- Synthesis method of tetra (4-aminophenyl) porphyrin metal complex
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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.
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Paragraph 0054-0055; 0057
(2021/06/13)
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- Porphyrin-based NiFe Porous Organic Polymer Catalysts for the Oxygen Evolution Reaction
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Porphyrin-based NiFe porous organic polymers (POPs) have been synthesized with good porosity and large BET surface areas (261 to 313 m2 g?1). These bimetallic POPs exhibit RuO2-like OER activity, with the reaction for catalyst FeTAPP-NiTCPP-POP reaching a current density of 10 mA cm?2 at a low overpotential of 338 mV and with a small Tafel slope of 52 mV dec?1. FeTAPP-NiTCPP-POP was stable over a long period under reaction conditions. These bimetallic POPs exhibit better catalytic activity than their monometallic counterparts, due to synergetic interactions between the iron and nickel centers to facilitate the electrocatalytic process.
- Meng, Jing,Xu, Ze,Li, Hongxi,James Young, David,Hu, Chuanjiang,Yang, Yonggang
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p. 1396 - 1402
(2021/02/03)
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- Two-dimensional porphyrin covalent organic frameworks with tunable catalytic active sites for the oxygen reduction reaction
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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
- Yue, Jie-Yu,Wang, Yu-Tong,Wu, Xin,Yang, Peng,Ma, Yu,Liu, Xuan-He,Tang, Bo
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supporting information
p. 12619 - 12622
(2021/12/07)
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- Donor-acceptor covalent organic frameworks of nickel(ii) porphyrin for selective and efficient CO2reduction into CO
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Donor-acceptor two-dimensional covalent organic frameworks, PD-COF-23 and PD-COF-23-Ni, are constructed and applied for selective CO2 reduction with CO conversion rates of 20.9 μmol g-1 h-1 and 40.0 μmol g-1 h-1, respectively, in the absence of any additional photosensitizers and noble metal co-catalysts within an operation time of 25 h. The multilayer nanosheet structure, efficient charge separation and transport, and internal reductive quenching cycle of the NiTAPP fragments of PD-COF-23-Ni result in its higher photocatalytic efficiency than that of PD-COF-23. This journal is
- Diao, Yingxue,Ke, Hanzhong,Qin, Xihao,Xu, Nanfeng,Xu, Zhengtao,Zhu, Xunjin
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supporting information
p. 15587 - 15591
(2020/11/24)
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- Photocatalytic Molecular Oxygen Activation by Regulating Excitonic Effects in Covalent Organic Frameworks
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Excitonic effects caused by Coulomb interactions between electrons and holes play subtle and significant roles on photocatalysis, yet have been long ignored. Herein, porphyrinic covalent organic frameworks (COFs, specifically DhaTph-M), in the absence or presence of different metals in porphyrin centers, have been shown as ideal models to regulate excitonic effects. Remarkably, the incorporation of Zn2+ in the COF facilitates the conversion of singlet to triplet excitons, whereas the Ni2+ introduction promotes the dissociation of excitons to hot carriers under photoexcitation. Accordingly, the discriminative excitonic behavior of DhaTph-Zn and DhaTph-Ni enables the activation of O2 to 1O2 and O2?-, respectively, under visible light irradiation, resulting in distinctly different activity and selectivity in photocatalytic terpinene oxidation. Benefiting from these results, DhaTph-Ni exhibits excellent photocatalytic activity in O2?-engaged hydroxylation of boronic acid, while DhaTph-Zn possesses superior performance in 1O2-mediated selective oxidation of organic sulfides. This work provides in-depth insights into molecular oxygen activation and opens an avenue to the regulation of excitonic effects based on COFs.
- Qian, Yunyang,Li, Dandan,Han, Yulan,Jiang, Hai-Long
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supporting information
p. 20763 - 20771
(2020/12/23)
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- Intrinsic Activity of Metal Centers in Metal-Nitrogen-Carbon Single-Atom Catalysts for Hydrogen Peroxide Synthesis
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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
- Liu, Chang,Li, Hao,Liu, Fei,Chen, Junsheng,Yu, Zixun,Yuan, Ziwen,Wang, Chaojun,Zheng, Huiling,Henkelman, Graeme,Wei, Li,Chen, Yuan
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p. 21861 - 21871
(2021/01/11)
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- Rational Design of Crystalline Covalent Organic Frameworks for Efficient CO2 Photoreduction with H2O
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Solar energy-driven conversion of CO2 into fuels with H2O as a sacrificial agent is a challenging research field in photosynthesis. Herein, a series of crystalline porphyrin-tetrathiafulvalene covalent organic frameworks (COFs) are synthesized and used as photocatalysts for reducing CO2 with H2O, in the absence of additional photosensitizer, sacrificial agents, and noble metal co-catalysts. The effective photogenerated electrons transfer from tetrathiafulvalene to porphyrin by covalent bonding, resulting in the separated electrons and holes, respectively, for CO2 reduction and H2O oxidation. By adjusting the band structures of TTCOFs, TTCOF-Zn achieved the highest photocatalytic CO production of 12.33 μmol with circa 100 % selectivity, along with H2O oxidation to O2. Furthermore, DFT calculations combined with a crystal structure model confirmed the structure–function relationship. Our work provides a new sight for designing more efficient artificial crystalline photocatalysts.
- Lu, Meng,Liu, Jiang,Li, Qiang,Zhang, Mi,Liu, Ming,Wang, Jin-Lan,Yuan, Da-Qiang,Lan, Ya-Qian
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supporting information
p. 12392 - 12397
(2019/08/16)
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- Impregnation of metal ions into porphyrin-based imine gels to modulate guest uptake and to assemble a catalytic microfluidic reactor
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A series of (metallo)porphyrin imine gels have been synthesized based on imine chemistry. The resulting aerogels have sponge-like porous networked structures consisting of interconnected nanoparticles with hierarchical porosity. The aerogels have high specific surface areas (up to 719 m2 g-1) and large pore volumes (up to 2.60 cm3 g-1). The effect of metal ions on the uptake of gases in these aerogels was investigated. The impregnation of various metal ions (Pd(ii), Ni(ii), Mn(iii), Fe(iii) and Sn(iv)) enhances the uptake capacity of various gases (e.g., CO2) despite their higher densities. Among the metal ions, Pd(ii) is the best to increase the adsorption capacity and the isosteric heat of CO2 adsorption. The Pd-tapp-A4 aerogel exhibits CO2 volumetric uptake (1.62 mmol g-1, 7.13 wt% at 298 K, 1 bar) with a high isosteric heat of adsorption (40.0 kJ mol-1). The gels also show potential applications in catalysis because of their unique hierarchical porosity and the availability of metal centers. In combination with microfluidic technology, a catalytic gel capillary reactor has been assembled with the Pd-tapp-A4 gel supported on the inner surface of a functionalized capillary.
- Zeng, Lihua,Liao, Peisen,Liu, Haoliang,Liu, Liping,Liang, Ziwei,Zhang, Jianyong,Chen, Liuping,Su, Cheng-Yong
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supporting information
p. 8328 - 8336
(2016/06/13)
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- Systematic selection of metalloporphyrin-based catalysts for oxygen reduction by modulation of the donor-acceptor intermolecular hardness
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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
- Masa, Justus,Schuhmann, Wolfgang
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p. 9644 - 9654
(2013/07/26)
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