Mattia Cattelan

Molecules–Oligomers–Nanowires–Graphene Nanoribbons: A Bottom-Up Stepwise On-Surface Covalent Synthesis Preserving Long-Range Order

We report on a stepwise on-surface polymerization reaction leading to oriented graphene nanoribbons on Au(111) as the final product. Starting from the precursor 4,4″-dibromo-p-terphenyl and using the Ullmann coupling reaction followed by dehydrogenation and C-C coupling, we have developed a fine-tuned, annealing-triggered on-surface polymerization that allows us to obtain an oriented nanomesh of graphene nanoribbons via two well-defined intermediate products, namely, p-phenylene oligomers with reduced length dispersion and ordered submicrometric molecular wires of poly(p-phenylene). A fine balance involving gold catalytic activity in the Ullmann coupling, appropriate on-surface molecular mobility, and favorable topochemical conditions provided by the used precursor leads to a high degree of long-range order that characterizes each step of the synthesis and is rarely observed for surface organic frameworks obtained via Ullmann coupling.

TiO2@CeOx core-shell nanoparticles as artificial enzymes with peroxidase-like activity.

The Ce4+↔Ce3+ redox switch is at the basis of an all-inorganic catalytic cycle that is capable of mimicking the activity of several natural redox enzymes. The efficiency of these artificial enzymes (nanozymes) strongly depends on the Ce4+/Ce3+ ratio. By capitalizing on the results obtained on oxide/oxide model systems, we implemented a simple and effective procedure to obtain conformal TiO2@CeOx core-shell nanoparticles whose thickness is controlled with single-layer precision. Since the Ce3+ species are stabilized only at the interface by the electronic hybridization with the TiO2 states, the modulation of the shell thickness offers a simple method to tailor the Ce4+/Ce3+ ratio and therefore the catalytic properties. The activity of these nanoparticles as artificial peroxidase-like enzymes was tested, showing exceptional performances, even better than natural horseradish peroxidase enzyme. The main advantage with respect to other oxide/oxide nanozymes is that our nanoparticles, having a tunable Ce4+/Ce3+ ratio, are efficient already at low H2O2 concentrations.

Unveiling the Mechanisms Leading to H2 Production Promoted by Water Decomposition on Epitaxial Graphene at Room Temperature.

By means of a combination of surface-science spectroscopies and theory, we investigate the mechanisms ruling the catalytic role of epitaxial graphene (Gr) grown on transition-metal substrates for the production of hydrogen from water. Water decomposition at the Gr/metal interface at room temperature provides a hydrogenated Gr sheet, which is buckled and decoupled from the metal substrate. We evaluate the performance of Gr/metal interface as a hydrogen storage medium, with a storage density in the Gr sheet comparable with state-of-the-art materials (1.42 wt %). Moreover, thermal programmed reaction experiments show that molecular hydrogen can be released upon heating the water-exposed Gr/metal interface above 400 K. The Gr hydro/dehydrogenation process might be exploited for an effective and eco-friendly device to produce (and store) hydrogen from water, i.e., starting from an almost unlimited source.

Multiple doping of graphene oxide foams and quantum dots: new switchable systems for oxygen reduction and water remediation

Single- and multi-boron, nitrogen, sulphur doped graphene oxide quantum dots and three-dimensional foams are synthesized by a simple and environmentally friendly electrochemical method. The electrochemical activity of these materials in the oxygen reduction reaction is investigated by cyclic voltammetry and rotating disk electrode measurements. The experimental data demonstrate that the reaction selectivity is controlled by the oxidation degree of the materials: as-prepared graphene oxide quantum dots, which present highly oxidized functional groups, follow a two-electron reduction pathway and produce hydrogen peroxide, whereas after a reduction treatment by NaBH4, the same materials favour a four-electron reduction of oxygen to water. The high selectivity and high efficiency of the graphene oxide quantum dots for the production of hydrogen peroxide can be efficiently used for water remediation applications (phenol decomposition).

Fast One-Pot Synthesis of MoS2/Crumpled Graphene p–n Nanonjunctions for Enhanced Photoelectrochemical Hydrogen Production

Aerosol processing enables the preparation of hierarchical graphene nanocomposites with special crumpled morphology in high yield and in a short time. Using modular insertion of suitable precursors in the starting solution, it is possible to synthesize different types of graphene-based materials ranging from heteroatom-doped graphene nanoballs to hierarchical nanohybrids made up by nitrogen-doped crumpled graphene nanosacks that wrap finely dispersed MoS2 nanoparticles. These materials are carefully investigated by microscopic (SEM, standard and HR TEM), diffraction (grazing incidence X-ray diffraction (GIXRD)) and spectroscopic (high resolution photoemission, Raman and UV-visible spectroscopy) techniques, evidencing that nitrogen dopants provide anchoring sites for MoS2 nanoparticles, whereas crumpling of graphene sheets drastically limits aggregation. The activity of these materials is tested toward the photoelectrochemical production of hydrogen, obtaining that N-doped graphene/MoS2 nanohybrids are seven times more efficient with respect to single MoS2 because of the formation of local p-n MoS2/N-doped graphene nanojunctions, which allow an efficient charge carrier separation.

On-surface photo-dissociation of C–Br bonds: towards room temperature Ullmann coupling

The surface-assisted synthesis of gold-organometallic hybrids on the Au(111) surface both by thermo- and light-initiated dehalogenation of bromo-substituted tetracene is reported. Combined X-ray photoemission (XPS) and scanning tunneling microscopy (STM) data reveal a significant increase of the surface order when mild reaction conditions are combined with 405 nm light irradiation.

Control of the Intermolecular Coupling of Dibromotetracene on Cu(110) by the Sequential Activation of CBr and CH Bonds

Dibromotetracene molecules are deposited on the Cu(110) surface at room temperature. The complex evolution of this system has been monitored at different temperatures (i.e., 298, 523, 673, and 723 K) by means of a variety of complementary techniques that range from STM and temperature-programmed desorption (TPD) to high-resolution X-ray spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). State-of-the-art density-functional calculations were used to determine the chemical processes that take place on the surface. After deposition at room temperature, the organic molecules are transformed into organometallic monomers through debromination and carbon-radical binding to copper adatoms. Organometallic dimers, trimers, or small oligomers, which present copper-bridged molecules, are formed by increasing the temperature. Surprisingly, further heating to 673 K causes the formation of elongated chains along the Cu(110) close-packed rows as a consequence of radical-site migration to the thermodynamically more stable molecule heads. Finally, massive dehydrogenation occurs at the highest temperature followed by ring condensation to nanographenic patches. This study is a paradigmatic example of how intermolecular coupling can be modulated by the stepwise control of a simple parameter, such as temperature, through a sequence of domino reactions.

Optoelectrochemical biorecognition by optically transparent highly conductive graphene-modified fluorine-doped tin oxide substrates.

Both optical and electrochemical graphene-based sensors have gone through rapid development, reaching high sensitivity at low cost and with fast response time. However, the complex validating biochemical operations, needed for their consistent use, currently limits their effective application. We propose an integration strategy for optoelectrochemical detection that overcomes previous limitations of these sensors used separately. We develop an optoelectrochemical sensor for aptamer-mediated protein detection based on few-layer graphene immobilization on selectively modified fluorine-doped tin oxide (FTO) substrates. Our results show that the electrochemical properties of graphene-modified FTO samples are suitable for complex biological detection due to the stability and inertness of the engineered electrodic interface. In addition, few-layer immobilization of graphene sheets through electrostatic linkage with an electrochemically grafted FTO surface allows obtaining an optically accessible and highly conductive platform. As a proof of concept, we used insulin as the target molecule to reveal in solution. Because of its transparency and low sampling volume (a few microliters), our sensing unit can be easily integrated in lab-on-a-chip cell culture systems for effectively monitoring subnanomolar concentrations of proteins relevant for biomedical applications.

Synthesis of graphene nanoribbons with a defined mixed edge-site sequence by surface assisted polymerization of (1,6)-dibromopyrene on Ag(110)

By a combination of scanning tunneling microscopy, X-ray spectroscopic techniques and density functional theory calculations, we prove the formation of extended patterns of parallel, graphene nanoribbons with alternate zig-zag and armchair edges and selected width by surface-assisted Ullmann coupling polymerization and dehydrogenation of 1,6-dibromopyrene (C16H8Br2). Besides the relevance of these nanostructures for their possible application in nanodevices, we demonstrate the peculiarity of halogenated pyrene derivatives for the formation of nanoribbons, in particular on Ag(110). These results open the possibility of tuning the shape and dimension of nanoribbons (and hence the correlated electronic properties) by choosing suitably tailored or on-purpose designed molecular precursors.

Aerosol Synthesis of N and N-S Doped and Crumpled Graphene Nanostructures

Chemically modified graphene–based materials (CMG) are currently attracting a vast interest in their application in different fields. In particular, heteroatom-doped graphenes have revealed great potentialities in the field of electrocatalysis as substitutes of fuel cell noble metal–based catalysts. In this work, we investigate an innovative process for doping graphene nanostructures. We optimize a novel synthetic route based on aerosol preparation, which allows the simultaneous doping, crumpling, and reduction of graphene oxide (GO). Starting from aqueous solutions containing GO and the dopant precursors, we synthesize N- and N,S-dual-doped 3D graphene nanostructures (N-cGO and N,S-cGO). In the aerosol process, every aerosol droplet can be considered as a microreactor where dopant precursors undergo thermal decomposition and react with the GO flakes. Simultaneously, thanks to the relatively high temperature, GO undergoes crumpling and partial reduction. Using a combination of spectroscopic and microscopic characterization techniques, we investigate the morphology of the obtained materials and the chemical nature of the dopants within the crumpled graphene sheets. This study highlights the versatility of the aerosol process for the design of new CMG materials with tailored electrocatalytic properties.