Ren Ruirui, Bi Sa, Wang Linhong, Zhao Wuduo, Wei Donghui, Li Tiesheng, Xu Wenjian, Liu Minghua, Wu Yangjie
College of Chemistry, Zhengzhou University Zhengzhou 450001 P. R. China.
Henan Institute of Advanced Technology, Zhengzhou University Zhengzhou 450001 P. R. China.
RSC Adv. 2020 Jun 17;10(39):23080-23090. doi: 10.1039/d0ra02195d. eCollection 2020 Jun 16.
Tailoring the structures of catalysts and the arrangement of organic bimetallic catalysts are essential in both fundamental research and applications. However, they still impose enormous challenges such as size and active species distribution, ordered uniformity, and controllable composition, which are critical in determining their specific activities and efficiency. Herein, a novel terpyridine-based hetero-bimetallic Ni/Pd nanosheet supported on graphene oxide (denoted as GO@Tpy-Ni/Pd) was fabricated, which exhibited higher catalytic activity, substrate applicability and recyclability for the Suzuki coupling reaction under mild conditions. The catalytic mechanism was heterogeneous catalysis at the interface and the synergetic effect between Pd and Ni resulted in a little Ni(0)/Pd(0) cluster including Pd(ii)/Ni(ii) as a whole being formed through electron transfer on the catalytic surface. This phenomenon could be interpreted as the nanoscale clusters of Ni/Pd being the real active centre stabilized by the ligand and GO and the synergetic effect. The absorption and desorption of different substrates and products on Ni/Pd clusters, as calculated by DFT, was proved to be another key factor.
调整催化剂的结构以及有机双金属催化剂的排列在基础研究和应用中都至关重要。然而,它们仍然面临着诸如尺寸和活性物种分布、有序均匀性以及可控组成等巨大挑战,这些对于确定其比活性和效率至关重要。在此,制备了一种负载在氧化石墨烯上的新型基于三联吡啶的异质双金属Ni/Pd纳米片(表示为GO@Tpy-Ni/Pd),其在温和条件下对铃木偶联反应表现出更高的催化活性、底物适用性和可回收性。催化机理是界面处的多相催化,Pd和Ni之间的协同效应导致通过催化表面上的电子转移形成了一个包含Pd(ii)/Ni(ii)整体的少量Ni(0)/Pd(0)簇。这种现象可以解释为Ni/Pd的纳米级簇是由配体和GO以及协同效应稳定的真正活性中心。通过DFT计算得出,不同底物和产物在Ni/Pd簇上的吸附和解吸被证明是另一个关键因素。