14609-54-2Relevant academic research and scientific papers
Efficient electrocatalytic hydrogen gas evolution by a cobalt-porphyrin-based crystalline polymer
Wu, Yanyu,Veleta, José M.,Tang, Diya,Price, Alex D.,Botez, Cristian E.,Villagrán, Dino
, p. 8801 - 8806 (2018)
Herein, we report a crystalline CoTcPP-based [TcPP = the anion of meso-tetra(4-carboxyphenyl)porphyrin] polymeric system, 1, as a hydrogen evolution reaction (HER) electrocatalyst in acidic aqueous media. The material was characterized by powder X-ray diffraction (p-XRD), Fourier transform infrared (FT-IR) spectroscopy, and energy dispersive X-ray (EDX) analysis and its morphology was probed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Polymer 1 shows a surface area of 441.74 m3 g-1, while the discrete CoTcPP molecule (2) shows a surface area of 3.44 m3 g-1. The HER catalytic performance was evaluated by means of linear sweep voltammetry in the presence of 0.5 M H2SO4 aqueous solution. To achieve 10 mA cm-2 cathodic current density, 1 and 2 respectively require an overpotential of 0.475 V and 0.666 V, providing strong evidence that the extended network of cobalt-based porphyrin leads to enhanced HER efficiency. The polymer also shows great tolerance for HER electrolysis in the presence of an acid remaining active over 10 hours.
Visible-Light Photoreduction of CO2 in a Metal-Organic Framework: Boosting Electron-Hole Separation via Electron Trap States
Xu, Hai-Qun,Hu, Jiahua,Wang, Dengke,Li, Zhaohui,Zhang, Qun,Luo, Yi,Yu, Shu-Hong,Jiang, Hai-Long
, p. 13440 - 13443 (2015)
It is highly desirable to convert CO2 to valuable fuels or chemicals by means of solar energy, which requires CO2 enrichment around photocatalysts from the atmosphere. Here we demonstrate that a porphyrin-involved metal-organic framework (MOF), PCN-222, can selectively capture and further photoreduce CO2 with high efficiency under visible-light irradiation. Mechanistic information gleaned from ultrafast transient absorption spectroscopy (combined with time-resolved photoluminescence spectroscopy) has elucidated the relationship between the photocatalytic activity and the electron-hole separation efficiency. The presence of a deep electron trap state in PCN-222 effectively inhibits the detrimental, radiative electron-hole recombination. As a direct result, PCN-222 significantly enhances photocatalytic conversion of CO2 into formate anion compared to the corresponding porphyrin ligand itself. This work provides important insights into the design of MOF-based materials for CO2 capture and photoreduction.
Control of Listeria innocua biofilms by biocompatible photodynamic antifouling chitosan based materials
Castro, Kelly A.D.F.,Moura, Nuno M.M.,Fernandes, Ana,Faustino, Maria A.F.,Sim?es, Mário M.Q.,Cavaleiro, José A.S.,Nakagaki, Shirley,Almeida, Adelaide,Cunha, ?ngela,Silvestre, Armando J.D.,Freire, Carmem S.R.,Pinto, Ricardo J.B.,Neves, Maria da Gra?a P.M.S.
, p. 265 - 276 (2017)
New materials obtained through the incorporation of meso-tetraarylporphyrins, bearing phenyl or pentafluorophenyl groups at the meso positions with or without acid groups, in chitosan films have been prepared and characterized in detail. The efficiency of these porphyrinic-chitosan films (PS-CF) to prevent Listeria innocua attachment and subsequent biofilm formation was evaluated under different irradiation protocols (dark, light, light + dark, dark + light). All tested porphyrinic-chitosan films were photostable and effective in reducing Listeria innocua attachment during a period of 24 h exposure to white light. Biofilm development was nearly completely inhibited in two of the PS-CF films (one containing the 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin and the other one of the thio-carboxylate porphyrins) after being exposed to white light for 24 h followed by incubation in the dark for 48 h. Experiments with the non-immobilized porphyrins against cell suspensions of the same Listeria innocua strain showed that, the photodynamic inactivation efficiency was dependent on porphyrin. The demonstrated antimicrobial activity of PS-CF films, associated with the easy recovery of these films, make them promising photodynamic antifouling materials.
A porphyrin cobalt(II) complex linked to a TiO2/BiVO4 nanocomposite: Alcohol oxidation using nanohybrid materials as a photocatalyst: Via a mechanism approach
Askari, Parvin,Mohebbi, Sajjad
, p. 1715 - 1724 (2018)
Herein, a new nanohybrid catalyst was synthesized via covalently linking a tetraacetate porphyrin cobalt(ii) complex to a TiO2/BiVO4 nanocomposite, and its photocatalytic efficiency towards alcohol oxidation under visible light irradiation was monitored by GC. This nanohybrid material was implemented as a photocatalyst and characterized by the following physicochemical techniques: FE-SEM imaging, EDS, XRD, DRS, BET analysis, and FTIR spectroscopy. Additionally, its role as a photocatalyst was evaluated using a mechanistic approach under aerobic conditions by changing several parameters such as solvent, substrate, oxidant, amount of catalyst, reaction temperature, and ratio of oxidant to substrate. The photocatalytic activity of this nanohybrid catalyst, with an average size of 24 nm, increased almost twice as compared to that of the TiO2/BiVO4 nanocomposite from 35% to 85% conversion, whereas the selectivity was 99%. A plausible mechanism was proposed. In fact, the cobalt porphyrin complex as a light sensitizer improves the photocatalytic activity through impregnation onto the TiO2 surface. The photocatalyst was reused several times without significant loss of its activity. Thus, this nanohybrid robust catalyst has excellent advantages such as facile synthesis, high activity and selectivity, and use of O2 and other environmentally friendly oxidants under mild conditions towards aldehyde production.
A zinc sulfide-supported iron tetrakis (4-carboxyl phenyl) porphyrin catalyst for aerobic oxidation of cyclohexane
Jiang, Yue-Xiu,Su, Tong-Ming,Qin, Zu-Zeng,Huang, Guan
, p. 24788 - 24794 (2015)
Zinc sulfide-supported iron tetrakis (4-carboxyl phenyl) porphyrin (Fe TCPP/ZnS) was prepared and used for aerobic cyclohexane oxidation. X-ray diffraction, ultraviolet-visible spectroscopy and Fourier-transform infrared spectroscopy were carried out. The effects of oxygen pressure, reaction temperature, amount of iron tetrakis (4-carboxyl phenyl) porphyrin (Fe TCPP) and reaction time on the Fe TCPP/ZnS-catalyzed cyclohexane oxidation process were investigated. Fe TCPP/ZnS exhibited excellent activity for aerobic cyclohexane oxidation. Under optimal reaction conditions, the turnover number, cyclohexane conversion, cyclohexanone and cyclohexanol yields were 8.6 × 105, 64.9% and 24.4%, respectively. The stability of Fe TCPP was improved after immobilization on zinc sulfide (ZnS), and the catalyst maintained nearly original levels of activity after several reaction cycles.
Synthesis and photocytotoxic activity of new chlorin-polyamine conjugates
Garcia, Guillaume,Sol, Vincent,Lamarche, Francois,Granet, Robert,Guilloton, Michel,Champavier, Yves,Krausz, Pierre
, p. 3188 - 3192 (2006)
This paper reports the synthesis of new chlorin-polyamine conjugates designed to improve the targeting of cancer cells. Photocytotoxic activity of these photosensitizers was tested against human chronic myelogenous leukemia cells (K562) and compared to the effects of Photofrin II and chlorin e6.
Facile synthesis, photophysical and electrochemical redox properties of octa- and tetracarboxamidophenylporphyrins and the first example of amido-imidol tautomerism in porphyrins
Yadav, Pinky,Sankar, Muniappan
, p. 651 - 657 (2017)
5,10,15,20-tetrakis(4′-carboxamidophenyl)porphyrin (1) and 5,10,15,20-tetrakis(3′,5′-dicarboxamidophenyl)porphyrin (2) have been synthesized in excellent yields and characterized by various spectroscopic techniques and cyclic voltammetric studies. Notably, 1 and 2 exhibited amido-imidol tautomerism in DMSO-d6. The imido tautomer ([sbnd]C(OH)[dbnd]NH) was stabilised in DMSO-d6 at 293?K while the same was converted into amido form ([sbnd]CONH2) at high temperature (418?K). This is a first example of amido-imidol tautomerism in porphyrins. The moderate electron withdrawing nature of imidol groups at meso-phenyl rings lead to 80–95?mV anodic shift in their first ring reduction potential whereas 50–110?mV anodic shift in first ring oxidation potential as compared to that of H2TPP.
Modulating the Acidic and Basic Site Concentration of Metal-Organic Framework Derivatives to Promote the Carbon Dioxide Epoxidation Reaction
Ji, Jinhua,Liu, Hao,Chen, Zewei,Fu, Yajun,Yang, Weijun,Yin, Shuang-Feng
, p. 11102 - 11109 (2021)
Metal-organic framework (MOF) is an ideal precursor/template for porous carbon, and its active components are uniformly doped, which can be used in energy storage and catalytic conversion fields. Metal-organic framework PCN-224 with carboxylporphyrin as t
N-confused porphyrin possessing glucamine-appendants: Aggregation and acid/base properties in aqueous media
Ikawa, Yoshiya,Ogawa, Hiroaki,Harada, Hiroyuki,Furuta, Hiroyuki
, p. 6394 - 6397 (2008)
A water-soluble derivative of N-confused porphyrin (NCP: 5,10,15,20-tetraaryl-2-aza-21-carbaporphyrin) was synthesized by introducing glucamine groups at the para-position of meso-aryl groups. The tetraglucamine-appended NCP (TG-NCP) exists as monocation in aqueous solution containing 6 mM sodium dodecyl sulfate (SDS) but exists as freebase to form aggregates in pure water. These properties are distinct from those of corresponding regular porphyrin, which exists as freebase in the micellar solution and practically insoluble in water.
Straightforward synthesis of a porous chromium-based porphyrinic metal-organic framework for visible-light triggered selective aerobic oxidation of benzyl alcohol to benzaldehyde
Daliran, Saba,García, Hermenegildo,Khajeh, Mostafa,Luque, Rafael,Oudi, Sara,Oveisi, Ali Reza,Sen, Unal
, (2021)
Among MOFs, chromium-based metal–organic frameworks (Cr-MOFs) represent attractive scaffolds for variety of potential applications due to their high porosity and stability. Nevertheless, Cr-MOFs are not very common due to complicate synthesis. Cr-MOFs of large linkers are one clear example of synthetic limitations, since their preparation takes place by post-synthetic routes, commonly starting from Fe-MOFs as precursors. Hence, in this work, the direct synthesis of a phorphyrinic chromium-based MOF, Cr-PCN-600 (PCN stands for Porous Coordination Network) under solvothermal conditions is reported. The resulting Cr-MOF exhibits high surface area, permanent porosity, and broad light absorption wavelength range. Interestingly, this Cr-MOF is a highly effective heterogeneous photocatalyst for the selective aerobic oxidation of benzyl alcohol to benzaldehyde under visible light irradiation without any additive. Importantly, the Cr-MOF showed good recyclability maintaining its activity for three runs. The present results lay the foundation for both synthesis and applications of Cr-MOFs as robust photocatalysts in advanced organic transformations. Notably, quenching studies confirmed the generation of superoxide radical anion (O2[rad]?) and singlet oxygen (1O2) (mostly) as reactive species under the reaction conditions.
