Mg-Al-NO_3层状双氢氧化物的制备及性能研究

制备了带正电荷的Mg-Al-NO_3层状双氢氧化物（LDH）,并对其组成、形貌、 电性能、离子交换性能等各种性质进行了表征。实验结果表明,所制备的正电纳米 颗粒具有可调控的层间自由空间。该方法为进一步研究聚合物/纳米复合材料提供 了一个合成前驱体的方法。     

La~(3+)掺杂NiCo层状双金属氢氧化物纳米片的合成及其电化学性能

稀土离子La~(3+)掺杂的NiCo层状双金属氢氧化物纳米片具有高的超级电容器性能,比容量达到1115 F/g(1A/g)、倍率性能为517 F/g(30 A/g)。研究表明,La~(3+)离子掺杂不改变NiCo层状双金属氢氧化物晶体结构,但会显著影响其电子和离子传导特性,从而改变其电化学性能。根据离子电负性标度,La~(3+)(1.327)和Co~(2+)(1.377)离子的电负性值最接近,掺杂La~(3+)会优先取代Co~(2+)离子位置。由于La~(3+)离子的尺寸作用(106 pm),使得最优掺杂比例较小仅为0.26%,电化学结果表明较少的La~(3+)掺杂比例依然会显著调节NiCo层状双金属氢氧化物的电子/离子输运性质。     

Remote Synthesis of Layered Double Hydroxide Nanosheets Through the Automatic Chemical Robot

As a family of two-dimensional functional materials, layered double hydroxides(LDHs) have the characteristics of adjustable lamellar element type and proportion, variable interlamellar anion, controllable particle size and thickness, providing a robust platform for photo/electro/thermal-catalysis. With the continuous progress of materials science, the synthesis of LDHs is becoming more and more refined. Herein, to achieve the fine preparation of LDHs materials, especailly for the no-chemical/material researchers, we successfully assembled the automatic synthesis device and wrote corresponding computer software to control this device, and the automatic synthesis of bulk and monolayer LDHs nanosheets on a laboratory scale can be realized. This work paves a new labor-saving way for the fine synthesis of LDHs nanostructures, further improving the development of LDHs-based materials.     

Hydrothermal Synthesis of Glutamic Acid/Layered Double Hydroxide Compounds

In this article, glutamic acid (Glu) was intercalated into the Zn-Al layered double hydroxides (Zn-Al LDHs) by hydrothermal method. The influence of the molar ratio of Zn/Al/Glu (R values for short), the aging time, and the pH value of the washing solution was systematically studied. The resulting Glu-LDH compounds were characterized by x-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), and scanning electron micrograph (SEM). The XRD results showed that the relative diffraction intensity first increased then decreased as the R value and the pH value of the washing solution increased. Moreover, the crystallinity degree decreased gradually with the increase of the aging time. The absorption peaks attributed to the stretch of (R-COO^?) were observed in the FTIR spectra. SEM graphs indicated that the morphology of the particles was largely influenced by the synthesis conditions.     

Nickel–Iron Layered Double Hydroxide Hollow Polyhedrons as a Superior Sulfur Host for Lithium–Sulfur Batteries

We have designed and synthesized novel hollow Ni/Fe layered double hydroxide (LDH) polyhedrons as an advanced sulfur host for enhancing the performance of lithium–sulfur (Li–S) batteries. The Ni/Fe LDH host shows multiple advantages. First, the Ni/Fe LDH shells can provide sufficient sulfiphilic sites for chemically bonding with polysulfides. Second, the hollow architecture can provide sufficient inner space for both loading a large amount of sulfur and accommodating its large volumetric expansion. Moreover, once the active material is confined within the host, the shells could easily restrict the outward diffusion of polysulfides, guaranteeing prolonged cycle life even with high sulfur loading. As a result, the S@Ni/Fe LDH cathode has successfully solved the main issues related to sulfur electrodes, and it exhibits significantly improved electrochemical performances with prolonged life over 1000 cycles and excellent rate properties.     

喜树碱插层的镁铝型层状双金属氢氧化物的合成及表征

采用共沉淀法把抗癌药物喜树碱（Camptothecin, CPT）插入层状双金属氢氧化物(layered double hydroxide, LDH)层间, 合成了CPT-LDH纳米杂化物。结果表明,在CPT-LDH纳米杂化物中,CPT在层间的排布方式有两种,即平行于层板的单层排列和垂直于层板的双层排列;缓释研究表明,CPT-LDH在pH 7.5的磷酸缓冲液中具有明显的缓释效果,其释放速率较相同pH值时CPT和LDH物理混合物的释放速率明显降低;考察了CPT-LDH的药物释放机理,在 pH 7.5的缓冲溶液中,释放过程受粒内扩散过程控制;CPT-LDH纳米杂化物的释放动力学符合准一级动力学过程。     

Preparation of New Layered Double Hydroxide,Co-TiLDH

Layer double hydroxide (LDH) is well known for its ability to intercalate anionic compounds. Most popular LDH is prepared only conventionally with bivalent and trivalent cations. In this study, Co-Ti LDH consisting of bivalent and tetravalent cations was prepared and characterized by chemical analysis, X-ray diffraction, IR spectra, thermal analysis and Scanning Electron Microscope (SEM). The experimental results indicate that the ageing procedure plays a vital role in the formation of Co-Ti LDH. The insertion of a cyanate anion into LDH was confirmed by chemical analysis and IR spectra. XRD patterns of the prepared LDH (Co-Ti-CNO) showed that the interlayer spacing of the LDH was 0.79 nm. The spacing was similar to that of usual LDH in which chloride or bromide anion is the guest. SEM images show that the morphology of Co-Ti LDH was a plate-like structure or a fibrous structure depending on the preparation conditions.This revised version was published online in July 2005 with a corrected issue number.     

双(羟基)金属复合氧化物的表面改性

水滑石;硬脂酸;湿法表面改性;双(羟基)金属复合氧化物的表面改性     

Controllable Modulation of Defects for Layered Double Hydroxide Nanosheets by Altering Intercalation Anions for Efficient Electrooxidation Catalysis

Hydrazine (N₂H₄) is considered as one of the most potential energy storage materials in liquid fuel cells, as it contains high energy and power density, and the high-efficiency oxidation of N₂H₄ in fuel cells has drawn great attention. However, the most used catalysts are expensive noble metal catalysts, thus the development of highly efficient non-noble metal catalysts is crucial to reduce the cost of hydrazine oxidation in practical industry. Herein, we synthesized a series of CoFe-layered double hydroxides (CoFe-LDHs) intercalated with different anions via a simple one-step co-precipitation method for the electrooxidation of hydrazine. Through altering the intercalated anions of CoFe-LDHs, the defects and the electronic structure can be well controlled, and the catalytic performance for the electrooxidation of hydrazine were well promoted by using NO₃⁻ intercalated into CoFe-LDH compared with other anions (like Cl⁻, BO₃³⁻, CO₃²⁻). This work developed a series of hydrazine electrooxidation catalysts and established the relationship between the intercalated anions, the fine structure of the catalyst and the electrocatalytic performance.     

二维水滑石纳米片对氧化铝/聚酰亚胺复合薄膜耐电晕性能的影响

将二维层状材料水滑石剥离为二维纳米片分散液,向其中加入纳米氧化铝,并进行聚酰亚胺(PI)的原位聚合,构筑PI/水滑石纳米片/氧化铝纳米粒子三元复合薄膜。 结果表明,在PI薄膜中同时加入质量分数为10%氧化铝和2%水滑石纳米片,比仅加入质量分数为10%氧化铝时的耐电晕时间(180 min)提高了12倍,拉伸强度提高了37.8%。 聚合物中同时加入纳米片、纳米粒子两种不同形貌填料,能够同时提升复合材料的耐电晕性能和机械性能。     

Multi‐Anion Intercalated Layered Double Hydroxide Nanosheet‐Assembled Hollow Nanoprisms with Improved Pseudocapacitive and Electrocatalytic Properties

Electrochemically active hollow nanostructured materials hold great promise in diverse energy conversion and storage applications, however, intricate synthesis steps and poor control over compositions and morphologies have limited the realization of delicate hollow structures with advanced functional properties. In this study, we demonstrate a one‐step wet‐chemical strategy for co‐engineering the hollow nanostructure and anion intercalation of nickel cobalt layered double hydroxide (NiCo‐LDH) to attain highly electrochemical active energy conversion and storage functionalities. Self‐templated pseudomorphic transformation of cobalt acetate hydroxide solid nanoprisms using nickel nitrate leads to the construction of well‐defined NiCo‐LDH hollow nanoprisms (HNPs) with multi‐anion intercalation. The unique hierarchical nanosheet‐assembled hollow structure and efficiently expanded interlayer spacing offer an increased surface area and exposure of active sites, reduced mass and charge transfer resistance, and enhanced stability of the materials. This leads to a significant improvement in the pseudocapacitive and electrocatalytic properties of NiCo‐LDH HNP with respect to specific capacitance, rate and cycling performance, and OER overpotential, outperforming most of the recently reported NiCo‐based materials. This work establishes the potential of manipulating sacrificial template transformation for the design and fabrication of novel classes of functional materials with well‐defined nanostructures for electrochemical applications and beyond.     

氟插层水滑石催化烯烃环氧化反应

制备了一系列不同Mg/Al比氟插层的水滑石(LDH-F),并用X射线衍射、傅里叶变换红外光谱、扫描电镜和BET比表面积检测法对催化剂进行了表征,考察了不同Mg/Al比的LDH-F在苯乙烯环氧化反应中的催化活性.结果表明,Mg/Al=5的LDH-F具有最佳催化活性.通过以乙腈和苯甲腈分别作为反应用腈的对比实验发现,苯甲腈的效果优于乙腈.以Mg/Al=5的LDH-F为催化剂,H2O2和苯甲腈为氧化剂对不同官能团化烯烃进行环氧化反应,结果表明,此催化体系具有良好的催化性能,在苯乙烯、茚、丙烯醇和烯丙基氯环氧化反应中转化率和选择性均在95%以上。     

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.     

Studies on Synthesis and Properties of Mg-Al-nitrate Layered Double Hydroxides

Layered double hydroxides (LDHs), or the so-called hydrotalcite-like compounds, are important clay materials owing to their intercalation ability of anionic species and other physicochemical properties for application as anion adsorbents, medicine stabilizers, ion-exchangers, ionic conductors, catalysts and catalyst supports 1-2. The general formula is, [MⅡ1-x MⅢx(OH)2]x+ [Xm-x/m·nH2O]x-, abbreviated by: [MⅡ-MⅢ-X]. The net positive charge, due to substitution of trivalent by divale…     

Intercalation of Azo Compounds into Layered Aluminium Dihydrogentriphosphate and a Layered Double Hydroxide

The inner surfaces of inorganic layered compounds such as aluminium dihydrogen-triphosphate (ADHP) and layered double hydroxide (LDH) were modified by azo compounds. Upon intercalation of 4-phenylazoaniline and 4,4-azodianiline into ADHP, the interlayer spacing increased from 6.4 to 21.5 Å and 20.6 Å, respectively. The intensity of IR peaks due to P-–OH of ADHP and amino groups of guests decreased by the thermal treatment of the intercalates. The interlayer spacings also decreased to 16.9 Å and 16.7 Å, respectively, indicating a dehydration reaction between P–-OH and amino groups. The LDH inner surface was modified by the reaction with trans-p-phenylazobenzoylchloride (PAB-Cl). Upon surface modification, the interlayer spacing increased from 7.6 Å to about 27 Å. The absorption of this surface-modified LDH near 410 nm increased upon irradiation with UV light and decreased upon irradation with visible light, indicating the occurrence of trans–cis isomerization of PAB-Cl between the layers.     

Introducing Fe2+ into Nickel–Iron Layered Double Hydroxide: Local Structure Modulated Water Oxidation Activity

Exploring materials with regulated local structures and understanding how the atomic motifs govern the reactivity and durability of catalysts are a critical challenge for designing advanced catalysts. Herein we report the tuning of the local atomic structure of nickel–iron layered double hydroxides (NiFe‐LDHs) by partially substituting Ni²⁺ with Fe²⁺ to introduce Fe‐O‐Fe moieties. These Fe²⁺‐containing NiFe‐LDHs exhibit enhanced oxygen evolution reaction (OER) activity with an ultralow overpotential of 195 mV at the current density of 10 mA cm^?2, which is among the best OER catalytic performance to date. In‐situ X‐ray absorption, Raman, and electrochemical analysis jointly reveal that the Fe‐O‐Fe motifs could stabilize high‐valent metal sites at low overpotentials, thereby enhancing the OER activity. These results reveal the importance of tuning the local atomic structure for designing high efficiency electrocatalysts.     

MgAl无机-有机杂化材料对Pb~(2+)的吸附

采用共沉淀法合成了结晶度良好、具有纯水滑石相的Mg-Al型层状双金属氢氧化物(LDH)及其乙二胺四乙酸二钠(EDTA)-LDH无机-有机杂化物,并进行了表征。考察了Mg-AlLDH和EDTA-LDH对Pb2+的吸附作用,其均有很好的吸附能力,EDTA在LDH通道中可能以直立平行方式排列成单层。在相同条件下,EDTA-LDH的吸附速率和吸附量均高于Mg-AlLDH。结果表明,EDTA的插入具有协同增效作用,吸附动力学符合准二级吸附速率方程。吸附等温线可分为吸附阶段和表面沉淀阶段,吸附阶段的等温线符合Freundlich吸附等温式。初始pH值对Pb2+的吸附基本无影响。Pb2+在LDH和EDTA-LDH上的吸附机理主要为表面沉淀,并存在化学键合和静电键合作用,EDTA-LDH存在EDTA与Pb2+的络合作用。     

In-Situ Formation of Modified Nickel–Zinc-Layered Double Hydroxide Followed by HPLC Determination of Neonicotinoid Insecticide Residues

A single-step preconcentration procedure using the in-situ formation of modified nickel–zinc-layered double hydroxides (LDHs) prior to high-performance liquid chromatography (HPLC) is investigated for the determination of neonicotinoid insecticide residues in honey samples. The LDHs could be prepared by the sequential addition of sodium hydroxide, sodium dodecyl sulfate, nickel nitrate 6-hydrate and zinc nitrate 6-hydrate, which were added to the sample solution. The co-precipitate phase and phase separation were obtained by centrifugation, and then the precipitate phase was dissolved in formic acid (concentrate) prior to HPLC analysis. Various analytical parameters affecting extraction efficiency were studied, and the characterization of the LDHs phase was performed using Fourier-transformed infrared spectroscopy and scanning electron microscopy. Under optimum conditions, the limit of detection of the studied neonicotinoids, in real samples, were 30 μg L⁻¹, for all analytes, lower than the maximum residue limits established by the European Union (EU). The developed method provided high enrichment, by a factor of 35. The proposed method was utilized to determine the target insecticides in honey samples, and acceptable recoveries were obtained.     

Utilization of Active Ni to Fabricate Pt–Ni Nanoframe/NiAl Layered Double Hydroxide Multifunctional Catalyst through In Situ Precipitation

Integration of different active sites into metallic catalysts, which may impart new properties and functionalities, is desirable yet challenging. Herein, a novel dealloying strategy is demonstrated to decorate nickel–aluminum layered double hydroxide (NiAl–LDH) onto a Pt–Ni alloy surface. The incorporation of chemical etching of Pt–Ni alloy and in situ precipitation of LDH are studied by joint experimental and theoretical efforts. The initial Ni‐rich Pt–Ni octahedra transform by interior erosion into Pt₃Ni nanoframes with enlarged surface areas. Furthermore, owing to the basic active sites of the decorated LDH together with the metallic sites of Pt₃Ni, the resulting Pt–Ni nanoframe/NiAl–LDH composites exhibit excellent catalytic activity and selectivity in the dehydrogenation of benzylamine and hydrogenation of furfural.