Dandan Ma

NaGdF4:Yb3+/Er3+@NaGdF4:Nd3+@Sodium-Gluconate: Multifunctional and Biocompatible Ultrasmall Core–Shell Nanohybrids for UCL/MR/CT Multimodal Imaging

Multimodal bioimaging nanoparticles by integrating diverse imaging ingredients into one system, represent a class of emerging advanced materials that provide more comprehensive and accurate clinical diagnostics than conventional contrast agents. Here monodisperse and biocompatible core-shell nanoparticles, NaGdF4: Yb(3+)/Er(3+)@NaGdF4:Nd@sodium-gluconate (termed as GNa-Er@Nd), with about 26 nm in diameter were successfully prepared by a facile two step reactions in high boiling solvents, and followed a ligand exchange process with sodium gluconate. The resulting GNa-Er@Nd nanoparticles were well characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectra (FTIR), and zeta potentials. These nanohybrids present brightly dual-wavelength excited upconversion luminescence (UCL) under both 980 and 793 nm laser because of the synergistic effect of Yb(3+)/Er(3+) and Nd(3+). They also exhibited excellent relaxivity parameters (r1) in magnetic resonance imaging (MRI) and Hounsfield units (HU) in X-ray computed tomography (CT) that are comparable to the clinical contrast agents. Therefore, these small and monodisperse nanoparticles provide options to construct a unique platform for potential multimodal UCL/CT/MRI imaging simultaneously.

Highly Efficient Photocatalyst Based on a CdS Quantum Dots/ZnO Nanosheets 0D/2D Heterojunction for Hydrogen Evolution from Water Splitting

A novel CdS/ZnO heterojunction constructed of zero-dimensional (0D) CdS quantum dots (QDs) and two-dimensional (2D) ZnO nanosheets (NSs) was rationally designed for the first time. The 2D ZnO NSs were assembled into ZnO microflowers (MFs) via an ultrasonic-assisted hydrothermal procedure (100 °C, 12 h) in the presence of a NaOH solution (0.06 M), and CdS QDs were deposited on both sides of every ZnO NS in situ by using the successive ionic-layer absorption and reaction method. It was found that the ultrasonic treatment played an important role in the generation of ZnO NSs, while NaOH was responsible to the assembly of a flower-like structure. The obtained CdS/ZnO 0D/2D heterostructures exhibited remarkably enhanced photocatalytic activity for hydrogen evolution from water splitting in comparison with other CdS/ZnO heterostructures with different dimensional combinations such as 2D/2D, 0D/three-dimensional (3D), and 3D/0D. Among them, CdS/ZnO-12 (12 deposition cycles of CdS QDs) exhibited the highest hydrogen evolution rate of 22.12 mmol/g/h, which was 13 and 138 times higher than those of single CdS (1.68 mmol/g/h) and ZnO (0.16 mmol/g/h), respectively. The enhanced photocatalytic activity can be attributed to several positive factors, such as the formation of a Z-scheme photocatalytic system, the tiny size effect of 0D CdS QDs and 2D ZnO NSs, and the intimate contact between CdS QDs and ZnO NSs. The formation of a Z-scheme photocatalytic system remarkably promoted the separation and migration of photogenerated electron-hole pairs. The tiny size effect effectively decreased the recombination probability of electrons and holes. The intimate contact between the two semiconductors efficiently reduced the migration resistance of photogenerated carriers. Furthermore, CdS/ZnO-12 also presented excellent stability for photocatalytic hydrogen evolution without any decay within five cycles in 25 h.

Intense white emission from a single-upconversion nanoparticle and tunable emission colour with laser power

The development of upconversion nanoparticles with tunable emissions, particularly white colour emission, has always been at the forefront of colour display technologies. In this study, a type of multilayer NaGdF4:Yb3+,Er3+@NaGdF4@NaGdF4:Yb3+,Tm3+@NaGdF4 (denoted as Gd:Er@Gd@Gd:Tm@Gd) upconversion nanoparticle with remarkable advantages, such as small size (<50 nm), intense white colour emission and tunable emission colour with excitation laser intensity, was developed. A special design for separating NaGdF4:Yb3+,Er3+ from NaGdF4:Yb3+,Tm3+ by the insertion of an additional NaGdF4 layer can effectively prevent the fluorescence quenching of Er3+ and Tm3+. As against the typical ion-dependent tuning of colour, herein multicolour tuning was realised by manipulating the exciting laser power. With increasing power density from 5 to 19 W cm−2 using a 980 nm laser, the emission colour was tuned from bright green to white. In addition, we demonstrated the use of the multilayer Gd:Er@Gd@Gd:Tm@Gd nanoparticles for providing the proof-of-concept of multicolour imaging for anti-counterfeiting applications.

Fabrication of g-C3N4/Au/C-TiO2 hollow structures as visible-light-driven Z-scheme photocatalysts with enhanced photocatalytic H2 evolution

The Z‐scheme photocatalytic system for water splitting based on semiconductors has exhibited great potential for H2 fuel production from renewable resources. In this work, we constructed g‐C3N4/Au/C‐TiO2 hollow spheres as an all‐solid‐state Z‐scheme photocatalytic system with Au nanoparticles as the electron mediator. The as‐synthesized g‐C3N4/Au/C‐TiO2 photocatalyst showed a remarkably enhanced photocatalytic H2 evolution rate under visible‐light irradiation (λ>420 nm), which was 86 and 42 times higher than those of pure C‐TiO2 and g‐C3N4, respectively. The enhancement of photocatalytic performance can be mainly attributed to the intentionally designed Z‐scheme system, which not only promoted the efficient transfer and separation of photogenerated electron–hole pairs, but also retained the strong redox ability of the charge carriers. In addition, the Z‐scheme system also achieved high visible‐light absorption and utilization owing to the surface plasmon resonance (SPR) effect of Au nanoparticles and hollow structures of C‐TiO2. All the factors synergistically promote the photocatalytic activity of the g‐C3N4/Au/C‐TiO2 hollow nanospheres, providing a promising method for the rational design of highly efficient visible‐light‐driven photocatalysts.

Rare‐Earth‐Based Nanoparticles with Simultaneously Enhanced Near‐Infrared (NIR)‐Visible (Vis) and NIR‐NIR Dual‐Conversion Luminescence for Multimodal Imaging

Multifunctional NaGdF4 :Yb(3+),Er(3+),Nd(3+) @NaGdF4 :Nd(3+) core-shell nanoparticles (called Gd:Yb(3+),Er(3+),Nd(3+) @Gd:Nd(3+) NPs) with simultaneously enhanced near-infrared (NIR)-visible (Vis) and NIR-NIR dual-conversion (up and down) luminescence (UCL/DCL) properties were successfully synthesized. The resulting core-shell NPs simultaneously emitted enhanced UCL at 522, 540, and 660 nm and DCL at 980 and 1060 nm under the excitation of a 793 nm laser. The enhanced UCL and DCL can be explained by complex energy-transfer processes, Nd(3+) →Yb(3+) →Er(3+) and Nd(3+) →Yb(3+) , respectively. The effects of Nd(3+) concentration and shell thickness on the UCL/DCL properties were systematically investigated. The UCL and DCL properties of NPs were observed under the optimal conditions: a shell Nd(3+) content of 20 % and a shell thickness of approximately 5 nm. Moreover, the Gd:Yb(3+) ,Er(3+) ,Nd(3+) @Gd:20 % Nd(3+) NPs exhibited remarkable magnetic resonance imaging (MRI) properties similar to that of a clinical agent, Omniscan. Thus, the core-shell NPs with excellent UCL/DCL/magnetic resonance imaging (MRI) properties have great potential for both in vitro and in vivo multimodal bioimaging.

Synergistically enhanced upconversion luminescence in Li+-doped core-shell-structured ultrasmall nanoprobes for dual-mode deep tissue fluorescence/CT imaging

The development of upconversion luminescence that allows for multimodal imaging in terms of resolution and penetration depth using a single system is attracting increasing interest for use in clinical molecular imaging and diagnostics. In this study, a simple method for inducing high-intensity upconversion luminescence by doping Li+ ions in a core-shell-structured NaLuF4:Yb,Tm system was developed. The synergistic effects of Li+ doping and the shell layer enhanced the luminescence intensity by approximately 210 times. In vitro and in vivo experiments showed that the high-intensity luminescence of nanoparticles exhibited a depth penetration ability for biological tissue. Owing to the heavy atom effect of the Lu3+ ions, the nanoparticles, which had a size of 23 nm, showed good CT imaging performance when compared with a clinical contrast agent, in addition to allowing for deep tissue imaging. The excellent optical and CT imaging properties of the Li+-doped high-luminescence core-shell upconversion nanoparticles suggest that they are highly suited for use in both deep tissue fluorescence imaging and CT imaging for multimodal diagnosis.

WS2/Graphitic Carbon Nitride Heterojunction Nanosheets Decorated with CdS Quantum Dots for Photocatalytic Hydrogen Production

Two-dimensional/two-dimensional (2D/2D) stacking heterostructures are highly desirable in fabricating efficient photocatalysts because face-to-face contact can provide a maximized interfacial region between the two semiconductors; this largely facilitates the migration of charge carriers. Herein, a WS2 /graphitic carbon nitride (CN) 2D/2D nanosheet heterostructure decorated with CdS quantum dots (QDs) has been designed, for the first time. Optimized CdS/WS2 /CN without another cocatalyst exhibits a significantly enhanced photocatalytic H2 evolution rate of 1174.5 μmol h-1  g-1 under visible-light irradiation (λ>420 nm), which is nearly 67 times higher than that of the pure CN nanosheets. The improved photocatalytic activity can be primarily attributed to the highly efficient charge-transfer pathways built among the three components, which effectively accelerate the separation and transfer of photogenerated electrons and holes, and thus, inhibit their recombination. Moreover, the extended light-absorption range also contributes to excellent photocatalytic efficiency. In addition, the CdS/WS2 /CN photocatalyst shows excellent stability and reusability without apparent decay in the photocatalytic H2 evolution within 4 cycles in 20 h. It is believed that this work may shed light on specifically designed 2D/2D nanosheet heterostructures for more efficient visible-light-driven photocatalysts.

Efficient spatial charge separation and transfer in ultrathin g-C3N4 nanosheets modified with Cu2MoS4 as a noble metal-free co-catalyst for superior visible light-driven photocatalytic water splitting

Developing photocatalysts with efficient spatial charge separation and transfer as well as a high light-harvesting ability remains a key challenge. Here, we report a facile in situ process to decorate ultrathin g-C3N4 nanosheets (NSs) with a co-catalyst, Cu2MoS4, for photocatalytic water splitting. The as-obtained Cu2MoS4/g-C3N4 exhibits a superior photocatalytic H2 evolution rate of 2170.5 μmol h−1 g−1 under visible light irradiation, which is nearly 677 and 34 times higher than that of bulk g-C3N4 and g-C3N4 NSs, respectively, and far exceeds that of most g-C3N4 catalysts modified with other sulphide co-catalysts reported in the literature, demonstrating that Cu2MoS4 can serve as a promising non-noble metal co-catalyst to couple with g-C3N4 for highly efficient photocatalysts. Structural characterization confirms the well-defined morphology of Cu2MoS4/g-C3N4 in which Cu2MoS4 hollow spheres are uniformly attached on the ultrathin g-C3N4 NSs with numerous micropores and vacancies. The optical properties indicate that Cu2MoS4/g-C3N4 possesses a superb visible light absorption ability. The photoluminescence spectra, photocurrent response, and electrochemical impedance spectra combine to prove the highly efficient separation and migration of photogenerated electrons and holes. All these factors synergistically enhance the photocatalytic activity of Cu2MoS4/g-C3N4 for photocatalytic water splitting, providing new insights into the rational design of high-performance visible light-driven photocatalysts based on earth-abundant elements.

Ce-doped titania nanoparticles: The effects of doped amount and calcination temperature on photocatalytic activity

A series of Ce-doped TiO2 nanoparticles with different doped amount and calcination temperature were prepared by sol-gel method. These obtained samples were characterized with X-ray diffraction (XRD), transmission electron microscope (TEM) and ultraviolet-visible diffuse reflectance spectra (DRS), and their photocatalytic activities were evaluated by the photocatalytic degradation of methyl orange. Results showed that Ce doping inhibits the growth of crystal size and the phase transformation from anatase to rutile, leads to lattice distortion and expansion of TiO2. Furthermore, Ce doping brings the red-shift of absorption profile and the increase of photons absorption in the range of 400-600 nm. Photocatalytic degradation of methyl orange shows that Ce doping improves the photocatalytic activity of TiO2. The optimal doped amount is 0.05 mol% and the optimal calcined temperature is 600 °C for the maximum photocatalytic degradation efficiency in our experiment.