Semiconducting metal-organic frameworks (MOFs) are emerging photocatalysts for H₂O₂ production via the two-electron oxygen reduction (2e-ORR) process. Whether and how the functional groups on MOF nodes affect the 2e-ORR mechanism and performance remain largely unexplored. Herein, we report that partial replacement of formate (-COO^-) by methoxy (-OMe) coordinated Zr-oxo cluster in UIO-66-NH₂ significantly enhances the H₂O₂ production. The introduction of -OMe groups induces lattice distortion in UIO-66-NH₂, resulting in the change of proton donor for the protonation of OOH* intermediate from -COOH to -NH₃⁺ with a lowered kinetic energy barrier. The -OMe groups with electron-donating effect contribute to promoted light harvesting and charge separation. The 2e-ORR selectivity of -OMe functionalized UIO-66-NH₂ is also enhanced, evidenced by rotating ring-disk electrode test and theoretical calculation. As a result, an improved photocatalytic ability is achieved with an H₂O₂ yield of 312.9 mM g⁻¹ h⁻¹, ~4.7 times higher than that of the original UIO-66-NH₂.

半导体金属有机框架 (MOF) 是通过双电子氧还原 (2e-ORR) 工艺生产H ₂ O _{2的新兴光催化剂。}MOF 节点上的功能组是否以及如何影响 2e-ORR 机制和性能在很大程度上仍未探索。在此，我们报告了在UIO-66-NH ₂中用甲氧基(-OMe) 配位的Zr-oxo 簇部分取代甲酸(-COO ^- )显着提高了H ₂ O ₂的产生。-OMe 基团的引入导致 UIO-66-NH ₂中的晶格畸变，导致用于 OOH* 中间体质子化的质子供体从 -COOH 变为 -NH ₃ ⁺具有较低的动能势垒。具有给电子效应的-OMe 基团有助于促进光捕获和电荷分离。_{-OMe功能化UIO-66-NH 2}的2e-ORR选择性也得到了增强，旋转环盘电极测试和理论计算证明了这一点。结果，以312.9 mM g ^-1 h ^-1的H ₂ O ₂产率实现了改进的光催化能力，比原始UIO-66-NH ₂高约4.7倍。