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.

中文翻译：

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轻松制备有序成分可调异双金属自组装纳米片以催化“点击”反应

如何最大限度地增加催化剂表面所需活性位点的数量并最大限度地减少促进不良副反应的位点数量是目前的一个重要研究课题。在这项研究中，开发了一种基于协同作用的新方法，成功制造了具有受控成分和单层中金属良好取向的有序异质双金属自组装单层（表示为BMSAM ）。制备了由菲咯啉和席夫碱基团组成的BMSAM ，并制备了其成分可控、位置固定的新型异质双金属（Cu和Pd）自组装单分子层锚定在硅上（记为Si-Fmp-Cu-Pd BMSAM ）并通过紫外、循环伏安法、拉曼、X射线光电子能谱（XPS）、扫描电子显微镜（SEM）、X射线衍射（XRD）、电感耦合等离子体原子发射光谱（ICP-AES）和水滴表征接触角（WDCA）分析。以“点击”反应为模板，通过WDCA、XPS、SEM、XRD、ICP-AES和非均相体系中的原位傅里叶变换红外分析，系统研究了Si-Fmp-Cu-Pd BMSAM对其催化性能的影响。结果表明，优异的催化特性可归因于表现出高密度特定原子团簇的活性位点的部分（有序或适当距离）隔离。点击反应的催化反应机理解释了催化过程主要发生在单分子层表面、内部活性位点（Pd）上，并合理化了Cu(I)物种和Pd(0)从Cu(II)和Pd(0)还原的过程。 Pd(II)催化剂是活性物种，两种不同金属之间具有适当的距离。铜酸三唑中间体和钯中间体是生产的关键步骤，应位于铜和活性钯位点之间的适当位置，这样可以提高金属转移反应速率，从而增加不需要的 Sonogashira 偶联的量产品。