Three-dimensional (3D) network structure of metal–organic framework (MOF) can accommodate outstanding electrocatalysis performances, but always collapse during the conversion to active materials or applications process. How to maintain the 3D network when producing active species is of great importance for full application of MOF. Herein, a new MOF material, In[Co(CN)₆] (In-Co PBA) nanocubes, are firstly synthesized. Through a controlled low-temperature deligandation process, the In-Co PBA nanocubes are transformed to a novel In₂O₃@In-Co PBA quasi-MOF nanocubes, which basically retain the 3D porous structure of PBA but with in situ generated In₂O₃ nanoparticles inside. When used as CO₂RR electrocatalyst, such a novel cubic composite structure exhibits excellent performances with faradaic efficiency of 85% for formate at a potential of −0.96 V and with current density of 31.5 mA·cm⁻² at −1.32 V, surpassing most of the reported indium-based catalysts. The excellent performance can be attributed to the special composite structure, which provides not only active sites by In₂O₃ nanoparticles to catalyze CO₂RR, but also the 3D porous framework by quasi-MOF to accelerate gaseous exchange and electrolyte permeation and prevent the electrode choking. This work offers a new strategy for the design of post-transition metal catalysts and the structure design of quasi-MOF.

金属有机骨架 (MOF) 的三维 (3D) 网络结构可以提供出色的电催化性能，但在转化为活性材料或应用过程中总是会崩溃。如何在产生活性物种时保持3D网络对于MOF的全面应用具有重要意义。在此，首次合成了一种新型 MOF 材料 In[Co(CN) ₆ ] (In-Co PBA) 纳米立方体。通过受控的低温脱配过程，In-Co PBA 纳米立方体转变为新型 In ₂ O ₃ @In-Co PBA 准 MOF 纳米立方体，基本上保留了 PBA 的 3D 多孔结构，但原位生成了 In ₂ O ₃纳米粒子内部。用作 CO _{2 时}RR 电催化剂，这种新型立方复合结构表现出优异的性能，在 -0.96 V 的电位下对甲酸盐的法拉第效率为 85%，在 -1.32 V 下的电流密度为 31.5 mA·cm ^-2，超过了大多数报道的铟-基催化剂。优异的性能归功于特殊的复合结构，它不仅提供了 In ₂ O ₃纳米粒子的活性位点来催化 CO ₂ RR，而且还提供了 3D 多孔骨架，以加速气体交换和电解质渗透并防止电极窒息。这项工作为后过渡金属催化剂的设计和准MOF的结构设计提供了新的策略。