Chiroptical Strain Sensors from Electrospun Cadmium Sulfide Quantum-Dot Fibers.

Controllable synthesis of homochiral nano/micromaterials has been a constant challenge for fabricating various stimuli-responsive chiral sensors. To provide an avenue to this goal, we report electrospinning as a simple and economical strategy to form continuous homochiral microfibers with strain-sensitive chiroptical properties. First, electrospun homochiral microfibers from self-assembled cadmium sulfide (CdS) quantum dot magic-sized clusters (MSCs) are produced. Highly sensitive and reversible strain sensors are then fabricated by embedding these chiroptically active fibers into elastomeric films. The chiroptical response on stretching is indicated quantitatively as reversible changes in magnitude, spectral position (wavelength), and sign in circular dichroism (CD) and linear dichroism (LD) signals and qualitatively as a prominent change in the birefringence features under cross-polarizers. The observed periodic twisted helical fibrils at the surface of fibers provide insights into the origin of the fibers' chirality. The measurable shifts in CD and LD are caused by elastic deformations of these helical fibrillar structures of the fiber. To elucidate the origin of these chiroptical properties, we used field emission-electron microscopy (FE-SEM), atomic force microscopy (AFM), synchrotron X-ray analysis, polarized optical microscopy, as well as measurements to isolate the true CD, and contributions from photoelastic modulators (PEM) and LD. Our findings thus offer a promising strategy to fabricate chiroptical strain-sensing devices with multiple measurables/observables using electric-field-assisted spinning of homochiral nano/microfibers.

Emergence and inversion of chirality in hierarchical assemblies of CdS nanocrystal fibers.

Arranging semiconducting nanocrystals into ordered superstructures is a promising platform to study fundamental light-matter interactions and develop programmable optical metamaterials. We investigated how the geometrical arrangement of CdS nanocrystals in hierarchical assemblies affects chiroptical properties. To create these structures, we controlled the evaporation of a colloidal CdS nanocrystal solution between two parallel plates. We combined in situ microscopy and computational modeling to establish a formation mechanism involving the shear-induced alignment of nanocrystal fibers and the subsequent mechanical relaxation of the stretched fibers to form Raman noodle-type band textures. The high linear anisotropy in these films shares many similarities with cholesteric liquid crystals. The films deposited on top and bottom surfaces exhibit opposite chirality. The mechanistic insights from this study are consequential to enable future advances in the design and fabrication of programmable optical metamaterials for further development of polarization-based optics toward applications in sensing, hyperspectral imaging, and quantum information technology.

Single-cell multimodal imaging uncovers energy conversion pathways in biohybrids.

Microbe-semiconductor biohybrids, which integrate microbial enzymatic synthesis with the light-harvesting capabilities of inorganic semiconductors, have emerged as promising solar-to-chemical conversion systems. Improving the electron transport at the nano-bio interface and inside cells is important for boosting conversion efficiencies, yet the underlying mechanism is challenging to study by bulk measurements owing to the heterogeneities of both constituents. Here we develop a generalizable, quantitative multimodal microscopy platform that combines multi-channel optical imaging and photocurrent mapping to probe such biohybrids down to single- to sub-cell/particle levels. We uncover and differentiate the critical roles of different hydrogenases in the lithoautotrophic bacterium Ralstonia eutropha for bioplastic formation, discover this bacterium's surprisingly large nanoampere-level electron-uptake capability, and dissect the cross-membrane electron-transport pathways. This imaging platform, and the associated analytical framework, can uncover electron-transport mechanisms in various types of biohybrid, and potentially offers a means to use and engineer R. eutropha for efficient chemical production coupled with photocatalytic materials.

Multiscale hierarchical structures from a nanocluster mesophase.

Spontaneous hierarchical self-organization of nanometre-scale subunits into higher-level complex structures is ubiquitous in nature. The creation of synthetic nanomaterials that mimic the self-organization of complex superstructures commonly seen in biomolecules has proved challenging due to the lack of biomolecule-like building blocks that feature versatile, programmable interactions to render structural complexity. In this study, highly aligned structures are obtained from an organic-inorganic mesophase composed of monodisperse Cd37S18 magic-size cluster building blocks. Impressively, structural alignment spans over six orders of magnitude in length scale: nanoscale magic-size clusters arrange into a hexagonal geometry organized inside micrometre-sized filaments; self-assembly of these filaments leads to fibres that then organize into uniform arrays of centimetre-scale bands with well-defined surface periodicity. Enhanced patterning can be achieved by controlling processing conditions, resulting in bullseye and 'zigzag' stacking patterns with periodicity in two directions. Overall, we demonstrate that colloidal nanomaterials can exhibit a high level of self-organization behaviour at macroscopic-length scales.

Bioelectronic Platform to Investigate Charge Transfer between Photoexcited Quantum Dots and Microbial Outer Membranes.

Photosynthetic semiconductor biohybrids (PSBs) convert light energy to chemical energy through photo-driven charge transfer from nanocrystals to microorganisms that perform bioreactions of interest. Initial proof-of-concept PSB studies with an emphasis on enhanced CO2 conversion have been encouraging; however, bringing the broad prospects of PSBs to fruition is contingent on establishing a firm fundamental understanding of underlying interfacial charge transfer processes. We introduce a bioelectronic platform that reduces the complexity of PSBs by focusing explicitly on interactions between colloidal quantum dots (QDs), microbial outer membranes, and native, small-molecule redox mediators. Our model platform employs a standard three-electrode electrochemical cell with supported outer membranes of Pseudomonas aeruginosa, pyocyanin redox mediators, and semiconducting CdSe QDs dispersed in an aqueous electrolyte. We present a comprehensive electrochemical analysis of this platform via electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and chronoamperometry (CA). EIS reveals the formation and electronic properties of supported outer membrane films. CV reveals the electrochemically active surface area of P. aeruginosa outer membranes and that pyocyanin is the sole species that performs redox with these outer membranes under sweeping applied potential. CA demonstrates that photoexcited charge transfer in this system is driven by the reduction of pyocyanin at the QD surface followed by diffusion of reduced pyocyanin through the outer membrane. The broad applicability of this platform across many bacterial species, QD architectures, and controlled environmental conditions affords the possibility to define design principles for future PSB systems to synergistically integrate concurrent advances in genetically engineered organisms and inorganic nanomaterials.

Re-entrant transition as a bridge of broken ergodicity in confined monolayers of hexagonal prisms and cylinders.

The entropy-driven monolayer assembly of hexagonal prisms and cylinders was studied under hard slit confinement. At the conditions investigated, the particles have two distinct and dynamically disconnected rotational states: unflipped and flipped, depending on whether their circular/hexagonal face is parallel or perpendicular to the wall plane. Importantly, these two rotational states cast distinct projection areas over the wall plane that favor either hexagonal or tetragonal packing. Monte Carlo simulations revealed a re-entrant melting transition where an intervening disordered Flipped-Unflipped (FUN) phase is sandwiched between a fourfold tetratic phase at high concentrations and a sixfold triangular solid at intermediate concentrations. The FUN phase contains a mixture of flipped and unflipped particles and is translationally and orientationally disordered. Complementary experiments were conducted with photolithographically fabricated cylindrical microparticles confined in a wedge cell. Both simulations and experiments show the formation of phases with comparable fraction of flipped particles and structure, i.e., the FUN phase, triangular solid, and tetratic phase, indicating that both approaches sample analogous basins of particle-orientation phase-space. The phase behavior of hexagonal prisms in a soft-repulsive wall model was also investigated to exemplify how tunable particle-wall interactions can provide an experimentally viable strategy to dynamically bridge the flipped and unflipped states.

Cu(I) Reducibility Controls Ethylene vs Ethanol Selectivity on (100)-Textured Copper during Pulsed CO2 Reduction.

The electrochemical CO2 reduction reaction (CO2RR) can convert widely available CO2 into value-added C2 products, such as ethylene and ethanol. However, low selectivity toward either compound limits the effectiveness of current CO2RR electrocatalysts. Here, we report the use of pulsed overpotentials to improve the ethylene selectivity to 67% with >75% overall C2 selectivity on (100)-textured polycrystalline Cu foil. The pulsed CO2RR can be made selective to either ethylene or ethanol by controlling the reaction temperature. We attribute the enhanced C2 selectivity to the improved CO dimerization kinetics on the active Cu surface on predominately (100)-textured Cu grains with the reduced hydrogen adsorption coverage during the pulsed CO2RR. The ethylene vs ethanol selectivity can be explained by the reducibility of the Cu(I) species during the cathodic potential cycle. Our work demonstrates a simple route to improve the ethylene vs ethanol selectivity and identifies Cu(I) as the species responsible for ethanol production.

Mapping Defect Relaxation in Quantum Dot Solids upon In Situ Heating.

Epitaxially connected quantum dot solids have emerged as an interesting class of quantum confined materials with the potential for highly tunable electronic structures. Realization of the predicted emergent electronic properties has remained elusive due in part to defective interdot epitaxial connections. Thermal annealing has shown potential to eliminate such defects, but a direct understanding of this mechanism hinges on determining the nature of defects in the connections and how they respond to heating. Here, we use in situ heating in the scanning transmission electron microscope to probe the effect of heating on distinct defect types. We apply a real space, local strain mapping technique, which allows us to identify tensile and shear strain in the atomic lattice, highlighting tensile, shear, and bending defects in interdot connections. We also track the out-of-plane orientation of individual QDs and infer the prevalence of out-of-plane twisting and bending defects as a function of annealing. We find that tensile and shear defects are fully relaxed upon mild thermal annealing, while bending defects persist. Additionally, out-of-plane orientation tracking reveals an increase in correctly oriented QDs, pointing to a relaxation of either twisting defects or out-of-plane bending defects. While bending defects remain, highlighting the need for further study of orientational ordering during the preattachment phase of superlattice formation, these atomic-scale insights show that annealing can effectively eliminate tensile and shear defects, a promising step toward delocalization of charge carriers and tunable electronic properties.

Processing-Structure-Performance Relationships of Microporous Metal-Organic Polymers for Size-Selective Separations.

Small-molecule impurities, such as N-nitrosodimethylamine (NDMA), have infiltrated the generic drug industry, leading to recalls in commonly prescribed blood pressure and stomach drugs in over 43 countries since 2018 and directly affecting tens of millions of patients. One promising strategy to remove small-molecule impurities like NDMA from drug molecules is by size exclusion, in which the contaminant is removed by selective adsorption onto a (micro)porous material due to its smaller size. However, current solution-phase size-exclusion separations are primarily limited by the throughput-selectivity trade-off. Here, we report a bioinspired solution to conquer these critical challenges by leveraging the assembly of atomically precise building blocks into hierarchically porous structures. We introduce a bottom-up approach to form micropores, mesopores, and macroscopic superstructures simultaneously using functionalized oxozirconium clusters as building blocks. Further, we leverage recent advances in photopolymerization to design macroscopic flow structures to mitigate backpressure. Based on these multiscale design principles, we engineer simple, inexpensive devices that are able to separate NDMA from contaminated drugs. Beyond this urgent model system, we expect this design strategy to open up hitherto unexplored avenues of nanomaterial superstructure fabrication for a range of size-exclusion purification strategies.

HI-Light: A Glass-Waveguide-Based "Shell-and-Tube" Photothermal Reactor Platform for Converting CO2 to Fuels.

In this work, we introduce HI-Light, a surface-engineered glass-waveguide-based "shell-and-tube" type photothermal reactor which is both scalable in diameter and length. We examine the effect of temperature, light irradiation, and residence time on its photo-thermocatalytic performance for CO2 hydrogenation to form CO, with a cubic phase defect-laden indium oxide, In2O3-x(OH)y, catalyst. We demonstrate the light enhancement effect under a variety of reaction conditions. Notably, the light-on performance for the cubic nanocrystal photocatalyst exhibits a CO evolution rate at 15.40 mmol gcat -1 hr-1 at 300°C and atmospheric pressure. This is 20 times higher conversion rate per unit catalyst mass per unit time beyond previously reported In2O3-x(OH)y catalyst in the cubic form under comparable operation conditions and more than 5 times higher than that of its rhombohedral polymorph. This result underscores that improvement in photo-thermocatalytic reactor design enables uniform light distribution and better reactant/catalyst mixing, thus significantly improving catalyst utilization.

Porous cage-derived nanomaterial inks for direct and internal three-dimensional printing.

The convergence of 3D printing techniques and nanomaterials is generating a compelling opportunity space to create advanced materials with multiscale structural control and hierarchical functionalities. While most nanoparticles consist of a dense material, less attention has been payed to 3D printing of nanoparticles with intrinsic porosity. Here, we combine ultrasmall (about 10 nm) silica nanocages with digital light processing technique for the direct 3D printing of hierarchically porous parts with arbitrary shapes, as well as tunable internal structures and high surface area. Thanks to the versatile and orthogonal cage surface modifications, we show how this approach can be applied for the implementation and positioning of functionalities throughout 3D printed objects. Furthermore, taking advantage of the internal porosity of the printed parts, an internal printing approach is proposed for the localized deposition of a guest material within a host matrix, enabling complex 3D material designs.

The Role of Dimer Formation in the Nucleation of Superlattice Transformations and Its Impact on Disorder.

The formation of defect-free two-dimensional nanocrystal (NC) superstructures remains a challenge as persistent defects hinder charge delocalization and related device performance. Understanding defect formation is an important step toward developing strategies to mitigate their formation. However, specific mechanisms of defect formation are difficult to determine, as superlattice phase transformations that occur during fabrication are quite complex and there are a variety of factors influencing the disorder in the final structure. Here, we use Molecular Dynamics (MD) and electron microscopy in concert to investigate the nucleation of the epitaxial attachment of lead chalcogenide (PbX, where X = S, Se) NC assemblies. We use an updated implementation of an existing reactive force field in an MD framework to investigate how initial orientational (mis)alignment of the constituent building blocks impacts the final structure of the epitaxially connected superlattice. This Simple Molecular Reactive Force Field (SMRFF) captures both short-range covalent forces and long-range electrostatic forces and allows us to follow orientational and translational changes of NCs during superlattice transformation. Our simulations reveal how robust the oriented attachment is with regard to the initial configuration of the NCs, measuring its sensitivity to both in-plane and out-of-plane misorientation. We show that oriented attachment nucleates through the initial formation of dimers, which corroborate experimentally observed structures. We present high-resolution structural analysis of dimers at early stages of the superlattice transformation and rationalize their contribution to the formation of defects in the final superlattice. Collectively, the simulations and experiments presented in this paper provide insights into the nucleation of NC oriented attachment, the impact of the initial configuration of NCs on the structural fidelity of the final epitaxially connected superlattice, and the propensity to form commonly observed defects, such as missing bridges and atomic misalignment in the superlattice due to the formation of dimers. We present potential strategies to mitigate the formation of superlattice defects.

Mechanistic Insights into Superlattice Transformation at a Single Nanocrystal Level Using Nanobeam Electron Diffraction.

Understanding the mechanism and ultimately directing nanocrystal (NC) superlattice assembly and attachment have important implications on future advances in this emerging field. Here, we use 4D-STEM to investigate a monolayer of PbS NCs at various stages of the transformation from a hexatic assembly to a nonconnected square-like superlattice over large fields of view. Maps of nanobeam electron diffraction patterns acquired with an electron microscope pixel array detector (EMPAD) offer unprecedented detail into the 3D crystallographic alignment of the polyhedral NCs. Our analysis reveals that superlattice transformation is dominated by translation of prealigned NCs strongly coupled along the <11n>AL direction and occurs stochastically and gradually throughout single grains. We validate the generality of the proposed mechanism by examining the structure of analogous PbSe NC assemblies using conventional transmission electron microscopy and selected area electron diffraction. The experimental results presented here provide new mechanistic insights into NC self-assembly and oriented attachment.

Coupled Dynamics of Colloidal Nanoparticle Spreading and Self-Assembly at a Fluid-Fluid Interface.

We investigated the physicochemical and transport phenomena governing the self-assembly of colloidal nanoparticles at the interface of two immiscible fluids. By combining in situ grazing-incidence small-angle X-ray scattering (GISAXS) with a temporal resolution of 200 ms and electron microscopy measurements, we gained new insights into the coupled effects of solvent spreading, nanoparticle assembly, and recession of the vapor-liquid interface on the morphology of the self-assembled thin films. We focus on oleate-passivated PbSe nanoparticles dispersed across an ethylene glycol subphase as a model system and demonstrate how solvent parameters such as surface tension, nanoparticle solubility, aromaticity, and polarity influence the mesoscale morphology of the nanoparticle superlattice. We discovered that a nanoparticle precursor monolayer film spreads in front of the bulk solution and influences the fluid spreading across the subphase. Improved understanding of the impact of kinetic phenomena (i.e., solvent spreading and evaporation) on the superlattice morphology is important to describe the formation mechanism and ultimately enable the assembly of high-quality superlattices with long-range order.

Orientational Disorder in Epitaxially Connected Quantum Dot Solids.

Periodic arrays of strongly coupled colloidal quantum dots (QDs) may enable unprecedented control of electronic band structure through manipulation of QD size, shape, composition, spacing, and assembly geometry. This includes the possibilities of precisely engineered bandgaps and charge carrier mobilities, as well as remarkable behaviors such as metal-insulator transitions, massless carriers, and topological states. However, experimental realization of these theoretically predicted electronic structures is presently limited by structural disorder. Here, we use aberration-corrected scanning transmission electron microscopy to precisely quantify the orientational disorder of epitaxially connected QD films. In spite of coherent atomic connectivity between nearest neighbor QDs, we find misalignment persists with a standard deviation of 1.9°, resulting in significant bending strain localized to the adjoining necks. We observe and quantify a range of out-of-plane particle orientations over thousands of QDs and correlate the in-plane and out-of-plane misalignments, finding QDs misoriented out-of-plane display a statistically greater misalignment with respect to their in-plane neighbors as well. Using the bond orientational order metric ψ4, we characterize the 4-fold symmetry and introduce a quantification of the local superlattice (SL) orientation. This enables direct comparison between local orientational order in the SL and atomic lattice (AL). We find significantly larger variations in the SL orientation and a statistically robust but locally highly variable correlation between the orientations of the two differently scaled lattices. Distinct AL and SL behaviors are observed about a grain boundary, with a sharp boundary in the AL orientations, but a more smooth transition in the SL, facilitated by lattice deformation between the neighboring grains. Coupling between the AL and SL is a fundamental driver of film growth, and these results suggest nontrivial underlying mechanics, implying that simplified models of epitaxial attachment may be insufficient to understand QD growth and disorder when oriented attachment and superlattice growth occur in concert.

Chemically reversible isomerization of inorganic clusters.

Structural transformations in molecules and solids have generally been studied in isolation, whereas intermediate systems have eluded characterization. We show that a pair of cadmium sulfide (CdS) cluster isomers provides an advantageous experimental platform to study isomerization in well-defined, atomically precise systems. The clusters coherently interconvert over an ~1-electron volt energy barrier with a 140-milli-electron volt shift in their excitonic energy gaps. There is a diffusionless, displacive reconfiguration of the inorganic core (solid-solid transformation) with first order (isomerization-like) transformation kinetics. Driven by a distortion of the ligand-binding motifs, the presence of hydroxyl species changes the surface energy via physisorption, which determines "phase" stability in this system. This reaction possesses essential characteristics of both solid-solid transformations and molecular isomerizations and bridges these disparate length scales.

Controlled Selectivity of CO2 Reduction on Copper by Pulsing the Electrochemical Potential.

We demonstrate a simple strategy to enhance the CO2 reduction reaction (CO2 RR) selectivity by applying a pulsed electrochemical potential to a polycrystalline copper electrode. By controlling the pulse duration, we show that the hydrogen evolution reaction (HER) is highly suppressed to a fraction of the original value (<5 % faradaic efficiency) and selectivity for the CO2 RR dramatically improves (>75 % CH4 and >50 % CO faradaic efficiency). We attribute the improved CO2 RR selectivity to a dynamically rearranging surface coverage of hydrogen and intermediate species during the pulsing. Our finding provides new insights into the interplay of transport and reaction processes as well as timescales of competing pathways to enable new opportunities to tune CO2 RR selectivity by adjusting the pulse profile. Additionally, the pulsed potential method we describe can be easily applied to other catalysts materials to improve their CO2 RR selectivity.

Mesophase Formation Stabilizes High-Purity Magic-Sized Clusters.

Magic-sized clusters (MSCs) are renowned for their identical size and closed-shell stability that inhibit conventional nanoparticle (NP) growth processes. Though MSCs have been of increasing interest, understanding the reaction pathways toward their nucleation and stabilization is an outstanding issue. In this work, we demonstrate that high concentration synthesis (1000 mM) promotes a well-defined reaction pathway to form high-purity MSCs (>99.9%). The MSCs are resistant to typical growth and dissolution processes. On the basis of insights from in situ X-ray scattering analysis, we attribute this stability to the accompanying production of a large (>100 nm grain size), hexagonal organic-inorganic mesophase that arrests growth of the MSCs and prevents NP growth. At intermediate concentrations (500 mM), the MSC mesophase forms, but is unstable, resulting in NP growth at the expense of the assemblies. These results provide an alternate explanation for the high stability of MSCs. Whereas the conventional mantra has been that the stability of MSCs derives from the precise arrangement of the inorganic structures (i.e., closed-shell atomic packing), we demonstrate that anisotropic clusters can also be stabilized by self-forming fibrous mesophase assemblies. At lower concentration (<200 mM or >16 acid-to-metal), MSCs are further destabilized and NPs formation dominates that of MSCs. Overall, the high concentration approach intensifies and showcases inherent concentration-dependent surfactant phase behavior that is not accessible in conventional (i.e., dilute) conditions. This work provides not only a robust method to synthesize, stabilize, and study identical MSC products but also uncovers an underappreciated stabilizing interaction between surfactants and clusters.

A Simple Preparation Method for Full-Range Electron Tomography of Nanoparticles and Fine Powders.

Electron tomography has become a valuable and widely used tool for studying the three-dimensional nanostructure of materials and biological specimens. However, the incomplete tilt range provided by conventional sample holders limits the fidelity and quantitative interpretability of tomographic images by leaving a "missing wedge" of unknown information in Fourier space. Imaging over a complete range of angles eliminates missing wedge artifacts and dramatically improves tomogram quality. Full-range tomography is usually accomplished using needle-shaped samples milled from bulk material with focused ion beams, but versatile specimen preparation methods for nanoparticles and other fine powders are lacking. In this work, we present a new preparation technique in which powder specimens are supported on carbon nanofibers that extend beyond the end of a tungsten needle. Using this approach, we produced tomograms of platinum fuel cell catalysts and gold-decorated strontium titanate photocatalyst specimens. Without the missing wedge, these tomograms are free from elongation artifacts, supporting straightforward automatic segmentation and quantitative analysis of key materials properties such as void size and connectivity, and surface area and curvature. This approach may be generalized to other samples that can be dispersed in liquids, such as biological structures, creating new opportunities for high-quality electron tomography across disciplines.