Direct selective transformation of greenhouse methane (CH4) 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 (CH4) to methanol using H2O2 as an oxidant. The superior catalytic activity can be attributed to the generation of high oxidation (NiIII═O) sites and selective C─H bond cleavage to generate •CH3 radicals on Ni centers, which can combine with •OH radicals to generate CH3OH.

Central European Institute of Technology Brno University of Technology Purkyňova 123 Brno 61200 Czech Republic

Department of Chemical and Petroleum Engineering University of Calgary 2500 University Drive NW Calgary Alberta T2N 1N4 Canada

Department of Experimental Physics Faculty of Science Palacký University Olomouc 17 listopadu 1192 12 Olomouc 77900 Czech Republic

Department of Inorganic Chemistry Faculty of Science Palacký University Olomouc Olomouc 77146 Czech Republic

Department of Mechanical and Mechatronics Engineering Waterloo Institute for Nanotechnology Materials Interface Foundry University of Waterloo Waterloo Ontario N2L 3G1 Canada

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