Electron Deficient Ir-O Bonds Promote Heterogeneous Ir-Catalyzed Anti-Markovnikov Hydroboration of Alkenes under Mild Neat Conditions.

Tuning electronic characteristics of metal-ligand bonds based on reaction pathways to achieve efficient catalytic processes has been widely studied and proven to be feasible in homogeneous catalysis, but it is scarcely investigated in heterogeneous catalysis. Herein, we demonstrate the regulation of the electronic configuration of Ir-O bonds in an Ir single-atom catalyst according to the borane activation mechanism. Ir-O bonds in Ir1/Ni(OH)x are found to be more electron-poor than those in Ir1/NiOx. Despite the mild solvent-free conditions and ambient temperature, Ir1/Ni(OH)x exhibits outstanding performance for the hydroboration of alkenes, furnishing the desired alkylboronic esters with a turnover frequency value of ≤3060 h-1 and 99% anti-Markovnikov selectivity, which is significantly better than that of Ir1/NiOx (42 h-1). It is further proven that the more electron-poor Ir-O bonds as active centers are more oxidative and so benefit the activation of the H-B bond in the reductive pinacolborane.

Effective Reduction of CO2 with Aromatic Amines into N-Formamides Triggered by Noble-Free Metal-Organic Framework Catalysts Under Mild Conditions.

The reductive transformation of carbon dioxide (CO2 ) into high-valued N-formamides matches well with the atom economy and the sustainable development intention. Nevertheless, developing a noble-free metal catalyst under mild reaction conditions is desirable and challenging. Herein, a caged metal-organic framework (MOFs) [H2 N(CH3 )2 ]2 {[Ni3 (µ3 -O)(XN)(BDC)3 ]·6DMF}n (1) (XN = 6″-(pyridin-4-yl)-4,2″:4″,4″'-terpyridine), H2 BDC = terephthalic acid) is harvested, presenting high thermal and chemical stabilities. Catalytic investigation reveals that 1 as a renewable noble-free MOFs catalyst can catalyze the CO2 reduction conversion with aromatic amines tolerated by broad functional groups at least ten times, resulting in various formamides in excellent yields and selectivity under the mildest reaction system (room temperature and 1 bar CO2 ). Density functional theory (DFT) theoretical studies disclose the applicable reaction path, in which the CO2 hydrosilylation process is initiated by the [Ni3 ] cluster interaction with CO2 via η2 -C, O coordination mode. This work may open up an avenue to seek high-efficiency noble-free catalysts in CO2 chemical reduction into high value-added chemicals.

Constructing tin oxides Interfacial Layer with Gradient Compositions for Efficient Perovskite/Silicon Tandem Solar Cells with Efficiency Exceeding 28.

Atomic layer deposition (ALD) growth of conformal thin SnOx films on perovskite absorbers offers a promising method to improve carrier-selective contacts, enable sputter processing, and prevent humidity ingress toward high-performance tandem perovskite solar cells. However, the interaction between perovskite materials and reactive ALD precursor limits the process parameters of ALD-SnOx film and requires an additional fullerene layer. Here, it demonstrates that reducing the water dose to deposit SnOx can reduce the degradation effect upon the perovskite underlayer while increasing the water dose to promote the oxidization can improve the electrical properties. Accordingly, a SnOx buffer layer with a gradient composition structure is designed, in which the compositionally varying are achieved by gradually increasing the oxygen source during the vapor deposition from the bottom to the top layer. In addition, the gradient SnOx structure with favorable energy funnels significantly enhances carrier extraction, further minimizing its dependence on the fullerene layer. Its broad applicability for different perovskite compositions and various textured morphology is demonstrated. Notably, the design boosts the efficiencies of perovskite/silicon tandem cells (1.0 cm2) on industrially textured Czochralski (CZ) silicon to a certified efficiency of 28.0%.

Toward Enhancing Performance of Electromagnetic Wave Absorption for Conductive Metal-Organic Frameworks: Nanostructure Engineering or Crystal Morphology Controlling.

Conductive metal-organic frameworks (cMOFs), which have high porosity and intrinsic electron conductivity, are regarded as ideal candidates for electromagnetic wave (EMW) absorption materials. Controlling the nanostructure of absorbers may be one of the effective strategies to improve the electromagnetic wave (EMW) absorption performance. Herein, a series of conductive Cu-HHTP MOFs (HHTP = 2,3,6,7,10,11-hexahydroxytriphenyl hydrates) with different nanostructures or crystal morphologies were successfully synthesized by using different structural inducers to regulate the changes in the morphology, thereby improving the EMW absorption performance. Specifically, when ammonia was used as an inducer, the obtained A-Cu-HHTP with a nanosheet structure exhibited excellent EMW absorption performance. The minimum reflection loss (RLmin) can reach -51.08 dB at 7.25 GHz with a thickness of 4.4 mm, and the maximum effective absorption bandwidth (EAB) can cover 5.73 GHz at 2.5 mm. The influence of the nanostructures of the cMOFs on the dielectric and EMW absorption performance was clarified. The nanosheet structure of A-Cu-HHTP increases its specific surface area, which expands multiple scattering and reflection paths of incident EMW; Meanwhile, the unique structure facilitates the formation of more heterogeneous interfaces, optimizing impedance matching. The significant improvement in EMW performance is mainly attributed to multiple reflections and scattering as well as impedance matching. This work not only provides a simple and effective strategy for improving electromagnetic wave absorption performance but also offers guidelines for preparing morphology functional cMOF materials.

Ultrasensitive Eu-Based MOF Luminescence Sensor for Clenbuterol Visible Recognition.

Clenbuterol (CLB) as an illegal feed additive may cause a great security risk to food safety. However, convenient and efficient detection means for CLB in practical application remain a formidable challenge. Herein, a stable Eu-based organic framework {[H2N(CH3)2]2[Eu2(ttca)2]·H2O}n (compound 1) (H4ttca = [1,1':2',1″-terphenyl]-4,4',4″,5'-tetracarboxylic acid) has been harvested, exhibiting excellent chemical stability and thermal stability. Luminescence investigation reveals that compound 1 can sensitively and selectively detect CLB without being affected by different components from simulated serum and urine (limit detection: 22.7 nM). Furthermore, sensor 1 can also be applicable to CLB recognition in real swine feeds, presenting excellent anti-interference performance. The good cyclicity of compound 1 endows CLB determination with many advantages: low cost, high stability, and simplicity. Importantly, in view of the indication of the luminescence color (red to blue), test membranes were fabricated and employed for convenient and fast CLB detection, providing a valuable scheme for the visual monitoring of CLB in meat products. This work enriches rare earth metal compounds and luminescence sensor portfolios and breaks the concentration record (nM) for detecting CLB compared with reported complex materials, providing an effective monitoring platform for CLB visually.

Surface Molecular Engineering for Fully Textured Perovskite/Silicon Tandem Solar Cells.

Developing large-scale monolithic perovskite/silicon tandem devices based on industrial Czochralski silicon wafers will likely have to adopt double-side textured architecture, given their optical benefits and low manufacturing costs. However, the surface engineering strategies that are widely used in solution-processed perovskites to regulate the interface properties are not directly applicable to micrometric textures. Here, we devise a surface passivation strategy by dynamic spray coating (DSC) fluorinated thiophenethylammonium ligands, combining the advantages of providing conformal coverage and suppressing phase conversion on textured surfaces. From the viewpoint of molecular engineering, theoretical calculation and experimental results demonstrate that introducing trifluoromethyl group provide more effective surface passivation through strong interaction and energy alignment by forming a dipole layer. Consequently, the DSC treatment of this bifunctional molecule enables the tandem cells based on industrial silicon wafers to achieve a certified stabilized power conversion efficiency of 30.89%. In addition, encapsulated devices display excellent operational stability by retaining over 97% of their initial performance after 600 h continuous illumination.

Terminal Group-Oriented Self-Assembly to Controllably Synthesize a Layer-by-Layer SnSe2 and MXene Heterostructure for Ultrastable Lithium Storage.

Heterostructured materials integrate the advantages of adjustable electronic structure, fast electron/ions transfer kinetics, and robust architectures, which have attracted considerable interest in the fields of rechargeable batteries, photo/electrocatalysis, and supercapacitors. However, the construction of heterostructures still faces some severe problems, such as inferior random packing of components and serious agglomeration. Herein, a terminal group-oriented self-assembly strategy to controllably synthesize a homogeneous layer-by-layer SnSe2 and MXene heterostructure (LBL-SnSe2 @MXene) is designed. Benefitting from the abundant polar terminal groups on the MXene surface, Sn2+ is induced into the interlayer of MXene with large interlayer spacing, which is selenized in situ to obtain LBL-SnSe2 @MXene. In the heterostructure, SnSe2 layers and MXene layers are uniformly intercalated in each other, superior to other heterostructures formed by random stacking. As an anode for lithium-ion batteries, the LBL-SnSe2 @MXene is revealed to possess strong lithium adsorption ability, the small activation energy for lithium diffusion, and excellent structure stability, thus achieving outstanding electrochemical performance, especially with high specific capacities (1311 and 839 mAh g-1 for initial discharge and charge respectively) and ultralong cycling stability (410 mAh g-1 at 5C even after 16 000 cycles). This work conveys an inspiration for the controllable design and construction of homogeneous layered heterostructures.

A Strategy to Enhance the Ferroelectric Behavior of MOF-802(Hf) via Doping Zr4+ Ions.

MOF ferroelectrics, as a crucial member of molecular ferroelectrics, have shown intriguing advantages owing to the designability of structures and tunability of physicochemical properties, which make them an appealing group of ferroelectric materials. However, the weak ferroelectric property still is a huge challenge for further development. Here, a series of Zr-doped MOF-802(Hf)s were successfully synthesized through doping Zr4+ ions into the parent MOF-802(Hf) to improve ferroelectric properties. The well-shaped P-E hysteresis loops of Zr-doped MOF-802(Hf)s illustrate their ferroelectricity, and ferroelectric properties are effectively enhanced compared with the parent MOF-802(Hf). What's more, remanent polarization reaches 0.511 µC/cm2 when the concentration of Zr4+ ions is 5%, which is 5 times higher than that of the parent MOF-802(Hf) and is on par with some perovskite ferroelectrics. The increased ferroelectric performance is attributed to the enhanced polarity of the whole structure triggered by lattice distortion when Hf4+ ions of the parent MOF-802(Hf) are substituted by Zr4+ ions. As far as we know, this is the first report on Hf-MOF exhibiting improved ferroelectric behaviors through doping metal ions into lattice nodes. This work demonstrates that introducing the second metal ions into lattice nodes of MOFs is an efficacious approach for exploiting MOF ferroelectrics with superior performance.

Effective Enhancement of the Ferroelectric Performance of Polar Co-Gallate MOF by Doping M2+ Ions (M = Mg, Mn, Ni) into Framework Nodes.

MOF ferroelectrics have been demonstrated to be a promising candidate owing to various structures and controllable properties. However, weak ferroelectricity hampers their boom. Herein, a convenient strategy, doping metal ions into the framework nodes of parent MOF, is adopted to enhance ferroelectric performance. A series of M-doped Co-Gallate (M = Mg, Mn, Ni) were synthesized to improve ferroelectric properties. The electrical hysteresis loop demonstrated its ferroelectric behaviors, exhibiting obviously improved ferroelectric properties compared with the parent Co-Gallate. The remanent polarization was enhanced by two times for Mg-doped Co-Gallate, six times for Mn-doped Co-Gallate, and four times for Ni-doped Co-Gallate. The promoted ferroelectric performances are ascribed to the enhanced polarity of the overall structure triggered by framework distortion. Intriguingly, ferroelectric behaviors increase in the order Mg < Ni < Mn, displaying the same tendency as the difference value in the ionic radius between Co2+ ions and M2+ metal ions (M = Mg, Mn, Ni). These results demonstrate doping of metal ions is a valid strategy to enhance ferroelectric performances, which may serve as a guide in modulating ferroelectric behaviors.

Cu2+1O/Ag Heterostructure for Boosting the Electrocatalytic Nitrate Reduction to Ammonia Performance.

Electrocatalytic nitrate reduction reaction (ENO3RR) is an alternative, sustainable, and environmentally friendly value-added NH3 synthesis method under ambient conditions relative to the traditional Haber-Bosch process; however, its low NH3 yield, low Faradaic efficiency (FE), low selectivity, and low conversion rate severely restrict the development. In this work, a Cu2+1O/Ag-CC heterostructured electrocatalyst was successfully fabricated by constructing a heterogeneous interface between Cu2+1O and Ag for selective electrochemical nitrate-to-ammonia conversion. The construction of the heterogeneous interface effectively promotes the synergistic effect of the catalytically active components Cu2+1O and Ag, which enhances the material conductivity, accelerates the interfacial electron transfer, and exposes more active sites, thus improving the performance of ENO3RR. Such Cu2+1O/Ag-CC manifests a high NH3 yield of 2.2 mg h-1 cm-2 and a notable ammonia FE of 85.03% at the optimal applied potential of -0.74 V vs RHE in a relatively low concentration of 0.01 M NO3--containing 0.1 M KOH. Moreover, it shows excellent electrochemical stability during the cycle tests. Our study not only provides an efficient catalyst for ammonia electro-synthesis from ENO3RR but also an effective strategy for the construction of ENO3RR electrocatalysts for electrocatalytic applications.

Fe1-xNix(PO3)2/Ni2P Heterostructure for Boosting Alkaline Oxygen Evolution Reaction in Fresh Water and Real Seawater at High Current Density.

Oxygen evolution reaction (OER) is a limiting reaction for highly efficient water electrolysis. Thus, the development of cost-effective and highly efficient OER catalysts is the key to large-scale water electrolysis for hydrogen production. Herein, by using an interfacial engineering strategy, a unique nanoflower-like Fe1-xNix(PO3)2/Ni2P/NF heterostructure with abundant heterogeneous interfaces is successfully fabricated. The catalyst exhibits excellent OER catalytic activity in alkaline fresh water and alkaline natural seawater at high current densities, which only, respectively, requires overpotentials of 318 and 367 mV to drive 1000 mA cm-2 in fresh water and natural seawater both containing 1 M KOH. Furthermore, Fe1-xNix(PO3)2/Ni2P/NF demonstrates excellent durability, which can basically remain stable for 80 h during the electrocatalytic OER processes, respectively, in alkaline fresh water and natural seawater. This work provides a new construction strategy for designing highly efficient electrocatalysts for OER at high current densities both in alkaline fresh water and in natural seawater.

An Adaptive Sampling Framework for Life Cycle Degradation Monitoring.

Data redundancy and data loss are relevant issues in condition monitoring. Sampling strategies for segment intervals can address these at the source, but do not receive the attention they deserve. Currently, the sampling methods in relevant research lack sufficient adaptability to the condition. In this paper, an adaptive sampling framework of segment intervals is proposed, based on the summary and improvement of existing problems. The framework is implemented to monitor mechanical degradation, and experiments are implemented on simulation data and real datasets. Subsequently, the distributions of the samples collected by different sampling strategies are visually presented through a color map, and five metrics are designed to assess the sampling results. The intuitive and numerical results show the superiority of the proposed method in comparison to existing methods, and the results are closely related to data status and degradation indicators. The smaller the data fluctuation and the more stable the degradation trend, the better the result. Furthermore, the results of the objective physical indicators are obviously better than those of the feature indicators. By addressing existing problems, the proposed framework opens up a new idea of predictive sampling, which significantly improves the degradation monitoring.

Interfacial Covalent Bonding Endowing Ti3 C2 -Sb2 S3 Composites High Sodium Storage Performance.

Antimony sulfide is attracting enormous attention due to its remarkable theoretical capacity as anode for sodium-ion batteries (SIBs). However, it still suffers from poor structural stability and sluggish reaction kinetics. Constructing covalent chemical linkage to anchor antimony sulfide on two-dimension conductive materials is an effective strategy to conquer the challenges. Herein, Ti3 C2 -Sb2 S3 composites are successfully achieved with monodispersed Sb2S3 uniformly pinned on the surface of Ti3 C2 Tx MXene through covalent bonding of Ti-O-Sb and S-Ti. Ti3 C2 Tx MXene serves as both charge storage contributor and flexible conductive buffer to sustain the structural integrity of the electrode. Systematic analysis indicates that construction of efficient interfacial chemical linkage could bridge the physical gap between Sb2S3 nanoparticles and Ti3 C2 Tx MXene, thus promoting the interfacial charge transfer efficiency. Furthermore, the interfacial covalent bonding could also effectively confine Sb2S3 nanoparticles and the corresponding reduced products on the surface of Ti3 C2 Tx MXene. Benefited from the unique structure, Ti3 C2 -Sb2 S3 anode delivers a high reversible capacity of 475 mAh g-1 at 0.2 A g-1 after 300 cycles, even retaining 410 mAh g-1 at 1.0 A g-1 after 500 cycles. This strategy is expected to shed more light on interfacial chemical linkage towards rational design of advanced materials for SIBs.

Multicomponent TiO2/Ag/Cu7S4@Se Heterostructures Constructed by an Interface Engineering Strategy for Promoting the Electrocatalytic Nitrogen Reduction Reaction Performance.

The electrocatalytic nitrogen reduction reaction (ECNRR) is a sustainable and environmentally friendly method for NH3 synthesis under environmental conditions relative to the Haber-Bosch process; however, its low selectivity (Faradaic efficiency (FE)) and low NH3 yield impede the progress. Herein, benefiting from the application of the interface engineering strategy, a multicomponent TiO2/Ag/Cu7S4@Se-CC heterogeneous electrocatalyst with a unique structure was successfully fabricated, generating a unique sandwich structure by using a Ag layer as an electric bridge intercalated between TiO2 and Cu7S4, in which the optimized catalyst can accelerate the electron transfer efficiency. Moreover, through the electronic structure adjustment, an electron-deficient region was constructed, which can inhibit the H2 adsorption but enhance the N2 adsorption, thereby improving the selectivity and the catalytic activity. Significantly, the FE and NH3 yield of TiO2/Ag/Cu7S4@Se-CC reached 51.05 ± 0.16% and 39.16 ± 2.31 µg h-1 cm-2, in which the FE is among the highest non-precious metal-based NRR electrocatalysts in alkaline electrolytes reported. This study provides insight into the rational design and construction of NRR electrocatalysts for electrocatalytic applications.

Significantly Enhancing the Lithium Ionic Conductivity of Metal-Organic Frameworks via a Postsynthetic Modification Strategy.

Metal-organic frameworks (MOFs), due to their possessing a porous structure, are potential candidates for solid-state ionic conduction materials. Moreover, uncoordinated carboxylic acid groups (-COOH) of MOFs can be used as postsynthetic modification sites, which are favorable for lithium ion exchange. Herein, we synthesized a unique multiple carboxylic zinc metal-organic framework (Zn-MOF-COOH) containing uncoordinated carboxylic acid groups. Zn-MOF-COOLi was synthesized through deprotonation using LiOH via a straightforward acid-base reaction at room temperature (RT), thereby exhibiting better good electrochemical properties. The lithium ionic conductivity (σ) increased from 1.81 × 10-5 to 1.65 × 10-4 S·cm-1, lithium ion transference number (tLi+) rose from 0.67 to 0.77, and the electrochemical window improved from 2.0-5.5 to 1.5-6.5 V. This work offers a new strategy to improve the σ of MOFs and a new perspective toward manufacturing of high-performance solid-state ionic conduction materials.

Fabrication of a "turn-on"-type enantioselective fluorescence sensor via a modified achiral MOF: applications for synchronous detection of phenylalaninol enantiomers.

Homochiral metal-organic frameworks (HMOFs) have garnered considerable attention due to their extrachiral properties and broad application for chiral recognition. However, assembling a pair of high-quality chiral MOFs for sensing enantiomers precisely is a formidable challenge because of the complicated chiral environment and uncontrollable coordinated conditions. Herein, one pair of homochiral UiO-66 analogues, S-1 (l-AP@UiO-66-(COOH)2) and R-1 (d-AP@UiO-66-(COOH)2), are reported for chiral recognition. They were fabricated via a condensation reaction between the carboxyl groups of UiO-66-(COOH)2 and amino groups of l/d-amino propanol (l/d-AP). These novel fluorescent probes exhibited highly enantioselective fluorescence enhancement towards l/d-phenylalaninol (l/d-PA). For example, when S-1 and R-1 were treated with l-PA or d-PA, they displayed different fluorescence responses: the enantiomeric fluorescence enhancement ratio (ef) was 2.51 and 0.41 for S-1 and R-1, respectively. Hence, a visible difference in fluorescence enhancement for l-PA and d-PA and excellent enantioselective behavior between S-1 and l-PA (or R-1 and d-PA) was displayed. Measurements of fluorescence lifetime, powder X-ray diffraction, molecular-dynamic simulations and Benesi-Hildebrand plots were employed to determine the observed high enantioselectivity for l/d-PA. In brief, we found that two post-modified HMOFs, S-1 and R-1, were outstanding enantioselective sensors for detecting l-PA and d-PA. They had a prominent difference in ef and remarkable enantioselectivity factor α and ΔΔG based on steric hindrance and stereochemical difference.

Stable Europium-based Metal-Organic Frameworks for Naked-eye Ultrasensitive Detecting Fluoroquinolones Antibiotics.

Fluoroquinolone antibiotic (FQ) residues, such as ciprofloxacin (CIP) and ofloxacin (OFLX), have aroused public concerns owing to their serious impact in environmental water or food fields which influence human health. A facile and high-performance sensory method for detecting FQs is highly desirable for practical requirements. Herein, we have presented a luminescent Eu-MOF with unique 2D (4-c) {44.62}-connected topology, which holds the outstanding fluorescent property and excellent chemical stability in aqueous solution for 15 days. Thus, Eu-MOF can be considered as a highly sensitive chemo-sensor for sensing CIP and OFLX with different fluorescent color conversion (red changes to green for OFLX and to blue for CIP) and a low detection limit of 0.693 and 0.802 ppb, respectively. Furthermore, the mechanism of sensing CIP and OFLX was exposed to the photoinduced electron transfer (PET) and dynamic quenching process, as evaluated by DFT calculations and fluorescence lifetime decay measurements. Our work first reports a simple and efficient strategy for recognizing CIP and OFLX with a special luminescence color-change phenomenon based on MOF materials, serving as a meaningful guide for researchers in beneficial applications.

Outstanding Drug-Loading/Release Capacity of Hollow Fe-Metal-Organic Framework-Based Microcapsules: A Potential Multifunctional Drug-Delivery Platform.

Owing to their characteristic structures, metal-organic frameworks (MOFs) are considered as the leading candidate for drug-delivery materials. However, controlling the synthesis of MOFs with uniform morphology and high drug-loading/release efficiencies is still challenging, which greatly limits their applications and promotion. Herein, a multifunctional MOF-based drug-delivery system (DDS) with a controlled pore size of 100-200 nm for both therapeutic and bioimaging purposes was successfully synthesized in one step. Fe-MOF-based microcapsules were synthesized through a competitive coordination method, which was profited from the intrinsic coordination characteristics of the Fe element and the host-guest supramolecular interactions between Fe3+ and polyoxometalates anions. This as-synthesized macroporous DDS could greatly increase the drug-loading/release rate (77%; 83%) and serve as a magnetic resonance (MR) contrast agent. Because an Fe-containing macroporous DDS presents ultrahigh drug loading/release, the obtained 5-FU/Fe-MOF-based microcapsules displayed good biocompatibility, extremely powerful inhibition of tumor growth, and satisfactory MR imaging capability. Given all these advantages, this study integrates high therapeutic effect and diagnostic capability via a simple and effective morphology-controlling strategy, aiming at further facilitating the applications of MOFs in multifunctional drug delivery.

The effects of Al-doped to cathode material based on hollow microspheres of nickel-manganese on sodium-ion batteries.

Sodium-ion batteries (SIBs) are expected to be a great substitute for lithium ion batteries. Although there are many difficulties to overcome, SIBs have become one of the most important research areas for large-scale energy storage equipment. The spherical particles are conducive to the contact between the cathode material and the electrolyte, which could increase the electrochemical reaction area, and improve the deintercalation rate of sodium ions during charging and discharging. In this paper, a precipitation method was used to prepare spherical MnCO3material as template and raw material. After all the raw materials were weighed with the molar ratios of Na0.67Mn0.67-0.75xNi0.33AlxO2, a series of hollow micro-spherical sodium-ion cathode materials were synthesized by the conventional high-temperature solid-state method. The effects of Al-doped on the structure and electrochemical performance of Na0.67Ni0.33Mn0.67O2was studied, and it was founded that the samples doped with Al had smaller particle size than that without Al. The electrochemical tests showed that Na0.67Mn0.595Ni0.33Al0.1O2(x= 0.1) exhibite superior high-rate capabilities and cyclic stability. And the hollow microsphere structure has a higher capacity, the first discharge capacity at 0.1C reach 128 mAh g-1.

Intriguing pH-modulated Luminescence Chameleon System based on Postsynthetic Modified Dual-emitting Eu3+@Mn-MOF and Its Application for Histidine Chemosensor.

Due to the disruption by other nonanalyte factors, single-emission probes have been limited in complicated detecting systems. In this work, a pH-modulated luminescence chameleon system based on lanthanide-based MOF (Eu3+@Mn-MOF), with stable structure and miraculous dual-emitting fluorescent properties, was synthesized by a postsynthetic modification (PSM) strategy of a simple hydrothermal and agitation method. Amazingly, not only can the Eu3+@Mn-MOF emit a broad emission at 500 nm attributed to the ligand-based fluorescence emission but it can also exhibit the characteristic emission of Eu3+ ions responding to the antenna effect. Moreover, the Eu3+@Mn-MOF displays an interesting luminescence color transition between acidic and basic solutions. Inspired by this phenomenon, a pH-modulated luminescence chameleon system was first constructed and employed to detect histidine, a kind of basic amino acid for a variety of biological matters, causing a unique fluorescence signal of the ratio-dependent color to change from yellow to light pink which differs from the color change of other water-soluble amino acids. Therefore, Eu3+@Mn-MOF can be as a practical pH-modulated luminescence chameleon system chemsensor for sensing histidine with low detection limit, high sensitivity, and rapid sensing time. In conclusion, the postsynthetic modified Eu3+@Mn-MOF has outstanding applications in the fields of chemical detection and human health.