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Apart from broadband absorption of solar radiation, the performance of photovoltaic devices is governed by the density and mobility of photogenerated charge carriers. The latter parameters indicate how many free carriers move away from their origin, and how fast, before loss mechanisms such as carrier recombination occur. However, only lower bounds of these parameters are usually obtained. Here we independently determine both density and mobility of charge carriers in a perovskite film by the use of time-resolved terahertz spectroscopy. Our data reveal the modification of the free carrier response by strong backscattering expected from these heavily disordered perovskite films. The results for different phases and different temperatures show a change of kinetics from two-body recombination at room temperature to three-body recombination at low temperatures. Our results suggest that perovskite-based solar cells can perform well even at low temperatures as long as the three-body recombination has not become predominant.

Stomatopods are shallow-water crustaceans that employ powerful dactyl appendages to hunt their prey. Deployed at high velocities, these hammer-like clubs or spear-like devices are able to inflict substantial impact forces. Here we demonstrate that dactyl impact surfaces consist of a finely-tuned mineral gradient, with fluorapatite substituting amorphous apatite towards the outer surface. Raman spectroscopy measurements show that calcium sulphate, previously not reported in mechanically active biotools, is co-localized with fluorapatite. Ab initio computations suggest that fluorapatite/calcium sulphate interfaces provide binding stability and promote the disordered-to-ordered transition of fluorapatite. Nanomechanical measurements show that fluorapatite crystalline orientation correlates with an anisotropic stiffness response and indicate significant differences in the fracture tolerance between the two types of appendages. Our findings shed new light on the crystallochemical and microstructural strategies allowing these intriguing biotools to optimize impact forces, providing physicochemical information that could be translated towards the synthesis of impact-resistant functional materials and coatings.

This paper reports on highly active and stable amorphous Pd nanoparticle electrocatalysts for the oxygen reduction reaction. The amorphous catalysts were synthesized by a remarkably facile and quick electroless deposition process newly developed in this study (process time <5 min). An electrode substrate (glassy carbon, carbon cloth) was sequentially dipped for 10 s into two separate solutions of a reducing agent (sodium hypophosphite (NaH2PO2)) and Pd ions to deposit amorphous Pd nanoparticles containing phosphorus (Pd-P). By repeating the deposition cycles, the specific and mass activities of the Pd nanoparticles can be actively tuned. Owing to the nanoscale amorphous nature, the obtained Pd-P nanoparticle electrocatalysts exhibited superior specific and mass activities compared with crystalline Pd nanoparticles synthesized by another reducing agent (N2H4) and commercial Pt-loaded carbon (Pt/C) and Pd-loaded carbon (Pd/C). The specific and mass activities of the amorphous Pd-P nanoparticles were over 4.5 times and 2.6 times higher than previously reported values of Pd and Pt catalysts.

Coiled coils with defined assembly properties and dissociation constants are highly attractive components in synthetic biology and for fabrication of peptide-based hybrid nanomaterials and nanostructures. Complex assemblies based on multiple different peptides typically require orthogonal peptides obtained by negative design. Negative design does not necessarily exclude formation of undesired species and may eventually compromise the stability of the desired coiled coils. This work describe a set of four promiscuous 28-residue de novo designed peptides that heterodimerize and fold into parallel coiled coils. The peptides are non-orthogonal and can form four different heterodimers albeit with large differences in affinities. The peptides display dissociation constants for dimerization spanning from the micromolar to the picomolar range. The significant differences in affinities for dimerization make the peptides prone to thermodynamic social self-sorting as shown by thermal unfolding and fluorescence experiments, and confirmed by simulations. The peptides self-sort with high fidelity to form the two coiled coils with the highest and lowest affinities for heterodimerization. The possibility to exploit self-sorting of mutually complementary peptides could hence be a viable approach to guide the assembly of higher order architectures and a powerful strategy for fabrication of dynamic and tuneable nanostructured materials.

Oxygen evolution reaction (OER) is the limiting step in a photoelectrochemical (PEC) water splitting process. In this paper, the effect of oxygen vacancies (Ovac) on BiVO4 photoanode for PEC water splitting is studied using first-principles calculations. The results indicate that the holes transfer at the electrode/electrolyte interface play a defining role in determining the surface catalytic activities, and thus functional characteristics of BiVO4 photoanode. There are two main reasons behind the enhancement of OER on the surface of the photoanode. First, the V site becomes the active site for PEC water splitting and the number of the active sites are greatly increased by inducing oxygen vacancies. Second, the adsorption energies of H2Oads, OHads, and Oads are higher in the presence of Ovac, which implies enhanced hole transfer from the photoanode surface to the electrolyte. The change of Gibbs free energy indicates a high possibility of spontaneous charge transfer to the electrolyte, facilitating OER on surfaces with Ovac. These results provide important insights into the roles of Ovac on BiVO4 surface for photocatalytic reactions.

Pseudo-topotactic conversion of carbon nanotubes into one-dimensional carbon nanowires is a challenging but feasible path to obtain desired diameters and morphologies. Here, a previously predicted but experimentally unobserved carbon allotrope, T-carbon, has been produced from pseudo-topotactic conversion of a multi-walled carbon nanotube suspension in methanol by picosecond pulsed-laser irradiation. The as-grown T-carbon nanowires have the same diameter distribution as pristine carbon nanotubes, and have been characterized by high-resolution transmission electron microscopy, fast Fourier transform, electron energy loss, ultraviolet–visible, and photoluminescence spectroscopies to possess a diamond-like lattice, where each carbon is replaced by a carbon tetrahedron, and a lattice constant of 7.80 Å. The change in entropy from carbon nanotubes to T-carbon reveals the phase transformation to be first order in nature. The computed electronic band structures and projected density of states are in good agreement with the optical absorption and photoluminescence spectra of the T-carbon nanowires.