Chungmoore1619

Three-dimensional (3D) current collectors have shown great potential in realizing dendrite-free lithium (Li) metal anodes. However, the rigid 3D current collectors could not simultaneously suppress Li dendrite growth and allow Li plating/stripping under high capacities and large current densities. Here, we report a dynamic intelligent Cu (DICu) current collector that dynamically accommodates the volume change by changing the packing density of the assembled particles. The Li/DICu electrode achieves a high Coulombic efficiency of 99.6% after 800 cycles. The symmetrical cell shows exceptional cycling stability under the high current density of 10 mA cm-2. Notably, when assembled in full-cell batteries, the Li/DICu|LiFePO4 battery maintains a specific capacity of 139.5 mAh g-1 at 1 C for 500 cycles, and the Li/DICu|S battery delivers a specific capacity of 804 mAh g-1 after 500 cycles at 0.5 C, corresponding to the best performance among Li metal batteries with Cu-based current collectors to date.We have developed a Mizoroki-Heck reaction of nitroarenes with alkenes under palladium catalysis. The use of a Pd/BrettPhos catalyst promoted the alkenylation, whereas other catalysts led to a decrease in the product yield. In addition to nitroarenes, nitroheteroarenes were also applicable to the present reaction. The combination of a nucleophilic aromatic substitution (SNAr) with the denitrative alkenylation produced a multifunctionalized arene in a one-pot operation.The available active surface area and the density of probes immobilized on this surface are responsible for achieving high specificity and sensitivity in electrochemical biosensors that detect biologically relevant molecules, including DNA. Here, we report the design of gold-coated, silicon micropillar-structured electrodes functionalized with modified poly-l-lysine (PLL) as an adhesion layer to concomitantly assess the increase in sensitivity with the increase of the electrochemical area and control over the probe density. By systematically reducing the center-to-center distance between the pillars (pitch), denser micropillar arrays were formed at the electrode, resulting in a larger sensing area. Azido-modified peptide nucleic acid (PNA) probes were click-reacted onto the electrode interface, exploiting PLL with appended oligo(ethylene glycol) (OEG) and dibenzocyclooctyne (DBCO) moieties (PLL-OEG-DBCO) for antifouling and probe binding properties, respectively. The selective electrochemical sandwich assay formation, composed of consecutive hybridization steps of the target complementary DNA (cDNA) and reporter DNA modified with the electroactive ferrocene functionality (rDNA-Fc), was monitored by quartz crystal microbalance. The DNA detection performance of micropillared electrodes with different pitches was evaluated by quantifying the cyclic voltammetric response of the surface-confined rDNA-Fc. By decrease of the pitch of the pillar array, the area of the electrode was enhanced by up to a factor 10.6. 5-Fluorouracil order A comparison of the electrochemical data with the geometrical area of the pillared electrodes confirmed the validity of the increased sensitivity of the DNA detection by the design of the micropillar array.Designing an appropriate set of collective variables is crucial to the success of several enhanced sampling methods. Here we focus on how to obtain such variables from information limited to the metastable states. We characterize these states by a large set of descriptors and employ neural networks to compress this information in a lower-dimensional space, using Fisher's linear discriminant as an objective function to maximize the discriminative power of the network. We test this method on alanine dipeptide, using the nonlinearly separable data set composed by atomic distances. We then study an intermolecular aldol reaction characterized by a concerted mechanism. The resulting variables are able to promote sampling by drawing nonlinear paths in the physical space connecting the fluctuations between metastable basins. Lastly, we interpret the behavior of the neural network by studying its relation to the physical variables. Through the identification of its most relevant features, we are able to gain chemical insight into the process.Searching for novel, high-performance, two-dimensional photovoltaic (2DPV) materials is an important pursuit for solar cell applications. In this work, an efficient method based on the machine learning algorithm combined with high-throughput screening is developed. Twenty-six 2DPV candidates are successfully ruled out from 187093 experimentally identified inorganic crystal structures, whose conversion efficiencies are predicted by density functional theory calculations. Our results indicate that Sb2Se2Te, Sb2Te3, and Bi2Se3 exhibit conversion efficiencies that are much higher than those of others, which make them promising 2DPV candidates for further applications. The superior photovoltaic performance is then analyzed, and the hidden structure-related relationships with photovoltaic properties are established, thus providing important information for the further examination of 2DPV materials. Given the rapid development of the database of materials, this approach not only provides an efficient way of searching for novel 2DPV materials but also can be applied to exploration of a broad range of functional materials.The dissociative photoionization of trans-1,3,3,3-tetrafluoropropene (HFO-1234ze) was investigated by imaging photoelectron photoion coincidence (PEPICO) spectroscopy. From the threshold photoelectron spectrum (TPES), an adiabatic ionization energy of 10.91 ± 0.05 eV is determined and reported for the first time. Over a 4-eV wide range, internal-energy selected trans-1,3,3,3-tetrafluoropropene cations decay by three parallel dissociative photoionization channels, which were modeled using statistical theory. The 0 K appearance energies of CF2CHCF2 (H-loss, m/z 113), CFHCHCF2 (F-loss, m/z 95), and CH2=CF2 (CF2-loss, m/z 64) fragment ions were determined to be 12.247 ± 0.030, 12.66 ± 0.10, and 12.80 ± 0.05 eV, respectively. From the last, the heat of formation of neutral trans-1,3,3,3-tetrafluoropropene was determined to be -779.9 ± 9.7 kJ/mol. While the lowest-energy fluorine loss occurs directly, the first H-loss and CF2-loss channels involve both a fluorine- and a hydrogen-migration prior to dissociation. At higher internal energies, several other rearrangement pathways open up, which involve fluorine and hydrogen transfer and, through fluorine loss, lead to the formation of several additional isomeric allylic fragment ions.Creating mesopores for the nano-ZSM-5 catalyst could further promote the diffusion of molecules in its micropores and improve the catalytic activity and stability. Inorganic alkali treatment of ZSM-5 usually removes internal silica for the existence of an aluminum distribution gradient and leads to a hollow structure. Herein, surface TPA+ adsorption-induced protective desilication and recrystallization successively occurred during hydrothermal treatment, and controllable mesopore fabrication was achieved. The evolution of mesopores and acid sites was characterized by N2 physisorption, XRD, XRF, TEM, NH3-TPD, Py-IR, 27Al MAS NMR, 29Si MAS NMR, and TG techniques. It was found that the TPAOH concentration influenced the formation of internal cavity and mesopores in the shell. Introducing TPABr into TPAOH solution increased the surface protection because of the increased TPA+ adsorption, and coated hollow ZSM-5 was obtained. The acidity was restructured during the above mesopore fabrication. High-concentration TPAOH solution promoted the insertion of destructive Al into the skeleton structure to form strong acid sites, and the catalytic lifetime was recovered and even obviously prolonged. This reflected the key role of strong acid sites on the catalytic performance. Applying hollow nano-ZSM-5 with a mesoporous shell and strong acidity increased the lifetime by 50% and the conversion capacity for liquid hydrocarbon by 20% compared to the parent sample.Two-dimensional van der Waals (vdW) magnetic materials are well-recognized milestones toward nanostructured spintronics. An interesting example is CrI3; its magnetic states can be modulated electrically, allowing spintronics applications that are highly compatible with electronics technologies. Here, we report the electric field alone induces the interlayer antiferromagnetic-to-ferromagnetic (AFM-to-FM) phase transition in CrI3 bilayers with critical field as low as 0.12 V/Å. The AFM-FM energy difference ΔE increases with electric field and is closely related to the field-induced on-site energy difference defined as the splitting between the electronic states of the two vdW layers. Our tight-binding model fits closely with ΔE as a function of electric field and gives a consistent estimation for orbital hopping, exchange splitting, and crystal field splitting. Furthermore, a CrI3-based spin field-effect device is suggested with the spin current switched on and off solely by the electric field. These findings not only reveal the physics underlying the transition but also provide guidelines for future discovery and design.We explored the possibility of nanoscale mechanical manipulation and control of photophysical properties of conjugated polymer nanoparticles. We carried out a simultaneous atomic force microscopy (AFM) and fluorescence microspectroscopy study on single nanoparticles of the conjugated polymer poly(9,9-dioctylfluorene). The nanoparticles are prepared by a reprecipitation method and have an average height of 27 nm, and their emission is dominated by the well-ordered β-phase conformation. Fluorescence polarization anisotropy and numerical simulations show that each particle contains at least three partly oriented straight β-phase segments surrounded by amorphous glass-phase polyfluorene chains. In the simultaneous experiments, an AFM tip was used to apply external force on a single nanoparticle, and a confocal fluorescence microscope was used to monitor in real time the resulting changes in the fluorescence intensity and spectra. In a nitrogen atmosphere, weak to moderate force of up to 1 μN acts mainly on the glass-phase polyfluorene chains by forming quenchers that cause an efficient and reversible fluorescence decrease, whereas the β-phase segments stay unaffected. A higher force of 5 μN, on the contrary, breaks the β-phase segments into multiple glass-phase segments, causing a net increase in fluorescence intensity. Under ambient air conditions, even a moderate force of 1 μN strongly accelerates the degradation of the nanoparticle by preferably photobleaching the β-phase and partially transforming it into the glass phase. These results will contribute to the fundamental knowledge on the relationship between photophysical and structural properties of polyfluorene nanostructures, and will also provide important feedback for potential applications of such nanostructures in flexible optoelectronic devices.The interaction of oxygen with a reactive metal is ubiquitous, yet the precise atomic-level mechanisms and pathways leading to the formation of a surface oxide are not well-understood. We report oxygen atom distributions inside Rh single nanoparticles using atom probe microscopy (APM) and demonstrate that mainly facets of the ⟨022̅⟩ crystallographic directions act as oxygen-permeable gateways. The highly anisotropic spatial distribution of incorporated oxygen atoms is in agreement with video-field emission analyses according to which 113 facets of the ⟨022̅⟩ zones act as portals for subsurface diffusion. In addition to providing a more fundamental understanding of the precursor states to metal corrosion, in particular for the case of nanosized metal particles, our studies are also relevant for heterogeneous catalysis where catalytic activity and selectivity conform to reaction-induced structural changes of metal nanoparticles.