RESUMO
Antiferroelectric materials with an electrocaloric effect (ECE) have been developed as promising candidates for solid-state refrigeration. Despite the great advances in positive ECE, reports on negative ECE remain quite scarce because of its elusive physical mechanism. Here, a giant negative ECE (maximum ΔS â¼ -33.3 J kg-1 K-1 with ΔT â¼ -11.7 K) is demonstrated near room temperature in organometallic perovskite, iBA2EA2Pb3I10 (1, where iBA = isobutylammonium and EA = ethylammonium), which is comparable to the greatest ECE effects reported so far. Moreover, the ECE efficiency ΔS/ΔE (â¼1.85 J cm kg-1 K-1 kV-1) and ΔT/ΔE (â¼0.65 K cm kV-1) are almost 2 orders of magnitude higher than those of classical inorganic ceramic ferroelectrics and organic polymers, such as BaTiO3, SrBi2Ta2O9, Hf1/2Zr1/2O2, and P(VDF-TrFE). As far as we know, this is the first report on negative ECE in organometallic hybrid perovskite ferroelectric. Our experimental measurement combined with the first-principles calculations reveals that electric field-induced antipolar to polar structural transformation results in a large change in dipolar ordering (from 6.5 to 45 µC/cm2 under the ΔE of 18 kV/cm) that is closely related to the entropy change, which plays a key role in generating such giant negative ECE. This discovery of field-induced negative ECE is unprecedented in organometallic perovskite, which sheds light on the exploration of next-generation refrigeration devices with high cooling efficiency.
RESUMO
Two-dimensional (2D) halide perovskites (HPs) are of significant interest to researchers because of their natural structural frameworks and intriguing optoelectronic properties. However, the direct fabrication of ordered mixed-spacer quasi-2D HPs remains challenging. Herein, a synthetic strategy inspired by the principle of supramolecular synthons is employed for the self-assembly of a series of ordered mixed-spacer bilayered HPs. The key innovation involves the introduction of intermolecular hydrogen bonds using a bifunctional 3-aminopropionitrile cation. Three homogeneous n = 2 structures are obtained, with a subtly ordered perovskite connected by two distinct types of organic cation layers, resulting in a recurrent ABAB' stacking sequence. These three compounds exhibit attractive semiconducting properties. Moderate bandgaps in the range of 2.70 to 2.76 eV with an absorption wavelength range of 448-459 nm exhibit excellent photoelectric response. Moreover, the ordered structures facilitate excellent polarization-sensitive photodetection, with an impressive on/off ratio of 103. The response speed ranged from 298 to 381 µs, and the out-of-plane polarization-related dichroism ratio is determined to be 1.19. Such ordered mixed-spacer bilayered perovskites have not been reported. These results enrich the HPs system and play a significant role in the direct assembly of novel perovskites with ordered structures.
RESUMO
2D multilayered organic-inorganic hybrid perovskites (OIHPs) have exhibited bright prospects for high-performance self-driven X-ray detection due to their strong radiation absorption and long carrier transport. However, as an effective tool for self-driven X-ray detection, radiation photovoltaics remain rare, and underdeveloped in multilayered OIHPs. Herein, chirality to induce radiation photovoltaics in 2D multilayered chiral OIHPs is first utilized for efficient self-driven X-ray detection. Specifically, under X-ray irradiation, a multilayered chiral-polar (S-BPEA)2FAPb2I7 (1-S, S-BPEA = (S)-1-4-Bromophenylethylammonium, FA = formamidinium) shows remarkable radiation photovoltaics of 0.85 V, which endows 1-S excellent self-driven X-ray detection performance with a considerable sensitivity of 87.8 µC Gyair -1 cm-2 and a detection limit low to 161 nGyair s-1. Moreover, the sensitivity is high up to 1985.9 µC Gyair -1 cm-2 under 80 V bias, higher than most those of 2D OIHPs. These results demonstrate that chirality-induced radiation photovoltaics is an efficient strategy for self-driven X-ray detection.
RESUMO
In recent years, there has been a surge in research enthusiasm on searching for solid-state nonlinear optical (NLO) switching materials in halide perovskites owing to their exceptional structural flexibility, compositional diversity, and broad property tenability. However, the majority of reported halide perovskite NLO switching materials contain toxic elements (e.g., Pb), which raise significant environmental concerns. Herein, we present a novel lead-free multilayered halide perovskite NLO switching material, (BA)2(EA)2Sn3Br10 (1, where BA is butylammonium and EA is ethylammonium). Driven by the stereochemically active lone-pair electrons of the Sn2+ cation and the cage-confined effect of EA rotators, 1 undergoes a phase transition with symmetry breaking from P4/mnc to Cmc21, which gives rise to a highly efficient modulation of the quadratic NLO property (0.7 times that of KH2PO4) at a high temperature of 353 K. Furthermore, crystallographic investigation combined with theoretical calculations reveals that the efficient modulation of NLO properties in 1 stems from the synergistic effects between stereochemically active lone pair-induced octahedral distortions and order/disorder transformation of organic cations. This study opens up an instructive avenue for designing and advancing environmentally friendly solid-state NLO switches in halide perovskites.
RESUMO
Reactive oxygen species (ROS) produced from the oxygenation of reactive Fe(II) species significantly affect the transformation of metalloids such as Sb at anoxic-oxic redox interfaces. However, the main ROS involved in Sb(III) oxidation and Fe (oxyhydr)oxides formation during co-oxidation of Sb(III) and Fe(II) are still poorly understood. Herein, this study comprehensively investigated the Sb(III) oxidation and immobilization process and mechanism during Fe(II) oxygenation. The results indicated that Sb(III) was oxidized to Sb(V) by the ROS produced in the aqueous and solid phases and then immobilized by formed Fe (oxyhydr)oxides via adsorption and coprecipitation. In addition, chemical analysis and extended X-ray absorption fine structure (EXAFS) characterization demonstrated that Sb(V) could be incorporated into the lattice structure of Fe (oxyhydr)oxides via isomorphous substitution, which greatly inhibited the formation of lepidocrocite (γ-FeOOH) and decreased its crystallinity. Notably, goethite (α-FeOOH) formation was favored at pH 6 due to the greater amount of incorporated Sb(V). Moreover, singlet oxygen (1O2) was identified as the dominant ROS responsible for Sb(III) oxidation, followed by surface-adsorbed ·OHads, ·OH, and Fe(IV). Our findings highlight the overlooked roles of 1O2 and Fe (oxyhydr)oxide formation in Sb(III) oxidation and immobilization during Fe(II) oxygenation and shed light on understanding the geochemical cycling of Sb coupled with Fe in redox-fluctuating environments.
Assuntos
Oxirredução , Oxigênio Singlete , Oxigênio Singlete/química , Antimônio/química , Ferro/química , Compostos Férricos/química , Compostos Ferrosos/química , Óxidos/química , Oxigênio/químicaRESUMO
Antimony(V) substitution is common in secondary ferrihydrite, especially in mining areas and tailings. However, its impact on the adsorption behavior of ferrihydrite is still unclear. Therefore, this study investigated the influential mechanisms of Sb(V) substitution on the lattice structure and surface properties of Sb-substituted ferrihydrite (SbFh), and its adsorption of coexisting Sb(OH)6-. Antimony(V) is substituted at Fe1 sites and is primarily distributed on the surface. Substitution has opposing effects on the outer- and inner-sphere complexation of Sb(OH)6-. On one hand, substituted-Sb(V) transfers more positive charges to ≡FeOH, reducing the number of H bonds. Subsequently, the charge saturation of ≡FeOH decreases, surface charge increases, and outer-sphere complexation is promoted. On the other hand, the elevated bond valence of Sb-O increases charge saturation of ≡FeOH, reducing the charge capacity that ≡FeOH can accommodate from inner-sphere complexes. Thus, inner-sphere complexation is inhibited. Inner-sphere complexation plays a more important role, and Sb(OH)6- adsorption is inhibited. Additionally, the primary complexation modes of Sb(OH)6- transform from bidentate to monodentate complexation. This research has important implications for understanding the environmental behavior of ferrihydrite, as well as the fate and bioavailability of antimony in mining areas and tailings.
Assuntos
Antimônio , Propriedades de Superfície , Antimônio/química , Adsorção , Compostos Férricos/químicaRESUMO
Three-dimensional (3D) organic-inorganic hybrid perovskites (OIHPs) have achieved tremendous success in direct X-ray detection due to their high absorption coefficient and excellent carrier transport. However, owing to the centrosymmetry of classic 3D structures, these reported X-ray detectors mostly require external electrical fields to run, resulting in bulky overall circuitry, high energy consumption, and operational instability. Herein, we first report the unprecedented radiation photovoltage in 3D OIHP for efficient self-driven X-ray detection. Specifically, the 3D polar OIHP MhyPbBr3 (1, Mhy=methylhydrazine) shows an intrinsic radiation photovoltage (0.47â V) and large mobility-lifetime product (1.1×10-3 â cm2 V-1 ) under X-ray irradiation. Strikingly, these excellent physical characteristics endow 1 with sensitive self-driven X-ray detection performance, showing a considerable sensitivity of 220â µC Gy-1 cm-2 , which surpasses those of most self-driven X-ray detectors. This work first explores highly sensitive self-driven X-ray detection in 3D polar OIHPs, shedding light on future practical applications.
RESUMO
Chemiresistive sensing has been regarded as the key monitoring technique, while classic oxide gas detection devices always need an external power supply. In contrast, the bulk photovoltage of photoferroelectric materials could provide a controllable power source, holding a bright future in self-powered gas sensing. Herein, we present a new photoferroelectric ([n-pentylaminium]2[ethylammonium]2Pb3I10, 1), which possesses large spontaneous polarization (â¼4.8 µC/cm2) and prominent visible-photoactive behaviors. Emphatically, driven by the bulk photovoltaic effect, 1 enables excellent self-powered sensing responses for NO2 at room temperature, including extremely fast response/recovery speeds (0.15/0.16 min) and high sensitivity (0.03 ppm-1). Such figures of merit are superior to those of typical inorganic systems (e.g., ZnO) using an external power supply. Theoretical calculations and in situ diffuse reflectance infrared Fourier transform spectroscopy measurements confirm the great selectivity of 1 for NO2. As far as we know, this is the first realization of ferroelectricity-driven self-powered gas detection. Our work sheds light on the self-powered sensing systems and provides a promising way to broaden the functionalities of photoferroelectrics.
RESUMO
The bulk anomalous photovoltaic (BAPV) effect of acentric materials refers to a distinct concept from traditional semiconductor-based devices, of which the above-bandgap photovoltage hints at a promise for solar-energy conversion. However, it is still a challenge to exploit new BAPV-active systems due to the lacking of knowledge on the structural origin of this concept. BAPV effects in single crystals of a 2D lead-free double perovskite, (BBA)2 CsAgBiBr7 (1, BBA = 4-bromobenzylammonium), tailored by mixing aromatic and alkali cations in the confined architecture to form electric polarization are acquired here. Strikingly, BAPV effects manifested by above-bandgap photovoltage (VOC ) show unique attributes of directional anisotropy and positive dependence on electrode spacing. The driving source stems from orientations of the polar aromatic spacer and Cs+ ion drift, being different from the known built-in asymmetry photovoltaic heterojunctions. As the first demonstration of the BAPV effect in the double perovskites, the results will enrich the family of environmentally green BAPV-active candidates and further facilitate their new optoelectronic application.
RESUMO
This study firstly investigated the effects of season, land use, and socioeconomic on the spatiotemporal changes of riverine antibiotic concentrations in a low urbanized and rural watershed. In the dry and wet seasons, water samples were collected and analyzed for 15 antibiotics. The results indicated that 14 antibiotics, excluding leucomycin, were detected. Monsoon led to significantly lower total antibiotic concentrations in the wet season (22.0ngL-1) than in the dry season (51.2ngL-1). Total antibiotic concentrations were dominated by amoxicillin (below limit of detection (Assuntos
Antibacterianos
, Poluentes Químicos da Água
, Humanos
, Antibacterianos/análise
, Estações do Ano
, População Rural
, Monitoramento Ambiental/métodos
, Poluentes Químicos da Água/análise
, Amoxicilina
, Trimetoprima
, Eritromicina
, Fatores Socioeconômicos
, China
RESUMO
Mining, smelting and tailing deposition activities can cause metal(loid) contamination in surrounding soils, threatening ecosystems and human health. Microbial indicators are sensitive to environmental factors and have a crucial role in soil ecological risk assessment. Xikuangshan, the largest active antimony (Sb) mine in the world, was taken as the research area. The soil properties, metal(loid) contents and microbial characteristics were investigated and their internal response relationships were explored by multivariate statistical analysis. The assessment of the single pollution index and Nemerow synthetic pollution index (PN) showed that the soils were mainly polluted by Sb, followed by Cd and As, in which sampling site S1 had a slight metal(loid) pollution and the other sampling sites suffered from severe synthetic metal(loid) pollution. The microbial characteristics were dissimilar among sampling points at different locations from the mining area according to hierarchical cluster analysis. The correlation analysis indicated that fluorescein diacetate hydrolase, acid phosphatase, soil basal respiration and microbial biomass carbon were negatively correlated with PN, indicating their sensitivity to combined metal(loid) contamination; that dehydrogenase was positively correlated with pH; and that urease, potential ammonia oxidation and abundance of ammonia-oxidizing bacteria and archaea were correlated with N (nitrogen) contents. However, ß-glucosidase activity had no significant correlations with physicochemical properties and metal(loid) contents. Principal components analysis suggested bioavailable Sb and pH were the dominant factors of soil environment in Xikuangshan Sb mining area. Our results can provide a theoretical basis for ecological risk assessment of contaminated soil.
Assuntos
Microbiota , Poluentes do Solo , Humanos , Solo/química , Antimônio/análise , Amônia/análise , Poluentes do Solo/análise , Microbiologia do Solo , Monitoramento Ambiental , Mineração , Metais/análiseRESUMO
Bulk photovoltaic effect, a promising optoelectronic phenomenon for generating polarized dependent steady-state photocurrent, has been widely applied in various photodetectors. However, incorporating stereochemically active lone pair to construct bulk photovoltage in organic-inorganic hybrid perovskite (OIHP) is still elusive and challenging. Herein, bulk photovoltage (1.2â V) has been successfully achieved by introducing the stereo-chemically active lone pair perovskitizer to construct a polar tri-layered hybrid perovskite, namely, (IBA)2 MHy2 Pb3 Br10 (1, IBA=iso-butylamine, MHy=methylhydrazine). Strikingly, owning to the promising bulk photovoltage, 1-based detectors exhibit an ultra-highly sensitive polarized photodetection (polarization ratio of up to 24.6) under self-powered mode. This ratio surpasses all the reported two-dimension OIHP single-crystal photodetectors. In addition, detectors exhibit outstanding responsivity (≈200â mA W-1 ) and detectivity (≈2.4×1013 Jones). More excitingly, further investigation confirms that lone pair electrons in MHy+ result in the separation of positive and negative charges to produce directional dipoles, which further directional alignment to generate bulk photovoltage, thereby resulting in polarization-dependent photocurrent. Our findings provide a new demonstration for polar multilayer materials' construction and may open opportunities for a host of high-sensitive polarized photodetection.
RESUMO
Photoferroelectrics, especially emerging halide perovskite ferroelectrics, have motivated tremendous interests owing to their fascinating bulk photovoltaic effect (BPVE) and cross-coupled functionalities. However, solid solutions of halide perovskite photoferroelectrics with controllable structure and enhanced performance are scarcely explored. Herein, through mixing cage cation, a homogeneous halide perovskite photoferroelectric PA2 FAx MA1-x Pb2 Br7 solid solution (PA, FA and MA are CH3 CH2 CH2 NH3 + , NH2 CHNH2 + and CH3 NH3 + , 0≤x≤1) has been developed, which demonstrates tunable Curie temperature in a wide range of 263-323â K and excellent optoelectrical features. As the component adjusted to x=0.7, the bulk crystal demonstrates ultrahigh pyroelectric coefficient up to 1.48â µC cm-2 K-1 around room temperature. Strikingly, benefiting from the light-induced pyroelectricity and remarkable BPVE, a self-powered and sensitive photodetector based solid solution crystals with boosted responsivity and detectivity over than 1300 % has been achieved. This pioneering work sheds light on the exploration of photoferroelectric solid solutions towards high-performance photoelectronic devices.
RESUMO
Chiral three-dimensional hybrid organic-inorganic perovskites (3D HOIPs) would show unique chiroptoelectronic performance due to the combination of chirality and 3D structure. However, the synthesis of 3D chiral HOIPs remains a significant challenge. Herein, we constructed a pair of unprecedented 3D chiral halide perovskitoids (R/S-BPEA)EA6 Pb4 Cl15 (1-R/S) (R/S-BPEA=(R/S)-1-4-Bromophenylethylammonium, EA=ethylammonium), in which the large chiral cations can be contained in the big "hollow" inorganic frameworks induced by mixing cations. Notably, 3D 1-R/S shows natural chiroptical activity, as evidenced by its significant mirror circular dichroism spectra and the ability to distinguish circularly polarized light. Moreover, based on the unique 3D structure, 1-S presents sensitive X-ray detection performance with a low detection limit of 398â nGyair s-1 , which is 14â times lower than the regular medical diagnosis of 5.5â µGyair s-1 . In this work, 3D chiral halide perovskitoids provide a new route to develop chiral material in spintronics and optoelectronics.
RESUMO
Circularly polarized light (CPL) detection has sparked overwhelming research interest for its widespread chiroptoelectronic and spintronic applications. Ferroelectric materials, especially emerging layered hybrid perovskite ferroelectrics, exhibiting striking bulk photovoltaic effect (BPVE) present significant possibilities for CPL detection by a distinctive working concept. Herein, for the first time, we demonstrate the realization of robust angular anisotropy of CPL detection in a new layered hybrid perovskite ferroelectric crystal (CPA)2FAPb2Br7 (1, CPA is chloropropylammonium, FA is formamidinium), which crystallized in an optically active achiral polar point group. Benefiting from the notable spontaneous polarization (5.1 µC/cm2) and excellent semiconducting characteristics, single crystals of 1 exhibit remarkable BPVE under light illumination, with a high current on/off switching ratio (ca. 103). More intriguingly, driven by the angular carrier drift originating from spin-dependent BPVE in optically active ferroelectrics, 1 displays highly sensitive self-powered CPL detection performance, showing a robust angular anisotropy factor up to 0.98, which is far more than those achieved by material intrinsic chirality. This work provides an unprecedented approach for realizing highly sensitive CPL detection, which sheds light on the further design of optically active ferroelectrics for chiral photonic applications.
RESUMO
Ferro-pyro-phototronic (FPP) effect is a triple coupling of ferroelectricity, light-induced pyroelectricity, and photo-excitation, which holds a bright promise for next-generation modern optoelectronic devices. However, except for few oxides (e.g., BaTiO3 ), new FPP-active candidates remain extremely scarce due to the knowledge lacking on the underlying role of three coupling components. By tailoring the interlayered spacers, the authors present a series of 2D cesium-based perovskite ferroelectrics, (A')2 CsPb2 Br7 (where A'-site cation is organic spacer), showing remarkable FPP-active properties. As expected, the dynamic ordering and reorientation of spacers along with atomic displacement of Cs+ in the perovskite cavity lead to their ferroelectric polarizations. Particularly, exceptional FPP properties are created through this cooperation; the most FPP-active candidate (n-hexylammonium)2 CsPb2 Br7 endows a giant contrast up to 1500% for photopyroelectric current to photovoltaic signal. This figure-of-merit is far beyond most inorganic oxide counterparts, such as ≈110% for BaTiO3 . Further, the electric switching and controlling of FPP directions confirm a crucial role of ferroelectric polarization to this coupling effect. To the authors' best knowledge, this is the first study on an FPP-active candidate of 2D hybrid perovskites, which affords a new avenue to design ferroelectrics with targeted physical properties and forward their potentials to smart optoelectronic device application.
RESUMO
BACKGROUND This single center study, which enrolled 108 patients with chronic hepatitis B virus infection treated with pegylated interferon-alpha (PEG-IFN-alpha), aimed to follow up and monitor off-treatment responses, including virological relapse, and analyze predictors of long-term efficacy of the PEG-IFN-alpha regimen. MATERIAL AND METHODS In total, 108 hepatitis B e antigen (HBeAg)-positive patients with chronic hepatitis B who had completed the PEG-IFN-alpha regimen and achieved virological suppression were enrolled. The patients were followed up for 5 years to monitor off-treatment responses. Twenty-eight relevant factors, including the history of antiviral therapy and HBeAg seroconversion, were analyzed using the Cox proportional hazards regression model. RESULTS The cumulative rates of virological suppression were 75.70%, 68.68%, 65.25%, 63.91%, and 63.91% at 1, 2, 3, 4, and 5 years of the follow-up period, respectively. Compared with the rates of virological suppression, the cumulative rates of clinical suppression were 88.41%, 79.83%, 78.59%, 75.65%, and 75.65%, respectively, for the 5 years. Alanine aminotransferase (ALT) normalization at 24 weeks after off-therapy (relative risk [RR]=3.430, P=0.013) was a potential predictor for sustained virological suppression, and the history of anti-viral therapy (RR=0.164, P=0.004), quantitative value of hepatitis B virus surface antigen (HBsAg) at 48 weeks of anti-viral therapy (RR=2.697, P=0.039), and ALT normalization at 24 weeks after off-therapy (RR=5.467, P=0.004) were potential predictors for sustained clinical suppression. CONCLUSIONS Our results suggested that increased HBsAg levels at 48 weeks and normalization of ALT at 24 weeks after off-therapy might be predictive factors for long-term treatment efficacy.[color=red] [/color].
Assuntos
Hepatite B Crônica , Antivirais/farmacologia , Antivirais/uso terapêutico , Seguimentos , Antígenos de Superfície da Hepatite B , Antígenos E da Hepatite B , Vírus da Hepatite B , Hepatite B Crônica/tratamento farmacológico , Humanos , Interferon-alfa/uso terapêutico , Polietilenoglicóis/uso terapêutico , Proteínas Recombinantes/uso terapêutico , Recidiva , Resultado do TratamentoRESUMO
Antimony (Sb) pollution has increased health risks to humans as a result of extensive application in diverse fields. Exposure to different levels of Sb and its compounds will directly or indirectly affect the normal function of the human body, whereas limited human health data and simulation studies delay the understanding of this element. In this review, we summarize current research on the effects of Sb on human health from different perspectives. First, the exposure pathways, concentration and excretion of Sb in humans are briefly introduced, and several studies have revealed that human exposure to high levels of Sb will cause higher concentrations in body tissues. Second, interactions between Sb and biomolecules or other nonbiomolecules affected biochemical processes such as gene expression and hormone secretion, which are vital for causing and understanding health effects and mechanisms. Finally, we discuss the different health effects of Sb at the biological level from small molecules to individual. In conclusion, exposure to high levels of Sb compounds will increase the risk of disease by affecting different cell signaling pathways. In addition, the appropriate form and dose of Sb contribute to inhibit the development of specific diseases. Key challenges and gaps in toxicity or benefit effects and mechanisms that still hinder risk assessment of human health are also identified in this review. Systematic studies on the relationships between the biochemical process of Sb and human health are needed.
Assuntos
Antimônio , Poluição Ambiental , Antimônio/análise , HumanosRESUMO
Children (n = 240) between the ages of 2 and 17 years were randomly selected from three cities in China. The total amount of soil and dust (SD) on their hands was measured and ranged from 3.50-187.39 mg (median = 19.49 mg). We screened for seven elements (Ce, V, Y, Al, Ba, Sc, and Mn), and Ce levels were used to calculate hand SD by variability and soil elements. The main factors affecting SD amount were location and age group, as identified using a conditional inference tree. Hand SD and the hand SD intake rate were highest in Gansu Province, followed by Guangdong and Hubei provinces, respectively. Hand SD and the hand SD intake rate were highest among children in primary school, followed by kindergarten and secondary school, respectively. The hand SD intake rate of the three typical areas was 11.9 mg/d, which was about 26.6% of the children's soil intake rate (44.8 mg/d), indicating that hand-to-mouth contact is not the main route for children's soil intake in the three areas of China.
Assuntos
Poeira , Poluentes do Solo , Adolescente , Criança , Pré-Escolar , China , Poeira/análise , Exposição Ambiental/análise , Humanos , Boca/metabolismo , Solo , Poluentes do Solo/análiseRESUMO
A mixed-cation 3D lead bromide hybrid perovskite (NMDAP)2 FAPb4 Br13 (1, NMDAP2+ = N-methyl-1,3-diaminopropanium, FA+ = formamidinium) is tailored by incorporating the large NMDAP2+ cation with the small FA+ ion into 3D FAPbBr3 . Structurally, the small FA+ ions occupy the prototypical cavities formed by distorted corner-sharing PbBr6 octahedra as in FAPbBr3 , while the bulky NMDAP2+ ions are confined to the expanded lattice which is defined by a new structural motif composed of eight corner-sharing PbBr6 octahedra and four edge-sharing octahedra. This localized lattice expansion from FAPbBr3 creates a new branch of the intriguing 3D hybrid perovskite family, breaking the limits of the conventional Goldschmidt tolerance factor rule. Moreover, a high two-photon absorption (2AP) coefficient of 60.8â cm MW-1 was demonstrated to near-infrared (NIR) 800â nm illumination, enabling sensitive NIR photoresponses with large on/off ratio (≈104 ) as well as favorable stability.