Tailoring the Cu(100) work function by substituted benzenethiolate self-assembled monolayers

The structure and electronic interface properties of five differently substituted benzenethiol based self-assembled monolayers (SAMs) on Cu(100) have been studied by means of low energy electron diffraction, thermal desorption spectroscopy, X-ray absorption spectroscopy (NEXAFS), and UV photoelectron spectroscopy. Because highly ordered SAMs are formed of which lateral density had been precisely determined, effective molecular dipole moments were derived from the measured work function shifts. These values are compared with gas phase dipole moments computed by quantum chemical calculations for the individual thiol molecules considering the molecular orientation determined from NEXAFS data. Furthermore, this comparison yields clear evidence for a coverage dependent depolarization effect of the adsorbed molecules within the SAMs.     

Nanoporous Pt@Au(x)Cu(100-x) by hydrogen evolution assisted electrodeposition of Au(x)Cu(100-x) and galvanic replacement of Cu with Pt: electrocatalytic properties

Electrodeposition of high-surface-area nanoporous Au-Cu foams under conditions of hydrogen codeposition is studied. The honeycomb-like Au(x)Cu(100-x) foams with 0 ≤ x ≤ 100 are electrodeposited by controlling the amount of corresponding ions in the solution. The amount of metal ions in deposited films follows that in used electrolytes. Compared to monometallic foams, the Au(x)Cu(100-x) structures are characterized by smaller ligament or particle sizes (less than 10 nm) and improved stability. The addition of even a small amount of Cu to the Au matrix is found to dramatically improve the stability of the structure in air environment or an acidic medium. Pt@Au(x)Cu(100-x) structures are formed by the galvanic displacement of Cu from Au(x)Cu(100-x) templates. During the displacement of Cu by Pt, Au serves as a buffer, decreasing mechanical stresses and preventing the detachment of the foam from the substrate. The surface ratio of Pt to Au atoms is controlled by adjusting the amount of Cu in the template. Pt@Au(x)Cu(100-x) electrodes are investigated as novel electrocatalysts for methanol oxidation in alkaline media. The Au-enriched surfaces show higher catalytic activity toward methanol oxidation, while the electrodes with a higher amount of Pt are more stable.     

Plasma-assisted oxidation of Cu(100) and Cu(111)

Oxidized copper surfaces have attracted significant attention in recent years due to their unique catalytic properties, including their enhanced hydrocarbon selectivity during the electrochemical reduction of CO₂. Although oxygen plasma has been used to create highly active copper oxide electrodes for CO₂RR, how such treatment alters the copper surface is still poorly understood. Here, we study the oxidation of Cu(100) and Cu(111) surfaces by sequential exposure to a low-pressure oxygen plasma at room temperature. We used scanning tunnelling microscopy (STM), low energy electron microscopy (LEEM), X-ray photoelectron spectroscopy (XPS), near edge X-ray absorption fine structure spectroscopy (NEXAFS) and low energy electron diffraction (LEED) for the comprehensive characterization of the resulting oxide films. O₂-plasma exposure initially induces the growth of 3-dimensional oxide islands surrounded by an O-covered Cu surface. With ongoing plasma exposure, the islands coalesce and form a closed oxide film. Utilizing spectroscopy, we traced the evolution of metallic Cu, Cu₂O and CuO species upon oxygen plasma exposure and found a dependence of the surface structure and chemical state on the substrate''s orientation. On Cu(100) the oxide islands grow with a lower rate than on the (111) surface. Furthermore, while on Cu(100) only Cu₂O is formed during the initial growth phase, both Cu₂O and CuO species are simultaneously generated on Cu(111). Finally, prolonged oxygen plasma exposure results in a sandwiched film structure with CuO at the surface and Cu₂O at the interface to the metallic support. A stable CuO(111) surface orientation is identified in both cases, aligned to the Cu(111) support, but with two coexisting rotational domains on Cu(100). These findings illustrate the possibility of tailoring the oxidation state, structure and morphology of metallic surfaces for a wide range of applications through oxygen plasma treatments.

A low-pressure oxygen plasma oxidized Cu(100) and Cu(111) surfaces at room temperature. The time-dependent evolution of surface structure and chemical composition is reported in detail for a range of exposure times up to 30 min.     

Structure and bonding of alkanethiols on Cu(111) and Cu(100)

The local structure of the sulfur atom of methanethiolate and ethanethiolate on the Cu(111) and Cu(100) surfaces was investigated from first principles employing the periodic supercell approach in the framework of density functional theory. On the 111 surface, we investigated the (square root 3 x square root 3)R30 degrees and (2 x 2) structures, whereas on the 100 surface, we investigated the p(2 x 2) and c(2 x 2) structures. The landscape of the potential energy surface on each metal surface presents distinctive features that explain the local adsorption structure of thiolates found experimentally. On the Cu(111) surface, the energy difference between the hollow and bridge sites is only 3 kcal/mol, and consequently, adsorption sites ranging from the hollow to the bridge site were observed for increasing surface coverages. On the Cu(100) surface, there is a large energy difference of 12 kcal/mol between the hollow and bridge sites, and therefore, only the 4-fold coordination was observed. The high stabilization of thiolates on the hollow site of Cu(100) may be the driving force for the pseudosquare reconstruction observed experimentally on Cu(111). Density of states analysis and density difference plots were employed to characterize the bonding on different surface sites. Upon interaction with the metal d bands, the pi* orbital of methanethiolate splits into several peaks. The two most prominent peaks are located on either edge of the metal d band. They correspond to bonding and antibonding S-Cu interactions. In the case of ethanethiolate, all the back-bonds are affected by the surface bonding, leading to alternating regions of depletion and accumulation of charge in the successive bonds.     

STM Images of Individual Porphyrin Molecules on Cu(100) and Cu(111) Surfaces

Simply sublime! Samples of monomeric and dimeric zinc porphyrins were sublimed onto a Cu surface under ultrahigh vacuum conditions. Images obtained by scanning tunneling microscopy at room and low temperature (98 K) show features attributed to individual porphyrin molecules with excellent resolution. In the case of the (relatively large) linear dimer shown, two distinct conformations were detected on a surface with low coverage area. R=CH₂CH₂COOCH₃.     

Probing enantioselectivity on chirally modified Cu(110), Cu(100), and Cu(111) surfaces

Temperature programmed desorption methods have been used to probe the enantioselectivity of achiral Cu(100), Cu(110), and Cu(111) single crystal surfaces modified by chiral organic molecules including amino acids, alcohols, alkoxides, and amino-alcohols. The following combinations of chiral probes and chiral modifiers on Cu surfaces were included in this study: propylene oxide (PO) on L-alanine modified Cu(110), PO on L-alaninol modified Cu(111), PO on 2-butanol modified Cu(111), PO on 2-butoxide modified Cu(100), PO on 2-butoxide modified Cu(111), R-3-methylcyclohexanone (R-3-MCHO) on 2-butoxide modified Cu(100), and R-3-MCHO on 2-butoxide modified Cu(111). In contrast with the fact that these and other chiral probe/modifier systems have exhibited enantioselectivity on Pd(111) and Pt(111) surfaces, none of these probe/modifier/Cu systems exhibit enantioselectivity at either low or high modifier coverages. The nature of the underlying substrate plays a significant role in the mechanism of hydrogen-bonding interactions and could be critical to observing enantioselectivity. While hydrogen-bonding interactions between modifier and probe molecule are believed to induce enantioselectivity on Pd surfaces (Gao, F.; Wang, Y.; Burkholder, L.; Tysoe, W. T. J. Am. Chem. Soc. 2007, 129, 15240-15249), such critical interactions may be missing on Cu surfaces where hydrogen-bonding interactions are believed to occur between adjacent modifier molecules, enabling them to form clusters or islands.     

Reactions of some bromofluorobenzenes with copper(I) benzenethiolate

The reactions of copper(I) benzenethiolate with some bromofluorobenzenes have resulted in the replacement of the bromine by a phenylthio group. Combinations of this method and the reactions of sodium thiolates with fluorobenzenes have enabled various isomeric phenylthio substituted fluorobenzenes C₆H_xF_y(SR)_z to be prepared. The new products have been characterized by elemental analyses, mass, infrared, and fluorine NMR spectroscopy.     

A comparison of the on-top dissociation of H2 on Ni(100) and Cu(100)

The on-top dissociations of H₂ on Ni(100) and Cu(100) are studied using a cluster approach. Correlation effects are accounted for through the use of CASSCF and CCI methods. The central metal atom is treated with all its electrons whereas the other cluster atoms are described by recently developed one electron ECP's. A molecular chemisorbed H₂ state on nickel, similar to that recently observed experimentally, was identified in the cluster calculations and also for the triatomic NiH₂. No such state was found on copper. The large differences found for the on top dissociation of H₂ on nickel and copper are attributed solely to the difference in 3d orbital occupation. The parallel between the on top dissociation reaction on the cluster and the dissociation on a single atom is also studied. While the neutral triatomic NiH₂ represents a qualitatively correct model in the nickel case, the negatively charged CuH ₂ ^– is required as a model in the copper case.     

Optical properties of Cu nanoclusters supported on MgO(100)

The vertical transitions of Cu atoms, dimers, and tetramers deposited on the MgO surface have been investigated by means of ab initio calculations based either on complete active space second-order perturbation theory or on time-dependent density functional theory. Three adsorption sites have been considered as representative of the complexity of the MgO surface: regular sites at flat (100) terraces, extended defects such as monoatomic steps, and point defects such as neutral oxygen vacancies (F or color centers). The optical properties of the supported Cu clusters have been compared with those of the corresponding gas-phase units. Upon deposition a substantial modification of the energy levels of the supported cluster is induced by the Pauli repulsion with the substrate. This causes shifts in the optical transitions going from free to supported clusters. The changes in cluster geometry induced by the substrate have a much smaller effect on the optical absorption bands. On F centers the presence of filled impurity levels in the band gap of MgO results in a strong mixing with the empty levels of the Cu atoms and clusters with consequent deep changes in the optical properties of the color centers. The results allow to interpret electron energy loss spectra of Cu atoms deposited on MgO thin films.     

The initial growth behavior of perylene on Cu(100)

Using scanning tunneling microscopy (STM) together with density functional theory (DFT) the growth behavior of perylene on the Cu(100) substrate has been investigated. As revealed by STM images, perylene molecules prefer to adopt lying configuration with their molecular plane parallel to the substrate, and two symmetrically equivalent ordered domains were observed. DFT calculations show that perylene molecule prefers to adsorb on the top site of substrate Cu atoms with its long molecular axis aligning along the [011] or [01-1] azimuth of the substrate which is the most stable adsorption geometry according to its highest binding energy. Consequently, two adsorption structures of c(8×4) and c(8×6), each containing two perylene molecules per unit cell, are proposed based on our STM images. The growth mechanism for ordered perylene domains on Cu(100) can be attributed to the balance between weak adsorbate-adsorbate interaction and comparable adsorbate-substrate interaction.     

洁净和氧吸附的Cu(100)表面重构的理论研究

The interaction of atomic oxygen with the clean Cu(100) surface has been studied by means of cluster and periodic slab models density functional theory in the present paper. The Cu(4,9,4) cluster and a three-layer slab with c(2×2) structure are used to model the perfect Cu(100) surface. Three possible adsorption sites,top, bridge and hollow site, were considered in the calculations. The predicted results show that the hollow site is the prefer site for atomic oxygen adsorbed on Cu(100) surface energetically. This is in good agreement with the experiment. The calculated binding energies are respective 2.014, 3.154 and 3.942 eV for top, bridge and hollow sites at mPW1PW91/LanL2dz level for the cluster model. The geometry of Cu(100) surface has also been optimized theoretically with various density functional methods and the results show that the prediction from the B3PW91/LanL2dz and mPW1PW91/LanL2dz reproduce the experimental observation.The frontier molecular orbitals and partial density of states analysis show that the electron transfer from the d orbital of substrate to the p orbital of the surface oxygen atom.     

Deposition of DNA rafts on cationic SAMs on silicon [100

We demonstrate a guided self-assembly approach to the fabrication of DNA nanostructures on silicon substrates. DNA oligonucleotides self-assemble into "rafts" 8 x 37 x 2 nm in size. The rafts bind to cationic SAMs on silicon wafers. Electron-beam lithography of a thin poly(methyl methacrylate) (PMMA) resist layer was used to define trenches, and (3-aminopropyl)triethoxysilane (APTES), a cationic SAM precursor, was deposited from aqueous solution onto the exposed silicon dioxide at the trench bottoms. The remaining PMMA can be cleanly stripped off with dichloromethane, leaving APTES layers 0.7-1.2 nm in thickness and 110 nm in width. DNA rafts bind selectively to the resulting APTES stripes. The coverage of DNA rafts on adjacent areas of silicon dioxide is 20 times lower than on the APTES stripes. The topographic features of the rafts, measured by AFM, are identical to those of rafts deposited on wide-area SAMs. Binding to the APTES stripes appears to be very strong as indicated by "jamming" of the rafts at a saturation coverage of 42% and the stability to repeated AFM scanning in air.     

Characterization of enantiospecific chemisorption on chiral Cu surfaces vicinal to Cu(111) and Cu(100) using density functional theory

Surfaces of simple fcc metals such as Cu with nonzero and unequal Miller indices are intrinsically chiral. Density functional theory (DFT) calculations are a useful way to study the enantiospecific adsorption of small chiral molecules on these chiral metal surfaces. We report DFT calculations of seven chiral molecules on several structurally distinct chiral Cu surfaces. These surfaces include two surfaces with (111)-oriented terraces and one with (100)-oriented terraces. Calculations are also described on a surface that was modified to mimic the surface structures that typically appear on real metal surfaces following thermally driven fluctuations in step edges. Our results provide initial information on how variation in the surface structure of intrinsically chiral metal surfaces can affect the enantiospecific adsorption of small molecules on these surfaces.     

Self-assembled monolayers (SAMs) with photo-functionalities

Self-assembled monolayers (SAMs) of alkylthiol on metals, especially on gold, with photo-functionalities, such as photo-induced electron transfer, control of photo-electrochemical properties, control of electron transfer by photoisomerization, luminescence, and photo-patterning, are reviewed.     

Ab Initio Cyclic Voltammetry on Cu(111), Cu(100) and Cu(110) in Acidic,Neutral and Alkaline Solutions

Electrochemical reactions depend on the electrochemical interface between the electrode surfaces and the electrolytes. To control and advance electrochemical reactions there is a need to develop realistic simulation models of the electrochemical interface to understand the interface from an atomistic point-of-view. Here we present a method for obtaining thermodynamic realistic interface structures, a procedure we use to derive specific coverages and to obtain ab initio simulated cyclic voltammograms. As a case study, the method and procedure is applied in a matrix study of three Cu facets in three different electrolytes. The results have been validated by direct comparison to experimental cyclic voltammograms. The alkaline (NaOH) cyclic voltammograms are described by H* and OH*, while in neutral medium (KHCO₃) the CO species are dominating and in acidic (KCl) the Cl* species prevail. An almost one-to-one mapping is observed from simulation to experiments giving an atomistic understanding of the interface structure of the Cu facets. Atomistic understanding of the interface at relevant eletrolyte conditions will further allow realistic modelling of electrochemical reactions of importance for future eletrocatalytic studies.     

Nitrate adsorption and reduction on Cu(100) in acidic solution

Nitrate adsorption and reduction on Cu(100) in acidic solution is studied by electrochemical methods, in situ electrochemical scanning tunneling microscopy (EC-STM), surface enhanced Raman spectroscopy (SERS), and density functional theory (DFT) calculations. Electrochemical results show that reduction of nitrate starts at -0.3 V vs Ag/AgCl and reaches maximum value at -0.58 V. Over the entire potential region interrogated adlayers composed of nitrate, nitrite, or other intermediates are observed by using in situ STM. From the open-circuit potential (OCP) to -0.22 V vs Ag|AgCl, the nitrate ion is dominant and forms a (2 x 2) adlattice on the Cu(100) surface while nitrate forms a dominantly c(2 x 2) structure from -0.25 to -0.36 V. The interconversion between the nitrate and nitrite adlattices is observed. DFT calculations indicate that both nitrate and nitrite are twofold coordinated to the Cu(100) surface.     

Metal-organic coordination interactions in Fe-terephthalic acid networks on Cu(100)

Metal-organic coordination interactions are prime candidates for the formation of self-assembled, nanometer-scale periodic networks with room-temperature structural stability. We present X-ray photoelectron spectroscopy measurements of such networks at the Cu(100) surface which provide clear evidence for genuine metal-organic coordination. This is evident as binding energy shifts in the O 1s and Fe 3p photoelectron peaks, corresponding to O and Fe atoms involved in the coordination. Our results provide the first clear evidence for charge-transfer coordination in metal-organic networks at surfaces and demonstrate a well-defined oxidation state for the coordinated Fe ions.     

Self-assembled monolayers (SAMs) for electrochemical sensing

The past, present, and future of the application of self-assembled monolayers (SAMs) in electroanalytical chemistry is reviewed. SAMs for electroanalytical applications have been introduced in the early 1990s and since then have been exploited for the detection of different species ranging from metal ions to biomolecules and microorganisms. This review describes the different types of monolayers, surfaces on which they have been assembled, the various analytes, which were determined, and the various electrochemical techniques employed. The prospective and perspectives of this topic are discussed.     

Formation of self-assembled chains of tetrathiafulvalene on a Cu(100) surface

Formation of self-assembled chains of tetrathiafulvalene (TTF) on the Cu(100) surface has been investigated by scanning tunneling microscopy and density functional theory calculations that include semiempirical van der Waals (vdW) interaction corrections. The calculations show that the chain structures observed in the experiments can only be explained by including the vdW interactions. The molecules are tilted along the chain in order to achieve maximal intermolecular interaction. The chains are metastable on the surface, which is consistent with the experimental observation that they disappear after annealing. The fact that all TTF chains observed in the experiment are short might be possibly explained by the interplay between the stabilizing vdW molecule-molecule interaction and the destabilizing rearrangement of surface atoms due to the strong molecule-substrate interaction.     

Oxidation‐induced nanostructures on Cu{100}, Cu(Ag) and Ag/Cu{100} studied by photoelectron spectroscopy

Initial surface oxidation and nanoscale morphology on Cu{100}, Cu(Ag) and Ag/Cu{100} have been investigated in situ by X‐ray photoelectron spectroscopy (XPS), X‐ray induced Auger electron spectroscopy (XAES) and the inelastic electron background analysis as a function of oxygen exposure at 3.7 × 10^?2 and 213 mbar pressures at a surface temperature of 373 K. Relative Cu₂O concentrations have been quantified by analysis of the peak shape of the XAES Cu LMM transition. The surface morphology of Cu₂O islands and the Ag layer has been characterized by inelastic electron background analysis of XAES O KLL and Ag 3d transitions. Oxygen‐induced segregation of Cu, as well as the subsequent Cu₂O island formation on Cu(Ag) and Ag/Cu{100} surfaces, has been investigated quantitatively. Our results indicate that Ag has a clear inhibitive effect on the initial oxidation and Cu₂O island formation on Cu(Ag) and Ag/Cu{100} surfaces. The Cu₂O islands are also observed to remain highly strained on Ag/Cu{100} even at higher O₂ exposures. The results suggest that strained Cu₂O islands eventually penetrate through the buried Ag layer, and in conjunction with segregating Cu atoms enable the oxidation to proceed at a similar rate to or even faster than on the unalloyed Cu surface. Copyright © 2007 John Wiley & Sons, Ltd.