Photocatalytic activity of CdS nanocrystals stabilized by a polymer shell and promoted by cobalt and nickel complexes in the reaction of hydrogen evolution

Nanocrystals (NCs) of CdS with oleate surface (NC-1) and octadecyl thiolate surface (NC-2), stabilized by a polycation shell, were doped with nickel bis(2-aminobenzenethiolate) (1), cobalt(III) chlorobis(dimethylglyoximato)(2-mercaptopyridine) (2), and also with 1,2-ethanedithiol and didodecylsulfide clathrochelates of cobalt(II) (3 and 4). The influence of doping on the photocatalytic activity in the hydrogen evolution reaction was investigated. Complex 1 appeared to be the most effective cocatalyst for H₂ evolution with the reaction rate increased by the factor of 8—11. Accomodating the complex in a polymer shell yields the best result. The rate of H₂ evolution increases monotonically with increasing concentration of this complex until the concentration achieves the ratio of one complex molecule per single NC. It is shown that the chemical composition of the surface has a significant influence on their photocatalytic activity in the hydrogen evolution reaction. The activity of NC-2 is 200 times that of NC-1. The replacement of oleate groups of the latter with sulfide increases the activity of these photocatalysts by a factor of 2000.     

Chemical synthesis and optical properties of CdS–poly(lactic acid) nanocomposites and their transparent fluorescent films

This paper describes the first synthesis of cadmium sulfide (CdS)-poly(lactic acid) (PLA) nanocomposites and their transparent fluorescent films by covalently grafting PLA onto the surfaces of CdS nanocrystals (NCs). Synthesis of the nanocomposites involved two steps. Lactic acid (LA)-capped CdS NCs were first prepared by reacting cadmium chloride (CdCl₂) with sodium sulfide (Na₂S) using LA as the organic ligand in H₂O/N,N-dimethylformamide (DMF) solution. CdS–PLA nanocomposites were then formed by in situ ring-opening polymerization of lactide on the surface of modified CdS NCs. We also demonstrated herein the fabrication of the transparent fluorescent films of CdS–PLA nanocomposites by blending as-prepared nanocomposites with high-molecular-weight PLA. The as-prepared CdS NCs and their nanocomposites were studied by transmission electron microscopic imaging, thermogravimetric analyses, and spectroscopic measurements (ultraviolet–visible absorption and photoluminescence). The results revealed that the CdS–polymer nanocomposites exhibited good optical properties in terms of their photoluminescence and transparency.     

Photocatalytic Hydrogen Evolution by Oleic Acid‐Capped CdS,CdSe, and CdS0.75Se0.25 Alloy Nanocrystals

Photocatalytic generation of hydrogen by using oleic acid‐capped CdS, CdSe, and CdS_0.75Se_0.25 alloy nanocrystals (quantum dots) has been investigated under visible‐light irradiation by employing Na₂S and Na₂SO₃ as hole scavengers. Highly photostable CdS_0.75Se_0.25 alloy nanocrystals gave the highest hydrogen evolution rate (1466 μmol h^?1 g^?1), which was about three times higher than that of CdS and seven times higher than that of CdSe.     

Graphene enhanced electrochemiluminescence of CdS nanocrystal for H2O2 sensing

Graphene-CdS (G-CdS) nanocomposites were successfully prepared by CdS nanocrystals (CdS NCs) formed in situ on the surface of graphene sheets, using graphene oxide (GO) sheets with rich negatively charged carboxylic acid groups as starting materials. Compared with pure CdS NCs, the presence of the graphene doped in G-CdS nanocomposites could facilitate the electrochemical redox process of CdS NCs; further, the as-prepared G-CdS nanocomposite can react with H₂O₂ to generate strong and stable electrochemiluminescent (ECL) emission, which not only enhances its ECL intensity by about 4.3-fold but also decreases its onset potential for about 320 mV. The as-prepared solid-state ECL H₂O₂ sensor shows acceptable linear response from 5 μM up to 1 mM with a detection limit of 1.7 μM (S/N = 3). The ECL H₂O₂ sensor exhibits excellent reproducibility and long-term stability. Such a property would promote the potential application of the graphene as enhanced materials in fabricating sensors for chemical and biochemical analysis.     

Monodisperse AgSbS2 Nanocrystals: Size‐Control Strategy,Large‐Scale Synthesis,and Photoelectrochemistry

We report an efficient approach to the synthesis of AgSbS₂ nanocrystals (NCs) by colloidal chemistry. The size of the AgSbS₂ NCs can be tuned from 5.3 to 58.3 nm with narrow size distributions by selection of appropriate precursors and fine control of the experimental conditions. Over 15 g of high‐quality AgSbS₂ NCs can be obtained from one single reaction, indicative of the up‐scalability of the present synthesis. The resulting NCs display strong absorptions in the visible‐to‐NIR range and exceptional air stability. The photoelectrochemical measurements indicate that, although the pristine AgSbS₂ NC electrodes generate a cathodic photocurrent with a relatively small photocurrent density and poor stability, both of them can be significantly improved subject to CdS surface modification, showing promise in solar energy conversion applications.     

Electrogenerated chemiluminescence and electrochemical bi-functional sensors for H2O2 based on CdS nanocrystals/hemoglobin multilayers

A novel bi-functional sensor, based on CdS nanocrystals (NCs) and hemoglobin (Hb) multilayer films, designated as {Hb/CdS}_n, modified glassy carbon electrode (GCE) by layer-by-layer (LbL) assembly, has been presented. The electrogenerated chemiluminescence (ECL) and electrochemical properties of {Hb/CdS}_n have been investigated in detail. Hb in the multilayer films can enhance the stability of electrogenerated species of CdS NCs, and CdS NCs can also promote the direct electron transfer between Hb and GCE. As a consequence experimentally, the multilayer films modified GCE is suitable to be used as a bi-functional sensor, ECL sensor and electrochemical sensor, to determine H₂O₂ in obviously different concentration. In high concentration of H₂O₂, this sensor as an ECL sensor shows a linear response from 15 μM up to 18 mM. In the lower concentration of H₂O₂, it as an amperometric one shows two linear ranges of amperometric responses to the concentration of H₂O₂ ranging from 6.0 to 31.0 μM and from 6.0 μM down to 40 nM with a detection limit of 20 nM, based on the high stability of ECL by {Hb/CdS}_n and the excellent electrocatalytical ability of Hb to H₂O₂. Thus, {CdS/Hb}_n modified electrodes would have a great merit to expand the application of biosensors to life science and environmental science.     

Greatly enhanced electrochemiluminescence of CdS nanocrystals upon heating in the presence of ammonia

CdS nanocrystals (NCs) usually exhibit very weak electrochemiluminescence (ECL) emission. It is showed that when CdS NCs were treated by heating in the presence of ammonia (heated-CdS–NH₃), greatly enhanced ECL was observed. The ECL of the heated-CdS–NH₃ modified glassy carbon electrode (heated-CdS–NH₃/GCE) in phosphate buffer solution (pH 7.0) containing 0.1 M K₂S₂O₈ was ca. 310 times higher than that of CdS/GCE. The treatment caused the changes in the morphology and surface electronic structure of CdS NCs, which facilitated the reduction process of CdS, consequently improved the quantity of the excited states (CdS*), leading to enormous enhancement in ECL.     

普鲁士蓝/CdS纳米复合物电致化学发光及其H2O2传感应用

通过一定体积比的CdS和普鲁士蓝(PB)胶体纳米溶液的简单混合,制备了PB/CdS纳米复合物。在共反应剂存在条件下,PB纳米粒子含量较低时,在ITO电极上CdS纳晶的电致化学发光(ECL)强度可以增强3倍左右。PB纳米粒子含量较高时,CdS纳晶的ECL强度则显著降低。详细讨论了PB纳米粒子对CdS纳晶ECL影响的机理。PB纳米粒子对CdS纳晶的ECL增强可用于H2O2传感。该传感器对H2O2响应的线性范围为3.3×10-8～6.5×10-3 mol.L-1(R=0.999 2),检测限为12 nmol.L-1(S/N=3),传感器具有良好的稳定性和重现性。     

Synthesis of nanocrystalline CdS from cadmium(II) complex of S-benzyl dithiocarbazate as a precursor

The single X-ray crystal structure of the cadmium(II)–S-benzyl dithiocarbazate (SBDTC) complex, [Cd(SBDTC)Cl₂]₂, is reported. The compound has been found to be an effective single-source precursor for the preparation of CdS nanocrystals (NCs) via solvothermal method. CdS NCs including spheres and rods were prepared at a relatively low temperature by thermolysis of the precursor using chelating solvent like ethylene glycol (EG), ethylenediamine (EN), hydrazine hydrate (HH) or in a mixture of EG and EN. The influence of solvent, temperature and reaction time was investigated on the size and morphology of the NCs. Use of EG afforded spherical CdS NCs while EN uniquely yielded rod-shaped NCs, and mixture of spheres and rods are obtained from the mixture of EN and EG with a ratio 0.2 (v/v: EN/EG). UV–visible spectroscopy established pronounced quantum confinement with enhanced band gap and XRD analyses revealed hexagonal crystal phase for so obtained CdS NCs. The NCs were also characterized by transmission electron microscopy (TEM), photoluminescence spectroscopy (PL), energy-dispersive X-ray spectroscopy (EDS) and FTIR. The possible formation mechanism for the anisotropic growth of NCs was also discussed.     

Controllable synthesis of functionalized CdS nanocrystals and CdS/PMMA nanocomposite hybrids

We reported controllable synthesis of CdS nanocrystal-polymer transparent hybrids by using polymethylmethacrylate (PMMA) as a polymer matrix. In a typical run, the appropriate amounts of cadmium chloride (CdCl₂) and sodium sulfide (Na₂S) in the presence of 2-mercaptoethanol (ME) as the organic ligand are well dispersed in H₂O/DMF solution without any aggregation. From a combination of transmission electron microscopy (TEM) and a computing method of Brus’s model according UV-vis absorption spectra, the particle size of as-prepared hydroxyl-coated CdS nanocrystal was determined to be about 5 nm. Then, with the surface treatment with methacryloxypropyltrimethoxysilane (MPS), CdS-PMMA hybrids were obtained via free radical polymerization in situ. FT-IR characterization indicates the formation of robust bonding between CdS nanocrystals and the organic ligand and the formation of double-bond functional CdS nanocrystals. The TGA measurement displays CdS-PMMA hybrids possess better thermal stability compared with pure PMMA polymer. The fluorescence measurement shows that CdS nanocrystals and CdS-PMMA hybrids exhibit good optical properties. Also, the luminescent photographs taken under ultraviolet light prove the luminescence properties.     

Spectroscopic investigations on II–VI-semiconductor nanocrystals and their assemblies

This review points out that (magneto-)optical measurements may help to shine light on the recombination processes taking place in semiconductor nanocrystals. The surface capping with thiols creates a CdS shell around CdTe cores and forms a Cd site that is not fourfold-coordinated at the surface. It is pointed out how specific cappings such as thio-amines and thio-acids assist in coupling NCs and how we may distinguish between NC–NC interactions via electrostatic and covalent linking with the aid of the optical measurements. Furthermore, with static and time-resolved ODMR studies on IR-active core-shell HgTe/Hg _x Cd_1−x Te(S) particles it is demonstrated how the nature of the recombination emission being associated with a Cd–Hg mixed site is elucidated and by this yielding structural information on the NC core-shell interface. With these examples we show that and how nanomaterials of probable technological interest are studied beneficially with advanced spectroscopic techniques.     

Glycine-Functionalized CsPbBr3 Nanocrystals for Efficient Visible-Light Photocatalysis of CO2 Reduction

Capping ligands are indispensable for the preparation of metal-halide-perovskite (MHP) nanocrystals (NCs) with good stability; however, the long alkyl-chain capping ligands in conventional MHP NCs will be unfavorable for CO₂ adsorption and hinder the efficient carrier separation on the surface of MHP NCs, leading to inferior catalytic activity in artificial photosynthesis. Herein, CsPbBr₃ nanocrystals with short-chain glycine as ligand are constructed through a facile ligand-exchange strategy. Owing to the reduced hindrance of glycine and the presence of the amine group in glycine, the photogenerated carrier separation and CO₂ uptake capacity are noticeably improved without compromising the stability of the MHP NCs. The CsPbBr₃ nanocrystals with glycine ligands exhibit a significantly increased yield of 27.7 μmol g⁻¹ h⁻¹ for photocatalytic CO₂-to-CO conversion without any organic sacrificial reagents, which is over five times higher than that of control CsPbBr₃ NCs with conventional long alkyl-chain capping ligands.     

Controllable synthesis of ZnS/PMMA nanocomposite hybrids generated from functionalized ZnS quantum dots nanocrystals

We reported controllable synthesis of ZnS nanocrystal-polymer transparent hybrids by using polymethylmethacrylate (PMMA) as a polymer matrix. In a typical run, the appropriate amounts of zinc chloride (ZnCl₂) and sodium sulfide (Na₂S) in the presence of 2-mercaptoethanol (ME) as the organic ligand were well dispersed in H₂O/dimethylformamide solution without any aggregation. In addition, the Mn-doped ZnS nanocrystals (NCs) were synthesized with similar method. Then, ZnS-PMMA hybrids were obtained via free radical polymerization in situ by using ZnS NCs functionalized with methacryloxypropyltrimethoxysilane (MPS). FT-IR characterization indicates the formation of robust bonding between ZnS NCs and the organic ligand. The TEM images show that ZnS NCs are well dispersed in PMMA matrix, and particle size of as-prepared ZnS NCs is about 2.6 nm, in agreement with the computing results of Brus’s model and Debye–Scherrer formula. The photoluminescence measurements present that ZnS NCs, Mn-doped ZnS NCs, and ZnS/PMMA hybrid show good optical properties.     

Catalytic activity of Pt-promoted CdS nanocrystals covered with a polymer in photoelectrochemical hydrogen production by water splitting

Photocatalytic properties of Pt-promoted CdS nanocrystals functionalized by the polymer coating were investigated. Deposition of Pt on the surface of the nanoparticles followed by polymer functionalization provides a high photocatalytic activity (1.45 mmol h^–1 mg^–1 at 0.93 W cm^–2) and apparent quantum yield (7%, λ = 445 nm) of the particles. Dependence of the rate of H₂ evolution on Pt loading is described by a curve with the maximum, whereas the quantum yield decreases with an increase in the light flux density. The photocatalytic activity of the nanocrystals increases more than 2 times with polymer coatining.     

The First Study on the Reactivity of Water Vapor in Metal–Organic Frameworks with Platinum Nanocrystals

We first studied the reactivity of H₂O vapor in metal–organic frameworks (MOFs) with Pt nanocrystals (NCs) through the water–gas shift (WGS) reaction. A water‐stable MOF, UiO‐66, serves as a highly effective support material for the WGS reaction compared with ZrO₂. The origin of the high catalytic performance was investigated using in situ IR spectroscopy. In addition, from a comparison of the catalytic activities of Pt on UiO‐66, where Pt NCs are located on the surface of UiO‐66 and Pt@UiO‐66, where Pt NCs are coated with UiO‐66, we found that the competitive effects of H₂O condensation and diffusion in the UiO‐66 play important roles in the catalytic activity of Pt NCs. A thinner UiO‐66 coating further enhanced the WGS reaction activity of Pt NCs by minimizing the negative effect of slow H₂O diffusion in UiO‐66.     

Fabrication of Ni Nanoclusters-Modified Brookite TiO2 Quasi Nanocubes and Its Photocatalytic Hydrogen Evolution Performance

The development of low-cost, earth-abundant and highly-efficient cocatalysts is still important to promote the photocatalytic H₂ evolution reaction over semiconductors. Herein, a series of Ni nanoclusters (NCs) modified brookite TiO₂ quasi nanocubes (BTN) (marked as Ni/BTN) are fabricated via a chemical reduction process. It is found that the loading content and oxidation state of Ni NCs can significantly influence the optical absorption, photocat-alytic activity, and stability of Ni/BTN composites. Among the resultant Ni NCs-loaded products, 0.1%Ni/BTN composite delivers the best H₂ evolution activity (156 μmol/h), which is 4.3 times higher than that of the BTN alone (36 μmol/h). Furthermore, the Ni NCs with ultra ne size (∽2 nm) and high dispersity enable shorter charge transfer distance by quickly capturing the photoexcited electrons of BTN, and thus result in the improved activity even though the oxidization of some Ni NCs on BTN is harmful to the activity for H₂ evolution due to the much lower electron capturing capability of NiO than metallic Ni. This study not only clari es that brookite TiO₂ would be a promising high-efficient photo-catalyst for H₂ evolution, but also reveals vital clues for further improving its photocatalytic performance using low-cost Ni-based cocatalyst.     

Polyelectrolyte multilayers as a platform for luminescent nanocrystal patterned assemblies

The fabrication of uniform and patterned nanocrystal (NC) assemblies has been investigated by exploiting the possibility of carefully tailoring colloidal NC surface chemistry and the ability of polyelectrolyte (PE) to functionalize substrates through an electrostatic layer-by-layer (LbL) strategy. Appropriate deposition conditions, substrate functionalization, and post-preparative treatments were selected to tailor the substrate surface chemistry to effectively direct the homogeneous electrostatic-induced assembly of NCs. Water-dispersible luminescent NCs, namely, (CdSe)ZnS and CdS, were differently functionalized by (1) ligand-exchange reaction, (2) growth of a hydrophilic silica shell, and (3) formation of a hydrophilic inclusion complex, thus providing functional NCs stable in a defined pH range. The electrostatically charged functional NCs represent a comprehensive selection of examples of surface-functionalized NCs, which enables the systematic investigation of experimental parameters in NC assembly processes carried out by combining LbL procedures with microcontact printing and also exploiting NC emission, relevant for potential applications, as a prompt and effective probe for evaluating assembly quality. Thus, an ample showcase of combinations has been investigated, and the spectroscopic and morphological features of the resulting NC-based structures have been discussed.     

Comparative Structural,Optical, and Photoluminescence Studies of YF3:Pr,YF3:Pr@LaF3, and YF3:Pr@LaF3@SiO2 Core–Shell Nanocrystals

Praseodymium (Pr³⁺)‐doped YF₃ (core) and LaF₃ ‐covered YF₃ :Pr (core–shell) nanocrystals (NCs ) were prepared successfully by an ecofriendly, polyol‐based, co‐precipitation process, which were then coated with a silica shell by using a sol–gel‐based Stober method. X‐ray diffraction (XRD), transmission electron microscopy (TEM ), thermal analysis, Fourier transform infrared (FTIR) , UV /vis, energy bandgap, and photoluminescence studies were used to analyze the crystal structure, morphology, and optical properties of the nanomaterial. XRD and TEM results show that the grain size increases after sequential growth of crystalline LaF₃ and the silica shell. The silica surface modification enhances the solubility and colloidal stability of the core–shell‐SiO₂ NCs . The results indicate that the surface coating affects the optical properties because of the alteration in crystalline size of the materials. The emission intensity of silica‐modified NCs was significantly enhanced compared to that of core and core–shell NCs . These results are attributed to the formation of chemical bonds between core–shell and noncrystalline SiO₂ shell via La–O–Si bridges, which activate the “dormant” Pr³⁺ ions on the surfaces of the nanoparticles. The luminescence efficiency of the as‐prepared core, core–shell, and core–shell‐SiO₂ NCs are comparatively analyzed, and the observed differences are justified on the basis of the surface modification surrounding the luminescent seed core NCs .     

Synthesis and green up-conversion fluorescence of colloidal La0.78Yb0.20Er0.02F3/SiO2 core/shell nanocrystals

Water-soluble PVP-stabilized hexagonal-phase La_0.78Yb_0.20Er_0.02F₃ nanocrystals (NCs) were synthesized by hydrothermal method. The NCs were coated with a very thin silica shell, and amino groups were introduced to the surface of silica shells by copolymerization of 3-aminopropyl(triethoxy)silane. The core/shell NCs can be dispersed in ethanol and water to form stable colloidal solution. The transmission electron microscopy (TEM), selected area electron diffraction (SAED), powder X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR) were used to characterize the core/shell materials. In addition, the green up-conversion fluorescence mechanism of La_0.78Yb_0.20Er_0.02F₃/SiO₂ NCs was studied with a 980-nm diode laser as excitation source. The water solubility, small core/shell particles size, and well colloidal stability mean the green up-conversion fluorescence NCs have potential applications in bioassay.     

One-pot hydrothermal synthesis of willow branch-shaped MoS2/CdS heterojunctions for photocatalytic H2 production under visible light irradiation

Willow branch-shaped MoS₂/CdS heterojunctions are successfully synthesized for the first time by a facile one-pot hydrothermal method. The as-prepared samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption measurements, diffuse reflectance spectroscopy, and photoelectrochemical and photoluminescence spectroscopy tests. The photocatalytic hydrogen evolution activities of the samples were evaluated under visible light irradiation. The resulting MoS₂/CdS heterojunctions exhibit a much improved photocatalytic hydrogen evolution activity than that obtained with CdS and MoS₂. In particular, the optimized MC-5 (5 at.% MoS₂/CdS) photocatalyst achieved the highest hydrogen production rate of 250.8 μmol h^-1, which is 28 times higher than that of pristine CdS. The apparent quantum efficiency (AQE) at 420 nm was 3.66%. Further detailed characterizations revealed that the enhanced photocatalytic activity of the MoS₂/CdS heterojunctions could be attributed to the efficient transfer and separation of photogenerated charge carriers resulting from the core-shell structure and the close contact between MoS₂ nanosheets and CdS single-crystal nanorods, as well as to increased visible light absorption. A tentative mechanism for photocatalytic H₂ evolution by MoS₂/CdS heterojunctions was proposed. This work will open up new opportunities for developing more efficient photocatalysts for water splitting.