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

Abstract 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.