Enhanced interfacial water dissociation on a hydrated iron porphyrin single-atom catalyst in graphene.

Single Atom Catalysis (SAC) is an expanding field of heterogeneous catalysis in which single metallic atoms embedded in different materials catalyze a chemical reaction, but these new catalytic materials still lack fundamental understanding when used in electrochemical environments. Recent characterizations of non-noble metals like Fe deposited on N-doped graphitic materials have evidenced two types of Fe-N4 fourfold coordination, either of pyridine type or of porphyrin type. Here, we study these defects embedded in a graphene sheet and immersed in an explicit aqueous medium at the quantum level. While the Fe-pyridine SAC model is clear cut and widely studied, it is not the case for the Fe-porphyrin SAC that remains ill-defined, because of the necessary embedding of odd-membered rings in graphene. We first propose an atomistic model for the Fe-porphyrin SAC. Using spin-polarized ab initio molecular dynamics, we show that both Fe SACs spontaneously adsorb two interfacial water molecules from the solvent on opposite sides. Interestingly, we unveil a different catalytic reactivity of the two hydrated SAC motives: while the Fe-porphyrin defect eventually dissociates an adsorbed water molecule under a moderate external electric field, the Fe-pyridine defect does not convey water dissociation.

Unified non-equilibrium simulation methodology for flow through nanoporous carbon membrane.

The emergence of new nanoporous materials, based, e.g., on 2D materials, offers new avenues for water filtration and energy. There is, accordingly, a need to investigate the molecular mechanisms at the root of the advanced performances of these systems in terms of nanofluidic and ionic transport. In this work, we introduce a novel unified methodology for Non-Equilibrium classical Molecular Dynamic simulations (NEMD), allowing to apply likewise pressure, chemical potential, and voltage drops across nanoporous membranes and quantifying the resulting observables characterizing confined liquid transport under such external stimuli. We apply the NEMD methodology to study a new type of synthetic Carbon NanoMembranes (CNM), which have recently shown outstanding performances for desalination, keeping high water permeability while maintaining full salt rejection. The high water permeance of CNM, as measured experimentally, is shown to originate in prominent entrance effects associated with negligible friction inside the nanopore. Beyond, our methodology allows us to fully calculate the symmetric transport matrix and the cross-phenomena, such as electro-osmosis, diffusio-osmosis, and streaming currents. In particular, we predict a large diffusio-osmotic current across the CNM pore under a concentration gradient, despite the absence of surface charges. This suggests that CNMs are outstanding candidates as alternative, scalable membranes for osmotic energy harvesting.

Coupled Interactions at the Ionic Graphene-Water Interface.

We compute ionic free energy adsorption profiles at an aqueous graphene interface by developing a self-consistent approach. To do so, we design a microscopic model for water and put the liquid on an equal footing with the graphene described by its electronic band structure. By evaluating progressively the electronic and dipolar coupled electrostatic interactions, we show that the coupling level including mutual graphene and water screening permits one to recover remarkably the precision of extensive quantum simulations. We further derive the potential of mean force evolution of several alkali cations.

Extraction of Chemical Reactivity and Structural Relaxations of an Organic Dye from the Short-Range Interaction with a Molecular Probe.

A CO-functionalized atomic force microscope tip is used to locally probe local chemical reactivity and subtle structural relaxations of a single phthalocyanine molecule at different stages of pyrrolic-H abstraction. Spatially resolved vertical force spectroscopy unveils a variation of the maximum short-range attraction between CO and intramolecular sites, which is interpreted as a measure for the local chemical reactivity. In addition, the vertical position of the point of maximum attraction is observed to vary across the molecules. These changes follow the calculated adsorption heights of the probed molecular atoms.

Tracking the Interaction between a CO-Functionalized Probe and Two Ag-Phthalocyanine Conformers by Local Vertical Force Spectroscopy.

Intentionally terminating scanning probes with a single atom or molecule belongs to a rapidly growing field in the quantum chemistry and physics at surfaces. However, the detailed understanding of the coupling between the probe and adsorbate is in its infancy. Here, an atomic force microscopy probe functionalized with a single CO molecule is approached with picometer control to two conformational isomers of Ag-phthalocyanine adsorbed on Ag(111). The isomer with the central Ag atom pointing to CO exhibits a complex evolution of the distance-dependent interaction, while the conformer with Ag bonded to the metal surface gives rise to a Lennard-Jones behavior. By virtue of spatially resolved force spectroscopy and the comparison with results obtained from microscope probes terminated with a single Ag atom, the mutual coupling of the protruding O atom of the tip and the Ag atom of the phthalocyanine molecule is identified as the cause for the unconventional variation of the force. Simulations of the entire junction within density functional theory unveil the presence of ample relaxations in the case of one conformer, which represents a rationale for the peculiar vertical-distance evolution of the interaction. The simulations highlight the role of physisorption, chemisorption, and unexpected junction distortions at the verge of bond formation in the interpretation of the distance-dependent force between two molecules.

Quantifying Force and Energy in Single-Molecule Metalation.

An atomic force microscope is used to determine the attractive interaction at the verge of adding a Ag atom from the probe to a single free-base phthalocyanine molecule adsorbed on Ag(111). The experimentally extracted energy for the spontaneous atom transfer can be compared to the energy profile determined by density functional theory using the nudged-elastic-band method at a defined probe-sample distance.

Chemisorbed vs physisorbed surface charge and its impact on electrokinetic transport: Carbon vs boron nitride surface.

The possibility of controlling electrokinetic transport through carbon and hexagonal boron nitride (hBN) nanotubes has recently opened new avenues for nanofluidic approaches to face outstanding challenges such as energy production and conversion or water desalination. The pH-dependence of experimental transport coefficients points to the sorption of hydroxide ions as the microscopic origin of the surface charge and recent ab initio calculations suggest that these ions behave differently on carbon and hBN, with only physisorption on the former and both physisorption and chemisorption on the latter. Using classical non-equilibrium molecular dynamics simulations of interfaces between an aqueous electrolyte and three models of hBN and graphite surfaces, we demonstrate the major influence of the sorption mode of hydroxide ions on the interfacial transport properties. Physisorbed surface charge leads to a considerable enhancement of the surface conductivity as compared to its chemisorbed counterpart, while values of the ζ-potential are less affected. The analysis of the MD results for the surface conductivity and ζ-potential in the framework of Poisson-Boltzmann-Stokes theory, as is usually done to analyze experimental data, further confirms the importance of taking into account both the mobility of surface hydroxide ions and the decrease in the slip length with increasing titratable surface charge density.

Fluctuation-induced quantum friction in nanoscale water flows.

The flow of water in carbon nanochannels has defied understanding thus far1, with accumulating experimental evidence for ultra-low friction, exceptionally high water flow rates and curvature-dependent hydrodynamic slippage2-5. In particular, the mechanism of water-carbon friction remains unknown6, with neither current theories7 nor classical8,9 or ab initio molecular dynamics simulations10 providing satisfactory rationalization for its singular behaviour. Here we develop a quantum theory of the solid-liquid interface, which reveals a new contribution to friction, due to the coupling of charge fluctuations in the liquid to electronic excitations in the solid. We expect that this quantum friction, which is absent in Born-Oppenheimer molecular dynamics, is the dominant friction mechanism for water on carbon-based materials. As a key result, we demonstrate a marked difference in quantum friction between the water-graphene and water-graphite interface, due to the coupling of water Debye collective modes with a thermally excited plasmon specific to graphite. This suggests an explanation for the radius-dependent slippage of water in carbon nanotubes4, in terms of the electronic excitations of the nanotubes. Our findings open the way for quantum engineering of hydrodynamic flows through the electronic properties of the confining wall.

Borophenes made easy.

To date, the scalable synthesis of elemental two-dimensional materials beyond graphene still remains elusive. Here, we introduce a versatile chemical vapor deposition (CVD) method to grow borophenes, as well as borophene heterostructures, by selectively using diborane originating from traceable byproducts of borazine. Specifically, metallic borophene polymorphs were successfully synthesized on Ir(111) and Cu(111) single-crystal substrates and conjointly with insulating hexagonal boron nitride (hBN) to form atomically precise lateral borophene-hBN interfaces or vertical van der Waals heterostructures. Thereby, borophene is protected from immediate oxidation by a single hBN overlayer. The ability to synthesize high-quality borophenes with large single-crystalline domains in the micrometer scale by a straight-forward CVD approach opens up opportunities for the study of their fundamental properties and for device incorporation.

Actinide Coordination Chemistry on Surfaces: Synthesis, Manipulation, and Properties of Thorium Bis(porphyrinato) Complexes.

Actinide-based metal-organic complexes and coordination architectures encompass intriguing properties and functionalities but are still largely unexplored on surfaces. We introduce the in situ synthesis of actinide tetrapyrrole complexes under ultrahigh-vacuum conditions, on both a metallic support and a 2D material. Specifically, exposure of a tetraphenylporphyrin (TPP) multilayer to an elemental beam of thorium followed by a temperature-programmed reaction and desorption of surplus molecules yields bis(porphyrinato)thorium (Th(TPP)2) assemblies on Ag(111) and hexagonal boron nitride/Cu(111). A multimethod characterization including X-ray photoelectron spectroscopy, scanning tunneling microscopy, temperature-programmed desorption, and complementary density functional theory modeling provides insights into conformational and electronic properties. Supramolecular assemblies of Th(TPP)2 as well as individual double-deckers are addressed with submolecular precision, e.g., demonstrating the reversible rotation of the top porphyrin in Th(TPP)2 by molecular manipulation. Our findings thus demonstrate prospects for actinide-based functional nanoarchitectures.

Direct observation of water-mediated single-proton transport between hBN surface defects.

Aqueous proton transport at interfaces is ubiquitous and crucial for a number of fields, ranging from cellular transport and signalling, to catalysis and membrane science. However, due to their light mass, small size and high chemical reactivity, uncovering the surface transport of single protons at room temperature and in an aqueous environment has so far remained out-of-reach of conventional atomic-scale surface science techniques, such as scanning tunnelling microscopy. Here, we use single-molecule localization microscopy to resolve optically the transport of individual excess protons at the interface of hexagonal boron nitride crystals and aqueous solutions at room temperature. Single excess proton trajectories are revealed by the successive protonation and activation of optically active defects at the surface of the crystal. Our observations demonstrate, at the single-molecule scale, that the solid/water interface provides a preferential pathway for lateral proton transport, with broad implications for molecular charge transport at liquid interfaces.

Structure and chemistry of graphene oxide in liquid water from first principles.

Graphene oxide is a rising star among 2D materials, yet its interaction with liquid water remains a fundamentally open question: experimental characterization at the atomic scale is difficult, and modeling by classical approaches cannot properly describe chemical reactivity. Here, we bridge the gap between simple computational models and complex experimental systems, by realistic first-principles molecular simulations of graphene oxide (GO) in liquid water. We construct chemically accurate GO models and study their behavior in water, showing that oxygen-bearing functional groups (hydroxyl and epoxides) are preferentially clustered on the graphene oxide layer. We demonstrated the specific properties of GO in water, an unusual combination of both hydrophilicity and fast water dynamics. Finally, we evidence that GO is chemically active in water, acquiring an average negative charge of the order of 10 mC m-2. The ab initio modeling highlights the uniqueness of GO structures for applications as innovative membranes for desalination and water purification.

Spontaneous liquid water dissociation on hybridised boron nitride and graphene atomic layers from ab initio molecular dynamics simulations.

Two-dimensional materials such as graphene (G) and hexagonal boron nitride (BN) have demonstrated potential applications in membrane science and in particular for the harvesting of blue energy. Although pure G and BN atomic layers are known to remain inert towards neutral water, one may wonder about the aqueous reactivity of hybridized monolayers formed by joining BN and G sheets in a planar fashion. Here, we perform ab initio molecular dynamics calculations of liquid water in contact with all possible planar heterostructures. Remarkably, we could observe the spontaneous chemisorption and dissociation of the interfacial water molecule into its self-ions at one specific and non-standard one-dimensional border. Our simulations predict that this type of heterostructure is prone to ionize liquid water in the absence of any electrical gating.

On-Surface Synthesis of Nonmetal Porphyrins.

We report the on-surface synthesis of a nonmetal porphyrin, namely, silicon tetraphenylporphyrin (Si-TPP), by the deposition of atomic silicon onto a free-base TPP layer on a Ag(100) surface under ultrahigh vacuum (UHV) conditions. Scanning tunneling microscopy provides insights into the self-assembly of the TPP molecules before and after Si insertion. Silicon coordinates with all four nitrogen atoms of the TPP macrocycle and interacts with a silver atom of the substrate as confirmed by scanning tunneling spectroscopy, X-ray photoelectron spectroscopy, and complementary density functional theory calculations. The Si-TPP complex presents a saddle-shaped conformation that is stable under STM manipulation. Our study shows how protocols established for the on-surface metalation of tetrapyrroles can be adopted to achieve nonmetal porphyrins. Complementary experiments yielding Si-TPP and Ge-TPP on Ag(111) highlight the applicability to different main group elements and supports. The success of our nonmetal porphyrin synthesis procedure is further corroborated by a temperature-programmed desorption experiment, revealing the desorption of Ge-TPP. This extension of interfacial complex formation beyond metal elements opens promising prospects for new tetrapyrrole architectures with distinct properties and functionalities.

In-Situ Growth of Gadolinium Phthalocyaninato Sandwich Complexes on the Ag(111) Surface.

We report a low-temperature scanning tunneling microscopy investigation of the in-situ growth of gadolinium phthalocyaninato complexes by combined deposition of free-base phthalocyanines and gadolinium atoms on a smooth Ag(111) substrate. A careful control of the stoichiometry allows the expression of a multilevel structurecomposed of irregularly distributed Gdx-1 (Pc)x complexes, x=2-5, thus paving new avenues for surface-confined columnar growth.

Versatile electrification of two-dimensional nanomaterials in water.

The recent emergence of nanofluidics has highlighted the exceptional properties of graphene and its boron-nitride counterpart as confining nanomaterials for water and ion transport. Surprisingly, ionic transport experiments have unveiled a consequent electrification of the water/carbon surfaces, with a contrasting response for its water/boron-nitride homologue. In this paper, we report free energy calculations based on ab initio molecular dynamics simulations of hydroxide OH- ions in water near graphene and hexagonal boron nitride (h-BN) layers. Our results disclose that both surfaces get charged through hydroxide adsorption, but two strongly different mechanisms are evidenced. The hydroxide species shows weak physisorption on the graphene surface while it exhibits also strong chemisorption on the h-BN surface. Interestingly OH- is shown to keep very fast lateral dynamics and interfacial mobility within the physisorbed layer on graphene. Taking into account the large ionic surface conductivity, an analytic transport model allows to reproduce quantitatively the experimental data.

Spin in a Closed-Shell Organic Molecule on a Metal Substrate Generated by a Sigmatropic Reaction.

Inert metal surfaces present more chances of hosting organic intact radicals than other substrates, but large amounts of delocalized electronic states favor charge transfer and thus spin quenching. Lowering the molecule-substrate interaction is a usual strategy to stabilize radicals on surfaces. In some works, thin insulating layers were introduced to provide a controllable degree of electronic decoupling. Recently, retinoid molecules adsorbed on gold have been manipulated with a scanning tunneling microscope (STM) to exhibit a localized spin, but calculations failed to find a radical derivative of the molecule on the surface. Now the formation of a neutral radical spatially localized in a tilted and lifted cyclic end of the molecule is presented. An allene moiety provokes a perpendicular tilt of the cyclic end relative to the rest of the conjugated chain, thus localizing the spin of the dehydrogenated allene in its lifted subpart. DFT calculations and STM manipulations give support to the proposed mechanism.

Ligand-Induced Energy Shift and Localization of Kondo Resonances in Cobalt-Based Complexes on Cu(111).

Magnetic sandwich complexes are of particular interest for molecular spintronics. Using scanning tunneling microscopy, we evidence the successful deposition of 1,3,5-tris(η6-borabenzene-η5-cyclopentadienylcobalt) benzene, a molecule composed of three connected magnetic sandwich units, on Cu(111). Scanning tunneling spectra reveal two distinct spatial-dependent narrow resonances close to the Fermi level for the trimer molecules as well as for molecular fragments composed of one and two magnetic units. With the help of density functional theory, these resonances are interpreted as two Kondo resonances originating from two distinct nondegenerate d-like orbitals. These Kondo resonances are found to have defined spatial extents dictated by the hybridization of the involved orbitals with that of the ligands. These results opens promising perspectives for investigating complex Kondo systems composed of several "Kondo" orbitals.

Efficient Spin-Flip Excitation of a Nickelocene Molecule.

Inelastic electron tunneling spectroscopy (IETS) within the junction of a scanning tunneling microscope (STM) uses current-driven spin-flip excitations for an all-electrical characterization of the spin state of a single object. Usually decoupling layers between the single object, atom or molecule, and the supporting surface are needed to observe these excitations. Here we study the surface magnetism of a sandwich nickelocene molecule (Nc) adsorbed directly on Cu(100) by means of X-ray magnetic circular dichroism (XMCD) and density functional theory (DFT) calculations and show with IETS that it exhibits an exceptionally efficient spin-flip excitation. The molecule preserves its magnetic moment and magnetic anisotropy not only on Cu(100), but also in different metallic environments including the tip apex. By taking advantage of this robusteness, we are able to functionalize the microscope tip with a Nc, which can be employed as a portable source of inelastic excitations as exemplified by a double spin-flip excitation process.

Fusing tetrapyrroles to graphene edges by surface-assisted covalent coupling.

Surface-assisted covalent linking of precursor molecules enables the fabrication of low-dimensional nanostructures, which include graphene nanoribbons. One approach to building functional multicomponent systems involves the lateral anchoring of organic heteromolecules to graphene. Here we demonstrate the dehydrogenative coupling of single porphines to graphene edges on the same metal substrate as used for graphene synthesis. The covalent linkages are visualized by scanning probe techniques with submolecular resolution, which directly reveals bonding motifs and electronic features. Distinct configurations are identified that can be steered towards entities predominantly fused to graphene edges through two pyrrole rings by thermal annealing. Furthermore, we succeeded in the concomitant metallation of the macrocycle with substrate atoms and the axial ligation of adducts. Such processes combined with graphene-nanostructure synthesis has the potential to create complex materials systems with tunable functionalities.