Herein, DUT-67/RGO aerogel photocatalysts with three-dimensional (3D) macroscopic morphology were first prepared by a facile hydrothermal and freeze-drying process. It was observed that DUT-67 endowed aerogels with strong adsorption/activation capacity for CO₂ molecules. Besides, RGO not only dispersed DUT-67 as a macroscopic carrier, but also improved the utilization rate of light energy. The high conductivity of RGO and the strong interaction with DUT-67 enhanced the electron coupling effect, which was conducive to the separation of carriers. 15D/R achieved near 99.6% selectivity at the gas–solid interface for UV–Vis light-driven CO₂ reduction to CO, with a rate of 42.41 μmol·g⁻¹. The adsorption behavior of products at the interface and formation process of intermediates were monitored based on CO-TPD and in situ Fourier transform infrared spectra. The extremely high selectivity for CO came from the weak adsorption of CO on the surface of 15D/R and formation of CH₄ required more complex intermediates.

在此，首先通过简便的水热和冷冻干燥工艺制备了具有三维 (3D) 宏观形态的 DUT-67/RGO 气凝胶光催化剂。观察到DUT-67赋予气凝胶对CO ₂分子的强吸附/活化能力。此外，RGO不仅分散了DUT-67作为宏观载体，还提高了光能的利用率。RGO的高电导率以及与DUT-67的强相互作用增强了电子耦合效应，有利于载流子的分离。15D/R 在气固界面上实现了接近 99.6% 的 UV-Vis 光驱动 CO ₂还原为 CO 的选择性，速率为 42.41 μmol·g ^-1. 基于CO-TPD和原位傅里叶变换红外光谱监测产物在界面的吸附行为和中间体的形成过程。对 CO 的极高选择性来自于 CO 在 15D/R 表面的弱吸附以及 CH ₄的形成需要更复杂的中间体。