The generation of hydrogen from water using sunlight could potentially form the basis of a clean and renewable source of energy. Various water-splitting methods have been investigated previously, but the use of photocatalysts to split water into stoichiometric amounts of H2 and O2 (overall water splitting) without the use of external bias or sacrificial reagents is of particular interest because of its simplicity and potential low cost of operation. However, despite progress in the past decade, semiconductor water-splitting photocatalysts (such as (Ga1-xZnx)(N1-xOx)) do not exhibit good activity beyond 440 nm (refs 1,2,9) and water-splitting devices that can harvest visible light typically have a low solar-to-hydrogen efficiency of around 0.1%. Here we show that cobalt(II) oxide (CoO) nanoparticles can carry out overall water splitting with a solar-to-hydrogen efficiency of around 5%. The photocatalysts were synthesized from non-active CoO micropowders using two distinct methods (femtosecond laser ablation and mechanical ball milling), and the CoO nanoparticles that result can decompose pure water under visible-light irradiation without any co-catalysts or sacrificial reagents. Using electrochemical impedance spectroscopy, we show that the high photocatalytic activity of the nanoparticles arises from a significant shift in the position of the band edge of the material.
Amine-linked covalent organic frameworks (COFs) were synthesized by the reduction of parent imine-linked COFs by crystal-to-crystal transformation. The excellent chemical stability of these COFs in combination with the presence of a large amount of amine functional groups led to a robust and molecularly defined interface at the silver metal surface as an electrode for the electrochemical reduction of CO 2. The concerted operation of COF and the metal surface resulted in high conversion efficiency and excellent selectivity against the reduction of water.
Electrochemical measurements, atomic force microscopy, and scanning tunneling microscopy have been combined to present the first direct images of the potential-controlled phase transition between the hemimicellar and condensed states of a dodecyl sulfate (SDS) film at the Au(111) electrode surface. The adsorbed SDS forms stripe-shaped hemimicellar aggregates at small or moderate charge densities at the electrode. High-resolution STM images of these aggregates revealed that adsorbed SDS molecules are ordered and form a long-range two-dimensional lattice. A unit cell of this lattice consists of two vectors that are 4.4 and 0.5 nm long and are oriented at an angle of 70°. We propose that each unit cell contains two flat-laying SDS molecules stretched out along the longer axis of the cell with the hydrocarbon tails directed toward the interior of the cell. The remaining SDS molecules in the hemimicelle assume a tilted orientation. This long-range structure is stabilized by the interactions of sulfate groups belonging to the adjacent cells. The sulfate groups of the flat-laying SDS molecules are arranged into a characteristic (√3 × √7) structure in which the sulfate groups along the √7 direction are bridged by hydrogen-bonded water molecules. When the positive charge on the metal either becomes equal to or exceeds the charge of adsorbed surfactant, the surface aggregates melt to form a condensed film. The transition between the hemimicellar and condensed states of the film is reversible. The hemimicellar aggregates may be re-formed by decreasing the charge density at the electrode surface. The charging and discharging of the gold electrode can be easily controlled by a proper variation of the electrode potential.
2D PEG-ylated MoS2/Bi2 S3 composite nanosheets are successfully constructed by introducing bismuth ions to react with the two extra S atoms in a (NH4)2 MoS4 molecule precursor for solvothermal synthesis of MoS2. The MBP nanosheets can serve as a promising platform for computed tomography and photoacoustic-imaging-guided tumor diagnosis, as well as combined tumor photothermal therapy and sensitized radiotherapy.
Biodegradability of inorganic nanoparticles is one of the most critical issues in their further clinical translations. In this work, a novel "metal ion-doping" approach has been developed to endow inorganic mesoporous silica-based nanoparticles with tumor-sensitive biodegradation and theranostic functions, simply by topological transformation of mesoporous silica to metal-doped composite nanoformulations. "Manganese extraction" sensitive to tumor microenvironment was enabled in manganese-doped hollow mesoporous silica nanoparticles (designated as Mn-HMSNs) to fast promote the disintegration and biodegradation of Mn-HMSNs, further accelerating the breakage of Si-O-Si bonds within the framework. The fast biodegradation of Mn-HMSNs sensitive to mild acidic and reducing microenvironment of tumor resulted in much accelerated anticancer drug releasing and enhanced T1-weighted magnetic resonance imaging of tumor. A high tumor-inhibition effect was simultaneously achieved by anticancer drug delivery mediated by PEGylated Mn-HMSNs, and the high biocompatibility of composite nanosystems was systematically demonstrated in vivo. This is the first demonstration of biodegradable inorganic mesoporous nanosystems with specific biodegradation behavior sensitive to tumor microenvironment, which also provides a feasible approach to realize the on-demand biodegradation of inorganic nanomaterials simply by "metal ion-doping" strategy, paving the way to solve the critical low-biodegradation issue of inorganic drug carriers.
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