Experimental Observation of the Fully Ferroelectric-Fully Ferroelastic Effect in Multiferroic Hybrid Perovskites.

Since the concept of "multiferroic" was first proposed in 1968, the coupling effect between different ferroic orders has attracted great interest in energy, information, and biomedical fields. However, the fully ferroelectric-fully ferroelastic effect has never been experimentally observed in hybrid perovskites, even though this effect was predicted to exist half a century ago. Realizing such cross-linking effects of polarization vectors and strain tensors has always been a huge challenge because of the complex difference in these two ferroic origins. Here, we report a multiferroic with full ferroelectricity and full ferroelasticity in two-dimensional (2D) hybrid perovskites based on ferroelectrochemistry. The dynamic molecular reorientations endow (cyclohexanemethylaminium)2PbCl4 with a desired symmetry change of 4̅2mFmm2 at a Curie temperature of 411.8 K. More strikingly, the switchable evolution of ferroelastic domains was directly observed under the control of either electric or mechanical fields, which is the first experimental observation of a fully ferroelectric-fully ferroelastic effect in hybrid perovskites. This work would provide new insights into understanding the intrinsic cross-linking mechanism between ferroelectricity and ferroelasticity toward the development of multichannel interactive microelectronic devices.

Metal-Free Perovskite Ferroelectrics with the Most Equivalent Polarization Axes.

Ferroelectricity in metal-free perovskites (MFPs) has emerged as an academic hotspot for their lightweight, eco-friendly processability, flexibility, and degradability, with considerable progress including large spontaneous polarization, high Curie temperature, large piezoelectric response, and tailoring coercive field. However, their equivalent polarization axes as a key indicator are far from enough, although multiaxial ferroelectrics are highly preferred for performance output and application flexibility that profit from as many equivalent polarization directions as possible with easier reorientation. Here, by implementing the synergistic overlap of regulating anionic geometries (from spherical I- to octahedral [PF6]- and to tetrahedral [ClO4]- or [BF4]-) and cationic asymmetric modification, we successfully designed multiaxial MFP ferroelectrics CMDABCO-NH4-X3 (CMDABCO = N-chloromethyl-N'-diazabicyclo[2.2.2]octonium; X = [ClO4]- or [BF4]-) with the lowest P1 symmetry. More impressively, systemic characterizations indicate that they possess 24 equivalent polarization axes (Aizu notations of 432F1 and m3̅mF1, respectively)─the maximum number achievable for ferroelectrics. Benefiting from the multiaxial feature, CMDABCO-NH4-[ClO4]3 has been demonstrated to have excellent piezoelectric sensing performance in its polycrystalline sample and prepared composite device. Our study provides a feasible strategy for designing multiaxial MFP ferroelectrics and highlights their great promise for use in microelectromechanical, sensing, and body-compatible devices.

Material and Microstructure Analysis of Wood Color Paintings from Shaanxi Cangjie Temple, China.

Cangjie Temple was built to commemorate Cangjie, the legendary inventor of Chinese characters. It stands as one of the few remaining temples in China dedicated to the invention and creation of writing. In this study, the material properties of wooden paintings from the Cangjie temple were characterized using Polarized Light Microscopy (PLM), Scanning Electron Microscopy coupled with Energy Dispersive X-ray Spectroscopy (SEM-EDS), Micro-confocal Raman Spectroscopy, X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), and Pyrolysis-Gas Chromatography-Mass Spectrometry (Py-GC/MS). It was confirmed that the pigments of the paintings included cinnabar, lapis lazuli, lead white, Paris green, and carbon black. The proteinaceous glue was used as an adhesive in the pigment samples, with tung oil likely being utilized as a primer for the wooden structures before painting. This study not only provides valuable data support for the conservation and restoration of the architectural features of Cangjie Temple but also provides useful reference for the maintenance and inheritance of similar ancient buildings.

Study on the Properties of FEVE Modified with Ag2O/OH-MWCNTS Nanocomposites for Use as Adhesives for Wooden Heritage Objects.

The durability of wooden heritage objects and sites can be affected by external environmental factors, leading to decay, cracking, and other forms of deterioration, which might ultimately result in significant and irreversible loss. In this study, a FEVE resin was modified with Ag2O/OH-MWCNTS (MA), denoted as MAF, where three concentrations were prepared using in situ precipitation, and the resulting composite adhesive was characterized by a high viscosity and effective bacteriostatic properties, demonstrating a better viscosity and thermal stability, as well as antibacterial properties, than pure FEVE resin. The results show that MAF adhesives present good thermal stability, as evidenced by a lower mass loss rate following treatment at 800 °C compared to the pure FEVE resin. At a consistent shear rate, the viscosity of MAF demonstrates a notable increase with the proportion of MA, which is better than that of FEVE. This suggests that the nano-Ag2O particles in MA act as physical crosslinking agents in FEVE, improving the viscosity of the composite adhesive MAF. The adhesion strength between MAF and wood exhibits a similar trend, with wooden samples showing higher shear strengths as the proportion of MA increases in comparison to FEVE. Simultaneously, the antibacterial effects of the MAF adhesive exceeded 1 mm for Trichoderma, Aspergillus niger, and white rot fungi. The antibacterial activity of the MAF adhesive exhibited a direct correlation with the concentration of Ag2O/OH-MWCNTS, with the most pronounced inhibitory effect observed on Trichoderma. The MAF adhesive demonstrates promising prospects as an adhesive for wooden heritage artifacts, offering a novel approach for the rapid, environmentally friendly, and efficient development of composite adhesives with superior adhesive properties.

Organic-Inorganic Hybrid Ferroelectric and Antiferroelectric with Afterglow Emission.

Luminescent ferroelectrics are holding exciting prospect for integrated photoelectronic devices due to potential light-polarization interactions at electron scale. Integrating ferroelectricity and long-lived afterglow emission in a single material would offer new possibilities for fundamental research and applications, however, related reports have been a blank to date. For the first time, we here achieved the combination of notable ferroelectricity and afterglow emission in an organic-inorganic hybrid material. Remarkably, the presented (4-methylpiperidium)CdCl3 also shows noticeable antiferroelectric behavior. The implementation of cationic customization and halogen engineering not only enables a dramatic enhancement of Curie temperature of 114.4 K but also brings a record longest emission lifetime up to 117.11 ms under ambient conditions, realizing a leapfrog improvement of at least two orders of magnitude compared to reported hybrid ferroelectrics so far. This finding would herald the emergence of novel application potential, such as multi-level density data storage or multifunctional sensors, towards the future integrated optoelectronic devices with multitasking capabilities.

Fluorescence Emission Is Highly Structure-Dependent in Hybrid Lead Halides.

Hybrid lead halide perovskites have received extensive scientific attention owing to their great potential in the field of fluorescent displays and light-emitting diodes. Currently, most luminescent materials contain functional molecular and rare-earth metal ion parts. However, the mechanism of photoluminescence property in two-dimensional hybrid lead halide perovskites with different layered inorganic skeletons has been reported rarely. To better understand the effect of an inorganic skeleton on the fluorescence property, here, we report three organic-inorganic hybrid materials with different layered inorganic frameworks: (MACH)2·PbBr4 (Prv-1, MACH = cyclohexylmethylammonium), (2-MPQ)·PbBr4 (Prv-2, 2-MPQ = 2-methylpiperazinium), and (TMBA)4·Pb3Br10 (Prv-3, TMBA = N'N'N'-trimethylbenzylammonium). Among them, Prv-1 is a (100)-oriented perovskite, Prv-2 belongs to the (110)-oriented perovskite, and the inorganic framework of Prv-3 possesses [Pb3Br10] units. Interestingly, Prv-1 has a strong blue-violet fluorescence emission, while the luminescence effect of Prv-2 is very weak; notably, Prv-3 emits a charming bright-orange light. Meanwhile, results of theoretical computational studies also reveal that the electronic structure of all three compounds is highly dependent on structurally distorted [PbBr6] octahedra, and the frontier molecular orbital (FMO) analysis further suggests that HOMO and LUMO of Prv-3 are contributed by inorganic and organic components, respectively. In addition, all three materials belong to direct band gap semiconductors, and the band gaps are 2.79, 2.97, and 2.76 eV, respectively. Significantly, there are obvious differences in conduction bands. Based on the above analysis, the photoluminescence mechanism of three hybrid materials is explained from the electronic levels. Consequentially, this work might provide practical strategies and perspectives for exploring novel structure-related properties.

Syntheses, crystal structure, and photoelectric properties of two Zn-based chalcogenidoantimonates Zn-Sb-Q (Q = S, Se).

Metal chalcogenides are a special class of semiconducting materials characterized by their rich structures and compositions, making them a promising option for a broad range of applications in the field of inorganic chemistry. However, the path forward is not without its challenges, notably in the realms of interface management and enhancing carrier concentration. To address these issues, we solvothermally synthesized two novel chalcogenidoantimonates [Zn(tren)]2Sb2Se5 (1) [tren = tris (2-aminoethyl) amine] and [Zn(tepa)H]2Sb2S6 (2) (tepa = tetraethylenepentamine) utilizing transition metal Zn by band gap optimization strategy in the visible region. Both compounds exhibited distinct zero-dimensional cluster structures, with transition metal complex cations acting as structure-directing agents. A comprehensive analysis of the electronic structure, band gap, and photocurrent response of these crystals was undertaken, revealing significantly enhanced photocatalytic properties compared to preceding studies. This research underscores the potential of antimony chalcogenides in the realm of photoelectric properties and promotes the applications of chalcogenides.

Syntheses, crystal structure, and photoelectric properties of two selenoantimonates A-Zn-Sb-Se (A = Rb and Cs).

Metal chalcogenides, as a new class of semiconductor materials, have a broad range of applications in synthetic chemistry due to their rich structures and excellent properties. We have synthesized two selenoantimonates A4Zn2Sb2Se7 [A = Rb(1), Cs(2)] under solvothermal conditions in the visible region using a band gap optimization strategy with alkali metals as structure-directing agents. Compounds 1 and 2 have a two-dimensional layered structure consisting of charge-balanced Rb+(1) or Cs+(2) cations and [Zn2Sb2Se7]4- anions with novel 20-membered rings (20-MR) [Zn6Sb4Se10] with an aperture of 5.6949 × 13.7741 Å2 formed in the middle. Furthermore, we have investigated the crystal structure, band gap, photoelectronic properties, and energy band structure.

A Study on the Materials Used in Ancient Wooden Architectural Paintings at DaZhong Gate in Confucius Temple, Qufu, Shandong, China.

This study analyzes the pigments and binders used in the painted wooden structure of DaZhong Gate in the Confucius Temple in Qufu, Shandong Province, China. Five samples were collected from the building and analyzed using techniques such as polarized light microscopy (PLM), energy-dispersive X-ray spectroscopy (EDX), micro-Raman spectroscopy (m-RS), and Fourier-transform infrared spectroscopy (FT-IR). The findings reveal that the red, yellow, green, and blue pigments are identified as lead red, lead chromate yellow, emerald green, and ultramarine, respectively. The white pigment is determined to be a combination of chalk and lead white or anglesite. Considering the production period of the yellow and green pigments, it is inferred that architectural paintings underwent restoration or repainting during the late Qing Dynasty. The analysis of the binder in the pigment using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) reveals that the binder employed is a protein-based glue. Additionally, the detected presence of Heat-bodied tung oil suggests a potential connection to traditional Chinese painting techniques on wooden surfaces. This discovery not only contributes to the historical research of the Confucius Temple but also provides crucial data for the conservation and restoration efforts of this culturally significant heritage site.

Halogen engineering of organic-inorganic hybrid perovskites displaying nonlinear optical, fluorescence properties and phase transition.

In order to meet the needs of social development, increasing research attention has been paid to multifunctional molecular-based phase-transition materials. The traditional phase-transition materials with a single functional property can be transformed into magnificent ones by adding additional functional properties-for instance photoluminescence and magnetic order- because having two or more functional properties simultaneously greatly broadens the fields of their applications. At present, there are very few multifunctional phase-transition materials showing excellent performance, and the crystal structure design and performance optimization of materials still need to be studied in depth. Herein, we report the development of two organic-inorganic hybrid materials: (MBA)2ZnI4 (1, MBA = 4-methoxybenzylammonium) with switchable dielectricity and a high phase-transition temperature (Tc = 359.55 K), and (MBA)2ZnBr4 (2) with green luminescence (λexc = 314 nm) and nonlinear optical properties (0.75× KDP). A two-dimensional (2D) fingerprint analysis of the Hirshfeld surface plots revealed a significant difference between the hydrogen-bonding interaction before the phase transition and that afterwards. The two compounds were further verified, from energy band structure calculations, to be direct-band-gap semiconductors. In conclusion, this work has provided a viable strategy, involving the application of chemical modifications, for designing various functional materials.

A Study on the Materials Used in the Ancient Architectural Paintings from the Qing Dynasty Tibetan Buddhist Monastery of Puren, China.

Situated in the village of Lama Temple on the eastern bank of the Wulie River in Chengde, Puren Temple stands as one of the few remaining royal temples of great importance from the Kangxi era (1662-1722 AD). This ancient edifice has greatly contributed to the advancement of our comprehension regarding the art of royal temple painting. The present study undertakes a comprehensive analysis and identification of nine samples obtained from the beams and ceiling paintings within the main hall of Puren Temple. Furthermore, a systematic examination of their mineral pigments and adhesives is conducted. The findings from polarized light microscopy (PLM), energy-type X-ray fluorescence spectrometer (ED-XRF), micro-Raman spectroscopy (m-RS), and X-ray diffractometer (XRD) analyses reveal that the pigments present in the main hall beams of Puren Temple are cinnabar, lead white, lapis lazuli, and lime green, while the pigments in the ceiling paintings consist of cinnabar, staghorn, lead white, lapis lazuli, and lime green. The use of animal glue as a binder for these pigments on both the main hall beams and ceiling paintings is confirmed via pyrolysis-gas chromatography-mass spectrometry (Py-Gc/Ms) results. These findings hold significant implications for the future restoration of Puren Temple, as they provide valuable guidance for the selection of appropriate restoration materials.

Nicotinic acid bromide: a simple organic salt optical-electrical ferroelastic with high Tc.

A new ferroelastic organic salt nicotinic acid bromide (N-Br) was connected by hydrogen bonding with nicotinic acid cations via a halogen substitution strategy. It exhibits a ferroelastic phase transition from P21/m to P1̄ with 2/mF1̄ Aizu notation with a high Curie temperature (Tc) of 402 K. Moreover, optical regulation from blue light to white light was achieved by halogen substitution.

Strong Photocurrent Response of Selenoarsenates With Different Transition Metal Complexes as Structure-Directing Agents.

Four selenoarsenates with different transition-metal complexes [Co(tren)2H]AsSe4 [tren = tris(2-aminoethyl)amine] (1); [Ni2(dien)4](As2Se5) (dien = diethylenetriamine) (2); [Zn(tren)]2(As2Se5) (3) and [Mn(tren)]2(As2Se5) (4) were solvothermally synthesized in a mixed solvent of organic amine and alcohol solution. The compounds 1-4 have pyramidal/tetrahedral structures (AsSe3/AsSe4), and contain transition metal (Co2+, Ni2+, Zn2+ and Mn2+) complex that form distinct zero-dimensional (0-D) clusters. Arsenic atoms form a tetrahedron in compounds 1 and 2; 1 consists of discrete tetrahedral (AsSe4) and transition metal complex [Co(tren)2]2+; 2 is composed of an anion [As2Se5]4- cluster and transition metal complex [Ni(dien)2]2+. In compounds 3 and 4, arsenic atom forms a pyramidal AsSe3 and the two pyramidal AsSe3 share a corner connection to form a dimer [As2Se5]4-; 3 is characterized as a cluster consisting of two unsaturated [Zn(tren)]2+ caiton linked by a dimer (As2Se5)4- linkage; in 4, unsaturated [Mn(tren)]2+ caiton is linked to two trigonal-bipyramidal [Mn(tren)]Se via dimer (As2Se5)4- to form [Mn(tren)]4[As4Se10] cluster. To our knowledge, [Zn(tren)]2(As2Se5) (3) is the first zinc selenoarsenate containing the (As2Se5)4- anion type. Furthermore, the Mn2+ ions adopt a trigonal-biyramidal (five-coordinate) and octahedral (six-coordinate) environment. Adding K2CO3/Cs2CO3 to the synthesis system is necessary and may act as a mineralizer. Several properties of compounds 1-4 have been characterized in our studies, in particular their strong photocurrent response characteristics under visible light irradiation.

Shade Delayed Flowering Phenology and Decreased Reproductive Growth of Medicago sativa L.

Alfalfa (Medicago sativa L.) is an important forage in intercropping or rotation ecosystem, and shading is the principal limiting factor for its growth under the crop or forest. Agronomic studies showed that shading would systematically reduce the biomass of alfalfa. However, little is known about the reproduction of alfalfa under shading conditions. In order to study the effect of shading on the reproductive characteristics of alfalfa, two alfalfa cultivars ("Victoria" and "Eureka") were used to study the effect of shading levels (full light, 56.4% shade, and 78.7% shade) on alfalfa flowering phenology, pollen viability, stigma receptivity, and seed quality. Results showed that shading delayed flowering phenology, shortened the flowering stage, faded the flower colors, and significantly reduced pollen viability, stigma receptivity, the number of flowers, quantity, and quality of seeds. Under shading conditions, seed yield per plant was obviously positively correlated with germination potential, germination rate, pollen viability, and 1,000-seed weight. The number of flower buds, pollen viability, 1,000-seed weight, and germination rate had the greatest positive direct impact on seed yield per plant. Our findings suggested that delayed flowering and reducing reproduction growth were important strategies for alfalfa to cope with shading and pollen viability was the key bottleneck for the success of alfalfa reproduction under shading. However, given that alfalfa is a perennial vegetative-harvest forage, delaying flowering in a weak light environment was beneficial to maintain the high aboveground biomass of alfalfa. Therefore, this should be taken into account when breeding alfalfa cultivars suitable for intercropping. Future research should further reveal the genetic and molecular mechanism of delayed flowering regulating the accumulation and distribution of assimilates between vegetative and reproductive organs of alfalfa under shading, so as to provide a theoretical basis for breeding of shade-tolerant alfalfa cultivars.