Quantum Size Effect Research Articles

Fluorescent Quantum Dots and Its Composites for Highly Sensitive Detection of Heavy Metal Ions and Pesticide Residues: A Review

Quantum dots nanomaterials have attracted extensive interest for fluorescence chemical sensors due their attributes, such as excellent optical characteristics, quantum size effects, interface effects, etc. Moreover, the fluorescence properties of quantum dots can be adjusted by changing their structure, size, morphology, composition, doping, and surface modification. In recent years, quantum dots nanomaterials have been considered the preferred sensing materials for the detection of heavy metal ions and pesticide residues by the interactions between quantum dots and various analytes, showing excellent sensitivity, selectivity, and interference, as well as reducing the cost of equipment compared with traditional measurement methods. In this review, the applications and sensing mechanisms of semiconductor quantum dots and carbon-based quantum dots are comprehensively discussed. The application of semiconductor quantum dots, carbon quantum dots, graphene quantum dots, and their nanocomposites that are utilized as fluorescence sensors are discussed in detailed, and the properties of various quantum dots for heavy metal ion and pesticide residue determination are also presented. The recent advances in and application perspectives regarding quantum dots and their composites are also summarized.

A Blue-Light-Emitting 3 nm-Sized CsPbBr3 Perovskite Quantum Dot with ZnBr2 Synthesized by Room-Temperature Supersaturated Recrystallization

Recently, tuning the green emission of CsPbBr3 quantum dots (QDs) to blue through quantum size and confinement effects has received considerable attention due to its remarkable photophysical properties. However, the synthesis of such a blue-emitting QD has been challenging. Herein, supersaturated recrystallization was successfully implemented at room temperature to synthesize a broadband blue-emitting ZnBr2-doped CsPbBr3 QD with an average size of ~3 nm covering the blue spectrum. The structural and optical properties of CsPbBr3 QDs demonstrated that QD particle size may decrease by accommodating ZnBr2 dopants into the perovskite precursor solution. Energy-dispersive spectroscopy confirmed the presence of zinc ions with the QDs. This work provides a new strategy for synthesizing strongly quantum-confined QD materials for photonic devices such as light-emitting diodes and lighting.

Dispersive response of polar optical phonon modes on the dielectric and size effects in a nitride nanostructure

Within the framework of the macroscopic dielectric continuum model, the dispersive spectra of polar optical phonon modes of III-nitride based nanostructures with different inner and outer dielectric media are investigated in this paper. The dielectric and quantum size effects on the dispersive frequencies of phonon modes are focused and emphasized. In the case of GaN quantum rings (QRs), we found that the dielectric constant of the inner/outer medium could significantly influence the dispersive spectra of the surface optical (SO) phonon mode as the high/low-frequency SO phonon modes are mainly localized at the inner/outer surface of QRs, respectively. Moreover, such effects associated with different crystallographic structures of GaN, i.e., the wurtzite (WZ) and zinc blende (ZB) crystal structures, are also studied in detail, showing the different degenerating behavior and electron–phonon coupling strength. The results obtained in this study provide a beneficial opportunity to independently adjust dispersive spectra of the two branches of SO modes in GaN nanostructures; thus, it could be used to design and develop phonon-based detectors and sensors.

Guanidium iodide treatment of size-controlled CsPbI3 quantum dots for stable crystal phase and highly efficient red LEDs

The optoelectronic properties of lead-halide perovskite quantum dots (QDs) can be tuned according to their halogen composition ratio and quantum size effect. However, the pure red emission of CsPbI3 QDs exhibits poor phase stability, thereby resulting in a phase transition to a nonphotoactive yellow phase at room temperature. These phase instabilities are accompanied by crystal strain and instability of the QD surface, which induce ion diffusion and desorption. Herein, we demonstrate the precise size control and postsynthetic guanidinium iodide (GAI) treatment to stabilize the crystal phase of CsPbI3 QDs. These synergistic effect results in higher ambient photoluminescence stability and photostability than those of pristine QDs. More importantly, the CsPbI3 QD light-emitting diodes achieve excellent external quantum efficiency of 22.5% and longer operational stability of over 10 h by the synergy effect of QD size control and GAI treatment.

Efficient photosynthesis of hydrogen peroxide by triazole-modified covalent triazine framework nanosheets

Two-dimensional (2D) polymeric semiconductors, especially covalent triazine framework (CTF) nanosheets with aromatic triazine linkages are emerging as attractive metal-free photocatalysts owing to their predictable structures, good semiconducting properties, and high stability. However, the quantum size effect and ineffective electron screening of 2D CTF nanosheets cause an enlargement of electronic band gap and high excited electron-hole binding energies, which lead to low-level enhancements in photocatalytic performance. Herein, we present a novel triazole groups functionalized CTF nanosheet (CTF-LTZ) synthesized by facile combination of ionothermal polymerization and freeze-drying strategy from the unique letrozole precursor. The incorporation of the high-nitrogen-containing triazole group effectively modulates the optical and electronic properties, resulting in narrowed bandgap from 2.92 eV for unfunctionalized CTF to 2.22 eV for CTF-LTZ and dramatically improved charge separation, as well as highly-active sites for O2 adsorption. As a result, CTF-LTZ photocatalyst exhibits excellent performance and superior stability in H2O2 photosynthesis, with a high H2O2 production rate of 4068 μmol h−1 g−1 and a remarkable apparent quantum efficiency of 4.5 % at 400 nm. This work provides a simple and effective approach for rational design highly-efficient polymeric photocatalysts for H2O2 production.

Preparation of Structure Vacancy Defect Modified Diatomic-Layered g-C3 N4 Nanosheet with Enhanced Photocatalytic Performance.

Structure self-modification of graphitic carbon nitride (g-C3 N4 ) without the assistance of other species has attracted considerable attention. In this study, the structure vacancy defect modified diatomic-layered g-C3 N4 nanosheet (VCN) is synthesized by thermal treatment of bulk g-C3 N4 in a quartz tube with vacuum atmosphere that will generate a pressure-thermal dual driving force to boost the exfoliation and formation of structure vacancy for g-C3 N4 . The as-prepared VCN possesses a large specific surface area with a rich pore structure to provide more active centers for catalytic reactions. Furthermore, the as-formed special defect level in VCN sample can generate a higher exciton density at photoexcitation stage. Meanwhile, the photogenerated charges will rapidly transfer to VCN surface due to the greatly shortened transfer path resulting from the ultrathin structure (≈1.5nm), which corresponds to two graphite carbon nitride atomic layers. In addition, the defect level alleviates the drawback of enlarged bandgap caused by the quantum size effect of nano-scaled g-C3 N4 , resulting in a well visible-light utilization. As a result, the VCN sample exhibits an excellent photocatalytic performance both in hydrogen production and photodegradation of typical antibiotics.

Green synthesis, antioxidant and anticancer activities of TiO2 nanoparticles using aqueous extract of Tulbhagia violacea

In this study, titanium oxide nanoparticles represented as TiO2(1), TiO2(2), and TiO2(3) were prepared using different volumes (10, 20, and 40 mL, respectively) of aqueous leaf extract of Tulbhagia violacea. The physicochemical characteristics of these materials were established using X-ray diffraction (XRD), ultraviolet–visible (UV–vis) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy. The obtained XRD pattern confirmed the formation of the anatase TiO2 phase in all the prepared materials irrespective of the volume of extracts used. Nevertheless, TiO2(2) nanoparticles obtained using 20 mL of plant extract showed the highest crystallinity. The maximum absorption wavelength found in the region between 260 and 267 nm in the UV–vis spectroscopy study suggested a quantum size effect. All synthesized TiO2 nanoparticles appeared to possess varying shapes and sizes, mostly dominated by rectangular shapes that were irregularly distributed across the materials. The material was found to be highly agglomerated due to the high calcination temperature. The antioxidant assay showed weak to moderate activity relative to the standard ascorbic acid. Also, compared to 5-Fluorouracil, all the nanoparticles exhibited moderate cytotoxicity against HEK 293 and HeLa cell lines. The TiO2 (1) showed the best specificity towards the cancer cell line with IC50 values of 29.73 and 34.27 µg/mL for both HeLa and HEK 293 cell lines, respectively. This suggests its potential as a promising candidate in applications where it is important to protect healthy cells.

Quantum size effects and transport properties of Bi2(Te1-xSex)3 3D-topological insulator thin films

In this work, it was established that the room-temperature thickness (d = 16–207 nm) dependences of the Seebeck coefficient, Hall coefficient, and electrical conductivity in n-Bi2(Te0.9Se0.1)3 topological insulator thin films grown on glass substrates, in the thickness range of d = 16–85 nm exhibit an undamped oscillatory behavior with a large amplitude and are well approximated by a harmonic function with a period Δd=(8.0 ± 0.5)nm. The anionic substitution leads to some changes in the quantum size effects manifestation. The experimental results are consistent with theoretical calculations of Δd based on the infinitely deep potential well model. A sustained character of the oscillations is attributed to topologically protected surface states.

UV Photoluminescence Microscopy of Individual ZnO Nanostructured Clusters

Ultraviolet (UV) photoluminescence (PL) spectra were acquired from individual nanostructured ZnO clusters less than 1 μm in size. The nanostructured clusters were formed by aggregation of a small number of nanoparticles. This analysis employed a microscopy apparatus specially designed for PL assessments of nanostructures at UV wavelengths with a spatial resolution of 0.395 μm. Atomic force microscopy was also employed to ascertain the sizes and morphologies of the nanostructured clusters. The ZnO samples were prepared by laser ablation in liquid (LAL) and comprised spherical, rhomboid, or gel-coated particles. PL emissions originating from free excitons (FX), FX phonon replicas, and defects were observed. The FX peak widths and positions were found to vary (with positions from 3.30 to 3.36 eV), suggesting that a range of particle sizes and morphologies was obtained from the LAL process. FX peaks at higher energies exhibited greater widths as a consequence of a quantum size effect originating from the crystallites comprising the nanostructured clusters. The rhomboid particles showed less-intense emissions related to defects compared with the other two types while also exhibiting the least intense emissions related to FX phonon replicas. This work also examined the mechanism by which nanoparticles were produced by LAL on the basis of the spectroscopic data. The information presented herein is expected to assist in the design and fabrication of semiconductor nanoparticles for future nanotechnology applications.

Quantum size effect to induce colossal high-temperature energy storage density and efficiency in polymer/inorganic cluster composites.

Polymer dielectrics need to operate at high temperatures to meet the demand of electrostatic energy storage in modern electronic and electrical systems. The polymer nanocomposite approach, an extensively proved strategy for the performance improvement, encounters the bottleneck of reduced energy density and poor discharge efficiency beyond 150°C. Here, we report a polymer/metal oxide cluster composite prepared based on the "site isolation" strategy. Capitalizing on the quantum size effect, the bandgap and surface defect states of the ultra-small inorganic clusters (2.2nm diameter) are modulated to markedly differ from the regular-sized nanoparticles. Experimental results in conjunction with computational simulation demonstrate that, the presence of ultra-small inorganic clusters can introduce more abundant, deeper traps in the composite dielectric with respect to the conventional polymer/nanoparticle blends. Unprecedented high-temperature capacitive performance including colossal energy density (6.8 Jcm-3 ), ultra-high discharge efficiency (95%) and superior stability at different electric field frequencies, are achieved in these polymer/cluster composites up to 200°C. Along with the advantages in material preparation (inexpensive precursors and one-pot synthesis), such polymer/inorganic cluster composite approach is promising for high-temperature dielectric energy storage in practical power apparatus and electronic devices. This article is protected by copyright. All rights reserved.

Specular Electron Focusing between Gate-Defined Quantum Point Contacts in Bilayer Graphene.

We report multiterminal measurements in a ballistic bilayer graphene (BLG) channel, where multiple spin- and valley-degenerate quantum point contacts (QPCs) are defined by electrostatic gating. By patterning QPCs of different shapes along different crystallographic directions, we study the effect of size quantization and trigonal warping on transverse electron focusing (TEF). Our TEF spectra show eight clear peaks with comparable amplitudes and weak signatures of quantum interference at the lowest temperature, indicating that reflections at the gate-defined edges are specular, and transport is phase coherent. The temperature dependence of the focusing signal shows that, despite the small gate-induced bandgaps in our sample (≲45 meV), several peaks are visible up to 100 K. The achievement of specular reflection, which is expected to preserve the pseudospin information of the electron jets, is promising for the realization of ballistic interconnects for new valleytronic devices.

C, F co-doping Ag/TiO2 with visible light photocatalytic performance toward degrading Rhodamine B

The organic pollutants in industrial wastewater continuously endanger human health. Therefore, effective treatment of organic pollutants is very urgent. Photocatalytic degradation technology is an excellent solution to remove it. TiO2 photocatalysts are easy to prepare and have high catalytic activity, unfortunately, TiO2 only absorbs ultraviolet light limiting its utilization of visible light. In this study, a facile environmentally friendly synthesis of Ag-coated on micro-wrinkled TiO2-based catalysts in order to extend the absorption of Visible light. Firstly, a fluorinated titanium dioxide precursor was prepared by a one-step solvothermal method, and the precursor was calcined at high temperature in a nitrogen atmosphere to form a carbon dopant, and then a surface silver-deposited carbon/fluorine co-doped TiO2 photocatalyst C/F–Ag–TiO2 was prepared by a hydrothermal method The results showed that the Ag was coated on the wrinkled TiO2 layer and C/F–Ag–TiO2 photocatalyst was synthetized successfully. Benefit from the synergistic effect of doped carbon and fluorine atoms in combination with the quantum size effect of the surface silver nanoparticles, the band gap energy of C/F–Ag–TiO2 (2.56 eV) is obviously lower than anatase (3.2eV). The photocatalyst achieved an impressive degradation rate of 84.2% for Rhodamine B in 4 h, with a degradation rate constant of 0.367 h−1, which was 17 times higher than that of P25 under visible light. Therefore, the C/F–Ag–TiO2 composite is a promising candidate as a highly efficient photocatalyst for environmental remediation.

Role of interfacial electric field on thermal conductivity of In x Al1−x N/GaN superlattice (x = 0.17)

Abstract In this paper, we report the role of the interfacial polarization electrical field in thermal conductivity of In x Al1−x N/GaN superlattice. Thermal conductivity reduction is one recent effort to improve thermoelectric device efficiency because a small reduction in thermal conductivity can enhance the figure of merit significantly. Quantum size effect and thermal boundary resistance are responsible for this reduction. The theoretical results demonstrate that the interfacial polarization electric field modifies acoustic phonon properties through elastic moduli and phonon group velocity as a result of the inverse piezoelectric effect. This enhances phonon scattering and thermal boundary resistance. Consequently, the thermal conductivity of the superlattice is reduced. Room temperature thermal conductivity is found to be 2.94 (3.35) W m−1 K−1 for In x Al1−x N/GaN superlattice (x = 0.17) in the presence (absence) of an electric field.

Fine-tuning of plasmonics by Au@AuY/Au core–shell nanoparticle monolayer for enhancement of third-order nonlinearity

The manipulation of plasmonics on noble metal nanoparticles (NPs) is of great interest in developing nonlinear photonic devices, such as all-optical switches and frequency combs. An Au@AuY-core/Au-shell nanoparticle (Au@AuY/Au NP) monolayer is proposed for the fine-tuning of plasmonics and enhanced third-order nonlinearity. Based on the different thermodynamic mechanisms of Au and Y ions, the compact Au@AuY/Au core–shell architectures are designed and surface-modified in fused silica (SiO2) with enhanced free electron density, mobility, and quantum size effect. The flexible modulation of plasmonics is realized, resulting in significant absorption enhancement (165% for interband absorption and 38% for free electron absorption, respectively) and fine-tuning of the localized surface plasma resonance (LSPR) band. In addition, the physical mechanism is investigated by density functional theory (DFT) and Mie theory, which reveals a transition from size-independence to size-dependence of LSPR owing to the synergistic effect of multiple physical factors such as free electron density and mobility. With the above advantages, the third-order nonlinearity is enhanced by 4.4 times compared with traditional Au NPs. It indicates the significant potential of Au@AuY/Au core–shell NP monolayer in the performance improvement of nonlinear photonic devices.

Experimental Study on Microbial Attachment Degree of New Polymer Nanomaterials on the Surface of Oil Field Development Platform Equipment

Nanomaterials have surface effects and quantum size effects, which can affect the structure and function of some biological macromolecules such as proteins and nucleic acid molecules. Nanomaterials were introduced into the development of Marine antifouling paint to solve the attachment problem of Marine fouling organisms. In this paper, the method of gene cloning was used to identify the early microbial species of oil field development platform equipment fouling. Finally, the antifouling effect of 13 kinds of nanomaterials and their combinations was tested by conventional PCR and real-time quantitative PCR. The experimental simulation shows that titanium nano polymer alloy coatings have obvious technical advantages in adhesion, impact resistance, coating hardness, wear resistance, high temperature resistance, high pressure resistance and chemical corrosion resistance.

Boosting cobalt ditelluride quantum-rods anode materials for excellent potassium-ion storage via hierarchical physicochemical encapsulation

The exploration of anode materials that can store large-sized K-ion to solve the poor kinetics and large volume expansion issues has become the key scientific bottlenecks hindering the development of potassium-ion batteries (PIBs). Herein, ultrafine CoTe2 quantum rods physiochemically encapsulated by graphene and nitrogen-doped carbon (CoTe2@rGO@NC) are regarded as anode electrodes for PIBs. Dual physicochemical confinement and quantum size effect not only enhance electrochemical kinetics but also restrain large lattice stress during repeated K-ion insertion/extraction process. Superior electronic conductivity, K-ion adsorption, and diffusion ability can be acquired for CoTe2@rGO@NC, confirmed through first-principles calculations and kinetics study. K-ion insertion/extraction proceeds via a typical conversion mechanism relying on Co as the redox site, where the robust chemical bond of COCo plays an important role in maintaining the electrode stability. Accordingly, CoTe2@rGO@NC contributes a high initial capacity of 237.6 mAh·g−1 at 200 mA·g−1, a long lifetime over 500 cycles with low-capacity decay of 0.10% per cycle. This research will lay the materials science foundation for the construction of quantum-rod electrodes.

Enhanced visible-light photocatalytic hydrogen evolution using two-dimensional carbon nitride sheets with the removal of amine groups

Two-dimensional (2D) carbon nitride sheets (CNs) with atomically thin structures are regarded as one of the most promising materials for solar energy conversion. However, due to their substantially enlarged bandgap caused by the strong quantum size effect and their incomplete polymerisation with a large number of non-condensed surface amino groups, the practical applicability of CNs in photocatalysis is limited. In this study, CNs with broad visible-light absorption were synthesised using a 5-min fast thermal annealing. The removal of uncondensed amine groups reduces the bandgap of CNs from 3.06 eV to 2.60 eV, increasing their absorption of visible light. Interestingly, the CNs were distorted after annealing, which can differentiate the spatial positions of electrons and holes, enhancing the visible-light absorption efficiency. As a result, when exposed to visible light, the photocatalytic hydrogen production activity of atomically thin 2D CNs rose by 8.38 times. This research presents a dependable and speedy method for creating highly effective visible-light photocatalysts with narrowed bandgaps and improved visible-light absorption.

Synthesis of two-dimensional CeO2-δ-GQD composites and their structural and optical properties

The present study reports on the synthesis of two-dimensional (2D) ceria and graphene quantum dots (CeO2-δ-GQD) composites and their functional properties. Composites were prepared by a simple liquid phase deposition (LPD) method followed by a thermal treatment in air at 250 and 400 °C. The structural and optical properties of composites were investigated by X-ray diffraction (XRD), Field Emission Scanning Electron Microscope (FESEM), High-Resolution Transmission Electron Microscopy (HR-TEM), Raman spectroscopy, Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), UV-Vis and photoluminescence (PL). The composites consist of crystalline CeO2-δ regions of about 1.8–2.9 nm in size, coexisting with highly disordered GQDs areas. The CeO2-δ-GQD composites experience gradual dehydration and oxidation of carbon processes during thermal treatment, influencing the CeO2 crystal size, Ce3+/Ce4+ ratio, and O vacancies presence. These effects allow for the control of some of the composite functional properties. Specifically, the CeO2-GQD250 composites exhibit a low recombination rate of charge carriers due to the synergistic interaction between the components and low presence of Ce3+. In contrast, the CeO2-GQD400 composites show a high Eg of 3.8 eV (Eg ∼3.2 eV for CeO2NPs) associated with a CeO2 quantum size effect and extremely low fraction of GQDs.

Quantum size effects in stacked multilayer graphene

In this paper,we study the quantum size effects in multilayer graphene sheets using first principles methods within the framework of density functional theory. Four different types of functionals are adopted respectively to describe the van der Waals interactions between graphene layer sheets: the DFT-GGA(PBE), the DFT-D2, the vdW-DF and the optPBE-vdW. By inspecting the binding energy as a function of increasing graphene layers, we find that the PBE functional can not well describe the van der Waals interactions between different layers of graphene sheets. In contrast, the other three methods exhibit similar results with monotonic increasing binding energy as a function of graphene layers towards the bulk limit, concluding that the layered graphene structure is stabilized by van der Waals interactions. The density of states at zero temperature indicate that the multilayer graphene sheets is a semi-metal, which is independent of sheet layers number. The finite temperature (about 200 K) density of states at Fermi surface are studied as a function of the number of stacking graphene layers. The systematic oscillating behavior of finite temperature density of states between odd and even number of layers is a demonstration of quantum size effects. The Fermi wavelength will converge to two times the inter-layer distance of graphite, which is consistent with the theory describing the motion of particles in a quantum well. Finally, we study the adsorption of single H atom on multilayer graphene sheets to test the role of quantum size effects. The adsorption energies and the vibration frequencies are calculated for comparison with experiments. Our results shed light on understanding the stacking process of multilayer graphene in vacuum both theoretically and experimentally.

Pd-Nanoparticles-Catalyzed C(sp2)–H Arylation for the Synthesis of Functionalized Heterocycles: Recent Progress and Prospects

AbstractTransition-metal-nanoparticles-catalyzed C–H activation/functionalization is a prominent topic in contemporary research, enabling the functionalization of privileged heterocyclic scaffolds that hold a significant space in the scientific community due to their immense applications in materials science and in medicinal, natural product, and agricultural chemistry. Among transition-metal-based nanoparticles, Pd nanoparticle catalysis has emerged as the most attractive tool for promoting a wide array of practical synthetic transformations of heterocycles. In the last few years, the catalytic application of Pd nanoparticles in C–H functionalization has gained popularity in generating relatively inaccessible bonds with a high degree of selectivity and efficiency via the activation of surface metal atoms at the nanoscale level. The quantum size effect of nanoparticles offers a large surface area, with typically many easily accessible active sites/unit areas. These unique characteristics of nanoparticles are considered primary factors of enhanced catalytic activity compared to bulk materials. The nanoparticle catalysts anchored on solid-supports plus unsupported types (e.g., magnetic nanoparticles) allow easy separation from the reaction mixture, enabling recycling multiple times, which contributes notably to sustainable management and cost efficiency of a production process. In the current review, we discuss Pd-nanoparticles-catalyzed C(sp2)–H arylation for the synthesis of functionalized heterocycles, covering literature reports from 2010 to 2021. The preparation of Pd nanoparticles and the mechanistic realizations in their corresponding reactions are also explained briefly.1 Introduction2 Arylation of Heterocyclic Scaffolds2.1 Synthesis of Functionalized Indole Derivatives2.2 Synthesis of Functionalized (Benzo)thiazole/Benzoxazole Derivatives2.3 Synthesis of Functionalized Triazoles2.4 Synthesis of Functionalized Pyridines and Related Scaffolds2.5 Synthesis of Functionalized Furan, Thiophene and N-Methylpyrrole Scaffolds2.6 Synthesis of Functionalized Multiple Heterocycles via Single-Step Strategies3 Conclusions