The Role of Alkyl Chains in the Thermoresponse of Supramolecular Network.

Supramolecular materials provide a pathway for achieving precise, highly ordered structures while exhibiting remarkable response to external stimuli, a characteristic not commonly found in covalently bonded materials. The design of self-assembled materials, where properties could be predicted/design from chemical nature of the individual building blocks, hinges upon our ability to relate macroscopic properties to individual building blocks - a feat which has thus far remained elusive. Here, a design approach is demonstrated to chemically engineer the thermal expansion coefficient of 2D supramolecular networks by over an order of magnitude (\boldmath 120 to \boldmath 1000 × 10-6 K-1). This systematic study provides a clear pathway on how to carefully design the thermal expansion coefficient of a 2D molecular assembly. Specifically, a linear relation has been identified between the length of decorating alkyl chains and the thermal expansion coefficient. Counter-intuitively, the shorter the chains the larger is the thermal expansion coefficient. This precise control over thermo-mechanical properties marks a significant leap forward in the de-novo design of advanced 2D materials. The possibility to chemically engineer their thermo-mechanical properties holds promise for innovations in sensors, actuators, and responsive materials across diverse fields.

Nonmonotonic Velocity Dependence of Atomic Friction Induced by Multiple Slips.

The transition from single to multiple atomic slips, theoretically expected and important in atomic-scale friction, has never been demonstrated experimentally as a function of velocity. Here we show by high-resolution friction force microscopy on monolayer MoS_{2}/Au(111) that multiple slips leave a unique footprint-a frictional velocity weakening. Specifically, in a wide velocity interval from 10 to 100 nm/s, friction surprisingly decreases. Model simulations show a similar nonmonotonic behavior at velocities in quantitative agreement with experiment. Results suggest a velocity-corrugation phase diagram, whose validity is proposed more generally.

Moiré-Tile Manipulation-Induced Friction Switch of Graphene on a Platinum Surface.

Friction control and technological advancement are intimately intertwined. Concomitantly, two-dimensional materials occupy a unique position for realizing quasi-frictionless contacts. However, the question arises of how to tune superlubric sliding. Drawing inspiration from twistronics, we propose to control superlubricity via moiré patterning. Friction force microscopy and molecular dynamics simulations unequivocally demonstrate a transition from a superlubric to dissipative sliding regime for different twist angles of graphene moirés on a Pt(111) surface triggered by the normal force. This follows from a novel mechanism at superlattice level where, beyond a critical load, moiré tiles are manipulated in a highly dissipative shear process connected to the twist angle. Importantly, the atomic detail of the dissipation associated with the moiré tile manipulation─i.e., enduring forced registry beyond a critical normal load─allows the bridging of disparate sliding regimes in a reversible manner, thus paving the road for a subtly intrinsic control of superlubricity.

Velocity Dependence of Moiré Friction.

Friction force microscopy experiments on moiré superstructures of graphene-coated platinum surfaces demonstrate that in addition to atomic stick-slip dynamics, a new dominant energy dissipation route emerges. The underlying mechanism, revealed by atomistic molecular dynamics simulations, is related to moiré ridge elastic deformations and subsequent relaxation due to the action of the pushing tip. The measured frictional velocity dependence displays two distinct regimes: (i) at low velocities, the friction force is small and nearly constant; and (ii) above some threshold, friction increases logarithmically with velocity. The threshold velocity, separating the two frictional regimes, decreases with increasing normal load and moiré superstructure period. Based on the measurements and simulation results, a phenomenological model is derived, allowing us to calculate friction under a wide range of room temperature experimental conditions (sliding velocities of 1-104 nm/s and a broad range of normal loads) and providing excellent agreement with experimental observations.

Calcined Clays from Nigeria-Properties and Performance of Supplementary Cementitious Materials Suitable for Producing Level 1 Concrete.

In this work, four naturally occurring (two kaolinite-rich and two smectite-rich) clay samples were collected from different areas around the Ashaka cement production plant, located in Gombe State, Nigeria and calcined in a laboratory. The mineralogical characterization of the clays was carried out by XRD. The hydration kinetics of the calcined clay-cement systems were monitored by isothermal calorimetry. Workability was determined using the flow table method. The reactivity of the calcined clays was determined from the solubility of Si and Al ions and the strength activity index. All calcined clays studied met the requirements of ASTM C618 for the use of natural pozzolans as a partial replacement for hydraulic cement. The metasmectite clays yielded a higher specific surface area, increased water demand, and less reactive Si and Al ions compared to the metakaolin clays. The two calcined clay groups require the addition of superplasticizer to achieve a workability class similar to the Portland cement mortar system. They can be used to replace Portland cement at replacement levels of up to 45%, in combination with limestone powder to form an LC3 cement, thereby achieving at least a "Level 1" reduction in greenhouse gas emissions.

Solution-Synthesized Extended Graphene Nanoribbons Deposited by High-Vacuum Electrospray Deposition.

Solution-synthesized graphene nanoribbons (GNRs) facilitate various interesting structures and functionalities, like nonplanarity and thermolabile functional groups, that are not or not easily accessible by on-surface synthesis. Here, we show the successful high-vacuum electrospray deposition (HVESD) of well-elongated solution-synthesized GNRs on surfaces maintained in ultrahigh vacuum. We compare three distinct GNRs, a twisted nonplanar fjord-edged GNR, a methoxy-functionalized "cove"-type (or also called gulf) GNR, and a longer "cove"-type GNR both equipped with alkyl chains on Au(111). Nc-AFM measurements at room temperature with submolecular imaging combined with Raman spectroscopy allow us to characterize individual GNRs and confirm their chemical integrity. The fjord-GNR and methoxy-GNR are additionally deposited on nonmetallic HOPG and SiO2, and fjord-GNR is deposited on a KBr(001) surface, facilitating the study of GNRs on substrates, as of now not accessible by on-surface synthesis.

Synthesis of Giant Dendritic Polyphenylenes with 366 and 546 Carbon Atoms and Their High-vacuum Electrospray Deposition.

Dendritic polyphenylenes (PPs) can serve as precursors of nanographenes (NGs) if their structures represent 2D projections without overlapping benzene rings. Here, we report the synthesis of two giant dendritic PPs fulfilling this criteria with 366 and 546 carbon atoms by applying a "layer-by-layer" extension strategy. Although our initial attempts on their cyclodehydrogenation toward the corresponding NGs in solution were unsuccessful, we achieved their deposition on metal substrates under ultrahigh vacuum through the electrospray technique. Scanning probe microscopy imaging provides valuable information on the possible thermally induced partial planarization of such giant dendritic PPs on a metal surface.

2D KBr/Graphene Heterostructures-Influence on Work Function and Friction.

The intercalation of graphene is an effective approach to modify the electronic properties of two-dimensional heterostructures for attractive phenomena and applications. In this work, we characterize the growth and surface properties of ionic KBr layers altered by graphene using ultra-high vacuum atomic force microscopy at room temperature. We observed a strong rippling of the KBr islands on Ir(111), which is induced by a specific layer reconstruction but disappears when graphene is introduced in between. The latter causes a consistent change in both the work function and the frictional forces measured by Kelvin probe force microscopy and frictional force microscopy, respectively. Systematic density functional theory calculations of the different systems show that the change in work function is induced by the formation of a surface dipole moment while the friction force is dominated by adhesion forces.

Influence of electrospray deposition on C60 molecular assemblies.

Maintaining clean conditions for samples during all steps of preparation and investigation is important for scanning probe studies at the atomic or molecular level. For large or fragile organic molecules, where sublimation cannot be used, high-vacuum electrospray deposition is a good alternative. However, because this method requires the introduction into vacuum of the molecules from solution, clean conditions are more difficult to be maintained. Additionally, because the presence of solvent on the surface cannot be fully eliminated, one has to take care of its possible influence. Here, we compare the high-vacuum electrospray deposition method to thermal evaporation for the preparation of C60 on different surfaces and compare, for sub-monolayer coverages, the influence of the deposition method on the formation of molecular assemblies. Whereas the island location is the main difference for metal surfaces, we observe for alkali halide and metal oxide substrates that the high-vacuum electrospray method can yield single isolated molecules accompanied by surface modifications.

Reconstruction of a 2D layer of KBr on Ir(111) and electromechanical alteration by graphene.

A novel reconstruction of a two-dimensional layer of KBr on an Ir(111) surface is observed by high-resolution noncontact atomic force microscopy and verified by density functional theory (DFT). The observed KBr structure is oriented along the main directions of the Ir(111) surface, but forms a characteristic double-line pattern. Comprehensive calculations by DFT, taking into account the observed periodicities, resulted in a new low-energy reconstruction. However, it is fully relaxed into a common cubic structure when a monolayer of graphene is located between substrate and KBr. By using Kelvin probe force microscopy, the work functions of the reconstructed and the cubic configuration of KBr were measured and indicate, in accordance with the DFT calculations, a difference of nearly 900 meV. The difference is due to the strong interaction and local charge displacement of the K+/Br- ions and the Ir(111) surface, which are reduced by the decoupling effect of graphene, thus yielding different electrical and mechanical properties of the top KBr layer.

Reactivity of Metakaolin in Alkaline Environment: Correlation of Results from Dissolution Experiments with XRD Quantifications.

Systematic investigation of filtrates and filter residues resulting from a 24 h treatment of metakaolin in different alkaline solutions were performed. On filtered metakaolin particles, inductively coupled plasma-optical emission spectrometry (ICP-OES) measurements reveal an enrichment of iron and titanium, which suggests an inhomogeneous distribution of these cations. Since the SiO2/Al2O3 ratio remains constant in all filter residues examined, the dissolution of the Si and Al monomers is congruent. Structural differences, identified by attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) as a consequence of alkali uptake, influence the X-ray scattering contribution of metakaolin, and thus quantifications with the partial or no known crystal structure (PONKCS) method. This leads to deviations between the degree of reaction calculated from Si and Al solubility from filtrate and that quantified by quantitative powder X-ray diffraction (QPXRD) using the filter residue. Nevertheless, the described changes do not cause a shift in the X-ray amorphous hump in case of congruent dissolution, and thus allow the quantification of the metakaolin before and after dissolution with the same hkl-phase model.

Giant thermal expansion of a two-dimensional supramolecular network triggered by alkyl chain motion.

Thermal expansion, the response in shape, area or volume of a solid with heat, is usually large in molecular materials compared to their inorganic counterparts. Resulting from the intrinsic molecule flexibility, conformational changes or variable intermolecular interactions, the exact interplay between these mechanisms is however poorly understood down to the molecular level. Here, we investigate the structural variations of a two-dimensional supramolecular network on Au(111) consisting of shape persistent polyphenylene molecules equipped with peripheral dodecyl chains. By comparing high-resolution scanning probe microscopy and molecular dynamics simulations obtained at 5 and 300 K, we determine the thermal expansion coefficient of the assembly of 980 ± 110 × 10-6 K-1, twice larger than other molecular systems hitherto reported in the literature, and two orders of magnitude larger than conventional materials. This giant positive expansion originates from the increased mobility of the dodecyl chains with temperature that determine the intermolecular interactions and the network spacing.