Epitaxial Metal Electrodeposition Controlled by Graphene Layer Thickness.

Control over material structure and morphology during electrodeposition is necessary for material synthesis and energy applications. One approach to guide crystallite formation is to take advantage of epitaxy on a current collector to facilitate crystallographic control. Single-layer graphene on metal foils can promote "remote epitaxy" during Cu and Zn electrodeposition, resulting in growth of metal that is crystallographically aligned to the substrate beneath graphene. However, the substrate-graphene-deposit interactions that allow for epitaxial electrodeposition are not well understood. Here, we investigate how different graphene layer thicknesses (monolayer, bilayer, trilayer, and graphite) influence the electrodeposition of Zn and Cu. Scanning transmission electron microscopy and electron backscatter diffraction are leveraged to understand metal morphology and structure, demonstrating that remote epitaxy occurs on mono- and bilayer graphene but not trilayer or thicker. Density functional theory (DFT) simulations reveal the spatial electronic interactions through thin graphene that promote remote epitaxy. This work advances our understanding of electrochemical remote epitaxy and provides strategies for improving control over electrodeposition.

Hydrogen-mediated polarity compensation on the (110) surface terminations of ABO3 perovskites.

Polar surfaces undergo polarity compensation, which can lead to significantly different surface chemistry from their nonpolar counterparts. This process in turn can substantially alter the binding of adsorbates on the surface. Here, we find that hydrogen binds much more strongly to the polar (110) surface than the nonpolar (100) surface for a wide range of ABO3 perovskites, forming a hydroxyl layer on the O24- termination and a hydride layer on the ABO4+ termination of the (110) surface. The stronger adsorption on the polar surfaces can be explained by polarity compensation: hydrogen atoms can act as electron donors or acceptors to compensate for the polarity of perovskite surfaces. The relative stability of the surface terminations is further compared under different gas environments and several perovskites have been found to form stable surface hydride layers under oxygen-poor conditions. These results demonstrate the feasibility of creating stable surface hydrides on perovskites by polarity compensation which might lead to new hydrogenation catalysts based on ABO3 perovskites.

Layer-specific strain in patients with cardiac amyloidosis using tissue tracking MR.

Background: Cardiac infiltration is the major predictor of poor prognosis in patients with systemic amyloidosis, thus it becomes of great importance to evaluate cardiac involvement. Purpose: We aimed to evaluate left ventricular myocardial deformation alteration in patients with cardiac amyloidosis (CA) using layer-specific tissue tracking MR. Material and Methods: Thirty-nine patients with CA were enrolled. Thirty-nine normal controls were also recruited. Layer-specific tissue tracking analysis was done based on cine MR images. Results: Compared with the control group, a significant reduction in LV whole layer strain values (GLS, GCS, and GRS) and layer-specific strain values was found in patients with CA (all P < 0.01). In addition, GRS and GLS, as well as subendocardial and subepicardial GLS, GRS, and GCS, were all diminished in patients with CA and reduced LVEF, when compared to those with preserved or mid-range LVEF (all P < 0.05). GCS showed the largest AUC (0.9952, P = 0.0001) with a sensitivity of 93.1% and specificity of 90% to predict reduced LVEF (<40%). Moreover, GCS was the only independent predictor of LV systolic dysfunction (Odds Ratio: 3.30, 95% CI:1.341-8.12, and P = 0.009). Conclusion: Layer-specific tissue tracking MR could be a useful method to assess left ventricular myocardial deformation in patients with CA.

Intermittent Defect Fluctuations in Oxide Heterostructures.

The heterogeneous nature, local presence, and dynamic evolution of defects typically govern the ionic and electronic properties of a wide variety of functional materials. While the last 50 years have seen considerable efforts into development of new methods to identify the nature of defects in complex materials, such as the perovskite oxides, very little is known about defect dynamics and their influence on the functionality of a material. Here, the discovery of the intermittent behavior of point defects (oxygen vacancies) in oxide heterostructures employing X-ray photon correlation spectroscopy is reported. Local fluctuations between two ordered phases in strained SrCoOx with different degrees of stability of the oxygen vacancies are observed. Ab-initio-informed phase-field modeling reveals that fluctuations between the competing ordered phases are modulated by the oxygen ion/vacancy interaction energy and epitaxial strain. The results demonstrate how defect dynamics, evidenced by measurement and modeling of their temporal fluctuations, give rise to stochastic properties that now can be fully characterized using coherent X-rays, coupled for the first time to multiscale modeling in functional complex oxide heterostructures. The study and its findings open new avenues for engineering the dynamical response of functional materials used in neuromorphic and electrochemical applications.

Efficient Voltage-Driven Oxidation of Water and Alcohols by an Organic Molecular Catalyst Directly Attached to a Carbon Electrode.

The integration of heterogeneous electrocatalysis and molecular catalysis is a promising approach to designing new catalysts for the oxygen evolution reaction (OER) and other processes. We recently showed that the electrostatic potential drop across the double layer contributes to the driving force for electron transfer between a dissolved reactant and a molecular catalyst immobilized directly on the electrode surface. Here, we report high current densities and low onset potentials for water oxidation attained using a metal-free voltage-assisted molecular catalyst (TEMPO). Scanning electrochemical microscopy (SECM) was used to analyze the products and determine faradic efficiencies for the generation of H2O2 and O2. The same catalyst was employed for efficient oxidations of butanol, ethanol, glycerol, and H2O2. DFT calculations show that the applied voltage alters the electrostatic potential drop between TEMPO and the reactant as well as chemical bonding between them, thereby increasing the reaction rate. These results suggest a new route for designing next-generation hybrid molecular/electrocatalysts for OER and alcohol oxidations.

Robust Copper-Based Nanosponge Architecture Decorated by Ruthenium with Enhanced Electrocatalytic Performance for Ambient Nitrogen Reduction to Ammonia.

Electrochemical conversion of nitrogen to green ammonia is an attractive alternative to the Haber-Bosch process. However, it is currently bottlenecked by the lack of highly efficient electrocatalysts to drive the sluggish nitrogen reduction reaction (N2RR). Herein, we strategically design a cost-effective bimetallic Ru-Cu mixture catalyst in a nanosponge (NS) architecture via a rapid and facile method. The porous NS mixture catalysts exhibit a large electrochemical active surface area and enhanced specific activity arising from the charge redistribution for improved activation and adsorption of the activated nitrogen species. Benefiting from the synergistic effect of the Cu constituent on morphology decoration and thermodynamic suppression of the competing hydrogen evolution reaction, the optimized Ru0.15Cu0.85 NS catalyst presents an impressive N2RR performance with an ammonia yield rate of 26.25 µg h-1 mgcat.-1 (corresponding to 10.5 µg h-1 cm-2) and Faradic efficiency of 4.39% as well as superior stability in alkaline medium, which was superior to that of monometallic Ru and Cu nanostructures. Additionally, this work develops a new bimetallic combination of Ru and Cu, which promotes the strategy to design efficient electrocatalysts for electrochemical ammonia production under ambient conditions.

The Atomic Drill Bit: Precision Controlled Atomic Fabrication of 2D Materials.

The ability to deterministically fabricate nanoscale architectures with atomic precision is the central goal of nanotechnology, whereby highly localized changes in the atomic structure can be exploited to control device properties at their fundamental physical limit. Here, an automated, feedback-controlled atomic fabrication method is reported and the formation of 1D-2D heterostructures in MoS2 is demonstrated through selective transformations along specific crystallographic orientations. The atomic-scale probe of an aberration-corrected scanning transmission electron microscope (STEM) is used, and the shape and symmetry of the scan pathway relative to the sample orientation are controlled. The focused and shaped electron beam is used to reliably create Mo6 S6 nanowire (MoS-NW) terminated metallic-semiconductor 1D-2D edge structures within a pristine MoS2 monolayer with atomic precision. From these results, it is found that a triangular beam path aligned along the zig-zag sulfur terminated (ZZS) direction forms stable MoS-NW edge structures with the highest degree of fidelity without resulting in disordering of the surrounding MoS2 monolayer. Density functional theory (DFT) calculations and ab initio molecular dynamic simulations (AIMD) are used to calculate the energetic barriers for the most stable atomic edge structures and atomic transformation pathways. These discoveries provide an automated method to improve understanding of atomic-scale transformations while opening a pathway toward more precise atomic-scale engineering of materials.

Phase Transition Dynamics in a Complex Oxide Heterostructure.

Understanding the behavior of defects in the complex oxides is key to controlling myriad ionic and electronic properties in these multifunctional materials. The observation of defect dynamics, however, requires a unique probe-one sensitive to the configuration of defects as well as its time evolution. Here, we present measurements of oxygen vacancy ordering in epitaxial thin films of SrCoO_{x} and the brownmillerite-perovskite phase transition employing x-ray photon correlation spectroscopy. These and associated synchrotron measurements and theory calculations reveal the close interaction between the kinetics and the dynamics of the phase transition, showing how spatial and temporal fluctuations of heterointerface evolve during the transformation process. The energetics of the transition are correlated with the behavior of oxygen vacancies, and the dimensionality of the transformation is shown to depend strongly on whether the phase is undergoing oxidation or reduction. The experimental and theoretical methods described here are broadly applicable to in situ measurements of dynamic phase behavior and demonstrate how coherence may be employed for novel studies of the complex oxides as enabled by the arrival of fourth-generation hard x-ray coherent light sources.

Reversible Hydrogen-Induced Phase Transformations in La0.7Sr0.3MnO3 Thin Films Characterized by In Situ Neutron Reflectometry.

We report on the mechanism for hydrogen-induced topotactic phase transitions in perovskite (PV) oxides using La0.7Sr0.3MnO3 as a prototypical example. Hydrogenation starts with lattice expansion confirmed by X-ray diffraction (XRD). The strain- and oxygen-vacancy-mediated electron-phonon coupling in turn produces electronic structure changes that manifest through the appearance of a metal insulator transition accompanied by a sharp increase in resistivity. The ordering of initially randomly distributed oxygen vacancies produces a PV to brownmillerite phase (La0.7Sr0.3MnO2.5) transition. This phase transformation proceeds by the intercalation of oxygen vacancy planes confirmed by in situ XRD and neutron reflectometry (NR) measurements. Despite the prevailing picture that hydrogenation occurs by reaction with lattice oxygen, NR results are not consistent with deuterium (hydrogen) presence in the La0.7Sr0.3MnO3 lattice at steady state. The film can reach a highly oxygen-deficient La0.7Sr0.3MnO2.1 metastable state that is reversible to the as-grown composition simply by annealing in air. Theoretical calculations confirm that hydrogenation-induced oxygen vacancy formation is energetically favorable in La0.7Sr0.3MnO3. The hydrogenation-driven changes of the oxygen sublattice periodicity and the electrical and magnetic properties similar to interface effects induced by oxygen-deficient cap layers persist despite hydrogen not being present in the lattice.

A combined first principles study of the structural, magnetic, and phonon properties of monolayer CrI3.

The first magnetic 2D material discovered, monolayer (ML) CrI3, is particularly fascinating due to its ground state ferromagnetism. However, because ML materials are difficult to probe experimentally, much remains unresolved about ML CrI3's structural, electronic, and magnetic properties. Here, we leverage Density Functional Theory (DFT) and high-accuracy Diffusion Monte Carlo (DMC) simulations to predict lattice parameters, magnetic moments, and spin-phonon and spin-lattice coupling of ML CrI3. We exploit a recently developed surrogate Hessian DMC line search technique to determine CrI3's ML geometry with DMC accuracy, yielding lattice parameters in good agreement with recently published STM measurements-an accomplishment given the ∼10% variability in previous DFT-derived estimates depending upon the functional. Strikingly, we find that previous DFT predictions of ML CrI3's magnetic spin moments are correct on average across a unit cell but miss critical local spatial fluctuations in the spin density revealed by more accurate DMC. DMC predicts that magnetic moments in ML CrI3 are 3.62 µB per chromium and -0.145 µB per iodine, both larger than previous DFT predictions. The large disparate moments together with the large spin-orbit coupling of CrI3's I-p orbital suggest a ligand superexchange-dominated magnetic anisotropy in ML CrI3, corroborating recent observations of magnons in its 2D limit. We also find that ML CrI3 exhibits a substantial spin-phonon coupling of ∼3.32 cm-1. Our work, thus, establishes many of ML CrI3's key properties, while also continuing to demonstrate the pivotal role that DMC can assume in the study of magnetic and other 2D materials.

Voltage-Driven Molecular Catalysis of Electrochemical Reactions.

Heterogeneous electrocatalysis and molecular redox catalysis have developed over several decades as two distinct ways to facilitate charge-transfer processes essential for energy conversion and storage. Whereas electrocatalytic reactions are driven by the applied voltage, molecular catalytic processes are driven by the difference between standard potentials of the catalyst and the reactant. Here, we demonstrate that the rate of electron transfer between a dissolved reactant and a molecular catalyst immobilized directly on the surface of a carbon nanoelectrode is governed by combination of chemical driving force and electrostatic potential drop across the double layer. DFT calculations show that varying the applied voltage alters the potential drop between the surface-bound and dissolved redox species. These results suggest a new route for designing next-generation hybrid molecular/electrocatalysts.

RP11-616M22.7 recapitulates imatinib resistance in gastrointestinal stromal tumor.

Emerging evidence has shown that long non-coding RNAs (lncRNAs) play crucial roles in human cancers. However, systematic characterization of lncRNAs and their roles in gastrointestinal stromal tumor (GIST) therapy have been lacking. We performed high-throughput RNA sequencing (RNA-seq) of 20 GIST and paired adjacent normal samples. We characterized the transcriptional landscape and dysregulation of lncRNAs in GIST. We identified 866 upregulated and 1,268 downregulated lncRNAs in GIST samples, the majority of which were GIST-specific over other cancer types. Most hallmarks were found to be dysregulated in GIST samples, and lncRNAs were highly associated with cancer-related hallmarks. RP11-616M22.7 was identified to increase in imatinib-resistant samples compared to those in non-resistant samples. Further analysis revealed that RP11-616M22.7 was closely associated with the Hippo signaling pathway. By treating GIST cells with different doses of imatinib, we verified that RP11-616M22.7 knockdown promotes the sensitivity of tumor cells, whereas RP11-616M22.7 overexpression induces resistance to imatinib. We further confirmed reducing of resistance to imatinib by knocking down RP11-616M22.7 in vivo. Additionally, RP11-616M22.7 was observed to interact with RASSF1 protein. Our study revealed that deficiency of RP11-616M22.7 was able to reduce resistance of the GIST cell response to imatinib treatment both in vitro and in vivo.

Fundamental Flaw in the Current Construction of the TiO2 Electron Transport Layer of Perovskite Solar Cells and Its Elimination.

The top-performing perovskite solar cells (efficiency > 20%) generally rely on the use of a nanocrystal TiO2 electron transport layer (ETL). However, the efficacies and stability of the current stereotypically prepared TiO2 ETLs employing commercially available TiO2 nanocrystal paste are far from their maximum values. As revealed herein, the long-hidden reason for this discrepancy is that acidic protons (∼0.11 wt %) always remain in TiO2 ETLs after high-temperature sintering due to the decomposition of the organic proton solvent (mostly alcohol). These protons readily lead to the formation of Ti-H species upon light irradiation, which act to block the electron transfer at the perovskite/TiO2 interface. Affront this challenge, we introduced a simple deprotonation protocol by adding a small amount of strong proton acceptors (sodium ethoxide or NaOH) into the common TiO2 nanocrystal paste precursor and replicated the high-temperature sintering process, which wiped out nearly all protons in TiO2 ETLs during the sintering process. The use of deprotonated TiO2 ETLs not only promotes the PCE of both MAPbI3-based and FA0.85MA0.15PbI2.55Br0.45-based devices over 20% but also significantly improves the long-term photostability of the target devices upon 1000 h of continuous operation.

Work Function Engineering of 2D Materials: The Role of Polar Edge Reconstructions.

2D materials have attracted tremendous interest as functional materials because of their diverse and tunable properties, especially at their edges. A material's work function is a critical parameter in many electronic devices; however, a fundamental understanding and a path toward large alterations of the work function in 2D materials still remain elusive. Here, we report the first evidence for anisotropy of the work function in 2D MoS2 from first-principles calculations. We also demonstrate large work-function tunability (in the range of 3.45-6.29 eV) choosing the 2H phase of MoS2 as a model system by sampling various edge configurations. We furthermore reveal the origin of this work function anisotropy and tunability by extending the existing work function relation to the local dipole moment at surfaces of 3D materials to those at edges in 2D materials. We then use machine-learning approaches to correlate work function with edge structures. These results pave the way for intrinsic edge engineering for electronic and catalytic applications.

Machine learned features from density of states for accurate adsorption energy prediction.

Materials databases generated by high-throughput computational screening, typically using density functional theory (DFT), have become valuable resources for discovering new heterogeneous catalysts, though the computational cost associated with generating them presents a crucial roadblock. Hence there is a significant demand for developing descriptors or features, in lieu of DFT, to accurately predict catalytic properties, such as adsorption energies. Here, we demonstrate an approach to predict energies using a convolutional neural network-based machine learning model to automatically obtain key features from the electronic density of states (DOS). The model, DOSnet, is evaluated for a diverse set of adsorbates and surfaces, yielding a mean absolute error on the order of 0.1 eV. In addition, DOSnet can provide physically meaningful predictions and insights by predicting responses to external perturbations to the electronic structure without additional DFT calculations, paving the way for the accelerated discovery of materials and catalysts by exploration of the electronic space.

Low prognostic nutrition index predicts poorer quality of life in late-stage lung cancer.

BACKGROUND: Quality of life (QOL) is one of the most important endpoints in lung cancer care. Both nutritional and immune status reportedly correlate with QOL, so we investigated whether the prognostic nutritional index (PNI), a reliable marker of nutritional and immune status, can predict QOL in late-stage lung cancer. METHODS: We enrolled 80 lung cancer patients and their clinical data including PNI were obtained. The FACT-L questionnaire in Chinese version 4 was administered to every patient. RESULTS: Of the 80 lung cancer patients, 16 were stage III and 64 were stage IV. The average PNI value was 44.24±5.53. The average FACT-L score was 99.58±21.84, indicating impaired QOL. The FACT-L score in the stage IV group was significantly lower than that in the stage III group (P=0.001), especially for the four subscales of physical, social/family, emotional, and functioning well-being. In the stage IV group, the FACT-L score in the high PNI group was significantly higher than that in the low PNI group (P=0.042), with especially higher score for the physical well-being subscale. PNI was significantly related to both the FACT-L score (r=0.3265, P=0.0085) and physical well-being subscale (r=0.4746, P<0.0001). CONCLUSIONS: PNI is a simple but valuable biomarker of QOL in stage IV lung cancer patients. A lower PNI may indicate the need for detailed QOL evaluation and intervention.

Metal-insulator transition tuned by oxygen vacancy migration across TiO2/VO2 interface.

Oxygen defects are essential building blocks for designing functional oxides with remarkable properties, ranging from electrical and ionic conductivity to magnetism and ferroelectricity. Oxygen defects, despite being spatially localized, can profoundly alter global properties such as the crystal symmetry and electronic structure, thereby enabling emergent phenomena. In this work, we achieved tunable metal-insulator transitions (MIT) in oxide heterostructures by inducing interfacial oxygen vacancy migration. We chose the non-stoichiometric VO2-δ as a model system due to its near room temperature MIT temperature. We found that depositing a TiO2 capping layer on an epitaxial VO2 thin film can effectively reduce the resistance of the insulating phase in VO2, yielding a significantly reduced ROFF/RON ratio. We systematically studied the TiO2/VO2 heterostructures by structural and transport measurements, X-ray photoelectron spectroscopy, and ab initio calculations and found that oxygen vacancy migration from TiO2 to VO2 is responsible for the suppression of the MIT. Our findings underscore the importance of the interfacial oxygen vacancy migration and redistribution in controlling the electronic structure and emergent functionality of the heterostructure, thereby providing a new approach to designing oxide heterostructures for novel ionotronics and neuromorphic-computing devices.

Dual Roles of Polymeric Capping Ligands in the Surface-Protected Etching of Colloidal Silica.

In this work, we reveal the dual roles of polymeric capping ligands in the hollowing of silica nanospheres during their surface-protected etching. We first show that polymeric capping ligands, if they have a stronger interaction with the surface Si-OH groups than water, can reduce the condensation of the silica network, allowing the diffusion of OH- ions through the shell to dissolve the inner silica. Also, the polymeric ligands can passivate the surface silica, making it less likely to be dissolved by OH- ions. The combination of these two roles ensures highly selective etching of the interior of the colloidal silica spheres, making the surface-protected etching a robust process for the synthesis of hollow silica nanoshells. Our insight into the specific roles of the ligands is expected to elucidate the impact of polymeric ligands on the colloidal chemistry of silica, particularly in its condensation and etching behaviors, and offer new opportunities in the design of silica and other oxide-based nanostructures.

Hydrogen in Nanocatalysis.

Hydrogen is ubiquitous in catalysis. It is involved in many important reactions such as water splitting, N2 reduction, CO2 reduction, and alkane activation. In this Perspective, we focus on the hydrogen atom and follow its electron as it interacts with a catalyst or behaves as part of a catalyst from a computational point of view. We present recent examples in both nanocluster and solid catalysts to elucidate the parameters governing the strength of the hydrogen-surface interactions based on site geometry and electronic structure. We further show the interesting behavior of hydride in nanometal and oxides for catalysis. The key take-home messages are: (1) the in-the-middle electronegativity and small size of hydrogen give it great versatility in interacting with active sites on nanoparticles and solid surfaces; (2) the strength of hydrogen binding to an active site on a surface is an important descriptor of the chemical and catalytic properties of the surface; (3) the energetics of the hydrogen binding is closely related to the electronic structure of the catalyst; (4) hydrides in nanoclusters and oxides and on surfaces offer unique reactivity for reduction reactions.

Integrated Evaporator for Efficient Solar-Driven Interfacial Steam Generation.

Solar-driven interfacial steam generation is a promising technique for clean water production because it can minimize thermal loss by localizing solar-to-heat conversion at the air/liquid interface. Here we report an integrated solar evaporator by partially growing 2D polypyrrole microsheets within a melamine foam through chemical vapor polymerization. These microsheets can induce multiple light reflections within the foam, enable omnidirectional light absorption, provide abundant surfaces to promote heat transfer, and achieve spatially defined hydrophobicity to facilitate vapor escape. Meanwhile, the inherent hydrophilicity of the bottom part of the foam promotes spontaneous upward water transport and suppresses heat loss. The composite foam exhibits an excellent apparent evaporation rate of ∼2 kg/(m2·h) and solar-to-vapor efficiency of ∼91%. The combined advantages of large surface area, high efficiency, low cost, all-weather application, excellent durability, and scalable manufacturing make our integrated design promising for fabricating large-scale solar steam generation systems that are suitable for practical clean water production.