Fast Room-Temperature Cation Exchange Synthesis of Mn-Doped CsPbCl3 Nanocrystals Driven by Dynamic Halogen Exchange.

Currently, it is of great challenge to achieve cation exchange in CsPbX3 (X = Cl, Br, I) perovskite nanocrystals (NCs) on account of rigid Pb2+ octahedral coordination protected by six halogen anions (PbX64-). Herein, we demonstrate that dynamic halogen exchange can effectively open up PbX64- octahedrons and enable fast Mn-to-Pb cation exchange at room temperature in a few seconds. Importantly, Cl concentration rather than Mn one is demonstrated to be a dominant factor for cation exchange, where different Mn2+/Cl- salts can be adopted as Mn/Cl sources and Cl-to-Cl or Cl-to-Br anion exchange is the necessary prerequisite. Such a facile synthesizing method can lead to the feasibility of tuning emissive colors for the Mn-doped CsPb(Cl/Br)3 NCs by controlling both cation and anion exchanges and open a new way to replace Pb2+ in CsPbX3 NCs by other nontoxic metal elements.

Tunable CsPbBr3/Cs4PbBr6 phase transformation and their optical spectroscopic properties.

As a novel type of promising materials, metal halide perovskites are a rising star in the field of optoelectronics. On this basis, a new frontier of zero-dimensional perovskite-related Cs4PbBr6 with bright green emission and high stability has attracted an enormous amount of attention, even though its photoluminescence still requires to clarification. Herein, the controllable phase transformation between three-dimensional CsPbBr3 and zero-dimensional Cs4PbBr6 is easily achieved in a facile ligand-assisted supersaturated recrystallization synthesis procedure via tuning the amount of surfactants, and their unique optical properties are investigated and compared in detail. Both Cs4PbBr6 and CsPbBr3 produce remarkably intense green luminescence with quantum yields up to 45% and 80%, respectively; however, significantly different emitting behaviors are observed. The fluorescence lifetime of Cs4PbBr6 is much longer than that of CsPbBr3, and photo-blinking is easily detected in the Cs4PbBr6 product, proving that the zero-dimensional Cs4PbBr6 is indeed a highly luminescent perovskite-related material. Additionally, for the first time, tunable emissions over the visible-light spectral region are demonstrated to be achievable via halogen composition modulations in the Cs4PbX6 (X = Cl, Br, I) samples. Our study brings a simple method for the phase control of CsPbBr3/Cs4PbBr6 and demonstrates the intrinsic luminescence nature of the zero-dimensional perovskite-related Cs4PbX6 products.

High light harvesting efficiency CuInS2 quantum dots/TiO2/MoS2 photocatalysts for enhanced visible light photocatalytic H2 production.

Expanding the photoresponse range of TiO2-based photocatalysts is of great interest for photocatalytic H2 production. Herein, noble-metal-free CuInS2 quantum dots were employed as a novel inorganic dye to expand the visible light absorption of TiO2/MoS2 for solar H2 generation. The as-prepared CuInS2/TiO2/MoS2 photocatalysts exhibit broad absorption from the ultraviolet to near-infrared region. Under visible light irradiation (λ > 420 nm), the CuInS2/TiO2/MoS2 photocatalyst with 0.6 mmol g-1 CuInS2 and 0.5 wt% MoS2 showed the highest H2 evolution rate with a value of 1034 µmol h-1 g-1. Moreover, a considerable H2 evolution rate of 141 µmol h-1 g-1 was obtained under the irradiation of the optimized CuInS2/TiO2/MoS2 photocatalyst with >500 nm light. The reaction mechanism of the CuInS2/TiO2/MoS2 photocatalyst for photocatalytic H2 evolution was investigated in detail by photoluminescence decay study, and the results showed that the photoexcited electrons of CuInS2 can be transferred efficiently through TiO2 to MoS2 and then react with the absorbed protons to generate H2. The reported sensitization strategy tremendously improves the visible light absorption capacity and the photocatalytic performance of TiO2-based photocatalysts.

Silica-Coated Mn-Doped CsPb(Cl/Br)3 Inorganic Perovskite Quantum Dots: Exciton-to-Mn Energy Transfer and Blue-Excitable Solid-State Lighting.

Tunability of emitting colors of perovskite quantum dots (PQDs) was generally realized via composition/size modulation. Due to their bandgap absorption and ionic crystal features, the mixing of multiple PQDs inevitably suffers from reabsorption and anion-exchange effects. Herein, we address these issues with high-content Mn2+-doped CsPbCl3 PQDs that can yield blue-excitable orange Mn2+ emission benefited from exciton-to-Mn energy transfer and Cl-to-Br anion exchange. Silica-coating was applied to improve air stability of PQDs, suppress the loss of Mn2+, and avoid anion-exchange between different PQDs. As a direct benefit of intense multicolor emissions from Mn2+-doped PQD@SiO2 solid phosphors, a prototype white light-emitting diode with excellent optical performance and superior light stability was constructed using green CsPbBr3@SiO2 and orange Mn: CsPb(Cl/Br)3@SiO2 composites as color converters, verifying their potential applications in the field of optoelectronics.

Full-Spectral Fine-Tuning Visible Emissions from Cation Hybrid Cs1-mFAmPbX3 (X = Cl, Br, and I, 0 ≤ m ≤ 1) Quantum Dots.

Full-color visible emissions are particularly crucial for applications in displays and lightings. In this work, we developed a facile room-temperature ligand-assisted supersaturated recrystallization synthesis of monodisperse, cubic structure Cs1-mFAmPbX3 (X = Cl, Br, and I or their mixtures Cl/Br and Br/I, 0 ≤ m ≤ 1) hybrid perovskite quantum dots (QDs). Impressively, cation substitution of Cs+ by FA+ was beneficial in finely tuning the band gap and in exciton recombination kinetics, improving the structural stability, and raising the absolute quantum yields up to 85%. With further assistance of anion replacement, full-spectral visible emissions in the wavelength range of 450-750 nm; narrow full width at half-maxima, and a wide color gamut, encompassing 130% of National Television System Committee television color standard, were achieved. Finally, Cs1-mFAmPbX3-polymer films retaining multicolor luminescence are prepared and a prototype white light-emitting diode device was constructed using green Cs0.1FA0.9PbBr3 and red Cs0.1FA0.9Br1.5I1.5 QDs as color converters, certainly suggesting their potential applications in the optoelectronics field.

Noble-metal-free MoS2 nanosheet modified-InVO4 heterostructures for enhanced visible-light-driven photocatalytic H2 production.

Noble-metal-free, visible-light-responsive and "green" MoS2 nanosheet modified-InVO4 heterostructures were synthesized as efficient photocatalysts for photocatalytic H2 production. The positive effect of intimate nanojunctions formed between MoS2 and InVO4 resulted in the excellent activity of MoS2/InVO4 which is even higher than that of Pt-loaded InVO4.