A recyclable dynamic semiconducting polymer consisting of Pauli-paramagnetic diradicaloids promoted and stabilized by catechol-boron coordination.

Coordination between 5,5',6,6'-tetrahydroxyindigo (4OH-ID) and boron tribromide unexpectedly affords a novel dynamic covalent polymer, namely P(ID-O-B), consisting of alternating indigo and indigo diradicaloid units. The catechol-boron dynamic bond plays a vital role in promoting the diradicaloid formation and stabilizing the formed diradicaloid segments. The diradicaloid segment in the polymer has a triplet ground state and a thermally populated doublet state, which has been confirmed by the EPR study.

Regulating the Oxygen Vacancy and Electronic Structure of NiCo Layered Double Hydroxides by Molybdenum Doping for High-Power Hybrid Supercapacitors.

Amelioration of nickel-cobalt layered double hydroxides (NiCo-LDH) with a high specific theoretical capacitance is of great desire for high-power supercapacitors. Herein, a molybdenum (Mo) doping strategy is proposed to improve the charge-storage performance of NiCo-LDH nanosheets growing on carbon cloth (CC) via a rapid microwave process. The regulation of the electronic structure and oxygen vacancy of the LDH is consolidated by the density functional theory (DFT) calculation, which demonstrates that Mo doping narrows the band gap, reduces the formation energy of hydroxyl vacancies, and promotes ionic and charge transfer as well as electrolyte adsorption on the electrode surface.

Water-solid contact electrification causes hydrogen peroxide production from hydroxyl radical recombination in sprayed microdroplets.

Contact electrification between water and a solid surface is crucial for physicochemical processes at water-solid interfaces. However, the nature of the involved processes remains poorly understood, especially in the initial stage of the interface formation. Here we report that HO is spontaneously produced from the hydroxyl groups on the solid surface when contact occurred.

Cyclic Single Atom Vertical Manipulation on a Nonmetallic Surface.

Motivated by the quest for experimental procedures capable of controlled manipulation of single atoms on surfaces, we set up a computational strategy that explores the cyclical vertical manipulation of a broad set of single atoms on the GaAs(110) surface. First-principles simulations of atomic force microscope tip-sample interactions were performed considering families of GaAs and Au-terminated tip apexes with varying crystalline termination. We identified a subset of tips capable of both picking up and depositing an adatom (Ga, As, Al, and Au) any number of times via a modify-restore cycle that "resets" the apex of the scanning probe to its original structure at the end of each cycle.

Tailoring the Energy Band Structure and Interfacial Morphology of the ETL via Controllable Nanocluster Size Achieves High-Performance Planar Perovskite Solar Cells.

Planar-type perovskite solar cells (p-PSCs) based on SnO have garnered further attention due to their simple and low-temperature fabrication. Improving the critical properties of the electron transport layer (ETL) is an effective way to enhance the performance of p-PSC devices. Here, a brand-new method is developed to relieve the contact recombination caused by the rough fluorine-doped tin oxide (FTO) surface and further boosts the electrical concentration of the ETL.

Chemical shielding of HO and HF encapsulated inside a C cage.

Molecular surgery provides the opportunity to study relatively large molecules encapsulated within a fullerene cage. Here we determine the location of an HO molecule isolated within an adsorbed buckminsterfullerene cage, and compare this to the intrafullerene position of HF. Using normal incidence X-ray standing wave (NIXSW) analysis, coupled with density functional theory and molecular dynamics simulations, we show that both HO and HF are located at an off-centre position within the fullerene cage, caused by substantial intra-cage electrostatic fields generated by surface adsorption of the fullerene.

Single hydrogen atom manipulation for reversible deprotonation of water on a rutile TiO (110) surface.

The discovery of hydrogen atoms on the TiO surface is crucial for many practical applications, including photocatalytic water splitting. Electronically activating interfacial hydrogen atoms on the TiO surface is a common way to control their reactivity. Modulating the potential landscape is another way, but dedicated studies for such an activation are limited.

Electrophoretic Deposited Black Phosphorus on 3D Porous Current Collectors to Regulate Li Nucleation for Dendrite-Free Lithium Metal Anodes.

Li metal is considered a highly desirable anode for next-generation high-energy-density rechargeable lithium batteries. However, irregular Li dendrite formation and infinite relative volume changes prevent the commercial adoption of Li-metal anodes. Here, electrophoretic deposition of black phosphorus (BP) on commercial Cu foam (BP@Cu foam) is reported to regulate Li nucleation for the first time.

Long-range ordered and atomic-scale control of graphene hybridization by photocycloaddition.

Chemical reactions that convert sp to sp hybridization have been demonstrated to be a fascinating yet challenging route to functionalize graphene. So far it has not been possible to precisely control the reaction sites nor their lateral order at the atomic/molecular scale. The application prospects have been limited for reactions that require long soaking, heating, electric pulses or probe-tip press.

Imaging oxygen molecular adsorption and dissociation on the Ti site of rutile TiO(110) surface with real configuration at 78 K by atomic force microscopy.

Understanding oxygen adsorption and dissociation on the five-fold coordinated titanium (Ti5c) site of the rutile TiO2 surface is important in clarifying chemical reaction processes. Accordingly, three different configurations of molecularly adsorbed O2, including parallel side-on, inclined side-on and end-on configurations, and their dissociation were directly observed with atomic resolution at 78 K by atomic force microscopy. Our results experimentally demonstrated that the three adsorbed O2 configurations could be changed by electric field stimulation.

An Endergonic Synthesis of Single Sondheimer-Wong Diyne by Local Probe Chemistry.

Recent advances in scanning probe microscopy on surface enable not only direct observation of molecular structures but also local probe reactions, in which unstable short-lived products have been synthesized and analyzed. Now, an endergonic reaction to synthesize a single Sondheimer-Wong diyne from 6,13-dibromopentaleno[1,2-b:4,5-b']dinaphthalene by local probe chemistry on a ultra-thin film of NaCl formed on a Cu(111) surface at 4.3 K is presented.

Low-Temperature Growing Anatase TiO/SnO Multi-dimensional Heterojunctions at MXene Conductive Network for High-Efficient Perovskite Solar Cells.

A multi-dimensional conductive heterojunction structure, composited by TiO, SnO, and TiCT MXene, is facilely designed and applied as electron transport layer in efficient and stable planar perovskite solar cells. Based on an oxygen vacancy scramble effect, the zero-dimensional anatase TiO quantum dots, surrounding on two-dimensional conductive TiCT sheets, are in situ rooted on three-dimensional SnO nanoparticles, constructing nanoscale TiO/SnO heterojunctions. The fabrication is implemented in a controlled low-temperature anneal method in air and then in N atmospheres.

Externally driven molecular ratchets on a periodic potential surface: a rate equations approach.

The long time dynamics of molecular ratchets on a 1D periodic potential energy surface (PES) subjected to an external stimulus is studied using the rate equation method. The PES consisting of repeated waveforms made of two peaks is considered as an example of a spatially symmetric or asymmetric PES. This PES may, for example, correspond to diffusion of a bipedal molecule that moves along an atomic track via an inchworm walk mechanism [Raval et al.

Correction: Controlling the preferential motion of chiral molecular walkers on a surface.

[This corrects the article DOI: 10.1039/C9SC01135H.].

Controlling the preferential motion of chiral molecular walkers on a surface.

Molecular walkers standing on two or more "feet" on an anisotropic periodic potential of a crystal surface may perform a one-dimensional Brownian motion at the surface-vacuum interface along a particular direction in which their mobility is the largest. In thermal equilibrium the molecules move with equal probabilities both ways along this direction, as expected from the detailed balance principle, well-known in chemical reactivity and in the theory of molecular motors. For molecules that possess an asymmetric potential energy surface (PES), we propose a generic method based on the application of a time-periodic external stimulus that would enable the molecules to move preferentially in a single direction thereby acting as Brownian ratchets.

Going Nano with Confined Effects to Construct Pomegranate-like Cathode for High-Energy and High-Power Lithium-Ion Batteries.

Pomegranate-like LiV(PO)@C (LVP@C) cathode materials are fabricated through confined effect helped by the vacuum-assisted capillary action. The performance of LiV(PO) ( = 0-5) at an extended working voltage of 1.2-4.

Tip-Induced Control of Charge and Molecular Bonding of Oxygen Atoms on the Rutile TiO (110) Surface with Atomic Force Microscopy.

We study a low-temperature on-surface reversible chemical reaction of oxygen atoms to molecules in ultrahigh vacuum on the semiconducting rutile TiO(110)-(1 × 1) surface. The reaction is activated by charge transfer from two sources, natural surface/subsurface polarons and experimental Kelvin probe force spectroscopy as a tool for electronic charge manipulation with single electron precision. We demonstrate a complete control over the oxygen species not attainable previously, allowing us to deliberately discriminate in favor of charge or bond manipulation, using either direct charge injection/removal through the tip-oxygen adatom junction or indirectly via polarons.

Xanthine Quartets on Au(111).

The quartet of xanthine (X), a purine base ubiquitously distributed in most human body tissues and fluids, has been for the first time fabricated and visualized, as the first alternative purine quartet besides the known guanine (G)-quartet. The X-quartet network is demonstrated to be the most stable phase on Au(111). Unlike guanine, the fabrication of the X-quartets is not dependent on the presence of metal atoms, which makes it the first metal-free purine quartet.

Three-Dimensional Branched TiO2 Architectures in Controllable Bloom for Advanced Lithium-Ion Batteries.

Three-dimensional branched TiO2 architectures (3D BTA) with controllable morphologies were synthesized via a facile template-free one-pot solvothermal route. The volume ratio of deionized water (DI water) and diethylene glycol in solvothermal process is key to the formation of 3D BTA assembled by nanowire-coated TiO2 dendrites, which combines the advantages of 3D hierarchical structure and 1D nanoscale building blocks. Benefiting from such unique structural features, the BTA in full bloom achieved significantly increased specific surface areas and shortened Li(+) ion/electrons diffusion pathway.

Efficient and stable perovskite solar cells prepared in ambient air irrespective of the humidity.

Poor stability of organic-inorganic halide perovskite materials in humid condition has hindered the success of perovskite solar cells in real applications since controlled atmosphere is required for device fabrication and operation, and there is a lack of effective solutions to this problem until now. Here we report the use of lead (II) thiocyanate (Pb(SCN)2) precursor in preparing perovskite solar cells in ambient air. High-quality CH3NH3PbI3-x(SCN)x perovskite films can be readily prepared even when the relative humidity exceeds 70%.

A small molecule walks along a surface between porphyrin fences that are assembled in situ.

An on-surface bimolecular system is described, comprising a simple divalent bis(imidazolyl) molecule that is shown to "walk" at room temperature via an inchworm mechanism along a specific pathway terminated at each end by oligomeric "fences" constructed on a monocrystalline copper surface. Scanning tunneling microscopy shows that the motion of the walker occurs along the [110] direction of the Cu surface with remarkably high selectivity and is effectively confined by the orthogonal construction of covalent porphyrin oligomers along the [001] surface direction, which serve as barriers. Density functional theory shows that the mobile molecule walks by attaching and detaching the nitrogen atoms in its imidazolyl "legs" to and from the protruding close-packed rows of the metal surface and that it can transit between two energetically equivalent extended and contracted conformations by overcoming a small energy barrier.

Identifying tips for intramolecular NC-AFM imaging via in situ fingerprinting.

A practical experimental strategy is proposed that could potentially enable greater control of the tip apex in non-contact atomic force microscopy experiments. It is based on a preparation of a structure of interest alongside a reference surface reconstruction on the same sample. Our proposed strategy is as follows.

Mapping the force field of a hydrogen-bonded assembly.

Hydrogen bonding underpins the properties of a vast array of systems spanning a wide variety of scientific fields. From the elegance of base pair interactions in DNA to the symmetry of extended supramolecular assemblies, hydrogen bonds play an essential role in directing intermolecular forces. Yet fundamental aspects of the hydrogen bond continue to be vigorously debated.

Self-assembly of KxWO3 nanowires into nanosheets by an oriented attachment mechanism.

The KxWO3 nanosheets consisting of superfine nanowires were successfully synthesized in ambient air. The detailed electron microscopy and X-ray diffraction investigations imply that the nanosheets were obtained by self-assembly of the ordered nanowires with exposed {0110}H facets. The sheet morphology is closely related with the growth conditions including temperature and time, etc.

Polarization-induced charge distribution at homogeneous zincblende/wurtzite heterostructural junctions in ZnSe nanobelts.

Homogeneous heterostructural wurtzite (WZ)/zincblende (ZB) junctions are successfully fabricated in ZnSe nanobelts. Polarity continuity across the ZB/WZ interface is demonstrated. The saw-tooth-like potential profile induced by spontaneous polarization across the WZ/ZB/WZ interfaces is identified directly at the nanoscale.