Solving complex nanostructures with ptychographic atomic electron tomography.

Transmission electron microscopy (TEM) is essential for determining atomic scale structures in structural biology and materials science. In structural biology, three-dimensional structures of proteins are routinely determined from thousands of identical particles using phase-contrast TEM. In materials science, three-dimensional atomic structures of complex nanomaterials have been determined using atomic electron tomography (AET). However, neither of these methods can determine the three-dimensional atomic structure of heterogeneous nanomaterials containing light elements. Here, we perform ptychographic electron tomography from 34.5 million diffraction patterns to reconstruct an atomic resolution tilt series of a double wall-carbon nanotube (DW-CNT) encapsulating a complex ZrTe sandwich structure. Class averaging the resulting tilt series images and subpixel localization of the atomic peaks reveals a Zr11Te50 structure containing a previously unobserved ZrTe2 phase in the core. The experimental realization of atomic resolution ptychographic electron tomography will allow for the structural determination of a wide range of beam-sensitive nanomaterials containing light elements.

Evolution of nanopores in hexagonal boron nitride.

The engineering of atomically-precise nanopores in two-dimensional materials presents exciting opportunities for both fundamental science studies as well as applications in energy, DNA sequencing, and quantum information technologies. The exceptional chemical and thermal stability of hexagonal boron nitride (h-BN) suggest that exposed h-BN nanopores will retain their atomic structure even when subjected to extended periods of time in gas or liquid environments. Here we employ transmission electron microscopy to examine the time evolution of h-BN nanopores in vacuum and in air and find, even at room temperature, dramatic geometry changes due to atom motion and edge contamination adsorption, for timescales ranging from one hour to one week. The discovery of nanopore evolution contrasts with general expectations and has profound implications for nanopore applications of two-dimensional materials.

All-Liquid Reconfigurable Electronics Using Jammed MXene Interfaces.

Rigid, solid-state components represent the current paradigm for electronic systems, but they lack post-production reconfigurability and pose ever-increasing challenges to efficient end-of-life recycling. Liquid electronics may overcome these limitations by offering flexible in-the-field redesign and separation at end-of-life via simple liquid phase chemistries. Up to now, preliminary work on liquid electronics has focused on liquid metal components, but these devices still require an encapsulating polymer and typically use alloys of rare elements like indium. Here, using the self-assembly of jammed 2D titanium carbide (Ti3 C2 Tx ) MXene nanoparticles at liquid-liquid interfaces, "all-liquid" electrically conductive sheets, wires, and simple functional devices are described including electromechanical switches and photodetectors. These assemblies combine the high conductivity of MXene nanosheets with the controllable form and reconfigurability of structured liquids. Such configurations can have applications not only in electronics, but also in catalysis and microfluidics, especially in systems where the product and substrate have affinity for solvents of differing polarity.

Targeting One- and Two-Dimensional Ta-Te Structures via Nanotube Encapsulation.

Fine control over material synthesis on the nanoscale can facilitate the stabilization of competing crystalline structures. Here, we demonstrate how carbon nanotube reaction vessels can be used to selectively create one-dimensional TaTe3 chains or two-dimensional TaTe2 nanoribbons with exquisite control of the chain number or nanoribbon thickness and width. Transmission electron microscopy and scanning transmission electron microscopy reveal the detailed atomic structure of the encapsulated materials. Complex superstructures such as multichain spiraling and apparent multilayer moirés are observed. The rare 2H phase of TaTe2 (1H in monolayer) is found to be abundant as an encapsulated nanoribbon inside carbon nanotubes. The experimental results are complemented by density functional theory calculations for the atomic and electronic structure, which uncovers the prevalence of 2H-TaTe2 due to nanotube-to-nanoribbon charge transfer and size confinement. Calculations also reveal new 1T' type charge density wave phases in TaTe2 that could be observed in experimental studies.

Structured-Liquid Batteries.

Chemical systems may be maintained far from equilibrium by sequestering otherwise reactive species into different microenvironments. It remains a significant challenge to control the amount of chemical energy stored in such systems and to utilize it on demand to perform useful work. Here, we show that redox-active molecules compartmentalized in multiphasic structured-liquid devices can be charged and discharged to power a load on an external circuit. The two liquid phases of these devices feature charge-complementary polyelectrolytes that serve a dual purpose: they generate an ionically conductive coacervate membrane at the liquid-liquid interface, providing structural support; they also mitigate active-material crossover between phases via ion pairing with the oppositely charged anolyte and catholyte active materials. Structured-liquid batteries enabled by this design were rechargeable over hundreds of hours. We envision that these devices may be integrated with soft electronics to enable functional circuits for smart textiles, medical implants, and wearables.

Chemical crystallography by serial femtosecond X-ray diffraction.

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.

Exchange Capability of Cationic Silver 4,4'-Bipyrdine Materials for Potential Water Remediation: Structure, Stability, and Anion Exchange Properties.

An in-depth study of the class of cationic materials [Ag(4,4'-bipy)+][X-] (where X- = CH3CO2-, NO3-, BF4-, ClO4-, and MnO4-) has led to key insights on the relationship between anion hydration energy, material structure, solubility, and stability. Since these materials show promise for their potential as water remediation tools, understanding their properties in detail is of significant importance. The structure of the starting and ending materials is the main driving force behind the resultant stability and solubility and can be successfully used to predict the ion exchange capabilities. The solubility trend was determined to be, from most soluble to least soluble, X- = CH3CO2- > NO3- ∼ BF4- > ClO4- > MnO4-. Kinetics and thermal stability also follow predictable trends but involve additional factors. For instance, the kinetics of NO3- to MnO4- exchange was much slower than expected based on that seen for NO3- to ClO4-. Powder X-ray diffraction (PXRD) and Fourier transform infrared spectroscopy (FTIR) were used to characterize the materials. Solubility was determined by inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis. Ion exchange was analyzed with ion chromatography (IC) and ultraviolet-visible spectroscopy (UV-vis), and thermal stability was determined with thermogravimetric analysis (TGA).

Competing Roles of Crystallization and Degradation of a Metal-Organic Chalcogenolate Assembly under Biphasic Solvothermal Conditions.

Metal-organic chalcogenolate assemblies have attracted recent interest as ensemble nanomaterials that contain one- or two-dimensional inorganic nanostructures in a periodic array with supramolecular isolation provided by an associated organic ligand lattice. Biphasic immiscible synthesis at liquid-liquid interfaces is a convenient way to grow crystalline d10 metal-organic chalcogenolate assemblies. However, there has been little systematic study of the role of temperature on the nucleation, growth, and stability of hybrid chalcogenolates during biphasic synthesis. Silver benzeneselenolate, a robustly blue-luminescent, lamellar metal-organic chalcogenolate assembly, was crystallized at biphasic immiscible liquid-liquid interfaces under solvothermal conditions. A positive correlation between temperature and nucleation density was observed, and the luminescence was conserved in all examples of the crystalline phase. Applying solvothermal conditions to the biphasic synthesis generally increased the lateral dimensions of the crystals and strongly favored the crystalline phase of the compound. Although thin, well-formed crystals were observed within 1 h for interfacial reactions performed at high temperatures, degradation was observed in long duration growths resulting in aggregated silver metal. A study of the thermal stability of the material via thermogravimetric analysis revealed that the decomposition is likely a redox reaction reverting the compound to silver metal and diphenyl diselenide. In situ analysis of this degradation was performed by grazing-incidence wide-angle X-ray scattering, which confirmed that the decomposition occurs in a single step with no preceding changes to the structure of the material. This work demonstrates that biphasic solvothermal methods are amenable to the synthesis of hybrid metal-organic chalcogenolate assemblies and that temperature can be used to control product morphology and lateral crystal growth at the immiscible interface.

Tarnishing Silver Metal into Mithrene.

Silver metal exposed to the atmosphere corrodes and becomes tarnished as a result of oxidation and precipitation of the metal as an insoluble salt. Tarnish has so poor a reputation that the word itself connotes corruption and disrespectability; however, tarnishing is a facile synthetic approach for preparing thin metal-sulfide films on silver or copper metal that might be exploited to prepare more elaborate materials with desirable optoelectronic properties. In this work, we prepare luminescent semiconducting thin films of mithrene, a metal-organic chalcogenolate assembly, by replacing the tarnish-causing atmospheric sulfur source with diphenyl diselenide. Mithrene, or silver benzeneselenolate [AgSePh]∞, is a crystalline solid that contains both an organic supramolecular phase and a two-dimensional inorganic coordination polymer phase. This compound gradually accumulates as the sole product of silver metal corrosion. The chemical reaction is carried out on metallic silver thin films and yields crystalline films with thicknesses ranging from 5 to 100 nm. We use the large-area films (>6 cm2) afforded by this method to measure the optical properties of this compound. The mild-temperature, wafer-scale processing of hybrid chalcogenolate thin films may prove useful in the application of hybrid organic-inorganic materials in semiconductor devices and hierarchical architectures.