Hydrogen-bond-assisted supramolecular assembly of 1,3,5-tris(5-carboxyamyloxy)benzene at the liquid-solid interface: an scanning tunneling microscopy study.

The well-ordered self-assembled structure of 1,3,5-tris(5-carboxyamyloxy)benzene (TCAB) on Au(111) has been studied by electrochemical scanning tunneling microscopy (ECSTM) in HClO4 solution. Close examination indicates that the complex supramolecular network is formed by the TCAB molecules with flat-lying adsorption geometry and mainly stabilized by the hydrogen bonding interactions between carboxyl groups, except for the molecule-substrate interactions. It is particularly noteworthy that two types of hydrogen bonds, the dimers and tetramers of carboxyl group, coexist at the interface to balance the molecule-molecule and molecule-substrate interactions as well as to minimize the surface energy. Interestingly, the propeller-like motifs in STM image are fabricated by the bent alkoxy chains from four neighboring molecules respectively, bonded together by the cyclic carboxyl group tetramers. Moreover, there are two propellers in one lattice of TCAB adlayer, rotating in the clockwise and counterclockwise directions, respectively. Careful inspection shows that two structure domains of the TCAB adlayer are mirror images of each other since the molecular self-organization breaks the reflection symmetry of the substrate underneath. Our results give a good example of the flexibility adopted by alkyl chains functionalized by carboxyl group for the supramolecular assemblies at the liquid-solid interface.

Enhancing CO2 methanation over a metal foam structured catalyst by electric internal heating.

We develop an electric internal heating method based on a Ni-foam structured catalyst for CO2 methanation, in which the Joule heat generated by electric current passing through the catalyst drives the reaction. Compared with the conventional external heating method, EIH significantly enhances the catalytic activity and anti-poisoning ability of the catalyst.

Scanning tunneling microscopy investigation of a supramolecular self-assembled three-dimensional chiral prism on a Au(111) surface.

Spontaneous symmetry-breaking of a racemic mixture of supramolecular triginal prisms into chiral domains on a Au(111) surface is observed by scanning tunneling microscopy (STM). High-resolution STM analysis enables the structural aspects of each enantiomeric domain to be elucidated. The ability to resolve chirality on achiral surfaces has potential applications in heterogeneous stereoselective synthesis and catalysis.

TNT adsorption on Au(111): electrochemistry and adlayer structure.

Electrochemistry and adlayer structure of trinitrotoluene (TNT) on an Au(111) electrode were investigated using cyclic voltammetry and in situ electrochemical scanning tunneling microscopy (ECSTM).

Light-induced structural transformation in self-assembled monolayer of 4-(amyloxy)cinnamic acid investigated with scanning tunneling microscopy.

UV light irradiation effect on the structural transformation in a self-assembled monolayer of 4-(amyloxy)cinnamic acid (AOCA) on Au(111) has been investigated by using electrochemical scanning tunneling microscopy (ECSTM), cyclic voltammetry, and infrared (IR) spectroscopy. A well-defined 4-(amyloxy)cinnamic acid adlayer with a (4 x 11) symmetry was first prepared on Au(111). After UV-light irradiation onto the adlayer, a new adlayer is observed with different molecular arrangement and a symmetry of (5 x 8). On the basis of the results from high-resolution STM image and photochemical reaction, a dimerizaion of AOCA molecules in the adlayer with structural transformation is concluded. Schematic models have been proposed for the unirradiated and irradiated adlayers, respectively. The direct evidence at molecular level about photodimerization of cinnamic acid on metal substrate is presented.

Donor/acceptor complex of triphenylene and trinitrotoluene on Au(111): a scanning tunneling microscopy study.

The co-adsorption of trinitrotoluene (TNT), a typical π-electron acceptor, and triphenylene (TP), a typical π-electron donor, on a Au(111) surface was investigated by in situ Electrochemical Scanning Tunneling Microscopy (ECSTM). DFT calculations proved that parallelly stacked and well-overlapped TP and TNT molecules can form Donor-Acceptor dyads through intermolecular π-π charge transfer, which agree well with the experimental results in the present work.

Adlayer structures of aza- and/or oxo-bridged calix[2]arene[2]triazines on Au(111) investigated by scanning tunneling microscopy (STM).

The adlayers formed by a series of aza- and/or oxo-bridged calix[2]arene[2]triazines on Au(111) surfaces were investigated by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. 1,3-Alternate configurations of these molecules are preserved on gold surfaces as in their three-dimensional crystals. STM images show that the cavity sizes of these molecules are finely tuned by substituting the bridging nitrogen atom with oxygen atoms, which change the strengths and densities of the intermolecular hydrogen bonds. Hydrogen bond interaction influences the molecular orientation and conformation in the adlayers, and it plays a key role in the formation of these two-dimensional supramolecular architectures. Coadsorption of calix[2]arene[2]triazine with 1,3,5-tris(5-carboxyamyloxy)benzene (TCAB) intervenes with the intermolecular hydrogen bond formations among the calix[2]arene[2]triazine molecules and consequently causes a conformational transition of the calixarene molecules from rhombic to square. These results demonstrate the role of hydrogen bonds in molecular assembly formations.

Scanning tunneling microscopy of the formation, transformation, and property of oligothiophene self-organizations on graphite and gold surfaces.

Two alkyl-substituted dual oligothiophenes, quarterthiophene (4T)-trimethylene (tm)-octithiophene (8T) and 4T-tm-4T, were used to fabricate molecular structures on highly oriented pyrolytic graphite and Au(111) surfaces. The resulted structures were investigated by scanning tunneling microscopy. The 4T-tm-8T and 4T-tm-4T molecules self-organize into long-range ordered structures with linear and/or quasi-hexagonal patterns on highly oriented pyrolytic graphite at ambient temperature. Thermal annealing induced a phase transformation from quasi-hexagonal to linear in 4T-tm-8T adlayer. The molecules adsorbed on Au(111) surface in randomly folded and linear conformation. Based on scanning tunneling microscopy results, the structural models for different self-organizations were proposed. Scanning tunneling spectroscopy measurement showed the electronic property of individual molecules in the patterns. These results are significant in understanding the chemistry of molecular structure, including its formation, transformation, and electronic properties. They also help to fabricate oligothiophene assemblies with desired structures for future molecular devices.

C-H...F hydrogen bonding: the origin of the self-assemblies of bis(2,2'-difluoro-1,3,2-dioxaborine).

The effect of the molecular structure on the self-assembly of specially designed two-core 1,3,2-dioxaborines has been studied with various techniques. It was found that the molecules spontaneously adsorbed on HOPG surfaces and self-organized into well-ordered two-dimensional (2D) monolayers. The structural details of the 2D assemblies were investigated by scanning tunneling microscopy (STM). From X-ray analysis of the corresponding three-dimensional (3D) crystal and from theoretical calculation, we were able to reveal the driving force behind the specific self-assembly. The C-H...F hydrogen bonding between the ortho carbon of the phenyl ring and the fluorine of the BF2 group plays an important role in the formation of the adlayers. The different electron affinities and geometries of the molecules affect the intermolecular interactions which further lead to different properties in the bulk materials.

Functionalized carbon nanotubes as sensitive materials for electrochemical detection of ultra-trace 2,4,6-trinitrotoluene.

This report demonstrates a novel electrochemical method for fast and sensitive detection of ultra-trace 2,4,6-trinitrotoluene (TNT) based on modified electrodes by functionalized MWCNTs. To fabricate new kind of functionalized MWCNTs material sensitive to TNT, our work first theoretically investigated the interaction between triphenylene (TP) and TNT by calculating their electrostatic potentials, and secondly characterized this interaction by the fluorescence spectra. The functionalized MWCNTs of TP-MWCNTs were thoroughly characterized by fluorescence and UV-visible spectra, and by analysing these results, the interaction between TP and MWCNTs was also examined. Electrochemical experiment suggests, compared to MWCNTs- and TP- modified electrodes, TP-MWCNTs-modified electrodes result in both fast response and enhanced sensitivity to TNT detection. These results show the attachment of TP on MWCNTs leads to better sensing unit with more receptor site to TNT, associated with the coordinative recognition of TP and MWCNTs to TNT, finally result in the improvement of response and sensitivity. And this improved recognition process is attributed to the geometric and electrostatic complementarity between TP and TNT. The present study demonstrates TP-MWCNTs-modified electrode holds promising and important implications for the detection of ultra-trace TNT.