A porous alkynylporphyrin conjugated organic polymer (MnE-TPP) was synthesized by Sonogashira coupling reaction with Mn(II) 5,10,15,20-tetrakis(4′-ethynylphenyl)porphyrin and Mn(II) 5,10,15,20-tetrakis(4′-bromophenyl)porphyrin as building blocks. The polymer was characterized using nitrogen adsorption–desorption isotherms, field-emission scanning electron microscopy, high-resolution transmission electron microscopy, Fourier transform infrared and UV–visible spectroscopies, X-ray diffraction, thermogravimetry and inductively coupled plasma atomic emission spectrometry. The electrochemical behaviors of MnE-TPP were investigated by cyclic voltammetry. MnE-TPP was developed as a heterogeneous catalyst for the activation of molecular oxygen to oxidize toluene under mild conditions. The selectivity of total benzaldehyde and benzyl alcohol remained above 70.0% with a conversion of toluene up to 10.2%. The turnover number was as high as 13 653. Also, MnE-TPP remained structurally stable and the toluene conversion rate hardly decreased after 5 h of reaction and five cycles of reuse.
Organic electrode materials with bipolar-redox activity are a promising candidate for high-energy aluminum-ion batteries (AIBs), but face the capacity ceiling due to limited active sites and low electron transfer number. To universally address this issue, seeking for a kind of multisite bipolar organic material to achieve multielectron transfer is a prerequisite but challenging. Herein, we develop a 12-electron transfer tetraalkynylporphyrin macrocycle positive electrode with two p-type amine (‒NH‒) motifs, two n-type imine (C = N) motifs and four n-type alkynyl (C ≡ C) motifs. The bipolar 18π-electron porphyrin macrocycle can alternately bind and release AlCl 4 − anions at ‒NH‒ sites and AlCl 2 + cations at C = N sites (oxidized from 18π to 16π or reduced from 18π to 20π), achieving four electrons transfer. Furthermore, each terminal C ≡ C site can also coordinate with two AlCl 2 + cations, thereby delivering eight electrons. The designed aluminum-organic battery achieves a high capacity of up to 347 mAh g −1 (3-6 times that of conventional graphite positive electrode, 60-120 mAh g −1 ) and a high specific energy of 312 Wh kg −1 (up to 150% compared to cells with graphite as positive electrode) based on the mass of positive electrode materials.
危险品化学品经营许可证（带存储）