Achieving metal-like catalysis from semiconductor for on-surface synthesis.

Free of posttransfer, on-surface synthesis (OSS) of single-atomic-layer nanostructures directly on semiconductors holds considerable potential for next-generation devices. However, due to the high diffusion barrier and abundant defects on semiconductor surfaces, extended and well-defined OSS on semiconductors has major difficulty. Furthermore, given semiconductors' limited thermal catalytic activity, initiating high-barrier reactions remains a significant challenge. Herein, using TiO 2 (011) as a prototype, we present an effective strategy for steering the molecule adsorption and reaction processes on semiconductors, delivering lengthy graphene nanoribbons with extendable widths. By introducing interstitial titanium (Ti int ) and oxygen vacancies (O v ), we convert TiO 2 (011) from a passive supporting template into a metal-like catalytic platform. This regulation shifts electron density and surface dipoles, resulting in tunable catalytic activity together with varied molecule adsorption and diffusion. Cyclodehydrogenation, which is inefficient on pristine TiO 2 (011), is markedly improved on Ti int /O v -doped TiO 2 . Even interribbon cyclodehydrogenation is achieved. The final product's dimensions, quality, and coverage are all controllable. Ti int doping outperforms O v in producing regular and prolonged products, whereas excessive Ti int compromises molecule landing and coupling. This work demonstrates the crucial role of semiconductor substrates in OSS and advances OSS on semiconductors from an empirical trial-and-error methodology to a systematic and controllable paradigm.