Hydroxylated graphene quantum dots as fluorescent probes for sensitive detection of metal ions

Highly sensitive methods are important for monitoring the concentration of metal ions in industrial wastewater.Here,we developed a new probe for the determination of metal ions by fluorescence quenching.The probe consists of hydroxylated graphene quantum dots(H-GQDs),prepared from GQDs by electrochemical method followed by surface hydroxylation.It is a non-reactive indicator with high sensitivity and detection limits of 0.01μM for Cu2+,0.005μM for Al3+,0.04μM for Fe3+,and 0.02μM for Cr3+.In addition,the low biotoxicity and excellent solubility of H-GQDs make them promising for application in wastewater metal ion detection.

Ionic polymer metal composites actuators with enhanced driving performance by incorporating graphene quantum dots

In order to further improve the driving performance of ionic polymer metal composites(IPMCs),Nafion/graphene quantum dots(GQDs)hybrid membranes incorporating GQDs with various contents of 0,0.1 wt.%,0.5 wt.%,1.0 wt.%,2.0 wt.%and 4.0 wt.%were fabricated by solution casting,and then IPMCs were manufactured by electroless plating.The water contents and elastic moduli of the hybrid membranes were tested.The morphology characteristics of the hybrid membranes and the IPMCs were observed,and the current,AC impedance,blocking force and displacement of the IPMCs were measured.The results show that the elastic modulus of the hybrid membranes decreases,the water content increases,and the actuation performance of the IPMCs improves significantly after the addition of GQDs.IPMC with 1.0 wt.%GQDs exhibits the best driving property.Compared with the IPMC without GQDs,the working current,ion conductivity,blocking force,and tip displacement increase by 94.67%,311.11%,53.66%,and 66.07%,respectively.These results lay a solid foundation for the preparation of IPMCs with high performance,and further broaden their applications in biomedical devices and bionic robots.

Spin-flip process through double quantum dots coupled to two half-metallic ferromagnetic leads

We investigate the spin-flip process through double quantum dots coupled to two half-metallic ferromagnetic leads in series. By means of the slave-boson mean-field approximation, we calculate the density of states in the Kondo regime for two different configurations of the leads. It is found that the transport shows some remarkable properties depending on the spin-flip strength. These effects may be useful in exploiting the role of electronic correlation in spintronics.

Photoluminescence and lasing properties of InAs/GaAs quantum dots grown by metal-organic chemical vapour deposition

Photoluminescence （PL） and lasing properties of InAs/GaAs quantum dots （QDs） with different growth procedures prepared by metalorganic chemical vapour deposition are studied. PL measurements show that the low growth rate QD sample has a larger PL intensity and a narrower PL line width than the high growth rate sample. During rapid thermal annealing, however, the low growth rate sample shows a greater blueshift of PL peak wavelength. This is caused by the larger InAs layer thickness which results from the larger 2-3 dimensional transition critical layer thickness for the QDs in the low-growth-rate sample. A growth technique including growth interruption and in-situ annealing, named indium flush method, is used during the growth of GaAs cap layer, which can flatten the GaAs surface effectively. Though the method results in a blueshift of PL peak wavelength and a broadening of PL line width, it is essential for the fabrication of room temperature working QD lasers.

Electrically tunable spin diode effect in a tunneling junction of quantum dot

Control over the tunneling current in spintronic devices by electrical methods is an interesting topic, which is experiencing a burst of activity. In this paper, we theoretically investigate the transport property of electrons in a spin-diode structure consisting of a single quantum dot(QD) weakly coupled to one nonmagnetic(NM) and one half-metallic ferromagnet(HFM) leads, in which the QD has an artificial atomic nature. By modulating the gate voltage applied on the dot, we observe a pronounced decrease in the current for one bias direction. We show that this rectification is spin-dependent, which stems from the interplay between the spin accumulation and the Coulomb blockade on the quantum dot. The degree of such spin diode behavior is fully and precisely tunable using the gate and bias voltages. The present device can be realized within current technologies and has potential application in molecular spintronics and quantum information processing.

Lithiated Graphdiyne Quantum Dots for Stable Lithium Metal Anodes

Here,a facile strategy is proposed for the preparation of lithiated graphdiyne quantum dots(GDY-Li QDs)with conjugated sp-and sp2-hybridized carbons by the self-assembly technique ofπ–πstacking of lithiated hexaethynylbezene under mild conditions.The as-prepared GDY-Li QDs,containing stacked multialkynyl aromatic backbone and abundant lithium(Li),show an average diameter of about 2.6 nm and good dispersion in the solvents.These distinctive structures endow GDY-Li QDs with superior properties that cannot be matched by traditional QDs,such as strong ion adsorption,Li-ion self-concentration,high Li-ion conductivity,the nanoconfinement effect,and ion solvation regulation.Benefiting from these features,GDY-Li QDs can stabilize Limetal anodes to effectively suppress Li-dendrite growth and significantly improve its Li plating/stripping coulombic efficiency(99.3%in the carbonate electrolyte).The full cells with GDY-Li QDs protected Li-metal anodes,and LiNi_(0.8)Co_(0.1)Mn^(0.1)O_(2)cathodes delivered high capacity and excellent cycling stability at high rates,which demonstrates the great potential of GDY-Li QDs for application in fast-charging Li-metal batteries.

Enhanced interfacial charge transfer on Bi metal@defective Bi_(2)Sn_(2)O_(7) quantum dots towards improved full-spectrum photocatalysis:A combined experimental and theoretical investigation

To mitigate the water pollution problem by photocatalytic degradation of typical antibiotics of tetracycline(TC),we prepared defective Bi_(2)Sn_(2)O_7(BSO)quantum dots(QDs)with a full spectral response due to Bi metal deposition,using a one-pot hydrothermal method,labeled as Bi@BSO-OV.The optimized Bi@BSOOV showed 73.4% removal of TC in 1 h under irradiation with a 50 W LED lamp in the wavelength band in the visible-near-infrared(vis-NIR)light,a rate that is substantially greater than that of pure BSO(14.7%).The synergistic interaction of Bi metal and oxygen vacancies(OVs)is crucial to boosting photocatalytic performance.The near-infrared region of the photo-response is extended by the surface plasmon resonance(SPR)effect of Bi metal,enhancing the photocatalytic performance and dramatically raising the efficiency of solar energy utilization.In addition to inducing defect levels in BSO,the OVs also activate the surface adsorbed O_(2) to promote the production of·O_(2)^(-)and ^(1)O_(2).DFT calculations reveal that Bi metal and OVs can mutually tune the charge transfer pathways.On the one hand,Bi metal can act as both a charge transfer bridge and an electron donor to assist charge separation.On the other hand,OVs-induced defect levels allow electrons that leap to the conduction band(CB)to first leap from the valence band(VB)to the defect levels,notably improving interfacial charge separation and transfer.The concept of design executed in this study for altering the catalyst by introducing both OVs and Bi metal can provide a rational design idea and potential insight for improving the photocatalytic activity for environmental applications.

Advances in green colloidal synthesis of metal selenide and telluride quantum dots

During the past three decades, metal selenide and telluride quantum dots (QDs) have been deemed one of the most vital nanomaterials in virtue of their extensive applications, including lighting, solar harvesting,photocatalysis, biolabelling, quantum computing and so forth. With the growing demands for the QDrelated products, environmental friendly, energy-efficient and timesaving approaches to synthesize functional metal selenide and telluride QDs are greatly welcome. On the basis of the development in synthesis of chalcogen precursors, this mini review summarizes the recent progress in the green methods for synthesizing metal selenide and telluride QDs. At first, the panorama of basic synthetic methodology of metal chalcogenide QDs is briefly introduced. Then, numerous evolving colloidal synthetic methods are discussed, highlighting the phosphine-free precursors and the aqueous ionic precursors. Finally, this review ends with remaining challenges and future prospects in synthetic schemes. We hope this review will provide some stimulating information to promote further advancement in this area.

DNA Directed Self-Assembly of Fluorescent Colloidal Semiconductor Quantum Dots and Plasmonic Metal Nanoparticles Heterogeneous Nanomaterials

The exciton-plasmon interaction between fluorescent colloidal semiconductor quantum dots and plasmonic metal nanoparticles may lead to emission quenching or enhancement of quantum dots, which have potential appli- cations in renewable energy, nanophotonics, and biosensing. Semiconductor quantum dots and metal nanoparticles hybrids with controlled geometry, distance, and stoichiometry are crucial for the potential applications. While DNA nanotechnology, based on Watson-Crick base-pairing interactions between two single-stranded DNAs, has provided unique opportunities to generate fully programmable, functional metal nanoparticles and semiconductor quantum dots hybrid nanomaterials, and offers precisely control over the spacing, orientation, and chirality of the compo- nents. This review provides the highlights of the recent progresses in DNA directed self-assembly of colloidal sem- iconductor quantum dots and metallic nanoparticles heterogeneous nanomaterials. We also discuss the challenges and the trends in DNA directed self-assembly of semiconductor quantum dots and metallic nanoparticles hybrid nanomaterials.

Metal sulfide quantum dots-aggregated PAMAM dendrimer for cadmium ion-selective electrode-based immunoassay of alpha-fetoprotein

An ion-selective electrode(ISE)-based immunoassay has been innovatively designed for the sensitive detection of liver cancer biomarker(alpha-fetoprotein,AFP),using metal sulfide quantum dot(QD)-based nano labels.Cd S QDs-aggregated PAMAM dendrimer(QD-DE)was first synthesized and functionalized with polyclonal rabbit anti-human AFP antibodies.Thereafter,a sandwich immunoreaction was implemented on monoclonal mouse anti-human AFP antibody-coated microplate by using antibody-functionalized QD-DE as the secondary antibody.Accompanying the immunocomplex,subsequent potentiometric detection of cadmium ion dissolved from the QD-DE under acidic condition was conducted on a portable cadmium ion-selective electrode(Cd-ISE).Results revealed that the electrode potential of the Cd-ISE increased with the increment of AFP concentration from 0.1 to 100 ng m L^(-1)at a detection limit(LOD)of 68 pg m L^(-1).The relative standard deviations(RSD)were below9.09%and 10.54%for the intra-and inter-assay,respectively.Additionally,six human serum specimens were determined on CdISE-based immunosensor by using commercial human AFP ELISA kit as the reference,and gave good relationship between two methods.Importantly,Cd-ISE-based immunoassay offers the promise for simple and cost-effective screening of disease-related biomarkers.

Trimetallic synergistic optimization of 0D NiCoFe-P QDs anchoring on 2D porous carbon for efficient electrocatalysis and high-energy supercapacitor

Developing multi-functional and low-cost noble-metal-free catalysts such as transition metal phosphides(TMPs)to replace noble-metal is of practical significance for energy conversion and storage.However,the low-durability and the agglomeration phenomenon during the electrochemical process limit their practical applications.Herein,using metal–organic frameworks(MOFs)as the precursor and a combined strategy of gradient temperature calcination and thermal phosphorization,a 0D/2D heterostructure of NiCoFe-P quantum dots(QDs)anchored on porous carbon was successfully developed as highly efficient electrode materials for overall water splitting and supercapacitors.Owing to this distinctive 0D/2D heterostructure and the synergistic effect of multi-metallic TMPs,the NiCoFe-P/C exhibits excellent electrocatalytic activity and durability of HER(87 mV at 10 mA cm^(-2))and OER(257 mV at 100 mA cm^(-2))in the KOH electrolyte.When NiCoFe-P/C is used as the two electrodes of electrolyzed water,only 1.55 V can drive the current density to 10 m A cm^(-2).At the same time,our NiCoFe-P/C possessed extraordinary property for charge storage.In particular,an ultra-high energy density of 100.8 Wh kg^(-1) was achieved at a power density of 900.0 W kg^(-1) for our assembled hybrid supercapacitor device NiCoFe-P/C(2:1)//activated carbon(AC).This work may open a potential way for the design of 0D/2D hybrid multifunctional nanomaterials based on TMPs QDs.

Nanosurface chemistry and dose govern the bioaccumulation and toxicity of carbon nanotubes, metal nanomaterials and quantum dots in vivo

The chemical and biological mechanisms of life processes mostly consist of multistep and programmed processes at nanoscale levels. Interestingly enough, cell, the basic functional unit and platform that maintains life processes, is composed of various organelles fulfilling sophisticated functions through the precise control on the biomolecules （e.g., proteins, phospholipid, nucleic acid and ions） in a spatial dimension of nanoscale sizes. Thus, understanding of the activities of manufactured nanoscale materials including their interaction with biological sys- tems is of great significance in chemistry, materials sci- ence, life science, medicine, environmental science and toxicology. In this brief review, we summarized the recent advances in nanotoxicological chemistry through the dis- section of pivotal factors （primarily focusing on dose and nanosurface chemistry） in determining nanomaterial- induced biological/toxic responses with particular empha- sis on the nanomaterial bioaccumulation （and interaction organs or target organs） at intact animal level. Due to the volume of manufacture and material application, we deliberately discussed carbon nanotubes, metal/metal oxide nanomaterials and quantum dots, severing as representativematerial types to illustrate the impact of dose and nanosurface chemistry in these toxicological scenarios. Finally, we have also delineated the grand challenges in this field in a conceptual framework of nanotoxicological chemistry. It is noted that this review is a part of our persistent endeavor of building the systematic knowledge framework for toxicological properties of engineered nanomaterials.

Metal-organic Chemical Vapor Deposition of GaSb/GaAs Quantum Dots： the Dependence of the Morphology on Growth Temperature and Vapour V/Ⅲ Ratio

GaSb quantum dots have been widely applied in optoelectronic devices due to its unique electrical and optical properties.The effects of metal-organic chemical vapor deposition（MOCVD） parameters,such as growth temperature and vapour V/Ⅲ ratio[V/Ⅲ ratio means the molar ratio of trimethylgallium（TMGa） and triethylantimony（TESb）],were systematically investigated to achieve GaSb quantum dots with high quality and high density.The features of surface morphology of uncapped GaSb quantum dots were characterized by atomic force microscope（AFM） images.The results show that the surface morphologies of quantum dots are strongly dependent on growth temperature and vapour V/Ⅲ ratio.GaSb quantum dots with an average height of 4.94 nm and a density of 2.45× 1010 cm-2 were obtained by optimizing growth temperature and V/Ⅲ ratio.

Graphene quantum dots as efficient, metal-free, visible-light-active photocatalysts

This paper reports on new applications of water-dispersible graphene quantum dots(GQDs) that we recently developed. The prepared GQDs not only show broad absorption in the visible spectrum from 400 to 700 nm, but can also serve as smart photosensitizers with high singlet oxygen(1O2) production under visible-light irradiation(≥420 nm). We showed that the prepared GQDs can potentially be used as a metal-free, visible-light-active, sensitized photocatalyst via energy transfer mechanism, in which the light energy was converted by GQDs to produce 1O2, which can kill nearby microorganisms and degrade organic dyes.

A metal-free composite photocatalyst of graphene quantum dots deposited on red phosphorus

A simple approach to enhance the photocatalytic activity of red phosphorus（P） was developed.A mechanical ball milling method was applied to reduce the size of red P and to deposit graphene quantum dots onto red P. The product was characterized by scanning electron microscopy, transmission electron microscopy, contact angle measurements, zeta-potential measurements, X-ray diffraction and UV–vis absorption spectroscopy. The product exhibited high visible-light-driven photocatalytic performance in the photodegradation of rhodamine B.

Linear dipole behavior of single quantum dots encased in metal oxide semiconductor nanoparticles films

Understanding of charge/energy exchange processes and interfacial interactions that occur between quantum dots (QDs) and the metal oxides is of critical importance to these QD-based optoelectronic devices. This work reports on linear dipole behavior of single near-infrared emitting CdSeTe/ZnS core/shell QDs which are encased in indium tin oxide (ITO) semiconductor lianoparticles films. A strong polarization anisotropy in photohiminescence emission is observed by defocused wide-field imaging and polarization measuremen11echniques, and the average polarization degree is up to 0.45. A possible mechanism for the observation is presented in which the electrons, locating at single QD surface from ITO by electron transfer due to the equilibration of the Fermi levels, result in a significant Stark distortion of the QD electron/hole wavefunctions. The Stark distortion results in the linear polarization property of the single QDs. The investigation of linear dipole behavior for single QDs encased in ITO films would be helpful for further improving QD-based device performance.

Metal halide perovskites quantum dots:Synthesis and modification strategies for solar CO_(2)conversion

In the past few years,environmental and energy challenges arising from extensive burning of fossil fuels and CO_(2)emission have become the increasingly severe issue.One effective solution to address these problems is the reduction of CO_(2)into valuable solar fuels such as CO,CH_(4),and HCO_(2)H through the semiconductor-based pho-tocatalysis technology.Metal halide perovskites quantum dots(MHPs QDs)represent a new generation of pho-tosensitizers that possess excellent photoelectric properties and have been attracting enormous attention in the field of photocatalytic CO_(2)reduction.This review provides a concise introduction on different types and prep-aration methods of MHPs QDs and discusses the specific applications especially photocatalytic CO_(2)reduction mechanism of MHPs QDs.Furthermore,future opportunities and challenges for constructing high-performance MHPs QDs-based photocatalysts are further elucidated.We anticipate that our review could provide enriched information on the photocatalytic application of MHPs QDs toward solar-to-fuel conversion.

Optical properties and dynamic process in metal ions doped on CdSe quantum dots sensitized solar cells

In recent years, the nanostructure for solar cells have attracted considerable attention from scientists as a result of a promising candidate for low cost devices. In this work, quantum dots sensitized solar cells with effective performance based on a co-sensitized Cd S∕Cd Se：Mn2＋（or Cu2＋） nanocrystal, which was made by successive ionic layer absorption and reaction, are discussed. The optical, physical, chemical, and photovoltaic properties of quantum dots sensitized solar cells were sensitized to Mn2＋and Cu2＋dopants. Therefore, the short current（JSC）of the quantum dot sensitized solar cells is boosted dramatically from 12.351 mA∕cm2 for pure Cd Se nanoparticles to 18.990 mA∕cm2 for Mn2＋ions and 19.915 mA∕cm2 for Cu2＋ions. Actually, metal dopant extended the band gap of pure Cd Se nanoparticles, reduced recombination, enhanced the efficiency of devices, and improved the charge transfer and collection. In addition, Mn2＋and Cu2＋dopants rose to the level of the conduction band of pure Cd Se nanoparticles, which leads to the reduction of the charge recombination, enhances the lightharvesting efficiency, and improves the charge diffusion and collection. The results also were confirmed by the obtained experimental data of photoluminescence decay and electrochemical impedance spectroscopy.

金属卤化物CH_(3)NH_(3)PbBr_(3)钙钛矿量子点快速检测新烟碱类农药

以新烟碱类农药为靶标物,结合荧光传感策略构建了基于金属卤化物钙钛矿量子点CH_(3)NH_(3)PbBr_(3)(Perovskite quantum dots,PQDs)荧光探针快速检测新烟碱类农药的新方法。该方法的线性检测范围为0.0~20 mg/L,相关系数为0.9939,检出限和定量限分别为0.17 mg/kg和0.56 mg/kg。对萝卜和香蕉样品中噻虫胺的加标回收率在79.3%~115.4%之间,日内日间相对标准偏差在3.8%~9.4%之间。该方法具有高灵敏度、高选择性和适用性,为农产品中新烟碱类农药残留的风险防控提供了一种有效的检测技术。对噻虫胺与钙钛矿量子点之间的相互作用进行了研究,结果表明,钙钛矿量子点与噻虫胺之间的相互作用是一个动态过程,噻虫胺对钙钛矿量子点的荧光猝灭方式为通过氢键或范德华力形成了新的复合物的静态猝灭。其内容可作为其他光谱分析手段的技术基础,其分析检测结果可为果蔬安全监管提供有价值的建议。

液相超声法制备金属及化合物量子点研究进展

量子点(Quantum Dots,QDs)的电子结构及光学性质等与传统材料显著不同,由于其独特的尺寸效应和表面效应而受到广泛关注,除金属硫化物量子点外,其他含金属元素的量子点有Ⅴ族金属单质、Ⅱ-Ⅵ族量子点、Ⅳ-Ⅵ族量子点及碳化物量子点等。液相超声法是一种制备量子点的重要手段,具有操作简单、反应速度快、产率高和粒径可控性好等优势。量子点具有可调控的光学性质、高量子效率和荧光亮度、优越的电子输运性能、良好的化学稳定性和生物兼容性等良好的特性,使其在光电子学、光催化和生物医学等领域得到了深入的研究。本文综述了超声法制备不同金属及金属化合物量子点的研究进展,并对其应用进行了归纳和总结。最后,对超声法制备金属单质及金属化合物量子点进行了展望。