Electron-Delocalization-Stabilized Photoelectrocatalytic Coupling of Methane by NiO-Polyoxometalate Sub-1 nm Heterostructures

The oxidative coupling of methane to C2 oxygenates merits great scientific and technological potential yet remains a challenge due to its inferior selectivity. Subnanomaterials (SNMs) with p-n-p-n-type heteroconstructions feature enhanced external field coupling properties and tunable electronic structures, serving as promising catalysts for the selective partial oxidation of methane. Here we develop NiO-polyoxometalate (POM) subnanocoils with a thickness of 1.8 nm, showing excellent catalytic activity toward photoelectrochemical coupling of methane into a C2 product under mild conditions (1 bar, 25 degrees C) with a notable productivity (up to 4.48 mmol g(cat)(-1) h(-1)) and a high selectivity (>99%). Under photoelectrochemical coupling, C-H bonds can be activated by NiO, and the resulted *COOH intermediates are stabilized by the delocalized electrons in POM clusters. The contiguous active sites of NiO and POM at the molecular level allow the in situ coupling of *COOH into oxalate. This work points out an economic way for the oxidation of methane under mild conditions and may enlighten the design of functional SNMs from fundamental standpoints.

Automated summary

By developing NiO-polyoxometalate subnanocoils, researchers achieved efficient catalysis of methane through photoelectrochemical coupling to C2 products under mild conditions. This offers an economical approach for methane oxidation and may inspire the design of functional subnanomaterials.