Light-Mediated Multilevel Flexible High-Efficiency Perovskite Resistive Switching Memory Based on Mn:CsPbCl3 Nanocrystals.

Herein, the electrical characteristics, photoelectric properties, resistive switching (RS) mechanism, and flexible storage application of Ag/PMMA&Mn:CsPbCl3/ITO (PMMA = poly(methyl methacrylate)) devices are studied by using the photoelectric material Mn:CsPbCl3 nanocrystals (NCs) embedded in PMMA as the RS layer. The devices exhibit bipolar RS behavior with low operating voltage, excellent cycling endurance (>1000 times), long retention time (≥104 s), high ON/OFF ratio (≈104), and good environmental stability. The flexible memory devices have demonstrated reliable mechanical stability of consecutive 1000 bending cycles. In addition, multilevel data storage is realized by introducing the UV light, and the adjustive resistive switching characteristics is achieved through photoelectric synergistic work. The resistive switching mechanism under the excitation of light has been studied comprehensively. This work may pave a new way for developing the next generation of high-density data storage and photoelectric memristor.

Unveiling Sb3+ Doping and Tricolor Luminescence from Intrinsic Self-Trapped Excitons in Cs2ZnCl4 Crystals.

Zero-dimensional (0D) lead-free halide perovskites have lately received significant interest owing to their captivating broadband emissions. An in-depth understanding of the luminescence mechanism of self-trapped excitons (STEs) and realization of effective regulation of luminescence properties have become a major challenge in the research of lead-free metal halides. Herein, we have synthesized the Cs2ZnCl4 and Sb3+-doped Cs2ZnCl4 crystals and conducted a comprehensive investigation into their distinct electronic structures and optical characteristics. The findings from both experimental and theoretical investigations indicate that the tricolor luminescence in Cs2ZnCl4 and blue emission in Sb3+-doped Cs2ZnCl4 stem from intrinsic STEs, and the near-infrared emission originates from extrinsic STEs associated with the Sb3+ ion in Sb3+-doped Cs2ZnCl4. Sb3+ doping increases the quantum yield of Cs2ZnCl4 to a large extent. In addition, intersystem crossing, exciton self-trapping, and lattice relaxation are the main reasons for the large Stokes shift. The present study is expected to provide a novel perspective for researchers in comprehending the luminescent mechanism of STEs and advancing the utilization of 0D lead-free metal halides in optoelectronic applications.

Copper Modulated Lead-Free Cs4 MnSb2 Cl12 Double Perovskite Microcrystals for Photocatalytic Reduction of CO2.

In order to deal with the global energy crisis and environmental problems, reducing carbon dioxide through artificial photosynthesis has become a hot topic. Lead halide perovskite is attracted people's attention because of its excellent photoelectric properties, but the toxicity and long-term instability prompt people to search for new photocatalysts. Herein, a series of <111> inorganic double perovskites Cs4 Mn1-x Cux Sb2 Cl12 microcrystals (x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5) are synthesized and characterized. Among them, Cs4 Mn0.7 Cu0.3 Sb2 Cl12 microcrystals have the best photocatalytic performance, and the yields of CO and CH4 are 503.86 and 68.35 µmol g-1 , respectively, after 3 h irradiation, which are the highest among pure phase perovskites reported so far. In addition, in situ Fourier transform infrared (FT-IR) spectroscopy and electron spin resonance (ESR) spectroscopy are used to explore the mechanism of the photocatalytic reaction. The results highlight the potential of this class of materials for photocatalytic reduction reactions.

In situ and General Multidentate Ligand Passivation Achieves Efficient and Ultra-Stable CsPbX3 Perovskite Quantum Dots for White Light-Emitting Diodes.

Inorganic CsPbX3 perovskite quantum dots (PeQDs) show great potential in white light-emitting diodes (WLEDs) due to excellent optoelectronic properties, but their practical application is hampered by low photoluminescence quantum yield (PLQY) and especially poor stability. Herein,  we developed an in-situ and general multidentate ligand passivation strategy that allows for CsPbX3 PeQDs not only near-unit PLQY, but significantly improved stability against storage, heat, and polar solvent. The enhanced optical property arises from high effectiveness of the multidentate ligand, diethylenetriaminepentaacetic acid (DTPA) with five carboxyl groups, in passivating uncoordinated Pb2+ defects and suppressing nonradiative recombination. First-principles calculations reveal that the excellent stability is attributed to tridentate binding mode of DTPA that remarkably boosts the adsorption capacity to PeQD core. Finally, combining the green and red PeQDs with blue chip,  we demonstrated highly luminous WLEDs with distinctly enhanced operation stability, a wide color gamut of 121.3% of national television system committee, standard white light of (0.33,0.33) in CIE 1931, and tunable color temperatures from warm to cold white light readily by emitters' ratio. This study provides an operando yet general approach to achieve efficient and stable PeQDs for WLEDs and accelerates their progress to commercialization.

Tellurium-Doped 0D Organic-Inorganic Hybrid Lead-Free Perovskite for X-ray Imaging.

The application of X-ray imaging in military, industrial flaw detection, and medical examination is inseparable from the wide application of scintillator materials. In order to substitute for lead, lower costs, and reduce self-absorption, organic-inorganic hybrid lead-free perovskite scintillators are emerging as a new option. In this work, novel (TEA)2Zr1-xTexCl6 perovskite microcrystals (MCs) were successfully synthesized by a hydrothermal method, with Te4+ doping, which leads to yellow triplet-state self-trapped excitons emission. The emission peak of (TEA)2Zr1-xTexCl6 located at 605 nm under X-ray excitation, which was applied to X-ray imaging, shows a clear wiring structure inside the USB connector. The detection limit (DL) of 820 nGyair/s for (TEA)2Zr0.9Te0.1Cl6 is well below the dose rate corresponding to a standard medical X-ray diagnosis is 5.5 µGyair/s. This work opens up a new path for organic-inorganic hybrid lead-free scintillators.

Boosting CO2 Conversion by Synergy of Lead-Free Perovskite Cs2SnCl6 and Plasma with H2O.

Although dielectric barrier discharge (DBD) plasma is a promising technique for CO2 conversion, realizing CO2-to-alcohol is still challenging via the use of H2O. Herein, for the first time, efficient CO2 conversion was achieved via the synergism between the Cs2SnCl6 photocatalyst and DBD plasma assisted by H2O. The CO2 conversion ratio of plasma photocatalysis was 6.5% higher than that of only the plasma and photocatalysis, implying that the synergism of plasma catalysis and photocatalysis was achieved. Furthermore, the DBD plasma assisted by the Cs2SnCl6 photocatalyst could convert CO2 and H2O to CO and a small amount of methanol and ethanol. The CO2 conversion ratio was enhanced by 50.6% in the presence of H2O, which was attributed to the improvement of charge transfer due to the increased electrical conductivity of the photocatalyst surface during plasma discharge. This work provides a new idea for developing an efficient system for CO2 utilization.

Enhanced photocatalytic activity and mechanism insight of copper-modulated lead-free Cs2AgSbCl6 double perovskite microcrystals.

Lead halide perovskites are prospective candidates for CO2 photoconversion. Herein, we report copper-doped lead-free Cs2AgSbCl6 double perovskite microcrystals (MCs) for gas-solid phase photocatalytic CO2 reduction. The 0.2Cu@Cs2AgSbCl6 double perovskite MCs display unprecedented CO2 photoreduction capability with CO and CH4 yields of 412 and 128 µmol g-1, respectively. The ultrafast transient absorption spectroscopy reveals the enhanced separation of photoexcited carriers in copper-doped Cs2AgSbCl6 MCs. The active sites and reaction intermediates on the surface of the doped Cs2AgSbCl6 are dynamically monitored and precisely unraveled based on the in-situ Fourier transform infrared spectroscopy investigation. In combination with density functional theory calculations, it is revealed that the copper-doped Cs2AgSbCl6 MCs facilitate sturdy CO2 adsorption and activation and strikingly enhance the photocatalytic performance. This work offers an in-depth interpretation of the photocatalytic mechanism of Cs2AgSbCl6 doped with copper, which may provide guidance for future design of high-performance photocatalysts for solar fuel production.

Insights into oxidation of pentachlorophenol (PCP) by low-dose ferrate(VI) catalyzed with α-Fe2O3 nanoparticles.

In this study, the catalytic performance of α-Fe2O3 nanoparticles (nα-Fe2O3) in the low-dose ferrate (Fe(VI)) system was systematically studied through the degradation of pentachlorophenol (PCP). Based on the established quadratic functions between nα-Fe2O3 amount and observed pseudo first-order rate constant (kobs), two linear correlation equations were offered to predict the optimum catalyst dosage and the maximum kobs at an applied Fe(VI) amount. Moreover, characterization and cycling experiments showed that nα-Fe2O3 has good stability and recyclability. According to the results of reactive species identification and quenching experiment and galvanic oxidation process, the catalytic mechanism was proposed that Fe(III) on the surface of nα-Fe2O3 may react with Fe(VI) to enhance the generation of highly reactive Fe(IV)/Fe(V) species, which rapidly extracted a single electron from PCP molecule for its further reaction. Besides, two possible PCP degradation pathways, i.e., single oxygen transfer mediated hydroxylation and single electron transfer initiated polymerization were proposed. The formation of coupling products that are prone to precipition and separation was largely improved. This study proved that nα-Fe2O3 can effectively catalyze PCP removal at low-dose Fe(VI), which provides some support for the application of Fe(VI) oxidation technology in water treatment in the context of low-carbon emissions.

Comparative study on the removal of 1- naphthol and 2-naphthol by ferrate (VI): Kinetics, reaction mechanisms and theoretical calculations.

In this study, the oxidation of 1-naphthol (1-NAP) and 2-naphthol (2-NAP) by Fe(VI) was investigated. The impacts of operating factors were investigated through a series of kinetic experiments, including Fe(VI) dosages, pH and coexisting ions (Ca2+, Mg2+, Cu2+, Fe3+, Cl-, SO42-, NO3- and CO32-). Almost 100% elimination of both 1-NAP and 2-NAP could be achieved within 300 s at pH 9.0 and 25 °C. Cu2+ could significantly improve the degradation efficiency of 1-NAP and 2-NAP, but the impacts of other ions were negligible. The liquid chromatography-mass spectrometry was used to identify the transformation products of 1-NAP and 2-NAP in Fe(VI) system, and the degradation pathways were proposed accordingly. Electron transfer mediated polymerization reaction was the dominant transformation pathway in the elimination of NAP by Fe(VI) oxidation. After 300 s of oxidation, heptamers and hexamers were found as the final coupling products during the removal of 1-NAP and 2-NAP, respectively. Theoretical calculations demonstrated that the hydrogen abstraction and electron transfer reaction would easily occur at the hydroxyl groups of 1-NAP and 2-NAP, producing NAP phenoxy radicals for subsequent coupling reaction. Moreover, since the electron transfer reactions between Fe(VI) and NAP molecules were barrierless and could occur spontaneously, the theoretical calculation results also confirmed the priority of coupling reaction in Fe(VI) system. This work indicated that the Fe(VI) oxidation was an effective way for removing naphthol, which may help us understand the reaction mechanism between phenolic compounds with Fe(VI).

Capping Ligand Engineering Enables Stable CsPbBr3 Perovskite Quantum Dots toward White-Light-Emitting Diodes.

All-inorganic perovskite quantum dots (PeQDs) have sparked extensive research focus on white-light-emitting diodes (WLEDs), but stability and photoluminescence efficiency issues are still remain obstacles impeding their practical application. Here, we reported a facile one-step method to synthesize CsPbBr3 PeQDs at room temperature using branched didodecyldimethylammonium fluoride (DDAF) and short-chain-length octanoic acid as capping ligands. The obtained CsPbBr3 PeQDs have a near-unity photoluminescence quantum yield of 97% due to the effective passivation of DDAF. More importantly, they exhibit much improved stability against air, heat, and polar solvents, maintaining >70% of initial PL intensity. Making use of these excellent optoelectronic properties, WLEDs based on CsPbBr3 PeQDs, CsPbBr1.2I1.8 PeQDs, and blue LEDs were fabricated, which show a color gamut of 122.7% of the National Television System Committee standard, a luminous efficacy of 17.1 lm/W, with a color temperature of 5890 K, and CIE coordinates of (0.32, 0.35). These results indicate that the CsPbBr3 PeQDs have great practical potential in wide-color-gamut displays.

Recent Advances and Future Perspectives of Lead-Free Halide Perovskites for Photocatalytic CO2 Reduction.

It is still challenging to design and develop the state-of-the-art photocatalysts toward CO2 photoreduction. Enormous researchers have focused on the halide perovskites in the photocatalytic field for CO2 photoreduction, due to their excellent optical and physical properties. The toxicity of lead-based halide perovskites prevents their large-scale applications in photocatalytic fields. In consequence, lead-free halide perovskites (LFHPs) without the toxicity become the promising alternatives in the photocatalytic application for CO2 photoreduction. In recent years, the rapid advances of LFHPs have offer new chances for the photocatalytic CO2 reduction of LFHPs. In this review, we summarize not only the structures and properties of A2 BX6 , A2 B(I)B(III)X6 , and A3 B2 X9 -type LFHPs but also their recent progresses on the photocatalytic CO2 reduction. Furthermore, we also point out the opportunities and perspectives to research LFHPs photocatalysts for CO2 photoreduction in the future.

Investigation on the surface charge separation in Pt-supported morphology-related-TiO2 and its effect on water splitting.

Lowering Pt loading in the catalyst while maintaining its superior catalytic efficiency during hydrogen evolution reaction (HER) is essential for the large-scale application of water splitting. The utilization of strong metal-support interaction (SMSI) through morphology engineering has emerged as an effective strategy in fabricating Pt-supported catalysts. However, a simple and explicit routine to realize the rational design of morphology-related SMSI remains challenging. Here we report a protocol for the photochemical deposition of Pt, which benefits from the intrinsic difference in absorption capability of TiO2 to establish proper Pt+ species and charge separation domains on the surface. With a comprehensive investigation of the surface environment through experiments and Density functional theory (DFT) calculations, charge transfer from Pt to Ti, the separation of electron-hole pairs, and the enhanced electron transfer in the TiO2 matrix were confirmed. It is reported that H2O molecules can be spontaneously dissociated by the surface Ti and O, generating OH stabilized by adjacent Ti and Pt. Such adsorbed OH group induces changes in the electron density of Pt, consequently favours the H adsorption and enhances the HER. Benefiting from the preferable electronic state, the annealed Pt@TiO2-pH9 (PTO-pH9@A) exhibits an overpotential of 30 mV to reach 10 mA cm-2 geo and a mass activity of 3954 A g-1Pt, which is 17-fold higher than the commercial Pt/C. Our work provides a new strategy for the high-efficient catalyst design by the surface state- regulated SMSI.

Achieving adjustable digital-to-analog conversion in memristors with embedded Cs2AgSbBr6 nanoparticles.

In this work, the proportions of Cs2AgSbBr6 nanoparticles (NPs) mixed in a PMMA film are adjusted to the digital and analog types of resistive switching (RS) behaviors in Ag/PMMA&Cs2AgSbBr6-NPs/ITO memristor devices. It is confirmed that when the concentration of NPs doped in the PMMA film is about 5 wt%, the memristor devices demonstrate bipolar digital RS behaviors with excellent electrical characteristics such as low operating voltage, high ON/OFF ratio (>500), good endurance (>800 cycles), and stable retention ability (>104 s). However, the devices showed a transition to analog-type memristive behavior when the concentration of NPs doped in the PMMA film is around 10 wt%, and several artificial synapse behaviors are successfully simulated. The device model simulation is also used to explore the effect of the NPs on the local electric field and growing filaments. Our work provides an opportunity to explore next-generation artificial synapse devices based on lead-free halide perovskites.

GaN nanowires prepared by Cu-assisted photoelectron-chemical etching.

A novel Cu-assisted photoelectron-chemical etching is proposed to fabricate GaN nanowires. The functional mechanism of assisted metals, etchant concentrations, and the addition of H2O2 was investigated based on theoretical analysis and experiments. The low-cost metal-assisted etchant (CuSO4) proved more favorable than the conventional noble one (AgNO3) for the preparation of GaN nanowires in this work. The formed Ag dendrite blocked the etching when adopting the Ag-assisted etchant, while the Cu-assisted one did not. Moreover, the etchant consisting of 0.01 M CuSO4 and 5 M HF was demonstrated to realize a relatively good surface morphology and fast etching rate. In addition, the common oxidant H2O2 introduced a quasi-stable configuration between the Cu deposition and dissolution, slowing down the formation of the GaN nanowires. The proposed Cu-assisted photoelectron-chemical etching with the advantages of low cost, room temperature, and controllability could offer a new way to fabricate GaN nano-devices.

Photochemical transformation of anthracene (ANT) in surface soil: Chlorination and hydroxylation.

To reveal the fate of anthracene (ANT) in soil, the photodegradation behavior of ANT was systematically studied using SiO2 to simulate a soil environment. Under xenon lamp irradiation, more than 90% of ANT loaded on SiO2 could be removed after 240 min. Moreover, the effects of water content, chloride ions (Cl-) and humic acid (HA) were examined. It was found that the presence of water and HA can significantly inhibit the photolysis of ANT on SiO2, while the addition of chloride alone has no obvious effect. However, when water is present, the inhibition effect of chloride became more obvious. According to radical quenching experiments and electron paramagnetic resonance (EPR) spectra, hydroxyl radicals (•OH) and chlorine radicals (Cl•) were formed in the system. Possible reaction pathways were speculated based on products identified by mass spectrometry. ANT was attacked by •OH to form hydroxylated products, which can be further hydroxylated and oxidized with the final formation of ring-opening products. ANT directly excited by light may also react with Cl• to produce chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs). Finally, the experimental results were verified on real soil. This study provides important information for understanding the photochemical transformation mechanism of ANT at the soil/air interface.

Novelty All-Inorganic Titanium-Based Halide Perovskite for Highly Efficient Photocatalytic CO2 Conversion.

Lead halide perovskite materials have great potential for photocatalytic reaction due to their low fabrication cost, unique optical absorption coefficient, and suitable band structures. However, the main problems are the toxicity and instability of the lead halide perovskite materials. Therefore, a facile synthetic method is used to prepare lead-free environmentally friendly Cs2 TiX6 (X = Cl, Cl0.5 Br0.5 , Br) perovskite materials. Their structural and optical characteristics are systematically investigated. The band gaps of the produced samples are illustrated to be from 1.87 to 2.73 eV. Moreover, these materials can keep high stability in harsh environments such as illumination and heating, and the Cs2 Ti(Cl0.5 Br0.5 )6 microcrystals demonstrate the yields of 176 µmol g-1 for CO and 78.9 µmol g-1 for CH4 after light irradiation for 3 h, which is of the first report of Ti-based perovskite photocatalysts. This finding demonstrates that the Ti-based perovskites will create opportunities for photocatalytic applications, which may offer a new idea to construct low-cost, eco-friendly, and bio-friendly photocatalysts.

Highly Thermally Sensitive Cascaded Wannier-Mott Exciton Ionization/Carrier Localization in Manganese-Doped Perovskite Nanocrystals.

Transition-metal doping in perovskite nanocrystals strongly alters the photophysical properties of these nanocrystals. However, the details of the underlying thermal and optical processes within such an intriguing symmetry-breaking nanosystem are far from clear. Herein, we study the sensitively temperature-dependent and highly competent delocalized exciton and transition-metal ion-captured carrier recombination processes in manganese-doped CsPbBr0.6Cl2.4 nanocrystals. The combined experimental and theoretical studies reveal that both the exciton ionization and capture of the band-edge carriers by the manganese ions play the dominant roles in determining the proportion of the manganese ions-dominated recombination process. A density functional theory calculation of the temporal fluctuation of the manganese ions-accommodated localized orbitals further confirms that the thermally enhanced nonadiabatic electron-phonon coupling promotes the probability of the carrier localization. These findings reveal the respective crucial roles of the exciton ionization and carrier capture in the localized recombination process in the transition-metal-doped semiconductor nanocrystals.

Enhanced Resistive Switching Performance through Air-Stable Cu2AgSbI6 Thin Films for Flexible and Multilevel Storage Application.

Herein, the lead-free halide perovskite films with different Cu-to-Ag ratios (Cu3-xAgxSbI6, x = 0, 1, 2, or 3) have been prepared by a spin-coating method at low temperature. The enhanced resistive switching (RS) performance of more uniform SET/RESET voltages and the endurance up to at least 1600 cycles are found in the RS memory with a device structure of Ag/PMMA/Cu2AgSbI6/ITO. The device performance is not degraded under different bending angles and after 103 bending cycles, which is beneficial for flexible memory applications. The appropriately increased activation energy of the perovskites with the partial substitution of Ag atoms, which would lead to a more robust filament formed, is proposed to explain the enhanced RS mechanism. Importantly, the effective size and number of filaments measured by conductive AFM are introduced to confirm the multilevel storage effect of Cu2AgSbI6. The multilevel storage characteristics with four resistance levels are demonstrated by various compliance currents. Moreover, the Cu2AgSbI6 memory devices still exhibit enhanced RS properties and multilevel storage after 75 days of exposure to ambient conditions. Our study provides a strategy for improving the stability and high-density storage applications of halide perovskite RS memory devices.

High-Performance Resistive Random Access Memories Based on Two-Dimensional HAPbI4 Organic-Inorganic Hybrid Perovskite.

Organic-inorganic hybrid perovskites have attracted extensive attention for potential memory applications because of their excellent properties, such as high charge carrier mobility and fast ion migration. Herein, the two-dimensional HAPbI4 perovskite with an octahedral structure and high stability was prepared by a facile solution method. Moreover, the resistive random access memory (RRAM) with the Ag/PMMA/HAPbI4/ITO structure has been successfully fabricated by spin coating and vacuum thermal evaporation. The as-prepared RRAM device based on HAPbI4 demonstrated superior resistive switching performance. The on/off ratio is as high as 105, and the corresponding retention of the device exceeds 10 000 s; furthermore, the RRAM device could be kept stable after being kept in the air for 24 weeks.

Lead-Free Cs2TeX6 (X = Cl, Br, and I) Perovskite Microcrystals with High Stability for Efficient Photocatalytic CO2 Reduction.

In response to calling for a sustainable and carbon-neutral economy, the conversion of CO2 to useful chemicals using the solar energy is a potential tactic to relieve the global energy dilemma and environmental issues, which has been a hot topic so far. Recently, the lead halide perovskites as novel photocatalysts have attracted researchers' interests. However, they generally encounter poor stability and lead toxicity, restricting their large-scale practical applications. Here, the lead-free Cs2TeX6 (X = Cl, Cl0.5Br0.5, Br, Br0.5I0.5, and I) perovskite microcrystals with strong stability were prepared and used to realize the CO2 photocatalytic reduction efficiently. The prepared Cs2TeBr6 microcrystals delivered stronger photocatalytic ability than many previously reported photocatalysts, with the CO and CH4 yields of 308.63 and 60.42 µmolg-1, respectively, under 3 h of illumination. The presented strategy in our work provides new ideas of designing and preparing efficient and practical CO2 reduction photocatalysts based on nonleaded and high-stability halide perovskites.