The on-surface polymerization of 1,3,6,8-tetrabromopyrene (Br4 Py) on Cu(111) and Au(111) surfaces under ultrahigh vacuum conditions was investigated by a combination of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations. Deposition of Br4 Py on Cu(111) held at 300 K resulted in a spontaneous debromination reaction, generating the formation of a branched coordination polymer network stabilized by C-Cu-C bonds. After annealing at 473 K, the C-Cu-C bonds were converted to covalent C-C bonds, leading to the formation of a covalently linked molecular network of short oligomers. In contrast, highly ordered self-assembled two-dimensional (2D) patterns stabilized by both Br-Br halogen and Br-H hydrogen bonds were observed upon deposition of Br4 Py on Au(111) held at 300 K. Subsequent annealing of the sample at 473 K led to a dissociation of the C-Br bonds and the formation of disordered metal-coordinated molecular networks. Further annealing at 573 K resulted in the formation of covalently linked disordered networks. Importantly, we found that the chosen substrate not only plays an important role as catalyst for the Ullmann reaction, but also influences the formation of different types of intermolecular bonds and thus, determines the final polymer network morphology. DFT calculations further support our experimental findings obtained by STM and XPS and add complementary information on the reaction pathway of Br4 Py on the different substrates.
The epitaxial growth of graphene
on catalytically active metallic surfaces via chemical vapor deposition (CVD) is known
to be one of the most reliable routes toward high-quality large-area
graphene. This CVD-grown graphene is generally coupled to its metallic
support resulting in a modification of its intrinsic properties. Growth
on oxides is a promising alternative that might lead to a decoupled
graphene layer. Here, we compare graphene on a pure metallic to graphene
on an oxidized copper surface in both cases grown by a single step
CVD process under similar conditions. Remarkably, the growth on copper
oxide, a high-k dielectric material, preserves the intrinsic properties
of graphene; it is not doped and a linear dispersion is observed close
to the Fermi energy. Density functional theory calculations give additional
insight into the reaction processes and help explaining the catalytic
activity of the copper oxide surface.
The adsorption behaviour as well as the influence of bromine substituents on the formation of highly-ordered two-dimensional structures of pyrene derivatives on Au(111) are studied by a combination of scanning tunnelling microscopy (STM) and density functional theory (DFT) calculations.
A facile approach for the preparation of a novel hybrid material containing graphene and an inorganic semiconducting material, cadmium sulfide quantum dots (CdS QDs), is demonstrated for the first time. First, amino-functionalized CdS QDs were prepared by modifications of the kinetic trapping method. Then, pristine graphite was oxidized and exfoliated to obtain graphene oxide nanosheets (GONS), which were then acylated with thionyl chloride to introduce acyl chloride groups on their surface. Subsequently, immobilization of the CdS QDs on the GONS surface was achieved through an amidation reaction between the amino groups located on the CdS QDs surface and the acyl chloride groups bound to the GONS surface. Fourier transform infrared spectroscopy (FT-IR), (1)H nuclear magnetic resonance ((1)H-NMR), x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), and energy dispersive x-ray (EDX) spectroscopy were employed to investigate the changes in the surface functionalities, while high resolution transmission electron microscopy (HR-TEM) and field emission scanning electronic microscopy (FE-SEM) were used to study the morphologies and distribution of the CdS QDs on the GONS surface. Thermogravimetric analysis (TGA) was employed to characterize the weight loss of the samples on heating. Photoluminescence (PL) measurements were used to study the optical properties of the prepared CdS QDs and the CdS-graphene hybrid material.
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