Perovskite Nanocrystals In Situ Encapsulated in TiO2 Microspheres for Stable CO2 Photoreduction in Water.

Photoreduction of carbon dioxide (CO2) into fuels presents a promising approach to mitigate global warming and energy crises. Halide perovskite nanocrystals (NCs) with prominent optoelectronic properties have triggered substantial attention as photocatalysts but are limited by the charge recombination and instability. Here, we develop stable CsPbBr3/titania microspheres (TMs) by in situ growth of CsPbBr3 NCs inside mesoporous TMs through solid-state sintering, which significantly improves the stability of perovskite NCs, making them applicable in water with efficient CO2 photoreduction performance. Notably, the CsPbBr3/TMs demonstrates a 6.73- and 9.23-fold increase in the rate of CH4 production compared to TMs and CsPbBr3, respectively. The internal electric field facilitates S-scheme charge transfer, enhancing the separation of electron-hole pairs, as evidenced by X-ray photoelectron spectroscopy and electron paramagnetic resonance analysis, which is pivotal for the selective photoreduction of CO2. These insights pave the way for the design of CsPbBr3-based photocatalysts with superior efficiency and stability.

Damage-Free Silica Coating for Colloidal Nanocrystals Through a Proactively Water-Generating Amidation Reaction at High Temperature.

Silica is a promising shell coating material for colloidal nanoparticles due to its excellent chemical inertness and optical transparency. To encapsulate high-quality colloidal nanocrystals with silica shells, the silane coupling hydrolysis is currently the most effective approach. However, this reaction requires water, which often adversely affects the intrinsic physicochemical properties of nanocrystals. Achieving a damage-free silica encapsulation process to nanocrystals by hydrolysis is a huge challenge. Here, a novel strategy is developed to coat colloidal nanocrystals with a denser silica shell via a proactively water-generating reaction at high temperature. In this work, water molecules are continuously and proactively released into the reaction system through the amidation reaction, followed by in situ hydrolysis of silane, completely avoiding the impacts of water on nanocrystals during the silica coating process. In this work, water sensitive perovskite nanocrystals (CsPbBr3 ) are selected as the typical colloidal nanocrystals for silica coating. Notably, this high-temperature in situ encapsulation technology greatly improves the optical properties of nanocrystals, and the silica shells exhibit a denser structure, providing nanocrystals with better protection. This method overcomes the challenge of the influence of water on nanocrystals during the hydrolysis process, and provides an important reference for the non-destructive encapsulation of colloidal nanocrystals.

Interface defects repair of core/shell quantum dots through halide ion penetration.

The interface defects of core-shell colloidal quantum dots (QDs) affect their optoelectronic properties and charge transport characteristics. However, the limited available strategies pose challenges in the comprehensive control of these interface defects. Herein, we introduce a versatile strategy that effectively addresses both surface and interface defects in QDs through simple post-synthesis treatment. Through the combination of fine chemical etching methods and spectroscopic analysis, we have revealed that halogens can diffuse within the crystal structure at elevated temperatures, acting as "repairmen" to rectify oxidation and significantly reducing interface defects within the QDs. Under the guidance of this protocol, InP core/shell QDs were synthesized by a hydrofluoric acid-free method with a full width at half-maximum of 37.0 nm and an absolute quantum yield of 86%. To further underscore the generality of this strategy, we successfully applied it to CdSe core/shell QDs as well. These findings provide fundamental insights into interface defect engineering and contribute to the advancement of innovative solutions for semiconductor nanomaterials.

Fluorine Passivation Inhibits "Particle Talking" Behaviors under Thermal and Electrical Conditions of Pure Blue Mixed Halide Perovskite Nanocrystals.

Owing to outstanding optoelectronic properties, lead halide perovskite nanocrystals (PNCs) are considered promising emitters for next-generation displays. However, the development of pure blue (460-470 nm) perovskite nanocrystal light-emitting diodes (PNC-LEDs), which correspond to the requirements of Rec. 2020 standard, lag far behind that of their green and red counterparts. Here, pure blue CsPb(Br/Cl)3 nanocrystals with remarkable optical performance are demonstrated by a facile fluorine passivation strategy. Prominently, the fluorine passivation on halide vacancies and strong bonding of Pb-F intensely enhance crystal structure stability and inhibit "particle talking" behaviors under both thermal and electrical conditions. Fluorine-based PNCs with high resistance of luminescence thermal quenching retain 70% of photoluminescent intensity when heated to 343 K, which can be attributed to the elevated activation energy for carrier trapping and unchanged grain size. Fluorine-based PNC-LEDs also exhibit stable pure blue electroluminescence (EL) emission with sevenfold promoted luminance and external quantum efficiencies (EQEs), where the suppression of ion migration is further evidenced by a lateral structure device with applied polarizing potential.

Inverted semitransparent perovskite nanocrystal light-emitting diodes with a conjugated polymer as an electron transport layer.

Perovskite nanocrystals have attracted much attention due to their unique optical and electronic properties. Much progress has also been made in the development of light-emitting diodes based on perovskite nanocrystals in the past years. However, compared with the widely reported opaque perovskite nanocrystal light-emitting diodes, semitransparent perovskite nanocrystal light-emitting diodes are rarely studied, which affects the potential application of perovskite nanocrystals in the translucent display field in the future. Here, poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN), a conjugated polymer, was used as an electron transport layer to fabricate the inverted opaque and semitransparent perovskite light-emitting diodes. The maximum external quantum efficiency and luminance were improved from 0.13% and 1041 cd m-2 to 2.07% and 12 540 cd m-2, respectively, through device optimization in opaque light-emitting diodes. The corresponding semitransparent device also demonstrated high transmittance (average 61% from 380 to 780 nm) and high brightness of 1619 and 1643 cd m-2 for the bottom and top sides, respectively.

A Novel Strategy to Enhance the Photostability of InP/ZnSe/ZnS Quantum Dots with Zr Doping.

Plentiful research of InP semiconductor quantum dots (QDs) has been launched over the past few decades for their excellent photoluminescence properties and environmentally friendly characteristics in various applications. However, InP QDs show inferior photostability because they are extremely sensitive to the ambient environment. In this study, we propose a novel method to enhance the photostability of InP/ZnSe/ZnS QDs by doping zirconium into the ZnS layer. We certify that Zr can be oxidized to Zr oxides, which can prevent the QDs from suffering oxidation during light irradiation. The InP/ZnSe/ZnS:Zr QDs maintained 78% of the original photoluminescence quantum yields without significant photodegradation under the irradiation of LED light (450 nm, 3.0 W power intensity) for 14 h, while conventional InP/ZnSe/ZnS QDs dramatically decreased to 29%.

Stable Lead-Free Tin Halide Perovskite with Operational Stability >1200 h by Suppressing Tin(II) Oxidation.

Sn-based perovskites are the most promising alternative materials for Pb-based perovskites to address the toxicity problem of lead. However, the development of SnII -based perovskites has been hindered by their extreme instability. Here, we synthesized efficient and stable lead-free Cs4 SnBr6 perovskite by using SnF2 as tin source instead of easily oxidized SnBr2 . The SnF2 configures a fluorine-rich environment, which can not only suppress the oxidation of Sn2+ in the synthesis, but also construct chemically stable Sn-F coordination to hinder the electron transfer from Sn2+ to oxygen within the long-term operation process. The SnF2 -derived Cs4 SnBr6 perovskite shows a high photoluminescence quantum yield of 62.8 %, and excellent stability against oxygen, moisture, and light radiation for 1200 h, representing one of the most stable lead-free perovskites. The results pave a new pathway to enhance the optical properties and stability of lead-free perovskite for high-performance light emitters.

Suppressing thermal quenching of lead halide perovskite nanocrystals by constructing a wide-bandgap surface layer for achieving thermally stable white light-emitting diodes.

Lead halide perovskite nanocrystals as promising ultrapure emitters are outstanding candidates for next-generation light-emitting diodes (LEDs) and display applications, but the thermal quenching behavior of light emission has severely hampered their real-world applications. Here, we report an anion passivation strategy to suppress the emission thermal quenching behavior of CsPbBr3 perovskite nanocrystals. By treating with specific anions (such as SO4 2-, OH-, and F- ions), the corresponding wide-bandgap passivation layers, PbSO4, Pb(OH)2, and PbF2, were obtained. They not only repair the surface defects of CsPbBr3 nanocrystals but also stabilize the phase structure of the inner CsPbBr3 core by constructing a core-shell like structure. The photoluminescence thermal resistance experiments show that the treated sample could preserve 79% of its original emission intensity up to 373 K, far superior to that (17%) of pristine CsPbBr3. Based on the thermally stable CsPbBr3 nanocrystals, we achieved temperature-stable white LED devices with a stable electroluminescence spectrum, color gamut and color coordinates in thermal stress tests (up to 373 K).

High-Efficiency Semitransparent Light-Emitting Diodes with Perovskite Nanocrystals.

Artificial intelligence offers new opportunities for translucent displays. However, achieving translucent light-emitting diodes (LEDs) with high efficiency and high color purity remains a challenge. Here, we propose a strategy of using an alkali metal/inert metal (calcium/silver) bilayer metal electrode as a top electrode and perovskite nanocrystals as an emitter layer in the device structure, which allows us to not only fabricate excellent opaque LEDs but also manufacture highly efficient semitransparent LEDs with high color purity, total brightness (over 7000 cd m-2), total external quantum efficiency (over 12%), and 56% transmittance around 520 nm. This is the highest external quantum efficiency report about semitransparent LED based on perovskite materials or inorganic quantum dots so far, which presents great application potential in the field of translucent display with high color purity and wide color gamut.

Thiol/methylthio-functionalized porous aromatic frameworks for simultaneous capture of aromatic pollutants and Hg(II) from water.

Simultaneously capturing organic pollutants and heavy metal can greatly reduce the water remediation time and cost, however it is still a great challenge presently. Herein, two novel thiol/methylthio-functionalized porous aromatic frameworks were synthesized as sorbents via the Sonogashira-Hagihara reaction of 1,3,5-triethynylbenzene and 1,3,5-tris(4-bromophenyl) benzene, the subsequent chloromethylation of the phenyl rings, and the final nucleophile substitution of -Cl groups by NaSH/NaSMe. These two sorbents were characterized by FT-IR spectra, energy dispersive X-ray spectra, scanning electron microscope, nitrogen adsorption analysis, thermo-gravimetric analysis, and elemental analyses. Adsorption experiments displayed that new sorbents had high uptake abilities and fast adsorption kinetics for aromatic pollutants and mercury (II) (Hg(II)). The maximum adsorption capacity (Qmax) of toluene and m-xylene on both new sorbents were 531.9-571.4 mg/g with the kinetic binding rate constants (kobs) of 0.00276-0.02422 g/mg/min, and the Qmax values of Hg(II) were 148.1-180.3 mg/g with kobs of 0.00592-0.01573 g/mg/min. Moreover, new sorbents indicated high simultaneous uptake abilities for these pollutants with good reusability, and finally they were successfully applied to the simultaneous remediation of these pollutants in two simulated sewages with high and low concentration, indicating their great practical application potential in wastewater remediation.

Quick start-up and performance of microbial fuel cell enhanced with a polydiallyldimethylammonium chloride modified carbon felt anode.

It is of significant importance to simultaneously shorten the start-up time and enhance the electricity generation performance for practical application of microbial fuel cell (MFC). In this paper, the polydiallyldimethylammonium chloride (PDDA) modified carbon felt (PDDA-CF) electrode was prepared and used as the anode of PDDA-MFC. The anode significantly enhanced the start-up speed and electricity generation and dye wastewater degradation performances of the PDDA-MFC. The start-up time of PDDA-MFC is only 9 h, which is only 7.5% that of the unmodified carbon felt anode MFC (CF-MFC). The charge transfer resistance, the maximum output voltage and the maximum output power density of PDDA-MFC were 9.7 Ω, 741 mV and 537.8 mW m-2 respectively, which were 70.3% lower than, 1.7 times and 3.3 times greater than those of CF-MFC respectively. In addition, the color and chemical oxygen demand (COD) removal rates of Reactive Brilliant Red X-3B for PDDA-MFC reached 95.94% and 64.24% at 24 h respectively, which were 41.5% and 51.2% higher than those of CF-MFC respectively. Due to the electrostatic attraction of PDDA, the adhesion and metabolic mass transfer rate of exoelectrogens are accelerated, thus the PDDA-CF electrode has excellent electrochemical properties and bio-affinity. This paper provides a new idea to enhance the start-up speed and performance of MFC simultaneously.

Enhanced electricity generation performance and dye wastewater degradation of microbial fuel cell by using a petaline NiO@ polyaniline-carbon felt anode.

A new electrode which embedded polyaniline (PANI) in petaline NiO (NiO@PANI-CF) was prepared through in-situ growth and in-situ polymerization. The NiO@PANI-CF integrated the high capacitive character of NiO and the high conductivity of PANI, which effectively increased electricity generation capacity of NiO@PANI-MFC. The maximum output power density and the charge transfer resistance of NiO@PANI-MFC were 1078.8 mW·m-2 and 10.4â€¯Ω respectively, which were 6.6 times and 68% lower than that of CF-MFC respectively. Moreover, NiO@PANI-MFC could effectively biodegrade dye wastewater due to high biocompatibility of NiO@PANI-CF. The color and COD removal efficiencies of Reactive Brilliant Red X-3B reached 95.94% and 64.24% at 48 h respectively. The results demonstrate that the NiO@PANI-CF has the advantage of high conductivity, high capacitance, high specific surface area, super hydrophilicity, low polarization performance, low charge transfer resistance, high biocompatibility and high stablity.

Heavy metal accumulation in balsam pear and cowpea related to the geochemical factors of variable-charge soils in the Pearl River Delta, South China.

Variable-charge (v-c) soils in subtropical areas contain considerable amounts of iron/aluminum (Fe/Al) oxides that can strongly influence the fate of heavy metals in agricultural ecosystems. However, the relationship between heavy metal accumulation in vegetables and the geochemical factors associated with v-c soils in subtropical regions remains unknown. The present study investigated heavy metal accumulation under field conditions in the Pearl River Delta (PRD) by measuring the content of 8 heavy metals (zinc (Zn), arsenic (As), copper (Cu), mercury (Hg), lead (Pb), chromium (Cr), nickel (Ni) and cadmium (Cd)) in 43 pairs of v-c soil and vegetable (balsam pear and cowpea) samples. Soil physicochemical properties including pH, texture, organic matter and oxide minerals (Fe2O3, SiO2, Al2O3, CaO, MgO, K2O and Na2O) were also analyzed. Heavy metal accumulation from soil to vegetables was assessed based on bioconcentration factors (BCFs). The results showed that soil extractable Fe, oxide minerals and chemical weathering indices of v-c soils strongly affected heavy metal accumulation, whereas the content of Zn, Cu, Cr and Ni in vegetables was strongly affected by the soil clay content. Significant correlations were found between the BCFs of heavy metals and oxide minerals. However, no significant relationship was found between pH and heavy metal accumulation (except for Cu) in balsam pear and cowpea. Correlation analyses showed that a lower oxalate/DCB- extractable Fe content might indicate greater heavy metal (Zn, Cu, Hg, Cr and Ni) accumulation in vegetables. Therefore, it can be deduced that oxalate/DCB- extractable Fe content is a critical geochemical factor that determines the bioavailability of heavy metals and that iron biogeochemical cycles play vital roles in the fate of heavy metals in vegetable fields in this area. These findings provide new insights into the behaviors and fate of heavy metals in subtropical v-c soils and can be used to develop possible guidelines for vegetable safety management.

Phosphorus leaching risk assessment with manure fertilizer application in south China.

To investigate the phosphorus (P) leaching risk caused by applying manure fertilizer, six different manure fertilizers, namely, 0 (CK), 3,000 (F200), 4,500 (F300), 7,500 (F500), 10,500 (F700), and 15,000 kg ha(-2) (F1000), were applied to the surface soil (0-20 cm) prior to vegetable planting. The maximum Olsen P decreased with increasing amounts of the manure fertilizer. Total P did not change with treatments below 7,500, but decreased in the higher manure treatments. Water dissolved P (WDP) was highest in the upper (0-20 cm soil) layer, intermediate in the middle (20-40 cm soil) layer, and lowest in the lower (40-60 cm soil) layer. The 7,500, 10,500, and 15,000 treatments increased the WDPs in both the middle and lower soil layers and enhanced the degree of P saturation in the lower layer. This indicates that vertical leachate movement of P accumulation in the middle soil layer may be underestimated and the P leaching risk is enhanced using manure fertilizer levels >7,500 kg ha(-2).

Compounds with DNA cleaving activity from Kadsura ananosma.

Two DNA cleavage agents, meso-dihydroguaiaretic acid (1) and isobavachalcone (2) together with the known alpha-ylangene, beta-sitosterol, daucosterol, pentacosane, hexacosanic acid and cerotic acid 1-monoglyceride were isolated from the stem barks of Kadsura ananosma Kerr for the first time. Compounds 1 and 2 showed relaxation of supercoiled DNA to nicked DNA. 1 represented a new structural type of DNA cleavage agent, while 2 was reported to show DNA strand-scission activity for the first time. 1 also showed significant cytotoxic effect on Hela and Leukemia cells in vitro.

Lignans from Schisandra hernyi with DNA cleaving activity and cytotoxic effect on leukemia and Hela cells in vitro.

The lignans, gomisin G (1), schisantherin A (2), benzoylgomisin Q (3) and isoanwulignan (4) were isolated from the stems of Schisandra henryi. Compound 1 showed moderate DNA strand scission activity and significant cytotoxic effect on leukemia and Hela cells in vitro. Compound 1 represents a new type of DNA strand scission agent.

Ananosic acids B and C, two new 18(13-->12)-abeo-lanostane triterpenoids from Kadsura ananosma.

Two new 18(13-->12)-abeo-lanostane triterpenoid acids, ananosic acids B (1) and C (2), were isolated from the stems of Kadsura anaosma. Their structures were elucidated by spectral studies and chemical transformation. Compounds 1 and 2 were evaluated for cytotoxicity using CCRF-CEM leukemia cells and HeLa cells.

Triterpenoids from Schisandra henryi with cytotoxic effect on leukemia and Hela cells in vitro.

Four known lanostane triterpenoids, schiprolactone A (1), schisanlactone B (2), nigranoic acid (3) and schisandronic acid (4) were isolated from the stems of Schisandra henryi for the first time. Their structures were characterized by IR, MS and NMR techniques. Compounds 1, 2 and 4 showed moderate cytotoxic activity against Leukemia cells in vitro. Cytotoxic activity of compounds 1-4 showed IC50 of 0.0097, 0.01, 0.097 and 0.0099 micromol/mL respectively toward Leukemia cells and IC50 of 0.097, 0.1, 0.097 and 0.099 micromol/mL toward Hela cells respectively. It is the first report that these compounds possess cytotoxic activity on Leukemia and Hela cells.