Synergistic effect of composition gradient and morphology on the catalytic activity of amorphous FeCoNi-LDH.

The rational design of electrocatalysts with well-designed compositions and structures for the oxygen evolution reaction (OER) is promising and challenging. Herein, we developed a novel strategy - a one-step double-cation etching sedimentation equilibrium strategy - to synthesize amorphous hollow Fe-Co-Ni layered double hydroxide nanocages with an outer surface of vertically interconnected ultrathin nanosheets (Fe-Co-Ni-LDH), which primarily depends on the in situ etching sedimentation equilibrium of the template interface. This unique vertical nanosheet-shell hierarchical nanostructure possesses enhanced charge transfer, increased active sites, and favorable kinetics during electrolysis, resulting in superb electrocatalytic performance for the oxygen evolution reaction (OER). Specifically, the Fe-Co-Ni-LDH nanocages exhibited remarkable OER activity in alkaline electrolytes and achieved a current density of 100 mA cm-2 at a low overpotential of 272 mV with excellent stability. This powerful strategy provides a profound molecular-level insight into the control of the morphology and composition of 2D layered materials.

Type-II/type-II band alignment to boost spatial charge separation: a case study of g-C3N4 quantum dots/a-TiO2/r-TiO2 for highly efficient photocatalytic hydrogen and oxygen evolution.

Efficient spatial charge separation and transfer that are critical factors for solar energy conversion primarily depend on the energetic alignment of the band edges at interfaces in heterojunctions. Herein, we first report that constructing a 0D/0D type-II(T-II)/T-II heterojunction is an effective strategy to ingeniously achieve long-range charge separation by taking a ternary heterojunction of TiO2 and graphitic carbon nitride (g-C3N4) as a proof-of-concept. Incorporating g-C3N4 quantum dots (QCN), as the third component, into the commercial P25 composed of anatase (a-TiO2) and rutile (r-TiO2) can be realized via simply mixing the commercially available Degussa P25 and QCN solution followed by heat treatment. The strong coupling and matching band structures among a-TiO2, r-TiO2 and QCN result in the construction of novel T-II/T-II heterojunctions, which would promote the spatial separation and transfer of photogenerated electrons and holes. Moreover, QCN plays a key role in reinforcing light absorption. Particularly, the unique 0D/0D architecture possesses the advantages of abundant active sites for the photocatalytic reaction. As a result, the optimized QCN/a-TiO2/r-TiO2 heterojunctions exhibit enhanced photocatalytic H2 and O2 evolution, especially the hydrogen evolution rate (49.3 µmol h-1) is 11.7 times that of bare P25 under visible light irradiation, and sufficient catalytic stability as evidenced by the recycling experiments. The remarkably enhanced photocatalytic activity can be attributed to the synergistic effects of the energy level alignment at interfaces, the dimensionality and component of the heterojunctions. This work provides a stepping stone towards the design of novel heterojunctions for photocatalytic water splitting.

Interfacial charge modulation: carbon quantum dot implanted carbon nitride double-deck nanoframes for robust visible-light photocatalytic tetracycline degradation.

Steering charge kinetics at the interface is essential to improve the photocatalytic performance of two-dimensional (2D) material-based heterostructures. Herein, we developed a novel strategy-simultaneously building two kinds of heterojunctions- to modulate interfacial charge kinetics in polymeric carbon nitride (CN) for improving the photocatalytic activity. Using a simple one-step thermal condensation of carbon quantum dot (CQD)-contained supramolecular precursors formed in water, the controllable CQD embedded CN nanoframes possessed two kinds of heterogeneous interfaces within seamlessly stitched micro-area two-dimensional in-plane and out-of-plane domains. These two kinds of heterojunctions can effectively enhance its intrinsic driving force to accelerate the separation and transfer of charge along different directions. Furthermore, the hollow double-deck porous CN-CQD nanoframes with a high surface area (296.74 m2 g-1) endowed more exposed active sites. The remarkable visible-light photocatalytic activity of hollow porous CN-CQD nanoframes was demonstrated by degrading tetracycline (TC) and rhodamine (RhB) as the models, whose robust degradation rate constant is approximately 11 and 29 times higher than that of pristine CN, respectively. This work provides a novel strategy for the interfacial design of the heterophase junction with atomic precision.

Strategy to boost catalytic activity of polymeric carbon nitride: synergistic effect of controllable in situ surface engineering and morphology.

Polymeric carbon nitride (CN) is a promising metal-free catalyst plagued by a low intrinsic activity. Herein, a novel strategy based on controllable in situ surface engineering and morphology was developed to synergistically boost the catalytic activity of CN by tuning the hydroxyl groups on its surface and constructing a unique nanostructure. The controllable introduction of hydroxyl groups on CN nanoshells, prepared by the thermal condensation of oxygen-containing supramolecular precursors formed in water, led to spatial separation of the HOMO and LUMO, and effective exciton dissociation, as verified by experiments and ab initio calculations. Furthermore, the hollow hemispherical nanoshell endowed more exposed active sites, optimal mass transport, and dynamic modulations. The optimized hollow hemispherical CN nanoshells exhibited remarkable catalytic activity, with a photoelectrocatalytic OER overpotential of about 330 mV at a current density of 10 mA cm-2, outperforming state-of-the-art precious-metal catalyst IrO2. High activity for the visible-light photocatalytic HER and pollutant degradation were also observed. This study proposes that, through rational surface group modification, a polymer material with high catalytic activity can be practically realized, which is promising for the design of efficient metal-free catalysts.

Doping-Induced Hydrogen-Bond Engineering in Polymeric Carbon Nitride To Significantly Boost the Photocatalytic H2 Evolution Performance.

Unlike graphene, graphitic carbon nitride (CN) polymer contains a weak hydrogen bond and van der Waals (vdWs) interactions besides a strong covalent bond, which controls its final morphology and functionality. Herein, we propose a novel strategy, hydrogen-bond engineering, to tune hydrogen bonds in polymeric CN through nonmetal codoping. Incorporation of B and P dopants breaks partial hydrogen bonds within the layers and simultaneously weakens the vdWs interaction between neighboring layers, resulting in ultrathin codoped CN nanosheets. The two-dimensional structure of the ultrathin sheet, broken hydrogen bonds, and incorporated dopants endow them with efficient visible light harvesting, improved charge separation, and increased active edge sites that synergistically enhance the photocatalytic activity of doped CN. Specifically, the B/P-codoped CN exhibits an extremely high hydrogen-evolution rate of 10877.40 µmol h-1 g-1, much higher than most reported values of CN. This work demonstrates that hydrogen bond engineering is an effective strategy to modify the structure and properties of polymers for various applications.

Doping-induced enhancement of crystallinity in polymeric carbon nitride nanosheets to improve their visible-light photocatalytic activity.

Structural defects can greatly inhibit electron transfer in two-dimensional (2D) layered polymeric carbon nitride (CN) unit, seriously lowering its utilization ratio of photogenerated charges during photocatalysis. Herein, we propose a new strategy based on intra-melon hydrogen bonding interactions in 2D CN frameworks to improve the crystallinity of CN. This concept was validated by removing some amino groups and connecting melon using codoped B and F atoms via a simple one-step sodium fluoroborate-assisted thermal treatment. The enhancement in crystallinity effectively promoted exciton dissociation and charge transfer in the CN nanosheets. Furthermore, the B/F dopants also improved the separation of photogenerated carriers by promoting charge capture. The highly efficient visible-light photocatalytic activity of the crystalline B/F-codoped CN nanosheets was demonstrated by degrading methyl orange, Rhodamine B, colorless phenol and tetracycline hydrochloride as models, where their degradation rate constant was more than 10, 5, 32 and 3 times higher than that of pure CN, respectively. Moreover, the B/F-codoped CN exhibited an excellent photoelectrocatalytic performance for the oxygen evolution reaction (OER), outperforming the precious-metal IrO2 catalyst. The simple and effective strategy proposed herein provides a direct route to engineer high crystallinity in 2D materials for tunable charge carrier separation and migration for electronic and optoelectronic applications.

[Risk factors for recurrent wheezing in infants and young children suffering from dust mite allergy after their first wheezing].

OBJECTIVE: To investigate the risk factors for recurrent wheezing in infants and young children suffering from dust mite allergy after their first wheezing. METHODS: A total of 1 236 infants and young children who experienced a first wheezing episode and were hospitalized between August 2014 and February 2015 were enrolled, among whom 387 were allergic to dust mites. These infants and young children were followed up to 1 year after discharge. A total of 67 infants and young children who experienced 3 or more recurrent wheezing episodes within 1 year were enrolled as the recurrent wheezing group, while 84 infants and young children who did not experience recurrent wheezing during follow-up were enrolled as the control group. Univariate analysis and multivariate logistic stepwise regression analysis were performed to investigate the risk factors for recurrent wheezing in these patients. RESULTS: The univariate analysis showed that the age on admission, wheezing time before admission, Mycoplasma pneumoniae infection rate, and influenza virus infection rate were associated with recurrent wheezing. The multivariate logistic stepwise regression analysis showed that the older age on admission (OR=2.21, P=0.04) and Mycoplasma pneumoniae infection (OR=3.54, P=0.001) were independent risk factors for recurrent wheezing. CONCLUSIONS: Infants and young children who are allergic to dust mites, especially young children, have a significantly increased risk of recurrent wheezing if they are complicated by Mycoplasma pneumoniae infection during the first wheezing episode.

Tuning near-gap electronic structure, interface charge transfer and visible light response of hybrid doped graphene and Ag3PO4 composite: Dopant effects.

The enhanced photocatalytic performance of doped graphene (GR)/semiconductor nanocomposites have recently been widely observed, but an understanding of the underlying mechanisms behind it is still out of reach. As a model system to study the dopant effects, we investigate the electronic structures and optical properties of doped GR/Ag3PO4 nanocomposites using the first-principles calculations, demonstrating that the band gap, near-gap electronic structure and interface charge transfer of the doped GR/Ag3PO4(100) composite can be tuned by the dopants. Interestingly, the doping atom and C atoms bonded to dopant become active sites for photocatalysis because they are positively or negatively charged due to the charge redistribution caused by interaction. The dopants can enhance the visible light absorption and photoinduced electron transfer. We propose that the N atom may be one of the most appropriate dopants for the GR/Ag3PO4 photocatalyst. This work can rationalize the available experimental results about N-doped GR-semiconductor composites, and enriches our understanding on the dopant effects in the doped GR-based composites for developing high-performance photocatalysts.

Facile ion-exchange synthesis of mesoporous Bi2S3/ZnS nanoplate with high adsorption capability and photocatalytic activity.

Novel Bi2S3/ZnS nanoplates have been successfully prepared by simple reflux and cation exchange reaction between the preformed ZnS spheres and Bi(NO3)3·5H2O. The synthesized Bi2S3/ZnS nanoplates are mesoporous structures, possess a high specific surface area of 101.30m(2)/g and exhibit high adsorption capability and photocatalytic activity for methylene blue (MB) degradation under UV light irradiation. The high adsorption capability and photocatalytic activity can be ascribed to the fact that the formation of Bi2S3/ZnS nanoplates with large specific surface area provides more reactive sites and facilitates the separation of photogenerated electron-hole pairs. The possible formation mechanism of Bi2S3/ZnS nanoplates is proposed based on the time-dependent observation. Moreover, a tentative mechanism for degradation of MB over Bi2S3/ZnS has been proposed involving OH radical and photoinduced holes as the active species, which is confirmed by using methanol or ammonium oxalate as scavengers. This work provides a cost-effective method for large-scale synthesis of composite with controlled architectural morphology and highly promising applications in photocatalysis.