Crystal Distortion Research Articles

First-Principles Study on the Electronic Structure and Optical Properties of BiOIO3 Doped with As, Se, and Te

This study calculates the electronic structure and optical properties of intrinsic BiOIO3 and X-BiOIO3 (X = As, Se, or Te) using PBE (Perdew–Burke–Ernzerhof) and MBJ (Modified Becke–Johnson) functionals based on density functional theory, with MBJ showing better correlation with experimental values. The X-BiOIO3 systems exhibit relative stability under MBJ potential and show crystal lattice distortion compared to intrinsic BiOIO3, creating localized potential differences that enhance polarization and adjust the bandgap. Doping reduces the bandwidth and increases energy level density, promoting electron transitions. Consequently, based on the computational results presented in this paper, it can be inferred that both BiOIO3 and X-BiOIO3 facilitate water hydrolysis and oxygen generation due to their favorable energy band positions. Notably, Se-BiOIO3 exhibits the highest visible light absorption capacity, which may enhance photocatalytic efficiency by strengthening the built-in electric field and promoting charge carrier generation.

Efficient Emission of Lanthanide Ion in Double Perovskite Nanocrystals Enabled by Synergistic Effect of Energy Level Modulation and Crystal‐Field Engineering

AbstractTrivalent lanthanide (Ln3+) ions with ladderlike 4f energy levels, as dopants, can endow luminescent matrix with more diverse optoelectronic properties, and a wider application. However, their luminescent intensity is usually limited by the parity forbidden transition rule and the energy level mismatch between the host and dopant. Herein, Ln3+ ions doped Cs2Na1‐xKxY0.97Sb0.03Cl6 nanocrystals (NCs) are prepared, and the photoluminescence quantum yields of all samples with visible and near‐infrared emissions have surprisingly reached over 50%, therein, the value of Tb3+ doped Cs2Na0.6K0.4Y0.97Sb0.03Cl6 NCs is dramatically up to 83.3%, which is a new breakthrough in the field of lead‐free perovskite NCs. From the first principles calculations, crystal structure, and spectroscopic analysis, this benefits from the synergistic effect of deformation energy levels provided by Sb3+ ions doping and crystal field environment distortion induced K+ ions doping. That is, the localized distortion of the crystal field induced by K+ ions doping causes energy level splitting of Sb3+ ions, resulting in more effective energy transfer efficiency from the host to Ln3+ ions, simultaneously introducing opposite odd parity, and breaking the forbidden transition rule, promoting luminescence intensity of Ln3+ ions. This work will open a route to develop efficient Ln3+ ions doped luminescent materials.

Study of Variability Phenomena in Direct Energy Deposition of Nickel-Based Superalloy on Geometric Accuracy and Residual Stress Formation

This paper studies the effect of the direct energy deposition (DED) process parameters varying within 20% on the geometric accuracy and formation of residual stresses in the products. In the course of the study, an experiment was carried out according to Taguchi's L9 plan to fabricate samples by varying the laser travel speed, effective focusing distance, feed rate of metal powder composition, and process pause, which were then compared with the rates of geometry change and crystal lattice distortion. The obtained results were subjected to statistical analysis using correlation, regression and factor analysis to determine the influence and significance of factors. As a result, correlations between the process parameters and sample characteristics were identified. As correlation and factor analysis showed, a change in process factors within 20% does not significantly affect most of the quality parameters, except for the level of residual stresses. Geometric and strain parameters are weakly correlated with each other, but no statistically significant correlations were found between them. The analysis of variance showed that the fusion rate and powder flow rate have the greatest influence on the geometric accuracy parameters. These factors have the most significant statistical influence on the response, indicating the importance of controlling these parameters to achieve high geometry accuracy. Regression analysis allowed to obtain adequate models of residual stress level. It was found that the model for residual stress level by planes (200) is more reliable than the model for residual stress level by crystallographic plane (111). The obtained data allow to optimize the DED process in order to achieve a given geometric accuracy and reduce residual stresses in the manufactured products.

Sodium-Ion Storage in Na4VMn(PO4)3/C Porous Nanorods Electrode.

Na4VMn(PO4)3 (NVMP) is a prospective cathode for sodium-ion batteries (SIBs) due to its low cost and extraordinary structural stability. However, poor conductivity restricts the electrochemical performance of NVMP, which limits its development and application. Herein, carbon-encapsulated NVMP porous nanorods are prepared via a convenient electrospinning method. The prepared one-dimensional (1D) structure can effectively accelerate the transmission rate of electrons, and the porous structure of NVMP/C nanorods can increase the contact area between the electrolyte and electrode material, which can enhance the diffusion rate of sodium ions. Owing to this advantageous nanoarchitecture, the obtained NVMP/C porous nanorods delivered an initial reversible capacity of 90.9 mA h·g-1 at 0.2 C and a discharge capacity of 68.0 mA h g-1 at 5.0 C. NVMP/C can also achieve a good cycling stability with ideal capacity retentions of 90.4% and 89.8% after 800 cycles at 1 and 3 C, respectively. Moreover, even at a temperature of -30 °C at 0.3 C, the discharge capability was up to 40.1% of that at 20 °C, suggesting an impressive low-temperature tolerance. In situ X-ray diffraction demonstrated that there was no crystal distortion of the NVMP/C electrode during charge and discharge. This work can provide a high-performance strategy on modification of polyanion-positive electrode materials for SIBs.

Thermophysical properties of AlxCoCrCuFeNi high entropy alloys

The AlxCoCrCuFeNi (x = 0.25, 0.5, 1, 2) high entropy alloys (HEAs) were prepared by arc melting and spray casting techniques. Their microstructures, hardness, and thermophysical properties such as fusion enthalpy, entropy, thermal diffusion coefficients, thermal expansion coefficients, were investigated. XRD results indicated that AlxCoCrCuFeNi (x = 0.25 and 0.5) alloys were composed of a high-entropy FCC phase and Cu-rich nanophase. As the Al content increased to 1 and 2, the phase structures included the AlNi-rich B2 phase, FeCr-rich A2 phase and Cu-rich nanophase. With the increased Al content, the microstructures of AlxCoCrCuFeNi HEAs transitioned from coarse dendrites to petal-like dendrites, and the grains were continuously refined. Moreover, the Al additions reduced the density whereas increased the Vickers hardness of the alloys. The maximum hardness observed in Al2CoCrCuFeNi HEA was approximately 2.4 times greater than that of the Al0.25CoCrCuFeNi HEA. The thermal diffusion coefficients of alloys initially increased and subsequently decreased as the temperature elevated. The phase transformation induced by Al content was an effective method for rapidly homogenizing the internal temperature of alloys. Furthermore, the crystal structure, elemental segregation, lattice distortion, enthalpy and entropy of fusion, and lattice vibration frequency all mutually affected the thermal diffusion and expansion coefficients of AlxCoCrCuFeNi HEAs.

Enhancing photovoltaic cell design with multilayer sequential neural networks: A study on neodymium-doped ZnO nanoparticles

Multilayer sequential neural networks, a powerful machine learning model, demonstrate the ability to learn intricate relationships between input features and desired outputs. This study focuses on employing such models to design photovoltaic cells. Specifically, neodymium (Nd)-doped ZnO nanoparticles (NPs) were utilized as a photoanode for fabricating dye-sensitized solar cells (DSSCs). A natural dye extracted from Spinacia oleracea was employed, while two types of electrolytes, liquid and gel (polyethylene glycol-based), were used for comparative analysis. Extensive material characterization of the photoanode highlights the impact of Nd content on the physicochemical properties of ZnO. Notably, when the doped photoanode and gel electrolyte were combined, a substantial 110% improvement in power conversion efficiency (PCE) was achieved. Building on these findings, the machine learning model in this research accurately predicts the current-voltage (I-V) curve values for such photoanodes, with an impressive accuracy of 98%. Additionally, the model illuminates the significance of variables like crystal distortion, texture coefficient, and doping concentration, underscoring their importance in the context of photovoltaic cell design.

Synthesis and evaluation of an environmentally friendly phosphorus-free and nitrogen-free polymer as a scale and corrosion inhibitor

Polyepoxysuccinic acid (PESA) was modified by glycidyl (Gly) to obtain a phosphate-free and nitrogen-free polymer (Gly-PESA), and its scale and corrosion inhibition properties were studied.The effects of Gly-PESA concentration, calcium ion concentration and temperature to scale inhibition performance were studied by static scale inhibition method. The corrosion inhibition performance of Gly-PESA was studied by static weight-loss method. The morphology and structure of calcium scale and steel surface were characterized by spectroscopic and microscopic methods. The scale inhibition efficiency of Gly-PESA for CaCO3 and CaSO4 was 98.06% and 92.6%, respectively. Under the same experimental conditions, the scale inhibition effect of Gly-PESA was obviously better than that of PESA. Gly-PESA could effectively inhibit the growth of CaCO3 and CaSO4 crystals and cause their crystal lattice distortion or crystal dispersion. The corrosion inhibition efficiency of Gly-PESA for carbon steel was 78.17%. The adsorption of Gly-PESA on the surface of the steel test piece followed Langmuir adsorption isotherm, and formed a protective film, which increased the corrosion resistance of the steel test piece, thus effectively protecting the steel test piece. Therefore, Gly-PESA was a green scale and corrosion inhibitor, which solved the problem of environmental pollution.

Promoted room temperature NH3 gas sensitivity using interstitial Na dopant and structure distortion in Fe0.2Ni0.8WO4.

The demand for gas-sensing operations with lower electrical power and guaranteed sensitivity has increased over the decades due to worsening indoor air pollution. In this report, we develop room-temperature operational NH3 gas-sensing materials, which are activated through electron doping and crystal structure distortion effect in Fe0.2Ni0.8WO4. The base material, synthesized through solid-state synthesis, involves Fe cations substitutionally located at the Ni sites of the NiWO4 crystal structure and shows no gas-sensing response at room temperature. However, doping Na into the interstitial sites of Fe0.2Ni0.8WO4 activates gas adsorption on the surface via electron donation to the cations. Additionally, the hydrothermal method used to achieve a more than 70-fold increase in the surface area of structure-distorted Na-doped Fe0.2Ni0.8WO4 powder significantly enhances gas sensitivity, resulting in a 4-times increase in NH3 gas response (Rg/Ra). Photoluminescence and XPS results indicate negligible oxygen vacancies, demonstrating that cation contributions are crucial for gas-sensing activities in Na-doped Fe0.2Ni0.8WO4. This suggests the potential for modulating gas sensitivity through carrier concentration and crystal structure distortion. These findings can be applied to the development of room-temperature operational gas-sensing materials based on the cations.

Intense Circular Dichroism and Spin Selectivity in AgBiS2 Nanocrystals by Chiral Ligand Exchange.

Chiral semiconducting nanomaterials offer many potential applications in photodetection, light emission, quantum information, and so on. However, it is difficult to achieve a strong circular dichroism (CD) signal in semiconducting nanocrystals (NCs) due to the complexity of chiral ligand surface engineering and multiple, uncertain mechanisms of chiroptical behavior. Here, a chiral ligand exchange strategy with cysteine on the ternary metal chalcogenide AgBiS2 NCs is developed, and a strong, long-lasting CD signal in the near-UV region is achieved. By carefully optimizing the ligand concentration, the CD peaks are observed at 260 and 320nm, respectively, giving insight into the different ligand binding mechanisms influencing the CD signal of AgBiS2 NCs. Using density-functional theory, a large degree of crystal distortion by the bidentate mode of ligand chelation, and efficient ligand-NC electron transfer, synergistically resulting in the strongest CD signal (g-factor over 10-2) observed in chiral ligand-exchanged semiconductor NCs to date, is demonstrated. To demonstrate the effective chiral properties of these AgBiS2 NCs, a spin-filter device with over 86% efficiency is fabricated. This work represents a considerable leap in the field of chiral semiconductor NCs and points toward their future applications.

Performance variations of light burned magnesia under different calcination parameters and its effects on magnesium oxysulfate cement preparation

This study systematically investigated the impact of different calcination temperatures and holding times on MgO reactivity, as well as the influence of varying reactivity and lattice distortion of MgO on the properties of magnesium oxysulfate cement (MOSC). Results indicated that at temperatures of 700–900℃, magnesite underwent decomposition, resulting in increased lattice distortion, and heightened reactivity. At temperatures of 1000–1100℃, magnesia began sintering, nucleating, and experienced reduced crystal distortion, leading to decreased reactivity. Notably, the appearance of the pseudomorphic mother rock at calcination temperatures of 900℃ and 1000℃ was associated with decreased magnesia reactivity. Moreover, the compressive strength of MOSC prepared using MgO calcined at 900℃ for 6 h increased to 77 MPa after 28 d of air curing. The hydration reactivity and lattice distortion of MgO could be regulated through changing the calcining temperature and holding time, which provided a theoretical basis for the preparation of magnesium oxysulfate cement with excellent mechanical properties.

Degree of Crystal Structure Distortion-Induced Tunable LiGaO2 Long Persistent Luminescence for Optical Information Encryption.

Tunable long persistent luminescence (LPL) phosphor materials have great potential for optoelectronic cryptographic applications. However, the mainstream techniques of modulating LPL generally have the characteristics of complex preparation processes, demanding crystal field environments, or expensive dopant ions, which restrict large-scale commercial application. Herein, we develop a simple, high-efficiency, and low-cost strategy to optimize the LPL of LiGaO2(LGO):Cu2+ by changing the sintering time to regulate the degree of crystal structure distortion. The Cu2+ as charge compensation will substantially enhance the emission intensity of LGO by a factor of 11.02 originating from the appropriate ionic size and coordination mode. Besides, the LPL time of LGO:Cu2+ can be extended effectively to 2 h by adjusting the sintering temperature and time (900 °C@24 h). The extension mechanism is that Li and Ga can be substituted for each other more easily and induce crystal structure distortion due to the special crystal structure of LGO, resulting in an optimal trap concentration in LGO:Cu2+. Thus, our findings provide a simple way to modulate long persistent luminescence and further consider their potential impact on optical information encryption.

A novel dual-function antiscalant carboxymethyl cellulose-graft-protocatechuic acid for efficient scaling and biofouling prevention

Despite antiscalants playing a critical role in desalination and cooling water systems, their potential to support microbial growth pose a significant threat to water treatment processes by promoting biofouling. In this work, a novel dual-function antiscalant carboxymethyl cellulose-graft-protocatechuic acid (CMC-g-PA) was prepared using plant-derived antibacterial protocatechuic acid (PA) and natural polysaccharide cellulose, and its scale inhibition effect on CaSO4 scale and antibacterial performance on Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were evaluated. Results indicated that the inhibition efficiency against CaSO4 scale and the induction time of CaSO4 crystallization process in the presence of CMC-g-PA were remarkably enhanced compared to unmodified CMC. Microscope and XRD characterizations demonstrated significant alterations in the crystal morphology and size of the formed scale using CMC-g-PA as antiscalant. Molecular dynamics (MD) analysis also showed that CMC-g-PA could intensively interact with the crystal plane of CaSO4 with the binding energy reaching 746.73 kcal/mol, thereby affecting crystal growth and causing crystal distortion. Additionally, an obvious inhibitory effect of CMC-g-PA on the growth of E. coli and S. aureus was observed, attributed primarily to the antibacterial activity of the introduced phenolic hydroxyl groups. In short, bio-derived CMC-g-PA, characterized in its environmental-friendliness, antiscaling efficiency and antibacterial activity, holds immense potential for mitigating scaling and biofouling in desalination/cooling water systems.

Enhancement of upconversion luminescence in NaBiF4: Er3+/Yb3+/Lu3+ for temperature detection

Optical thermometer has got lots of attention by virtue of non-contact, fast response speed, high sensitivity, anti-interference ability, which is less affected by the environment. However, most fluorescent thermometers still suffer from low sensitivity. Here, an optical thermometer based on NaBiF4: Er3+/Yb3+/Lu3+ with enhanced upconversion luminescence is reported. The sample emits strong green light of Er3+ under 980 nm laser excitation and with the increase of Lu3+, the whole luminescence intensity of NaBiF4: 2 % Er3+/20 % Yb3+/ 2.5 % Lu3+ is enhanced by about 3 times, which due to local crystal field distortion. Meanwhile, the lifetime of Er3+ is prolonged and the temperature detection performance is also improved with the substitution of Lu3+. The relative sensitivity reaches a maximum of 0.841 % K−1 at 301 K. The results suggest that it is an optical nanothermometer with great potential.

Atomic-scale understanding of microstructural evolution in electrochemical additive manufacturing of metallic nickel

Atomic-level manufacturing is fundamentally concerned with the precise removal, addition, and migration of material at the atomic and close-to-atomic scale (ACS). Tip-based electrochemical deposition, a quintessential ACS electrochemical additive manufacturing technique, offers promising prospects for achieving bottom-up fabrication of metallic micro/nano structures. However, the complex physicochemical reactions involved in electrodes lead to a limited understanding of the mechanisms underlying atomic electrodeposition and structural evolution. For the first time, this study proposes electric double-layer controlled electrochemical kinetics and investigates the effect of direct current (DC) and pulse current (PC) on nickel atomic electrodeposition using molecular dynamics (MD) simulations. The findings reveal that compared to DC electrodeposition, PC electrodeposition results in more orderly deposition morphology, improved surface smoothness, reduced dislocation density, and lower crystal distortion, with these effects being particularly pronounced under low pulse duty ratio conditions. In addition, the pulse frequency significantly influences the morphology and structure of the deposit. The high pulse frequency yields smoother surfaces with local protrusions, while the low frequency favors the formation of orderly and dense structures excepting slightly increased roughness. This study provides critical insights into understanding the microscopic mechanisms of atomic-scale electrodeposition processes and achieving atomically controlled tip-based electrochemical additive manufacturing of micro/nanodevices.

Ti3+-mediated MIL-125(Ti) by metal substitution for boosting photocatalytic N2 fixation

Photocatalysis, which uses sunlight, N2 and H2O to produce NH3, is a more sustainable approach to N2 fixation than the Haber-Bosch process. However, its efficiency is severely limited by the difficulty of activating NN bonds. This work presents metal (M = Cu, Fe, V)-substituted MIL-125(Ti) (MIL-(MTi)) for photocatalytic N2 fixation without using any sacrificial agents. Structural characterizations reveal that the active sites including oxygen vacancies (OV) and Ti3+ species are formed by the resulting crystal distortion due to the partial substitution of Ti4+ by other metal ions (Cu+, Fe2+, V3+) in MIL-125(Ti). MIL-(CuTi) possesses a larger number of OV and Ti3+ compared to MIL-(FeTi) and MIL-(VTi) due to the larger valence difference between Cu+ and Ti4+. These active sites not only promote the adsorption and activation of N2 and H2O, but also facilitate the photogenerated charge mobility. Photogenerated holes oxidize H2O to produce O2 and H+. Photogenerated electrons reduce N2 activated on Ti3+ sites by combining with H+ to form NH4+. Therefore, MIL-(CuTi) shows the highest NH4+ production rate 46.5 µmol·h−1·g−1, which is much higher than that (1.2 µmol·h−1·g−1) of the pristine MIL-125(Ti). This work provides a new insight into rational design for artificial N2 fixation systems by the construction of the active site.

Influence of Nb Doping on the Performance of Oxygen Reduction Reaction on TiO2 in Acidic Environmental

Polymer electrolyte fuel cells (PEFCs) have attracted attention as one of the next-generation power sources that are environmentally friendly. However, the high manufacturer's costs, short service life, and insufficient cell performance are solved to realize widespread commercialization. A non-platinum group metal catalyst is relatively low in cost and highly durable. In particular, the oxides of group 4 and 5 elements were reported to show high oxygen reduction reaction (ORR) activity and durability. Their oxides are considered dominant candidates for the non-platinum group metal catalysts, although they have a fateful flaw that their ORR activity is clearly poorer than traditional platinum-supported carbon catalysts. It was reported that introducing oxygen vacancies and other transition metals into the crystal structure of 4- and 5-group metal oxides effectively enhanced the ORR activity. The active site of 4- and 5-group metal oxides is unclear despite it being well-known that the oxygen vacancies and dopant atoms are related to its ORR activity. It is now indicated that candidates of active site were the oxygen vacancies around the dopant atom and the crystal distortion. However, it is hard to separate their effects because both dopant atoms and oxygen vacancies distort the local crystal structure. On the other hand, identifying the ORR active site leads to obtaining the catalyst design with high ORR activity. We focused on the oxide nanosheet, the simplest structure formed by a six-coordinate octahedral, as the model electrode. The thickness of oxide nanosheets is about 1 nm, and forming a single layer on a substrate is relatively easy. Thus, it was expected that the electron conductivity was guaranteed enough by the tunnel effect. This study employed titanium oxide nanosheets (TiO2ns) as the model catalyst and niobium as a dopant to investigate the effect of dopant atoms on ORR activity. The ratio of Nb/Ti in the prepared model electrode was 0/1, 1/1, and 2/1. In addition, the oxygen vacancies were introduced into all prepared electrodes to study the impact of oxygen vacancies on ORR activity at each Nb/Ti ratio. The thickness of Nb-doped TiO2ns (Nb-TiO2ns) was about 1.2 nm for the 1/1 ratio and slightly thicker for the 0/1 ratio. In contrast, the thickness of the 2/1 ratio of Nb-TiO2ns was about two times thicker than the 1/1 ratio. The thicknesses of Nb-TiO2ns in each ratio were increased by the reduction treatment to introduce the oxygen vacancies. One reason for this thickness increase may be related to the phase transition into the anatase structure. ORR activity was evaluated from the on-set potential of ORR (E ORR) measured at the step scan with 3 minutes step width. E ORR was slightly elevated with Nb doping. The ion radii of Nb and Ti atoms are 3 pm different when it is assumed that both ions are six-coordinated and their valence is Nb5+ and Ti4+. These results showed that the crystal structure distortion probably has a slight but positive effect on ORR activity.After the reduction treatments, the E ORR of the 0/1 ratio of Nb-TiO2ns increased and was the same as that of the 2/1 ratio. The introduction of oxygen vacancies certainly enhanced the ORR activity of the 0/1 ratio of Nb-TiO2ns. The oxygen vacancies are thought to be necessary to enhance the ORR activity, although the reduction condition wasn’t optimized for the Nb-doped samples.From the above results, we consider that the active site is the oxygen vacancy site rather than the crystal distortion site at this time.

(Invited) Phase Engineering for Enhanced Stability of Perovskite Nanowire Optoelectronics

The crystallization of halide perovskites (HPs) into one-dimensional structures has generated considerable research interest for their promising prospects in studying electron transport characteristics and multifunctional nanoscale devices. Various strategies have been developed to achieve in-plane growth of one-dimensional (1D) structures, including epitaxy, capillary-bridge-manipulated graphoepitaxy, and van der Waals epitaxy. Typically, the VLS growth mode, which involves the initial seeding of metallic catalytic nanoparticles to facilitate the process, has realized the out-of-plane and bottom-up synthesis route, opening up a new pathway for the one-dimensional perovskite electronics and optoelectronics.Among many recent advances, Zinc (Zn) has become a significant suppressor of vacancy formation in halide perovskites, establishing its pivotal role in defect engineering for these materials. Herein, we report the Zn-catalyzed vapor-liquid-solid (VLS) route to render black-phase CsPbI3 nanowires operationally stable at room temperature. Based on first-principle calculations, the doped Zn2+ can not only lead to the partial crystal lattice distortion but also reduce the formation energy value from the black phase to the yellow phase, improving the stability of the desired black phase. A series of contrast tests further confirm the stabilization effect of the Zn-doped strategy. Besides, the polarization-sensitive characteristics of black phase CsPbI3 nanowires were revealed. Our work highlights the importance of phase stabilization engineering for CsPbI3 nanowires and their potential applications in anisotropic optoelectronics.

Multi‐Point Collaborative Passivation of Surface Defects for Efficient and Stable Perovskite Solar Cells

AbstractThe inherent defects (lead iodide inversion and iodine vacancy) in perovskites cause non‐radiative recombination and there is also ion migration, decreasing the efficiency and stability of perovskite devices. Eliminating these inherent defects is critical for achieving high‐efficiency perovskite solar cells. Herein, an organic molecule with multiple active sites (4,7‐bromo‐5,6‐fluoro‐2,1,3‐phenylpropyl thiadiazole, M4) is introduced to modify the upper interface of perovskites. When M4 interacts with the perovskite surface, the active bromine (Br) site interacts with lead (Pb) at the surface to repair iodine atomic vacancy defects. The fluorine (F) site of M4 interacts with Pb to correct octahedral crystal lattice distortions and eliminate PbI defects. Additionally, sulfur–iodine (S–I) interactions reduce I–I dimerization and eliminate IPb defects. It is also calculated that the energy level of M4 aligns with the band gap, promoting charge transfer. As a result, the perovskite devices achieve an efficiency of 25.1%, a stabilized power output (SPO) of 25.0%, a voltage of 1.19 V, and a fill factor of 85.2%. The device retains 95% of its initial efficiency after 2000 h of ageing in a nitrogen atmosphere. Thus, multi‐point cooperative passivation of surface defects provides an effective method to improve the efficiency and stability of perovskite solar cells.

Active site modulation in UiO-66(Ce) MOFs by Al3+ doping for boosting photocatalysis

A series of Al3+-doped UiO-66(Ce) MOFs (U(CexAl1−x)) was developed to reveal the roles of metal doping on active site formation and substrate activation in photocatalytic selective transformation of amines to imines. Al3+ doping induced crystal structure distortion to form coordinately unsaturated metal (Al, Ce) sites as Lewis acid sites to chemisorb and activate benzylamine (BA). In situ FTIR revealed that the Al site with stronger acid strength facilitated BA activation. The activation degree of N–H bonds in BA was evaluated by changes of calculated force constant. The intermediate products were confirmed through time-dependent in situ FTIR. The Al3+-doped sample U(Ce0.90Al0.10), the optimal catalyst, showed a significantly increased BA conversion (97.6 %) than that (47.5 %) of undoped sample, which was attributed to enough active sites and the optimal charge mobility. Finally, the present study proposes a synergistic photocatalytic mechanism associated with molecular activation to demonstrate selective oxidation pathways at the molecular level.

Electrically Induced Crystal Field Distortion in a Ferroelectric Perovskite Revealed by Electron Paramagnetic Resonance.

The magnetoelectric material has attracted multidisciplinary interest in the past decade for its potential to accommodate various functions. Especially, the external electric field can drive the quantum behaviors of such materials via the spin-electric coupling effect, with the advantages of high spatial resolution and low energy cost. In this work, the spin-electric coupling effect of Mn2+-doped ferroelectric organic-inorganic hybrid perovskite [(CH3)3NCH2Cl]CdCl3 with a large piezoelectric effect was investigated. The electric field manipulation efficiency for the allowed transitions was determined by the pulsed electron paramagnetic resonance. The orientation-included Hamiltonian of the spin-electric coupling effect was obtained via simulating the angle-dependent electric field modulated continuous-wave electron paramagnetic resonance. The results demonstrate that the applied electric field affects not only the principal values of the zero-field splitting tensor but also its principal axis directions. This work proposes and exemplifies a route to understand the spin-electric coupling effect originating from the crystal field imposed on a spin ion being modified by the applied electric field, which may guide the rational screening and designing of hybrid perovskite ferroelectrics that satisfy the efficiency requirement of electric field manipulation of spins in quantum information applications.