The efficient C–H polarization is the prerequisite for the low-temperature photocatalytic CH₄ conversion, which is restricted by the poor C–H stretching ability of short-distance adjacent lattice atoms. Here, a frustrated Lewis pair (FLP) composed of doped metal in TiO₂ as Lewis acid (LA) and neighboring Ti–OH as Lewis base (LB) with a long distance (0.31–0.37 nm) was designed through DFT calculation and fabricated by hydrogenation treatment of metal-doped TiO₂–SiO₂ with macroporous-mesoporous structure. Benefitting from the long LA-LB distance and matched acid-base intensity, hydrogenated Ga-doped composite achieves superior C–H stretching with a high photocatalytic CH₄ conversion rate (139 μmol g⁻¹ h⁻¹). The photo-irradiation causes electron excitation from Ga to Ti–OH according to the time-dependent DFT calculation and in situ EPR analysis, which promotes the formation and coupling of ·CH₃. This work provides a key underpinning for regulating the characteristics of FLP for C–H activation and C–C coupling via light irradiation.

有效的C-H极化是低温光催化CH ₄转化的先决条件，但受限于短距离相邻晶格原子的C-H伸缩能力差。_{在这里，通过DFT计算设计了由TiO 2}中的掺杂金属作为路易斯酸（LA）和相邻的Ti-OH作为路易斯碱（LB）组成的受挫路易斯对（FLP），具有长距离（0.31-0.37 nm）并制造通过氢化处理具有大孔-中孔结构的金属掺杂的TiO ₂ -SiO _{2 。}得益于较长的 LA-LB 距离和匹配的酸碱强度，氢化 Ga 掺杂复合材料实现了优异的 C-H 拉伸和高光催化 CH ₄转化率（139 μmol g^-1 h ^-1 )。根据时间相关的DFT计算和原位EPR分析，光辐照引起从Ga到Ti-OH的电子激发，这促进了·CH ₃的形成和耦合。这项工作为通过光照射调节 FLP 的 C-H 活化和 C-C 耦合特性提供了关键基础。