Co-reporter:Junhui Zhu;Zhiwei Tan
Macromolecular Research 2017 Volume 25( Issue 8) pp:792-798
Publication Date(Web):04 July 2017
DOI:10.1007/s13233-017-5096-7
A series of conjugated metalloporphyrin polymers (MPP-AMnPs) were synthesized by using inexpensive, environmentally friendly and high-efficiency CuI/N,N-dimethyl glycine as catalytic system, and 5,10,15,20-mesotetra(4-aminophenyl) porphyrin manganese and p-dibromobenzene as building blocks. Scanning electron microscopy, N2 adsorption-desorption isotherms and scanning electron microscopy indicated that the polymers had large surface areas and homogeneous microporous structures. Thermogravimetric analysis showed that the polymers had remarkable thermostability. The catalytic performance of MPP-AMnP was tested by oxidizing cyclic ketones with dioxygen as oxidant. The conversion was high in a mild environment in l,2-dichloroethane solvent at 60 °C. Moreover, MPP-AMnP remained stable in the reaction process and highly catalytically active after ten successive recycles.
Co-reporter:Yongjin Li;Chuanrong Liu
New Journal of Chemistry (1998-Present) 2017 vol. 41(Issue 16) pp:8214-8221
Publication Date(Web):2017/08/07
DOI:10.1039/C7NJ00564D
Herein, porphyrin-conjugated organic polymers, Mn(III)P-CMP and Fe(III)P-CMP, were synthesized by Suzuki coupling reaction with manganese/iron tetraphenylporphyrin (T(p-Br)PPMn/FeCl) and 1,4-phenyldiboronic acid as building blocks. The structures of the pore and surface were characterized by nitrogen adsorption and desorption isotherm, FE-SEM, and HR-TEM. The electrochemical behavior of Mn(III)P-CMP was tested by cyclic voltammetry. For the catalytic oxidation of higher inert C–H bond in cyclohexane, Mn(III)P-CMP and Fe(III)P-CMP with hyper-conjugated and microporous structures functioned better than the monomer metalloporphyrin. With MnP-CMP as the preferred catalyst, after 3.5 h of reaction, the yield of cyclohexanol and cyclohexanone was 21.6%, and the conversion of cyclohexane reached 29.9% at the Mn3+/cyclohexane molar ratio of 1/168 000, 150 °C, and 0.8 MPa. Mn(III)P-CMP and Fe(III)P-CMP were structurally stable and insoluble in common solvents and hardly degraded below 300 °C; hence, they had excellent reusability.
Co-reporter:Minggao Qin, Haoliang Zhao, Weijun Yang, Yuanrong Zhou and Feng Li
RSC Advances 2016 vol. 6(Issue 28) pp:23905-23912
Publication Date(Web):01 Mar 2016
DOI:10.1039/C5RA24848E
High purity birnessite (δ-MnO2) was obtained by a facile one-pot method using MnSO4·H2O as a Mn resource, ethylenediamine tetraacetic acid disodium salt (EDTA-Na) as a complexing agent and oxygen in the air as an oxidant under alkaline conditions. The as-prepared birnessite presented three-dimensional microflowers composed of two-dimensional ultrathin nanosheets. Degradation results indicated that the prepared δ-MnO2 possessed excellent abilities for removal of rhodamine B (RhB). Typically, 50 mL of RhB (10 mg L−1) could be degraded completely with a 10 mg sample in 5 min without any additives such as hydrogen peroxide, peroxysulphate or any supplementary means such as microwaves or ultrasound. The samples were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), and N2 gas adsorption–desorption and thermogravimetry analysis (TGA) techniques. The mechanism of the degradation process was proposed and it was discussed that a redox reaction between birnessite and RhB occurred in an acidic environment. Clearly, the as-prepared birnessite provides great potential for the rapid degradation of dyes and organic pollutants. As it has easily available starting materials, a simple method for synthesis and undemanding degradation conditions, the as-prepared birnessite has high practical value in treating environmental pollutants.
Co-reporter:Yuanrong Zhou;Minggao Qin ;Haoliang Zhao
Applied Organometallic Chemistry 2016 Volume 30( Issue 4) pp:188-192
Publication Date(Web):
DOI:10.1002/aoc.3415
With [5,10,15,20-tetra(4-carboxyphenyl)porphyrin]Mn(III) and sterically controlled 2,2¢-dimethyl-4,4¢-pyridine as the main raw materials, metal–organic framework thin films containing metalloporphyrin (MnPor-MOF) with catalytically active sites were built up on functionalized quartz glass surfaces using a layer-by-layer self-assembly method. Retaining active catalytic sites and having a porous reticular structure, the MnPor-MOF films possessed remarkable photocatalytic activity for oxidative degradation of methylene blue in the presence of hydrogen peroxide under visible-light irradiation. Most meaningfully, the MnPor-MOF films were highly stable and simply and conveniently reusable, and are thus a potentially new organic material for photocatalytic wastewater treatment. Copyright © 2015 John Wiley & Sons, Ltd.
Co-reporter:Haoliang Zhao;Xiaojuan Qu;Minggao Qin
Journal of Solid State Electrochemistry 2016 Volume 20( Issue 10) pp:2773-2780
Publication Date(Web):2016 October
DOI:10.1007/s10008-016-3286-4
A new composite electrode material with iron-manganic oxide coating (Fe-Mn/Mn2O3) was prepared, and its catalytic performance for oxidizing cyclohexanol was investigated in this work. The new electrode material, based on iron substrate covered with electrolytic manganese, was obtained by further coating the manganese surface with 50 % manganese nitrate solution and then conducting program thermal decomposition treatment. X-ray diffraction (XRD) was used to determine the surface crystal phase compositions, which were Mn and Mn2O3. The catalytic results showed an excellent electrocatalytic performance on the oxidation of cyclohexanol, and the main products were cyclohexanone and hexanedioic acid. According to our experiment results and the literature reports, the existence of mixed valent MnIII and MnIV played a key role in the electrocatalytic oxidation process. A probable process was proposed: the MnIV seized the hydrogen from cyclohexanol, the resulting cyclohexaneoxy radical was oxidized into cyclohexanone, and then the absorbed cyclohexanone was further oxidized into hexanedioic acid.
Co-reporter:Yun-jing Huang 黄云敬;Wei-jun Yang 阳卫军
Journal of Central South University 2016 Volume 23( Issue 7) pp:1603-1610
Publication Date(Web):2016 July
DOI:10.1007/s11771-016-3214-x
Rubidium phosphate can be more conveniently obtained by extracting trace Rb+ from the salt lake brine. Rb3PO4 was found to be an excellent heterogeneous catalyst for transfer hydrogenation. Rb3PO4 lost 70% of its active sites after adsorbing water, but the remaining was not affected. The reductions of aldehydes and ketones, when promoted by Rb3PO4, were allowed at room temperature. The activities of substrates at room temperature followed a descending order of 2,6-dichlorobenzaldehyde>4-bromobenzaldehyde>benzaldehyde>acetophenone>anisaldehyde>butanone. A new catalytic cycle postulating a six-membered cyclic transition state for the reductions of aldehydes and ketones was proposed. These results exploited the catalytic usage of Rb3PO4 and worth in industrial application.
Co-reporter:Genlin Sun;Kewen Tang;Panliang Zhang;Guoqing Sui
Journal of Separation Science 2014 Volume 37( Issue 14) pp:1736-1741
Publication Date(Web):
DOI:10.1002/jssc.201400281
High-speed countercurrent chromatography (HSCCC) combined with biphasic chiral recognition was successfully applied to the resolution of phenylsuccinic acid enantiomers. d-Isobutyl tartrate and hydroxypropyl-β-cyclodextrin were employed as lipophilic and hydrophilic selectors dissolved in the organic stationary phase and aqueous mobile phase, respectively. The two-phase solvent system was made up of n-hexane/methyl tert-butyl ether/water (0.5:1.5:2, v/v/v). Impacts of the type and concentration of chiral selectors, the pH value of the aqueous phase solution as well as the temperature on the separation efficiency were investigated. By means of preparative HSCCC, pure enantiomer was obtained by separating 810 mg of racemate with a purity >99.5% and a recovery rate between 82 and 85%. The experimental results indicate that biphasic recognition HSCCC provide a promising means for efficient separation of racemates.
Co-reporter:Wei-jun Yang 阳卫军;Chao Fang 方超;Ji-cang Zhou 周济苍
Journal of Central South University 2013 Volume 20( Issue 3) pp:629-633
Publication Date(Web):2013 March
DOI:10.1007/s11771-013-1528-5
Perfluorolyether is characterized by highly chemical inertness, oxidative stability, anticorrosion as well as radiation resistance. It can be used as lubricant especially in harsh environmental conditions. In this work, hexafluoropylene oxide was catalytically polymerized at low temperature using the methods of anionic polymerization, and perfluorolyethers were obtained with number-average degree of polymerization more than 15. CsF and RbF were used as catalysts and their catalytic activities were investigated. Experimental results show that perfluorolyethers with number-average molar masses up to 3 000 g/mol could be obtained using the two kinds of catalysts, respectively. As compared to CsF, the number-average degree of polymerization is higher and the relative molecular mass distribution interval is narrower when RbF is used as catalyst. The effect of factors such as impurities’ content, reaction temperature and reaction time on the number-average degree of polymerization was also investigated. It is found that low impurities’ content and low temperature are beneficial to the generation of high number-average degree of perfluorolyethers. The optimization reaction time is 24 h, and further increase of reaction time does not significantly affect the average relative molecular mass. The product was characterized by IR, 19F NMR and GC-MS, and the catalytic mechanism was analyzed finally.
Co-reporter:Zhiwei Tan, Junhui Zhu, Weijun Yang
Catalysis Communications (5 May 2017) Volume 94() pp:60-64
Publication Date(Web):5 May 2017
DOI:10.1016/j.catcom.2017.02.011
•A kind of metalloporphyrin conjugated polymer (CuII-APP) was synthesized.•CuII-APP was a nano-material catalyst with porous structure.•CuII-APP exhibited high catalytic activity to cyclohexylbenzene.•N-hydroxyphthalimide exhibited excellent co-catalytic effect with CuII-APP.•CuII-APP still maintained high catalytic activity after 5 catalytic cycle.A nanomaterial catalyst of azo-bridged Cu(II) porphyrin polymer (CuII-APP) was synthesized and characterized by scanning electron microscopy, transmission electron microscopy and N2 adsorption measurement. CuII-APP had a nanoporous structure, with the particle size of about 30 nm. Owing to the special structure, CuII-APP acted as an efficient heterogeneous catalyst for selective oxidation of cyclohexylbenzene into cyclohexylbenzene-1-hydroperoxide. When N-hydroxyphthalimide was used as co-catalyst, this binary catalyst system showed an obvious synergic effect. After being recovered and reused, CuII-APP and NHPI still had high catalytic activities.Download high-res image (225KB)Download full-size image
Co-reporter:Yongjin Li, Baoshuai Sun, Weijun Yang
Applied Catalysis A: General (10 April 2016) Volume 515() pp:
Publication Date(Web):10 April 2016
DOI:10.1016/j.apcata.2016.02.003
•A kind of metalloprophyrin conjugated polymer (MnP-AMP) was synthesized.•MnP-AMP was a highly ordered, highly developed micro- and mesoporous polymer.•MnP-AMP has a large surface area and was developed as a heterogeneous catalyst.•MnP-AMP contained CN groups and exhibited high catalytic activity to alcohols.•The catalyst still maintained high catalytic activity after reused 5 times.A series of conjugated metalloporphyrin polymers (MnP-AMPs) were synthesized based on Buchwald-Hartwig aromatic amination with p-phenylenediamine and manganese tetraphenylporphyrin as building blocks, and N-heterocyclic carbene-palladium complex as catalyst. Brunauer–Emmett–Teller surface area analysis, scanning electron microscopy and transmission electron microscopy showed that MnP-AMPs had large surface areas and uniform pore sizes. The stable porous and superreticular conjugated structure of MnP-AMP further activated manganese ions in the porphin ring compared with those in the original monomanganeseporphyrin. Moreover, introducing CN bonds in MnP-AMP increased its polarity and affinity to alcohols, so MnP-AMP exhibited high catalytic activity when applied to aerobic oxidation of alcohols. For the catalysis of selective oxidation of benzyl alcohol to benzaldehyde with air, the conversion and aldehyde selectivity both reached up to 100% under mild condition in acetonitrile at 40 °C. MnP-AMP also remained stable in oxidation reaction system and still had high catalytic activity after several recycles.Download high-res image (107KB)Download full-size image
![21H,23H-Porphine, 5,10,15,20-tetrakis[4-[2-(trimethylsilyl)ethynyl]phenyl]-](/data/chemimg/2944500/145362-97-6.png)
![21H,23H-Porphine, 5,10,15,20-tetrakis[4-[2-(trimethylsilyl)ethynyl]phenyl]-](/data/chemimg/2944500/145362-97-6_b.png)
