Lu Fei, Wang Jingnan, Chai Shanshan, Wang Yan, Yao Yongbin, Wang Xi
College of Physical Science and Technology and Microelectronics Industry Research Institute, Yangzhou University, Yangzhou, 225002, P. R. China.
Molecular Engineering Plus,College of Chemistry, Fuzhou University, Fuzhou, 350108, P. R. China.
Angew Chem Int Ed Engl. 2025 Jan 10;64(2):e202414719. doi: 10.1002/anie.202414719. Epub 2024 Oct 24.
Heterogeneous metal catalysts with bifunctional active sites are widely used in chemical industries. Although their improvement process is typically based on trial-and-error, it is hindered by the lack of model catalysts. Herein, we report an effective vacancy-pair capturing strategy to fabricate 12 heterogeneous binuclear-site catalysts (HBSCs) comprising combinations of transition metals on titania. During the synthesis of these HBSCs, proton-passivation treatment and step-by-step electrostatic anchorage enabled the suppression of single-atom formation and the successive capture of two target metal cations on the titanium-oxygen vacancy-pair site. Additionally, during acetylene hydrogenation at 20 °C, the HBSCs (e.g., PtPd-TiO) consistently generated more than two times the ethylene produced by their single-atom counterparts (e.g., Pd-TiO). Furthermore, the PtPd binuclear sites in PtPd-TiO were demonstrated to catalyze CH hydrogenation via a bifunctional active-site mechanism: initially CH chemisorb on the Pt site, then H dissociates and migrates from Pd to Pt, and finally hydrogenation occurs at the Pt-Pd interface.
具有双功能活性位点的多相金属催化剂在化学工业中广泛应用。尽管其改进过程通常基于反复试验，但由于缺乏模型催化剂而受到阻碍。在此，我们报告了一种有效的空位对捕获策略，用于制备12种多相双核位点催化剂（HBSCs），其由二氧化钛上的过渡金属组合而成。在这些HBSCs的合成过程中，质子钝化处理和逐步静电锚定能够抑制单原子的形成，并在钛氧空位对位点上连续捕获两种目标金属阳离子。此外，在20℃乙炔加氢过程中，HBSCs（如PtPd-TiO）产生的乙烯始终是其单原子对应物（如Pd-TiO）的两倍以上。此外，PtPd-TiO中的PtPd双核位点被证明通过双功能活性位点机制催化CH加氢：最初CH化学吸附在Pt位点上，然后H解离并从Pd迁移到Pt，最后在Pt-Pd界面发生加氢反应。
