Precisely Constructed Metal Sulfides with Localized Single‐Atom Rhodium for Photocatalytic C−H Activation and Direct Methanol Coupling to Ethylene Glycol

Abstract Although there are many studies on photocatalytic environmental remediation, hydrogen evolution, and chemical transformations, less success has been achieved for the synthesis of industrially important and largely demanded bulk chemicals using semiconductor photocatalysis, which holds great potential to drive unique chemical reactions that are difficult to implement by the conventional heterogeneous catalysis. The performance of semiconductors used for photochemical synthesis is, however, usually unsatisfactory due to limited efficiencies in light harvesting, charge‐carrier separation, and surface reactions. The precise construction of heterogeneous photocatalysts to facilitate these processes is an attractive but challenging goal. Here, single‐atom rhodium‐doped metal sulfide nanorods composed of alternately stacked wurtzite/zinc‐blende segments are successfully designed and fabricated, which demonstrate record‐breaking efficiencies for visible light‐driven preferential activation of C−H bond in methanol to form ethylene glycol (EG), a key bulk chemical used for the production of polyethylene terephthalate (PET) polymer. The wurtzite/zinc‐blende heterojunctions lined regularly in one dimension accelerate the charge‐carrier separation and migration. Single‐atom rhodium selectively deposited onto the wurtzite segment with photogenerated holes accumulated facilitates methanol adsorption and C−H activation. The present work paves the way to harnessing photocatalysis for bulk chemical synthesis with structure‐defined semiconductors.