Iron phthalocyanine (FePc) with an ideal N-coordinated environment has been regarded as a promising catalyst for the oxygen reduction reaction (ORR). However, its self-aggregation and inferior stability remain to be solved for further application. Herein, poly-FePc-based hyper-crosslinked polymers with tetrathiafulvalene (TTF) modification (named pFePc-TTF) are innovatively constructed and applied as an efficient ORR catalyst for aluminum–air batteries (AABs). Thanks to the donor (TTF)–acceptor (FePc) effect, the resultant pFePc-TTF catalyst exhibits satisfactory ORR activity with a half-wave potential of 0.90 V, a four-electron transfer process, methanol tolerance, and excellent stability in alkaline electrolytes. The improved electrocatalytic performance might be ascribed to the introduction of TTF as an electron donor, which effectively modulates the electron distribution of the Fe atom and optimizes the absorption energy of intermediate species. As expected, both liquid AABs and all-solid-state flexible AABs equipped with pFePc-TTF display outstanding battery performance in comparison to those equipped with commercial Pt/C. This novel metal macrocycle-based compound provides an effective strategy for the design of efficient and durable ORR catalysts for energy-related applications.

中文翻译：

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具有调制电子结构的供体-受体铁酞菁基超交联聚合物，可在铝空气电池中进行有效的氧还原反应

具有理想的N配位环境的铁酞菁（FePc）被认为是氧还原反应（ORR）的有前途的催化剂。然而，其自聚集和稳定性较差的问题仍有待进一步解决。在此，创新地构建了四硫富瓦烯（TTF）改性的基于聚FePc的超交联聚合物（称为pFePc-TTF），并将其用作铝空气电池（AAB）的高效ORR催化剂。由于给体（TTF）-受体（FePc）效应，所得的pFePc-TTF催化剂表现出令人满意的ORR活性，半波电位为0.90 V，四电子转移过程，甲醇耐受性以及在碱性电解质中优异的稳定性。电催化性能的提高可能归因于引入TTF作为电子供体，它有效地调节了Fe原子的电子分布并优化了中间物质的吸收能。正如预期的那样，与配备商用 Pt/C 的电池相比，配备 pFePc-TTF 的液态 AAB 和全固态柔性 AAB 均表现出出色的电池性能。这种新型金属大环化合物为能源相关应用的高效耐用 ORR 催化剂的设计提供了有效的策略。