Direct electronic communication at bio-interfaces assisted by layered-metal-hydroxide slab arrays with controlled nano-micro structures

The electronic transfer (eT) at bio-interfaces has been achieved by orientating 2D inorganic slabs in a regular arrangement with the slab ab-planes vertical to the electrode substrate. The eT rate is effectively promoted by tuning the nano-micro scale structures of perpendicular LDH arrays.     

羟基喜树碱-类水滑石纳米杂化的共组装制备及表征

采用共组装法在水溶液中制备羟基喜树碱(HCPT)-层状双金属氢氧化物(LDH)纳米杂化物.先利用微通道反应器通过共沉淀法制备了Zn₂Al-NO₃ LDH纳米片,然后与羧酸盐型HCPT在水介质中共组装,制备了HCPT插层LDH的纳米杂化物.利用酸处理,可将层间HCPT由非生物活性的羧酸盐型转化为生物活性的内酯型,这对高生物活性HCPT-LDH纳米杂化物的绿色制备具有重要意义.共组装法制备HCPT-LDH纳米杂化物,耗时短、载药量高、分散性好,且利用原料配比可方便地调控载药量. HCPT分子在LDH层间以其长轴倾斜于层板呈双层排列.所制备的HCPT-LDH纳米杂化物具有良好的药物缓释性能,颗粒内部扩散是药物释放过程的控速步骤.药物释放过程可用准二级动力学模型描述.可以用于构筑LDH基药物输送-控释体系.     

Self-assembled Nanohybrid from Opposite Charged Sheets: Alternate Stacking of CoAl LDH and MoS_2

Hybrid materials are attracting intensive attention for their applications in electronics, photoelectronics, LEDs, field-effect transistors, etc. Engineering new hybrid materials and further exploiting their new functions will be significant for future science and technique development. In this work, alternatively stacked self-assembled CoAl LDH/MoS_2 nanohybrid has been successfully synthesized by an exfoliation-flocculation method from positively charged CoAl LDH nanosheets(CoAl-NS) with negatively charged MoS_2 nanosheets(MoS_2-NS). The CoAl LDH/MoS_2 hybrid material exhibits an enhanced catalytic performance for oxygen evolution reaction(OER) compared with original constituents of CoAl LDH nanosheets and MoS_2 nanosheets. The enhanced OER catalytic performance of CoAl LDH/MoS_2 is demonstrated to be due to the improved electron transfer, more exposed catalytic active sites, and accelerated oxygen evolution reaction kinetics.     

Layered Double Hydroxide Nanosheets with Multiple Vacancies Obtained by Dry Exfoliation as Highly Efficient Oxygen Evolution Electrocatalysts

Layered double hydroxides (LDHs) with two-dimensional lamellar structures show excellent electrocatalytic properties. However, the catalytic activity of LDHs needs to be further improved as the large lateral size and thickness of the bulk material limit the number of exposed active sites. However, the development of efficient strategies to exfoliate bulk LDHs into stable monolayer LDH nanosheets with more exposed active sites is very challenging. On the other hand, the intrinsic activity of monolayer LDH nanosheets can be tuned by surface engineering. Herein, we have exfoliated bulk CoFe LDHs into ultrathin LDH nanosheets through Ar plasma etching, which also resulted in the formation of multiple vacancies (including O, Co, and Fe vacancies) in the ultrathin 2D nanosheets. Owing to their ultrathin 2D structure, the LDH nanosheets expose a greater number of active sites, and the multiple vacancies significantly improve the intrinsic activity in the oxygen evolution reaction (OER).     

Synthesis of Mg2Al-Cl layered double hydroxide nanosheets in a surfactant-free reverse microemulsion

The synthesis of Mg₂Al-Cl layered double hydroxide (LDH) nanosheets in a surfactant-free reverse microemulsion is described. The microemulsion was composed of toluene, isopropanol, and an aqueous solution as the dispersed phase. An aqueous LDH nanosheet dispersion was obtained by a double-microemulsion technique. LDH nanosheets were characterized by X-ray powder diffraction, transmission electron microscopy, scanning electron microscopy, atomic force microscopy, Fourier transform infrared spectroscopy, and thermogravimetric and elemental analyses. The LDH nanosheets consisted of a single brucite layer without any loading of organic molecules. To the best of our knowledge, this is the first report of a naked LDH monolayer aqueous dispersion being directly obtained. The LDH monolayers can be used as building blocks for LDH-based functional materials.     

ZnCr Layered Double Hydroxide (LDH) Nanosheets Assisted Formation of Hierarchical Flower‐Like CdZnS@LDH Microstructures with Improved Visible‐Light‐Driven H2 Production

The development of new semiconductor photocatalysts toward splitting water has supplied a promising way to obtain sustainable and clean hydrogen energy. Herein, CdZnS@layered double hydroxide (LDH) composites with a hierarchical flower‐like microstructure have been fabricated with the aid of ZnCr–LDH nanosheets as templates. XRD, SEM and HRTEM show that the ZnCr–LDH nanosheets are uniformly dispersed within the composites. The surface of the hierarchical structures is rough and composed of numerous nanocrystals of CdZnS. The HRTEM images indicate that the surface of CdZnS nanocrystals is mainly composed of the (111) plane. Moreover, the visible‐light‐driven H₂ production performance of the CdZnS in the presence and absence of ZnCr–LDH nanosheets has been measured. The results show that ZnCr–LDH nanosheets play an important role in the hierarchical morphology and photocatalytic activity of the as‐prepared samples. In the water‐splitting process, the visible‐light‐driven H₂‐production rate of hierarchical flower‐like CdZnS@LDH is 4.03 times and nearly 10 times higher than that of pristine CdZnS microsphere and pure commercial CdS, respectively. Therefore, this work not only achieves enhanced catalytic performance of the CdZnS by the introduction of ZnCr–LDH nanosheets, but also supplies an insight into the relationship between the hierarchical morphology and the semiconductor photocatalytic activity.     

Layer-by-layer assembly and spontaneous flocculation of oppositely charged oxide and hydroxide nanosheets into inorganic sandwich layered materials

Exfoliated oxide nanosheets such as Ti0.91O2 and Ca2Nb3O10 and layered double hydroxide (LDH) nanosheets of Mg2/3Al1/3(OH)2 were restacked into inorganic sandwich layered materials. Sequential adsorption of these oppositely charged nanosheets from their colloidal suspensions yielded multilayer ultrathin films while their simple mixing produced lamellar flocculates. Eliminating carbonate ions from the reaction system was found to be essential for successfully achieving the sandwich structures. The flocculated materials as well as the films were characterized by atomic force microscopy (AFM), UV-visible absorption spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), and chemical analysis, which all supported the formation of the ordered sandwich structures. AFM observations revealed alternate dense tiling of LDH nanosheets and oxide nanosheets onto a substrate surface. UV-visible absorption spectra exhibited progressive enhancement of optical density due to oxide nanosheets as a function of deposition cycles, providing strong evidence for regular growth of multilayer films. The combinations of Mg2/3Al1/3(OH)2/Ti0.91O2 and Mg2/3Al1/3(OH)2/Ca2Nb3O10 produced XRD Bragg peaks having multilayer spacings of 1.2 and 2.0 nm, respectively. These basal spacing values are compatible with the sum of thickness of LDH nanosheets and corresponding oxide nanosheets. TEM images of flocculated samples displayed lamellar features with two different constituent layers appearing alternately.     

Exfoliation of layered double hydroxides by use of zwitterionic surfactants in aqueous solution

A new strategy to exfoliate inorganic layered double hydroxide (LDH) solids to micrometer-sized and positively-charged nanosheets in aqueous solution is presented. The procedure involves intercalation of zwitterionic surfactant into the decarbonated LDH by ion exchange, followed by simply stirring the surfactant-intercalated LDH in an aqueous solution of pH?=?2. Since the charge of zwitterionic surfactant can be varied from anionic to cationic by adjusting the pH, the zwitterionic ions present in the interlayer were converted to cationic at pH?=?2, resulting in the exfoliation of LDH by electrostatic repulsion. The delaminated LDHs nanosheets were confirmed by XRD, TEM, and AFM analyses. This simple method did not need reflux at high temperature, overcame the drawback of using organic solvents, and even resulted in a stably colloidal dispersion of nanosheets.     

Generalized Low‐Temperature Fabrication of Scalable Multi‐Type Two‐Dimensional Nanosheets with a Green Soft Template

Two‐dimensional nanosheets with high specific surface areas and fascinating physical and chemical properties have attracted tremendous interests because of their promising potentials in both fundamental research and practical applications. However, the problem of developing a universal strategy with a facile and cost‐effective synthesis process for multi‐type ultrathin 2 D nanostructures remains unresolved. Herein, we report a generalized low‐temperature fabrication of scalable multi‐type 2 D nanosheets including metal hydroxides (such as Ni(OH)₂, Co(OH)₂, Cd(OH)₂, and Mg(OH)₂), metal oxides (such as ZnO and Mn₃O₄), and layered mixed transition‐metal hydroxides (Ni‐Co LDH, Ni‐Fe LDH, Co‐Fe LDH, and Ni‐Co‐Fe layered ternary hydroxides) through the rational employment of a green soft‐template. The synthesized crystalline inorganic nanosheets possess confined thickness, resulting in ultrahigh surface atom ratios and chemically reactive facets. Upon evaluation as electrode materials for pseudocapacitors, the Ni‐Co LDH nanosheets exhibit a high specific capacitance of 1087 F g^?1 at a current density of 1 A g^?1, and excellent stability, with 103 % retention after 500 cycles. This strategy is facile and scalable for the production of high‐quality ultrathin crystalline inorganic nanosheets, with the possibility of extension to the preparation of other complex nanosheets.     

Reverse Micelle Synthesis of Colloidal Nickel–Manganese Layered Double Hydroxide Nanosheets and Their Pseudocapacitive Properties

Colloidal nanosheets of nickel–manganese layered double hydroxides (LDHs) have been synthesized in high yields through a facile reverse micelle method with xylene as an oil phase and oleylamine as a surfactant. Electron microscopy studies of the product revealed the formation of colloidal nanoplatelets with sizes of 50–150 nm, and X‐ray diffraction, energy dispersive X‐ray spectroscopy, and X‐ray photoelectron spectroscopy studies showed that the Ni–Mn LDH nanosheets had a hydrotalcite‐like structure with a formula of [Ni₃Mn(OH)₈](Cl^?) ? n H₂O. We found that the presence of both Ni and Mn precursors was required for the growth of Ni‐Mn LDH nanosheets. As pseudocapacitors, the Ni–Mn LDH nanosheets exhibited much higher specific capacitance than unitary nickel hydroxides and manganese oxides.     

Intercalation of Norfloxacin into Layered Double Hydroxides by Delamination/Restacking Process and its Controlled-Release Property

Norfloxacin (NFX)-layered double hydroxide (LDH) intercalated nanocomposite was synthesized by delamination/restacking process. In this method, LDH particles were first delaminated to well-dispersed two-dimensional nanosheets in formamide, and then the LDH nanosheets and NFX anions co-assembled into NFX-LDH nanocomposite. Characterization by powder x-ray diffraction, Fourier transform infrared spectroscopy, elemental analysis, and thermogravimetry revealed that the product had an expanded LDH structure. This finding indicated that NFX was successfully intercalated into LDH layers, and NFX had both horizontal and vertical orientation in the interlayers of NFX-LDH nanocomposite. Additionally, the delamination/restacking method displayed various remarkable advantages such as simple procedure, short reaction time, and mild conditions compared with the conventional methods of ion exchange, co-precipitation, and reconstruction. Results further showed that the thermal stability of NFX greatly improved after intercalation into LDH layers and that NFX release of the NFX-LDH nanocomposite was gradual, suggesting potential use as an effective drug delivery system.     

Hollow nanoshell of layered double hydroxide

Hollow nanoshells of layered double hydroxide (LDH) have been fabricated using exfoliated LDH nanosheets as a shell building block and polystyrene beads as a sacrificial template.     

Facile synthesis of thin NiFe-layered double hydroxides nanosheets efficient for oxygen evolution

Ultrathin NiFe-layered double hydroxide (LDH) nanosheets are facilely and cost-effectively fabricated. The as-prepared NiFe-LDH nanosheets are highly active and stable electrocatalysts for water oxidation in alkaline environment, exhibiting a much higher oxygen evolution activity and lower overpotential with the enhanced stability, much superior to the previously reported LDH-derived catalysts. This work provides a facile methodology for the fabrication of thin nanosheets, which are promising in the renewable energy conversion.     

Water-swellable MgAl-LDH (layered double hydroxide) hybrids: synthesis, characterization, and film preparation

LDH hybrids were synthesized from Cl (-)MgAl-LDHs by anion exchange with short-chain alkyl carboxylate intercalants: C n H 2 n+1 COO (-) ( n = 0-3). Among them, LDH3 (LDH with Mg/Al = 3) hybrids containing acetate ( n = 1) and propionate ( n = 2) exhibited swelling behavior in water. The action of water on acetate-LDH3 (AcO-LDH3) and propionate-LDH3 (PrO-LDH3) led to semitransparent suspensions via a viscous gel state. From the X-ray diffraction profiles of the gels, only a broad feature was observed by the loss of the sharp reflections. The reflections reappeared for the films obtained by drying the gel, indicating the restacking of the LDH nanosheets into the original stacked structure. Observation using atomic force microscopy revealed delaminated nanosheets with a thickness of 1.1-1.5 nm with the same morphological features as the starting LDHs. XRD measurement and AFM observation supported the formation of unilamellar LDH sheets. Semitransparent self-standing LDH films were obtained by peeling off the films formed on a PE (polyethylene) substrate by drying the colloidal suspension thereon. The thickness of the obtained flexible films ranged from 10 to 25 microm, and they could be anion exchanged with inorganic and organic anions in the film state.     

Ordered Ultrathin Films of Perylene Anions and Layered Double Hydroxide Using Exfoliation‐coassembly Method

Recently, the fabrication of ordered luminescent ultrathin film (UTF) materials based on layered double hydroxides (LDHs) has received much attention. However, how to obtain these UTFs assembled by small anions and LDHs nanosheets is still a challenge. Herein, perylene 3,4,9,10‐tetracarboxylate (PTCB) was firstly chosen as the anion with the aim to obtain PTCB/LDH UTFs, which cannot be formed based on typical layer‐by‐layer (LBL) method. Then, the polymer anions (such as poly 4‐styrene sulfonate (PSS) and poly vinyl sulfonate (PVS)) were further chosen as the co‐assembled units with PTCB, which can act as carriers to assemble with LDH nanosheets. The as‐obtained PTCB@PSS/LDH and PTCB@PVS/LDH UTFs present long range ordered structures confirmed by powder X‐ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Moreover, these two UTF systems show polarized luminescence with the emissive anisotropy of ca. 0.62 and 0.73. Therefore, this work presents an exfoliation‐coassembly way to develop LDH‐based ordered luminescent films, which may benefit their future optical display applications.     

From Zn-Al layered double hydroxide to ZnO nanostructure:Gradually etching by sodium hydroxide

Zn-Al layered double hydroxide(LDH) was used as precursor to produce ZnO nanostructures through dissolution of aluminum hydroxide in caustic soda.The Zn-Al LDH could transform into different nanostructures of ZnO on LDH nanosheets and even pure ZnO nanorods under various NaOH concentration.The formed ZnO nanorods vertically aligned on both LDH sides.UV-vis diverse reflectance spectra show that the obtained ZnO nanorods have a band gap of approximately 3.05 eV.Such ZnO/LDH nanostructures might be used as photocatalyst in the organic pollutant decomposition.     

Surfactantless synthesis of multiple shapes of gold nanostructures and their shape-dependent SERS spectroscopy

A useful method for the synthesis of various gold nanostructures is presented. The results demonstrated that flowerlike nanoparticle arrays, nanowire networks, nanosheets, and nanoflowers were obtained on the solid substrate under different experimental conditions. In addition, surface-enhanced Raman scattering (SERS) spectra of 4-aminothiophenol (4-ATP) on the as-prepared gold nanostructures of various shapes were measured, and their shape-dependent properties were evaluated. The intensity of the SERS signal was the smallest for the gold nanosheets, and the flowerlike nanoparticle arrays gave the strongest SERS signals.     

Hierarchical Hollow Nanoprisms Based on Ultrathin Ni‐Fe Layered Double Hydroxide Nanosheets with Enhanced Electrocatalytic Activity towards Oxygen Evolution

The oxygen evolution reaction (OER) is involved in various renewable energy systems, such as water‐splitting cells and metal–air batteries. Ni‐Fe layered double hydroxides (LDHs) have been reported as promising OER electrocatalysts in alkaline electrolytes. The rational design of advanced nanostructures for Ni‐Fe LDHs is highly desirable to optimize their electrocatalytic performance. Herein, we report a facile self‐templated strategy for the synthesis of novel hierarchical hollow nanoprisms composed of ultrathin Ni‐Fe LDH nanosheets. Tetragonal nanoprisms of nickel precursors were first synthesized as the self‐sacrificing template. Afterwards, these Ni precursors were consumed during the hydrolysis of iron(II) sulfate for the simultaneous growth of a layer of Ni‐Fe LDH nanosheets on the surface. The resultant Ni‐Fe LDH hollow prisms with large surface areas manifest high electrocatalytic activity towards the OER with low overpotential, small Tafel slope, and remarkable stability.     

Heck reaction catalyzed by colloids of delaminated Pd-containing layered double hydroxide

A novel ligand-free catalyst, Pd(II)-doped colloidal layered double hydroxide (LDH) has been prepared from delamination of glycinate-intercalated ternary-component MgPdAl-LDH ([Mg_0.95Pd_0.05Al_1/3(OH)₂][Gly_1/3·mH₂O]) in formamide. The catalytic performance of these mono-dispersed ultrathin nanosheets of LDH for Heck reaction was evaluated. Owing to the largely enhanced accessibility for reactant molecules resulting from the nature of high inner surface area of LDHs, these palladium-bearing nanosheets showed excellent efficiency in Heck reactions in a wide range of substrate molecules. The presence of Mg, Al and OH⁻ ions in the LDH-lamellas favors control the size growth of the in situ formed Pd(0) species implanted in the LDH layer matrixes, helping to prevent the formed Pd(0) from extraction from the lamellas followed by Pd-black formation. Moreover, the Pd sites and basic sites on the brucite-like nanosheets are combined at a molecular level and interact with each other closely because of the co-precipitation method employed; so the basic sites on the LDH monolayers might function as basic ligands. This new catalyst, delaminated MgPdAl-LDH, was characterized by XRD, TEM, HRTEM and EDX analysis.     

Synthesis, anion exchange, and delamination of Co-Al layered double hydroxide: assembly of the exfoliated nanosheet/polyanion composite films and magneto-optical studies

This paper describes a systematic study on the synthesis, anion exchange, and delamination of Co-Al layered double hydroxide (LDH), with the aim of achieving fabrication and clarifying the properties of LDH nanosheet/polyanion composite films. Co-Al-CO3 LDH hexagonal platelets of 4 mum in lateral size were synthesized by the urea method under optimized reaction conditions. The as-prepared CO3(2-)-LDH was converted to Cl- -LDH by treating with a NaCl-HCl mixed solution, retaining its high crystallinity and hexagonal platelike morphology. LDHs intercalated with a variety of anions (such as NO3-, ClO4-, acetate, lactate, dodecyl sulfate, and oleate) were further prepared from Cl- -LDH via an anion-exchange process employing corresponding salts. Exchanged products in various anion forms were found to show different delamination behaviors in formamide. Among them, best results were observed for NO3- -LDH in terms of the exfoliating degree and the quality of the exfoliated nanosheets. The delamination gave a pink transparent suspension containing well-defined nanosheets with lateral sizes of up to 2 microm. The resulting nanosheets were assembled layer-by-layer with an anionic polymer, poly(sodium styrene 4-sulfonate) (PSS), onto quartz glass substrates to produce composite films. Magnetic circular dichroism (MCD) measurements revealed that the assembled multilayer films exhibited an interesting magneto-optical response.