67201-98-3Relevant academic research and scientific papers
Construction of Donor–Acceptor Heterojunctions in Covalent Organic Framework for Enhanced CO2 Electroreduction
Wu, Qiao,Mao, Min-Jie,Wu, Qiu-Jin,Liang, Jun,Huang, Yuan-Biao,Cao, Rong
, (2021)
Covalent organic frameworks (COFs) are promising candidates for electrocatalytic reduction of carbon dioxide into valuable chemicals due to their porous crystalline structures and tunable single active sites, but the low conductivity leads to unmet current densities for commercial application. The challenge is to create conductive COFs for highly efficient electrocatalysis of carbon dioxide reduction reaction (CO2RR). Herein, a porphyrin-based COF containing donor–acceptor (D–A) heterojunctions, termed TT-Por(Co)-COF, is constructed from thieno[3,2-b]thiophene-2,5-dicarbaldehyde (TT) and 5,10,15,20-tetrakis(4-aminophenyl)-porphinatocobalt (Co-TAPP) via imine condensation reaction. Compared with COF-366-Co without TT, TT-Por(Co)-COF displays enhanced CO2RR performance to produce CO due to its favorable charge transfer capability from the electron donor TT moieties to the acceptor Co-porphyrin ring active center. The combination of strong charge transfer properties and enormous amount of accessible active sites in the 2D TT-Por(Co)-COF nanosheets results in good catalytic performance with a high Faradaic efficiency of CO (91.4%, ?0.6?V vs reversible hydrogen electrode (RHE) and larger partial current density of 7.28?mA cm?2 at ?0.7?V versus RHE in aqueous solution. The results demonstrate that integration of D–A heterojunctions in COF can facilitate the intramolecular electron transfer, and generate high current densities for CO2RR.
Systematic selection of metalloporphyrin-based catalysts for oxygen reduction by modulation of the donor-acceptor intermolecular hardness
Masa, Justus,Schuhmann, Wolfgang
, p. 9644 - 9654 (2013)
Incisive modulation of the intermolecular hardness between metalloporphyrins and O2 can lead to the identification of promising catalysts for oxygen reduction. The dependency of the electrocatalytic reduction of O2 by metalloporphyrins on the nature of the central metal yields a volcano-type curve, which is rationalized to be in accordance with the Sabatier principle by using an approximation of the electrophilicity of the complexes. By using electrochemical and UV/Vis data, the influence of a selection of meso-substituents on the change in the energy for the π→π* excitation of manganese porphyrins was evaluated allowing one to quantitatively correlate the influence of the various ligands on the electrocatalysis of O2 reduction by the complexes. A manganese porphyrin was identified that electrocatalyzes the reduction of oxygen at low overpotentials without generating hydrogen peroxide. The activity of the complex became remarkably enhanced upon its pyrolysis at 650 °C. Finding the strength: Incisive modulation of the intermolecular hardness between metalloporphyrins and O2 can lead to the identification of promising catalysts for the oxygen reduction reaction (see figure). The feasibility of this principle is demonstrated in the selection and design of a manganese metalloporphyrin with promising high activity for electrocatalytic oxygen reduction. Copyright
Intrinsic Activity of Metal Centers in Metal-Nitrogen-Carbon Single-Atom Catalysts for Hydrogen Peroxide Synthesis
Liu, Chang,Li, Hao,Liu, Fei,Chen, Junsheng,Yu, Zixun,Yuan, Ziwen,Wang, Chaojun,Zheng, Huiling,Henkelman, Graeme,Wei, Li,Chen, Yuan
, p. 21861 - 21871 (2020)
Metal-nitrogen-carbon (M-N-C) single-atom catalysts (SACs) show high catalytic activity for many important chemical reactions. However, an understanding of their intrinsic catalytic activity remains ambiguous because of the lack of well-defined atomic str
Synthesis method of tetra (4-aminophenyl) porphyrin metal complex
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Paragraph 0078; 0080, (2021/06/13)
The invention discloses a synthesis method of a tetra (4-aminophenyl) porphyrin metal complex. The method comprises the following steps: 1) taking organic acid as a solvent and pyrrole and 4-halogen benzaldehyde as substrates, and carrying out condensation reaction to obtain a (4-halogen phenyl) porphyrin solid; 2) dissolving the (4-halogen phenyl) porphyrin solid in an organic solvent, adding a metal salt, and reacting to obtain a (4-halogen phenyl) porphyrin metal complex; and 3) taking the (4-halophenyl) porphyrin metal complex and ammonia water as substrates, and carrying out carbon-nitrogen coupling reaction in the presence of a catalyst and an organic solvent to obtain the tetra (4-aminophenyl) porphyrin metal complex. The method is mild in reaction condition, low in toxicity, green and environment-friendly.
Two-dimensional porphyrin covalent organic frameworks with tunable catalytic active sites for the oxygen reduction reaction
Yue, Jie-Yu,Wang, Yu-Tong,Wu, Xin,Yang, Peng,Ma, Yu,Liu, Xuan-He,Tang, Bo
supporting information, p. 12619 - 12622 (2021/12/07)
Four novel two-dimensional porphyrin COFs (M-TP-COF, M = H2, Co, Ni and Mn) with donor-acceptor dyads were fabricated and served as electrocatalysts for the oxygen reduction reaction (ORR). The ORR catalytic activity of M-TP-COF was tuned by changing the
Post-modified porphyrin imine gels with improved chemical stability and efficient heterogeneous activity in CO2 transformation
Liao, Peisen,Cai, Guangmei,Shi, Jianying,Zhang, Jianyong
supporting information, p. 10017 - 10024 (2019/07/04)
Efficient heterogeneous gel catalysts have been developed based on dynamic covalent chemistry and post-modification methods for the chemical fixation of CO2. Various porphyrin-based imine gels are synthesized and subsequent reduction of imine bonds and metallation with various metal centers yields gel catalysts. The gels are characterized by a number of techniques including SEM, TEM, EDX, FT-IR, CP/MAS 13C NMR, and XPS. The resulting gels not only have network structures including micro-, meso- and macropores, but also show improved chemical stability and strong interactions between CO2 and pore channels. The gel catalysts show good catalytic activity towards the cycloaddition of epoxides with CO2 to cyclic carbonates using wet gels. Post-modified gel catalysts with a Zn(ii) center (ZnTAPP-Go-r) show a high product yield and high stability with recyclability over 5 cycles.
Study of factors influencing the fabrication of Co-porphyrin porous coordination polymer via metal–organic gel intermediate
Li, Jun,Zhao, Jiale,Cheng, Minglun,Yi, Jiajia,Yuan, Lin,Wang, Ning,Li, Jun
, (2019/09/10)
In this work, 5, 10, 15, 20-Tetra-(4-aminophenyl) porphyrin (TAPP) was used as gelator to prepare metal-porphyrin porous coordination polymer (PCP) via solvothermal process, Soxhlet extraction and supercritical CO2 extraction. Firstly, the metal-porphyrin organic gel (MOG) was prepared as intermediate with solvothermal method. The generation of gels is associated with many factors. When four acetates [Co(Ac)2?4H2O, Zn(Ac)2?2H2O, Mn(Ac)2?4H2O and Ni(Ac)2?7H2O] reacted with TAPP, only the reaction between Co(Ac)2?4H2O and TAPP could form desired metal-porphyrin organic gel. The influences of solvent, concentration and anions were investigated in the gelation process. Secondly, the residual reactants and solvent molecules in MOG were removed through Soxhlet extraction and supercritical CO2 extraction. The Co-PCP is an amorphous material with a hierarchical porous structure can effectively catalyze the oxidation of ethylbenzene and also exhibits a strong adsorptive capacity for the strong-polar solvent molecules.
Electrochemical hydrogen evolution by cobalt (II) porphyrins: Effects of ligand modification on catalytic activity, efficiency and overpotential
Beyene, Belete B.,Mane, Sandeep B.,Hung, Chen-Hsiung
, p. H481 - H487 (2018/07/06)
Electrochemical H2 evolution of a series of cobalt(II) porphyrins with electron-withdrawing (EW) and electron-donating (ED) substituents at the para positions of the meso-phenyl rings has been investigated in DMSO using acetic acid as a proton source. Our study showed that the nature of substituents significantly influences catalytic activity, efficiency, and the potential at which catalysis occurs. Faradaic efficiencies (FE) ranging from 44 to 99%, turnover numbers (TONs) from 1.5 to 104 (~11 h electrolysis), turnover frequencies (TOFs) from 0.23 to 9.1 h?1, and onset overpotentials from 25 to 445 mV were obtained by tuning the porphyrinic substituents. Cobalt porphyrins with -SO3H, -COOH, or -NH2 groups as the substituents showed high activity and efficiency with more positive onset potentials as compared to the parent [Co(TPP)]. Supports also from the low hydrogen generation activities for complexes with -COOMe, -OMe and -OH groups as the substituents suggest that the acidity of the meso-phenyl substituent plays a key role in enhancing the hydrogen evolution activities during the catalytic processes.
