1D Chiral Enantiomer Lead-Free Perovskites Induced Chiralopical Activity and Photoelectric Response.

Chirality is a fascinating geometrical concept with widespread applications in biology, chemistry, and materials. Incorporating chirality into hybrid perovskite materials can induce novel physical properties (chiral optical activity, nonlinear optics, etc.). Hybrid lead-free or lead-substituted perovskite materials, as representatives of perovskites, have been widely used in fields such as photovoltaics, sensors, catalysis, and detectors. However, the successful introduction of chirality into hybrid lead-free perovskites, which can enable their potential applications in areas such as circularly polarized light photodetectors, memories, and spin transistors, remains a challenging research topic. Here, we synthesized two new chiral lead-free perovskites, [(R)-2-methylpiperazine][BiI5] and [(S)-2-methylpiperazine][BiI5]. The material possesses a perovskite structure with a one-dimensional (1D) arrangement, denoted as ABX5. This structure is composed of chiral cations, specifically methylpiperazine, and endless chains of [BiI3] along the a-axis. These chains are assembled from distorted coplanar [BiI5]2- octahedra. The testing results revealed that (R)-1 and (S)-1 have narrow band gaps (Eg-R = 2.016 eV, Eg-S = 1.964 eV), high photoelectric response, and long carrier lifetime [R = 4.94 µs (τ), S = 7.85 µs (τ)]. It is worth noting that 1D chiral lead-free perovskites (R)-1 and (S)-1, which are synthesized in this study with narrow band gaps, high photoelectric response, and long carrier lifetime, have the potential to serve as alternative materials for the perovskite layer in future iterations of lead-free perovskite solar cells. Moreover, this research will inspire the preparation of multifunctional, lead-free perovskites.

Efficient C2H6/C2H4 adsorption separation by a microporous heterometal-organic framework.

Purification of ethylene (C2H4) is an essential and energy-intensive process in the petrochemical industry. Adsorption separation using ethane (C2H6)-selective porous adsorbents is a highly efficient and straightforward method for obtaining polymer-grade C2H4 from a binary C2H6/C2H4 mixture. However, the design and construction of C2H6-selective adsorbents are very challenging tasks. Herein, we demonstrate a microporous heterometal-organic framework, CuIn(ina)4, can preferentially enrich C2H6 than C2H4. Experimental results revealed that CuIn(ina)4 exhibited remarkable separation performance for the C2H6/C2H4 mixture with a high C2H6 loading capacity (3.3 mmol/g), high IAST selectivity (2.3) and separation potential (1578 mmol/L for equimolar C2H6/C2H4 mixture) under ambient conditions. The effectiveness of CuIn(ina)4 for C2H6/C2H4 adsorption separation was confirmed by theoretical calculations and breakthrough experiments.

Precise Design of Molecular Ferroelectrics with High TC and Tunable Band Gap by Molecular Modification.

Molecular ferroelectric materials are widely applied in piezoelectric converters, non-volatile memorizers, and photovoltaic devices due to their advantages of adjustable structure, lightweight, easy processing, and environmental friendliness. However, designing multifunctional molecular ferroelectrics with excellent properties has always been a great challenge. Herein, a multiaxial molecular ferroelectric is successfully designed by modifying the quasi-spherical cation dabco with CuBr2 to obtain halogenated [Bretdabco]CuBr4 (Bretdabco = N-bromoethyl-N'-diazabicyclo [2.2.2]octane), which crystallizes in polar point groups (C6). Typical ferroelectric behaviors featured by the P-E hysteresis loop and switched ferroelectric domain are exhibited. Notably, the molecular ferroelectric shows a high TC of 460 K, which is rare in the field and could greatly expand the application range of this material. In addition, the band gap is adjustable through the regulation of halogen. Both the UV absorption spectra and theoretical calculations indicate that the molecular ferroelectrics belong to a direct band gap (2.14 eV) semiconductor. This tunable and narrow band gap semiconductor molecular ferroelectric material with high TC can be utilized more effectively in the study of optoelectronics and sensors, including piezoelectric energy harvesters. This research may provide a promising approach for the development of multiaxial molecular ferroelectrics with a tiny band gap and high TC.

Facile Control of Ferroelectricity Driven by Ingenious Interaction Engineering.

Construction of ferroelectric and optimization of macroscopic polarization has attracted tremendous attention for next generation light weight and flexible devices, which brings fundamental vitality for molecular ferroelectrics. However, effective molecular tailoring toward cations makes ferroelectric synthesis and modification relatively elaborate. Here, the study proposes a facile method to realize triggering and optimization of ferroelectricity. The experimental and theoretical investigation reveals that orientation and alignment of polar cations, dominated factors in molecular ferroelectrics, can be controlled by easily processed anionic modification. In one respect, ferroelectricity is induced by strengthened intermolecular interaction. Moreover, ≈50% of microscopic polarization enhancement (from 8.07 to 11.68 µC cm-2 ) and doubling of equivalent polarization direction (from 4 to 8) are realized in resultant ferroelectric FEtQ2ZnBrI3 (FEQZBI, FEtQ = N-fluoroethyl-quinuclidine). The work offers a totally novel platform for control of ferroelectricity in organic-inorganic hybrid ferroelectrics and a deep insight of structure-property correlations.

Realizing near white and warm light emission of cuprous iodide complexes by alkyl-isomerization of ligands.

Four novel all-in-one structured cuprous iodide hybrid materials are presented. Isomerization of the alkyl chain on the ligand improved material thermal stability and regulated their luminescence to warm and near-white light emission, with the internal quantum yield increasing from 5% to 83%. This provides a reasonable route for designing white light emitting cuprous iodide materials for solid-state lighting in future.

An integrated process for struvite recovery and nutrient removal from ship domestic sewage.

Marine pollution caused by the untreated and substandard discharge of ship domestic sewage has received widespread attention. A novel integrated process for struvite recovery and nutrient removal from ship domestic sewage (SRNR-SDS) based on seawater magnesium source was developed in this study. Removal efficiencies of the total nitrogen (TN) and total phosphorus (TP) for the activated sludge unit in SRNR-SDS process were approximately 67.61% and 41.35%, respectively, under the salinity of 7.85 g/L. The coupling-induced struvite crystallization unit significantly improved the removal efficiency of TN and TP, and the scanning electron microscopy and X-ray diffraction demonstrated that magnesium ammonium phosphate (MAP) crystals were successfully formed on the surface of zeolite. The SRNR-SDS process had an ideal performance for pollutant removal and MAP recovery under the optimal hydraulic retention time of 20 h. The effluent concentrations of COD, NH4+-N, TN and TP in SRNR-SDS process were approximately 34.73 mg/L, 4.31 mg/L, 10.07 mg/L and 0.23 mg/L, respectively, which meet the Chinese and international ship sewage discharge standards. SRNR-SDS process has obvious environmental, social and economic benefits, which could save 6.20%∼57.14% of the operation cost of ship domestic sewage treatment via MAP recovery. The results could provide theoretical and technical support for the development and application of ship sewage treatment process with the functions of pollutant removal and resource recovery.

Three Robust Blue-Emitting Anionic Metal-Organic Frameworks with High Stability and Good Proton Conductivities.

Three anionic luminescent metal-organic frameworks (LMOFs; [M(tcbpe)(CH3)2NH2]·H2O; M = In3+, Eu3+, Gd3+; tcbpe = 4',4‴,4‴″,4‴‴'-(ethene-1,1,2,2-tetrayl)tetrakis[(1,1'-biphenyl)-4-carboxylic acid]) are synthesized by employing the tetraphenylethene core ligand H4tcbpe with M3+ ions. They stack in the similarly 4-fold-interpenetrated three-dimensional porous structure. All give blue emission when excited at 365 nm, with fluorescence quantum yields of 34.8% (MOF-In), 7.1% (MOF-Eu), and 28.1% (MOF-Gd). Somewhat surprisingly, these three complexes are extremely stable both in various solvents and across a broad pH range: MOF-In is stable between pH = 0 and 14, and MOF-Eu and MOF-Gd are stable between pH = 0 and 13. Additionally, they also show good proton conductivities of 2.29 × 10-5 S·cm-1 (MOF-In), 2.02 × 10-4 S·cm-1 (MOF-Eu), and 1.24 × 10-4 S·cm-1 (MOF-Gd) at high temperature under 98% relative humidity. To the best of our knowledge, this is the first reported LMOF series combining aggregation-induced emission behavior with good proton conductivities.

Ni/Fe layered double hydroxide nanosheet/G-quadruplex as a new complex DNAzyme with highly enhanced peroxidase-mimic activity.

A novel and low-cost DNAzyme, Ni/Fe layered double hydroxide (LDH) nanosheet/G-quadruplex (without hemin) with enhanced peroxidase-mimic activity was designed. The catalytic mechanism was investigated. The detection of Cu(II) in actual serum samples could be realized sensitively via this efficient DNAzyme-based method.

Formation of unique hollow ZnSnO3@ZnIn2S4 core-shell heterojunction to boost visible-light-driven photocatalytic water splitting for hydrogen production.

Herein, it is reported that a batch of hollow core-shell heterostructure photocatalysts were carefully fabricated using a reliable and convenient low-temperature solvothermal method, and ultra-thin ZnIn2S4 nanosheets are grown in situ on the hollow ZnSnO3 cubes to achieve efficient photocatalytic hydrogen evolution. This unique layered hollow structure utilizes multiple light scattering/reflection within the cavity to enhance light absorption, the thin shell reduces the path of charge transfer, and the irregular nanosheets-wrapped outer layer not only enhances the adsorption power, but also provides an abundant active sites to promote the efficiency of photocatalytic water splitting to produce hydrogen. Therefore, due to the matching energy band and unique structure, the ZnSnO3@ZnIn2S4 hollow core-shell heterostructure photocatalyst exhibits superior H2 production efficiency (16340.18 µmol h-1 g-1) and outstanding stability. This work emphasizes the importance of carefully designing a suitable material structure in addition to adjusting the chemical composition.

Tuning Chromophore-Based LMOF Dimensionality to Enhance Detection Sensitivity for Fe3+ Ions.

Herein, we report the synthesis of two new manganese-based luminescent metal-organic frameworks (LMOFs) [Mn0.5(tipe)(1,4-ndc)] n (1) and [Mn(tipe)(1,4-ndc) (H2O)·(DMF)2·(H2O)3] n (2) [tipe = 1,1,2,2-tetrakis(4-(1H-imidazol-1-yl)phenyl)ethene (tipe) and 1,4-ndc = 1,4-naphthalenedicarboxylic acid] constructed from an aggregation-induced emission (AIE) chromophore ligand. Compound 1 can undergo a facile single-crystal-to-single-crystal transformation to form compound 2, which results in an increase in dimensionality from a two-dimensional (2D) network to a three-dimensional (3D) network. Both compounds demonstrate excellent performance for the solution-phase detection of Fe3+ ions through a significant and rapid quench in luminescence emission. Fluorescence titration experiments reveal that compound 2 is more selective toward Fe3+ compared to compound 1 because of its 3D stacking mode. The K sv value for compound 2 (32 378 M-1) is twice as large as that for compound 1 (15 854 M-1) for the detection of Fe3+ ions. We attribute this significant increase in performance to the increase in dimensionality. In addition, compound 2 demonstrates high selectivity and sensitivity for the detection of Cr3+ cations and Cr2O7 2- anions.

A multiaxial molecular ferroelectric with record high TC designed by intermolecular interaction modulation.

Through precise and ingenious molecular modification, we successfully obtained a multiaxial ferroelectric, [FEtDabco]ZnI3 (N-fluoroethyl-N'-ZnI3-1,4-diazabicyclo[2.2.2]octonium), with a record high Tc (540 K) among molecular ferroelectrics, which is promising for application under extreme thermal conditions.

Selective fluorescent sensing of LMOFs constructed from tri(4-pyridylphenyl)amine ligand.

Three new luminescent metal-organic frameworks (LMOFs), [Zn(tppa)(ndc)] n (1), [Cd(tppa)(oba)] n (2), [Zn2(tppa)(bpdc)2] n (3) (tppa = tri(4-pyridylphenyl)amine, ndc = 1,4-naphthalenedicarboxylic acid, oba = 4,4'-oxydibenzoic acid, bpdc = 4,4'-biphenyldicarboxylic acid) have been synthesized by solvothermal method. Complexes 1 and 2 are 2-D two-fold interpenetrating structures, aligning into a 3-D structure through C-H⋯π stacking interactions, while 3 is a 5-fold interpenetrating three-dimensional structure. The internal quantum yields (IQYs) of complexes 1-3 are 32.7%, 45.7% and 24.0% (λ ex = 365 nm), separately. Furthermore, all the complexes show different luminescence signal changes towards aromatic volatile organic compounds (AVOCs). Complex 1 exhibits a high sensitivity in the detection of both Fe3+ and Cr3+ with large quenching coefficients of K sv 2.57 × 104 M-1 and 2.96 × 104 M-1, respectively. All these results demonstrated potential applications in chemical sensing.

Recent Progress in Luminescent Cu(I) Halide Complexes: A Mini-Review.

Copper(I) halide complexes are well sought-after materials due to their rich structural diversities and photophysical properties. Profoundly, there is a direct relationship between each structural variation and luminescence of these complexes, for a purported use. In this review, recent publications within the last 2 years about copper(I) halide complexes, centering on their structural dimensionalities with derivatives of nitrogen, phosphorus, and sulfur ligands, have been considered alongside their effects on luminescence.

Synthesis and biological evaluations of a series of calycanthaceous analogues as antifungal agents.

Starting from indole-3-acetonitrile, a total of 66 new calycanthaceous alkaloid analogues were synthesised in excellent yields. The prepared compounds were evaluated for their biological activities against a broad range of plant pathogen fungi. The results of bioassays indicated that the majority of tested compounds displayed comparable or better in vitro bioactivities than the positive control. Notably, Compound a1 displayed a significant activities against B. cereus, Escherichia sp and R. solanacearum, even better than the positive control streptomycin and Penicillin, with the same MIC value of 15.63 µg mL-1. Compound a1 displayed a broad spectrum and remarkably activities among the tested calycanthaceous analogues and might be a novel potential leading compound for further development of antifungal agents. The results obtained in the study will be very helpful for further design and structural optimisation of calycanthaceous alkaloids as potential agrochemical lead for plant disease control.

A Low-Cost and High-Capacity SiO x /C@graphite Hybrid as an Advanced Anode for High-Power Lithium-Ion Batteries.

Silicon suboxide (SiO x ) is one of the most promising anodes for the next-generation high-power lithium-ion batteries because of its higher lithium storage capacity than current commercial graphite, relatively smaller volume variations than pure silicon, and appropriate working potential. However, the high cost, poor cycling stability, and rate capability hampered its industrial applications due to its complex production process, volume changes during Li+ insertion/extraction, and low conductivity. Herein, a low-cost and high-capacity SiO x /C@graphite (SCG) hybrid was designed and synthesized by a facile one-pot carbonization/hydrogen reduction process of the rice husk and graphite. As an advanced anode for lithium-ion batteries, the SiO x /C@graphite hybrid delivers a high reversible capacity with significantly enhanced cycling stability (842 mAh g-1 after 300 cycles at 0.5 A g-1) and rate capability (562 mAh g-1 after 300 cycles at 1 A g-1). The great improvement in performances could be attributed to the positive synergistic effect of SiO x nanoparticles as lithium storage active materials, the in situ-formed carbon matrix network derived from biomass functioning as an efficient three-dimensional conductive network and spacer to improve the rate capability and buffer the volume changes, and graphite as a conductor to further improve the rate capabilities and cycling stability by increasing the conductivity. The low-cost and high-capacity SCG derived from rice husk synthesized by a facile, scalable synthetic method turns out to be a promising anode for the next-generation high-power lithium-ion batteries.

High-Performance Metal-Organic Framework-Templated Sorbent for Selective Eu(III) Capture.

A stable porous sorbent M1 was achieved through the specific transformation of flexible thioalkyl groups and metal cluster sites in a zirconium MOF (metal-organic framework; Zr-L) template. The target polymer combines sulfoxide/sulfone and phosphoric acid in a single framework, which was fully characterized by 1H-NMR, PXRD, IR, and elemental analysis. When employed as the heavy metal adsorbent, M1 exhibit a remarkable Eu(III) sorption behavior, achieving both high chemical affinity (K d = 105) and sorption capacity (the maximum Eu(III) sorption capacity reached 220 mg g-1 at pH = 4.0 and T = 298 K calculated from the Langmuir model). Recyclability and selectivity test of M1 further prove that the sorbent is highly stable and effective for europium enrichment in the aqueous solution. This work takes focus on the introduction of multifunctional groups into a single polymeric framework in a feasible and environmentally friendly way and highlights the sorption efficiency for europium removal from the aqueous solution.

Precise Molecular Design Toward Organic-Inorganic Zinc Chloride ABX3 Ferroelectrics.

Organic-inorganic ABX3 (A, B = cations, X = anion) hybrids with perovskite structure have recently attracted tremendous interest due to their structural tunability and rich functional properties, such as ferroelectricity. However, ABX3 hybrid ferroelectrics with other structures have rarely been reported. Here, we successfully designed an ABX3 hybrid ferroelectric [(CH3)3NCH2F]ZnCl3 with a spontaneous polarization of 4.8 µC/cm2 by the molecular modification of [(CH3)4N]ZnCl3 through hydrogen/halogen substitution. It is the first zinc halide ABX3 ferroelectric, which contains one-dimensional [ZnCl3]-n chains of corner-sharing ZnCl4 tetrahedra, distinct from the anionic framework of corner-sharing or face-sharing BX6 octahedra in the ABX3 perovskites. From zero dimension to one dimension, the high symmetry of ZnCl4 tetrahedra is broken, and all of them align along one direction to form a polar [ZnCl3]-n chain, beneficial to the generation of ferroelectricity. This finding provides an efficient polar anionic framework for enriching the family of hybrid ferroelectrics by assembling with various cations and should inspire further exploration of new classes of organic-inorganic ABX3 ferroelectrics.

MoS2 nanosheets anchored on porous ZnSnO3 cubes as an efficient visible-light-driven composite photocatalyst for the degradation of tetracycline and mechanism insight.

In this study, MoS2/ZnSnO3 (MS-ZSO) composite photocatalyst with loading MS nanosheets onto the surface of porous ZSO microcubes was synthesized using a simple hydrothermal route. The prepared MS-ZSO composite can be easily excited under visible light, and 3 % MS-ZSO exhibits an outstanding photo-degradation (>80 % in 60 min) and mineralization performance (>42 % in 60 min) of the tetracycline. A remarkable improvement in the photocatalytic activity of MS-ZSO composite derived from a positive synergistic effect of well-matched energy level positions, increasement the absorption of visible light, prolonged life time decay and improved interfacial charge transfer between MS and ZSO. In-depth investigation on charge carrier separation mechanism toward MS/ZSO composite under visible light was proposed, which was further evidenced by capture experiments and electron spin resonance (ESR) techniques. Furthermore, the corresponding intermediates of tetracycline degradation over MS-ZSO composites were inspected by liquid chromatography-mass spectrometry (LC-MS) analysis, and the possible degradation paths were proposed.

Fe-Doped CoP Flower-Like Microstructure on Carbon Membrane as Integrated Electrode with Enhanced Sodium Ion Storage.

Poor cyclability and rate performance always impede the development of transition metal phosphide-based anode materials. Many strategies have been used to address the above problems, such as the designing of hierarchical structures, combination with carbon materials, and doping with other metal elements. Considering those strategies, a flower-like Fe-doped CoP material is designed. The synthesis consists of microsheets grown on a carbon membrane (CM, leaves as precursor) through a hydrothermal method and in situ phosphorization. The Fe doping and carbon membrane synergistically induce the formation of a flower-like hierarchical microstructure during the crystal-growing process. The unique hierarchical microstructure increases the contact area between electrode and electrolyte, and accommodates the volume expansion during cycling. The hierarchical Fe-doped CoP grown directly on the carbon membrane increases the active sites for intercalation of sodium species and further promotes the internal electron conduction in the Fe-doped CoP/CM electrode. Thereby, the Fe-doped CoP/CM as the anode electrode for sodium ion batteries exhibits a high specific capacity of 515 mA h g-1 at 100 mA g-1 after 100 cycles. Even if the current density rises to 500 mA g-1 , the specific capacity is still maintained at 324 mA h g-1 after 500 cycles, showing superior rate performances and cyclability.

Synthesis and biological evaluation of calycanthaceous alkaloid analogs.

Starting from 9-methyl-1,2,3,4,9,9a-hexahydro-4aH-pyrido[2,3-b]indol-4a-ol, or indole-3-acetonitrile, 40 new calycanthaceous alkaloid analogs were synthesized in excellent yields. The prepared compounds were evaluated for biological activity against acetylcholinesterase and a broad range of plant pathogen fungi. The results of bioassays indicated that the majority of tested compounds displayed comparable or better in vitro bioactivity than the positive control. Notably, compounds b8 and b9 showed higher activity against Verticillium dahlia than chlorothalonil, with MIC values of 62.5 and 7.81 µg mL-1, respectively. Compound b3 had a higher activity against Bacillus cereus, with a MIC value of 15.63 µg mL-1. Compounds c2 and c11 revealed potent activity against acetylcholinesterase, with MIC values of 0.01 and 0.1 ng mL-1, respectively. Analysis of the molecular docking modes of c2 and c11 with Torpedo californica acetylcholinesterase indicated a medium strong hydrogen bond interaction between the hydroxyl groups of both the ligands and the phenolic hydroxyl of Try121 at a distance of approximately 2.4 Å. The results obtained in this study will be useful for the further design and structural optimization of calycanthaceous alkaloids as potential agrochemical lead compounds for plant disease control.