Titanium-based metal-organic frameworks (MOFs) have received more attention for CO₂ capture and utilization because of their excellent stability and photoactivity, but they are limited by the high reactivity of Ti(IV) during their crystallization. Herein, we propose a titanium modulation strategy for rationally designing a series of Ti-modulated MOFs (TiM-MOFs and SNNU-90–92). Ti(IV) as a modulator changed the coordination equilibrium and regulated the inorganic building blocks from Co₄(OH)₄(COO)₄ to Co_3-xTi_xO(COO)₆ and Co_6-xTi_x(O/OH)₆(COO)₆, triggering a continuous structure transformation with high-quality single crystal. The CO₂ adsorption, separation, and catalytic properties of TiM-MOFs in flue gas were significantly improved over those of monometallic MOFs. Remarkably, TiM-MOFs can effectively convert flue gas to cyclic carbonates via photocatalysis with excellent yield and turnover efficiency, making them superior to all state-of-the-art MOF catalysts. Rational structure modulation, controllable Ti(IV) content, and extortionary chemical conversion efficiency make TiM-MOFs ideal candidates for the comprehensive utilization of flue gas.

钛基金属有机框架(MOF)因其优异的稳定性和光活性而在CO ₂捕获和利用方面受到越来越多的关注，但它们在结晶过程中受到Ti(IV)的高反应性的限制。在此，我们提出了一种钛调制策略，用于合理设计一系列钛调制MOF（TiM-MOF和SNNU-90-92）。 Ti(IV) 作为调节剂改变了配位平衡，并将无机结构单元从 Co ₄ (OH) ₄ (COO) ₄调节为 Co _{3- x} Ti _x O(COO) ₆和 Co _{6- x} Ti _x (O/ OH) ₆ (COO) ₆，引发高质量单晶的连续结构转变。 TiM-MOFs对烟气中CO ₂的吸附、分离和催化性能较单金属MOFs显着提高。值得注意的是，TiM-MOF 可以通过光催化有效地将烟气转化为环状碳酸酯，具有优异的产率和周转效率，使其优于所有最先进的 MOF 催化剂。合理的结构调控、可控的Ti(IV)含量和极高的化学转化效率使TiM-MOFs成为烟气综合利用的理想选择。