Direct Visualization of a Gold Nanoparticle Electron Trapping Effect.

A new atomic-scale anisotropy in the photoreaction of surface carboxylates on rutile TiO2(110) induced by gold clusters is found. STM and DFT+U are used to study this phenomenon by monitoring the photoreaction of a prototype hole-scavenger molecule, benzoic acid, over stoichiometric (s) s-TiO2, Au9/s-TiO2, and reduced (r) Au9/r-TiO2. STM results show that benzoic acid adsorption displaces a large fraction of Au clusters from the terraces toward their edges. DFT calculations explain that Au9 clusters on stoichiometric TiO2 are distorted by benzoic acid adsorption. The influence of sub-monolayers of Au on the UV/visible photoreaction of benzoic acid was explored at room temperature, with adsorbate depletion taken as a measure of activity. The empty sites, observed upon photoexcitation, occurred in elongated chains (2 to 6 molecules long) in the [11̅0] and [001] directions. A roughly 3-fold higher depletion rate is observed in the [001] direction. This is linked to the anisotropic conduction of excited electrons along [001], with subsequent trapping by Au clusters leaving a higher concentration of holes and thus an increased decomposition rate. To our knowledge this is the first time that atomic-scale directionality of a chemical reaction is reported upon photoexcitation of the semiconductor.

Trapping shape-controlled nanoparticle nucleation and growth stages via continuous-flow chemistry.

Continuous flow chemistry is used to trap the nucleation and growth stages of platinum-nickel nano-octahedra with second time resolution and high throughputs to probe their properties ex situ. The growth starts from poorly crystalline particles (nucleation) at 5 seconds, to crystalline 1.5 nm particles bounded by the {111}-facets at 7.5 seconds, followed by truncation and further growth to octahedral nanoparticles at 20 seconds.

pH-Induced Surface Modification of Atomically Precise Silver Nanoclusters: An Approach for Tunable Optical and Electronic Properties.

Noble metal nanoclusters (NCs) play a pivotal role in bridging the gap between molecules and quantum dots. Fundamental understanding of the evolution of the structural, optical, and electronic properties of these materials in various environments is of paramount importance for many applications. Using state-of-the-art spectroscopy, we provide the first decisive experimental evidence that the structural, electronic, and optical properties of Ag44(MNBA)30 NCs can now be tailored by controlling the chemical environment. Infrared and photoelectron spectroscopies clearly indicate that there is a dimerization between two adjacent ligands capping the NCs that takes place upon lowering the pH from 13 to 7.

The electronic structure of Au25 clusters: between discrete and continuous.

Here, an approach based on synchrotron resonant photoemission is employed to explore the transition between quantization and hybridization of the electronic structure in atomically precise ligand-stabilized nanoparticles. While the presence of ligands maintains quantization in Au25 clusters, their removal renders increased hybridization of the electronic states in the vicinity of the Fermi level. These observations are supported by DFT studies.

Tailoring ruthenium exposure to enhance the performance of fcc platinum@ruthenium core-shell electrocatalysts in the oxygen evolution reaction.

The catalytic properties of noble metal nanocrystals are a function of their size, structure, and surface composition. In particular, achieving high activity without sacrificing stability is essential for designing commercially viable catalysts. A major challenge in designing state-of-the-art Ru-based catalysts for the oxygen evolution reaction (OER), which is a key step in water splitting, is the poor stability and surface tailorability of these catalysts. In this study, we designed rapidly synthesizable size-controlled, morphology-selective, and surface-tailored platinum-ruthenium core-shell (Pt@Ru) and alloy (PtRu) nanocatalysts in a scalable continuous-flow reactor. These core-shell nanoparticles with atomically precise shells were produced in a single synthetic step with carbon monoxide as the reducing agent. By varying the metal precursor concentration, a dendritic or layer-by-layer ruthenium shell can be grown. The synthesized Pt@Ru and PtRu nanoparticles exhibit noticeably higher electrocatalytic activity in the OER compared to that of pure Pt and Ru nanoparticles. Promisingly, Pt@Ru nanocrystals with a ∼2-3 atomic layer Ru cuboctahedral shell surpass conventional Ru nanoparticles in terms of both durability and activity.

Heterovalent Dopant Incorporation for Bandgap and Type Engineering of Perovskite Crystals.

Controllable doping of semiconductors is a fundamental technological requirement for electronic and optoelectronic devices. As intrinsic semiconductors, hybrid perovskites have so far been a phenomenal success in photovoltaics. The inability to dope these materials heterovalently (or aliovalently) has greatly limited their wider utilizations in electronics. Here we show an efficient in situ chemical route that achieves the controlled incorporation of trivalent cations (Bi(3+), Au(3+), or In(3+)) by exploiting the retrograde solubility behavior of perovskites. We term the new method dopant incorporation in the retrograde regime. We achieve Bi(3+) incorporation that leads to bandgap tuning (∼300 meV), 10(4) fold enhancement in electrical conductivity, and a change in the sign of majority charge carriers from positive to negative. This work demonstrates the successful incorporation of dopants into perovskite crystals while preserving the host lattice structure, opening new avenues to tailor the electronic and optoelectronic properties of this rapidly emerging class of solution-processed semiconductors.

Porphyrinic supramolecular daisy chains incorporating pillar[5]arene-viologen host-guest interactions.

A porphyrin functionalised with pillar[5]arene and a viologen at its 5- and 15-meso positions assembles in a head-to-tail manner, producing linear supramolecular daisy chains in dichloromethane. At high concentrations, it forms an organogel which has been investigated by electron microscopy and rheological measurements, paving the way for the preparation of other functional supramolecular assemblies which harness viologen⊂pillararene host-guest interactions.

Solar cells. Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals.

The fundamental properties and ultimate performance limits of organolead trihalide MAPbX3 (MA = CH3NH3(+); X = Br(-) or I(-)) perovskites remain obscured by extensive disorder in polycrystalline MAPbX3 films. We report an antisolvent vapor-assisted crystallization approach that enables us to create sizable crack-free MAPbX3 single crystals with volumes exceeding 100 cubic millimeters. These large single crystals enabled a detailed characterization of their optical and charge transport characteristics. We observed exceptionally low trap-state densities on the order of 10(9) to 10(10) per cubic centimeter in MAPbX3 single crystals (comparable to the best photovoltaic-quality silicon) and charge carrier diffusion lengths exceeding 10 micrometers. These results were validated with density functional theory calculations.

The complete in-gap electronic structure of colloidal quantum dot solids and its correlation with electronic transport and photovoltaic performance.

The direct observation of the complete electronic band structure of a family of PbS CQD solids via photoelectron spectroscopy is reported. We investigate how materials processing strategies, such as the latest passivation methods that produce record-performance photovoltaics, achieve their performance advances. Halide passivated films show a drastic reduction in states in the midgap, contributing to a marked improvement in the device performance.