Adsorption of Glycine on TiO2 in Water from On-the-fly Free-Energy Calculations and In Situ Electrochemical Impedance Spectroscopy.

We report here an experimental-computational study of hydrated TiO2 anatase nanoparticles interacting with glycine, where we obtain quantitative agreement of the measured adsorption free energies. Ab initio simulations are performed within the tight binding and density functional theory in combination with enhanced free-energy sampling techniques, which exploit the thermodynamic integration of the unbiased mean forces collected on-the-fly along the molecular dynamics trajectories. The experiments adopt a new and efficient setup for electrochemical impedance spectroscopy measurements based on portable screen-printed gold electrodes, which allows fast and in situ signal assessment. The measured adsorption free energy is -30 kJ/mol (both from experiment and calculation), with preferential interaction of the charged NH3+ group which strongly adsorbs on the TiO2 bridging oxygens. This highlights the importance of the terminal amino groups in the adsorption mechanism of amino acids on hydrated metal oxides. The excellent agreement between computation and experiment for this amino acid opens the doors to the exploration of the interaction free energies for other moderately complex bionano systems.

Buried-Interface Engineering Enables Efficient and 1960-Hour ISOS-L-2I Stable Inverted Perovskite Solar Cells.

High-performance perovskite solar cells (PSCs) typically require interfacial passivation, yet this is challenging for the buried interface, owing to the dissolution of passivation agents during the deposition of perovskites. Here, this limitation is overcome with in situ buried-interface passivation-achieved via directly adding a cyanoacrylic-acid-based molecular additive, namely BT-T, into the perovskite precursor solution. Classical and ab initio molecular dynamics simulations reveal that BT-T spontaneously may self-assemble at the buried interface during the formation of the perovskite layer on a nickel oxide hole-transporting layer. The preferential buried-interface passivation results in facilitated hole transfer and suppressed charge recombination. In addition, residual BT-T molecules in the perovskite layer enhance its stability and homogeneity. A power-conversion efficiency (PCE) of 23.48% for 1.0 cm2 inverted-structure PSCs is reported. The encapsulated PSC retains 95.4% of its initial PCE following 1960 h maximum-power-point tracking under continuous light illumination at 65 °C (i.e., ISOS-L-2I protocol). The demonstration of operating-stable PSCs under accelerated ageing conditions represents a step closer to the commercialization of this emerging technology.

Low-loss contacts on textured substrates for inverted perovskite solar cells.

Inverted perovskite solar cells (PSCs) promise enhanced operating stability compared to their normal-structure counterparts1-3. To improve efficiency further, it is crucial to combine effective light management with low interfacial losses4,5. Here we develop a conformal self-assembled monolayer (SAM) as the hole-selective contact on light-managing textured substrates. Molecular dynamics simulations indicate that cluster formation during phosphonic acid adsorption leads to incomplete SAM coverage. We devise a co-adsorbent strategy that disassembles high-order clusters, thus homogenizing the distribution of phosphonic acid molecules, and thereby minimizing interfacial recombination and improving electronic structures. We report a laboratory-measured power conversion efficiency (PCE) of 25.3% and a certified quasi-steady-state PCE of 24.8% for inverted PSCs, with a photocurrent approaching 95% of the Shockley-Queisser maximum. An encapsulated device having a PCE of 24.6% at room temperature retains 95% of its peak performance when stressed at 65 °C and 50% relative humidity following more than 1,000 h of maximum power point tracking under 1 sun illumination. This represents one of the most stable PSCs subjected to accelerated ageing: achieved with a PCE surpassing 24%. The engineering of phosphonic acid adsorption on textured substrates offers a promising avenue for efficient and stable PSCs. It is also anticipated to benefit other optoelectronic devices that require light management.

Tautomeric mixture coordination enables efficient lead-free perovskite LEDs.

Lead halide perovskite light-emitting diodes (PeLEDs) have demonstrated remarkable optoelectronic performance1-3. However, there are potential toxicity issues with lead4,5 and removing lead from the best-performing PeLEDs-without compromising their high external quantum efficiencies-remains a challenge. Here we report a tautomeric-mixture-coordination-induced electron localization strategy to stabilize the lead-free tin perovskite TEA2SnI4 (TEAI is 2-thiopheneethylammonium iodide) by incorporating cyanuric acid. We demonstrate that a crucial function of the coordination is to amplify the electronic effects, even for those Sn atoms that aren't strongly bonded with cyanuric acid owing to the formation of hydrogen-bonded tautomeric dimer and trimer superstructures on the perovskite surface. This electron localization weakens adverse effects from Anderson localization and improves ordering in the crystal structure of TEA2SnI4. These factors result in a two-orders-of-magnitude reduction in the non-radiative recombination capture coefficient and an approximately twofold enhancement in the exciton binding energy. Our lead-free PeLED has an external quantum efficiency of up to 20.29%, representing a performance comparable to that of state-of-the-art lead-containing PeLEDs6-12. We anticipate that these findings will provide insights into the stabilization of Sn(II) perovskites and further the development of lead-free perovskite applications.

Water on ceria{111}: Comparison between 23 experimental vibrational studies in the literature and new modeling.

Theoretical and experimental vibrational signatures of H2O and OH- (dissociated water) adsorbed on stoichiometric ceria{111} surfaces are compared. The experimental ones were collected from low-coverage experiments in the literature, and the theoretical anharmonic frequencies were generated using density functional theory calculations employing the optPBE-vdW functional for coverages from 0.5 to a few monolayers. It is found that (i) the experiments and our calculations overall agree well, lending credibility to both; (ii) the calculations manage to resolve the large class of H-bonded motifs into frequency classes that can guide experimental assignments; (iii) it is possible to find a geometrical H-bond definition that also captures the OH vibrational frequency downshifts well: R(H⋯O) ≤2.5 Å and the O-H⋯O angle θ ≥ 100°; and (iv) the frequency vs electric field relations for water and hydroxides (i.e., dissociated water) follow different and well-separated curves.

Origin of the Hydrophobic Behaviour of Hydrophilic CeO2.

The nature of the hydrophobicity found in rare-earth oxides is intriguing. The CeO2 (100) surface, despite its strongly hydrophilic nature, exhibits hydrophobic behaviour when immersed in water. In order to understand this puzzling and counter-intuitive effect we performed a detailed analysis of the confined water structure and dynamics. We report here an ab-initio molecular dynamics simulation (AIMD) study which demonstrates that the first adsorbed water layer, in immediate contact with the hydroxylated CeO2 surface, generates a hydrophobic interface with respect to the rest of the liquid water. The hydrophobicity is manifested in several ways: a considerable diffusion enhancement of the confined liquid water as compared with bulk water at the same thermodynamic condition, a weak adhesion energy and few H-bonds above the hydrophobic water layer, which may also sustain a water droplet. These findings introduce a new concept in water/rare-earth oxide interfaces: hydrophobicity mediated by specific water patterns on a hydrophilic surface.

Vertical-Flow Paper Sensor for On-Site and Prompt Evaluation of Chloride Contamination in Concrete Structures.

Corrosion occurring in reinforced concrete has turned into a primary concern of the current century, concrete being the most ubiquitous and predominant material used in the construction industry. Among the many interrelated processes that trigger corrosion of metallic reinforcements, the penetration of chloride ions into the concrete matrix is the most insidious threat. Herein, we developed the first electrochemical device entirely made of paper that allows for the direct, prompt, and noninvasive evaluation of free chloride ion contamination in concrete-based constructions. Our device is based on a three-layer wax-modified filter paper, consisting of two Ag/AgCl screen-printed electrodes that are interfaced by a junction pad in a sandwich-like configuration. Filter paper allows for generating a vertical-flow potentiometric device capable of measuring the electrochemical potential between two solutions containing different concentrations of chloride ions, which are separately drop-cast on the top and bottom layers. After demonstrating the analytical performance of the device, the same principle was applied to the evaluation of the chloride contents in different concrete samples, exploiting paper as a suitable interfacing material for potentiometric measurements on the cement solid surface. Laboratory-prepared concrete samples with known chloride contents were first assessed, and then, the paper-based vertical-flow device was applied to real concrete structures at the Giacomo Manzù Museum (Ardea, Italy) for the evaluation of chloride contamination caused by the proximity to the seaside. The capability of our device to provide timely warning of the risk conditions of concrete-based artifacts was demonstrated.

Supercooled liquid-like dynamics in water near a fully hydrated titania surface: Decoupling of rotational and translational diffusion.

We report an ab initio molecular dynamics (MD) simulation investigating the effect of a fully hydrated surface of TiO2 on the water dynamics. It is found that the universal relation between the rotational and translational diffusion characteristics of bulk water is broken in the water layers near the surface with the rotational diffusion demonstrating progressive retardation relative to the translational diffusion when approaching the surface. This kind of rotation-translation decoupling has so far only been observed in the supercooled liquids approaching glass transition, and its observation in water at a normal liquid temperature is of conceptual interest. This finding is also of interest for the application-significant studies of the water interaction with fully hydrated nanoparticles. We note that this is the first observation of rotation-translation decoupling in an ab initio MD simulation of water.

Self-assembly of a triply periodic continuous mesophase with Fddd symmetry in simple one-component liquids.

Triply periodic continuous morphologies (networks) arising as a result of the microphase separation in block copolymer melts have so far never been observed self-assembled in systems of particles with spherically symmetric interaction. We report a molecular dynamics simulation where two simple one-component liquids form upon cooling an equilibrium network with the Fddd space group symmetry. This complexity reduction in the liquid network formation in terms of the particle geometry and the number of components evidences the generic nature of this class of phase transition, suggesting opportunities for producing these structures in a variety of new systems.

Hexatic smectic phase with algebraically decaying bond-orientational order.

The hexatic phase predicted by the theories of two-dimensional melting is characterized by the power-law decay of the orientational correlations, whereas the in-layer bond orientational order in all the hexatic smectic phases observed so far was found to be long range. We report a hexatic smectic phase where the in-layer bond orientational correlations decay algebraically, in quantitative agreement with the hexatic ordering predicted by the theory for two dimensions. The phase was formed in a molecular dynamics simulation of a one-component system of particles interacting via a spherically symmetric potential. The present results thus demonstrate that the theoretically predicted two-dimensional hexatic order can exist in a three-dimensional system.

Diffusion and reaction pathways of water near fully hydrated TiO2 surfaces from ab initio molecular dynamics.

Ab initio molecular dynamics simulations are reported for water-embedded TiO2 surfaces to determine the diffusive and reactive behavior at full hydration. A three-domain model is developed for six surfaces [rutile (110), (100), and (001), and anatase (101), (100), and (001)] which describes waters as "hard" (irreversibly bound to the surface), "soft" (with reduced mobility but orientation freedom near the surface), or "bulk." The model explains previous experimental data and provides a detailed picture of water diffusion near TiO2 surfaces. Water reactivity is analyzed with a graph-theoretic approach that reveals a number of reaction pathways on TiO2 which occur at full hydration, in addition to direct water splitting. Hydronium (H3O+) is identified to be a key intermediate state, which facilitates water dissociation by proton hopping between intact and dissociated waters near the surfaces. These discoveries significantly improve the understanding of nanoscale water dynamics and reactivity at TiO2 interfaces under ambient conditions.

Reactive wetting properties of TiO2 nanoparticles predicted by ab initio molecular dynamics simulations.

Small-sized wet TiO2 nanoparticles have been investigated by ab initio molecular dynamics simulations. Chemical and physical adsorption of water on the TiO2-water interface was studied as a function of water content, ranging from dry nanoparticles to wet nanoparticles with monolayer coverage of water. The surface reactivity was shown to be a concave function of water content and driven by surface defects. The local coordination number at the defect was identified as the key factor to decide whether water adsorption proceeds through dissociation or physisorption on the surface. A consistent picture of TiO2 nanoparticle wetting at the microscopic level emerges, which corroborates existing experimental data and gives further insight into the molecular mechanisms behind nanoparticle wetting. These calculations will facilitate the engineering of metal oxide nanoparticles with a controlled catalytic water activity.

Water driven adsorption of amino acids on the (101) anatase TiO2 surface: an ab initio study.

Arg, Lys and Asp amino acids are known to play a critical role in the adhesion of the RKLPDA engineered peptide on the (101) surface of the titania anatase phase. To understand their contribution to peptide adhesion, we have considered the relevant charge states due to protonation (Arg and Lys) or deprotonation (Asp) occurring in neutral water solution, and studied their adsorption on the (101) anatase TiO2 surface by ab initio total energy calculations based on density functional theory. The adsorption configurations on the hydrated surface are compared to those on the dry surface considering also the presence of the hydration shell around amino acid side-chains. This study explains how water molecules mediate the adsorption of charged amino acids showing that protonated amino acids are chemically adsorbed much more strongly than de-protonated Asp. Moreover it is shown that the polar screening of the hydration shell reduces the adsorption energy of the protonated amino acids to a small extent, thus evidencing that both Arg and Lys strongly adhere on the (101) anatase TiO2 surface in neutral water solution and that they play a major role in the adhesion of the RKLPDA peptide.