Heterogeneous Interface Design with Oxygen Vacancy-Rich Assistance High-Capacity Titanium-Based Oxide Anode Materials for Sodium-Ion Batteries.

Researchers are paying more attention to sodium-ion batteries (SIBs) because of their abundant supply of sodium resources and affordable price. TiO2 offers excellent safety and a long lifespan as an anode material for SIBs. However, the process kinetics is slow due to its limited Na+ storage efficiency, weak conductivity, and irreversible Na+ capture. In order to address these issues, this review uses a mix of the template approach and the double-hydrolysis method to manage the structure and diffusion of TiO2-based anode materials by synthesizing FeTiO3/TiO2 heterostructured double-shell microspheres (FTO). Through the built-in electric field effect caused by their heterostructures, FTO materials improve reaction kinetics, boost electronic conductivity, and lower the diffusion energy barrier of Na+. Their distinctive double-shell structure can increase electrolyte infiltration, shorten the diffusion distance between ions and electrons, and accommodate volume expansion during cycling. Furthermore, the irreversible capture of Na+ and the unfavorable interactions between the surface active site and electrolyte can be successfully inhibited by FTO heterostructures. FTO has an exceptionally high capacity (reaching 362.7 mA h g-1 after 60 cycles at 20 mA g-1) and excellent cycle stability (with a decay rate of 0.0061% after 1000 cycles at 2 A g-1). The strategy of constructing heterogeneous interfaces assists with high-performance SIB anode design.

Chiral three-dimensional organic-inorganic lead iodide hybrid semiconductors.

Chiral hybrid metal halides (CHMHs) have received a considerable amount of attention in chiroptoelectronics, spintronics, and ferroelectrics due to their superior optoelectrical properties and structural flexibility. Owing to limitations in synthesis, the theoretical prediction of room-temperature stable chiral three-dimensional (3D) CHFClNH3PbI3 has not been successfully prepared, and the optoelectronic properties of such structures cannot be studied. Herein, we have successfully constructed two pairs of chiral 3D lead iodide hybrids (R/S/Rac-3AEP)Pb2I6 (3R/S/Rac, 3AEP = 3-(1-aminoethyl)pyridin-1-ium) and (R/S/Rac-2AEP)Pb2I6 (2R/S/Rac, 2AEP = 2-(1-aminoethyl)pyridin-1-ium) through chiral introduction and ortho substitution strategies, and obtained bulk single crystals of 3R/S/Rac. The 3R/S exhibits optical activity and bulk photovoltaic effect induced by chirality. The 3R crystal device exhibits stable circularly polarized light performance at 565 nm with a maximum anisotropy factor of 0.07, responsivity of 0.25 A W-1, and detectivity of 3.4 × 1012 jones. This study provides new insights into the synthesis of chiral 3D lead halide hybrids and the development of chiral electronic devices.

Rational Design of 2D Metal Halide Perovskites with Low Congruent Melting Temperature and Large Melt-Processable Window.

Metal halide perovskites (MHPs) have garnered significant attention due to their distinctive optical and electronic properties, coupled with excellent processability. However, the thermal characteristics of these materials are often overlooked, which can be harnessed to cater to diverse application scenarios. We showcase the efficacy of lowering the congruent melting temperature (Tm) of layered 2D MHPs by employing a strategy that involves the modification of flexible alkylammonium through N-methylation and I-substitution. Structural-property analysis reveals that the N-methylation and I-substitution play pivotal roles in reducing hydrogen bond interactions between the organic components and inorganic parts, lowering the rotational symmetry number of the cation and restricting the residual motion of the cations. Additional I···I interactions enhance intermolecular interactions and lead to improved molten stability, as evidenced by a higher viscosity. The 2D MHPs discussed in this study exhibit low Tm and wide melt-processable windows, e.g., (DMIPA)2PbI4 showcasing a low Tm of 98 °C and large melt-processable window of 145 °C. The efficacy of the strategy was further validated when applied to bromine-substituted 2D MHPs. Lowering the Tm and enhancing the molten stability of the MHPs hold great promise for various applications, including glass formation, preparation of high-quality films for photodetection, and fabrication of flexible devices.

Room-Temperature Anisotropic Actuation Driven by a Synergistic Order-Disorder and Displacive Phase Transition in a Ferroelectric Crystal.

Actuating materials convert different forms of energy into mechanical responses. To satisfy various application scenarios, they are desired to have rich categories, novel functionalities, clear structure-property relationships, fast responses, and, in particular, giant and reversible shape changes. Herein, we report a phase transition-driven ferroelectric crystal, (rac-3-HOPD)PbI3 (3-HOPD = 3-hydroxypiperidine cation), showing intriguingly large and anisotropic room-temperature actuating behaviors. The crystal consists of rigid one-dimensional [PbI3] anionic chains running along the a-axis and discrete disk-like cations loosely wrapping around the chains, leaving room for anisotropic shape changes in both the b- and c-axes. The shape change is switched by a ferroelectric phase transition occurring at around room temperature (294 K), driven by the exceptionally synergistic order-disorder and displacive phase transition. The rotation of the cations exerts internal pressure on the stacking structure to trigger an exceptionally large displacement of the inorganic chains, corresponding to a crystal lattice transformation with length changes of +24.6% and -17.5% along the b- and c-axis, respectively. Single crystal-based prototype devices of circuit switches and elevators have been fabricated by exploiting the unconventional negative temperature-dependent actuating behaviors. This work provides a new model for the development of multifunctional mechanically responsive materials.

Tuning ferroelectric phase transition temperature by enantiomer fraction.

Tuning phase transition temperature is one of the central issues in phase transition materials. Herein, we report a case study of using enantiomer fraction engineering as a promising strategy to tune the Curie temperature (TC) and related properties of ferroelectrics. A series of metal-halide perovskite ferroelectrics (S-3AMP)x(R-3AMP)1-xPbBr4 was synthesized where 3AMP is the 3-(aminomethyl)piperidine divalent cation and enantiomer fraction x varies between 0 and 1 (0 and 1 = enantiomers; 0.5 = racemate). With the change of the enantiomer fraction, the TC, second-harmonic generation intensity, degree of circular polarization of photoluminescence, and photoluminescence intensity of the materials have been tuned. Particularly, when x = 0.70 - 1, a continuously linear tuning of the TC is achieved, showing a tunable temperature range of about 73 K. This strategy provides an effective means and insights for regulating the phase transition temperature and chiroptical properties of functional materials.

Enabling Further Organic Electrolyte Infiltration of Cellulose-Based Separators via Defect-Rich Polypyrrole Modification for High Sodium Ion Transport in Sodium Metal Batteries.

Sodium metal batteries (SMBs) have high-density and cost-effective characteristics as one of the energy storage systems, but uncontrollable dendrite growth and poor rate performance still hinder their practical applications. Herein, a nitrogen-rich modified cellulose separator with released abundant ion transport tunnels in organic electrolyte was synthesized by in situ polymerization of polypyrrole, which is based on the high permeability of cellulose in aqueous solution and the interfacial interaction between cellulose and polypyrrole. Meanwhile, the introduction of abundant structural defects such as branch chains, oxygen-containing functional groups, and imine-like structure to disrupt polypyrrole conjugation enables the utilization of conductive polymers in composite separator applications. With the electrolyte affinity surface on, the modified separator exhibits reinforced electrolyte uptake (254%) and extended electrolyte wettability, thereby leading to accelerated ionic conductivity (2.77 mS cm-1) and homogeneous sodium deposition by facilitating the establishment of additional pathways for ion transport. Benefiting from nitrogen-rich groups, the polypyrrole-modified separator demonstrates selective Na+ transport by the data of improved Na+ transference number (0.62). Owing to the above advantages, the battery assembled with the modified separators exhibits outstanding rate performance and prominent capacity retention two times that of the pristine cellulose separator at a high current density under the condition of fluorine-free electrolyte.

Halogen Substitution Regulates High Temperature Dielectric Switch in Lead-Free Chiral Hybrid Perovskites.

Hybrid metal halides (HMHs) based phase transition materials have received widespread attention due to their excellent performance and potential applications in energy harvesting, optoelectronics, ferroics, and actuators. Nevertheless, effectively regulating the properties of phase transitions is still a thorny problem. In this work, two chiral lead-free HMHs (R-3FP)2 SbCl5 (1; 3FP=3-fluoropyrrolidinium) and (R-3FP)2 SbBr5 (2) were synthesized. By replacing the halide ions in the inorganic skeleton, the phase transition temperature of 2 changes with an increase of about 20 K, compared with 1. Meanwhile, both compounds display reversible dielectric switching properties. Through crystal structure analysis and Hirshfeld surface analysis, their phase transitions are ascribed to the disorder of the cations and deformation of the inorganic chains.

A Two-Dimensional Hybrid Lead Bromide Ferroelectric Semiconductor with an Out-of-Plane Polarization.

A two-dimensional (2D) organic-inorganic hybrid perovskite (OIHP) material with out-of-plane ferroelectricity is the key to the miniaturization of vertical-sandwich-type ferroelectric optoelectronic devices. However, 2D OIHP ferroelectrics with out-of-plane polarization are still scarce, and effective design strategies are lacking. Herein, we report a novel 2D Dion-Jacobson perovskite ferroelectric semiconductor synthesized by a rigid-to-flexible cationic tailoring strategy, achieving an out-of-plane polarization of 1.7 µC/cm2 and high photoresponse. Integrating out-of-plane ferroelectricity with excellent photoelectric properties affords a promising platform to investigate ferroelectricity-related effects in vertical optoelectronic devices.

Circularly Polarized Luminescence in Zero-Dimensional Antimony Halides: Structural Distortion Controlled Luminescence Thermometer.

Materials emitting circularly polarized luminescence (CPL) have been intensively studied for their promising applications in various fields. However, developing tunable and responsive CPL materials in a wide wavelength range remains a great challenge. Here, a pair of chiral (R,R/S,S-DCDA)3Sb2Cl12 (DCDA = dimethyl-1,2-cyclohexanediamine divalent cation) shows efficient broadband yellow emission with a photoluminescence (PL) quantum yield of 27.6% with a CPL asymmetry factor of 3 × 10-3. The associated chiroptical activity is attributed to the efficient chiral transfer as well as the self-trapped exciton emission originating from the large distortion of the inorganic blocks. Notably, (R,R/S,S-DCDA)3Sb2Cl12 exhibits a large red-shift emission exceeding 100 nm upon lowering temperature. An excellent linear correlation of the PL wavelength on temperature indicates that the compounds can be used as PL thermometers, which originates from a temperature-dependent linear structural distortion of the [SbCl6] emitter. This work inspires the potential utilization of CPL-emitting materials as responsive light sources.

Photoassisted Electrochemical Hydrogen Evolution Reaction of MFe2O4@Ultrathin Black Phosphorus Amorphous-Crystalline Interface.

Exploring highly active, stable, and low-cost catalysts for photoelectrochemical hydrogen evolution reaction (PE-HER) is vital in the field of energy conversion. Herein, we construct a new amorphous crystalline interface that amorphous iron-based spinel oxide (A-MFe2O4 (M = Ni, Co, Zn)) is uniformly anchored on the crystalline exfoliated black phosphorus (C-EBP) nanosheets via electrochemical and solvothermal strategies. Among these A-MFe2O4@C-EBP catalysts, more oxygen defects of A-NiFe2O4@C-EBP interface provide a larger effective electrochemical active area of 32.33 mF cm-2 as well as a turnover frequency of 0.44 s-1 and allow for an optimum equilibrium of the hydrogen-containing adsorption intermediates. Furthermore, A-NiFe2O4@C-EBP exhibits significant PE-HER performance with an overpotential of 42 mV at 10 mA cm-2 under visible-light irradiation. Density functional theory (DFT) calculations show that the amorphous-crystalline composite structure causes a large number of oxygen defects enhancing the intrinsic activity of A-NiFe2O4@C-EBP, which A-NiFe2O4@C-EBP significantly improves its adsorption capacity for H* for HER and has the lowest Gibbs free energy change for HER. This study not only provides a superior multifunctional amorphous-crystalline interface catalysts but also helps to understand the catalytic mechanism of PE-HER.

Near-room-temperature martensitic actuation profited from one-dimensional hybrid perovskite structure.

Martensitic transformation, usually accompanied by ferroelastic and thermoelastic behaviors, is an interesting and useful mechanical-related property upon external stimuli. For molecular crystals, however, martensitic systems to show reversible stimuli-actuation behaviors are still limited because of a lack of designability and frequent crystal collapse due to large stress releases during the transformations. Here, a one-dimensional hybrid perovskite semiconductor (NMEA)PbI3 (NMEA = N-methylethylammonium) was prepared by following a dimensionality reduction design principle. The crystal undergoes reversible ferroelastic and thermoelastic martensitic transformations, which are attributed to weak intermolecular interactions among the chains that easily trigger the interchain shearing movement. The actuation behavior occurring during the phase transition is very close to room temperature and demonstrated to behave as a mechanical actuator for switching. This work provides an effective approach to designing molecular actuators with promising applications in next-generation intelligence devices.

Correction: Eliciting an immune hot tumor niche with biomimetic drug-based multi-functional nanohybrids augments immune checkpoint blockade-based breast cancer therapy.

Correction for 'Eliciting an immune hot tumor niche with biomimetic drug-based multi-functional nanohybrids augments immune checkpoint blockade-based breast cancer therapy' by Wei Du et al., Nanoscale, 2020, 12, 3317-3329, https://doi.org/10.1039/C9NR09835F.

[(4AMTP)PbBr2]2PbBr4: a Nontypical Cation-Coordinated Perovskite Showing Deep-Blue Emissions and Blue-Light Photoelectric Response.

Metal-halide perovskites have been extensively investigated due to their fascinating structural diversity and outstanding optoelectronic properties. We report the photoluminescence and photoelectric response behavior of a nontypical Dion-Jacobson perovskite [(4AMTP)PbBr2]2PbBr4 (4AMTP = 4-aminomethyltetrahydropyran cation), featuring neutral PbBr2 layers incorporated into the cationic layers between the anionic [PbBr4]2- layers. A 4AMTP-coordinated PbBr2 unit constitutes the unique nontypical dication layer. The seven-coordinated PbBr6O unit forms a largely distorted decahedron with a short distance from the inorganic [PbBr4]2- layer. The photoluminescence behavior of [(4AMTP)PbBr2]2PbBr4 shows crystal size dependence. Larger crystals show purplish-blue emission with two peaks at 414 and 431 nm, whereas smaller grain size (<50 µm) crystals demonstrate a single emission peak at 425 nm. Meanwhile, it shows a blue-light photoelectric response under the illumination of 405 nm with an on/off ratio of 175 for single-crystal devices and 97 for thin-film devices. The photoresponse performance is proportional to the molar extinction coefficient of the absorption band edge.

Chiral Rashba Ferroelectrics for Circularly Polarized Light Detection.

Direct detection of circularly polarized light (CPL) is a challenging task due to limited materials and ambiguous structure-property relationships that lead to low distinguishability of the light helicities. Perovskite ferroelectric semiconductors incorporating chirality provide new opportunities in dealing with this issue. Herein, a pair of 2D chiral perovskite ferroelectrics is reported, which have enhanced CPL detection performance due to interplays among lattice, photon, charge, spin, and orbit. The chirality-transfer-induced chiral&polar ferroelectric phase enhances the asymmetric nature of the photoactive sublattice and achieves a switchable self-powered detection via the bulk photovoltaic effect. The single-crystal-based device exhibits a CPL-sensitive detection performance under 430 nm with an asymmetric factor of 0.20 for left- and right-CPL differentiation, about two times that of the pure chiral counterparts. The enhanced CPL detection performance is ascribed to the Rashba-Dresselhaus effect that originates from the bulk inversion asymmetry and strong spin-orbit coupling, shown with a large Rashba coefficient, which is demonstrated by density functional theory calculation and circularly polarized light excited photoluminescence measurement. These results provide new perspectives on chiral Rashba ferroelectric semiconductors for direct CPL detection and ferroelectrics-based chiroptics and spintronics.

cis/trans-Isomeric Cation Tuning Photoluminescence and Photodetection in 2D Perovskites.

Cationic components in the organic-inorganic hybrid perovskites (OIHPs) play an important role in the arrangement and tilting of the inorganic part that is responsible for semiconducting, luminescent, and photoelectronic properties. Herein, we report two 2D OIHP compounds, (cis-4ACHO)2(H3OBr)PbBr4 (1) and (trans-4ACHO)2(H3OCl)PbBr4 (2) (4ACHO = 4-aminocyclohexanol), showing both photoluminescence (PL) and photodetection (PD) that are tuned by the cis- and trans configurational isomerism of 4ACHO. Crystals of 1 and 2 exhibit similar packing structures but with different crystallographic symmetries. Compound 2 displays a broadband white-light emission with a higher PL efficiency (6.6%) than 1 (2.1%) that emits narrowband blue light while the PD property of 1 is better than 2 with a higher on/off ratio under the same conditions. The PL and PD of the two compounds show a seesaw relationship, which provides a new perspective for understanding the PL and PD properties in OIHPs.

Induction of Bone Remodeling by Raloxifene-Doped Iron Oxide Functionalized with Hydroxyapatite to Accelerate Fracture Healing.

Repairing fractures in the presence of infection is a major challenge that is currently declining using nanotechnology. By producing iron oxide nanoparticles (NPs) containing hydroxyapatite and Raloxifene (R-IONPs-HA), this study tries to target drug delivery, control infection and promotion of the cells proliferation/differentiation to repair damaged tissue. After the production of R-IONPs-HA through co-precipitation, the physicochemical features of the NPs were considered by SEM, TEM, DLS and XRD methods, and the possibility of drug release. The effect of R-IONPs-HA on MC3T3-E1 cell proliferation/differentiation was determined by CCK-assay and microscopic observations. Also, Gram-negative and -positive bacteria were applied to evaluate the antibacterial activity. Finally, cell differentiation biomarkers like an ALP, OCN, and RUNX-2 genes were examined by real time (RT)-PCR. The results showed that R-IONPs-HA was spherical with dimensions of 98.1 ± 1.17 nm. In addition, the results of Zeta and XRD confirmed the loading HA and R on IONPs. Also, the release rate of R and HA in 64 h with pH 6 reached 61.4 and 30.4%, respectively. The anti-bacterial activity of R-IONPs-HA on Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa bacteria showed a significant reduction in infection. Also, MC3T3-E1 cells showed greater proliferation and differentiation by R-IONPs-HA compared to other groups. Increased expression of ossification genes such as OCN, and RUNX-2 confirmed this claim. Finally, R-IONPs-HA with good biocompatibility, antibacterial activity and ossification induction has great potential to repair bone fractures and prevent infection.

Synthesis of Co2-xNixO2 (0 < x < 1.0) hexagonal nanostructures as efficient bifunctional electrocatalysts for overall water splitting.

Designing low-cost and high-performance bifunctional electrocatalysts towards hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is vitally important for water splitting. Herein, we synthesize Co2-xNixO2 (0 < x < 1.0) hexagonal nanosheets with different Co/Ni molar ratios via a facile coprecipitation process followed by calcination under an Ar atmosphere. Changing the Co/Ni molar ratios of the Co2-xNixO2 products is found to have a momentous influence on the microstructures, specific surface areas and electrocatalytic performances. At a Co/Ni molar ratio of 0.6, the Co1.4Ni0.6O2 nanosheet exhibits the largest specific surface area of 60.63 m2 g-1, the best OER with an onset overpotential of 278.5 mV, and HER of 72.8 mV as a bifunctional electrocatalyst. Meanwhile, the minimum Tafel slope is 113.6 mV dec-1 for OER and 77.4 mV dec-1 for HER. The Co1.4Ni0.6O2 nanosheet has excellent OER and HER activity at 0.1 mg cm-2 trace loading. Moreover, we construct an overall water splitting cell using the Co1.4Ni0.6O2 bifunctional electrocatalyst in a two-electrode system to further demonstrate the practical application, which needs a cell voltage of 1.75 V at a current density of 10 mA cm-2 and exhibits great long-term stability. These results provide an efficient strategy for the rational design of Co-based oxides towards bifunctional overall water electrocatalysts.

In Situ Mannosylated Nanotrinity-Mediated Macrophage Remodeling Combats Candida albicans Infection.

Deep Candida albicans infection is one of the major causes of death in immunosuppressed hosts. Remodeling macrophages to phenotype M1 can decrease fungus burden and facilitate combating C. albicans under an immunosuppressive state. In this study, a nanotrinity was exploited to direct fungicidal macrophage polarization by leveraging the regulation pathways in macrophage redifferentiation. Conventional chemotherapeutic imatinib, which can abrogate M2 macrophage polarization via "shutting off" the STAT6 phosphorylation pathway, was encapsulated in biodegradable polymeric nanoparticles. In house-customized dual functional mannosylated chitosan oligosaccharides were then coated on the surface of the imatinib-laden nanoparticles, and thus, a mannosylated nanotrinity was achieved with ternary functions for macrophage remodeling: (i) imatinib-blocked STAT6 phosphorylation pathway for decreasing M2 macrophage population; (ii) chitosan oligosaccharides-mediated TLR-4 pathway activation that could promote macrophage redifferentiation to M1 phenotype; (iii) mannose motif-enhanced macrophage targeting. After physiochemical characterization, regulatory effects of the mannosylated nanotrinity on macrophages and the anti-C. albicans efficacy were evaluated at the cellular level and animal level, respectively. The results demonstrated that our mannosylated nanotrinity could efficiently induce macrophage polarization toward the M1 phenotype, decrease M2 phenotype production, and markedly lessen fungus burden and increased the median survival time of mice infected with C. albicans. Therefore, the mannosylated nanotrinity developed in this study could significantly induce macrophage remodeling in situ by the two-pronged process, "turning on" M1 phenotype polarization meanwhile "shutting off" M2 phenotype polarization, and thus allowed to eradicate C. albicans infection.

Eliciting an immune hot tumor niche with biomimetic drug-based multi-functional nanohybrids augments immune checkpoint blockade-based breast cancer therapy.

Immune checkpoint blockade (ICB) has emerged as one of the breakthrough approaches for tumor immunotherapy. However, known as an immune "cold" tumor, breast cancer harbors an immunosuppressive tumor niche that compromises ICB-based therapy. Chemoimmunotherapy combines a chemotherapeutic with an immune-modulating agent, representing a promising tactic to combat cancers, while the lack of effectively targeted co-delivery strategy is one of the main obstacles to achieve the synergistic utilization. Herein, self-assembled PEGylated pure drug-based nanohybrids (DNH) were created, which could evoke immunogenic cell death (ICD), aiding ICB-based immunotherapy by controlling the spatiotemporal release of oxaliplatin (OXA) and small molecular inhibitor 1-methyl-d-tryptophan (1-MT). Furthermore, biomimetic functionalization was exploited by nature killer cell membrane camouflaging to target cancerous cells as well as by elicit immune response through inducing M1 macrophage polarization. The drug release profiles of the nanosystem were investigated in the presence of low pH and intracellular reductants. Systemic in vivo bio-behaviors were evaluated via pharmacokinetics and biodistribution. As an "all-in-one" pure drug-based codelivery system, our biomimetic nanoplatform possessed multiple immunomodulation functions, which markedly aided in increasing the frequency of immune responders and generate an immune "hot" breast tumor niche, and eventually allowed to boost breast cancer therapy.