Terpyridine-based Pd(ii)/Ni(ii) organometallic framework nano-sheets supported on graphene oxide-investigating the fabrication, tuning of catalytic properties and synergetic effects.

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.

Facile Fabrication of Ordered Component-Tunable Heterobimetallic Self-Assembly Nanosheet for Catalyzing "Click" Reaction.

How to maximize the number of desirable active sites on the surface of the catalyst and minimize the number of sites promoting undesirable side reactions is currently an important research topic. In this study, a new way based on the synergism to achieve the successful fabrication of an ordered heterobimetallic self-assembled monolayer (denoted as BMSAM) with a controlled composition and an excellent orientation of metals in the monolayer was developed. BMSAM consisting of phenanthroline and Schiff-base groups was prepared, and its novel heterobimetallic (Cu and Pd) self-assembled monolayer anchored in silicon (denoted as Si-Fmp-Cu-Pd BMSAM) with a controlled composition and a fixed position was fabricated and characterized by UV, cyclic voltammetry, Raman, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), X-ray diffraction (XRD), inductively coupled plasma atomic emission spectroscopy (ICP-AES), and water-drop contact angle (WDCA) analyses. The effects of Si-Fmp-Cu-Pd BMSAM on its catalytic properties were also systematically investigated using "click" reaction as a template by WDCA, XPS, SEM, XRD, ICP-AES and in situ Fourier transform infrared analyses in a heterogeneous system. The results showed that the excellent catalytic characteristic could be attributed to the partial (ordered or proper distance) isolation of active sites displaying high densities of specific atomic ensembles. The catalytic reaction mechanism of the click reaction interpreted that the catalytic process mainly occurred on the surface of the monolayer, internal active site (Pd) and rationalized that the Cu(I) species and Pd(0) reduced from the Cu(II) and Pd(II) catalyst were active species, which had a proper distance between two different metals. The cuprate-triazole intermediate and the palladium intermediate, whose production is the key step, should lie in a proper position between the copper and active palladium sites, with which the reaction rate of transmetalation would be improved to increase the amount of the undesired Sonogashira coupling product.