Diao Binxuan, Jiang Fuhao, Ye Heqing, Wang Rui, Li Hongjiang, Zhang Haoran, Joo Sang Woo, Cong Chenhao, Kim Se Hyun, Li Xinlin
College of Mechanical and Electrical Engineering, Qingdao University, Qingdao 266071, China.
School of Flexible Electronics (SoFE) and Henan Institute of Flexible Electronics (HIFE), Henan University, 379 Mingli Road, Zhengzhou 450046, China.
J Colloid Interface Sci. 2025 Jan;677(Pt B):862-871. doi: 10.1016/j.jcis.2024.08.123. Epub 2024 Aug 16.
Two-dimensional metal-organic frameworks (2D MOFs) hold great promise as electrochemically active materials. However, their application in MOF nanocomposite electrodes in solution engineering is limited by structural self-stacking and imperfect conductive pathways. In this study, we used meso-tetra(4-carboxyphenyl) porphine (TCPP) with off-domain π-bonds to reconstitute Zn-TCPP (ZMOF) and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) through an interfacial modulation strategy involving electrostatic coupling and hydrogen bonding, creating a conductive composite with a nanosheet structure. The negatively charged PSS and ZMOF formed a three-dimensional interconnected conductive network with excellent interfaces. The positively charged PEDOT, fine tuned with the lamellar structure, established strong π-π stacking interactions between the porphyrin and thiophene rings. ZMOF also induced changes in the PEDOT chain structure, weakening PSS entanglement and enhancing charge-transport properties. The specific capacitance of the prepared supercapacitor was as high as 967.8 F g. Flexible supercapacitors produced on a large scale using dispensing printing technology exhibited an energy density of 1.85 μWh cm and a power density of 7.08 μW cm. This interfacial modulation strategy also exhibited excellent wearable properties, with 96 % capacitance retention at a 180° bending angle and stable cycling performance. This study presented a significant advancement in the functionalization of 2D materials, highlighting their potential for device-grade capacitive architectures.
二维金属有机框架材料（2D MOFs）作为电化学活性材料具有巨大潜力。然而，它们在溶液工程中的MOF纳米复合电极中的应用受到结构自堆叠和不完善导电途径的限制。在本研究中，我们使用具有离域π键的中位四（4 - 羧基苯基）卟啉（TCPP），通过涉及静电耦合和氢键的界面调制策略来重构Zn - TCPP（ZMOF）和聚（3,4 - 乙撑二氧噻吩）聚苯乙烯磺酸盐（PEDOT:PSS），从而创建具有纳米片结构的导电复合材料。带负电荷的PSS和ZMOF形成了具有优异界面的三维互连导电网络。带正电荷的PEDOT经层状结构微调后，在卟啉环和噻吩环之间建立了强大的π - π堆积相互作用。ZMOF还引起了PEDOT链结构的变化，减弱了PSS的缠结并增强了电荷传输性能。所制备超级电容器的比电容高达967.8 F g。使用点胶印刷技术大规模生产的柔性超级电容器表现出1.85 μWh cm的能量密度和7.08 μW cm的功率密度。这种界面调制策略还表现出优异的可穿戴性能，在180°弯曲角度下电容保持率为96%，且具有稳定的循环性能。本研究在二维材料功能化方面取得了重大进展，突出了它们在器件级电容架构中的潜力。
