Ruinian Hua

Optical transition, electron-phonon coupling and fluorescent quenching of La2(MoO4)3:Eu3+ phosphor

La2(MoO4)3 phosphors with various Eu3+ concentrations were prepared via a facile co-precipitation process. The crystal structure and morphology of the phosphors were characterized by means of XRD and field emission scanning electron microscope. The crystal unit cell parameters a, b, and c for the monoclinic phase La2(MoO4)3 were calculated to be 16.989, 11.927, and 16.086 A, respectively. The average size of the phosphor particles was estimated to be around 88.5 nm. The Huang–Rhys factor was derived from the phonon sideband spectra to be 0.073. The self-generated quenching process of Eu3+ was explained based on Auzel’s model, and the intrinsic radiative transition lifetime for 5D0 level was confirmed to be 0.99 ms. A new approach for calculating the Judd–Ofelt parameters was developed, meanwhile the Judd–Ofelt parameters Ωλ (λ = 2, 4, 6) of Eu3+ in La2(MoO4)3 phosphors were confirmed to be 10.70 × 10−20, 1.07 × 10−20, and 0.56 × 10−20 cm2, respectively. Finally, the optimal doping concentration for achiev...

Self-assembled 3D flower-shaped NaY(WO4)2:Eu3+ microarchitectures: Microwave-assisted hydrothermal synthesis, growth mechanism and luminescent properties

Three dimensional (3D) flower-shaped microarchitectures of NaY(WO4)2 were synthesized via a microwave-assisted hydrothermal process in the presence of trisodium citrate (Na3Cit) and a post-calcination process. The effects of reaction conditions on the morphology of precursor microstructures were studied. It was found that Na3Cit, as the chelating agent and shape modifier, plays a key role in the microstructure growth. A possible growth mechanism for the flower-shaped microarchitectures was proposed. The as-formed precursor can completely transform into NaY(WO4)2 with its original flower-shaped morphology via a heat treatment process. The concentration and temperature quenching behaviors of Eu3+ fluorescence in the flower-shaped NaY(WO4)2 were studied, and the optimal doping concentration was confirmed, meanwhile the activation energy was obtained. Judd-Ofelt parameters Ωλ (λ = 2, 4 and 6) of Eu3+ in the flower-shaped NaY(WO4)2 phosphor were obtained by using the emission spectrum of Eu3+, moreover the radiative transition properties were analyzed.

Excitation pathway and temperature dependent luminescence in color tunable Ba5Gd8Zn4O21:Eu3+ phosphors

A series of polycrystalline Ba5Gd8Zn4O21:Eu3+ phosphors were synthesized by a solid state reaction for the first time. The crystal structures were examined by means of X-ray diffraction. The luminescence spectra and decay curves were investigated as a function of Eu3+ concentration and temperature. It was found that the luminescent color of phosphor can be adjusted from white to red with the increase of Eu3+ concentration. Interestingly, emission spectra with different 5D0/5D1,2,3 ratios were observed when excited at 276 (corresponding to the O2− → Eu3+ charge transfer band) and 395 nm (f–f transition 7F0 → 5L6). The energy transfers between Eu3+ ions in Ba5Gd8Zn4O21 have been confirmed to be resonant type via exchange interaction for the 5D0 level and electric dipole–dipole interaction for 5DJ (J = 1–3) levels. Temperature dependent measurements revealed that the crossover process is the main mechanism for quenching luminescence of the 5D0 level of Eu3+ in the Ba5Gd8Zn4O21:Eu3+ phosphors. Finally, Judd–Ofelt parameters of Eu3+ in the Ba5Gd8Zn4O21 phosphors were calculated by a facile method in the framework of the J–O theory, in which the refractive index of Ba5Gd8Zn4O21 was deduced to be about 1.95.

Controllable synthesis and luminescent properties of three-dimensional nanostructured CaWO4:Tb3+ microspheres.

Three-dimensional (3D) nanostructured CaWO(4):Tb(3+)microspheres assembled by submicrospindles were synthesized via a mild sonochemical route from an aqueous solution of CaCl(2), TbCl(3) and Na(2)WO(4) with the aid of surfactant Polyglycol 600 (PEG-600). The crystal structure and morphology of the as-prepared products were characterized by using X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). Rietveld refinement was carried out on the XRD data. The results showed that the CaWO(4):Tb(3+)nanoparticles can be formed without ultrasonic irradiation or addition of PEG-600. With continuously increasing irradiation time the submicrospindles and microspheres could be self-assembled. The central diameter and length of the submicrospindles are around 190 and 500 nm, respectively. The 3D CaWO(4):Tb(3+)nanostructured microspheres with diameter of 2-4 μm were assembled by the submicrospindles. A possible formation mechanism for the 3D-structured CaWO(4):Tb(3+)microspheres was proposed. The Photoluminescent (PL) properties of Tb(3+) ions in the nanostructured CaWO(4) microspheres were studied. The energy transfer processes in CaWO(4):Tb(3+)microspheres were analyzed. The electric dipole-dipole energy transfers related to (5)D(3) level were studied by inspecting the fluorescence decay of (5)D(3) level. The energy transfer critical distance was estimated.

Microwave-assisted hydrothermal synthesis and temperature sensing application of Er3+/Yb3+ doped NaY(WO4)2 microstructures

Laurustinus shaped NaY(WO4)2 micro-particles assembled by nanosheets were synthesized via a microwave-assisted hydrothermal (MH) route. The growing mechanisms for the obtained resultants with various morphologies were proposed based on the observation of scanning electron microscopic (SEM) images. It was found that Na3Cit added into the reaction solution greatly influenced the formation and size dimension of the nano-sheets, furthermore determined assembling of the laurustinus shaped micro-particles. The temperature sensing performance of NaY(WO4)2:Er(3+)/Yb(3+) was evaluated. Thermal effect induced by the 980nm laser irradiation in laurustinus-shaped NaY(WO4)2:Er(3+)/Yb(3+) phosphor was studied. It was found that the green upconversion luminescence intensity increased in the first stage of laser irradiation, and then decreased after reaching a maximum. Based on the thermal sensing technology the laurustinus NaY(WO4)2:Er(3+)/Yb(3+) microparticles were used as thermal probe to discover thermal effect of upconversion luminescence in laurustinus NaY(WO4)2:Tm(3+)/Yb(3+) micro-particles.

Temperature sensing and optical heating in Er3+ single-doped and Er3+/Yb3+ codoped NaY(WO4)2 particles

Temperature sensing properties and laser induced thermal effects in rare earth doped materials could inspire some critical applications in accurate temperature detection and thermal therapy. In this paper, a microwave-assisted hydrothermal method was used to synthesize rare earth doped NaY(WO4)2 microstructures. Microstructured NaY(WO4)2 samples with various morphologies were derived by controlling the amount of trisodium citrate in reaction solution. Microscopic image and crystal structure of the obtained samples were characterized by XRD, SEM and HRTEM. It was found that all the received samples exhibited pure phase, and the Cit3−/Y3+ ratio considerably influenced the morphology but the rare earth concentration did not. The temperature sensing performance for the samples with various morphologies and different rare earth concentrations was evaluated. It was confirmed that both the morphology and doping concentration slightly affected the temperature property. Furthermore, based on the temperature sensing technique of Er3+ doped materials, the 980 nm laser irradiation induced thermal effect in NaY(WO4)2 microstructures was studied. It was also found that the sample temperature was very sensitive to the sample morphology and the doping concentration of Er3+ and Yb3+.

Hydrothermal synthesis and tunable luminescence of persimmon-like sodium lanthanum tungstate:Tb3+, Eu3+ hierarchical microarchitectures

Persimmon-like NaLa(WO(4))(2) microarchitectures were prepared via hydrothermal process with using trisodium citrate (Na(3)Cit) as chelated reagent and characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), photoluminescence (PL), and fluorescent dynamics. The influences of Na(3)Cit concentration, organic additivities, and reaction time on the morphologies of NaLa(WO(4))(2) phosphor were studied. The results revealed that Na(3)Cit species had double functions of strong ligand and structure-directing reagent that could efficiently control the formation of persimmon-like NaLa(WO(4))(2) microarchitectures. The possible mechanism for the growth of persimmon-like NaLa(WO(4))(2) microarchitectures was attributed to the Ostwald ripening mechanism. The energy transfer from Tb(3+) to Eu(3+) in the persimmon-like NaLa(WO(4))(2) phosphors was observed. The energy transfer efficiencies and emission colors can be tuned by changing the concentration of Eu(3+). Finally, it was deduced that the electric dipole-dipole interaction (D-D) is the main mechanism for energy transfer between Tb(3+) and Eu(3+) in the persimmon-like NaLa(WO(4))(2) phosphor.

Lanthanide dopant-induced phase transition and luminescent enhancement of EuF3 nanocrystals

A novel strategy is proposed to prepare hexagonal EuF3 nanocrystals by doping lanthanide ions (Ln3+) with large ionic radius (such as La3+, Ce3+, Pr3+, Nd3+ and Sm3+). Complete phase transition from orthorhombic to hexagonal phase can be achieved with the increase of ionic radius or doping concentration of Ln3+ ions. Meanwhile, the size and self-assembly degree of the product can be reduced dramatically. The possible growth and phase transformation mechanism of EuF3 nanocrystals was proposed. Finally, Eu3+ ion was used as the structural probe to investigate the effect of phase transition on the luminescence. It was found that the emissions of the 5D0 level of Eu3+ are greatly enhanced with the phase transition from orthorhombic to hexagonal phase. The luminescent enhancement is attributed to the larger radiative transition rate of the 5D0 level in the environment with lower symmetry, which can be confirmed by Judd–Ofelt (J–O) theory.

Supported black phosphorus nanosheets as hydrogen-evolving photocatalyst achieving 5.4% energy conversion efficiency at 353 K

Solar-driven water splitting using powdered catalysts is considered as the most economical means for hydrogen generation. However, four-electron-driven oxidation half-reaction showing slow kinetics, accompanying with insufficient light absorption and rapid carrier combination in photocatalysts leads to low solar-to-hydrogen energy conversion efficiency. Here, we report amorphous cobalt phosphide (Co-P)-supported black phosphorus nanosheets employed as photocatalysts can simultaneously address these issues. The nanosheets exhibit robust hydrogen evolution from pure water (pH = 6.8) without bias and hole scavengers, achieving an apparent quantum efficiency of 42.55% at 430 nm and energy conversion efficiency of over 5.4% at 353 K. This photocatalytic activity is attributed to extremely efficient utilization of solar energy (~75% of solar energy) by black phosphorus nanosheets and high-carrier separation efficiency by amorphous Co-P. The hybrid material design realizes efficient solar-to-chemical energy conversion in suspension, demonstrating the potential of black phosphorus-based materials as catalysts for solar hydrogen production.In order to displace fossil fuel technologies, it is crucial to develop efficient solar-to-fuel conversion materials using abundant, cheap elements. Here, the authors prepare few-layer black phosphorous with amorphous cobalt phosphide and produce hydrogen gas with light at high efficiencies.

Facile bottom-up synthesis of partially oxidized black phosphorus nanosheets as metal-free photocatalyst for hydrogen evolution

Significance Black phosphorus (BP) nanosheet is a “hot” class of 2D material having wide applications in optoelectronics, catalysis, biomedicine, etc. However, facile synthesis of BP nanosheets is not achieved by far. Currently, BP nanosheets are mainly prepared via solution-based exfoliation of bulk crystals, a process that is complicated, time-consuming, and costly. Moreover, the as-prepared BP nanosheets are not stable. Here, we developed a facile bottom-up protocol for preparing BP nanosheets in solution at low temperature. Our synthetic procedure is conceptually simple and can be performed in common chemical laboratories. The estimated synthesis cost is less than 1 US dollar per gram. Our work, therefore, offers the community an unlimited access to such 2D material. Few-layer black phosphorus (BP) nanosheets were first reported as a 2D material for the application of field-effect transistors in 2014 and have stimulated intense activity among physicists, chemists, and material and biomedical scientists, driving research into novel synthetic techniques to produce BP nanosheets. At present, exfoliation is the main route toward few-layer BP nanosheets via employing bulk BP as raw material. However, this is a complicated and time-consuming process, which is difficult for the large-scale synthesis of BP nanosheets. Moreover, BP degrades rapidly when exfoliated to nanoscale dimensions, resulting in the rapid loss of semiconducting properties. Here, we report the direct wet-chemical synthesis of few-layer BP nanosheets in gram-scale quantities in a bottom-up approach based on common laboratory reagents at low temperature, showing excellent stability due to partial oxidation of surface. Solvent and temperature are two critical factors, controlling not only the formation of BP nanosheets but also the thickness. The as-prepared BP nanosheets can extract hydrogen from pure water (pH = 6.8), exhibiting more than 24-fold higher activity than the well-known C3N4 nanosheets. Our results reporting the ability to prepare few-layer BP nanosheets with a facile, scalable, low-cost approach take us a step closer to real-world applications of phosphorene including next-generation metal-free photocatalysts for photosynthesis.