Water-Assisted Hole Trapping at the Highly Curved Surface of Nano-TiO2 Photocatalyst.

Heterogeneous photocatalysis is vital in solving energy and environmental issues that this society is confronted with. Although photocatalysts are often operated in the presence of water, it has not been yet clarified how the interaction with water itself affects charge dynamics in photocatalysts. Using water-coverage-controlled steady and transient infrared absorption spectroscopy and large-model (∼800 atoms) ab initio calculations, we clarify that water enhances hole trapping at the surface of TiO2 nanospheres but not of well-faceted nanoparticles. This water-assisted effect unique to the nanospheres originates from water adsorption as a ligand at a low-coordinated Ti-OH site or through robust hydrogen bonding directly to the terminal OH at the highly curved nanosphere surface. Thus, the interaction with water at the surface of nanospheres can promote photocatalytic reactions of both oxidation and reduction by elongating photogenerated carrier lifetimes. This morphology-dependent water-assisted effect provides a novel and rational basis for designing and engineering nanophotocatalyst morphology to improve photocatalytic performances.

Interfacing CRYSTAL/AMBER to Optimize QM/MM Lennard⁻Jones Parameters for Water and to Study Solvation of TiO2 Nanoparticles.

Metal oxide nanoparticles (NPs) are regarded as good candidates for many technological applications, where their functional environment is often an aqueous solution. The correct description of metal oxide electronic structure is still a challenge for local and semilocal density functionals, whereas hybrid functional methods provide an improved description, and local atomic function-based codes such as CRYSTAL17 outperform plane wave codes when it comes to hybrid functional calculations. However, the computational cost of hybrids are still prohibitive for systems of real sizes, in a real environment. Therefore, we here present and critically assess the accuracy of our electrostatic embedding quantum mechanical/molecular mechanical (QM/MM) coupling between CRYSTAL17 and AMBER16, and demonstrate some of its capabilities via the case study of TiO2 NPs in water. First, we produced new Lennard⁻Jones (LJ) parameters that improve the accuracy of water⁻water interactions in the B3LYP/TIP3P coupling. We found that optimizing LJ parameters based on water tri- to deca-mer clusters provides a less overstructured QM/MM liquid water description than when fitting LJ parameters only based on the water dimer. Then, we applied our QM/MM coupling methodology to describe the interaction of a 1 nm wide multilayer of water surrounding a spherical TiO2 nanoparticle (NP). Optimizing the QM/MM water⁻water parameters was found to have little to no effect on the local NP properties, which provide insights into the range of influence that can be attributed to the LJ term in the QM/MM coupling. The effect of adding additional water in an MM fashion on the geometry optimized nanoparticle structure is small, but more evident effects are seen in its electronic properties. We also show that there is good transferability of existing QM/MM LJ parameters for organic molecules⁻water interactions to our QM/MM implementation, even though these parameters were obtained with a different QM code and QM/MM implementation, but with the same functional.

Modelling realistic TiO2 nanospheres: A benchmark study of SCC-DFTB against hybrid DFT.

TiO2 nanoparticles (NPs) are nowadays considered fundamental building blocks for many technological applications. Morphology is found to play a key role with spherical NPs presenting higher binding properties and chemical activity. From the experimental point of view, the characterization of these nano-objects is extremely complex, opening a large room for computational investigations. In this work, TiO2 spherical NPs of different sizes (from 300 to 4000 atoms) have been studied with a two-scale computational approach. Global optimization to obtain stable and equilibrated nanospheres was performed with a self-consistent charge density functional tight-binding (SCC-DFTB) simulated annealing process, causing a considerable atomic rearrangement within the nanospheres. Those SCC-DFTB relaxed structures have been then optimized at the DFT(B3LYP) level of theory. We present a systematic and comparative SCC-DFTB vs DFT(B3LYP) study of the structural properties, with particular emphasis on the surface-to-bulk sites ratio, coordination distribution of surface sites, and surface energy. From the electronic point of view, we compare HOMO-LUMO and Kohn-Sham gaps, total and projected density of states. Overall, the comparisons between DFTB and hybrid density functional theory show that DFTB provides a rather accurate geometrical and electronic description of these nanospheres of realistic size (up to a diameter of 4.4 nm) at an extremely reduced computational cost. This opens for new challenges in simulations of very large systems and more extended molecular dynamics.

Optimizing electronic structure and quantum transport at the graphene-Si(111) interface: an ab initio density-functional study.

We use ab initio density-functional calculations to determine the interaction of a graphene monolayer with the Si(111) surface. We find that graphene forms strong bonds to the bare substrate and accommodates the 12% lattice mismatch by forming a wavy structure consisting of free-standing conductive ridges that are connected by ribbon-shaped regions of graphene, which bond covalently to the substrate. We perform quantum transport calculations for different geometries to study changes in the transport properties of graphene introduced by the wavy structure and bonding to the Si substrate. Our results suggest that wavy graphene combines high mobility along the ridges with efficient carrier injection into Si in the contact regions.

Impact of surface curvature, grafting density and solvent type on the PEGylation of titanium dioxide nanoparticles.

TiO2 nanoparticles (NPs) are attracting materials for biomedical applications, provided that they are coated with polymers to improve solubility, dispersion and biocompatibility. Conformation, coverage density and solvent effects largely influence their functionality and stability. In this work, we use atomistic molecular dynamics simulations to study polyethylene glycol (PEG) grafting to highly curved TiO2 NPs (2-3 nm) in different solvents. We compare the coating polymer conformations on NPs with those on (1 0 1) flat surfaces. In water, the transition from mushroom to brush conformation starts only at high density (σ = 2.25 chains/nm2). In dichloromethane (DCM), at low-medium coverage (σ < 1.35 chains/nm2), several interactions between the PEG chains backbone and undercoordinated Ti atoms are established, whereas at σ = 2.25 chains/nm2 the conformation clearly becomes brush-like. Finally, we demonstrate that these spherical brushes, when immersed in water, but not in DCM, follow the Daoud-Cotton (DC) classical scaling model for the polymer volume fraction dependence with the distance from the center of star-shaped systems.

Proton Transfers at a Dopamine-Functionalized TiO2 Interface.

Despite the many successful syntheses and applications of dopamine-functionalized TiO2 nanohybrids, there has not yet been an atomistic understanding of the interaction of this 1,2-dihydroxybenzene derivative ligand with the titanium dioxide surfaces. In this work, on the basis of a wide set of dispersion-corrected hybrid density functional theory (DFT) calculations and density functional tight binding (DFTB) molecular dynamics simulations, we present a detailed study of the adsorption modes, patterns of growth, and configurations of dopamine on the anatase (101) TiO2 surface, with reference to the archetype of 1,2-dihydroxybenzene ligands, i.e., catechol. At low coverage, the isolated dopamine molecule prefers to bend toward the surface, coordinating the NH2 group to a Ti5c ion. At high coverage, the packed molecules succeed in bending toward the surface only in some monolayer configurations. When they do, we observe a proton transfer from the surface to the ethyl-amino group, forming terminal NH3 + species, which highly interact with the O atoms of a neighboring dopamine molecule. This strong Coulombic interaction largely stabilizes the self-assembled monolayer. On the basis of these results, we predict that improving the probability of dopamine molecules being free to bend toward the surface through thermodynamic versus kinetic growth conditions will lead to a monolayer of fully protonated dopamine molecules.

Computational Electrochemistry of Water Oxidation on Metal-Doped and Metal-Supported Defective h-BN.

Metal-doped and metal-supported two-dimensional materials are attracting a lot of interest as potentially active electrocatalysts for reduction and oxidation processes. Previously, when a non-regular 2 D h-BN layer was grown on a Cu(111) surface, metal adatoms were found to spontaneously emerge from the bulk to fill the atomic holes in the structure and become available for surface catalysis. Herein, computational electrochemistry is used to investigate and compare the performance of Cu-doped and Cu-supported pristine and defective h-BN systems for the electrocatalytic water oxidation reaction. For the various model systems, the intermediate species of this multistep oxidation process are identified and the free-energy variations for each step of reaction are computed, even for those steps that do not involve an electron or a proton transfer. Both associative and O2 direct evolution mechanisms are considered. On this thermodynamic basis, the potential-determining step, the thermodynamic-determining step, and consequently the theoretical overpotential are determined for comparison with experiments. Small Cu clusters (tetramers) trapped in the h-BN defective lattice on a Cu(111) support are found to be very active for the water oxidation reaction since such systems are characterized by a low overpotential and by a small energy cost for O2 release from the catalyst, which is often observed to be a major limit for other potential electrocatalysts.

Optimizing PEGylation of TiO2 Nanocrystals through a Combined Experimental and Computational Study.

PEGylation of metal oxide nanoparticles is the common approach to improve their biocompatibility and in vivo circulation time. In this work, we present a combined experimental and theoretical study to determine the operating condition that guarantee very high grafting densities, which are desirable in any biomedical application. Moreover, we present an insightful conformational analysis spanning different coverage regimes and increasing polymer chain lengths. Based on 13C NMR measurements and molecular dynamics simulations, we show that classical and popular models of polymer conformation on surfaces fail in determining the mushroom-to-brush transition point and prove that it actually takes place only at rather high grafting density values.

Publisher Correction: An electrochemical thermal transistor.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Curved TiO2 Nanoparticles in Water: Short (Chemical) and Long (Physical) Range Interfacial Effects.

In most technological applications, nanoparticles are immersed in a liquid environment. Understanding nanoparticles/liquid interfacial effects is extremely relevant. This work provides a clear and detailed picture of the type of chemistry and physics taking place at the prototypical TiO2 nanoparticles/water interface, which is crucial in photocatalysis and photoelectrochemistry. We present a multistep and multiscale investigation based on hybrid density functional theory (DFT), density functional tight-binding, and quantum mechanics/molecular mechanics calculations. We consider increasing water partial pressure conditions from ultra-high vacuum up to the bulk water environment. We first investigate single water molecule adsorption modes on various types of undercoordinated sites present on a realistic curved nanoparticle (2-3 nm) and then, by decorating all the adsorption sites, we study a full water monolayer to identify the degree of water dissociation, the Brønsted-Lowry basicity/acidity of the nanoparticle in water, the interface effect on crystallinity, surface energy, and electronic properties, such as the band gap and work function. Furthermore, we increase the water coverage by adding water multilayers up to a thickness of 1 nm and perform molecular dynamics simulations, which evidence layer structuring and molecular orientation around the curved nanoparticle. Finally, we clarify whether these effects arise as a consequence of the tension at the water drop surface around the nanosphere by simulating a bulk water up to a distance of 3 nm from the oxide surface. We prove that the nanoparticle/water interfacial effects go rather long range since the dipole orientation of water molecules is observed up to a distance of 5 Å, whereas water structuring extends at least up to a distance of 8 Å from the surface.

An electrochemical thermal transistor.

The ability to actively regulate heat flow at the nanoscale could be a game changer for applications in thermal management and energy harvesting. Such a breakthrough could also enable the control of heat flow using thermal circuits, in a manner analogous to electronic circuits. Here we demonstrate switchable thermal transistors with an order of magnitude thermal on/off ratio, based on reversible electrochemical lithium intercalation in MoS2 thin films. We use spatially-resolved time-domain thermoreflectance to map the lithium ion distribution during device operation, and atomic force microscopy to show that the lithiated state correlates with increased thickness and surface roughness. First principles calculations reveal that the thermal conductance modulation is due to phonon scattering by lithium rattler modes, c-axis strain, and stacking disorder. This study lays the foundation for electrochemically-driven nanoscale thermal regulators, and establishes thermal metrology as a useful probe of spatio-temporal intercalant dynamics in nanomaterials.

Water at the Interface Between Defective Graphene and Cu or Pt (111) Surfaces.

The presence of defects in the graphenic layers deposited on metal surfaces modifies the nature of the interaction. Unsaturated carbon atoms, due to vacancies in the lattice, form strong organometallic bonds with surface metal atoms that highly enhance the binding energy between the two materials. We investigate by means of a wide set of dispersion-corrected density functional theory calculations how such strong chemical bonds affect both the electronic properties of these hybrid interfaces and the chemical reactivity with water, which is commonly present in the working conditions. We compare different metal substrates (Cu vs Pt) that present a different type of interaction with graphene and with defective graphene. This comparative analysis allows us to unravel the controlling factors of water reactivity, the role played by the carbon vacancies and by the confinement or "graphene cover effect". Water is capable of breaking the C-Cu bond by dissociating at the undercoordinated carbon atom of the vacancy, restoring the weak van der Waals type of interaction between the two materials that allows for an easy detachment of graphene from the metal, but the same is not true in the case of Pt, where C-Pt bonds are much stronger. These conclusions can be used to rationalize water reactivity at other defective graphene/metal interfaces.

Water Multilayers on TiO2 (101) Anatase Surface: Assessment of a DFTB-Based Method.

A water/(101) anatase TiO2 interface has been investigated with the DFT-based self-consistent-charge density functional tight-binding theory (SCC-DFTB). By comparison of the computed structural, energetic, and dynamical properties with standard DFT-GGA and experimental data, we assess the accuracy of SCC-DFTB for this prototypical solid-liquid interface. We tested different available SCC-DFTB parameters for Ti-containing compounds and, accordingly, combined them to improve the reliability of the method. To better describe water energetics, we have also introduced a modified hydrogen-bond-damping function (HBD). With this correction, equilibrium structures and adsorption energies of water on (101) anatase both for low (0.25 ML) and full (1 ML) coverages are in excellent agreement with those obtained with a higher level of theory (DFT-GGA). Furthermore, Born-Oppenheimer molecular dynamics (MD) simulations for mono-, bi-, and trilayers of water on the surface, as computed with SCC-DFTB, evidence similar ordering and energetics as DFT-GGA Car-Parrinello MD results. Finally, we have evaluated the energy barrier for the dissociation of a water molecule on the anatase (101) surface. Overall, the combined set of parameters with the HBD correction (SCC-DFTB+HBD) is shown to provide a description of the water/water/titania interface, which is very close to that obtained by standard DFT-GGA, with a remarkably reduced computational cost. Hence, this study opens the way to the future investigations on much more extended and realistic TiO2/liquid water systems, which are extremely relevant for many modern technological applications.

Ab Initio Investigation of Polyethylene Glycol Coating of TiO2 Surfaces.

In biomedical applications, TiO2 nanoparticles are generally coated with polymers to prevent agglomeration, improve biocompatibility, and reduce cytotoxicity. Although the synthesis processes of such composite compounds are well established, there is still a substantial lack of information on the nature of the interaction between the titania surface and the organic macromolecules. In this work, the adsorption of polyethylene glycol (PEG) on the TiO2 (101) anatase surface is modeled by means of dispersion-corrected density functional theory (DFT-D2) calculations. The two extreme limits of an infinite PEG polymer [-(OCH2CH2) n ], on one side, and of a short PEG dimer molecule [H(OCH2CH2)2OH], on the other, are analyzed. Many different molecular configurations and modes of adsorption are compared at increasing surface coverage densities. At low and medium coverage, PEG prefers to lay down on the surface, while at full coverage, the adsorption is maximized when PEG molecules bind perpendicularly to the surface and interact with each other through lateral dispersions, following a mushroom to brush transition. Finally, we also consider the adsorption of competing water molecules at different coverage densities, assessing whether PEG would remain bonded to the surface or desorb in the presence of the aqueous solvent.

Hierarchical thermoelectrics: crystal grain boundaries as scalable phonon scatterers.

Thermoelectric materials are strategically valuable for sustainable development, as they allow for the generation of electrical energy from wasted heat. In recent years several strategies have demonstrated some efficiency in improving thermoelectric properties. Dopants affect carrier concentration, while thermal conductivity can be influenced by alloying and nanostructuring. Features at the nanoscale positively contribute to scattering phonons, however those with long mean free paths remain difficult to alter. Here we use the concept of hierarchical nano-grains to demonstrate thermal conductivity reduction in rocksalt lead chalcogenides. We demonstrate that grains can be obtained by taking advantage of the reconstructions along the phase transition path that connects the rocksalt structure to its high-pressure form. Since grain features naturally change as a function of size, they impact thermal conductivity over different length scales. To understand this effect we use a combination of advanced molecular dynamics techniques to engineer grains and to evaluate thermal conductivity in PbSe. By affecting grain morphologies only, i.e. at constant chemistry, two distinct effects emerge: the lattice thermal conductivity is significantly lowered with respect to the perfect crystal, and its temperature dependence is markedly suppressed. This is due to an increased scattering of low-frequency phonons by grain boundaries over different size scales. Along this line we propose a viable process to produce hierarchical thermoelectric materials by applying pressure via a mechanical load or a shockwave as a novel paradigm for material design.

Novel metastable metallic and semiconducting germaniums.

Group-IVa elements silicon and germanium are known for their semiconducting properties at room temperature, which are technologically critical. Metallicity and superconductivity are found at higher pressures only, Ge ß-tin (tI4) being the first high-pressure metallic phase in the phase diagram. However, recent experiments suggest that metallicity in germanium is compatible with room conditions, calling for a rethinking of our understanding of its phase diagram. Missing structures can efficiently be identified based on structure prediction methods. By means of ab initio metadynamics runs we explored the lower-pressure region of the phase diagram of germanium. A monoclinic germanium phase (mC16) with four-membered rings, less dense than diamond and compressible into ß-tin phase (tI4) was found. Tetragonal bct-5 appeared between diamond and tI4. mC16 is a narrow-gap semiconductor, while bct-5 is metallic and potentially still superconducting in the very low pressure range. This finding may help resolving outstanding experimental issues.

Theoretical investigation of the electronic structure and quantum transport in the graphene-C(111) diamond surface system.

We investigate the interaction of a graphene monolayer with the C(111) diamond surface using ab initio density functional theory. To accommodate the lattice mismatch between graphene and diamond, the overlayer deforms into a wavy structure that binds strongly to the diamond substrate. The detached ridges of the wavy graphene overlayer behave electronically as free-standing polyacetylene chains with delocalized π electrons, separated by regions containing only sp(3) carbon atoms covalently bonded to the (111) diamond surface. We performed quantum transport calculations for different geometries of the system to study how the buckling of the graphene layer and the associated bonding to the diamond substrate affect the transport properties. The system displays high carrier mobility along the ridges and a wide transport gap in the direction normal to the ridges. These intriguing, strongly anisotropic transport properties qualify the hybrid graphene-diamond system as a viable candidate for electronic nanodevices.

Redox-switchable devices based on functionalized graphene nanoribbons.

The possibility of tuning the electronic properties of graphene by tailoring the morphology at the nanoscale or by chemical functionalization opens interesting perspectives towards the realization of devices for nanoelectronics. Indeed, the integration of the intrinsic high carrier mobilities of graphene with functionalities that are able to react to external stimuli allows in principle the realization of highly efficient nanostructured switches. In this paper, we report a novel approach to the design of reversible switches based on functionalized graphene nanoribbons, operating upon application of an external redox potential, which exhibit unprecedented ON/OFF ratios. The properties of the proposed systems are investigated by electronic structure and transport calculations based on density functional theory and rationalized in terms of valence-bond theory and Clar's sextet theory.