Visible-Light-Initiated Acceptor-Less Dehydrogenation of Alcohols to Vicinal Diols over UiO-66(Zr): Surface Complexation and Role of Bridging Hydroxyl
Mingming Hao, Yuhuan Qin, Jiexuan Shen, Bingqing Wang, Zhaohui Li
Abstract
UiO-66(Zr), a UV-responsive Zr-based metal–organic framework (MOF) material, is found to be highly active and chemoselective for the visible-light-initiated acceptor-less dehydrogenation of alcohols to coproduce vicinal diols and H2. The formation of a colored surface alkoxide complex between alcohols and UiO-66(Zr) enables the UV-responsive UiO-66(Zr) to be active under visible light, while the formation of a hydrogen bond between alcohols and μ3-OH in UiO-66(Zr) is responsible for its high selectivity to vicinal diols. The elucidation of the involved mechanism will provide some guidance for the controllable syntheses of vicinal diols and aldehydes, a very important reaction in the chemical industry, via the visible-light-initiated acceptor-less dehydrogenation of alcohols.