Probing Basal and Prismatic Planes of Graphitic Materials for Metal Single Atom and Subnanometer Cluster Stabilization.

Supported metal single atom catalysis is a dynamic research area in catalysis science combining the advantages of homogeneous and heterogeneous catalysis. Understanding the interactions between metal single atoms and the support constitutes a challenge facing the development of such catalysts, since these interactions are essential in optimizing the catalytic performance. For conventional carbon supports, two types of surfaces can contribute to single atom stabilization: the basal planes and the prismatic surface; both of which can be decorated by defects and surface oxygen groups. To date, most studies on carbon-supported single atom catalysts focused on nitrogen-doped carbons, which, unlike classic carbon materials, have a fairly well-defined chemical environment. Herein we report the synthesis, characterization and modeling of rhodium single atom catalysts supported on carbon materials presenting distinct concentrations of surface oxygen groups and basal/prismatic surface area. The influence of these parameters on the speciation of the Rh species, their coordination and ultimately on their catalytic performance in hydrogenation and hydroformylation reactions is analyzed. The results obtained show that catalysis itself is an interesting tool for the fine characterization of these materials, for which the detection of small quantities of metal clusters remains a challenge, even when combining several cutting-edge analytical methods.

Highly tunable ground and excited state excitonic dipoles in multilayer 2H-MoSe2.

The fundamental properties of an exciton are determined by the spin, valley, energy, and spatial wavefunctions of the Coulomb-bound electron and hole. In van der Waals materials, these attributes can be widely engineered through layer stacking configuration to create highly tunable interlayer excitons with static out-of-plane electric dipoles, at the expense of the strength of the oscillating in-plane dipole responsible for light-matter coupling. Here we show that interlayer excitons in bi- and tri-layer 2H-MoSe2 crystals exhibit electric-field-driven coupling with the ground (1s) and excited states (2s) of the intralayer A excitons. We demonstrate that the hybrid states of these distinct exciton species provide strong oscillator strength, large permanent dipoles (up to 0.73 ± 0.01 enm), high energy tunability (up to ~200 meV), and full control of the spin and valley characteristics such that the exciton g-factor can be manipulated over a large range (from -4 to +14). Further, we observe the bi- and tri-layer excited state (2s) interlayer excitons and their coupling with the intralayer excitons states (1s and 2s). Our results, in good agreement with a coupled oscillator model with spin (layer)-selectivity and beyond standard density functional theory calculations, promote multilayer 2H-MoSe2 as a highly tunable platform to explore exciton-exciton interactions with strong light-matter interactions.

Quasi van der Waals Epitaxy of Rhombohedral-Stacked Bilayer WSe2 on GaP(111) Heterostructure.

The growth of bilayers of two-dimensional (2D) materials on conventional 3D semiconductors results in 2D/3D hybrid heterostructures, which can provide additional advantages over more established 3D semiconductors while retaining some specificities of 2D materials. Understanding and exploiting these phenomena hinge on knowing the electronic properties and the hybridization of these structures. Here, we demonstrate that a rhombohedral-stacked bilayer (AB stacking) can be obtained by molecular beam epitaxy growth of tungsten diselenide (WSe2) on a gallium phosphide (GaP) substrate. We confirm the presence of 3R-stacking of the WSe2 bilayer structure using scanning transmission electron microscopy (STEM) and micro-Raman spectroscopy. Also, we report high-resolution angle-resolved photoemission spectroscopy (ARPES) on our rhombohedral-stacked WSe2 bilayer grown on a GaP(111)B substrate. Our ARPES measurements confirm the expected valence band structure of WSe2 with the band maximum located at the Γ point of the Brillouin zone. The epitaxial growth of WSe2/GaP(111)B helps to understand the fundamental properties of these 2D/3D heterostructures, toward their implementation in future devices.

Capacitively and Inductively Coupled Excitons in Bilayer MoS_{2}.

The coupling of intralayer A and B excitons and interlayer excitons (IE) is studied in a two-dimensional semiconductor, homobilayer MoS_{2}. It is shown that the measured optical susceptibility reveals both the magnitude and the phase of the coupling constants. The IE and B excitons couple via a 0-phase (capacitive) coupling; the IE and A excitons couple via a π-phase (inductive) coupling. The IE-B and IE-A coupling mechanisms are interpreted as hole tunneling and electron-hole exchange, respectively. The couplings imply that even in a monolayer, the A and B excitons have mixed spin states. Using the IE as a sensor, the A-B intravalley exchange coupling is determined. Finally, we realize a bright and highly tunable lowest-energy momentum-direct exciton at high electric fields.

Interlayer exciton mediated second harmonic generation in bilayer MoS2.

Second-harmonic generation (SHG) is a non-linear optical process, where two photons coherently combine into one photon of twice their energy. Efficient SHG occurs for crystals with broken inversion symmetry, such as transition metal dichalcogenide monolayers. Here we show tuning of non-linear optical processes in an inversion symmetric crystal. This tunability is based on the unique properties of bilayer MoS2, that shows strong optical oscillator strength for the intra- but also interlayer exciton resonances. As we tune the SHG signal onto these resonances by varying the laser energy, the SHG amplitude is enhanced by several orders of magnitude. In the resonant case the bilayer SHG signal reaches amplitudes comparable to the off-resonant signal from a monolayer. In applied electric fields the interlayer exciton energies can be tuned due to their in-built electric dipole via the Stark effect. As a result the interlayer exciton degeneracy is lifted and the bilayer SHG response is further enhanced by an additional two orders of magnitude, well reproduced by our model calculations. Since interlayer exciton transitions are highly tunable also by choosing twist angle and material combination our results open up new approaches for designing the SHG response of layered materials.

Nanocatalysts for High Selectivity Enyne Cyclization: Oxidative Surface Reorganization of Gold Sub-2-nm Nanoparticle Networks.

Ultrasmall gold nanoparticles (NPs) stabilized in networks by polymantane ligands (diamondoids) were successfully used as precatalysts for highly selective heterogeneous gold-catalyzed dimethyl allyl(propargyl)malonate cyclization to 5-membered conjugated diene. Such reaction usually suffers from selectivity issues with homogeneous catalysts. This control over selectivity further opened the way to one-pot cascade reaction, as illustrated by the 1,6-enyne cycloisomerization-Diels-Alder reaction of dimethyl allyl propargyl malonate with maleic anhydride. The ability to assemble nanoparticles with controllable sizes and shapes within networks concerns research in sensors, medical diagnostics, information storage, and catalysis applications. Herein, the control of the synthesis of sub-2-nm gold NPs is achieved by the formation of dense networks, which are assembled in a single step reaction by employing ditopic polymantanethiols. By using 1,1'-bisadamantane-3,3'-dithiol (BAd-SH) and diamantane-4,9-dithiol (DAd-SH), serving both as bulky surface stabilizers and short-sized linkers, we provide a simple method to form uniformly small gold NPs (1.3 ± 0.2 nm to 1.6 ± 0.3 nm) embedded in rigid frameworks. These NP arrays are organized alongside short interparticular distances ranging from 1.9 to 2.7 nm. The analysis of gold NP surfaces and their modification were achieved in joint experimental and theoretical studies, using notably XPS, NMR, and DFT modeling. Our experimental studies and DFT analyses highlighted the necessary oxidative surface reorganization of individual nanoparticles for an effective enyne cycloisomerization. The modifications at bulky stabilizing ligands allow surface steric decongestion for the alkyne moiety activation but also result in network alteration by overoxidation of sulfurs. Thus, sub-2-nm nanoparticles originating from networks building create convenient conditions for generating reactive Au(I) surface single-sites-in the absence of silver additives-useful for heterogeneous gold-catalyzed enyne cyclization. These nanocatalysts, which as such ease organic products separation, also provide a convenient access for building further polycyclic complexity, owing to their high reactivity and selectivity.

Diversity of the Hydrogen Bond Network and Its Impact on NMR Parameters of Amylose B Polymorph: A Study Using Molecular Dynamics and DFT Calculations Within Periodic Boundary Conditions.

Classical molecular dynamics simulations have been combined with quantum (DFT) calculations of 13C NMR parameters in order to relate the experimental spectrum of the double-helix form of the amylose B-polymorph in highly crystalline conditions not only to its 3D structure but also to the arrangement of atoms in the crystal lattice. Structures obtained from these simulations or from geometry optimization procedures at the DFT level have shown the presence of hydrogen bond networks between sugars of the same helix or between residues of the two chains of the double helix. 13C NMR parameter calculations have revealed the impact of such a network on the chemical shifts of carbon atoms. In addition, DFT calculations using periodic boundary conditions were compulsory to highlight the presence of two types of sugar within the crystal sample. It allows us to confirm, theoretically, the experimental hypothesis that the existence of two distinct sugar types in the NMR spectrum is a consequence of crystal packing.

Giant Stark splitting of an exciton in bilayer MoS2.

Transition metal dichalcogenides (TMDs) constitute a versatile platform for atomically thin optoelectronics devices and spin-valley memory applications. In monolayer TMDs the optical absorption is strong, but the transition energy cannot be tuned as the neutral exciton has essentially no out-of-plane static electric dipole1,2. In contrast, interlayer exciton transitions in heterobilayers are widely tunable in applied electric fields, but their coupling to light is substantially reduced. In this work, we show tuning over 120 meV of interlayer excitons with a high oscillator strength in bilayer MoS2 due to the quantum-confined Stark effect3. We optically probed the interaction between intra- and interlayer excitons as they were energetically tuned into resonance. Interlayer excitons interact strongly with intralayer B excitons, as demonstrated by a clear avoided crossing, whereas the interaction with intralayer A excitons is substantially weaker. Our observations are supported by density functional theory (DFT) calculations, which include excitonic effects. In MoS2 trilayers, our experiments uncovered two types of interlayer excitons with and without in-built electric dipoles. Highly tunable excitonic transitions with large in-built dipoles and oscillator strengths will result in strong exciton-exciton interactions and therefore hold great promise for non-linear optics with polaritons.

Controlling interlayer excitons in MoS2 layers grown by chemical vapor deposition.

Combining MoS2 monolayers to form multilayers allows to access new functionalities. Deterministic assembly of large area van der Waals structures requires concrete indicators of successful interlayer coupling in bilayers grown by chemical vapor deposition. In this work, we examine the correlation between the stacking order and the interlayer coupling of valence states in both as-grown MoS2 homobilayer samples and in artificially stacked bilayers from monolayers, all grown by chemical vapor deposition. We show that hole delocalization over the bilayer is only allowed in 2H stacking and results in strong interlayer exciton absorption and also in a larger A-B exciton separation as compared to 3R bilayers. Comparing 2H and 3R reflectivity spectra allows to extract an interlayer coupling energy of about t⊥ = 49 meV. Beyond DFT calculations including excitonic effects confirm signatures of efficient interlayer coupling for 2H stacking in agreement with our experiments.

A Theory/Experience Description of Support Effects in Carbon-Supported Catalysts.

The support plays an important role for supported metal catalysts by positioning itself as a macromolecular ligand, which conditions the nature of the active site and contributes indirectly but also sometimes directly to the reactivity. Metal species such as nanoparticles, clusters, or single atoms can be deposited on carbon materials for various catalytic reactions. All the carbon materials used as catalyst support constitute a large family of compounds that can vary both at textural and at structural levels. Today, the recent developments of well-controlled synthesis methodologies, advanced characterization techniques, and modeling tools allow one to correlate the relationships between metal/support/reactant at the molecular level. Based on these considerations, in this Review article, we wish to provide some answers to the question "How and why anchoring metal nanoparticles, clusters, or single atoms on carbon materials for catalysis?". To do this, we will rely on both experimental and theoretical studies. We will first analyze what sites are available on the surface of a carbon support for the anchoring of the active phase. Then, we will describe some important effects in catalysis inherent to the presence of a carbon-type support (metal-support interaction, confinement, spillover, and surface functional group effects). These effects will be commented on by putting into perspective catalytic results obtained in numerous reactions of thermal catalysis, electrocatalysis, or photocatalysis.

Dependence of the magnetic interactions in MoS2 monolayer on Mn-doping configurations.

Understanding the magnetic properties of the various Mn doping configurations that can be encountered in 2H-MoS2 monolayer could be beneficial for its use in spintronics. Using density functional theory plus Hubbard term (DFT + U) approach, we study how a single isolated, double- and triple-substitution configurations of Mn atoms within a MoS2 monolayer could contribute to its total magnetization. We find that the doping-configuration plays a critical role in stabilizing a ferromagnetic state in a Mn-doped MoS2 monolayer. Indeed, the Mn-Mn magnetic interaction is found to be ferromagnetic and strong for Mn in equidistant substitution positions where the separation average range of 6-11 [Formula: see text]. The strongest ferromagnetic interaction is found when substitutions are in second nearest neighbor Mo-sites of the armchair chain. Clustering is energetically favorable but it strongly reduces the ferromagnetic exchange energies. Furthermore, in term of electronic properties, we show that the Mn-doped MoS2 monolayer can change its electronic behavior from semiconductor to half-metallic depending on the doping configuration. Our results suggest that ordering the Mn dopants on MoS2 monolayer is needed to increase its potential ferromagnetism.

Evaluation of Gas-to-Liquid 17O Chemical Shift of Water: A Test Case for Molecular and Periodic Approaches.

Modeling liquid water features is a challenging and ongoing task that brings together a number of computational issues related to the description both of its electronic and geometrical structure. In order to go a step further in the understanding of this peculiar liquid, we present a thorough analysis of NMR gas-to-liquid 17O and 1H shifts of water using density functional theory based molecular dynamics. In order to be as consistent as possible, we consider the influence of basis sets, exchange-correlation functionals, and structural models, in both molecular and periodic schemes, to evaluate 17O and 1H nuclear shieldings. We show that strong error compensations between functional and basis-set expansion can be obtained in molecular approaches which artificially produces good 17O gas-to-liquid shifts with relatively small basis sets. We also demonstrate that, despite their ability to provide reliable liquid phase structures, generalized-gradient approximation based exchange-correlation functionals lead to strongly inconsistent values for 17O gas-to-liquid shift. This latter property is shown to be strongly influenced by intramolecular electronic delocalization, accentuated by the surrounded molecules. In contrast, 1H is less sensitive to this effect. By including a Hartree-Fock exchange term, through the use of hybrid functionals which partially correct the self-interaction error, better agreement with experimental values is obtained. The present study provides a detailed guideline to properly evaluate gas-to-liquid shifts in hydrogen bonded systems and emphasizes that, for nuclear shieldings, an accurate electronic structure evaluation prevails over the description of the liquid structure.

Resolving the Framework Position of Organic Structure-Directing Agents in Hierarchical Zeolites via Polarized Stimulated Raman Scattering.

The direct synthesis of hierarchically intergrown silicalite-1 can be achieved using a specific diquaternary ammonium agent. However, the location of these molecules in the zeolite framework, which is critical to understand the formation of the material, remains unclear. Where traditional characterization tools have previously failed, herein we use polarized stimulated Raman scattering (SRS) microscopy to resolve molecular organization inside few-micron-sized crystals. Through a combination of experiment and first-principles calculations, our investigation reveals the preferential location of the templating agent inside the linear pores of the MFI framework. Besides illustrating the attractiveness of SRS microscopy in the field of material science to study and spatially resolve local molecular distribution as well as orientation, these results can be exploited in the design of new templating agents for the preparation of hierarchical zeolites.

Hexakis [60]Fullerene Adduct-Mediated Covalent Assembly of Ruthenium Nanoparticles and Their Catalytic Properties.

The C66 (COOH)12 hexa-adduct has been successfully used as a building block to construct carboxylate bridged 3D networks with very homogeneous sub-1.8 nm ruthenium nanoparticles. The obtained nanostructures are active in nitrobenzene selective hydrogenation.

Enlightening the ultrahigh electrical conductivities of doped double-wall carbon nanotube fibers by Raman spectroscopy and first-principles calculations.

Highly aligned, packed, and doped carbon nanotube (CNT) fibers with electrical conductivities approaching that of copper have recently become available. These fibers are promising for high-power electrical applications that require light-weight, high current-carrying capacity cables. However, a microscopic understanding of how doping affects the electrical conductance of such CNT fibers in a quantitative manner has been lacking. Here, we performed Raman spectroscopy measurements combined with first-principles calculations to determine the position of the average Fermi energy and to obtain the temperature of chlorosulfonic-acid-doped double-wall CNT fibers under high current. Due to the unique way in which double-wall CNT Raman spectra depend on doping, it is possible to use Raman data to determine the doping level quantitatively. The correspondence between the Fermi level shift and the carbon charge transfer is derived from a tight-binding model and validated by several calculations. For the doped fiber, we were able to associate an average Fermi energy shift of ∼-0.7 eV with a conductance increase by a factor of ∼5. Furthermore, since current induces heating, local temperature determination is possible. Through the Stokes-to-anti-Stokes intensity ratio of the G-band peaks, we estimated a temperature rise at the fiber surface of ∼135 K at a current density of 2.27 × 108 A m-2 identical to that from the G-band shift, suggesting that thermalization between CNTs is well achieved.

Spin-orbit engineering in transition metal dichalcogenide alloy monolayers.

Binary transition metal dichalcogenide monolayers share common properties such as a direct optical bandgap, spin-orbit splittings of hundreds of meV, light-matter interaction dominated by robust excitons and coupled spin-valley states. Here we demonstrate spin-orbit-engineering in Mo(1-x)WxSe2 alloy monolayers for optoelectronics and applications based on spin- and valley-control. We probe the impact of the tuning of the conduction band spin-orbit spin-splitting on the bright versus dark exciton population. For MoSe2 monolayers, the photoluminescence intensity decreases as a function of temperature by an order of magnitude (4-300 K), whereas for WSe2 we measure surprisingly an order of magnitude increase. The ternary material shows a trend between these two extreme behaviours. We also show a non-linear increase of the valley polarization as a function of tungsten concentration, where 40% tungsten incorporation is sufficient to achieve valley polarization as high as in binary WSe2.

Theoretical study of polyiodide formation and stability on monolayer and bilayer graphene.

The presence of polyiodide complexes have been reported several times when carbon-based materials were doped by iodine molecules, but their formation mechanism remains unclear. By using first-principles calculations that include nonlocal correlation effects by means of a van der Waals density functional approach, we propose that the formation of triiodide (I3(-)) and pentaiodide (I5(-)) is due to a large density of iodine molecules (I2) in interaction with a carbonaceous substrate. As soon as the concentration of surface iodine reaches a threshold value of 12.5% for a graphene monolayer and 6.25% for a bilayer, these complexes spontaneously appear. The corresponding structural and energetic aspects, electronic structures and vibrational frequencies support this statement. An upshift of the Dirac point from the Fermi level with values of 0.45 and 0.52 eV is observed for adsorbed complexes on graphene and intercalated complexes between two layers, respectively. For doped-graphene, it corresponds to a graphene hole density of around 1.1 × 10(13) cm(-2), in quantitative agreement with experiments. Additionally, we have studied the thermal stability at room temperature of these adsorbed ions on graphene by means of ab initio molecular dynamics, which also shows successful p-doping with polyiodide complexes.

Theoretical gas to liquid shift of (15)N isotropic nuclear magnetic shielding in nitromethane using ab initio molecular dynamics and GIAO/GIPAW calculations.

Chemical shift requires the knowledge of both the sample and a reference magnetic shielding. In few cases as nitrogen (15N), the standard experimental reference corresponds to its liquid phase. Theoretical estimate of NMR magnetic shielding parameters of compounds in their liquid phase is then mandatory but usually replaced by an easily-get gas phase value, forbidding direct comparisons with experiments. We propose here to combine ab initio molecular dynamic simulations with the calculations of magnetic shielding using GIAO approach on extracted cluster's structures from MD. Using several computational strategies, we manage to accurately calculate 15N magnetic shielding of nitromethane in its liquid phase. Theoretical comparison between liquid and gas phase allows us to extrapolate an experimental value for the 15N magnetic shielding of nitromethane in gas phase between -121.8 and -120.8 ppm.

Magnetic properties of bcc Iron surfaces and the influence of the chemical environment: electronic structure calculations.

We have investigated the magnetic properties of low-indexed iron surfaces and the influence of the chemical environment on these properties. We have considered the (1 0 0), (1 1 0), (1 1 1), (2 1 1) and (3 1 0) surfaces, both, bare and with the presence of adsorbates. These were chosen to mimic realistic chemical synthesis environments, being H, Cl, HCl, NH3, NH4Cl, or CH3COOH. We have found an increased magnetization at all bare surfaces. Upon H adsorption the magnetization is generally reduced, but still above the bulk value. All other ligands and their dissociated parts alter the magnetic properties of the surfaces only weakly. Our calculations do not indicate that ligands are responsible for experimental observations of Fe nanoparticles with average magnetizations below the bulk value.

Surfaces of a colloidal iron nanoparticle in its chemical environment: a DFT description.

Describing and understanding surface chemistry on the atomic scale is of primary importance in predicting and rationalize nanoparticle morphology as well as their physical and chemical properties. Here we present the results of comprehensive density functional theory studies on the adsorption of several small organic species, representing the major species (H2, Cl2, HCl, NH3, NH4Cl, and CH3COOH), present in the reaction medium during colloidal iron nanoparticle synthesis on various low-index iron surface models, namely, (100), (110), (111), (211), and (310). All of the tested ligands strongly interact with the proposed surfaces. Surface energies are calculated and ligand effects on the morphologies are presented, including temperature effects, based on a thermodynamic approach combined with the Wulff construction scheme. The importance of taking into account vibrational contributions during the calculation of surface energies after adsorption is clearly demonstrated. More importantly, we find that thermodynamic ligand effects can be ruled out as the unique driving force in the formation of recently experimentally observed iron cubic nanoparticles.