Dual Covalent and Spatial Sulfur Confinement in NTDA-Derived Graphene Frameworks for Photo/Biocatalytic Methanol Production and Oxathiolane Synthesis

Integrating heterogeneous photocatalysis with enzymatic redox transformations remains challenging due to inefficient cofactor regeneration and limited charge transport across hybrid interfaces. Herein, we report a sulfur-mediated covalent triazine framework (S/M-CTF) assembled by the cyclotrimerization of a 1,4,5,8-naphthalene tetracarboxylic dianhydride (NTDA)-derived monomer and in situ cyclotrimerization onto tridoped graphene sheets (G) enriched with boron, selenium, and nitrogen, fabricating a hybrid architecture (S/M-CTFs@G) with enhanced charge carrier transport and heterogeneous electronic structure. Spatial encapsulation and covalent anchoring afford efficient photoinduced 1,4-NADH regeneration (91.31 ± 0.17%, TON = 14.38, TOF = 14.38 h–1, AQY = 4.27% with a rate of 1835.8 μmol g–1h–1) and selective methanol production (26.84 ± 0.75 μM, TON = 4.22, TOF = 4.22 h–1, STMe = 0.0054% with a rate of 536.77 μmol g–1h–1) driven by Saccharomyces cerevisiae-derived alcohol dehydrogenase (ADH), facilitating enzymatic reduction under mild conditions. Beyond cofactor cycling and enzymatic reduction, the confined system also supports the synthesis of sulfur-containing heterocycles, namely a pharmaceutically relevant oxathiolane scaffolds (98.40 ± 0.02%, TON = 49.0, TOF = 6.12 h–1). Collectively, these results establish tridoped graphene-supported, sulfur confined CTFs as a versatile platform for the synergistic photobiocatalytic upgrading of C1 feedstocks.