranes provided improved flux and BSA rejection compared with performance of bare PVDF membrane; 41.6% BSA rejection was obtained with 4% Fe_3O_4-PVDF whereas it was only 6.7% for PVDF. Fe_3O_4-PVDF composites performed high activity for the benzyl alcohol oxidation in batch reactor and also better filtration at filtration cell. These results promise to obtain practical and low cost membrane material for catalytic reactors usable in microwave support to get fast results.
文摘Chloromethylated styrene-divinylbenzene copolymer beads with 8% crosslink were chemically modified by reaction with Ethylenediaminetetraaceticacid leading to the incorporation of nitrogen as ligating site on the surface of the polymer. The polymeric ligand on treatment with a solution of Copper chloride gave the corresponding metal complex. The polymer supported Cu(II) complex was characterized by elemental analyses, IR,GC-MS, scanning electron micrographs (SEM). The oxidation of various alcohols such as benzyl alcohol, 2-butanol, and 2-propanol was investigated using the supported metal complexes in presence of molecular oxygen as the oxidant. The swelling studies were done by using different solvents. Kinetic data indicate that the catalysts could be recycled without significant degradation of polymer matrix.
基金the financial support from the National Natural Science Foundation of China–Academy of Engineering Physics(No.10976014)Natural Science Foundation of Jiangsu Province(No.BK2011697)
文摘A silica gel supported cobalt（lI） Schiff base complex was synthesized and used for the oxidation of alkyl aromatics using molecular oxygen as an oxidant under atmosphere pressure. The catalyst shows a high conversion of alkyl aromatics and selectivity to benzylic ketones, and could be reused at least 5 times without significant loss of catalytic activity.
文摘采用表面反应改性法制备了ZrO2 SiO2(ZrSiO)表面复合物,用等体积浸渍法制备了ZrSiO负载的Ni Cu双金属催化剂,并用IR、TPD、TPSR和微反技术考察了CH4、H2O和O2在催化剂表面上的化学吸附及反应性能。结果表明,在Ni Cu ZrSiO催化剂上存在着Ni Cu金属位,Lewis酸位Znn+和碱位Zr O-三类活性中心;CH4和H2O在金属位和Lewis酸位Znn+和碱位Zr O-的协同作用下可形成解离吸附态;CH4、H2O和O2在Ni Cu ZrSiO催化剂表面上的主要反应产物为H2和CO2,选择性均在95%以上。
