Co-reporter:Xin Zhao, Xiao Liu, Mimi Yu, Chen Wang, Jun Li
Dyes and Pigments 2017 Volume 136() pp:648-656
Publication Date(Web):January 2017
DOI:10.1016/j.dyepig.2016.09.025
•MCPp–TiO2 photocatalysts has been synthesized with one-step method and characterized.•Cu, Co, Zn-porphyrins are profitable for TiO2 photocatalysis activity improvement.•MCPp–TiO2 with good stability display high activities in 4-nitrophenol degradation.•The possible mechanism of MCPp–TiO2 for photocatalytic efficiencies is proposed.A new series of carboxyl porphyrins with different center metals (Cu, Co, Zn) insertion has been successfully synthesized. Their corresponding CuCPp–TiO2, CoCPp–TiO2, and ZnCPp–TiO2 photocatalysts were obtained under a one-pot solvothermal condition. Characterization of these composites can be achieved by both spectroscopic techniques and nitrogen adsorption–desorption measurements. The findings indicate that the MCPp–TiO2 (M(II) = Cu, Co, Zn) composite photocatalysts, formed by the accumulation of disperse spherical nanoparticles, possess heterogeneous structure and large surface area, resulting in the photodegradation of 4-nitrophenol (4-NP) efficiently. The metalloporphyrins with carboxyl group display superior catalytic activities due to the strong interactions between COOH and TiO2. The order for the photocatalytic activities is as follows: CuCPp–TiO2 > CoCPp–TiO2 ≥ ZnCPp–TiO2 > bare TiO2. The reason for the high photocatalytic activity in CuCPp–TiO2 photocatalyst can possibly be explained by the fact that Cu(II) is more readily gaining an electron to reach a steady state, causing the isolation of electrons with holes compare to Co(II) and Zn(II) in MCPp–TiO2 composites. This possible mechanism of photocatalytic efficiencies was proposed based on the multiple tests. The findings of MCPp–TiO2 photocatalysts tests suggested that the metalloporphyrin-based MCPp–TiO2 composite photocatalysts are capable of maintaining superior stability in photocatalysis experiments even after six times cycling.
Co-reporter:Jingfei Hou, Hongliang Dai, Zengqi Zhang, Jun Li, Xiaokang Li, Ke Deng, and Qingdao Zeng
Langmuir 2017 Volume 33(Issue 1) pp:
Publication Date(Web):December 12, 2016
DOI:10.1021/acs.langmuir.6b03567
With the aid of scanning tunneling microscopy, we have examined the two-dimensional hydrogen-bonded networks of carboxyl-functionalized porphyrin derivative H2TCPp molecules at the heptanoic acid/HOPG interface. Moreover, we have successfully modulated the self-assembly structure of H2TCPp by introducing 1,2-di(4-pyridyl)ethylene molecules into the assembled system. By performing density functional theory calculations, we also revealed the formation mechanisms of the different assemblies and the modulation process. Comparing the self-assembly structures at the liquid/solid interface with those in bulk crystals, we have obtained deep insight into the differences in H2TCPp assemblies between 2D and 3D networks. Furthermore, this research is expected to deepen our understanding of on-surface phenomena and to provide a feasible process toward 2D assembly regulation.
Co-reporter:Shu Sun;Qiong Yu;Wei Zhang;Xin Zhao;Fengxing Zhang
Catalysis Letters 2017 Volume 147( Issue 1) pp:228-239
Publication Date(Web):28 November 2016
DOI:10.1007/s10562-016-1884-5
Six metalloporphyrin-based porous coordination polymers, MnII(TCP)-MnII (CP1), FeIII(TCP)-FeIII (CP2), CoII(TCP)-CoII (CP3), NiII(TCP)-NiII (CP4), CuII(TCP)-CuII (CP5) and ZnII(TCP)-ZnII (CP6), (TCP = 5,10,15,20-tetra(4-(phenoxy-4-yl)butanoic acid)porphyrin tetravalent anion) were prepared and characterized. CP1, CP2, CP3, CP4 and CP6 are amorphous aggregation supported by SEM, TEM and powder XRD. CP5 is a small particles aggregation with lower crystallinity. These coordination polymers exhibit effective dye scavenging and catalytic activities toward the oxidation of alkylbenzene to ketones, and can be reused by filtration with slight decreasing of catalytic activities.
Co-reporter:Xin Zhao;Ying Wang;Wenhua Feng;Hengtao Lei
RSC Advances (2011-Present) 2017 vol. 7(Issue 83) pp:52738-52746
Publication Date(Web):2017/11/10
DOI:10.1039/C7RA09585F
A promising fabrication strategy used for designing TiO2 photocatalysts, which enhanced the photocatalytic activity by combining TiO2 with a new carboxyl-group-containing Cu(II) porphyrin (CuPp) in a sol–gel processing TiO2 and a one-pot solvothermal condition, has been proposed. Both porphyrins and composite photocatalyst CuPp–TiO2 have been characterized by spectroscopic techniques. Their photocatalytic performances were investigated by testing the photodegradation of 4-nitrophenol (4-NP) in aqueous solution under UV-vis light irradiation. The results reveal that the methodology for the anatase TiO2 photocatalyst is easy to achieve, and the photocatalytic activity measurements illustrate that the Cu(II) porphyrin-based TiO2 photocatalyst we synthesized displays superior photocatalytic activity and good chemical stability for organic pollutant photodegradation due to the strong interactions between Cu(II) porphyrins and TiO2.
Co-reporter:Li Zhang;Lei Hou;Xin Zhao;Zengqi Zhang;Yongsong Wang
Inorganic Chemistry Frontiers 2017 vol. 4(Issue 2) pp:360-367
Publication Date(Web):2017/02/13
DOI:10.1039/C6QI00381H
In this paper, we designed and synthesized three novel free-base imidazolyl porphyrins via the Macdonald [2 + 2] method, and their reactions with different metal ions afforded three new metalloporphyrin frameworks (MPFs) [Co(tBu-Ph)2(Im-Ph)2Por]·2DMF (1), [Co(F3-Ph)2(Im-Ph)2Por]·1.5DMF (2), and [Fe(Me2N, F4-Ph)2(Im-Ph)2Por]·3DMF (3), which display rich structural diversity. Complexes 1 and 2 are isostructural two-dimensional (2D) grid layers, which feature the rare rotaxane-like bilayer and an offset-stacking ABCD fashion of layers, as well as the significantly saddled porphyrin macrocycles. Differently, complex 3 forms a 4-connected lvt 3D framework with the slightly ruffled porphyrin macrocycles, which contains not only interesting helical channels but also uncommon tetrahedral cages. Gas adsorption studies of three complexes reveal the moderate CO2 adsorption capacity. Meanwhile, all three complexes exhibit preferable catalytic activity for ethylbenzene oxidation.
Co-reporter:Xin Zhao, Lin Yuan, Zeng-qi Zhang, Yong-song Wang, Qiong Yu, and Jun Li
Inorganic Chemistry 2016 Volume 55(Issue 11) pp:5287-5296
Publication Date(Web):May 9, 2016
DOI:10.1021/acs.inorgchem.6b00274
A promising fabrication strategy used for designing porous porphyrin materials and a group of rigid carboxyl porphyrins based metal–organic–polymer aerogels (MOPAs) has been proposed recently. These newly synthesized MOPAs were exemplarily characterized by FT-IR, UV–vis–DRS, EDS, PXRD, TGA, SEM, TEM, and gas sorption measurements. A gelation study has shown that solvents, molar ratio, temperature, and peripheral carboxyl number in porphyrins all affect gel generation. The MOPA series exhibit eminent thermal stability, high removal efficiency in dye adsorption, versatile morphologies, and permanent tunable porosity; also the BET surface areas fall within the range 249–779 m2 g–1. All of the mentioned properties are significantly superior to some other porous materials, which enable these compounds to be potential candidates for dye uptake, gas storage, and separation.
Co-reporter:Ya-Hong Yao, Jun Li, Long-Fei Yuan, Zeng-Qi Zhang and Feng-Xing Zhang
RSC Advances 2016 vol. 6(Issue 51) pp:45681-45688
Publication Date(Web):28 Apr 2016
DOI:10.1039/C6RA05682B
Three novel porphyrin–Schiff base conjugates derived from tetra(4-aminophenyl)porphyrin (TAPP), namely, tetra[4-(4-hydroxy benzylideneamino)]phenyl porphyrin (3a), tetra[4-(2-thienyldeneamino)]phenyl porphyrin (3b) and tetra[4-(2-pyridyldeneamino)]phenyl porphyrin (3c), were synthesized and characterized by IR, UV-vis, 1H NMR, HRMS and elementary analysis. Their biological activities against human epidermoid carcinoma (A431) cells were evaluated with an MTT assay. As we expected, the porphyrin conjugates showed negligible cytotoxicity to A431 cells in the absence of light, while their phototoxic activities were improved after irradiated with LED lamp (425 nm) and increased significantly with increased doses. The fluorescence microscope pictures revealed that the three porphyrin–Schiff conjugates could diffuse into skin cancer cells, demonstrating that these compounds are potential candidates for photodynamic therapy agents.
Co-reporter:Yan-xia Du, Zeng-qi Zhang, Ya-hong Yao, Jun Li
Inorganic Chemistry Communications 2016 Volume 64() pp:19-22
Publication Date(Web):February 2016
DOI:10.1016/j.inoche.2015.12.010
•One new pyrazole-functionalized porphyrin and Co(II) porphyrin were synthesized and characterized structurally.•Insertion of Co(II) ion into porphyrin macrocycle leads to a saddle distortion of Co(II) porphyrin plane.•UV–vis and fluorescent spectra of the two compounds in CH2Cl2 and solid state were compared.•Co(II)Pp shows high catalytic activities to ethylbenzene oxidation with 83% conversion.In this work, one new porphyrin, 5, 10, 15, 20-tetrakis(4-N-pyrazolyl)phenyl porphyrin (H2Pp) was synthesized and characterized. The single crystal structures of H2Pp and its cobalt(II) porphyrin (Co(II)Pp) were obtained with a space group of P1− and I2/c, respectively. The porphyrin macrocycle is close to a perfect plane in H2Pp, while Co(II)Pp exhibits a saddle-type distortion due to the formation of shorter Co–N coordination bonds. In H2Pp, the molecules are interconnected through π⋯π and C–H⋯π interactions to form 3D architecture, while in Co(II)Pp the porphyrin molecules are interlinked only by C–H⋯π interactions to yield 3D structure. We examined the UV–vis spectra and fluorescent spectra of H2Pp and Co(II)Pp in CH2Cl2 and solid state at room temperature. In addition, the catalytic activities of Co(II)Pp to the ethylbenzene oxidation was examined, the results indicate that Co(II)Pp exhibits a high selectivity to acetophenone (> 99%) with the conversion of 83%.In H2Pp, the molecules are interconnected through π⋯π and C–H···π interactions to form 3D structure, while in Co(II)Pp the porphyrin molecules are interlinked only by C–H⋯π interactions to yield 3D structure. Co(II)Pp displays high catalytic activity with the only product acetophenone quantitatively in 83%.
Co-reporter:Ya-Hong Yao;Yun Luo;Feng-Xing Zhang
Helvetica Chimica Acta 2016 Volume 99( Issue 1) pp:24-29
Publication Date(Web):
DOI:10.1002/hlca.201500184
Abstract
Three novel porphyrins, including two Schiff-bases porphyrins, 5,10,15-triphenyl-20-[4-(2-(4-formyl)phenoxy)ethoxy]phenyl porphyrin (H2Pp(1)), 5,10,15-triphenyl-20-[4-(2-(4-hydroxyimino)phenoxy)ethoxy]phenyl porphyrin (H2Pp(2)) and 5,10,15-triphenyl-20-[4-(2-(4-m-hydroxyanilinodeneformyl)phenoxy)ethoxy]phenyl porphyrin (H2Pp(3)), as well as three metalloporphyrins (CuPp (1a), ZnPp (1b), and CoPp (1c)) of porphyrin H2Pp(1) were synthesized. Their molecular structures were characterized by 1H-NMR, MS, UV/VIS, and FT-IR spectra. Furthermore, they were evaluated by their cytotoxicities against human epidermal squamous cell carcinoma cell (A431) and normal human horn cells (HaCaT) in vitro with MTT assay. Interestingly, these porphyrins and metalloporphyrins, which had a negligible cytotoxicity to HaCaT cells, showed highly cytotoxicity against A431 cells with IC50 values in the range of 6.6–9.8 μM, and metalloporphyrins exhibited higher cytotoxicity than that of metal-free porphyrins.
Co-reporter:Shu Sun;Mi Pan;Xiaodong Hu;Weihao Shao;Fengxing Zhang
Catalysis Letters 2016 Volume 146( Issue 6) pp:1087-1098
Publication Date(Web):2016 June
DOI:10.1007/s10562-016-1729-2
Six MnIII(porphyrin)-based porous coordination polymers, MnIII(F5CPp)–MnII (CP1, F5CPp=5-(pentafluorophenyl)-10,15,20-tri(4-carboxyphenyl)porphyrin dianion), MnIII(F5CPp)–CoII (CP2), MnIII(F5CPp)–NiII (CP3), MnIII(F10CPp)–MnII (CP4, F10CPp=5,15-bis(pentafluorophenyl)-10,20-bis(4-carboxyphenyl)porphyrin dianion), MnIII(F10CPp)–CoII (CP5), and MnIII(F10CPp)–NiII (CP6), were prepared and characterized. The precursors were identified by UV–Vis, GC–MS, infrared spectra and elemental analysis in the procedures of MnIII(porphyrin)-based polymers synthesis. CP1, CP4, CP3 and CP6 are amorphous aggregation supported by SEM, TEM and powder XRD. CP2 and CP5 are rod-like microcrystalline particles supported by powder XRD and SAED. These polymers exhibit high catalytic activities and selectivities toward the oxidation of ethylbenzene to acetophenone in quantitative over 70 % yields, and can be reused by filtration with only slight decreasing of catalytic activities.
Co-reporter:Xiao Liu;Mimi Yu;Zengqi Zhang;Xin Zhao
Research on Chemical Intermediates 2016 Volume 42( Issue 6) pp:5197-5208
Publication Date(Web):2016 June
DOI:10.1007/s11164-015-2349-y
Four new copper(II) porphyrins CuPp(1, 2, 3, 4) with a different number of peripheral ester groups were synthesized and used to sensitize the mesoporous TiO2 under solvothermal condition, and accordingly, four mesoporous CuPp(1, 2, 3, 4)/TiO2 composites were obtained. These composites were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, BET nitrogen adsorption–desorption isotherms (BET), UV–vis diffuse reflectance spectroscopy (UV–vis-DRS), and Fourier-transform infrared spectroscopy (FT-IR). The results showed the crystal structure and morphology of mesoporous TiO2 were not affected by the porphyrin existence on its surface. The photocatalysis properties of mesoporous TiO2 and CuPp(1, 2, 3, 4)/TiO2 have been evaluated by conducting the photocatalytic degradation of 4-nitrophenol (4-NP) under visible-light irradiation, and the result showed their higher photocatalytic activities and the order is: CuPp(4)/TiO2 > CuPp(3)/TiO2 > CuPp(2)/TiO2 > CuPp(1)/TiO2 ≫ TiO2. The probable reasons are their large surface area and different number of peripheral groups in CuPp, which separate electron–hole pairs efficiently. The repetition test of CuPp(1, 2, 3, 4)/TiO2 composites demonstrated that they still maintained superior photocatalytic activity over six recycles.
Co-reporter:Na Li;Chong Dang;Wan-Jun Sun
Russian Journal of Electrochemistry 2016 Volume 52( Issue 1) pp:94-98
Publication Date(Web):2016 January
DOI:10.1134/S1023193516010055
5-Hydroxyphenyl-11,15,20-triphenylporphyrin H2Pp(1), and its six corresponding metalloporphyrins MnPp(2), FePp(3), CoPp(4), NiPp(5), CuPp(6), ZnPp(7) were synthesized and characterized. Their improvements to the Li/SOCl2 battery were tested. The results show that the discharge voltages of the battery catalyzed by 1–5 are increased by approximately 20–120 mV except 6 and 7. And the discharge time is lengthened by 26.7–157.6 s for 1, 2, 5 and 7. The maximum initial discharge voltages of battery in the presence of 1–7 are also increased. It shows that the central metal ion influences the charge transfer process during the reduction of thionyl chloride.
Co-reporter:Zengqi Zhang, Jun Li, Yahong Yao, and Shu Sun
Crystal Growth & Design 2015 Volume 15(Issue 10) pp:5028-5033
Publication Date(Web):September 21, 2015
DOI:10.1021/acs.cgd.5b00987
A new microporous hydrogen-bonded organic framework (HOF) based on a cobalt(II) porphyrin, namely, Co(II) 5,10,15,20-tetra(4-(4-acetateethyl)phenoxy)phenylporphyrin (1), has been synthesized and structurally characterized. Single crystal X-ray diffraction analysis reveals that porphyrin molecules connect each other by intermolecular hydrogen bonds to form 2D layer, and the 2D layer further links though π···π interactions to form 3D supramolecular structure, exhibiting one kind of micropore with 3.98 × 6.47 Å2. The HOF of 1 exhibits not only a permanent porosity with the Langmuir surface areas of 158.79 m2·g–1, and the Brunauer–Emmett–Teller surface areas of 97.70 m2·g–1, but also, more importantly, high catalytic efficiency and selectivity for oxidation of ethylbenzene to acetophenone in quantitative 83.1% yield.
Co-reporter:Xiao-qin Su, Jun Li, Zeng-qi Zhang, Mi-mi Yu, Lin Yuan
Journal of Alloys and Compounds 2015 Volume 626() pp:252-259
Publication Date(Web):25 March 2015
DOI:10.1016/j.jallcom.2014.11.172
•Two new crystal structures of copper porphyrins containing meso-tetra(ester and carboxyl) were obtained.•The two copper porphyrins were used to modify TiO2 for the first time.•The accumulated patterns of copper porphyrin molecules on the TiO2 surface is an important factor for the photocatalytic activity.•The peripheral groups of copper porphyrins influence their stacking patterns in solid state.The accumulated patterns of porphyrin molecules on the surface of TiO2 have an important effect on the photoactivity of porphyrin/TiO2 photocatalysts. Herein, two copper porphyrins containing flexible peripheral functional groups (meso-tetra(ester, carboxy)), Cu(II)5,10,15,20-tetrakis[4-(carboethoxymethyleneoxy)phenyl]porphyrin (CuPp(2a)) and Cu(II)5,10,15,20-tetrakis[4-(carboxymethyleneoxy)phenyl]porphyrin (CuPp(2b)), were synthesized and characterized spectroscopically. Their crystal structures were also determined by single crystal X-ray diffraction. The Cu(II) porphyrinTiO2 composites were also prepared and characterized. The accumulated patterns of synthesized copper porphyrins on the surface of TiO2 were proposed for the first time. The photoactivity of the composites was investigated by carrying out the degradation of 4-nitrophenol (4-NP) in aqueous solution under UV–visible light. The results indicated that the CuPp(2b)TiO2 showed the higher photocatalytic activity than that of CuPp(2a)TiO2. Above all, it can be concluded that the accumulated patterns of porphyrins on the surface of TiO2 is an important factor for the photocatalytic efficiency of porphyrin/TiO2.Graphical abstract
Co-reporter:Mi-Mi Yu, Chen Wang, Jun Li, Lin Yuan, Wan-Jun Sun
Applied Surface Science 2015 Volume 342() pp:47-54
Publication Date(Web):1 July 2015
DOI:10.1016/j.apsusc.2015.03.020
Highlights
- •
A novel mesoporous photocatalyst CuPp–TiO2 with large surface area was prepared.
- •
The CuPp–TiO2 was obtained by self-assembly following a solvothermal treatment.
- •
There exists heterojunction structure in CuPp–TiO2.
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The CuPp–TiO2 exhibits outstanding photocatalytic activity and stability.
Co-reporter:Li Zhang, Chen Wang, Xin Zhao, Fan Yu, Feng-Feng Yao, Jun Li
Inorganic Chemistry Communications 2015 Volume 55() pp:123-128
Publication Date(Web):May 2015
DOI:10.1016/j.inoche.2015.03.033
•5,15-Di(4-pyridyl)-10,20-bis(3,4,5-trifluorophenyl)porphyrin was synthesized firstly.•Three new 2D Fe(III), Co(II), and Ni(II) metalloporphyrin frameworks were obtained.•Three complexes reveal the high thermal stabilities.•Three complexes have relatively preferable H2 uptake capacities.•Three complexes have selective adsorption of CO2 over N2.We have achieved success in obtaining three novel two-dimensional porous metalloporphyrin frameworks (MPFs) through solvothermal reactions, by using 5,15-di(4-pyridyl)-10,20-bis(3,4,5-trifluorophenyl) porphyrin (trans-Py2(F3-ph)2Por) metalated with Fe (1), Co (2), and Ni (3) salts respectively. TGA reveals that they all have high thermal stabilities. Gas adsorption studies indicate that three MPFs have relatively preferable H2 uptake capacities and the selective adsorption of CO2 over N2.Three novel two-dimensional Fe(III), Co(II), and Ni(II) metalloporphyrin frameworks (MPFs) have been successfully synthesized and characterized, three complexes not only exhibit high thermal stabilities and porosity, but also have relatively preferable H2 uptake capacities and the selective adsorption of CO2 over N2.
Co-reporter:Wei-Xia Xu, Wei-Xia Zhou, Jun Li, Shi-Liang Huang, Jiao Niu, Feng-Xing Zhang
Inorganic Chemistry Communications 2014 40() pp: 220-222
Publication Date(Web):
DOI:10.1016/j.inoche.2013.12.016
Co-reporter:J. Niu;L. -F. Yuan;J. Li;H. Guo;F. -X. Zhang
Journal of Structural Chemistry 2014 Volume 55( Issue 6) pp:1101-1105
Publication Date(Web):2014 November
DOI:10.1134/S0022476614060158
Two new copper (II) complexes [Cu(2-Pic)2(4-NPA)2] (1) and [Cu(2-Pic)2]·2H2O (2), where 2-Pic is 2-picolinic acid and 4-NPA is 4-nitrophenylamine, are synthesized hydrothermally and their crystal structures are determined and analyzed. Complex 1 is crystallized in the monoclinic system space group P21/c and complex 2 is in the triclinic system space group P-1. Single crystal X-ray analysis reveals that the coordination environments around the Cu atoms of two complexes are four-coordinated and sixcoordinated respectively. Complex 1 forms a 2D layer of a supermolecular structure through hydrogen bonds, and complex 2 is a 1D stair-stepping polymer chain and two water molecules linked by a hydrogen bond intersperse among the chains.
Co-reporter:Lin Yuan;Wang-yang Ma;Chen Wang;Wei-xia Zhou;Jiao Niu
Transition Metal Chemistry 2014 Volume 39( Issue 8) pp:859-866
Publication Date(Web):2014 November
DOI:10.1007/s11243-014-9869-y
Three copper complexes {[Cu2(L1)2]·I3}n (1), [Cu(L2)2] (2), and [Cu2I2(L3)2(MBI)2] (3) (MBI = 2-mercaptobenzimidazole, L1 = N-(benzothiazol-2-yl)acetamidine anion, L2 = N-(thiazol-2-yl) acetamidine anion, L3 = 3-methyl-[1,2,4]thiadiazolo[4,5-a]benzimidazole) have been synthesized solvothermally by the reactions of CuI with 2-benzothiazolamine, 2-aminothiazole and 2-mercaptobenzimidazole (MBI), respectively, in acetonitrile. In situ C–N (or C–S) cross-coupling ligand reactions were observed in all three complexes, and hypothetical reaction mechanisms are proposed for the formation of the ligands and their complexes. The single-crystal X-ray structural analysis reveals that both the Cu(II) and Cu(I) atoms are located in pseudo-tetrahedral environments in complex 1, and L1 acts as a double bidentate ligand which coordinates with the Cu(I) and Cu(II) atoms to form a 1D coordination polymer. Unlike complex 1, the Cu(II) atom in complex 2 is in a square planar geometry, coordinated by two L2 ligands with relatively small steric hindrance. In complex 3, the Cu(I) atoms have a distorted tetrahedral geometry, being coordinated by one nitrogen atom from L3, two sulfur atoms of MBI ligands, and one iodide. The sulfur atoms from MBI ligands bridge two Cu(I) atoms to form a binuclear complex. All three complexes exhibit relatively high thermal stabilities. Complex 1 displays intense fluorescence emission at 382 nm and complex 3 displays two intense fluorescence emissions at 401 and 555 nm.
Co-reporter:Mi-mi Yu;Wan-jun Sun;Min Jiang;Feng-xing Zhang
Journal of Materials Science 2014 Volume 49( Issue 16) pp:5519-5528
Publication Date(Web):2014 August
DOI:10.1007/s10853-014-8132-4
Three new CuPp–TiO2 composite materials were prepared by impregnating copper(II) porphyrin with different peripheral substituent (–OH, –COOC2H5, and –COOH) onto the surface of polycrystalline TiO2 at room temperature and characterized by SEM, energy-dispersive X-ray spectrometry, X-ray diffraction, FT-IR, UV–Vis DRS, and photoluminescence. The effects of metalloporphyrins on the surface of TiO2 have been detected by the photodegradation of 4-nitrophenol (4-NP) and rhodamine B (RhB). The loading of metalloporphyrins onto TiO2 results in strong visible light absorption by the composite and, more importantly, a 1.47–2.47 times increase in visible light photocatalytic activity in the degradation of RhB. The metalloporphyrins dispersed on the TiO2 surface can act as a small-band-gap semiconductor to absorb visible light, giving rise to electron–hole separation. What’s more, these CuPp–TiO2 with different peripheral substituent (–OH, –COOC2H5, and –COOH) in meso-sites of porphyrin ring displayed different catalytic activities in the degradation of 4-NP and RhB, the CuPp containing –OH and –COOH showed better catalytic activity due to their strong interaction with TiO2. A possible mechanism of these higher photocatalytic efficiencies was proposed based on the relative experiments.
Co-reporter:Wei-Xia Zhou, Bing Yin, Jun Li, Wan-Jun Sun, Feng-Xing Zhang
Inorganica Chimica Acta 2013 Volume 408() pp:209-213
Publication Date(Web):1 November 2013
DOI:10.1016/j.ica.2013.05.029
Highlights•A C–S cross-coupling observed in situ reaction of 2-mercaptobenzothiazole with CuI.•A hypothesis reaction mechanism was provided for the formation of complex 1 and complex 2.•The two complexes show a exceptionally photoluminescence properties and thermal stabilities.Two new Cu(I) complexes, [CuI(MBT)2]2 (1) and [CuI(BBTM)]2 (2) (BBTM = 2,2′-thiobis(benzothiazole)) were solvothermally synthesized in a one pot reaction with 2-mercaptobenzothiazole (MBT) as ligand. An unexpected C–S cross-coupling ligand reaction in situ was observed in complex 2, and a hypothetical reaction mechanism was elucidated for the formation of complexes 1 and 2. The single-crystal X-ray structural analysis reveal that each Cu(I) ion in complex 1 is located at the core of a slightly distorted tetrahedron and coordinated by one neighboring I− and three S atoms of two MBT ligands. Two copper(I) are bridged by two S atoms of two MBT ligands. While in complex 2, two Cu(I) ions were bridged by two I- ions and coordinated respectively by two N atoms from BBTM ligand and exhibit a distorted tetrahedral geometry. Complexes 1 and 2 show good fluorescence properties and high thermal stabilities.Graphical abstractComplexes 1 and 2 were synthesized by the reaction of copper(I) iodide and 2-mercaptobenzothiazole ligand in one-pot. Meanwhile, an unexpected C–S cross-coupling ligand reaction in situ was observed firstly. And a hypothesis reaction mechanism was proposed.
Co-reporter:Long-fei Yuan, Jun Li, Rui-ping Liu, Bin Liu, Hui Guo, Feng-xing Zhang
Inorganica Chimica Acta 2013 Volume 404() pp:197-200
Publication Date(Web):1 August 2013
DOI:10.1016/j.ica.2013.02.004
A new coordination polymer {[Nd(bpdc)1.5(H2O)]·H2O}n(1) based on neodymium(III) and 2,2′-bipyridyl-4,4′-dicarboxylic acid (H2bpdc) has been prepared by hydrothermal method. And it has been characterized by elemental analysis, IR spectrum, thermogravimetric analysis (TGA), single-crystal X-ray diffraction and magnetic properties. The X-ray diffraction study shows that complex 1 has a 2-D (3,4,5)-connected net with (4·62)2(43·67)2(44·62) topology. And the 2-D framework is connected by hydrogen bonds to form an unusual 3-D layered architecture. The TGA indicates that complex 1 has a good thermal stability. And the measured magnetic susceptibility reveals that a weak antiferromagnetic interaction exists in 1.Graphical abstractWe reported a novel coordination polymer {[Nd(bpdc)1.5(H2O)] ·H2O}n(1) in which a 2-D (3,4,5)-connected topological structure was found firstly in rare earth complexes. The 2-D sandwich structure is connected by hydrogen bonds to form an unusual 3-D layered architecture as a–b–a rank..Highlights► A brand new 2D (3,4,5)-connected topological structure was found firstly in rare earth complexes. ► A novel 3D a–b–a layered supramolecular architecture of neodymium(III) coordination compound. ► Title compound is stable and probably displays a weak antiferromagnetic interaction.
Co-reporter:Wangyang Ma;Jingzhou Liu ;Meng Feng
Chinese Journal of Chemistry 2013 Volume 31( Issue 2) pp:230-236
Publication Date(Web):
DOI:10.1002/cjoc.201200420
Abstract
5-Mono-(2-thienyl)-10,15,20-triphenyl porphyrin (H2MTP) and its Co(II), Cu(II), Zn(II) metalloporphyrins (CoMTP, CuMTP, ZnMTP) were synthesized and characterized spectroscopically. The corresponding Co(II), Cu(II), Zn(II) metalloporphyrins-TiO2 photocatalysts were then prepared and characterized by means of scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), UV-vis spectra and FT-IR. The photocatalytic activities of these photocatalysts were investigated by testing the photodegradation of 4-nitrophenol (4-NP) in aqueous solution under irradiation with high-pressure mercury lamp and metal halide lamp respectively. The results indicated that these metalloporphyrins greatly enhanced the photocatalytic efficiency of bare TiO2 in degradating the 4-NP, and CuMTP-TiO2 exhibited the highest photocatalytic activity of all photocatalysts. In addition, the first order rate constants of these photocatalytic reactions were calculated.
Co-reporter:Xiang-fei Lü, Wan-jun Sun, Jun Li, Wei-xia Xu, Feng-xing Zhang
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2013 Volume 111() pp:161-168
Publication Date(Web):July 2013
DOI:10.1016/j.saa.2013.02.021
Three porphyrins containing different functional groups (OH, CO2C2H5, COOH), 5-(4-hydroxy) phenyl-10,15,20-triphenyl porphyrin (1a), 5-(4-ethylacetatatomethoxy) phenyl-10,15,20-triphenyl porphyrin (1b), 5-(4-carboxylatomethoxy) phenyl-10,15,20-triphenyl porphyrin (1c), were synthesized and characterized spectroscopically. The CuPp(2a, 2b, 2c)–TiO2 photocatalysts were then prepared and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectroscopy (UV–vis-DRS), Fourier-transform infrared spectroscopy (FT-IR). The photocatalytic activities of the photocatalysts were investigated by carrying out the photodegradation of 4-nitrophenol in aqueous solution under simulated solar irradiation. It was found that the CuPp(2a, 2b, 2c)–TiO2 enhanced the photocatalytic efficiency of bare TiO2 in photodegrading the 4-NP due to the interaction between CuPp(2a, 2b, 2c) and TiO2, resulted in the enhancement of the photogenerated electron–hole separation. The reasons of this enhanced photocatalytic activity were also discussed. Based on the present study, it could be considered as a promising photocatalyst for the further industrial application.Graphical abstractHighlights► The CuPp and CuPp(2a, 2b, 2c)–TiO2 were prepared and studied by XRD, TEM, UV–vis-DRS, FI-IR, XPS and PL spectroscopies. ► Higher photocatalytic activity of the CuPp(2a, 2b, 2c)–TiO2 than bare TiO2 was observed under simulated solar irradiation. ► The photocatalytic activity of CuPp(2a, 2b, 2c)–TiO2 is related closely to the interaction between CuPp and TiO2.
Co-reporter:Wan-jun Sun, Jun Li, Giuseppe Mele, Zeng-qi Zhang, Feng-xing Zhang
Journal of Molecular Catalysis A: Chemical 2013 Volume 366() pp:84-91
Publication Date(Web):January 2013
DOI:10.1016/j.molcata.2012.09.010
In this paper, a new organic–inorganic CuPp–ZnO photocatalyst was achieved by copper (II) 5-mono-[4-(2-ethyl-p-hydroxybenzoate)ethoxyl]-10,15,20-triphenylporphyrin (CuPp) impregnated onto the surface of ZnO with an effective mixing method. Then the CuPp–ZnO photocatalyst was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectroscopy (DRS), Fourier transform infrared (FT-IR) spectroscopy and photoluminescence spectra (PL). The results revealed that CuPp successfully impregnated onto the surface of ZnO and there existed an interaction between ZnO and CuPp. The photocatalytic activities of the CuPp–ZnO photocatalyst were evaluated in the photocatalytic degradation of rhodamine B (RhB) both under UV–vis and visible light (λ ≥ 420 nm) irradiation. It was found that the CuPp–ZnO photocatalyst showed much higher photodegradation efficiency than bare ZnO, which improved the separation of photogenerated electrons and holes. The active species during the photocatalytic reaction were detected by using different types of active species scavengers. Finally, the photocatalytic mechanisms both under UV–vis and visible light irradiation were proposed. In addition, the repetition test demonstrated that the CuPp–ZnO still maintained high photocatalytic activity over five recycles. Based on the present study, it could be considered as a promising photocatalyst for future applications.Graphical abstractA new CuPp–ZnO photocatalyst was prepared and characterized firstly. Then the CuPp–ZnO exhibited excellent photocatalytic activity and stability for the photodegradation of RhB under light irradiation. Based on the present study, the possible photodecatalytic mechanisms both under visible and UV–vis light irradiation were proposed by adding different types of active species scavengers.Highlights► A new CuPp–ZnO photocatalyst was successfully achieved and characterized. ► The CuPp–ZnO photocatalyst exhibited excellent photocatalytic activity and stability for the photodegradation RhB. ► A higher visible photocatalytic degradation of RhB was observed on CuPp–ZnO compared with CuPp–TiO2. ► Photocatalytic mechanisms both under visible and UV–vis light irradiation were proposed.
Co-reporter:Yun Luo, Jun Li, Gui-ping Yao and Feng-xing Zhang
Catalysis Science & Technology 2012 vol. 2(Issue 4) pp:841-846
Publication Date(Web):09 Jan 2012
DOI:10.1039/C2CY00419D
Two novel porphyrins, 5,10,15-tri-phenyl-20-[4-(2-(4-formoxyl) phenoxy)ethoxy]phenyl porphyrin and 5,10,15-tri-phenyl-20-[4-(2-(4-hydroxyimino) phenoxy)ethoxy]phenyl porphyrin, and their corresponding copper(II) complexes were synthesized and spectroscopically characterized. The Cu(II) porphyrin–TiO2 composites were also prepared and characterized. The photoactivity of the composites was investigated by carrying out the degradation of 4-nitrophenol (4-NP) in aqueous solution under UV-visible light. It was found that the photoactivity of Cu(II) porphyrin–TiO2 composites was evidently influenced by the interaction between porphyrin molecules and hydroxyls anchored on the TiO2. Furthermore, the photoactivity of Cu(II) porphyrin–TiO2 composites was also affected by dispersion of composites in 4-NP solution.
Co-reporter:Ming-yue Duan, Jun Li, Min Li, Zeng-qi Zhang, Chen Wang
Applied Surface Science 2012 Volume 258(Issue 14) pp:5499-5504
Publication Date(Web):1 May 2012
DOI:10.1016/j.apsusc.2012.02.069
Abstract
Three Pt(II) porphyrins 5,10,15,20-tetra-[2 or 3 or 4-(3-phenoxy)propoxy]phenyl porphyrin]platinum(II) (1–3) were synthesized and characterized spectroscopically. The corresponding Pt(II) porphyrins–TiO2 composites were then prepared and characterized by means of FT-IR and diffused reflectance spectra, X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of Pt(II) porphyrins–TiO2 catalyst was investigated by testing the photodegradation of 4-nitrophenol (4-NP) in aqueous solution under irradiation with Xenon lamp. The results indicated that Pt(II) porphyrins greatly enhanced the photocatalytic efficiency of bare TiO2 in photodegrading the 4-NP, and the distinct space tropisms of peripheral substituents in meso-sites of porphyrin ring led to different results.
Co-reporter:Wei-Xia Zhou, Jun Li, Wei-Xia Xu, Long-Fei Yuan, Dario Braga, Lucia Maini, Feng-xing Zhang
Inorganica Chimica Acta 2012 Volume 382() pp:162-166
Publication Date(Web):15 March 2012
DOI:10.1016/j.ica.2011.12.041
A novel non-interpenetrated 2D coordination polymer [Cu4I4(DACH)2]n bridged by the flexible trans-1,4-diaminocyclohexane (DACH) ligand has been synthesized under hydrothermal condition and characterized by single crystal X-ray diffraction, TG–DTA and the solid-state luminescence spectrum. In the compound, each Cu4I4 cluster is bridged by DACH ligand to form a quadrate-grid 2D network with the inner cavities of approximate size of 6.35 × 18.12 Å. It is unusual that these 2D networks are stacked and there exist the N–H…I hydrogen bonds between layers. The channels are finally formed along b-axis with small size of cavities. Thermal analysis shows that the complex is stable up to ca. 240 °C. The solid-state luminescence spectrum displays a strong yellow emission band at room temperature, characteristic of the Cu4I4 cluster centers.Graphical abstractA novel non-interpenetrated 2D coordination polymer [Cu4I4(DACH)2]n bridged by the flexible trans-1,4-diaminocyclohexane (DACH) ligand has been synthesized and characterized. The structure of the compound shows that each Cu4I4 cluster is bridged by DACH ligand to form a quadrate-grid 2D network and these 2D networks are stacked by the interaction of hydrogen bonds, and the channels are formed finally. The complex displays an exceptionally thermally stability and a strong photoluminescence at room temperature in the solid state.Highlights► A novel 2D non-interpenetrated CuI coordination polymer constructed from Cu4I4(DACH)4 tetrahedral units has been described. ► The structure shows an uncommon stack along b axis. ► The complex shows a strong photoluminescence at room temperature in the solid state. ► The complex is exceptionally thermally stable.
Co-reporter:Gui-ping Yao, Jun Li, Yun Luo, Wan-jun Sun
Journal of Molecular Catalysis A: Chemical 2012 Volumes 361–362() pp:29-35
Publication Date(Web):September 2012
DOI:10.1016/j.molcata.2012.04.013
A new imidazolyl-linked pophyrin, 5-[4-(2-imidazolyl)ethoxyl]phenyl-10,15,20-triphenylporphyrin and its copper(II) porphyrin were synthesized and characterized spectroscopically. The CuPp–TiO2 photocatalyst was also prepared and characterized by means of high-resolution transmission electron microscopy (TEM), X-ray diffraction (XRD), UV–vis spectra and FT-IR spectra. The photocatalytic activity was investigated by photodegradation of 4-nitrophenol (4-NP) in aqueous solution with a small amount of H2O2 under visible light irradiation (λ > 400 nm). The results indicated that H2O2 can enhance greatly the visible photocatalytic activity of CuPp–TiO2 photocatalyst. Additionally, a possible mechanism of the photocatalytic degradation was proposed.Graphical abstractA new imidazolyl-linked pophyrin, 5-[4-(2-imidazolyl)ethoxyl]phenyl-10,15,20-triphenylporphyrin, and its copper(II) porphyrin were synthesized and characterized spectroscopically. The CuPp–TiO2 photocatalyst was also prepared and characterized. The photocatalytic activity was investigated by photodegradation of 4-nitrophenol (4-NP) in aqueous solution with a small amount of H2O2 under visible light irradiation. The results indicated that H2O2 can enhance greatly the visible photocatalytic activity of CuPp–TiO2 photocatalyst. Additionally, a possible mechanism of the photocatalytic degradation was proposed.Highlights► A novel CuPp–TiO2 photocatalyst was prepared and characterized. ► The CuPp–TiO2 exhibited highly visible photocatalytic efficiency with H2O2. ► The possible photocatalytic mechanism was proposed.
Co-reporter:Wan-jun Sun, Jun Li, Gui-ping Yao, Feng-xing Zhang, Jun-Long Wang
Applied Surface Science 2011 Volume 258(Issue 2) pp:940-945
Publication Date(Web):1 November 2011
DOI:10.1016/j.apsusc.2011.09.032
Abstract
A new mono-functionalized porphyrin derivative, 5-mono-[4-(2-(4-hydroxy)-phenoxy)ethoxy]-10,15,20-triphenylporphyrin (3) and its Cu(II) (3a), Zn(II) (3b) and Ni(II) (3c) metalloporphyrins were synthesized and characterized by using various spectroscopic techniques. The corresponding 3a, 3b, 3c-TiO2 photocatalysts were then prepared and characterized by means of FT-IR and diffused reflectance spectra, X-ray diffraction (XRD) and scanning electron microscopy (SEM). The photocatalytic activities of 3a, 3b, 3c-TiO2 were investigated by testing the photodegradation of 4-nitrophenol (4-NP) in aqueous solution under the halogen lamp irradiation. The results indicated that all the 3a, 3b, 3c enhanced the photocatalytic efficiency of bare TiO2 in photodegrading the 4-NP, and 3a-TiO2 exhibited the highest photocatalytic activity. The result is considered a combined action of potential match of 3a with TiO2 CB and effective impregnated of 3a onto the surface of TiO2.
Co-reporter:Jun Li;Gerhard Raabe;Gao-mai Yang;Ming-yue Duan;Giuseppe Mele;Feng-xing Zhang
Journal of Physical Organic Chemistry 2011 Volume 24( Issue 11) pp:1030-1038
Publication Date(Web):
DOI:10.1002/poc.1822
Abstract
The nitration reaction of 5,10,15,20-tetranaphthylporphyrin (TNP) was investigated in detail and the mono-, di-, and tri-nitro-TNPs were synthesized in high yield using 65% HNO3. The 1H-NMR study shows that the preferred site of nitration of the naphthyl substituted porphyrin is the carbon atom of the meso-substituents para to its bond to the porphyrin ring. The reaction leads to exquisite regioselectivity in favor of the mono, di, and tri-nitro-TNP. Quantum-chemical ab initio calculations at different levels of theory were performed in order to explain the experimentally observed reactivity. Copyright © 2010 John Wiley & Sons, Ltd.
Co-reporter:Rui-ping Liu, Jun Li, Gui-ping Yao, Yun Luo, Dario Braga, Feng-Xing Zhang
Inorganic Chemistry Communications 2011 Volume 14(Issue 10) pp:1669-1672
Publication Date(Web):October 2011
DOI:10.1016/j.inoche.2011.07.003
A new 3D coordination polymer {[Gd2(bpdc)3(H2O)3]·H2O}n(1) has been isolated from the reaction of 2,2′-bipyridine-4,4′-dicarboxylic acid (H2bpdc) and Gd(III) salts under hydrothermal conditions. Single-crystal X-ray diffraction study shows that compound 1 is constructed from Gd2-based second building units (SBUs) [Gd2(bpdc)3(H2O)3] and displays a 3D (3,4,8)-connected net with (42·6)(32·42·52)(32·45·54·611·76) topology. A thermogravimetric analysis of 1 shows a high thermal stability. The magnetic behavior of 1 reveals a weak antiferromagnetic interaction between Gd(III) ions.A new (3,4,8)-connected 3D coordination polymer {[Gd2(bpdc)3(H2O)3]·H2O}n based on 2,2′-bipyridine-4,4′-dicarboxylic acid (H2bpdc) and Gd(III) salts was constructed. It displays high thermal stability and a weak antiferromagnetic interaction between Gd(III) ions.Highlights► A new 3D Gd(III) coordination polymer has been isolated under hydrothermal condition. ► Compound 1 shows a new (3,4,8)-connected 3D coordination network. ► The (3,4,8)-connected topology was first reported in the lanthanide complex here. ► The magnetic behavior of compound 1 revealed the weak antiferromagnetic interactions between two Gd ions.
Co-reporter:Min Jiang, Jun Li, Yong-qian Huo, Yun Xi, Jun-feng Yan, and Feng-xing Zhang
Journal of Chemical & Engineering Data 2011 Volume 56(Issue 4) pp:1185-1190
Publication Date(Web):February 10, 2011
DOI:10.1021/je101107w
Four complexes with general formulas MIIL2·CH3OH (M = Co, Zn) and MIIL2 (M = Ni, Cu) were synthesized by transition metal ions MII (Co, Ni, Cu, Zn) reacting with 2-(2-hydroxyphenyl)benzimidazole (HL). Their thermal properties were studied; the probable thermal decomposition mechanism for the first step of the Co(II) and Zn(II) complexes was suggested, and the kinetic parameters were also given.
Co-reporter:R. -P. Liu;M. -Yu. Duan;J. Li;Z. -P. Su;J. -H. Zhang
Journal of Structural Chemistry 2011 Volume 52( Issue 5) pp:935-940
Publication Date(Web):2011 October
DOI:10.1134/S0022476611050143
Two complexes [Zn(SALIMP)(CH3CO2)]2(1) and [Cu(SALIMP)Cl] (2) are obtained by the reactions of zinc(II) and copper(II) salts with a tridentate Schiff base ligand 2-[[(2-pyridinylmethyl) imino]methyl]phenol (HSALIMP). Their structure is determined by single crystal X-ray diffraction. Data for complex 1: C30H28N4O6Zn2, CCDC number: 668213, Mr = 671.3, monoclinic, C2/c, with a = 34.670(5) Å, b = 15.266(2) Å, c = 23.464(4) Å, β = 114.045(2)°, V = 11341(3) Å3, Z = 16, F(000) = 5504, GOOF(F2) = 0.894, the final R = 0.0520 and wR = 0.1272 for 10515 observed reflections with I > 2σ(I); complex 2: C13H12N2OClCu, CCDC number: 668211, Mr = 311.24, triclinic, P-1, with a = 7.4050(8) Å, b = 10.2369(11) Å, c = 16.2873(17) Å, α = 87.728(2)°, β = 87.818(2)°, γ = 78.279(2)°, V = 1207.4(2) Å3, Z = 4, F(000) = 632, GOOF(F2) = 1.077, the final R = 0.0326 and wR = 0.0381 for 4209 observed reflections with I > 2σ(I).
Co-reporter:Chen Wang, Jun Li, Giuseppe Mele, Ming-yue Duan, Xiang-fei Lü, Leonardo Palmisano, Giuseppe Vasapollo, Feng-xing Zhang
Dyes and Pigments 2010 Volume 84(Issue 2) pp:183-189
Publication Date(Web):February 2010
DOI:10.1016/j.dyepig.2009.08.001
Four novel porphyrins, 5-[3-(3-phenoxy)-propoxy]phenyl porphyrin, 5,15-di-[3-(3-phenoxy)-propoxy]phenyl porphyrin, 5,10,15-tri-[3-(3-phenoxy)-propoxy]phenyl porphyrin, 5,10,15,20-tetra-[3-(3-phenoxy)-propoxy]phenyl porphyrin, and their corresponding Cu(II) porphyrins, were synthesized and characterized spectroscopically. The photodegradation of 4-nitrophenol in aq. suspension was used to determine the photocatalytic activity of polycrystalline TiO2 samples which had been impregnated with the Cu(II) porphyrins, as sensitizers. The photocatalytic activity of the composite depends mainly on the amount of sensitizer on the TiO2 surface rather than the nature of the substituted porphyrins.
Co-reporter:Xiang-fei Lü, Jun Li, Chen Wang, Ming-yue Duan, Yun Luo, Gui-ping Yao, Jun-Long Wang
Applied Surface Science 2010 Volume 257(Issue 3) pp:795-801
Publication Date(Web):15 November 2010
DOI:10.1016/j.apsusc.2010.07.067
Abstract
Three novel porphyrins, 5,10,15-tri-phenyl-20-[4-(3-phenoxy)-propoxy]phenyl porphyrin, 5,15-di-phenyl-10,20-di-[4-(3-phenoxy)-propoxy]phenyl porphyrin and 5-phenyl-10,15,20-tri- [4-(3-phenoxy)-propoxy]phenyl porphyrin, and their corresponding copper(II) complexes were synthesized and characterized spectroscopically. The photocatalytic effects of TiO2 samples impregnated with copper(II) porphyrins was investigated by photodegradation of 4-nitrophenol (4-NP) in aqueous solution under visible light. The photocatalysts were characterized by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), UV–vis spectra and FT-IR spectra. The results indicated that CuPps were successfully loaded and interacted with the surface of TiO2 microsphere, which is crucial to enhance the activity of the catalytic composite under visible light.
Co-reporter:Ming-yue Duan, Jun Li, Giuseppe Mele, Chen Wang, Xiang-fei Lü, Giuseppe Vasapollo and Feng-xing Zhang
The Journal of Physical Chemistry C 2010 Volume 114(Issue 17) pp:7857-7862
Publication Date(Web):April 13, 2010
DOI:10.1021/jp911744a
Three dichloro Sn(IV) porphyrins, trans-dichloro[5,10,15,20-tetra-[2 or 3 or 4-(3-phenoxy)-propoxy]phenyl porphyrin]tin(IV) and the corresponding dihydroxo Sn(IV) porphyrins trans-dihydroxo[5,10,15,20-tetra-[2 or 3 or 4-(3-phenoxy)-propoxy]phenyl porphyrin]tin(IV) were synthesized and characterized spectroscopically. The dihydroxo Sn(IV) porphyrin−TiO2 composites were also prepared and characterized, and an interaction between TiO2 and tin porphyrin molecules involving the axial −OH ligand with the TiO2 surface was proposed. The photocatalytic activity was investigated by testing the photodegradation of 4-nitrophenol (4-NP) in aqueous solution under both visible and UV−vis light irradiation. It was found that the distinct space tropisms of peripheral substituents in meso sites of the porphyrin ring lead to different efficiencies in photodegrading the 4-NP.
Co-reporter:Gao-mai Yang;Yan-wei Ren;Hui Guo;Min-yue Duan
Transition Metal Chemistry 2009 Volume 34( Issue 2) pp:191-196
Publication Date(Web):2009 March
DOI:10.1007/s11243-008-9178-4
Four new dinuclear complexes of the type [M2(cyclen)2(suc)]Cl2 · nH2O (M = Co2+, Ni2+, Cu2+, Zn2+, cyclen = 1,4,7,10-tetraazacyclododecane, suc = succinate) have been obtained by the reaction of cyclen and succinate with the corresponding metal dichlorides in aqueous solution. All the complexes were characterized by physico-chemical and spectroscopic methods. The crystal structure of [Ni2(cyclen)2(suc)]Cl2 · 2H2O was determined. The four complexes have similar compositions and structures and are all bridged by succinate. Furthermore, the hydrolysis of bis(2,4-dinitrophenyl)phosphate (BDNPP) promoted by the four complexes was studied. The experimental results indicate that these complexes can efficiently catalyze hydrolysis of BDNPP, and their catalytic activities are in the order Ni > Zn > Cu > Co.
Co-reporter:Chen Wang, Gao-mai Yang, Jun Li, Giuseppe Mele, Rudolf Słota, Małgorzata A. Broda, Ming-yue Duan, Giuseppe Vasapollo, Xiongfu Zhang, Feng-Xing Zhang
Dyes and Pigments 2009 80(3) pp: 321-328
Publication Date(Web):
DOI:10.1016/j.dyepig.2008.08.008
Co-reporter:Hui Guo;Hai-Yan Zhu;Xian-Ling He;Zhen-Ping Su;Feng-Xing Zhang
Chinese Journal of Chemistry 2007 Volume 25(Issue 6) pp:
Publication Date(Web):14 JUN 2007
DOI:10.1002/cjoc.200790144
Two supramolecular complexes [Zn(tacd)2](C6H8O4)·6H2O (1) and [Cu(tacd)2]Cl2·4H2O (2) were synthesized and characterized by elemental analysis, IR spectra, TGA and single-crystal X-ray diffraction analysis. The crystal structure showed that the metal ions in complexes 1 and 2 had similar coordination circumstance. But for the complex 2, it formed a novel two-dimensional supramolecular network with 12-membered rings and four-membered rings via hydrogen bond interaction. The thermal gravimetric analyses indicated that the two complexes had similar steps of weight-loss. On the basis of experiment, the two complexes were calculated by DFT-B3LYP/6-31G(d) in Gaussian 03. The results of calculation are in good agreement with the experiment.
Co-reporter:Hui Guo;Yan-Wei Ren;Jing-Jing Liu
Journal of Chemical Crystallography 2007 Volume 37( Issue 4) pp:255-263
Publication Date(Web):2007 April
DOI:10.1007/s10870-006-9158-5
Two novel supramolecular complexes [Cu(tacd)2](C4H3O4)2 (1) and [Ni(tacd)2]Cl2·4H2O (2) were synthesized and their structures were characterized by elemental analysis, IR spectrum, TGA and single-crystal X-ray analysis. The results indicated that the complexes 1 and 2 assemble into different 2D supramolecular net-work structures with channels via hydrogen bonds interaction. TGA curves showed the steps of weight-loss for 1 and 2.
Co-reporter:Ren Yan-Wei;Wu Ai-Zhi;Li Jun;Zhang Feng-Xing;Zhang Jin-Hua
Chinese Journal of Chemistry 2005 Volume 23(Issue 2) pp:
Publication Date(Web):1 MAR 2005
DOI:10.1002/cjoc.200590132
Five new metal transition metal complexes formed with tripodal polyimidazole ligand tri{2-[2-(1-methyl)imi-dazoly](methylimino)ethyl}amine ((min)3tren), [Zn(min)3tren](ClO4)2 (1) [Cu(min)3tren](ClO4)2 (2), [Ni(min)3tren]-(ClO4)2 (3), [Co(min)3tren](ClO4)2 (4), and [Mn(min)3tren](ClO4)2·CH3CN (5) were synthesized and characterized by elemental analysis, molar conductances, IR and electronic spectra. Analytical results show 1:1 metal-ligand stoichiometry and 2:1 type of electrolyte in all metal complexes. The crystal structures of 4 and 5 have been determined. The metal atoms in 4 and 5, being in distorted [MN6] octahedra, are coordinated with three imine nitrogen atoms and three imidazole nitrogen atoms.
Co-reporter:Ren Yan-Wei;Li Jun;Zhang Feng-Xing;Zhang Jin-Hua;Guo Hui
Chinese Journal of Chemistry 2005 Volume 23(Issue 4) pp:
Publication Date(Web):11 MAY 2005
DOI:10.1002/cjoc.200590418
The mixed-valence manganese(III/IV) complex [Mn2(cyclen)2(μ-O)2](ClO4)3·4H2O(1) (cyclen=1,4,7,10-tetra-azacyclododecan) with chemical formula C16H48Cl3Mn2N8O18 has been synthesized and characterized by single crystal X-ray diffraction analysis, elemental analysis, IR and electronic spectra. The results showed that the manganese(III/IV) ions were six-coordinated by four nitrogen atoms from cyclen and two oxygen atoms from the oxygen bridge, forming a distorted octahedron geometry. There were two very strong peaks in the range of 400–700 nm in electronic spectrum, which was similar to Mn catalase and Mn ribonucleotide reductase extracted from organisms. Electrochemical study indicated that the complex underwent a quasi-reversible one-electron reduction and oxidation at E1/2=0.827 V in acetonitrile.
Co-reporter:Li Jun, Zhang Feng-Xing, Ren Yan-Wei, Hun Yong-Qian, Nan Ye-Fei
Thermochimica Acta 2003 Volume 406(1–2) pp:77-87
Publication Date(Web):28 November 2003
DOI:10.1016/S0040-6031(03)00221-1
The TG/DSC curves of K3[Cr(C2O4)3]·3H2O, K3[Al(C2O4)3]·3H2O, K3[Fe(C2O4)3]·3H2O and K2[Cu(C2O4)2]·2H2O in nitrogen were determined at the heating rate of 15, 10, 5, and 2 °C min−1, respectively. A non-linear optimization was applied for different reaction models to perform single and overall steps optimizations. Kinetic parameters were given, and the most probable mechanism functions were suggested.
Co-reporter:Wan-jun Sun, Jun Li, Gui-ping Yao, Min Jiang, Feng-xing Zhang
Catalysis Communications (30 November 2011) Volume 16(Issue 1) pp:90-93
Publication Date(Web):30 November 2011
DOI:10.1016/j.catcom.2011.09.013
A new functionalized porphyrin, 5-mono-[4-(2-(4-acetateethyl)-phenoxy) ethoxy]-10, 15, 20-triphenylporphyrin H2Pp (2) and its copper (II) porphyrin (CuPp) were synthesized. The corresponding CuPp-TiO2 photocatalyst was then prepared and characterized by means of FT-IR and diffused reflectance spectra, X-ray diffraction (XRD). The photocatalytic activity of CuPp-TiO2 was investigated by testing the photo-degradation of 4-nitrophenol (4-NP) in aqueous solution under visible light irradiation with the assistance of appropriate amount of H2O2. The results indicated that the photo-degradation of 4-NP was much enhanced compared with the bare TiO2. Additionally, a possible mechanism of the photocatalytic degradation was also proposed in the presence of H2O2 under visible light irradiation.Highlights► A new CuPp-TiO2 photocatalyst was prepared and characterized. ► There exists weak interaction between TiO2 surface and CuPp molecules. ► The CuPp-TiO2 photocatalyst displays highly photoactivity in the presence of H2O2. ► The high photoactivity is due to the quickly electronic transfer from TiO2 to H2O2.
Co-reporter:Chen Wang, Jun Li, Giuseppe Mele, Gao-Mai Yang, Feng-Xing Zhang, Leonardo Palmisano, Giuseppe Vasapollo
Applied Catalysis B: Environmental (15 November 2007) Volume 76(Issues 3–4) pp:218-226
Publication Date(Web):15 November 2007
DOI:10.1016/j.apcatb.2007.05.028
Co-reporter:Yun Luo, Jun Li, Gui-ping Yao and Feng-xing Zhang
Catalysis Science & Technology (2011-Present) 2012 - vol. 2(Issue 4) pp:NaN846-846
Publication Date(Web):2012/01/09
DOI:10.1039/C2CY00419D
Two novel porphyrins, 5,10,15-tri-phenyl-20-[4-(2-(4-formoxyl) phenoxy)ethoxy]phenyl porphyrin and 5,10,15-tri-phenyl-20-[4-(2-(4-hydroxyimino) phenoxy)ethoxy]phenyl porphyrin, and their corresponding copper(II) complexes were synthesized and spectroscopically characterized. The Cu(II) porphyrin–TiO2 composites were also prepared and characterized. The photoactivity of the composites was investigated by carrying out the degradation of 4-nitrophenol (4-NP) in aqueous solution under UV-visible light. It was found that the photoactivity of Cu(II) porphyrin–TiO2 composites was evidently influenced by the interaction between porphyrin molecules and hydroxyls anchored on the TiO2. Furthermore, the photoactivity of Cu(II) porphyrin–TiO2 composites was also affected by dispersion of composites in 4-NP solution.
Co-reporter:Li Zhang, Lei Hou, Xin Zhao, Zengqi Zhang, Yongsong Wang and Jun Li
Inorganic Chemistry Frontiers 2017 - vol. 4(Issue 2) pp:NaN367-367
Publication Date(Web):2016/12/15
DOI:10.1039/C6QI00381H
In this paper, we designed and synthesized three novel free-base imidazolyl porphyrins via the Macdonald [2 + 2] method, and their reactions with different metal ions afforded three new metalloporphyrin frameworks (MPFs) [Co(tBu-Ph)2(Im-Ph)2Por]·2DMF (1), [Co(F3-Ph)2(Im-Ph)2Por]·1.5DMF (2), and [Fe(Me2N, F4-Ph)2(Im-Ph)2Por]·3DMF (3), which display rich structural diversity. Complexes 1 and 2 are isostructural two-dimensional (2D) grid layers, which feature the rare rotaxane-like bilayer and an offset-stacking ABCD fashion of layers, as well as the significantly saddled porphyrin macrocycles. Differently, complex 3 forms a 4-connected lvt 3D framework with the slightly ruffled porphyrin macrocycles, which contains not only interesting helical channels but also uncommon tetrahedral cages. Gas adsorption studies of three complexes reveal the moderate CO2 adsorption capacity. Meanwhile, all three complexes exhibit preferable catalytic activity for ethylbenzene oxidation.
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