A visible light responsive plasmonic photocatalytic composite material is designed by rationally selecting Au nanocrystals and assembling them with the TiO(2)-based photonic crystal substrate. The selection of the Au nanocrystals is so that their surface plasmonic resonance (SPR) wavelength matches the photonic band gap of the photonic crystal and thus that the SPR of the Au receives remarkable assistance from the photonic crystal substrate. The design of the composite material is expected to significantly increase the Au SPR intensity and consequently boost the hot electron injection from the Au nanocrystals into the conduction band of TiO(2), leading to a considerably enhanced water splitting performance of the material under visible light. A proof-of-concept example is provided by assembling 20 nm Au nanocrystals, with a SPR peak at 556 nm, onto the photonic crystal which is seamlessly connected on TiO(2) nanotube array. Under visible light illumination (>420 nm), the designed material produced a photocurrent density of ~150 μA cm(-2), which is the highest value ever reported in any plasmonic Au/TiO(2) system under visible light irradiation due to the photonic crystal-assisted SPR. This work contributes to the rational design of the visible light responsive plasmonic photocatalytic composite material based on wide band gap metal oxides for photoelectrochemical applications.

Advanced materials with surfaces that have controllable oil wettability when submerged in aqueous media have great potential for various underwater applications. Here we have developed smart surfaces on commonly used materials, including non-woven textiles and polyurethane sponges, which are able to switch between superoleophilicity and superoleophobicity in aqueous media. The smart surfaces are obtained by grafting a block copolymer, comprising blocks of pH-responsive poly(2-vinylpyridine) and oleophilic/hydrophobic polydimethylsiloxane (i.e., P2VP-b-PDMS) on these materials. The P2VP block can alter its wettability and its conformation via protonation and deprotonation in response to the pH of the aqueous media, which provides controllable and switchable access of oil by the PDMS block, resulting in the switchable surface oil wettability in the aqueous media. On the other hand, the high flexibility of the PDMS block facilitates the reversible switching of the surface oil wettability. As a proof of concept, we also demonstrate that materials functionalized with our smart surfaces can be used for highly controllable oil/water separation processes.

Hydrogen generation through photoelectrochemical (PEC) water splitting using solar light as an energy resource is believed to be a clean and efficient way to overcome the global energy and environmental problems. Extensive research effort has been focused on n-type metal oxide semiconductors as photoanodes, whereas studies of p-type metal oxide semiconductors as photocathodes where hydrogen is generated are scarce. In this paper, highly efficient and stable copper oxide composite photocathode materials were successfully fabricated by a facile two-step electrochemical strategy, which consists of electrodeposition of a Cu film on an ITO glass substrate followed by anodization of the Cu film under a suitable current density and then calcination to form a Cu 2 O/CuO composite. The synthesized Cu 2 O/ CuO composite was composed of a thin layer of Cu 2 O with a thin film of CuO on its top as a protecting coating. The rational control of chemical composition and crystalline orientation of the composite materials was easily achieved by varying the electrochemical parameters, including electrodeposition potential and anodization current density, to achieve an enhanced PEC performance. The best photocathode material among all materials prepared was the Cu 2 O/CuO composite with Cu 2 O in (220) orientation, which showed a highly stable photocurrent of À1.54 mA cm À2 at a potential of 0 V vs reversible hydrogen electrode at a mild pH under illumination of AM 1.5G. This photocurrent density was more than 2 times that generated by the bare Cu 2 O electrode (À0.65 mAcm À2 ) and the stability was considerably enhanced to 74.4% from 30.1% on the bare Cu 2 O electrode. The results of this study showed that the top layer of CuO in the Cu 2 O/CuO composite not only minimized the Cu 2 O photocorrosion but also served as a recombination inhibitor for the photogenerated electrons and holes from Cu 2 O, which collectively explained much enhanced stability and PEC activity of the Cu 2 O/CuO composite. Thus, the electrochemical strategy proposed in this study for the synthesis of the Cu 2 O/CuO composite opens a new way to use copper oxides as photocathode materials in PEC cells for a highly stable and effective water splitting.

In this work, we propose a solution-based carbon precursor coating and subsequent carbonization strategy to form a thin protective carbon layer on unstable semiconductor nanostructures as a solution to the commonly occurring photocorrosion problem of many semiconductors. A proof-of-concept is provided by using glucose as the carbon precursor to form a protective carbon coating onto cuprous oxide (Cu₂O) nanowire arrays which were synthesized from copper mesh. The carbon-layer-protected Cu₂O nanowire arrays exhibited remarkably improved photostability as well as considerably enhanced photocurrent density. The Cu₂O nanowire arrays coated with a carbon layer of 20 nm thickness were found to give an optimal water splitting performance, producing a photocurrent density of -3.95 mA cm⁻² and an optimal photocathode efficiency of 0.56% under illumination of AM 1.5G (100 mW cm⁻²). This is the highest value ever reported for a Cu₂O-based electrode coated with a metal/co-catalyst-free protective layer. The photostability, measured as the percentage of the photocurrent density at the end of 20 min measurement period relative to that at the beginning of the measurement, improved from 12.6% on the bare, nonprotected Cu₂O nanowire arrays to 80.7% on the continuous carbon coating protected ones, more than a 6-fold increase. We believe that the facile strategy presented in this work is a general approach that can address the stability issue of many nonstable photoelectrodes and thus has the potential to make a meaningful contribution in the general field of energy conversion.

In this paper, we show that by varying the voltages during two-step anodization the morphology of the hierarchical top-layer/bottom-tube TiO 2 (TiO 2 NTs) can be finely tuned between nanoring/nanotube, nanopore/nanotube, and nanohole-nanocave/nanotube morphologies. This allows us to optimize the photoelectrochemical (PEC) water splitting performance on the hierarchical TiO 2 NTs. The optimized photocurrent density and photoconversion efficiency in this study, occurring on the nanopore/ nanotube TiO 2 NTs, were 1.59 mA cm À2 at 1.23 V vs. RHE and 0.84% respectively, which are the highest values ever reported on pristine TiO 2 materials under illumination of AM 1.5G. Our findings contribute to further improvement of the energy conversion efficiency of TiO 2-based devices.

We developed camptothecin (CPT)-conjugated, core-cross-linked (CCL) micelles that are subject to redox-responsive cleavage of the built-in disulfide bonds, resulting in disruption of the micellar structure and rapid release of CPT. CCL micelles were prepared via co-precipitation of disulfide-containing CPT-poly(Tyrosine(alkynyl)-OCA) conjugate and monomethoxy poly(ethylene glycol)-b-poly(Tyrosine(alkynyl)-OCA), followed by cross-linking of the micellar core via azide–alkyne click chemistry. CCL micelles exhibited excellent stability under physiological conditions while underwent rapid dissociation in reduction circumstance, resulting in burst release of CPT. These redox-responsive CCL micelles showed enhanced cytotoxicity against human breast cancer cells in vitro.

Monomethoxy poly(ethylene glycol)-b-poly(Tyr(alkynyl)-OCA), a biodegradable amphiphilic block copolymer, was synthesized by means of ring-opening polymerization of 5-(4-(prop-2-yn-1-yloxy)benzyl)-1,3-dioxolane-2,4-dione (Tyr(alkynyl)-OCA) and used to prepare core cross-linked polyester micelles via click chemistry. Core cross-linking not only improved the structural stability of the micelles but also allowed controlled release of cargo molecules in response to the reducing reagent. This new class of core cross-linked micelles can potentially be used in controlled release and drug delivery applications.

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