Doping-Enhanced Short-Range Order of Perovskite Nanocrystals for Near-Unity Violet Luminescence Quantum Yield.

All-inorganic perovskite nanocrystals (NCs) have emerged as a new generation of low-cost semiconducting luminescent system for optoelectronic applications. The room-temperature photoluminescence quantum yields (PLQYs) of these NCs in the green and red spectral range approach unity. However, their PLQYs in the violet are much lower, and an insightful understanding of such poor performance remains missing. We report a general strategy for the synthesis of all-inorganic violet-emitting perovskite NCs with near-unity PLQYs through engineering local order of the lattice by nickel ion doping. A broad range of experimental characterizations, including steady-state and time-resolved luminescence spectroscopy, X-ray absorption spectra, and magic angle spinning nuclear magnetic resonance spectra, reveal that the low PLQY in undoped NCs is associated with short-range disorder of the lattice induced by intrinsic defects such as halide vacancies and that Ni doping can substantially eliminate these defects and result in increased short-range order of the lattice. Density functional theory calculations reveal that Ni doping of perovskites causes an increase of defect formation energy and does not introduce deep trap states in the band gap, which is suggested to be the main reason for the improved local structural order and near-unity PLQY. Our ability to obtain violet-emitting perovskite NCs with near-perfect properties opens the door for a range of applications in violet-emitting perovskite-based devices such as light-emitting diodes, single-photon sources, lasers, and beyond.

Ion-Exchangeable Microporous Polyoxometalate Compounds with Off-Center Dopants Exhibiting Unconventional Luminescence.

The synthesis of luminescent polyoxometalates (POMs) typically relies on the assembly of POM ligands with rare earth or transition metals, placing significant constraints on the composition, structure, and hence the luminescence properties of the resultant systems. Herein, we show that the ion-exchange strategy can be used for the synthesis of novel POM-based luminescent materials. We demonstrate that introducing bismuth ions into an ion-exchangeable, microporous POM compound yields an unconventional system luminescing in the near-infrared region. Experimental characterization, coupled with quantum chemical calculations, confirms that bismuth ions site-specifically occupy an off-center site in the lattice, and have an asymmetric coordination geometry unattainable by other means, thus giving rise to peculiar emission. Our findings offer an effective strategy for the synthesis of POM-based luminescent materials, and the design concept may potentially be adapted to the creation of POM-based systems with other functionalities.

A sequential treatment of intermediate tropical landfill leachate using a sequencing batch reactor (SBR) and coagulation.

The increase in landfill leachate generation is due to the increase of municipal solid waste (MSW) as global development continues. Landfill leachate has constantly been the most challenging issue in MSW management as it contains high amount of organic and inorganic compounds that might cause pollution to water resources. Biologically treated landfill leachate often fails to fulfill the regulatory discharge standards. Thus, to prevent environmental pollution, many landfill leachate treatment plants involve multiple stages treatment process. The Papan Landfill in Perak, Malaysia currently has no proper leachate treatment system. In the current study, sequential treatment via sequencing batch reactor (SBR) followed by coagulation was used to treat chemical oxygen demand (COD), ammoniacal nitrogen (NH3-N), total suspended solids (TSS), and colour from raw landfill leachate. SBR optimum aeration rate, L/min, optimal pH and dosage (g/L) of Alum for coagulation as a post-treatment were determined. The two-step sequential treatment by SBR followed by coagulation (Alum) achieved a removal efficiency of 84.89%, 94.25%, 91.82% and 85.81% for COD, NH3-N, TSS and colour, respectively. Moreover, the two-stage treatment process achieved 95.0% 95.0%, 95.3%, 100.0%, 87.2%, 62.9%, 50.0%, 41.3%, 41.2, 34.8, and 22.9 removals of Cadmium, Lead, Copper, Selenium, Barium, Iron, Silver, Nickel, Zinc, Arsenic, and Manganese, respectively.

Biogas and biofertilizer production from organic fraction municipal solid waste for sustainable circular economy and environmental protection in Malaysia.

Waste management in Malaysia remains a persistent economic and environmental challenge. Up to date, more than 80% of Malaysian solid waste disposed at landfills and dumpsites. Therefore, Malaysia is facing an urgent need to move towards a sustainable solid waste management and thus resource recovery from organic solid waste. Hence, this study aims to investigate the feasibility of energy and bio fertilizer recovery from organic fraction municipal solid waste (OFMSW) via anaerobic digestion. The economic and environmental benefit analysis was investigated. Approximate and elementary analysis of OFMSW samples were carried out to estimate the potential production of biogas and bio fertilizer. It was found that organic waste contributes about 45% of the total MSW generated in Malaysia. Anaerobic digestion of 50% of organic waste is expected to produce 3941 MWh/day of electrical energy and 2500 t/day of bio fertilizer. In terms of environmental impacts, 2735 t/day of Carbon dioxide (CO2) emission, 1128 m2/day of landfilling area and 481 m3/day of leachate can be avoided. A net revenue of 3300 million RM (1 US Dollar ≈ 4.15 RM) can be generated by the sales of electricity via Feed-in-Tariff (FiT), sales of biofertilizer to local agricultural industries and inclusive of the saving generated from the reduction of OFMSW landfilling operations and leachate treatment at landfills. Economic development can go hand-in-hand with environmental sound practices in the field of waste management.

Cs4PbBr6/CsPbBr3 Perovskite Composites with Near-Unity Luminescence Quantum Yield: Large-Scale Synthesis, Luminescence and Formation Mechanism, and White Light-Emitting Diode Application.

All-inorganic perovskites have emerged as a new class of phosphor materials owing to their outstanding optical properties. Zero-dimensional inorganic perovskites, in particular the Cs4PbBr6-related systems, are inspiring intensive research owing to the high photoluminescence quantum yield (PLQY) and good stability. However, synthesizing such perovskites with high PLQYs through an environment-friendly, cost-effective, scalable, and high-yield approach remains challenging, and their luminescence mechanisms has been elusive. Here, we report a simple, scalable, room-temperature self-assembly strategy for the synthesis of Cs4PbBr6/CsPbBr3 perovskite composites with near-unity PLQY (95%), high product yield (71%), and good stability using low-cost, low-toxicity chemicals as precursors. A broad range of experimental and theoretical characterizations suggest that the high-efficiency PL originates from CsPbBr3 nanocrystals well passivated by the zero-dimensional Cs4PbBr6 matrix that forms based on a dissolution-crystallization process. These findings underscore the importance in accurately identifying the phase purity of zero-dimensional perovskites by synchrotron X-ray technique to gain deep insights into the structure-property relationship. Additionally, we demonstrate that green-emitting Cs4PbBr6/CsPbBr3, combined with red-emitting K2SiF6:Mn4+, can be used for the construction of WLEDs. Our work may pave the way for the use of such composite perovskites as highly luminescent emitters in various applications such as lighting, displays, and other optoelectronic and photonic devices.

X-ray-activated long persistent phosphors featuring strong UVC afterglow emissions.

Phosphors emitting visible and near-infrared persistent luminescence have been explored extensively owing to their unusual properties and commercial interest in their applications such as glow-in-the-dark paints, optical information storage, and in vivo bioimaging. However, no persistent phosphor that features emissions in the ultraviolet C range (200-280 nm) has been known to exist so far. Here, we demonstrate a strategy for creating a new generation of persistent phosphor that exhibits strong ultraviolet C emission with an initial power density over 10 milliwatts per square meter and an afterglow of more than 2 h. Experimental characterizations coupled with first-principles calculations have revealed that structural defects associated with oxygen introduction-induced anion vacancies in fluoride elpasolite can function as electron traps, which capture and store a large number of electrons triggered by X-ray irradiation. Notably, we show that the ultraviolet C afterglow intensity of the yielded phosphor is sufficiently strong for sterilization. Our discovery of this ultraviolet C afterglow opens up new avenues for research on persistent phosphors, and it offers new perspectives on their applications in terms of sterilization, disinfection, drug release, cancer treatment, anti-counterfeiting, and beyond.

Controlling Crystallization of All-Inorganic Perovskite Films for Ultralow-Threshold Amplification Spontaneous Emission.

All-inorganic lead halide perovskites have gained considerable interest owing to their potential applications in an array of high-performance optoelectronic devices. However, producing highly luminescent, nearly pinhole-free, all-inorganic perovskite films through a simple solution process remains challenging. Here, we provide a detailed investigation of the crystallization control of inorganic perovskite films fabricated by a one-step spin-coating process. Our results reveal that the coating temperature in the fabrication process is of paramount importance in influencing perovskite crystallization and that lowering the coating temperature and fine stoichiometry modification of the precursors favor the suppression of trap states in CsPbBr3 perovskite films. A broad range of experimental characterizations help us identify that nonsynergistic assembly of solutes, resulting from poor diffusion capability of inorganic salts, is the dominant cause for the inhomogeneous element distribution, low luminescence yield, and poor surface coverage of the resulting films. Importantly, we find that polyethylene glycol can also be used for tailoring the crystallization process, which enables the attainment of high-quality CsPbBr3 films with a maximum luminescence yield of ∼30%. Finally, we demonstrate that amplification spontaneous emission with an ultralow threshold can be readily accomplished by using the developed film as an emissive component. Our findings provide deep insights into the crystallization control of CsPbBr3 perovskite films and establish a systematic route to high-quality all-inorganic perovskite films, paving the way for widespread optoelectronic applications.

Ultrabroad Photoluminescence and Electroluminescence at New Wavelengths from Doped Organometal Halide Perovskites.

Doping of semiconductors by introducing foreign atoms enables their widespread applications in microelectronics and optoelectronics. We show that this strategy can be applied to direct bandgap lead-halide perovskites, leading to the realization of ultrawide photoluminescence (PL) at new wavelengths enabled by doping bismuth (Bi) into lead-halide perovskites. Structural and photophysical characterization reveals that the PL stems from one class of Bi doping-induced optically active center, which is attributed to distorted [PbI6] units coupled with spatially localized bipolarons. Additionally, we find that compositional engineering of these semiconductors can be employed as an additional way to rationally tune the PL properties of doped perovskites. Finally, we accomplished the electroluminescence at cryogenic temperatures by using this system as an emissive layer, marking the first electrically driven devices using Bi-doped photonic materials. Our results suggest that low-cost, earth-abundant, solution-processable Bi-doped perovskite semiconductors could be promising candidate materials for developing optical sources operating at new wavelengths.