Achieving metal- like catalysis from semiconductors for on- surface synthesis

• 成果类型: Article
• 署名作者: E., Wenlong; Yi, Wei; Ding, Honghe; Zhu, Junfa; Rosei, Federico; Yang, Xueming; Yu, Miao
• 署名单位: Chinese Academy of Sciences; Dalian Institute of Chemical Physics, CAS; Chinese Academy of Sciences; University of Chinese Academy of Sciences, CAS; Harbin Institute of Technology; Chinese Academy of Sciences; University of Science & Technology of China, CAS; University of Trieste; Southern University of Science & Technology; University of Electronic Science & Technology of China
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-12785
• DOI: 10.1073/pnas.2408919121
• 发表日期: 2024-09-10
• 关键词: graphene nanoribbons; electronic-structure; polymerization

摘要

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 TiO2(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 (Tiint) and oxygen vacancies (Ov), we convert TiO2(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 TiO2(011), is markedly improved on Tiint/Ov- doped TiO2. Even interribbon cyclodehydrogenation is achieved. The final product's dimensions, quality, and coverage are all controllable. Ti int doping outperforms Ov 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.