Nanoscale Metal-Organic Frameworks as a Photoluminescent Platform for Bioimaging and Biosensing Applications.

The tracking of nanomedicines in their concentration and location inside living systems has a pivotal effect on the understanding of the biological processes, early-stage diagnosis, and therapeutic monitoring of diseases. Nanoscale metal-organic frameworks (nano MOFs) possess high surface areas, definite structure, regulated optical properties, rich functionalized sites, and good biocompatibility that allow them to excel in a wide range of biomedical applications. Controllable syntheses and functionalization endow nano MOFs with better properties as imaging agents and sensing units for the diagnosis and treatment of diseases. This minireview summarizes the tunable synthesis strategies of nano MOFs with controllable size, shape, and regulated luminescent performance, and pinpoints their recent advanced applications as optical elements in bioimaging and biosensing. The current limitations and future development directions of nano MOF-contained materials in bioimaging and biosensing applications are also discussed, aiming to expand the biological applications of nano MOF-based nanomedicine and facilitate their production or clinical translation.

Harnessing cerium-based biomaterials for the treatment of bone diseases.

Bone, an actively metabolic organ, undergoes constant remodeling throughout life. Disturbances in the bone microenvironment can be responsible for pathologically bone diseases such as periodontitis, osteoarthritis, rheumatoid arthritis and osteoporosis. Conventional bone tissue biomaterials are not adequately adapted to complex bone microenvironment. Therefore, there is an urgent clinical need to find an effective strategy to improve the status quo. In recent years, nanotechnology has caused a revolution in biomedicine. Cerium(III, IV) oxide, as an important member of metal oxide nanomaterials, has dual redox properties through reversible binding with oxygen atoms, which continuously cycle between Ce(III) and Ce(IV). Due to its special physicochemical properties, cerium(III, IV) oxide has received widespread attention as a versatile nanomaterial, especially in bone diseases. This review describes the characteristics of bone microenvironment. The enzyme-like properties and biosafety of cerium(III, IV) oxide are also emphasized. Meanwhile, we summarizes controllable synthesis of cerium(III, IV) oxide with different nanostructural morphologies. Following resolution of synthetic principles of cerium(III, IV) oxide, a variety of tailored cerium-based biomaterials have been widely developed, including bioactive glasses, scaffolds, nanomembranes, coatings, and nanocomposites. Furthermore, we highlight the latest advances in cerium-based biomaterials for inflammatory and metabolic bone diseases and bone-related tumors. Tailored cerium-based biomaterials have already demonstrated their value in disease prevention, diagnosis (imaging and biosensors) and treatment. Therefore, it is important to assist in bone disease management by clarifying tailored properties of cerium(III, IV) oxide in order to promote the use of cerium-based biomaterials in the future clinical setting. STATEMENT OF SIGNIFICANCE: In this review, we focused on the promising of cerium-based biomaterials for bone diseases. We reviewed the key role of bone microenvironment in bone diseases and the main biological activities of cerium(III, IV) oxide. By setting different synthesis conditions, cerium(III, IV) oxide nanostructures with different morphologies can be controlled. Meanwhile, tailored cerium-based biomaterials can serve as a versatile toolbox (e.g., bioactive glasses, scaffolds, nanofibrous membranes, coatings, and nanocomposites). Then, the latest research advances based on cerium-based biomaterials for the treatment of bone diseases were also highlighted. Most importantly, we analyzed the perspectives and challenges of cerium-based biomaterials. In future perspectives, this insight has given rise to a cascade of cerium-based biomaterial strategies, including disease prevention, diagnosis (imaging and biosensors) and treatment.

Synthesis and Modulation of Low-Dimensional Transition Metal Chalcogenide Materials via Atomic Substitution.

In recent years, low-dimensional transition metal chalcogenide (TMC) materials have garnered growing research attention due to their superior electronic, optical, and catalytic properties compared to their bulk counterparts. The controllable synthesis and manipulation of these materials are crucial for tailoring their properties and unlocking their full potential in various applications. In this context, the atomic substitution method has emerged as a favorable approach. It involves the replacement of specific atoms within TMC structures with other elements and possesses the capability to regulate the compositions finely, crystal structures, and inherent properties of the resulting materials. In this review, we present a comprehensive overview on various strategies of atomic substitution employed in the synthesis of zero-dimensional, one-dimensional and two-dimensional TMC materials. The effects of substituting elements, substitution ratios, and substitution positions on the structures and morphologies of resulting material are discussed. The enhanced electrocatalytic performance and photovoltaic properties of the obtained materials are also provided, emphasizing the role of atomic substitution in achieving these advancements. Finally, challenges and future prospects in the field of atomic substitution for fabricating low-dimensional TMC materials are summarized.

Sub-10-nm-sized Au@AuxIr1-x metal-core/alloy-shell nanoparticles as highly durable catalysts for acidic water splitting.

The absence of efficient and durable catalysts for oxygen evolution reaction (OER) is the main obstacle to hydrogen production through water splitting in an acidic electrolyte. Here, we report a controllable synthesis method of surface IrOx with changing Au/Ir compositions by constructing a range of sub-10-nm-sized core-shell nanocatalysts composed of an Au core and AuxIr1-x alloy shell. In particular, Au@Au0.43Ir0.57 exhibits 4.5 times higher intrinsic OER activity than that of the commercial Ir/C. Synchrotron X-ray-based spectroscopies, electron microscopy and density functional theory calculations revealed a balanced binding of reaction intermediates with enhanced activity. The water-splitting cell using a load of 0.02 mgIr/cm2 of Au@Au0.43Ir0.57 as both anode and cathode can reach 10 mA/cm2 at 1.52 V and maintain activity for at least 194 h, which is better than the cell using the commercial couple Ir/C‖Pt/C (1.63 V, 0.2 h).

Controlled synthesis of sulfhydryl-dendritic mesoporous silica nanospheres for ultrafast extraction and sensitive analysis of organochlorine herbicides containing amide groups.

The distinctive morphology of dendritic mesoporous silica nanoparticles (DMSN) has recently attracted considerable attention in scientific community. However, synthesis of DMSN with well-defined structure and uniform size for ultrafast extraction of trace herbicide residues from environmental and food samples remains to be a compelling challenge. In this study, sulfhydryl functionalized dendritic mesoporous silica (SH-DMSN) was synthesized and the SH-DMSN showcases monodisperse microspheres with flower shape and precisely tailored and controllable pore sizes. This distinctive structural configuration accelerates mass transfer within the silica layer, resulting in heightened adsorption efficiencies. Furthermore, the particle sizes (455, 765, and 808) of the adsorbent can be meticulously fine-tuned by introducing distinct templates. Specifically, when the particle size is 765 nm, the optimized SH-DMSN exhibits a substantial specific surface area (691.32 m²/g), outstanding adsorption efficiencies (>90 %), remarkably swift adsorption and desorption kinetics (2 min and 3 min, respectively), and exceptional stability. The superior adsorption capabilities of this novel adsorbent, ranging from 481.65 to 1021.7 µg/g for organochlorine herbicides containing amide groups, can be attributed to the interplay of S-π interactions, halogen bonding, and electrostatic attraction interaction. These interactions involve the lone pair electrons of sulfhydryl and silanol groups with the π-electrons, halogen atoms and amide groups in herbicide molecules. This study not only offers a new perspective on advancing the practical utilization of dendritic mesoporous silica but also provides a pragmatic strategy for the separation and analysis of herbicides in diverse sample matrices.

Size-controllable synthesis of large-size spherical 3D covalent organic frameworks as efficient on-line solid-phase extraction sorbents coupled to HPLC.

BACKGROUND: Covalent organic frameworks (COFs) have found promising applications in separation fields due to their large surface area and high adsorption capacity, but the exiting COFs can not be directly used as the packing materials of on-line solid-phase extraction (SPE) coupled to HPLC and HPLC because their nano/submicron size or irregular shapes might cause ultrahigh column back pressure and low column efficiency. To synthesize the large-size spherical COFs larger than 3 µm as sorbents might be able to address these problems, however it is still a great challenge till now. RESULTS: In this work, two large-size spherical 3D COFs (COF-320 and COF-300) were size-controllably synthesized within 10-90 µm via a two-step strategy. These two spherical COFs showed large surface area, fine crystallinity, good chemical/mechanical stability, and good reproducibility. As an application case, when used as the on-line SPE sorbents coupled to HPLC, the large-size spherical COF-320 displayed high binding capacity for bisphenol F (Qmax of 452.49 mg/g), low column back pressure (6-8 psi at flow rate of 1 mL/min), and good reusability (at least 30 cycles). The developed on-line-SPE-HPLC-UV method presented good analytical performance with enrichment factor of 667 folds, linear range of 1.0-400 ng/mL, limit of detection (LOD, S/N = 3) of 0.3 ng/mL, limit of quantification (LOQ, S/N = 10) of 1.0 ng/mL, and recoveries of 100.3-103.2 % (RSDs of 2.0-3.5 %) and 95.2-97.0 % (RSDs of 4.3-5.6 %) for tap water and lake water samples, respectively. SIGNIFICANCE: This is the first case to synthesize the large-size spherical COFs within 10-90 µm, and this work made it possible to directly use COFs as the filling materials of on-line SPE coupled to HPLC and HPLC. The developed analytical method can be potentially applied to the rapid and sensitive detection of trace bisphenol F in environmental water samples.

Controllable synthesis of uniform flower-shaped covalent organic framework microspheres as absorbent for solid-phase extraction of trace 2,4-dichlorophenol.

Controllable synthesis of micro-flower covalent organic frameworks (MFCOFs) with controllable size, monodisperse, spherical, and beautiful flower shape was realized by using 2,5-diformylfuran (DFF) and p-phenylenediamine (p-PDA) as building blocks at room temperature. High-quality MFCOFs (5 - 7 µm) were synthesized by controlling the kind of solvent, amounts of monomers, catalyst content, and reaction time. The synthesized MFCOFs possessed uniform mesopores deriving from the intrinsic pores of frameworks and wide-distributed pores belonging to the gap between the petals. The MFCOFs-packed solid-phase extraction (SPE) column shows adsorption capacity of about 8.85 mg g-1 for 2,4-dichlorophenol (2,4-DCP). The MFCOF-based SPE combined with the HPLC method was established for the determination of 2,4-DCP in environmental water. The linear range of this method is 20-1000 ng mL-1 (R2 > 0.9994), and limit of detection (S/N = 3) is 10.9 ng mL-1. Spiked recoveries were 94.3-98.5% with relative standard deviations lower than 2.3%.

Recent Progress of Vertical Graphene: Preparation, Structure Engineering, and Emerging Energy Applications.

Vertical graphene (VG) nanosheets have garnered significant attention in the field of electrochemical energy applications, such as supercapacitors, electro-catalysis, and metal-ion batteries. The distinctive structures of VG, including vertically oriented morphology, exposed, and extended edges, and separated few-layer graphene nanosheets, have endowed VG with superior electrode reaction kinetics and mass/electron transportation compared to other graphene-based nanostructures. Therefore, gaining insight into the structure-activity relationship of VG and VG-based materials is crucial for enhancing device performance and expanding their applications in the energy field. In this review, the authors first summarize the fabrication methods of VG structures, including solution-based, and vacuum-based techniques. The study then focuses on structural modulations through plasma-enhanced chemical vapor deposition (PECVD) to tailor defects and morphology, aiming to obtain desirable architectures. Additionally, a comprehensive overview of the applications of VG and VG-based hybrids d in the energy field is provided, considering the arrangement and optimization of their structures. Finally, the challenges and future prospects of VG-based energy-related applications are discussed.

Vacancy Defects Inductive Effect of Asymmetrically Coordinated Single-Atom Fe─N3 S1 Active Sites for Robust Electrocatalytic Oxygen Reduction with High Turnover Frequency and Mass Activity.

The development of facile, efficient synthesis method to construct low-cost and high-performance single-atom catalysts (SACs) for oxygen reduction reaction (ORR) is extremely important, yet still challenging. Herein, an atomically dispersed N, S co-doped carbon with abundant vacancy defects (NSC-vd) anchored Fe single atoms (SAs) is reported and a vacancy defects inductive effect is proposed for promoting electrocatalytic ORR. The optimized catalyst featured of stable Fe─N3 S1 active sites exhibits excellent ORR activity with high turnover frequency and mass activity. In situ Raman, attenuated total reflectance surface enhanced infrared absorption spectroscopy reveal the Fe─N3 S1 active sites exhibit different kinetic mechanisms in acidic and alkaline solutions. Operando X-ray absorption spectra reveal the ORR activity of Fe SAs/NSC-vd catalyst in different electrolyte is closely related to the coordination structure. Theoretical calculation reveals the upshifted d band center of Fe─N3 S1 active sites facilitates the adsorption of O2 and accelerates the kinetics process of *OH reduction. The abundant vacancy defects around the Fe─N3 S1 active sites balance the OOH* formation and *OH reduction, thus synergetically promoting the electrocatalytic ORR process.

Large-size porous spherical 3D covalent organic framework for preconcentration of bisphenol F in water samples and orange juice.

Large-size spherical sorbents with particle size of 10-50 µm are widely applied in separation fields, however it is still a great challenge to synthesize such large-size spherical covalent organic framework (COF). In this work, a type of large-size porous 3D COF was size-controablly synthesized via a two-step strategy, in which a large-size porous 3D spherical polymer was prepared first through a Pickering emulsion polymerization using nano silica as the stabilizer, and subsequently it was converted into porous spherical 3D COF by a solvothermal method. The as-prepared porous spherical COF (COF-320 as a model) showed size-controllable uniform spherical morphology within 15-45 µm, large specific surface area, fine crystalline structure, and good chemical stability. When used as the sorbent for dispersive solid-phase extraction (d-SPE) of bisphenol F (BPF), the porous spherical COF-320 (15 µm) displayed high adsorption capacity (Qmax = 335.6 mg/g), high enrichment factor (80 folds), and good reusability (at least five cycles). By coupling the d-SPE method to HPLC, a new analytical approach was developed and successfully applied to the determination of trace BPF in two water samples, an orange juice and a standard sample with recoveries of 96.0-102.2 % (RSD = 1.1-1.5 %), 95.7-97.4 % (RSD = 1.4-4.4 %) and 98.7 % (RSD = 2.3 %), respectively. The limit of detection (S/N = 3) and limit of quantification (S/N = 10) were 0.1 and 0.3 ng/mL, respectively. The new synthesis strategy opens a viable way to prepare large-size porous spherical COFs, and the developed analytical method can be potentially applied to sensitively detect the trace BPF in water samples and beverages.

Controllable Synthesis of Defective UiO-66 for Efficient Degradation and Detection of Ozone.

Metal-organic framework (MOF) structures have gained significant attention for their exceptional catalytic performance in ozone degradation, even under high humidity conditions, which is attributed to the presence of unsaturated metal sites (MOF defects). However, the correlation between MOF defects and catalytic ozone remains ambiguous, and a general approach for the controllable synthesis of high-performance MOF structures is currently lacking. Herein, different defective UiO-66 materials with cluster or ligand defects were obtained by precisely controlling small molecular acid modulators. Their catalytic performance can be analyzed in real time through the specific cataluminescence (CTL) signal of ozone at the interface. The presence of ligand defects was found to be crucial for both catalytic degradation and luminescence of ozone, and the CTL signal exhibited a positive correlation with the endogenous hydroxyl group content in the material (R2 = 0.982), while external humidity further supplemented internal water molecules within the material. Furthermore, theoretical calculations were conducted to compare the adsorption behaviors of ozone on the defective UiO-66 under dry/wet conditions, leading to the proposal of two potential reaction pathways. Subsequently, UiO-66-DA with superior catalytic performance was employed to develop a highly efficient CTL sensor capable of accurately detecting ozone (LOD = 23.3 ppb). This study held significant value in elucidating the reaction site of ozone on MOFs and achieving optimal catalytic effects through the careful selection of modulators and humidity levels.

Controllable Synthesis, Photocatalytic Property, and Mechanism of a Novel POM-Based Direct Z-Scheme Nano-Heterojunction α-Fe2O3/P2Mo18.

In order to improve photocatalytic activity and maximize solar energy use, a new composite material Fe2O3/P2Mo18 was prepared by combining polyoxometalates (P2Mo18) with Fe2O3 nanosheets. FT-IR, XRD, XPS, SEM, TEM, UV-vis, EIS, and PL were used to characterize the composite material, and nano-Fe2O3 of different sizes and morphologies with a controllable absorption range was prepared by adjusting the reaction time, and, when combined with P2Mo18, a composite photocatalyst with efficient visible light response and photocatalytic activity was constructed. The EIS, Bode, and PL spectra analysis results show that the Fe2O3/P2Mo18 composite material has outstanding interfacial charge transfer efficiency and potential photocatalytic application possibilities. Model reactions of methylene blue (MB) and Cr (VI) photodegradation were used to evaluate the redox activity of Fe2O3/P2Mo18 composites under simulated visible light. The photocatalytic degradation rate was as high as 98.98% for MB and 96.86% for Cr (VI) when the composite ratio was Fe2O3/P2Mo18-5%. This research opens up a new avenue for the development of high-performance photocatalysts.

Controllable synthesis of Fe3C-reinforced petal-like lignin microspheres with boosted electrochemical performance and its application in high performance supercapacitors.

One more effective measure to solve the energy crisis caused by the shortage of fossil energy is to convert natural renewable resources into high-value chemical products for electrochemical energy storage. Lignin has broad application prospects in this field. In this paper, three kinds of lignin with different molecular weights were obtained by the ethanol/water grading of Kraft lignin (KL). Then, different surface morphology lignin microspheres were prepared by spray drying. Finally, petal-like microspheres were successfully prepared by mixing and grinding the above four kinds of surface morphology lignin microspheres with potassium ferrate and cyanogen chloride and carbonizing at 800 °C and were later used as electrode materials for supercapacitors. Compared with the other microspheres, LMS-F3@Fe3C has the highest specific surface area (1041.42 m2 g-1), the smallest pore size (2.36 nm) and the largest degree of graphitization (ID/IG = 1.06). At a current density of 1 A g-1, the maximum specific capacitance is 786.7 F g-1. At a power density of 1000 W kg-1, the high energy density of 83.3 Wh kg-1 is displayed. This work provides a novel approach to the modulation of surface morphology and structure of lignin microspheres.

Synthesis of oriented J type ZnIn2S4@CdIn2S4 heterojunction by controllable cation exchange for enhancing photocatalytic hydrogen evolution.

Construction of semiconductor heterojunctions which promote the separation and transport of photogenerated carriers is an effective strategy for improving photocatalytic reaction efficiency. Based on the anisotropic electrical conductivity of layered ZnIn2S4 (ZIS) photocatalyst, an efficient heterojunction should be constructed along the layer plane of ZIS, that is, a J type heterojunction. However, achieving controllable synthesis of the oriented heterojunction of ZIS faces challenges. Herein, we develop a facile, cost-effective and spatially-selective cation exchange synthesis approach to construct J type ZnIn2S4@CdIn2S4 (J-ZIS@CIS) heterojunction using a flower-like hexagonal ZIS as the parent material. The developed synthesis approach can also control crystal structure of the heterojunction component CIS. This work presents a facile and controllable synthesis strategy to construct oriented anisotropic heterojunctions that are otherwise inaccessible. The as-prepared J-ZIS@CIS heterojunction displays a greatly enhanced photocatalytic hydrogen evolution activity with a rate of 183 µmol h-1, 2.77 times higher than that of pristine ZIS. Furthermore, the possible photocatalytic reaction mechanism is presented for the heterojunction.

Controllable synthesis of lignin nanoparticles with antibacterial activity and analysis of its antibacterial mechanism.

As a kind of polyphenol substance, lignin is considered to have good biological activity and certain antibacterial properties. However, it is difficult to be applied because of its uneven molecular weight and difficulty in separation. In this study, by way of fractionation and antisolvent, we obtained lignin fractions with different molecular weight. Moreover, we increased the content of active functional groups and regulated microstructure of lignin, thereby increased lignin's antibacterial property. The classification of chemical components and the control of particle morphology also provided convenience for the exploration of lignin's antibacterial mechanism. The results showed that acetone with high hydrogen bonding ability could collect lignin with different molecular weights and increase the content of phenolic hydroxyl groups, up to 31.2 %. By adjusting the ratio of water/solvent (v/v) and stirring rate during the process of antisolvent, lignin nanoparticles (sphere 40-300 nm) with regular shape and uniform size can be obtained. Through observing the distribution of lignin nanoparticles in vivo and in vitro after co-incubation for different time, it could be found that lignin nanoparticles firstly damage structural integrity of bacterial cells externally, and then are swallowed into cells to affect their protein synthesis, which constitutes a dynamic antibacterial process.

Separating Crystal Growth from Nucleation Enables the In Situ Controllable Synthesis of Nanocrystals for Efficient Perovskite Light-Emitting Diodes.

Colloidal perovskite nanocrystals (PNCs) display bright luminescence for light-emitting diode (LED) applications; however, they require post-synthesis ligand exchange that may cause surface degradation and defect formation. In situ-formed PNCs achieve improved surface passivation using a straightforward synthetic approach, but their LED performance at the green wavelength is not yet comparable with that of colloidal PNC devices. Here, it is found that the limitations of in situ-formed PNCs stem from uncontrolled formation kinetics: conventional surface ligands confine perovskite nuclei but fail to delay crystal growth. A bifunctional carboxylic-acid-containing ammonium hydrobromide ligand that separates crystal growth from nucleation is introduced, leading to the formation of quantum-confined PNC solids exhibiting a narrow size distribution. Controlled crystallization is further coupled with defect passivation using deprotonated phosphinates, enabling improvements in photoluminescence quantum yield to near unity. Green LEDs are fabricated with a maximum current efficiency of 109 cd A-1 and an average external quantum efficiency of 22.5% across 25 devices, exceeding the performance of their colloidal PNC-based counterparts. A 45.6 h operating half-time is further documented for an unencapsulated device in N2 with an initial brightness of 100 cd m-2 .

Controllable Synthesis of Sheet-Flower ZnO for Low Temperature NO2 Sensor.

ZnO is a wide band gap semiconductor metal oxide that not only has excellent electrical properties but also shows excellent gas-sensitive properties and is a promising material for the development of NO2 sensors. However, the current ZnO-based gas sensors usually operate at high temperatures, which greatly increases the energy consumption of the sensors and is not conducive to practical applications. Therefore, there is a need to improve the gas sensitivity and practicality of ZnO-based gas sensors. In this study, three-dimensional sheet-flower ZnO was successfully synthesized at 60 °C by a simple water bath method and modulated by different malic acid concentrations. The phase formation, surface morphology, and elemental composition of the prepared samples were studied by various characterization techniques. The gas sensor based on sheet-flower ZnO has a high response value to NO2 without any modification. The optimal operating temperature is 125 °C, and the response value to 1 ppm NO2 is 125. At the same time, the sensor also has a lower detection limit (100 ppb), good selectivity, and good stability, showing excellent sensing performance. In the future, water bath-based methods are expected to prepare other metal oxide materials with unique structures.

Versatile Synthesis of Carbon Materials using Protic Ionic Liquids and Salts as Precursors.

Carbon materials (CMs) hold immense potential for applications across a wide range of fields. However, current precursors often confront limitations such as low heteroatom content, poor solubility, or complicated preparation and post-treatment procedures. Our research has unveiled that protic ionic liquids and salts (PILs/PSs), generated from the neutralization of organic bases with protonic acids, can function as economical and versatile small-molecule carbon precursors. The resultant CMs display attractive features, including elevated carbon yield, heightened nitrogen content, improved graphitic structure, robust thermal stability against oxidation, and superior conductivity, even surpassing that of graphite. These properties can be elaborate modulated by varying the molecular structure of PILs/PSs. In this Personal Account, we summarize recent developments in PILs/PSs-derived CMs, with a particular focus on the correlations between precursor structure and the physicochemical properties of CMs. We aim to impart insights into the foreseeable controlled synthesis of advanced CMs.

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.

Synthesis of Amorphous/Crystalline Hetero-Phase Nanozymes With Peroxidase-Like Activity by Coordination-Driven Self-Assembly for Biosensors.

Nanozymes and amorphous nanomaterials attract great attention owing to their extraordinary properties. However, the requirements for special synthesis conditions become the bottleneck of their development. Herein, a new strategy involving the DNA-based coordination-driven self-assembly is reported for the synthesis of a novel amorphous/crystalline hetero-phase nanozyme (Fe-DNA). For the synthesis of both nanozymes and amorphous materials, this strategy is simple and controllable, avoiding the traditionally employed harsh conditions. Benefitting from the amorphous structure and the superior physicochemical properties, the synthesized Fe-DNA nanozyme is subsequently found to exhibit a smaller Michaelis constant value for hydrogen peroxide (H2 O2 ) (0.81 mm) than that of horseradish peroxidase (HRP) (3.70 mm), demonstrating the stronger affinity of the Fe-DNA nanozyme toward H2 O2 . The Fe-DNA nanozyme also shows significant peroxidase-like activity but only negligible oxidase-like activity, a characteristic which releases the corresponding assay system from oxygen interference, thereby improving the performance of the nanozyme-based sensing platform. In addition, compared with other nanozymes, the novel Fe-DNA nanozyme is degradable via phosphate; thus, mitigating potential environmental threat. This work provides novel amorphous/crystalline hetero-phase nanozymes and opens a new avenue for the design of amorphous nanomaterials and nanozymes.