Synthesis and crystal structure of bis(O-methyl hydrogenato carbonodithioate)-Pb(II): structural,optical and photocatalytic studies of PbS nanoparticles from the complex

Abstract

Lead(II) methyl xanthate [Pb(S₂COMe)₂] was synthesized and characterized by single crystal X-ray crystallography. The molecular structure showed a distorted tetrahedral geometry around Pb(II) with each monomeric unit linked with another through Pb···S interactions. The compound was used to prepare hexadecylamine capped PbS (HDA-PbS) and oleylamine capped PbS (OLA-PbS) nanoparticles. The PbS nanoparticles were indexed to the cubic PbS crystalline phase with particle sizes of 4.5 – 34.5?nm. The estimated optical bandgaps obtained from the tauc’s plots were 3.47 and 3.30?eV for HDA-PbS and OLA-PbS, respectively, which are blue shifted in comparison to bulk PbS. The photodegradation of methylene blue using PbS as photocatalyst shows that HDA-PbS have the best degradation efficiency of 77.70% after 240?min.     

Synthesis of anisotropic PbS nanoparticles using heterocyclic dithiocarbamate complexes

We report the synthesis of lead piperidine and lead tetrahydroquinoline dithiocarbamate (DTC) complexes and their use as single source precursors for the preparation of anisotropic PbS nanoparticles. The complexes were thermolysed in coordinating solvents such hexadecylamime (HDA), tri-n-octylphosphine oxide (TOPO), oleylamine (OA) and decylamine (DA) at various reaction temperatures. The variation of the reaction conditions and precursors produced PbS particles with shapes ranging from spheres to cubes and rods. The size of the particles is generally larger than those synthesized by conventional precursor routes. The electron microscopy and X-ray diffraction data confirm the particles to be very crystalline with the dominant cubic rock salt phase present in all samples.     

Synthesis of single-crystalline CoP nanowires by a one-pot metal-organic route

A simple one-pot method has been used to prepare uniform single-crystalline CoP nanowires with a high aspect ratio by the thermal-decomposition reaction of cobalt(II) acetylacetone with long-chain alkylphosphonic acid in the presence of hexadecylamine (HDA) and trioctylphosphine oxide (TOPO) at high temperature. The crystal morphology of the resulting nanowires can be influenced by the ratio of HDA and TOPO.     

柠檬酸络合法制备La1-xPbxFeO3及其光催化性能

用柠檬酸络合法制备了钙钛矿型复合氧化物LaFeO3,并按不同比例进行掺杂,制备了La1-xPbxFeO3(x=0,0.1,0.3,0.5,0.7)。用XRD,SEM,IR,UV-vis等方法对其进行表征,其结构均为钙钛矿型。并测定了其对活性艳红X-3B水溶性染料脱色的光催化活性。实验结果表明:在A位掺杂Pb2 ,产生了较多氧空位,降低了光生电子与空穴的复合速率,使LaFeO3的光催化活性明显提高,其中La0.7Pb0.3FeO3效果最佳。     

Au纳米粒子负载的ZnO空心球复合材料的光生电荷转移行为及光催化活性

通过简单的两步法合成了不同负载量的Au/ZnO空心球。采用扫描电子显微镜(SEM),X射线衍射(XRD),X射线光电子能谱(XPS)及紫外-可见漫反射光谱(UV-Vis DRS)对样品的形貌、结构、组成和晶相等进行一系列的表征。以罗丹明B (RhB)为目标降解物,探究了Au/ZnO空心球的光催化活性。结果表明,适量Au修饰的ZnO光催化剂在混合光下20 min内对RhB的降解率达到73%。利用表面光电压谱(SPS)和瞬态光电压(TPV)技术,探讨了Au修饰后对ZnO光诱导电荷转移行为与光催化性能之间的关系。结果表明,混合光照下Au/ZnO空心球光降解性能的提高主要归因于作为电子受体的Au纳米粒子与ZnO之间形成的强的电子相互作用。适量Au纳米粒子的负载能够提高ZnO空心球中光生载流子的分离效率,相应地延长载流子的传输时间,增加光生电荷的寿命,从而促进其光催化活性的提高。     

Synthesis and photophysics of leadsulphide nanocrystallites

Nanoparticles of lead sulphide have been stabilized in the presence of excess Pb²⁺ in aqueous basic medium by a simple chemical route of synthesis. These PbS nanoparticles were synthesized very conveniently at room temperature using hexametaphosphate as stabilizer. These nanoparticles have an absorption extending into the NIR region. A significant quantum confinement effect made the bandgap of lead sulphide nanoparticles produce a blue shift from 0.41 eV to about 1.5 eV. The size and morphology of the particles were studied by TEM. Particles were relatively small sized (about 6 nm) having narrow size distribution. XRD data analysis indicate that the product is a mixture of PbS, PbO and Pb(OH)₂. Both XRD pattern and HRTEM images confirm the crystalline structure of lead sulphide crystals. IR spectroscopy indicates the formation of PbS. PbS nanoparticles were fairly stable and could be stored for about three weeks at room temperature and for about two months at 5°C without agglomeration. These particles were photoactive and sensitized the reaction of aniline by light leading to the formation of azobenzene.     

Synthesis,characterization and impregnation of lead sulphide semiconductor nanoparticles on polymer matrix

Lead sulphide nanoparticles were prepared using a precursor and dual sources methods. The composites were fabricated by stabilizing chemically synthesized semiconductor PbS nanocrystals into laurylmethacrylate and ethyleneglycol dimethacrylate matrix in the presence of tri-n-octylphosphine. PbS nanocrystals were dispersed in toluene as a compatible medium for the polymerization and cross-linking of poly laurylmethacrylate networks. The nano-sized particles and polymer composites were characterized by XRD and TEM. Possible formulations and incorporation of these PbS nanoparticles in polymer matrix have been discussed. The reported lead sulphide nanoparticles into tailered polymeric system show greater uniformity and stability.     

Sulfide Ion-Selective Electrode as Potentiometric Sensor for Lead(II) Ion in Aqueous and Nonaqueous Medium

Abstract

The possibilities of a sulfide ion-selective electrode (SISE) for the determination of lead(II) at different pH values is presented. Potential - time curves recorded after addition of lead(II) in sulfide solution constitute the primary data in this study. The influence of the pH and ethanol in ethanol-aqueous mixtures on the behaviour of a SISE and on formation of PbS was investigated. A relationship between the initial rate of decrease of the sulfide concentration in test solution and various amounts of lead(II) is discussed. The results of measurements showed the possibility of determining up to micromole quantities of lead(II).     

两个含双(3,5－二甲吡唑基)甲烷配体的铅(II)配合物的合成与结构表征

Reactions of lead（Ⅱ） nitrate or perchlorate with bis（3,5-dimethylpyrazolyl）methane （dmpzm）, produced two new Pb（Ⅱ） chelated complexes [Pb（dmpzm）2X2] （X=NO3^- 1, ClO4^- 2）. Both compounds were structurally characterized by elemental analysis, IR spectroscopy, thermal analysis, and single crystal X-ray diffraction. Both compounds are mononuclear with a distorted square antiprismatic PbN4O4 coordination geometry incorporating a pair of O,O＇-bidentate anions and N,N＇-bidentate dmpzm ligands. In the crystals of 1 or 2, the methyl or methylene groups of dmpzm ligand interact with the oxygen atoms of nitrates or perchlorates to afford intra- and intermolecular hydrogen bonding, thereby forming a two-dimensional network 1 or a three-dimensional structure 2.     

AuCu/ZnAl-LDO复合光催化剂的制备及其光催化性能

采用浸渍还原法成功将金铜纳米颗粒负载到锌铝水滑石表面(AuCu/ZnAl-LDHs),焙烧制得复合金属氧化物(AuCu/ZnAlLDO)。通过X射线粉末衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)和紫外-可见漫反射光谱(UV-Vis DRS)技术对材料的晶型、形貌、元素组成以及光吸收性能进行分析。以邻苯二酚为降解物,研究AuCu/ZnAl-LDO在可见光下的光催化性能。实验结果显示:相比于纯锌铝复合金属氧化物(ZnAl-LDO),AuCu/ZnAl-LDO具有更强的可见光吸收能力。Au、Cu负载比例为5∶1,焙烧温度为400℃的催化剂在5 h内对邻苯二酚的降解率为94.5%,其降解的反应速率常数为ZnAl-LDO的13.4倍。此外,借助理论计算推测了AuCu/ZnAl-LDO电子转移的路径,并以此提出可能的光催化降解机理。     

Co3O4-Bi2O3 heterojunction: An effective photocatalyst for photodegradation of rhodamine B dye

Recently, the research on the remediation of aqueous organic pollutants over visible-light-active photocatalysts has got much attention. Therefore, this study reports the fabrication of visible-light-active Co₃O₄-Bi₂O₃ heterojunction photocatalyst for the photodegradation of rhodamine B dye. The Co₃O₄-Bi₂O₃ heterojunction was synthesized by the coprecipitation method and characterized by XRD, EDS, SEM, TEM, TGA, and FTIR. The as-prepared Co₃O₄-Bi₂O₃ heterojunction was utilized as a photocatalyst for the abatement of rhodamine B dye. It was observed that Co₃O₄-Bi₂O₃ showed the best catalytic performance with ～92% degradation of rhodamine B dye than Co₃O₄ and Bi₂O₃ with 14 and 34% removal of rhodamine B dye, respectively. The rate constant for Co₃O₄-Bi₂O₃ catalyzed photodegradation of rhodamine B was 6 times and 3 times higher than the rate constant for Co₃O₄ catalyzed and Bi₂O₃ catalyzed photodegradation of rhodamine B, respectively. The as-prepared Co₃O₄-Bi₂O₃ exhibited the highest catalytic performance at pH 8.     

Core-shell microspherical Ti(1-x)Zr(x)O2 solid solution photocatalysts directly from ultrasonic spray pyrolysis

A series of Ti(1-x)Zr(x)O(2) solid solutions photocatalysts (x = 0.000, 0.045, 0.090, 0.135, and 0.180) was directly obtained by an ultrasonic spray pyrolysis method. Compared with previous methods for solid solutions, our preparation was very fast. The resulting samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, nitrogen adsorption, and UV-vis diffuse reflectance spectroscopy. The characterizations revealed core-shell spherical structures of the resulting solid solutions. We evaluated photocatalytic activities of the solid solutions on degradation of rhodamine B in aqueous solution under simulated solar light. It was found that Ti(0.91)Zr(0.09)O(2) solid solution exhibited the highest photocatalytic activity among all the as-prepared samples. Its activity was much higher than that of P25. The formation mechanism of core-shell spherical structures was proposed. Moreover, we successfully extended this method to prepare microspheres of ceria and ceria-zirconia solid solutions. We think this general method may be easily scaled up for industrial production of microspherical solid solutions photocatalysts and catalysts.     

Structure analysis and photocatalytic properties of spinel zinc gallium oxonitrides

This report describes a detailed structural, electronic, and catalytic characterization of zinc gallium oxonitride photocatalysts with a spinel crystal structure. The bandgap decreases to less than 3 eV with increasing nitrogen content (<3 wt%) and these photocatalysts are active in visible light (λ>420 nm) for the degradation of cresol and rhodamine B. Density functional theory calculations show that this bandgap reduction is in part associated with hybridization between the dopant N 2p states and Zn 3d orbitals at the top of the valence band. X-ray photoelectron measurements indicate that nitrogen is indeed interacting with the oxide precursor through the formation of both nitride- and oxonitride-type species. The incorporation of nitrogen reduces the uniformity of the local structure of the spinel Zn-Ga-O-N (ZGON) species, as reflected in X-ray absorption spectra and Raman measurements relative to zinc gallate, which suggests the presence of defects. The oxonitrides exhibit faster photocatalytic rates of reaction than the oxide precursor. The degradation mechanisms were determined to be via the attack by hydroxyl radicals and holes for rhodamine B and cresol, respectively. Addition of Pt as a co-catalyst increased the rate of photodegradation, a result attributed to better charge separation.     

Zeolitic Imidazolate Framework 8‐Derived Au@ZnO for Efficient and Robust Photocatalytic Degradation of Tetracycline

Tetracycline (TC) and other antibiotics accumulated in groundwater and soil pollute ecological environment and threaten human health. Gold nanoparticles doped on photocatalysts are able to enhance the photodegradation efficiency during removing these antibiotics, but preparation of Au nanoparticles of well‐dispersion on photocatalysts remains challenging. In this work, zeolite imidazolate (ZIF‐8) was employed as the precursor to prepare Au@ZnO photocatalyst via impregnation and in‐situ reduction method to efficiently degrade the tetracycline in the aqueous solution. Au nanoparticles are of 10 nm in size and uniformly dispersed on the surfaces of ZnO microstructures. The as‐prepared Au@ZnO is able to remove 85.5% of TC of 0.010 mg/mL within 2 h, presenting higher photocatalytic activity than pure ZnO catalyst. Most importantly, the catalyst shows its superior stability after five cycles without structure and activity changing. The mechanism of the photocatalytic degradation was discussed in detail.     

Photocatalytic Degradation of Single and Binary Mixture of Brilliant Green and Rhodamine B Dyes by Zinc Sulfide Quantum Dots

We present the preparation of octadecylamine-capped ZnS quantum dots from bis(morpholinyldithiocarbamato)Zn(II) complex. The complex was thermolyzed at 130 °C in octadecylamine at different times, to study the effect of reaction time on the morphological and photocatalytic properties of the ZnS quantum dots. Powder X-ray diffraction patterns confirmed a hexagonal wurtzite crystalline phase of ZnS, while HRTEM images showed particle sizes of about 1–3 nm, and energy band gaps of 3.68 eV (ZnS–1), 3.87 eV (ZnS–2), and 4.16 eV (ZnS–3) were obtained from the Tauc plot for the ZnS nanoparticles. The as-prepared ZnS were used as photocatalysts for the degradation of brilliant green, rhodamine B, and binary dye consisting of a mixture of brilliant green-rhodamine B. The highest photocatalytic degradation efficiency of 94% was obtained from ZnS–3 with low photoluminescence intensity. The effect of catalytic dosage and pH of the dyes solution on the photocatalytic process shows that pH 8 is optimal for the degradation of brilliant green, while pH 6.5 is the best for photocatalytic degradation of rhodamine B. The degradation of the binary dyes followed the same trends. The effect of catalytic dosage shows that 1 mg mL⁻¹ of the ZnS nano-photocatalyst is the optimum dosage for the degradation of organic dyes. Reusability studies show that the ZnS quantum dots can be reused five times without a significant reduction in degradation efficiency.     

Visible light photocatalytic activity of BiVO4 particles with different morphologies

Bismuth vanadate (BiVO₄) particles with different morphologies were synthesized by a one-step hydrothermal process and their optical and photocatalytic properties were investigated. Their crystal structure and microstructures were characterized using X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). XRD patterns demonstrate that the as-prepared samples are monoclinic cell. FESEM shows that BiVO₄ crystals can be fabricated in different morphologies by simply manipulating the reaction parameters of hydrothermal process. The UV–visible diffuse reflectance spectra (UV–vis DRS) reveal that the band gaps of BiVO₄ photocatalysts are about 2.07–2.21 eV. The as-prepared BiVO₄ photocatalysts exhibit higher photocatalytic activities in the degradation of rhodamine B (Rh B) under visible light irradiation (λ > 420 nm) compared with traditional N-doped TiO₂ (N-TiO₂). Furthermore, wheat like BiVO₄ sample reveals the highest photocatalytic activity. Up to 100% Rh B is decolorized after visible light irradiation for 180 min. The reason for the difference in the photocatalytic activities for BiVO₄ samples obtained at different conditions were systematically studied based on their shape, size and the variation of local structure.     

Studies on extraction of copper(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone

The extraction of Cu(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone (HA), in different organic solvents has been studied. The extraction mechanism of Cu(II) and the composition of the extracted species has been determined. Cu(II) was extracted as CuA₂, or in the presence of TOPO, as CuA₂TOPO. The extraction constants do not change regularly with increasing the length of acyl chain in the 1-phenyl-3-methyl-4-acyl-5-pyrazolone derivatives. The effect of the temperature on the extraction of Cu(II) has also been investigated.     

Effects of Halogen Bonding in Chemical Activity of Lead(II) Electron Pair: Sonochemical Synthesis,Structural Studies,and Thermal Analysis of Novel Lead(II) Nano Coordination Polymer

The nanoflower lead(II) coordination compound {[Pb(phen)(μ‐CH₃COO)][PF₆]}_n ( 1 ) (phen = 1,10‐phenanthroline) was synthesized by a sonochemical method. The nanostructure was characterized by using scanning electron microscopy (SEM), X‐ray powder diffraction, elemental analysis, and thermal analysis. The single‐crystal X‐ray structure shows that the overall structure of 1 is a 1D coordination polymer. Complex 1 has a bridging acetate pathway. Three halogen bonds observed in the structure and the strong halogen bonding of F–Pb causes chemical activity of the lead electron pair. This is further extended into a 3D supramolecular structure by weak π–π intermolecular interactions. The coordination number of the lead(II) ions is six, resulting in PbN₂O₄. PbO nanoparticles were obtained by the thermolysis of 1 at 180 °C with oleic acid as a surfactant. The morphology and size of the prepared PbO nanoparticles were further observed using scanning electron (SEM) and transmission electron microscopy (TEM), and were analyzed by X‐ray photoelectron spectroscopy (XPS).     

Crystallographic report: Bis(norfloxacin)dilead(II) tetranitrate, [Pb2(H‐Norf)2(ONO2)4]

The centrosymmetric binuclear structure of [Pb₂(H‐Norf)₂(ONO₂)₄]shows the geometry around each lead(II) atom to be distorted trigonal bipyramidal with Pb–O distances ranging from 2.357(3) to 2.769(4) Å. Copyright © 2003 John Wiley & Sons, Ltd.     

Short time deposition of TiO2 nanoparticles on SiC as photocatalysts for the degradation of organic dyes

The deposition of TiO₂ nanoparticles on SiC was carried out by mechanical milling under different conditions. SiC–TiO₂ samples were used as photocatalysts for the degradation of organic dyes such as methylene blue and rhodamine B. A short time deposition of TiO₂ nanoparticles was observed during mechanical milling (2 min at 200 rpm) to cover the SiC particles. The presence of SiC and TiO₂ (anatase and rutile) was confirmed by means of X-ray diffraction after thermal treatment at 450 °C. The deposition of TiO₂ on SiC was corroborated by scanning electron microscopy analysis; the thickness of the thin layer of TiO₂ deposited on SiC increases as the proportion of TiO₂ increases. The energy band gap values obtained for these compounds were around 3.0 eV. SiC–TiO₂ photocatalysts prepared by mechanical milling exhibited better activity under UV-light irradiation for the degradation of methylene blue and rhodamine B than commercial TiO₂ powder (titania P25).