Zhao Bin, Liu Bohan, Han Ji, Sun Ruigang, Xu Haidong, Sun Yuanbo, Chen Guangrui, Shi Zhaohui, Liu Chenxu, Gao Yanjing, Zhang Mingjie, Zhang Song Lin, Yamauchi Yusuke, Guan Buyuan
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University Qianjin Street 2699 Changchun 130012 P. R. China
Key Lab of Groundwater Resources and Environment, Ministry of Education, Jilin University Changchun 130021 P. R. China.
Chem Sci. 2025 Jun 16. doi: 10.1039/d5sc02354h.
In virtue of the smooth mass transfer and unique physical properties enabled by the special three-dimensional (3D) interconnected network, bicontinuous porous functional materials have received extensive attention in catalysis, energy conversion, and cargo delivery. However, endowing materials with meticulous inner bicontinuous geometries and achieving precise control over the pore structures remain a huge challenge. Herein, we report a facile heterogeneous interface-induced topological phase transition method to obtain unbalanced double primitive architectural cobalt/nitrogen-doped (Co/N-doped) carbon particles. The rationally designed dual metal-organic framework (MOF)-derived composite particles retain the original 3D channel with a single primitive cubic structure inherited from their precursors after the pyrolysis process. Noteworthily, a new set of continuous channels with the same topological structure is introduced into the originally solid pore wall by utilizing local thermal stability differences at the heterogeneous interface of two isostructural MOFs. The two sets of channels possess different volumes, presenting an unbalanced bicontinuous structure similar to 3̄, with the Co-N active sites anchored on the derived thin pore walls. Benefiting from the high-efficiency mass transfer enabled by the 3D open channels of the bicontinuous structure and high surface utilization enabled by the local thin-wall nanotube structure, unbalanced bicontinuous structural Co/N-doped carbon catalysts exhibit enhanced electrocatalytic activity in the oxygen reduction reaction (ORR). The assembled Zn-air battery delivers high peak power density (215 mW cm) and large specific capacity (766 mA h g). This methodology provides new insights for universally constructing extra channels to achieve 3D periodic interpenetrating networks from the rational structural design and processing of porous materials with appropriate heterogeneous interfaces.
由于特殊的三维（3D）互连网络实现了顺畅的传质和独特的物理性质，双连续多孔功能材料在催化、能量转换和货物输送等领域受到了广泛关注。然而，赋予材料精细的内部双连续几何结构并实现对孔结构的精确控制仍然是一个巨大的挑战。在此，我们报道了一种简便的异质界面诱导拓扑相变方法，以获得不平衡双原始结构的钴/氮掺杂（Co/N掺杂）碳颗粒。经过合理设计的双金属有机框架（MOF）衍生复合颗粒在热解过程后保留了从前驱体继承的具有单一原始立方结构的原始3D通道。值得注意的是，利用两种同构MOF的异质界面处的局部热稳定性差异，在原本实心的孔壁中引入了一组具有相同拓扑结构的新连续通道。这两组通道具有不同的体积，呈现出类似于3̄的不平衡双连续结构，Co-N活性位点锚定在衍生的薄孔壁上。受益于双连续结构的3D开放通道实现的高效传质以及局部薄壁纳米管结构实现的高表面利用率，不平衡双连续结构的Co/N掺杂碳催化剂在氧还原反应（ORR）中表现出增强的电催化活性。组装的锌空气电池具有高峰值功率密度（215 mW cm）和大比容量（766 mA h g）。该方法为通过合理的结构设计和具有适当异质界面的多孔材料的加工普遍构建额外通道以实现3D周期性互穿网络提供了新的见解。
