Rational design and exploration of low-cost and robust bifunctional oxygen electrocatalysts are vitally important for developing high-performance zinc-air batteries(ZABs).Herein,we reported a facile yet cost-efficient...Rational design and exploration of low-cost and robust bifunctional oxygen electrocatalysts are vitally important for developing high-performance zinc-air batteries(ZABs).Herein,we reported a facile yet cost-efficient approach to construct a bifunctional oxygen reduction reaction(ORR)/oxygen evolution reaction(OER)electrocatalyst composed of N-doped porous carbon nanosheet flowers decorated with Fe Co nanoparticles(Fe Co/N-CF).Rational design of this catalyst is achieved by designing Schiff-base polymer with unique molecular structure via hydrogen bonding of cyanuramide and terephthalaldehyde polycondensate in the presence of metal cations.It exhibits excellent activity and stability for electrocatalysis of ORR/OER,enabling ZAB with a high peak power density of 172 m W cm^(-2)and a large specific capacity of 811 m A h g^(-1)Znat large current.The rechargeable ZAB demonstrates excellent durability for 1000 h with slight voltage decay,far outperforming a couple of precious Pt/Ir-based catalysts.Density functional theory(DFT)calculations reveal that high activity of bimetallic Fe Co stems from enhanced O_(2)and OH-adsorption and accelerated O_(2)dissociation by OAO bond activation.展开更多
Glutamic acid-salicylaldehyde Schiff-base metal complexes are bound into bovine serum albumin （BSA）, which afforded BSA binding Schiff-base metal complexes （BSA-SalGluM, M=Cu, Co, Ni, Zn）. The BSA binding metal co...Glutamic acid-salicylaldehyde Schiff-base metal complexes are bound into bovine serum albumin （BSA）, which afforded BSA binding Schiff-base metal complexes （BSA-SalGluM, M=Cu, Co, Ni, Zn）. The BSA binding metal complexes were characterized by UV-vis spectra and Native PAGE. It showed that the protein structures of BSA kept after coordinating amino acid Schiff-bases metal complexes. The effect of the antioxidant activity was investigated. The results indicate that the antioxidant capacity of BSA increased more than 10 times after binding Schiff-base metal complexes.展开更多
Improving the selectivity of the electrocatalytic CO_(2) reduction reaction(CO_(2)RR)over hydrogen evolution in aqueous solutions is required but challenging because the two reactions occur at close thermodynamic pote...Improving the selectivity of the electrocatalytic CO_(2) reduction reaction(CO_(2)RR)over hydrogen evolution in aqueous solutions is required but challenging because the two reactions occur at close thermodynamic potentials and compete with each other.Herein,we report on the selective CO_(2)RR in aqueous solutions utilizing covalent Co porphyrin polymers with fine-tuned electronic structures.展开更多
Inhibiting the ions migration and even irreversible reactions have been regarded as one of the most important factors for fabricating efficient and stable perovskite solar cells(PSCs).Here,we employed the diamine coba...Inhibiting the ions migration and even irreversible reactions have been regarded as one of the most important factors for fabricating efficient and stable perovskite solar cells(PSCs).Here,we employed the diamine cobalt(II)porphyrin[Co(II)P]to treat a perovskite film to construct in situ Co(II)P-based coordination polymer on the perovskite film.The crystal structure of the polymer indicated a central cobalt(Co)ion in one Co(II)P coordinated with two amine units from a different neighboring Co(II)P to form an overall three-dimensional(3D)structure.Such a 3D network covered on the perovskite surface could prevent the migration of ions from the perovskite.Furthermore,the limited amount of diatomic iodine(I2)released in the perovskite due to iodide oxidation defects could be reduced to I–by the Co(II)ion in the polymer,and thus,achieve regeneration.Finally,the Co(Ⅱ/Ⅲ)ion pair formed in the polymer facilitated the charge transfer and boosted to the best efficiency up to 21.3%.Remarkably improved cell stability under moisture,heating,or light was also achieved.The control PSCs with Zn-based 3D polymer and Co-based 1D polymer exhibited the poor cell efficiencies and stabilities than those of the 3D Co porphyrin-based PSC to verify the effect of 3D Co porphyrin-based polymer in stabilizing the perovskite film.This work provides a new encapsulation and regeneration strategy via in situ construction of a Co(Ⅱ)porphyrin-based coordination polymer on perovskite film for efficient and stable PSCs.展开更多
The reactions of 5- (p-hydroxyphenyl)-10, 15, 20-tris (p-methoxyphenyl) porphyrin(H2Por) 1 respectively with triruthenium dodecacarbonyl [Ru3 (CO)12] and triosmiumdodecacarbonyl [Os3 (CO)12] under N2 gave complexes 2 ...The reactions of 5- (p-hydroxyphenyl)-10, 15, 20-tris (p-methoxyphenyl) porphyrin(H2Por) 1 respectively with triruthenium dodecacarbonyl [Ru3 (CO)12] and triosmiumdodecacarbonyl [Os3 (CO)12] under N2 gave complexes 2 and 3. Treatment of 2 (and 3) withMerrifield' peptide resin gave 4 (and 5) respectively.展开更多
The reaction of 5, 10, 15, 20-tetra-(4-pyridyl) porphyrin 1 with triruthenium dodecacarbonyl [Ru3(CO)12], zinc(II) acetate, copper(II) acetate, cobalt(II) acetate afforded complexes 2a?2d respectively. Treatment of 2a...The reaction of 5, 10, 15, 20-tetra-(4-pyridyl) porphyrin 1 with triruthenium dodecacarbonyl [Ru3(CO)12], zinc(II) acetate, copper(II) acetate, cobalt(II) acetate afforded complexes 2a?2d respectively. Treatment of 2a?2d with Merrifield’s peptide resin obtained 3a?3d. The compounds 3a?3d reacted with methyl iodide respectively gave 4a?4d. New complexes 4a?4d have been identified by IR, UV-visible spectra, and AES.展开更多
Photoluminescence properties and exciton decay dynamics in a porphyrin side-chain polymer, poly[porphyrin acrylate- acrylonitrile （abbreviated p[（por）A-AN]）, have been investigated by femtosecond time-resolved pho...Photoluminescence properties and exciton decay dynamics in a porphyrin side-chain polymer, poly[porphyrin acrylate- acrylonitrile （abbreviated p[（por）A-AN]）, have been investigated by femtosecond time-resolved photoluminescence spectroscopy. All the luminescences of p[（por）A-AN] films are due to the emissive decay of the photoexcited singlet excitons in the porphyrins. The luminescence efficiencies and lifetimes are increased for samples from pure films to dilute blend films. However, they are increased as the intrachain concentration of the porphyrin sidechain groups is decreased. The intrachain rotation motions of porphyrin sidechain groups result in the initial ultrafast luminescence decays, which are much faster than those due to the interchain interactions. All the samples show no significant red-shift and broadening of the transient luminescence spectra. The interchain and intrachain nonradiative exciton relaxation processes may play an important role in the luminescence dynamics in the p[（por）A-AN] films. The possible origin of different intrachain and interchain dynamic behaviours in p[（por）A-AN] films is discussed.展开更多
The reaction of pyrrole with 4-hydroxybenzaldehyde and 4-pyridinecarboxaldehyde afforded new porphyrin ligand 1. Treatment of 1 with copper( II ) acetate, cobalt ( II ) acetate gave complexes 2-3 respectively. 2 and 3...The reaction of pyrrole with 4-hydroxybenzaldehyde and 4-pyridinecarboxaldehyde afforded new porphyrin ligand 1. Treatment of 1 with copper( II ) acetate, cobalt ( II ) acetate gave complexes 2-3 respectively. 2 and 3 reacted with Merrifield's peptide resin produced 4 and 5. Complexes 4 and 5 reacted with methyl iodide respectively gave 6-7. The new compounds 1-7 have been identified by H-1 NMR, IR, MS and UV-visible spectra, elemental analysis and AES.展开更多
A novel tripyridylporphyrin monomer,5-[4-[2-（acryloyloxy）ethoxy]phenyl]-10,15,20-tris（4-pyridyl）porphyrin （TrPyP）,was synthesized and polymerized with acrylamide（AM） to prepare the hydrophobically associating ...A novel tripyridylporphyrin monomer,5-[4-[2-（acryloyloxy）ethoxy]phenyl]-10,15,20-tris（4-pyridyl）porphyrin （TrPyP）,was synthesized and polymerized with acrylamide（AM） to prepare the hydrophobically associating water-soluble polymer PAM-TrPyP.The aggregation behavior of porphyrin pendants was investigated by UV-Visible and fluorescence spectra.The polymer displays a strong tendency of hydrophobic association even in dilute solutions.With increasing the concentration,the maximum absorption wavelength of Soret band changes from 416 nm to 407 nm,and the fluorescence corrected for the inner filter effect exhibits moderate concentration quenching.All the results indicate thatπ-πinteraction of porphyrin pendants plays a key role in association of PAM-TrPyP,and H-aggregates of porphyrins are mainly formed in the concentrated solution.On the other hand,dynamic light scattering（DLS） and transmission electron microscopy（TEM） were used to follow the changes in size and structure of the macromolecular assemblies with the concentration increase.The polymer aggregation conformation changes from loose ＂vesicle-like＂ morphology to solid globule accordingly.When pH value of solution decreases to 4.3,pyridine moieties on porphyrin pendants could be protonated and the H-aggregates formed in macromolecular matrix are destroyed by electrostatic repulsion interactions.展开更多
Three alcohol/water-soluble porphyrins, Zn-TPyPMeI： zinc（II） meso-tetra（N-methyl-4-pyridyl） porphyrin tetra-iodide, Zn- TPyPAdBr： zinc（II） meso-tetra[1-（1-adamantylmethyl ketone）-4-pyridyl] porphyrin tetra-b...Three alcohol/water-soluble porphyrins, Zn-TPyPMeI： zinc（II） meso-tetra（N-methyl-4-pyridyl） porphyrin tetra-iodide, Zn- TPyPAdBr： zinc（II） meso-tetra[1-（1-adamantylmethyl ketone）-4-pyridyl] porphyrin tetra-bromide and MnC1-TPyPAdBr： man- ganese（III） meso-tetra[1-（1-adamantylmethyl ketone）-4-pyridyl] porphyrin tetra-bromide were employed as cathode interlayers to fabricate polymer solar cells （PSCs）. The PCvaBM （[6,6]-phenyl C71 butyric acid methyl ester） and PCDTBT （poly[N-9＂- hepta-decanyl-2,7-carbazole-alt-5,5-（4＇,7＇-di-2-thienyl-2＇,3＇-benzothiadiazole）]）-blend films were used as active layers in polymer solar cells （PSCs）. The PSCs with alcohol/water-soluble porphyrins interlayer showed obviously higher power con- version efficiency （PCE） than those without interlayers. The highest PCE, 6.86%, was achieved for the device with MnCl- TPyPAdBr as an interlayer. Ultraviolet photoemission spectroscopic （UPS）, carrier mobility, atomic force microscopy （AFM） and contact angle （0） characterizations demonstrated that the porphyrin molecules can result in the formation of interfacial dipole layer between active layer and cathode. The interfacial dipole layer can obviously improve the open-circuit voltage （Voc） and charge extraction, and sequentially lead to the increase of PCE.展开更多
We report a newly synthesized polymer of a star-shaped porphyrin compound(TPA-FxP) with four oligofluorene arms at its meso positions with the pronounced enhancement of the two-photon properties and the generation of ...We report a newly synthesized polymer of a star-shaped porphyrin compound(TPA-FxP) with four oligofluorene arms at its meso positions with the pronounced enhancement of the two-photon properties and the generation of singlet oxygen by utilizing the two-photon excited fluorescence resonance energy transfer.The steady-state spectra and transient triplet-triplet absorption spectra give evidence that the enhanced two-photon absorption cross section results from not only the through-space energy transfer(Frster) but also the through-bond energy transfer between conjugated peripheral oligofluorene arms and the porphyrin core.The two-photon absorption cross section at 780 nm up to 3360 GM(1 GM = 10-50 cm4·s/photon) of TPA-FxP was obtained,which is comparable to the highest values reported from other similar chemically modified porphyrin core compounds.Furthermore,the enhanced production of singlet oxygen under two-photon absorption conditions is also reported.展开更多
As two pivotal functional segments,triazine and porphyrin can be coupled to form a highly cross-linked conjugated polymer.Although the obtained conjugated polymers are almost insoluble in most solvents,a small amount ...As two pivotal functional segments,triazine and porphyrin can be coupled to form a highly cross-linked conjugated polymer.Although the obtained conjugated polymers are almost insoluble in most solvents,a small amount of protonic acid can cause the formation of a colloidal solution of polymers.The dissolution process has proved to be a surface charge effect induced by protonation of porphyrin units in the polymer framework.High-quality conjugated polymer films have been prepared on diverse substrates by solution drop-casting and then used for thermoelectric(TE)applications.The films exhibit remarkable TE performance with high Seebeck coefficients(−6650μV K^(−1))and electronic conductivities(0.042 S cm^(−1)),yielding a power factor of 185μW m^(−1) K^(−2),which,collectively,are the highest among all reported n-type organic TE materials.This work may pave the way for the design and development of solution-processed,cross-linked polymer films as promising TE materials.展开更多
Porphyrin-containing conjugated poly- mers with fluorene or carbazole as spacer groups were prepared by Sonogashira cross-coupling reac- tions. The polymers were of high molecular weight and the flexible alkyl chains ...Porphyrin-containing conjugated poly- mers with fluorene or carbazole as spacer groups were prepared by Sonogashira cross-coupling reac- tions. The polymers were of high molecular weight and the flexible alkyl chains on fluorene or carbazole units made the conjugated polymers soluble in common organic solvents, such as THF and methyl- ene chloride. The polymers could form high quality durable films from solution casting. Their optical and photocurrent responsive properties were investigated. It was found that the photocurrent response was di- rectly proportional to the content of porphyrin. The incorporation of carbazole units into the polymer chains also gave positive contribution to the photo- current generation in some extent.展开更多
基金supported by the National Science Foundation of China(21805235)the Opening Foundation of Creative Platform of the Key Laboratory of the Education Department of Hunan Province(20K131)the Construct Program of the Key Discipline in Hunan Province。
文摘Rational design and exploration of low-cost and robust bifunctional oxygen electrocatalysts are vitally important for developing high-performance zinc-air batteries(ZABs).Herein,we reported a facile yet cost-efficient approach to construct a bifunctional oxygen reduction reaction(ORR)/oxygen evolution reaction(OER)electrocatalyst composed of N-doped porous carbon nanosheet flowers decorated with Fe Co nanoparticles(Fe Co/N-CF).Rational design of this catalyst is achieved by designing Schiff-base polymer with unique molecular structure via hydrogen bonding of cyanuramide and terephthalaldehyde polycondensate in the presence of metal cations.It exhibits excellent activity and stability for electrocatalysis of ORR/OER,enabling ZAB with a high peak power density of 172 m W cm^(-2)and a large specific capacity of 811 m A h g^(-1)Znat large current.The rechargeable ZAB demonstrates excellent durability for 1000 h with slight voltage decay,far outperforming a couple of precious Pt/Ir-based catalysts.Density functional theory(DFT)calculations reveal that high activity of bimetallic Fe Co stems from enhanced O_(2)and OH-adsorption and accelerated O_(2)dissociation by OAO bond activation.
文摘Glutamic acid-salicylaldehyde Schiff-base metal complexes are bound into bovine serum albumin （BSA）, which afforded BSA binding Schiff-base metal complexes （BSA-SalGluM, M=Cu, Co, Ni, Zn）. The BSA binding metal complexes were characterized by UV-vis spectra and Native PAGE. It showed that the protein structures of BSA kept after coordinating amino acid Schiff-bases metal complexes. The effect of the antioxidant activity was investigated. The results indicate that the antioxidant capacity of BSA increased more than 10 times after binding Schiff-base metal complexes.
基金support from the National Natural Science Foundation of China(nos.21773146 and 22003036)the Fok Ying-Tong Education Foundation for Outstanding Young Teachers in Universitythe Fundamental Research Funds for the Central Universities,and the Research Funds of Shaanxi Normal University(nos.2020CBLZ005,GK202103045,and GK202103033).U.-P.A.thanks the Fraunhofer Internal Programs for their support under Grant No.Attract 097-602175 and the DFG under Germany’s Excellence Strategy—EXC-2033—Projektnummer 390677874“RESOLV”.
文摘Improving the selectivity of the electrocatalytic CO_(2) reduction reaction(CO_(2)RR)over hydrogen evolution in aqueous solutions is required but challenging because the two reactions occur at close thermodynamic potentials and compete with each other.Herein,we report on the selective CO_(2)RR in aqueous solutions utilizing covalent Co porphyrin polymers with fine-tuned electronic structures.
基金The authors acknowledge the National Natural Science Foundation of China(21801104 and 21871121)Young Elite Scientists Sponsorship Program by CAST(2018QNRC001)+1 种基金Fundamental Research Funds for the Central Universities(lzujbky-2019-sp01)Special Fund Project of Guiding Scientific and Technological Innovation Development of Gansu Province(2019ZX-04).
文摘Inhibiting the ions migration and even irreversible reactions have been regarded as one of the most important factors for fabricating efficient and stable perovskite solar cells(PSCs).Here,we employed the diamine cobalt(II)porphyrin[Co(II)P]to treat a perovskite film to construct in situ Co(II)P-based coordination polymer on the perovskite film.The crystal structure of the polymer indicated a central cobalt(Co)ion in one Co(II)P coordinated with two amine units from a different neighboring Co(II)P to form an overall three-dimensional(3D)structure.Such a 3D network covered on the perovskite surface could prevent the migration of ions from the perovskite.Furthermore,the limited amount of diatomic iodine(I2)released in the perovskite due to iodide oxidation defects could be reduced to I–by the Co(II)ion in the polymer,and thus,achieve regeneration.Finally,the Co(Ⅱ/Ⅲ)ion pair formed in the polymer facilitated the charge transfer and boosted to the best efficiency up to 21.3%.Remarkably improved cell stability under moisture,heating,or light was also achieved.The control PSCs with Zn-based 3D polymer and Co-based 1D polymer exhibited the poor cell efficiencies and stabilities than those of the 3D Co porphyrin-based PSC to verify the effect of 3D Co porphyrin-based polymer in stabilizing the perovskite film.This work provides a new encapsulation and regeneration strategy via in situ construction of a Co(Ⅱ)porphyrin-based coordination polymer on perovskite film for efficient and stable PSCs.
文摘The reactions of 5- (p-hydroxyphenyl)-10, 15, 20-tris (p-methoxyphenyl) porphyrin(H2Por) 1 respectively with triruthenium dodecacarbonyl [Ru3 (CO)12] and triosmiumdodecacarbonyl [Os3 (CO)12] under N2 gave complexes 2 and 3. Treatment of 2 (and 3) withMerrifield' peptide resin gave 4 (and 5) respectively.
文摘The reaction of 5, 10, 15, 20-tetra-(4-pyridyl) porphyrin 1 with triruthenium dodecacarbonyl [Ru3(CO)12], zinc(II) acetate, copper(II) acetate, cobalt(II) acetate afforded complexes 2a?2d respectively. Treatment of 2a?2d with Merrifield’s peptide resin obtained 3a?3d. The compounds 3a?3d reacted with methyl iodide respectively gave 4a?4d. New complexes 4a?4d have been identified by IR, UV-visible spectra, and AES.
基金Project supported by the National Natural Science Foundation of China （Grant Nos 60478013, 20571089 and 10274107）, the Natural Science Foundation of Guangdong Province, China （Grant No 05101819）, and the Doctoral Program Foundation of Institute of Higher Education of China（Grant No 20040558031）.
文摘Photoluminescence properties and exciton decay dynamics in a porphyrin side-chain polymer, poly[porphyrin acrylate- acrylonitrile （abbreviated p[（por）A-AN]）, have been investigated by femtosecond time-resolved photoluminescence spectroscopy. All the luminescences of p[（por）A-AN] films are due to the emissive decay of the photoexcited singlet excitons in the porphyrins. The luminescence efficiencies and lifetimes are increased for samples from pure films to dilute blend films. However, they are increased as the intrachain concentration of the porphyrin sidechain groups is decreased. The intrachain rotation motions of porphyrin sidechain groups result in the initial ultrafast luminescence decays, which are much faster than those due to the interchain interactions. All the samples show no significant red-shift and broadening of the transient luminescence spectra. The interchain and intrachain nonradiative exciton relaxation processes may play an important role in the luminescence dynamics in the p[（por）A-AN] films. The possible origin of different intrachain and interchain dynamic behaviours in p[（por）A-AN] films is discussed.
文摘The reaction of pyrrole with 4-hydroxybenzaldehyde and 4-pyridinecarboxaldehyde afforded new porphyrin ligand 1. Treatment of 1 with copper( II ) acetate, cobalt ( II ) acetate gave complexes 2-3 respectively. 2 and 3 reacted with Merrifield's peptide resin produced 4 and 5. Complexes 4 and 5 reacted with methyl iodide respectively gave 6-7. The new compounds 1-7 have been identified by H-1 NMR, IR, MS and UV-visible spectra, elemental analysis and AES.
文摘A novel tripyridylporphyrin monomer,5-[4-[2-（acryloyloxy）ethoxy]phenyl]-10,15,20-tris（4-pyridyl）porphyrin （TrPyP）,was synthesized and polymerized with acrylamide（AM） to prepare the hydrophobically associating water-soluble polymer PAM-TrPyP.The aggregation behavior of porphyrin pendants was investigated by UV-Visible and fluorescence spectra.The polymer displays a strong tendency of hydrophobic association even in dilute solutions.With increasing the concentration,the maximum absorption wavelength of Soret band changes from 416 nm to 407 nm,and the fluorescence corrected for the inner filter effect exhibits moderate concentration quenching.All the results indicate thatπ-πinteraction of porphyrin pendants plays a key role in association of PAM-TrPyP,and H-aggregates of porphyrins are mainly formed in the concentrated solution.On the other hand,dynamic light scattering（DLS） and transmission electron microscopy（TEM） were used to follow the changes in size and structure of the macromolecular assemblies with the concentration increase.The polymer aggregation conformation changes from loose ＂vesicle-like＂ morphology to solid globule accordingly.When pH value of solution decreases to 4.3,pyridine moieties on porphyrin pendants could be protonated and the H-aggregates formed in macromolecular matrix are destroyed by electrostatic repulsion interactions.
基金supported by the National Basic Research Program of China(2014CB643500)the National Natural Science Foundation of China(51273077,51173065)
文摘Three alcohol/water-soluble porphyrins, Zn-TPyPMeI： zinc（II） meso-tetra（N-methyl-4-pyridyl） porphyrin tetra-iodide, Zn- TPyPAdBr： zinc（II） meso-tetra[1-（1-adamantylmethyl ketone）-4-pyridyl] porphyrin tetra-bromide and MnC1-TPyPAdBr： man- ganese（III） meso-tetra[1-（1-adamantylmethyl ketone）-4-pyridyl] porphyrin tetra-bromide were employed as cathode interlayers to fabricate polymer solar cells （PSCs）. The PCvaBM （[6,6]-phenyl C71 butyric acid methyl ester） and PCDTBT （poly[N-9＂- hepta-decanyl-2,7-carbazole-alt-5,5-（4＇,7＇-di-2-thienyl-2＇,3＇-benzothiadiazole）]）-blend films were used as active layers in polymer solar cells （PSCs）. The PSCs with alcohol/water-soluble porphyrins interlayer showed obviously higher power con- version efficiency （PCE） than those without interlayers. The highest PCE, 6.86%, was achieved for the device with MnCl- TPyPAdBr as an interlayer. Ultraviolet photoemission spectroscopic （UPS）, carrier mobility, atomic force microscopy （AFM） and contact angle （0） characterizations demonstrated that the porphyrin molecules can result in the formation of interfacial dipole layer between active layer and cathode. The interfacial dipole layer can obviously improve the open-circuit voltage （Voc） and charge extraction, and sequentially lead to the increase of PCE.
基金Supported by the National Natural Science Foundation of China (Grant Nos. 20773139, 20825314, and 20833008)State Key Project for Fundamental Research (Grant Nos. 2006CB806000 and 2007CB815200)the Chinese Academy of Sciences (Grant No. KJCX2.Y.W.H06)
文摘We report a newly synthesized polymer of a star-shaped porphyrin compound(TPA-FxP) with four oligofluorene arms at its meso positions with the pronounced enhancement of the two-photon properties and the generation of singlet oxygen by utilizing the two-photon excited fluorescence resonance energy transfer.The steady-state spectra and transient triplet-triplet absorption spectra give evidence that the enhanced two-photon absorption cross section results from not only the through-space energy transfer(Frster) but also the through-bond energy transfer between conjugated peripheral oligofluorene arms and the porphyrin core.The two-photon absorption cross section at 780 nm up to 3360 GM(1 GM = 10-50 cm4·s/photon) of TPA-FxP was obtained,which is comparable to the highest values reported from other similar chemically modified porphyrin core compounds.Furthermore,the enhanced production of singlet oxygen under two-photon absorption conditions is also reported.
基金supported by the National Natural Science Foundation of China(nos.21975078 and 91833304)the Fundamental Research Funds for the Central Universities,the Introduced Innovative R&D Team of Guangdong Province(no.201101C0105067115)+1 种基金the Natural Science Foundation of Guangdong Province(no.2019B030301003)the 111 Project,and the Thousand Youth Talents Plan.
文摘As two pivotal functional segments,triazine and porphyrin can be coupled to form a highly cross-linked conjugated polymer.Although the obtained conjugated polymers are almost insoluble in most solvents,a small amount of protonic acid can cause the formation of a colloidal solution of polymers.The dissolution process has proved to be a surface charge effect induced by protonation of porphyrin units in the polymer framework.High-quality conjugated polymer films have been prepared on diverse substrates by solution drop-casting and then used for thermoelectric(TE)applications.The films exhibit remarkable TE performance with high Seebeck coefficients(−6650μV K^(−1))and electronic conductivities(0.042 S cm^(−1)),yielding a power factor of 185μW m^(−1) K^(−2),which,collectively,are the highest among all reported n-type organic TE materials.This work may pave the way for the design and development of solution-processed,cross-linked polymer films as promising TE materials.
基金This work was supported by the National Natural Science Foundation of China （Grant Nos. 20225415, 20423003 and 20374053）the Major State Basic Research Development Program （Grant No. 2002CB613401）.
文摘Porphyrin-containing conjugated poly- mers with fluorene or carbazole as spacer groups were prepared by Sonogashira cross-coupling reac- tions. The polymers were of high molecular weight and the flexible alkyl chains on fluorene or carbazole units made the conjugated polymers soluble in common organic solvents, such as THF and methyl- ene chloride. The polymers could form high quality durable films from solution casting. Their optical and photocurrent responsive properties were investigated. It was found that the photocurrent response was di- rectly proportional to the content of porphyrin. The incorporation of carbazole units into the polymer chains also gave positive contribution to the photo- current generation in some extent.
