Self‐Sustained Cycle of Hydrolysis and Etching at Solution/Solid Interfaces: A General Strategy To Prepare Metal Oxide Micro‐/Nanostructured Arrays for High‐Performance Electrodes

Assembling micro‐/nanostructured arrays on conducting substrates allows the integration of multiple functionalities into modern electronic devices. Herein, a novel self‐sustained cycle of hydrolysis and etching (SCHE) is exploited to selectively synthesize an extensive series of metal oxide micro‐/nanostructured arrays on a wide range of metal substrates, establishing the generality and efficacy of the strategy. To demonstrate the potential application of this method, the as‐prepared NiO porous nanobelt array was directly used as the anode for lithium‐ion batteries, exhibiting excellent capacity and rate capability. Conclusively, the SCHE strategy offers a systematic approach to design metal oxide micro‐/nanostructured arrays on metal substrates, which are valuable not only for lithium‐ion batteries but also for other energy conversion and storage systems and electronic devices at large.     

Unexpected high selectivity for acetate formation from CO2 reduction with copper based 2D hybrid catalysts at ultralow potentials

Copper-based catalysts are efficient for CO₂ reduction affording commodity chemicals. However, Cu(i) active species are easily reduced to Cu(0) during the CO₂RR, leading to a rapid decay of catalytic performance. Herein, we report a hybrid-catalyst that firmly anchors 2D-Cu metallic dots on F-doped Cu_xO nanoplates (Cu_xOF), synthesized by electrochemical-transformation under the same conditions as the targeted CO₂RR. The as-prepared Cu/Cu_xOF hybrid showed unusual catalytic activity towards the CO₂RR for CH₃COO⁻ generation, with a high FE of 27% at extremely low potentials. The combined experimental and theoretical results show that nanoscale hybridization engenders an effective s,p-d coupling in Cu/Cu_xOF, raising the d-band center of Cu and thus enhancing electroactivity and selectivity for the acetate formation. This work highlights the use of electronic interactions to bias a hybrid catalyst towards a particular pathway, which is critical for tuning the activity and selectivity of copper-based catalysts for the CO₂RR.

A two-dimensional (2D) copper hybrid catalyst (Cu/Cu_xOF) composed of metallic Cu well dispersed on 2D F-doped Cu_xO nanoplates (Cu_xOF) is reported, which shows high catalytic activity toward the CO₂RR for acetate generation.     

生物基高分子型止血材料和伤口敷料

伤口的快速止血和愈合对人类的生命保障和身体健康有十分重要的影响,使得伤口护理材料的研究备受关注.其中,从动植物中提取或由生物基单体合成而得的生物基高分子材料,因具有良好的物理性能、生物活性、生物相容性、生物降解性和生物可吸收性等优点,被人们通过物理或化学方法,进行改性或药物负载,制成具有止血、杀菌、保护和促进伤口愈合等...     

Large-scale synthesis of uniform nanotubes of a nickel complex by a solution chemical route

Novel layer-rolled nanotubes of a nickel complex have been successfully synthesized by a simple wet chemical method. The nanotubes are assembled by rolling the (111) sheets of [Ni(NH3)6]Cl2 with the assistance of a polymer. The remarkable uniformity and high yields of the nickel complex nanotubes point to future applications in various fields of nanotechnology.     

Studies on metallofullerene (Dy@C82) embedded in a DDAB film in aqueous solution

The electrochemical behavior of metallofullerene (Dy@C82) in didodecyldimethylammonium bromide (DDAB) films deposited on glassy carbon, quartz crystal microbalance (QCM) gold crystals, and indium tin oxide (ITO) electrodes in aqueous solution was investigated in detail. Four pairs of reversible redox peaks were observed, and for the first time, these peaks were characterized by vis/NIR spectroscopy. Different from previous fullerene/cationic lipid modified electrodes, one oxidation and three reduction processes were observed. The stability of Dy@C82 and its ions in the film toward air was detected by measuring its cyclic voltammogram after holding the potentials for 10 s, followed by introducing 10 microL of air to the solution. Dy@C82 and its first three anions are stable toward air and water, while some chemical reactions take place when the third anion is further reduced in the film. Dy@C82+ is less stable than Dy@C82- toward water and air. The electrochemical processes were measured in different electrolytes, which showed pronounced anionic dependence on either its cation or anions. The electrochemical processes were also monitored using electrochemical quartz crystal microbalance (EQCM), and from the result a possible electron-transfer mechanism of a Dy@C82/DDAB electrode in aqueous solution was presented. It showed that the anions of Dy@C82 were bound to the DDA+ cation in the film, while the anions of electrolyte diffused into the film to compensate the positive charges when a cation of Dy@C82 was generated.     

Copper-based nanowire materials: templated syntheses, characterizations, and applications

Well-aligned Cu(OH)2 nanoribbon and CuO nanorod arrays have been prepared on copper substrates by liquid-solid reactions. The effects of temperature, reaction time, solvent, and pH value on the morphology and composition of the products are systematically studied. Using the Cu(OH)2 nanoribbons array as a reactive and sacrificial template, we have successfully synthesized Cu2O, Cu9S8, and Cu nanoribbon/ nanowire arrays, demonstrating the versatility of the template. The extensive series of copper-based one-dimensional nanomaterials have been fully characterized by various structural, microscopic, and spectroscopic techniques. Moreover, the Cu nanowires are demonstrated to be an excellent surface-enhanced Raman scattering substrate with a sensitivity over an order of magnitude higher than that of a common roughened copper electrode.     

Insight into the origin of the thermosensitivity of poly[2-(dimethylamino)ethyl methacrylate].

We investigate the effects of pH and temperature on the conformational changes of poly[2-(dimethylamino)ethyl methacrylate] (PDEM) chains at the air/water interface by using Langmuir balance and sum frequency generation vibrational spectroscopy. At pH 4, the tertiary amine groups are fully charged and the PDEM chains are so hydrophilic that they completely enter into the water phase and do not exhibit thermosensitivity. At pH 7, these groups are only partially charged, and the accompanying hydration/dehydration--followed by repartitioning into the water and air phases--gives rise to a marked thermosensitivty. Finally, at pH 10, the tertiary amine groups become uncharged and thus preferentially stay in the hydrophobic air phase, devoid of associated water molecules, which results in the surface-pressure change (DeltaPi) being nearly independent of the temperature. Our Langmuir-balance experiments, coupled with surface-sensitive spectroscopy, demonstrate that: 1) the thermosensitivity of the PDEM chains relates to the hydration/dehydration of the tertiary amine groups, 2) the phase transition of thermosensitive polymers is most likely initiated by the dehydration of the chains, and 3) the phase transition of thermosensitive polymers at the air/water interface is markedly different from that in aqueous solution because of the redistribution of the macromolecular segments induced by the asymmetric forces at the air/water interface.     

Photoionization studies of transition metal clusters: Ionization potentials of ScnO (n=5−36)

The photoionization efficiency (PIE) spectra and ionization potentials are reported for scandium cluster monoxides (Sc _n O,n=5–36). As found for other transition metal clusters, strong dependence of ionization potential on cluster size is found for small clusters, with the ionization potentials of larger clusters decreasing relatively smoothly with increasing size. The IPs are 0.6–0.8 eV lower than that predicted by conducting spherical droplet model.Performed at Argonne National Laboratory     

From Nanorods to Atomically Thin Wires of Anatase TiO2: Nonhydrolytic Synthesis and Characterization

A nonhydrolytic two‐step chemical process has been developed to synthesize ultrathin, nearly monodisperse TiO₂ (anatase) wires with tunable diameters of 5 nm to approximately 4 Å, reaching the atomic length scale. The high‐quality anatase titania atomically thin wires can be doped and stabilized with nitrogen species by introducing suitable nitrogen‐containing molecules. The ultrathin wires, particularly the atomically thin wires, as well as the precursor, have been thoroughly characterized by an extensive series of structural, spectroscopic, and other techniques. Possible formation mechanisms for the rods and the wires are proposed on the basis of experimental results obtained under varying reaction conditions. Also demonstrated are the pronounced effects of size and N‐doping on the electronic, optical, and phononic properties of the anatase titania wires in the smallest size regime.     

过渡金属基层状双羟基化合物的调控及其在电化学水氧化中的应用

过渡金属基层状双羟基化合物(transition metals based layered double hydroxides,TM LDHs)由于大的比表面积,开放的微观结构,可调的层间距和化学成分等优势,近年来被广泛应用于催化领域。 本综述文章将集中介绍TM LDH在电催化水氧化中的应用,从其化学成分和微观结构的调控两方面入手,详述TM LDH具有优异催化水性能的原因,并对其催化性能未来进一步的可能发展进行展望。