Sodium-organic batteries utilizing natural abundance of sodium element and renewable active materials gain great attentions for grid-scale applications.However,the development is still limited by lack of suitable orga...Sodium-organic batteries utilizing natural abundance of sodium element and renewable active materials gain great attentions for grid-scale applications.However,the development is still limited by lack of suitable organic cathode materials with high electronic conductivity that can be operated stably in liquid electrolyte.Herein,we present 5,15-bis(ethynyl)-10,20-diphenylporphyrin(DEPP)and[5,15-bis(ethynyl)-10,20-diphenylporphinato]copper(II)(CuDEPP)as new cathodes for extremely stable sodium-organic batteries.The copper(II)ion partially contributes the charge storage and significantly stabilizes the structure of porphyrin complex for electrochemical energy storage.In situ electrochemical stabilization of organic cathode with a lower charging current density was identified which enables both improved high energy density and power density.An excellent longterm cycling stability up to 600 cycles and an extremely high power density of 28 kW kg−1 were achieved for porphyrin-based cathode.This observation would open new pathway for developing highly stable sodium-organic cathode for electrochemical energy storage.展开更多
Organic sodium-ion batteries(OSIBs)using eco-friendly organic materials as electrodes have recently received much attention.However,the practical applications of OSIBs are generally limited by the inherent disadvantag...Organic sodium-ion batteries(OSIBs)using eco-friendly organic materials as electrodes have recently received much attention.However,the practical applications of OSIBs are generally limited by the inherent disadvantages of organic electrodes,such as their low conductivity,poor stability,and high solubility in electrolytes.Herein,we presented[5,10,15,20-tetrathienylporphinato]M(II)(MTTP,M=2H,Ni)as new electrode materials in sodium-organic batteries.The incorporation of thiophene functionalized groups and nickel(II)ion in the molecular design of porphyrins enabled stable and excellent electrochemical performance in sodium storage systems.Benefiting from multiple charge storage sites and bipolar characteristics,the NiTTP anode has a reversible capacity of 434 mAh g^(-1)at a current density of 25 mA g^(-1).An excellent long-term cycling stability and high average voltage were obtained when NiTTP was used as a cathode.In a symmetrical battery,where NiTTP was used as both cathode and anode materials,a high average voltage of 2.3 V and a practical energy density of 93 Wh kg^(-1)was achieved.These results suggest that the thiophene-based porphyrin derivatives would be promising electrode materials for long-term organic sodium ion batteries for green and stable energy storage.展开更多
A novel sensitizer with imidazole zinc porphyrin as electron donor has been synthesized. The structure has been characterized by UV-Vis, elemental analyses and 1 H NMR.UV-Vis and fluorescence spectra show that it has ...A novel sensitizer with imidazole zinc porphyrin as electron donor has been synthesized. The structure has been characterized by UV-Vis, elemental analyses and 1 H NMR.UV-Vis and fluorescence spectra show that it has good light absorbing properties in the range of visible light and suggests that it has potential applications in dye-sensitized solar cells.展开更多
Ⅰ. INTRODUCTION Oxotransition metal porphyrin complexes are possible intermediates in cytochrome P-450 modal system. Several oxotransition metal porphyrin complexes such as titanium (Ⅳ), vanadium (Ⅳ) , molybdenum(...Ⅰ. INTRODUCTION Oxotransition metal porphyrin complexes are possible intermediates in cytochrome P-450 modal system. Several oxotransition metal porphyrin complexes such as titanium (Ⅳ), vanadium (Ⅳ) , molybdenum(Ⅳ, Ⅴ) and chromium (Ⅳ) having been isolated and characterized are not effective oxidizing agents, so they are not possible intermediates展开更多
Five lanthanide porphyrin complexes with 5- (4-nitrophenyl) -10, 15, 20-triphenylporphyrin and acetylacetonate ligands were synthesized and characterized by elemental analysis, IRspectra, Uv-visible spectra, IH NMR. T...Five lanthanide porphyrin complexes with 5- (4-nitrophenyl) -10, 15, 20-triphenylporphyrin and acetylacetonate ligands were synthesized and characterized by elemental analysis, IRspectra, Uv-visible spectra, IH NMR. The structures of the complexes were proposed.展开更多
Two novel sensitizers with pyridine-N-oxide zinc porphyrin and its zinc porphyrin as the anchor group and electron acceptor have been synthesized. The structures have been characterized by UV, elemental analyses and 1...Two novel sensitizers with pyridine-N-oxide zinc porphyrin and its zinc porphyrin as the anchor group and electron acceptor have been synthesized. The structures have been characterized by UV, elemental analyses and 1H NMR. UV and fluorescence spectra show that they have good light absorbing properties in the range of visible light and suggest that they have potential applications in dye-sensitized solar cells.展开更多
The interaction between amphiphilic porphyrin and phenothiazine in AOT/isooctane/water reverse micelle was investigated by UV-Vis spectra. A new absorption complex between the two species is formed in such circumstanc...The interaction between amphiphilic porphyrin and phenothiazine in AOT/isooctane/water reverse micelle was investigated by UV-Vis spectra. A new absorption complex between the two species is formed in such circumstances, which is ascribed to the enrichment of the components by the reverse micelle. The fluorescence quenching of CHTTP by PTH becomes more efficient after the formation of the absorption complex.展开更多
The properties of porphyrins can be changed through the choice of peripheral substituents and inserted metal ions. To obtain porphyrin complexes with novel structures, 5,10, 15,20-tetrakis（p-4-fluorobenzoyloxy） phen...The properties of porphyrins can be changed through the choice of peripheral substituents and inserted metal ions. To obtain porphyrin complexes with novel structures, 5,10, 15,20-tetrakis（p-4-fluorobenzoyloxy） phenyl perphyrin（TFBOPPH2 ） and its transition metal complexes {TFBOPPM [ M = Mn（ Ⅲ ）, Fe（ Ⅲ ）, Co（ Ⅱ ）, Ni（ Ⅱ ）, Cu（ Ⅱ ） and Zn（ Ⅱ ） ] } were synthesized and characterized by means of UV-Vis, IR photoacoustic speetrumetry, ^1H NMR, elemental analyses, molar conductance, and XPS methods. A structure is proposed, in which one porphyrln molecule is coordinated with a transition metal ion in a tetradentate fashion, while the chlorine ion is the balaneeable anion in Fe（ Ⅲ ） and Mn（ Ⅲ ） complexes.展开更多
Porphyrins and methyl viologen(MV;) are widely used as a photosensitizer and an electron acceptor respectively in photoinduced electron transfer systems. Literatures covered numerous examples of photochemical studies ...Porphyrins and methyl viologen(MV;) are widely used as a photosensitizer and an electron acceptor respectively in photoinduced electron transfer systems. Literatures covered numerous examples of photochemical studies of porphyrins covalently linked to various electron acceptor units, such as viologen, which functioned as both a photosensitizer and an electron acceptor in the same molecule. However, the length of the linked chain between porphyrin and viologen is very important. To improve the rate of photoin-展开更多
Transition metal complexes of meso-tetra(4-myristyloxyphenyl)porphyrin TMPPM [M =Mn, Fe, Co, Ni, Cu, Zn; TMPP=mesotetra(4-myristyloxyphenyl)porphyrin] have been synthesized and characterized by means of elemental an...Transition metal complexes of meso-tetra(4-myristyloxyphenyl)porphyrin TMPPM [M =Mn, Fe, Co, Ni, Cu, Zn; TMPP=mesotetra(4-myristyloxyphenyl)porphyrin] have been synthesized and characterized by means of elemental analyses, UV-Vis spectra, infrared photoacoustic spectra, 1H NMR spectra, molar conductance and differential scanning calorimetry(DSC). The ligand and the Zn complex show liquid crystalline behavior. According to the DSC thermogram of the Zn complex, it exhibits a lower phase transition temperature -7.453 ℃ and a wide mesophase temperature span, 77 ℃.展开更多
The interactions of mixed porphyrin-polypyridyl Ru（Ⅱ） complexes [m（Py-3＇）TPP-Ru（phen）2Cl]^＋（1） and its derivatives [Nim（Py-3＇）TPP-Ru（phen）2Cl]＋（2） and [Cum（Py-3＇）TPP-Ru（phen）2Cl]^＋（3）（phen=...The interactions of mixed porphyrin-polypyridyl Ru（Ⅱ） complexes [m（Py-3＇）TPP-Ru（phen）2Cl]^＋（1） and its derivatives [Nim（Py-3＇）TPP-Ru（phen）2Cl]＋（2） and [Cum（Py-3＇）TPP-Ru（phen）2Cl]^＋（3）（phen=1,10-phenanthroline; m（Py-3＇）TPP=5-（3＇-pyridyl）-10,15,20-triphenylporphyrin） with bovine serum albumin（BSA） were investigated by fluorescence, UV-Vis and circular dichroism（CD） spectroscopies. The UV-Vis and CD spectral experiments indicated that the secondary structures of the protein were perturbed in the presence of the porphyrin Ru（Ⅱ） complex and the perturbation was enhanced under the irradiation with ultra-violet light. The fluorescence quenching mechanism of BSA by the three complexes was determined to be a static process, and the apparent binding constant K values for complexes 1, 2 and 3 measured by fluorescence quenching method were （3.86±0.03）×10^3 L/mol（n=0.94±0.04）, （5.69±0.04）× 103 L/mol（n=1.03±0.06）, and （6.54±0.02）× 10^3 L/mol（n=1.03±0.05）, respectively.展开更多
MTBPyP (meso-tetrakis(4-N-benzylpyridyl)porphyrin, M=H-2, Zn) bearing positive charge has been shown to associate with SiW12O404- in water solution. The spectral evolution and Job's plots analyses reveal that the ...MTBPyP (meso-tetrakis(4-N-benzylpyridyl)porphyrin, M=H-2, Zn) bearing positive charge has been shown to associate with SiW12O404- in water solution. The spectral evolution and Job's plots analyses reveal that the relatively stable aggregates contain equal numbers of MTBPyP4(+) and SiW12O404-.展开更多
The treatment of tetrakis (4-pyridyl) porphyrin H2TPyP with a hydrated rare earth (III) acetylacetonate RE(acac)3 · nH2O (RE=Y, Eu, Gd) in 1,2, 4-trichlorobenzene (TCB) pro- duced a monomeric porphyrinato rare e...The treatment of tetrakis (4-pyridyl) porphyrin H2TPyP with a hydrated rare earth (III) acetylacetonate RE(acac)3 · nH2O (RE=Y, Eu, Gd) in 1,2, 4-trichlorobenzene (TCB) pro- duced a monomeric porphyrinato rare earth compound RE (TPyP) acac, which further reacted with dicyanobenzene in amyl alcohol in the presence of 1, 8-diazabicyclo [5. 4. 0] undec-7-ene (DBU), giving HRE(TPyP) (Pc) in a good yield. Upon exposure to air, part of the protonated mixed double-deckers in CHC13 solutions converted slowly to the corresponding neutral complexes RE (TPyP) (Pc). These protonated complexes were characterized by means of UV-V is, IR, NMR, mass spectroscopies. The quaternarization of these protonated mixed double-deckers with methyl iodide produced the salts of tetramethylated cations [HRE(TMPyP) (Pc)]4+.展开更多
Bipyridylporphyrin derivatives possessing a porphyrin moiety as the electron donor and bipyridyl moiety as the electron-acceptor were designed and synthesized for dye-sensitized solar cells （DSSCs）. The photo- physi...Bipyridylporphyrin derivatives possessing a porphyrin moiety as the electron donor and bipyridyl moiety as the electron-acceptor were designed and synthesized for dye-sensitized solar cells （DSSCs）. The photo- physical and electrochemical properties were investigated by absorption spectrometry and cyclic voltam- metry. Density functional theory （DFT） was employed to study electron distribution. From the photovoltaic performance measurements, a maximum conversion efficiency （η） of 0.38% was achieved based on the bipyridylporphyrin ruthenium dye A7 （Jsc = 1.33 mA/cm^2, Voc = 0.45 V, FF = 0.64） under 1,5 irradiation （100 mW/cm^2）.展开更多
基金financially supported by National Natural Science Foundation of China(21805236)Scientific Research Fund of Hunan Provincial Education Department(18B062)+1 种基金Fundamental Research Fund of Xiangtan University(18QDZ14)Guangdong Basic and Applied Basic Research Foundation(2019A1515110819)。
文摘Sodium-organic batteries utilizing natural abundance of sodium element and renewable active materials gain great attentions for grid-scale applications.However,the development is still limited by lack of suitable organic cathode materials with high electronic conductivity that can be operated stably in liquid electrolyte.Herein,we present 5,15-bis(ethynyl)-10,20-diphenylporphyrin(DEPP)and[5,15-bis(ethynyl)-10,20-diphenylporphinato]copper(II)(CuDEPP)as new cathodes for extremely stable sodium-organic batteries.The copper(II)ion partially contributes the charge storage and significantly stabilizes the structure of porphyrin complex for electrochemical energy storage.In situ electrochemical stabilization of organic cathode with a lower charging current density was identified which enables both improved high energy density and power density.An excellent longterm cycling stability up to 600 cycles and an extremely high power density of 28 kW kg−1 were achieved for porphyrin-based cathode.This observation would open new pathway for developing highly stable sodium-organic cathode for electrochemical energy storage.
基金the National Natural Science Foundation of China(22279109,22172137)the Natural Science Foundation of Hunan Province(2021JJ40526,2022JJ20036).
文摘Organic sodium-ion batteries(OSIBs)using eco-friendly organic materials as electrodes have recently received much attention.However,the practical applications of OSIBs are generally limited by the inherent disadvantages of organic electrodes,such as their low conductivity,poor stability,and high solubility in electrolytes.Herein,we presented[5,10,15,20-tetrathienylporphinato]M(II)(MTTP,M=2H,Ni)as new electrode materials in sodium-organic batteries.The incorporation of thiophene functionalized groups and nickel(II)ion in the molecular design of porphyrins enabled stable and excellent electrochemical performance in sodium storage systems.Benefiting from multiple charge storage sites and bipolar characteristics,the NiTTP anode has a reversible capacity of 434 mAh g^(-1)at a current density of 25 mA g^(-1).An excellent long-term cycling stability and high average voltage were obtained when NiTTP was used as a cathode.In a symmetrical battery,where NiTTP was used as both cathode and anode materials,a high average voltage of 2.3 V and a practical energy density of 93 Wh kg^(-1)was achieved.These results suggest that the thiophene-based porphyrin derivatives would be promising electrode materials for long-term organic sodium ion batteries for green and stable energy storage.
基金supported by the University Project of Gansu Province(2017A-095)13th Five-Year Period Education Plan of Gansu Province(GS[2017]GHB0360)the National Natural Science Foundation of China(21702089)
文摘A novel sensitizer with imidazole zinc porphyrin as electron donor has been synthesized. The structure has been characterized by UV-Vis, elemental analyses and 1 H NMR.UV-Vis and fluorescence spectra show that it has good light absorbing properties in the range of visible light and suggests that it has potential applications in dye-sensitized solar cells.
基金Project supported by the National Natural Science Foundation of China
文摘Ⅰ. INTRODUCTION Oxotransition metal porphyrin complexes are possible intermediates in cytochrome P-450 modal system. Several oxotransition metal porphyrin complexes such as titanium (Ⅳ), vanadium (Ⅳ) , molybdenum(Ⅳ, Ⅴ) and chromium (Ⅳ) having been isolated and characterized are not effective oxidizing agents, so they are not possible intermediates
文摘Five lanthanide porphyrin complexes with 5- (4-nitrophenyl) -10, 15, 20-triphenylporphyrin and acetylacetonate ligands were synthesized and characterized by elemental analysis, IRspectra, Uv-visible spectra, IH NMR. The structures of the complexes were proposed.
基金supported by the University Project of Gansu Province(2017A-095)the 13th Five-Year Period Education Plan of Gansu Province(GS[2017]GHB0360)
文摘Two novel sensitizers with pyridine-N-oxide zinc porphyrin and its zinc porphyrin as the anchor group and electron acceptor have been synthesized. The structures have been characterized by UV, elemental analyses and 1H NMR. UV and fluorescence spectra show that they have good light absorbing properties in the range of visible light and suggest that they have potential applications in dye-sensitized solar cells.
基金We thank the National Natural Science Foundation of China,the Ministry of ScienceTechnology of China(grant No.29971031,20073050,and G2000028204)for financial support.
文摘The interaction between amphiphilic porphyrin and phenothiazine in AOT/isooctane/water reverse micelle was investigated by UV-Vis spectra. A new absorption complex between the two species is formed in such circumstances, which is ascribed to the enrichment of the components by the reverse micelle. The fluorescence quenching of CHTTP by PTH becomes more efficient after the formation of the absorption complex.
文摘The properties of porphyrins can be changed through the choice of peripheral substituents and inserted metal ions. To obtain porphyrin complexes with novel structures, 5,10, 15,20-tetrakis（p-4-fluorobenzoyloxy） phenyl perphyrin（TFBOPPH2 ） and its transition metal complexes {TFBOPPM [ M = Mn（ Ⅲ ）, Fe（ Ⅲ ）, Co（ Ⅱ ）, Ni（ Ⅱ ）, Cu（ Ⅱ ） and Zn（ Ⅱ ） ] } were synthesized and characterized by means of UV-Vis, IR photoacoustic speetrumetry, ^1H NMR, elemental analyses, molar conductance, and XPS methods. A structure is proposed, in which one porphyrln molecule is coordinated with a transition metal ion in a tetradentate fashion, while the chlorine ion is the balaneeable anion in Fe（ Ⅲ ） and Mn（ Ⅲ ） complexes.
基金Supported by the National Natural Science Foundation of China
文摘Porphyrins and methyl viologen(MV;) are widely used as a photosensitizer and an electron acceptor respectively in photoinduced electron transfer systems. Literatures covered numerous examples of photochemical studies of porphyrins covalently linked to various electron acceptor units, such as viologen, which functioned as both a photosensitizer and an electron acceptor in the same molecule. However, the length of the linked chain between porphyrin and viologen is very important. To improve the rate of photoin-
文摘Transition metal complexes of meso-tetra(4-myristyloxyphenyl)porphyrin TMPPM [M =Mn, Fe, Co, Ni, Cu, Zn; TMPP=mesotetra(4-myristyloxyphenyl)porphyrin] have been synthesized and characterized by means of elemental analyses, UV-Vis spectra, infrared photoacoustic spectra, 1H NMR spectra, molar conductance and differential scanning calorimetry(DSC). The ligand and the Zn complex show liquid crystalline behavior. According to the DSC thermogram of the Zn complex, it exhibits a lower phase transition temperature -7.453 ℃ and a wide mesophase temperature span, 77 ℃.
基金Supported by the National Natural Science Foundation of China(Nos.20871056, 20771044 and 20901030)the Natural Science Foundation of Guangdong Province, China(Nos.8251063201000008 and 9451063201002077)+1 种基金the Planned Item of Science and Technology of Guangdong Province, China (No.2008A030201020)the "211" Project Grant of Jinan University,China
文摘The interactions of mixed porphyrin-polypyridyl Ru（Ⅱ） complexes [m（Py-3＇）TPP-Ru（phen）2Cl]^＋（1） and its derivatives [Nim（Py-3＇）TPP-Ru（phen）2Cl]＋（2） and [Cum（Py-3＇）TPP-Ru（phen）2Cl]^＋（3）（phen=1,10-phenanthroline; m（Py-3＇）TPP=5-（3＇-pyridyl）-10,15,20-triphenylporphyrin） with bovine serum albumin（BSA） were investigated by fluorescence, UV-Vis and circular dichroism（CD） spectroscopies. The UV-Vis and CD spectral experiments indicated that the secondary structures of the protein were perturbed in the presence of the porphyrin Ru（Ⅱ） complex and the perturbation was enhanced under the irradiation with ultra-violet light. The fluorescence quenching mechanism of BSA by the three complexes was determined to be a static process, and the apparent binding constant K values for complexes 1, 2 and 3 measured by fluorescence quenching method were （3.86±0.03）×10^3 L/mol（n=0.94±0.04）, （5.69±0.04）× 103 L/mol（n=1.03±0.06）, and （6.54±0.02）× 10^3 L/mol（n=1.03±0.05）, respectively.
基金This work was supported by the National NatUral Science Foundation of China under grant! No.29733090 and No. 29803003 the Re
文摘MTBPyP (meso-tetrakis(4-N-benzylpyridyl)porphyrin, M=H-2, Zn) bearing positive charge has been shown to associate with SiW12O404- in water solution. The spectral evolution and Job's plots analyses reveal that the relatively stable aggregates contain equal numbers of MTBPyP4(+) and SiW12O404-.
基金Educational Ministry of China, Natural Science Foundation of China (Grant No. 29701002, 29992590-4), the Visiting Scholar Foun
文摘The treatment of tetrakis (4-pyridyl) porphyrin H2TPyP with a hydrated rare earth (III) acetylacetonate RE(acac)3 · nH2O (RE=Y, Eu, Gd) in 1,2, 4-trichlorobenzene (TCB) pro- duced a monomeric porphyrinato rare earth compound RE (TPyP) acac, which further reacted with dicyanobenzene in amyl alcohol in the presence of 1, 8-diazabicyclo [5. 4. 0] undec-7-ene (DBU), giving HRE(TPyP) (Pc) in a good yield. Upon exposure to air, part of the protonated mixed double-deckers in CHC13 solutions converted slowly to the corresponding neutral complexes RE (TPyP) (Pc). These protonated complexes were characterized by means of UV-V is, IR, NMR, mass spectroscopies. The quaternarization of these protonated mixed double-deckers with methyl iodide produced the salts of tetramethylated cations [HRE(TMPyP) (Pc)]4+.
基金financially supported by the National Science and Technology Development Agency (BT-B-01-A5-09-5202)the Thailand Research Fund (TRF) under the Golden Jubilee Ph.D. Program (Duanglaor P.,Grant No.PHD/0226/2549+1 种基金3.C.CU/49/W.1)Rachadapiseksompot Endowment Fund of Chulalongkorn University for postdoctoral fellowship (Thiampanya P.)
文摘Bipyridylporphyrin derivatives possessing a porphyrin moiety as the electron donor and bipyridyl moiety as the electron-acceptor were designed and synthesized for dye-sensitized solar cells （DSSCs）. The photo- physical and electrochemical properties were investigated by absorption spectrometry and cyclic voltam- metry. Density functional theory （DFT） was employed to study electron distribution. From the photovoltaic performance measurements, a maximum conversion efficiency （η） of 0.38% was achieved based on the bipyridylporphyrin ruthenium dye A7 （Jsc = 1.33 mA/cm^2, Voc = 0.45 V, FF = 0.64） under 1,5 irradiation （100 mW/cm^2）.
