Nicolas Onofrio

La Théorie de la Fonctionnelle de la Densité (DFT) combinée avec la méthode de la Symétrie Brisée (BS) est aujourd'hui très utilisée dans le domaine du magnétisme moléculaire pour le calcul des constantes d'échange. Cette méthode (DFT-BS) reste cependant semi-quantitative et elle souffre de défauts déjà discutés dans la littérature. Dans le but de mieux en comprendre l'origine, nous avons réexaminé les contributions physiques qui participent au mécanisme d'échange. Nous proposons alors plusieurs formules analytiques construites suivant deux approches complémentaires (orbitales moléculaires et liaison de valence). Au cours de notre analyse, nous avons soulevé un problème inédit relatif à l'état de symétrie brisée tel que livré par le calcul DFT. Nos modèles seront appliqués au cas des dimères de cuivre(II) et nous verrons comment quantifier les différents paramètres afin de reconstruire les constantes d'échange. Qui plus est, notre travail permet d'établir une correspondance quantitative originale entre les deux approches pré-citées.

2D transition‐metal dichalcogenides (TMDs) based nanolaminates are promising candidates for water purification. However, fabricating nanochannels with tunable capillary widths remain a challenge. This study proposed a sulfur vacancy functionalization strategy for fabricating high performance nanolaminate membranes by grafting three kinds of thiol (S‐H) containing molecules (Cysteine, 3‐Mercapto‐1,2‐propanediol, 1‐Propanethiol) on MoS₂ nanosheets, in which propanethiol functionalized MoS₂ membrane exhibited best salt rejection (99.3%) and water/salt selectivity (800 bar⁻¹) in forward osmosis (draw solution: sucrose solution). It is found the capillary width increased from 0.2 Å in pristine MoS₂ to ≈5 Å in propanethiol functionalized MoS₂ membranes. Numerical simulations suggest that nanofluidic properties of the functionalized membranes are governed by the fundamental interaction between water and the corresponding S‐H functional group, and the interlayer distance. Importantly, since the S‐H containing molecules can repair MoS₂ nanosheets by fitting into the sulfur vacancies, the stability of the membranes is also improved with minimal swelling, which is promising for their practical applications.

Electrode–electrolyte interfacial properties characterize the functioning of electrochemical devices, and reactive molecular dynamics simulations, using reactive force fields (ReaxFF) and charge equilibration (QEq) techniques, are classical atomistic methods for investigating the processes that govern the device properties. However, the numerical implementation of ReaxFF and QEq treats Coulomb interaction with a short-distance cutoff for computational speed, thereby limiting interactions among atoms to a domain containing only their neighbor lists. Excluding long-distance Coulomb interactions makes the description of electrostatics in large-scale systems intractable. We apply Ewald sum in the extension of ReaxFF to include long-range Coulomb (LRC) interactions and investigate the effect of the inclusion on the electrostatic and capacitive properties of graphene–water interfaces at different applied potentials in comparison with the original ReaxFF. The study shows that with the inclusion of long-range Coulomb, the capacitance amounts to 4.9 ± 0.2 μF cm−2 compared with 4.4 ± 0.2 μF cm−2 predicted by the original ReaxFF [with short-range Coulomb (SRC)]; thus, indicating that SRC underestimates the capacitance of water between graphene walls by 12% when compared with the 5.0 μF cm−2 predicted with the extended simple point charge (SPC/E) water model. Thus, the results indicate that LRC ReaxFF/QEq have the ability and advantage to model electrochemical processes at a more realistic Coulomb interaction description and foster the processing of the details about the operation of electrochemical devices than the SRC.

Atomic description of electrochemical systems requires reactive interaction potential to explicitly describe the chemistry between atoms and molecules and the evolving charge distribution and polarization effects. Calculating Coulomb electrostatic interactions and polarization effects requires a better estimate of the partial charge distribution in molecular systems. However, models such as reactive force fields and charge equilibration (QEq) include Coulomb interactions up to a short-distance cutoff for better computational speeds. Ignoring long-distance electrostatic interaction affects the ability to describe electrochemistry in large systems. We studied the long-range Coulomb effects among charged particles and extended the QEq method to include long-range effects. By this extension, we anticipate a proper account of Coulomb interactions in reactive molecular dynamics simulations. We validate the approach by computing charges on a series of metal-organic frameworks and some simple systems. Results are compared to regular QEq and quantum mechanics calculations. The study shows slightly overestimated charge values in the regular QEq approach. Moreover, our method was combined with Ewald summation to compute forces and evaluate the long-range effects of simple capacitor configurations. There were noticeable differences between the calculated charges with/without long-range Coulomb interactions. The difference, which may have originated from the long-range influence on the capacitor ions, makes the Ewald method a better descriptor of Coulomb electrostatics for charged electrodes. The approach explored in this study enabled the atomic description of electrochemical systems with realistic electrolyte thickness while accounting for the electrostatic effects of charged electrodes throughout the dielectric layer in devices like batteries and emerging solid-state memory.

The electrochemical formation of liquid sulfur at room temperature on the basal plane of MoS₂ has attracted much attention due to the high areal capacity and rapid kinetics of lithium-liquid sulfur chemistry. However, the liquid sulfur is converted to the solid phase once it contacts the solid sulfur crystals generated from the edge of MoS₂. Thus, stable liquid sulfur cannot be formed on the entire MoS₂ surface. Herein, we report entire liquid sulfur generation on hydrogen-annealed MoS₂ (H₂-MoS₂), even under harsh conditions of large overpotentials and low working temperatures. The origins of the solely liquid sulfur formation are revealed to be the weakened interactions between H₂-MoS₂ and sulfur molecules and the decreased electrical polarization on the edges of the H₂-MoS₂. Progressive nucleation and droplet-merging growth behaviors are observed during the sulfur formation on H₂-MoS₂, signifying high areal capacities by releasing active H₂-MoS₂ surfaces. To demonstrate the universality of this strategy, other transition-metal dichalcogenides (TMDs) annealed in hydrogen also exhibit similar sulfur growth behaviors. Furthermore, the H₂ annealing treatment can induce sulfur vacancies on the basal plane and partial oxidation on the edge of TMDs, which facilitates liquid sulfur formation. Finally, liquid sulfur can be generated on H₂-MoS₂ flakes at an ultralow temperature of -50 °C, which provides a possible development of low-temperature lithium-sulfur batteries. This work demonstrates the potential of a pure liquid sulfur-lithium electrochemical system using functionalized two-dimensional materials.

The conversion of CO₂ into desirable multicarbon products via the electrochemical reduction reaction holds promise to achieve a circular carbon economy. Here, we report a strategy in which we modify the surface of bimetallic silver-copper catalyst with aromatic heterocycles such as thiadiazole and triazole derivatives to increase the conversion of CO₂ into hydrocarbon molecules. By combining operando Raman and X-ray absorption spectroscopy with electrocatalytic measurements and analysis of the reaction products, we identified that the electron withdrawing nature of functional groups orients the reaction pathway towards the production of C₂₊ species (ethanol and ethylene) and enhances the reaction rate on the surface of the catalyst by adjusting the electronic state of surface copper atoms. As a result, we achieve a high Faradaic efficiency for the C₂₊ formation of ≈80% and full-cell energy efficiency of 20.3% with a specific current density of 261.4 mA cm⁻² for C₂₊ products.

As the challenges in continued scaling of the integrated circuit technology escalate every generation, there is an urgent need to find viable solutions for both the front-end-of-line (transistors) and the back-end-of-line (interconnects). For the interconnect technology, it is crucial to replace the conventional barrier and liner with much thinner alternatives so that the current driving capability of the interconnects can be maintained or even improved. Due to the inherent atomically thin body thicknesses, 2D materials have recently been proposed and explored as Cu diffusion barrier alternatives. In this Perspective article, a variety of 2D materials that have been studied, ranging from graphene, h-BN, MoS₂, WSe₂ to TaS₂, will be reviewed. Their potentials will be evaluated based on several criteria, including fundamental material properties as well as the feasibility for technology integration. Using TaS₂ as an example, we demonstrate a large set of promising properties and point out that there remain challenges in the integration aspects with a few possible solutions waiting for validation. Applications of 2D materials for other functions in Cu interconnects and for different metal types will also be introduced, including electromigration, cobalt interconnects, and radio-frequency transmission lines.

The limit of polysulfides anchoring and the catalytic capability of MoS₂ is approached by the design of 1T MoS₂ nanodots.

Nanolaminate membranes made of two-dimensional materials such as graphene oxide are promising candidates for molecular sieving via size-limited diffusion in the two-dimensional capillaries, but high hydrophilicity makes these membranes unstable in water. Here, we report a nanolaminate membrane based on covalently functionalized molybdenum disulfide (MoS₂) nanosheets. The functionalized MoS₂ membranes demonstrate >90% and ~87% rejection for micropollutants and NaCl, respectively, when operating under reverse osmotic conditions. The sieving performance and water flux of the functionalized MoS₂ membranes are attributed both to control of the capillary widths of the nanolaminates and to control of the surface chemistry of the nanosheets. We identify small hydrophobic functional groups, such as the methyl group, as the most promising for water purification. Methyl- functionalized nanosheets show high water permeation rates as confirmed by our molecular dynamic simulations, while maintaining high NaCl rejection. Control of the surface chemistry and the interlayer spacing therefore offers opportunities to tune the selectivity of the membranes while enhancing their stability.