Efficient Photocatalytic Synthesis of Hydrogen Peroxide Facilitated by Triptycene-Based 3D Covalent Organic Frameworks

Covalent organic frameworks (COFs) are widely studied for hydrogen peroxide (H2O2) photosynthesis, with 3D COFs standing out for their porous structures and chemical stability. However, the difficult preparation of 3D COFs and the low efficiency in separating photo-generated electrons and holes (e- and h+) limits the efficient production of H2O2. In this study, two kinds of [6+3] 3D COFs (XJU-1, XJU-2) with significant charge separation, achieving record-breaking H2O2 photocatalysis rates of 34 777 and 11 922 mu mol g(-1) h(-1), respectively. XJU-1's superior efficiency stems from its larger pores, enhancing material transport and oxygen (O2) activation. Experimental and theoretical studies have demonstrated that triptycene monomers achieve significant charge separation toward triazine via imine bonds. Moreover, the dimer's smaller singlet-triplet energy gap (triangle ES-T) and triptycene's orthogonal configuration enhance singlet oxygen (1O2) production, enabling multiple H2O2 generation pathways. Ultimately, through the oxygen reduction reaction (ORR) pathway, rapid generation of H2O2 can be achieved at multiple catalytic sites. XJU-1 mainly follows a mixed pathway involving 1e--ORR and 2e--ORR, and XJU-2 primarily follows the 2e--ORR pathway, respectively. These open the door of triptycene-based 3D COFs applied in continuous, efficient, and stable photosynthesis of H2O2.