The delocalized π-electrons on the tetrapyrrole ring allow efficient electron transport properties of porphyrins so that they can serve as electrode materials in energy storage devices. We demonstrate a pair of natural chlorophyll-related protoporphyrins, namely protoporphyrin IX (Por) and Mn (III) protoporphyrin IX chloride (MnPor), as the precursors to prepare polyporphyrin (PolyPor and PolyMnPor) films through the electrochemical coupling of the vinyl groups on the porphyrin macrocycles. The extension of the π-conjugated backbone lengthens the intramolecular channel of electrons and allows the electron transporting in higher speed, leading to an excellent electrochemical performance. Under 100 cyclic voltammogram cycles of polymerization, single-layered PolyPor gives capacitance of 93 F g⁻¹, whereas laminar structure PolyMnPor provides significantly higher capacitance of up to 135 F g⁻¹ with an expanded potential window. The well-aligned layer structure effectively accelerating the diffusion of electrolyte ions and enabling more accessible two-dimensional nanochannels furtherly promotes the electrochemical performance. Besides, we also optimize PolyMnPor synthesis condition; larger mass loading and higher capacitance of 250 F/g are achieved. These remarkable results demonstrate polyprotoporphyrins are promising and potential candidates as organic electrode materials. This study could direct future development of cost-effective energy storage devices based on naturally abundant biomaterials.

四吡咯环上的离域 π 电子使卟啉具有有效的电子传输特性，因此它们可以用作能量存储设备中的电极材料。我们展示了一对天然叶绿素相关的原卟啉，即原卟啉 IX (Por) 和氯化锰 (III) 原卟啉 IX (MnPor)，作为通过乙烯基电化学偶联制备聚卟啉（PolyPor 和 PolyMnPor）薄膜的前体。卟啉大环。π共轭骨架的延伸延长了电子的分子内通道并允许电子以更高的速度传输，从而导致优异的电化学性能。在聚合的 100 个循环伏安循环下，单层 PolyPor 的电容为 93 F g ^-1，而层状结构 PolyMnPor 提供高达 135 F g ^{-1 的}显着更高电容，并具有扩展的电位窗口。排列良好的层状结构有效地加速了电解质离子的扩散，并使更容易接近的二维纳米通道进一步提升了电化学性能。此外，我们还优化了PolyMnPor的合成条件；实现了更大的质量负载和 250 F/g 的更高电容。这些显着的结果表明聚原卟啉作为有机电极材料是有前景的和潜在的候选材料。这项研究可以指导未来基于天然丰富的生物材料开发具有成本效益的储能设备。