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Inorganic-organic hybrid materials represent a large share of newly reported structures, owing to their simple synthetic routes and customizable properties1. This proliferation has led to a characterization bottleneck: many hybrid materials are obligate microcrystals with low symmetry and severe radiation sensitivity, interfering with the standard techniques of single-crystal X-ray diffraction2,3 and electron microdiffraction4-11. Here we demonstrate small-molecule serial femtosecond X-ray crystallography (smSFX) for the determination of material crystal structures from microcrystals. We subjected microcrystalline suspensions to X-ray free-electron laser radiation12,13 and obtained thousands of randomly oriented diffraction patterns. We determined unit cells by aggregating spot-finding results into high-resolution powder diffractograms. After indexing the sparse serial patterns by a graph theory approach14, the resulting datasets can be solved and refined using standard tools for single-crystal diffraction data15-17. We describe the ab initio structure solutions of mithrene (AgSePh)18-20, thiorene (AgSPh) and tethrene (AgTePh), of which the latter two were previously unknown structures. In thiorene, we identify a geometric change in the silver-silver bonding network that is linked to its divergent optoelectronic properties20. We demonstrate that smSFX can be applied as a general technique for structure determination of beam-sensitive microcrystalline materials at near-ambient temperature and pressure.

Interfacial Schottky barriers can impact the catalytic function of Pt on TiO2. Since the electronic structure is characteristic of each material, it may be advantageous to tailor the interfacial Schottky barrier by the addition of adsorbed layers. Here, we show that the Schottky barrier in Pt/TiO2can be mitigated by the insertion of self-assembled monolayers (SAM) of carboranethiols that possess an oriented dipole moment. A Pt substrate with the SAM on which TiO2nanoparticles are deposited is used to that effect. Kelvin Probe Force Microscopy shows thatm-9-carboranethiolate SAM with perpendicular dipole moments decreases the potential difference between TiO2and Pt by ∼0.3 eV due to the interfacial electric field of the SAM. Our findings open new opportunities for tailoring interfacial electronic structures not only in the metal-semiconductor junction, but also the semiconductor heterojunctions.

Two-dimensional (2D) excitons arise from electron-hole confinement along one spatial dimension. Such excitations are often described in terms of Frenkel or Wannier limits according to the degree of exciton spatial localization and the surrounding dielectric environment. In hybrid material systems, such as the 2D perovskites, the complex underlying interactions lead to excitons of an intermediate nature, whose description lies somewhere between the two limits, and a better physical description is needed. Here, we explore the photophysics of a tuneable materials platform where covalently bonded metal-chalcogenide layers are spaced by organic ligands that provide confinement barriers for charge carriers in the inorganic layer. We consider self-assembled, layered bulk silver benzeneselenolate, [AgSePh]∞, and use a combination of transient absorption spectroscopy and ab initio GW plus Bethe-Salpeter equation calculations. We demonstrate that in this non-polar dielectric environment, strongly anisotropic excitons dominate the optical transitions of [AgSePh]∞. We find that the transient absorption measurements at room temperature can be understood in terms of low-lying excitons confined to the AgSe planes with in-plane anisotropy, featuring anisotropic absorption and emission. Finally, we present a pathway to control the exciton behaviour by changing the chalcogen in the material lattice. Our studies unveil unexpected excitonic anisotropies in an unexplored class of tuneable, yet air-stable, hybrid quantum wells, offering design principles for the engineering of an ordered, yet complex dielectric environment and its effect on the excitonic phenomena in such emerging materials.

Ultrathin transition metal carbides with high capacity, high surface area, and high conductivity are a promising family of materials for applications from energy storage to catalysis. However, large-scale, cost-effective, and precursor-free methods to prepare ultrathin carbides are lacking. Here, we demonstrate a direct pattern method to manufacture ultrathin carbides (MoCx, WCx, and CoCx) on versatile substrates using a CO2 laser. The laser-sculptured polycrystalline carbides (macroporous, ~10-20 nm wall thickness, ~10 nm crystallinity) show high energy storage capability, hierarchical porous structure, and higher thermal resilience than MXenes and other laser-ablated carbon materials. A flexible supercapacitor made of MoCx demonstrates a wide temperature range (-50 to 300 °C). Furthermore, the sculptured microstructures endow the carbide network with enhanced visible light absorption, providing high solar energy harvesting efficiency (~72 %) for steam generation. The laser-based, scalable, resilient, and low-cost manufacturing process presents an approach for construction of carbides and their subsequent applications.

India represents one-third of the world's fluorosis burden and is the fifth global producer of bauxite ore, which has previously been identified as a potential resource for remediating fluoride-contaminated groundwater in impoverished communities. Here, we use thermal activation and/or groundwater acidification to enhance fluoride adsorption by Indian bauxite obtained from Visakhapatnam, an area proximate to endemic fluorosis regions. We compare combinatorial water treatment and bauxite-processing scenarios through batch adsorption experiments, material characterization, and detailed cost analyses. Heating Indian bauxite above 300 °C increases available surface area by > 15× (to ∼170 m2/g) through gibbsite dehydroxylation and reduces the bauxite dose for remediating 10 ppm F- to 1.5 ppm F- by ∼93% (to 21 g/L). Additionally, lowering groundwater pH to 6.0 with HCl or CO2 further reduces the average required bauxite doses by 43-73% for ores heated at 300 °C (∼12 g/L) and 100 °C (∼77 g/L). Product water in most examined treatment scenarios complies with EPA standards for drinking water (e.g., As, Cd, Pb, etc.) but potential leaching of Al, Mn, and Cr is of concern in some scenarios. Among the defluoridation options explored here, bauxite heated at 300 °C in acidified groundwater has the lowest direct costs ($6.86 per person per year) and material-intensity.

The monochromatic photoemission from diamondoid monolayers provides a new strategy to create electron sources with low energy dispersion and enables compact electron guns with high brightness and low beam emittance for aberration-free imaging, lithography, and accelerators. However, these potential applications are hindered by degradation of diamondoid monolayers under photon irradiation and electron bombardment. Here, we report a graphene-protected diamondoid monolayer photocathode with 4-fold enhancement of stability compared to the bare diamondoid counterpart. The single-layer graphene overcoating preserves the monochromaticity of the photoelectrons, showing 12.5 meV ful width at half-maximum distribution of kinetic energy. Importantly, the graphene coating effectively suppresses desorption of the diamondoid monolayer, enhancing its thermal stability by at least 100 K. Furthermore, by comparing the decay rate at different photon energies, we identify electron bombardment as the principle decay pathway for diamondoids under graphene protection. This provides a generic approach for stabilizing volatile species on photocathode surfaces, which could greatly improve performance of electron emitters.

Controlling inorganic structure and dimensionality through structure-directing agents is a versatile approach for new materials synthesis that has been used extensively for metal-organic frameworks and coordination polymers. However, the lack of 'solid' inorganic cores requires charge transport through single-atom chains and/or organic groups, limiting their electronic properties. Here, we report that strongly interacting diamondoid structure-directing agents guide the growth of hybrid metal-organic chalcogenide nanowires with solid inorganic cores having three-atom cross-sections, representing the smallest possible nanowires. The strong van der Waals attraction between diamondoids overcomes steric repulsion leading to a cis configuration at the active growth front, enabling face-on addition of precursors for nanowire elongation. These nanowires have band-like electronic properties, low effective carrier masses and three orders-of-magnitude conductivity modulation by hole doping. This discovery highlights a previously unexplored regime of structure-directing agents compared with traditional surfactant, block copolymer or metal-organic framework linkers.

Carboranethiol molecules self-assemble into upright molecular monolayers on Au{111} with aligned dipoles in two dimensions. The positions and offsets of each molecule's geometric apex and local dipole moment are measured and correlated with sub-Ångström precision. Juxtaposing simultaneously acquired images, we observe monodirectional offsets between the molecular apexes and dipole extrema. We determine dipole orientations using efficient new image analysis techniques and find aligned dipoles to be highly defect tolerant, crossing molecular domain boundaries and substrate step edges. The alignment observed, consistent with Monte Carlo simulations, forms through favorable intermolecular dipole-dipole interactions.

When alkanethiolate self-assembled monolayers on Au{111} are exchanged with alkaneselenols from solution, replacement of thiolates by selenols is rapid and complete, and is well described by perimeter-dependent island growth kinetics. The monolayer structures change as selenolate coverage increases, from being epitaxial and consistent with the initial thiolate structure to being characteristic of selenolate monolayer structures. At room temperature and at positive sample bias in scanning tunneling microscopy, the selenolate-gold attachment is labile, and molecules exchange positions with neighboring thiolates. The scanning tunneling microscope probe can be used to induce these place-exchange reactions.

We address the importance of the dynamic molecular ink concentration at a polymer stamp/substrate interface during microcontact displacement or insertion printing. We demonstrate that by controlling molecular flux, we can influence both the molecular-scale order and the rate of molecular exchange of self-assembled monolayers (SAMs) on gold surfaces. Surface depletion of molecular ink at a polymer stamp/substrate interface is driven predominantly by diffusion into the stamp interior; depletion occurs briefly at the substrate by SAM formation, but diffusion of molecules into the bulk of the stamp dominates over practical experimental time scales. As contact time is increased, the interface concentration varies significantly due to diffusion, affecting the quality and coverage of printed films. Controlling interfacial concentration improves printed film reproducibility and the fractional coverage of multicomponent films can be controlled to within a few percent. We first briefly review the important aspects of molecular ink diffusion at a stamp interface and how it relates to experimental duration. We then describe two examples that illustrate control over ink transfer during experiments: the role of contact time on monolayer reproducibility and molecular order, and the fine control of fractional monolayer coverage for the displacement printing of 1-adamantanethiolate SAMs by 1-dodecanethiol.

Author(s): Hao Yan [1, 2]; Fan Yang [1, 3]; Ding Pan [4, 5, 6]; Yu Lin [1]; J. Nathan Hohman [7]; Diego Solis-Ibarra [8]; Fei Hua Li [1, 2]; Jeremy [...]

A new method is described for preparing controllably displaceable monolayers by using a carboxyl-functionalized self-assembled monolayer and in situ Fischer esterification, simple and reversible chemical reaction. The generality of reversible lability is examined by applying the in situ esterification reaction to the structurally distinct carboxyl-functionalized molecule 3-mercapto-1-adamantanecarboxylic acid.