Partial Thermal Condensation Mediated Synthesis of High‐Density Nickel Single Atom Sites on Carbon Nitride for Selective Photooxidation of Methane into Methanol

Abstract Direct selective transformation of greenhouse methane (CH 4 ) to liquid oxygenates (methanol) can substitute energy‐intensive two‐step (reforming/Fischer–Tropsch) synthesis while creating environmental benefits. The development of inexpensive, selective, and robust catalysts that enable room temperature conversion will decide the future of this technology. Single‐atom catalysts (SACs) with isolated active centers embedded in support have displayed significant promises in catalysis to drive challenging reactions. Herein, high‐density Ni single atoms are developed and stabilized on carbon nitride (NiCN) via thermal condensation of preorganized Ni‐coordinated melem units. The physicochemical characterization of NiCN with various analytical techniques including HAADF‐STEM and X‐ray absorption fine structure (XAFS) validate the successful formation of Ni single atoms coordinated to the heptazine‐constituted CN network. The presence of uniform catalytic sites improved visible absorption and carrier separation in densely populated NiCN SAC resulting in 100% selective photoconversion of (CH 4 ) to methanol using H 2 O 2 as an oxidant. The superior catalytic activity can be attributed to the generation of high oxidation (Ni III ═O) sites and selective C─H bond cleavage to generate •CH 3 radicals on Ni centers, which can combine with •OH radicals to generate CH 3 OH.