Luminescent graphene quantum dots fabricated by pulsed laser synthesis

Graphene has been the subject of intense research in recent years due to its unique electrical, optical and mechanical properties. Furthermore, it is expected that quantum dots of graphene would make their way into devices due to their structure and composition which unify graphene and quantum dots properties. Graphene quantum dots (GQDs) are planar nano flakes with a few atomic layers thick and with a higher surface-to-volume ratio than spherical carbon dots (CDs) of the same size. We have developed a pulsed laser synthesis (PLS) method for the synthesis of GQDs that are soluble in water, measure 2–6 nm across, and are about 1–3 layers thick. They show strong intrinsic fluorescence in the visible region. The source of fluorescence can be attributed to various factors, such as: quantum confinement, zigzag edge structure, and surface defects. Confocal microscopy images of bacteria exposed to GQDs show their suitability as biomarkers and nano-probes in high contrast bioimaging.     

全无机纳米晶太阳能电池的研究进展

近年来,以胶体纳米晶半导体材料作为构建部分的第三代太阳能电池（又称为量子点太阳能电池）一直是研究的热门课题。胶体量子点在太阳能电池中应用之所以备受关注,是由于其具有类似溶液的可操作性,这无疑将极大地方便其整合到各种结构类型太阳能电池器件中。与传统硅基太阳能电池相比,量子点太阳能电池的制造成本可大幅度降低,重点介绍了几种...     

UV-assisted production of ferromagnetic graphitic quantum dots from graphite

Graphitic quantum dots (GQDs) are synthesized from natural graphite powder. This process involves a few steps such as oxidation, reduction and filtration to obtain the precursor to prepare GQDs. Finally, a combination of UV irradiation and sonication is used to produce GQDs. These quantum dots are further investigated by various characterization techniques. They exhibit blue luminescence and ferromagnetic behavior. The ferromagnetic nature of the GQDs is discussed and explained. Based on the experimental data obtained and theoretical models available in literature, a possible mechanism for the formation of GQDs is proposed. Their properties, including the production yield can be tuned by simply changing the synthesis parameters.     

Nitrogen Functionalities of Amino-Functionalized Nitrogen-Doped Graphene Quantum Dots for Highly Efficient Enhancement of Antimicrobial Therapy to Eliminate Methicillin-Resistant Staphylococcus aureus and Utilization as a Contrast Agent

There is an urgent need for materials that can efficiently generate reactive oxygen species (ROS) and be used in photodynamic therapy (PDT) as two-photon imaging contrast probes. In this study, graphene quantum dots (GQDs) were subjected to amino group functionalization and nitrogen doping (amino-N-GQDs) via annealing and hydrothermal ammonia autoclave treatments. The synthesized dots could serve as a photosensitizer in PDT and generate more ROS than conventional GQDs under 60-s low-energy (fixed output power: 0.07 W·cm⁻²) excitation exerted by a 670-nm continuous-wave laser. The generated ROS were used to completely eliminate a multidrug-resistant strain of methicillin-resistant Staphylococcus aureus (MRSA), a Gram-positive bacterium. Compared with conventional GQDs, the amino-N-GQDs had superior optical properties, including stronger absorption, higher quantum yield (0.34), stronger luminescence, and high stability under exposure. The high photostability and intrinsic luminescence of amino-N-GQDs contribute to their suitability as contrast probes for use in biomedical imaging, in addition to their bacteria tracking and localization abilities. Herein, the dual-modality amino-N-GQDs in PDT easily eliminated multidrug-resistant bacteria, ultimately revealing their potential for use in future clinical applications.     

Janus石墨烯量子点在生物膜中的输运行为：分子动力学模拟

作为纳米载体,石墨烯量子点已广泛应用于生物医药领域,然而对于异质结构的石墨烯量子点细胞膜内化路径研究不足。从空间异质性结构设计出发,构建了一系列不同氧化程度与空间异质分布的Janus石墨烯量子点。基于分子动力学模拟研究了不同结构的Janus石墨烯量子点跨膜输运行为,通过分析跨膜输运过程中的构型变化、分子间作用能量、溶剂可及面积等参数,发现Janus石墨烯量子点跨膜输运行为由亲水-亲油平衡、空间异质分布控制,且呈现外力牵引依赖性变化。本文在分子水平上系统研究了Janus石墨烯量子点与细胞膜相互作用规律,对其结构设计及生物医药应用提供理论指导。     

Janus石墨烯量子点在生物膜中的输运行为：分子动力学模拟

作为纳米载体,石墨烯量子点已广泛应用于生物医药领域,然而对于异质结构的石墨烯量子点细胞膜内化路径研究不足。从空间异质性结构设计出发,构建了一系列不同氧化程度与空间异质分布的Janus石墨烯量子点。基于分子动力学模拟研究了不同结构的Janus石墨烯量子点跨膜输运行为,通过分析跨膜输运过程中的构型变化、分子间作用能量、溶剂可及面积等参数,发现Janus石墨烯量子点跨膜输运行为由亲水-亲油平衡、空间异质分布控制,且呈现外力牵引依赖性变化。本文在分子水平上系统研究了Janus石墨烯量子点与细胞膜相互作用规律,对其结构设计及生物医药应用提供理论指导。     

石墨烯量子点的制备及应用

石墨烯量子点(GQDs)作为石墨烯家族的最新一员,除了继承石墨烯的优异性能,还因量子限制效应和边界效应而显现出一系列新的特性,引起了化学、物理、材料和生物等各领域科研工作者的广泛关注。GQDs的制备方法通常分自上而下和自下而上的方法。对其各种制备方法和应用分别进行了介绍,并结合各种应用对GQDs的要求给出了制备方法的建议。指出了GQDs研究中存在的问题及发展方向。     

Effect of modified graphene quantum dots on photocatalytic degradation property

The effective use of solar energy in sewage disposal has been extensively investigated. This work focuses on the photocatalytic property of graphene quantum dots (GQDs) and polymer-modified GQDs under visible light. A hydrothermal synthesis route to GQDs was developed by using citric acid as a carbon precursor. The GQDs were modified with polyethylenimine (PEI) and polyethylene glycol (PEG). The obtained GQDs, GQDs-PEIs, and GQDs-PEGs were characterized and their structural information was determined through Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), photoluminescence spectroscopy, and UV–Vis absorption spectroscopy. Results revealed that the GQDs were uniform in size (2–5 nm) and rich in oxygen-containing groups. The GQDs exhibited a strong blue and excitation-independent photoluminescent behavior under excitation wavelengths of 320–420 nm. The photocatalytic performance of these samples was demonstrated on the basis of methylene blue (MB) degradation. The photocatalytic rates of GQDs, GQDs-PEIs, and GQDs-PEGs decreased successively. The polymer-modified GQDs could qualitatively control the degradation rate of MB. Free radical species were generated to oxidize MB under light irradiation. Thus, photocatalytic organic matter degradation, sustained drug release, and tracking can be combined to implement proper sewage disposal.Prime noveltyThe main object of this work is to find out a novel property of graphene quantum dots (GQDs) as efficient nanomaterials for degradation of organic pollutant dyes under visible light irradiation. And, the GQDs exhibited a strong blue and excitation-independent photoluminescent behavior under excitation wavelengths of 320–420 nm. Moreover, the degradation rate could be qualitatively controlled by using different polymer-modified GQDs. Thus, photocatalytic organic matter degradation, sustained drug release, and tracking can be combined to implement proper sewage disposal. Also, the degradation mechanism is discussed.     

Ultrafine Cu2ZnSnS4 quantum dots functionalized TiO2 nanotube arrays for potential optoelectronic applications

Tremendous progress has been made in power conversion efficiency (PCE) of thin-film photovoltaics over the past few years, yet most current high-efficient photoactive layer usually contains rare or toxic elements accompanied by expensive and complicated vacuum processes, which increases the cost and limits the scope of the applications in the long run. Here we present a synergistic effect of quantum effect of an earth-abundant and low toxic ultrafine Cu₂ZnSnS₄ (CZTS) quantum dots (QDs) and low charge recombination in one dimensional TiO₂ nanotube arrays for optoelectronic devices. By ligands exchange, the as-obtained ultrafine CZTS QDs have been robustly anchored to a highly ordered TiO₂ nanotube arrays (TNAs) to be served as a function layer in a simple QDs sensitized solar cells. Such ultrafine CZTS QDs based solar cells exhibit significant enhancement up to 457% in PCE compared to that of CZTS QDs with larger size. The CZTS QDs functionalized TNAs has also shown excellent charge transport capability with lower recombination rate than QDs sensitized TiO₂ nanoparticles and it is expected to be used as a low-cost environment-friendly function layer for various potential optoelectronic applications.     

Development of Biodegradable GQDs-hMSNs for Fluorescence Imaging and Dual Cancer Treatment via Photodynamic Therapy and Drug Delivery

Recently, nano-based cancer therapeutics have been researched and developed, with some nanomaterials showing anticancer properties. When it comes to cancer treatment, graphene quantum dots (GQDs) contain the ability to generate ¹O₂, a reactive oxidative species (ROS), allowing for the synergistic imaging and photodynamic therapy (PDT) of cancer. However, due to their small particle size, GQDs struggle to remain in the target area for long periods of time in addition to being poor drug carriers. To address this limitation of GQDs, hollow mesoporous silica nanoparticles (hMSNs) have been extensively researched for drug delivery applications. This project investigates the utilization and combination of biomass-derived GQDs and Stöber silica hMSNs to make graphene quantum dots-hollow mesoporous silica nanoparticles (GQDs-hMSNs) for fluorescent imaging and dual treatment of cancer via drug delivery and photodynamic therapy (PDT). Although the addition of hMSNs made the newly synthesized nanoparticles slightly more toxic at higher concentrations, the GQDs-hMSNs displayed excellent drug delivery using fluorescein (FITC) as a mock drug, and PDT treatment by using the GQDs as a photosensitizer (PS). Additionally, the GQDs retained their fluorescence through the surface binding to hMSNs, allowing them to still be used for cell-labeling applications.     

Graphene quantum dots directly generated from graphite via magnetron sputtering and the application in thin-film transistors

This work presents a novel method to prepare graphene quantum dots (GQDs) directly from graphite. A composite film of GQDs and ZnO was first prepared using the composite target of graphite and ZnO via magnetron sputtering, followed with hydrochloric acid treatment and dialysis. Morphology and optical properties of the GQDs were investigated using a number of techniques. The as-prepared GQDs are 4–12 nm in size and 1–2 nm in thickness. They also exhibited typical excitation-dependent properties as expected in carbon-based quantum dots. To demonstrate the potential applications of GQDs in electronic devices, pure ZnO and GQD–ZnO thin-film transistors (TFTs) using ZrO_x dielectric were fabricated and examined. The ZnO TFT incorporating the GQDs exhibited enhanced performance: an on/off current ratio of 1.7 × 10⁷, a field-effect mobility of 17.7 cm²/Vs, a subthreshold swing voltage of 90 mV/decade. This paper provides an efficient, reproducible and eco-friendly approach for the preparation of monodisperse GQDs directly from graphite. Our results suggest that GQDs fabricated using magnetron sputtering method may envision promising applications in electronic devices.     

Cellular distribution and cytotoxicity of graphene quantum dots with different functional groups

Graphene quantum dots (GQDs) have been developed as promising optical probes for bioimaging due to their excellent photoluminescent properties. Additionally, the fluorescence spectrum and quantum yield of GQDs are highly dependent on the surface functional groups on the carbon sheets. However, the distribution and cytotoxicity of GQDs functionalized with different chemical groups have not been specifically investigated. Herein, the cytotoxicity of three kinds of GQDs with different modified groups (NH₂, COOH, and CO-N (CH₃)₂, respectively) in human A549 lung carcinoma cells and human neural glioma C6 cells was investigated using thiazoyl blue colorimetric (MTT) assay and trypan blue assay. The cellular apoptosis or necrosis was then evaluated by flow cytometry analysis. It was demonstrated that the three modified GQDs showed good biocompatibility even when the concentration reached 200 μg/mL. The Raman spectra of cells treated with GQDs with different functional groups also showed no distinct changes, affording molecular level evidence for the biocompatibility of the three kinds of GQDs. The cellular distribution of the three modified GQDs was observed using a fluorescence microscope. The data revealed that GQDs randomly dispersed in the cytoplasm but not diffused into nucleus. Therefore, GQDs with different functional groups have low cytotoxicity and excellent biocompatibility regardless of chemical modification, offering good prospects for bioimaging and other biomedical applications.     

Wurtzite copper-zinc-tin sulfide as a superior counter electrode material for dye-sensitized solar cells

Wurtzite and kesterite Cu₂ZnSnS₄ (CZTS) nanocrystals were employed as counter electrode (CE) materials for dye-sensitized solar cells (DSSCs). Compared to kesterite CZTS, the wurtzite CZTS exhibited higher electrocatalytic activity for catalyzing reduction of iodide electrolyte and better conductivity. Accordingly, the DSSC with wurtzite CZTS CE generated higher power conversion efficiency (6.89%) than that of Pt (6.23%) and kesterite CZTS (4.89%) CEs.     

Synthesis of Colloidal Halide Perovskite Quantum Dots/Nanocrystals: Progresses and Advances

Colloidal halide perovskite (CHP) quantum dots (QDs)/nanocrystals (NCs) have superior optoelectronic properties, such as high optical absorption coefficient, high photoluminescence quantum yield (PLQY), tunable bandgap, composition‐related luminescence, and low manufacturing cost, which have been considered as promising low‐dimensional semiconductor materials. Profiting from these unique characteristics, CHP NCs could be widely used in various optoelectronic devices, including light‐emitting diodes (LEDs), photodetectors (PDs), solar cells (SCs), and lasers. Synthesis is the basis for the wide use of CHP NCs, which plays a vital role in the research, development and application of CHPs. Therefore, we summarize the recent synthetic strategies, and their influencing factors (e. g., the effects of ligands, and anion exchange). Besides, a summary of their optoelectronic applications is plainly mentioned. Finally, we make a brief prospect and summarize the current problems and possible solutions of this area.     

Near-UV-emitting graphene quantum dots from graphene hydrogels

We report a novel method to prepare graphene quantum dots (GQDs) from graphene hydrogels. Graphene hydrogels were prepared using a hydrothermal technique, and GQDs were released from the hydrogels on immersion of the hydrogels in low-polarity organic solvents. This method did not require additional treatments such as the centrifugation, filtration and dialysis typical of the general hydrothermal method. These GQDs were observed to fluoresce, with their strongest emission in the near-UV region, at ∼347 nm. Moreover, these GQDs, when in their pure state, formed a highly viscous liquid insoluble in water due to their lack of many oxygen-containing functional groups.     

Photoluminescence of CdTe quantum dots ligated with caprylic acid synthesized at low temperature

Photoluminescent semiconductor nanocrystals or quantum dots (QDs) are usually produced using expensive ligands and solvents at high temperature above 280°C to ensure high-quality optical properties, particularly the photoluminescence of QDs. The reproducibility of highly stable photoluminescence in QD preparation, in most cases, varies depending on many effects, such as the ligand used and temperature. Here a facile preparation of photoluminescent semiconductor CdTe nanocrystals or quantum dots (QDs) is conducted in the presence of caprylic acid at moderate temperatures between 80–140°C, which are much lower than the high temperatures used in conventional organic-phase preparation of CdTe QDs. The results show that the optical properties of CdTe QDs depend considerably on the reaction time, temperature and ligand used.     

To lose is to gain: Effective synthesis of water-soluble graphene fluoroxide quantum dots by sacrificing certain fluorine atoms from exfoliated fluorinated graphene

Water-soluble and blue luminescent graphene fluoroxide quantum dots (GFOQDs) with tunable fluorine coverage and size were effectively synthesized from exfoliated fluorinated graphene (FG) by sacrificing certain fluorine to improved solubility and reaction activity. Morphology investigation indicates that the obtained GFOQDs possess narrow size distribution and the average size is 2.5–3.5 nm. Chemical composition analysis confirms that besides C–F covalent bonds, C–O bonds in the forms of hydroxyl and carbonyl co-exist on the structure of GFOQDs. Moreover, photoluminescence performance research considering the surface state and size has also been conducted, and as anticipated in carbon-based quantum dots the GFOQDs exhibit excitation wavelength-dependent properties. Additionally, rather different from other graphene quantum dots (GQDs) that are often susceptible to pH without additional surface passivation, the GFOQDs themselves are poised to resist pH effects and display stable luminescence in both acid and alkali conditions. These results indicate that our method not only opens up a new avenue to prepare GQDs decorated with fluorine and oxygen, but also can find practical applications in novel GQDs-based devices that require water solubility while keep chemical stability and resistance against pH.     

Etching single-wall carbon nanotubes into green and yellow single-layer graphene quantum dots

Single-walled carbon nanotubes (SWCNTs) have been used to prepare single-layered graphene quantum dots (GQDs) through a simple and green hydrothermal etching method. After the characterization of products and intermediates with scanning electronic microscopy, Raman and FTIR, a possible mechanism has been proposed for the formation of GQDs. The treatment of SWCNTs has resulted in two kinds of GQDs (i.e. GQD1 and GQD2), both of which are monodisperse and single-layered nanosheets with an average lateral dimension of 8 nm and an average height of 0.5 nm. Excited with 365 nm UV light, aqueous solutions of GQDs1 and GQDs2 give green and yellow luminescence, respectively. The differences in optical property between GQDs1 and GQDs2 mainly results from their differences in degree of oxidation.     

Electromagnetic interference shielding properties of graphene quantum-dots reinforced poly(vinyl alcohol)/polypyrrole blend nanocomposites

Graphene quantum dots (GQDs) reinforced poly(vinyl alcohol) (PVA)/polypyrrole (WPPy) nanocomposite films with various GQDs loadings were synthesized using the versatile solvent casting method. The structural and morphological properties of PVA/WPPy/GQDs nanocomposite films were investigated by employing Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy. The thermogravimetric analysis revealed enhanced thermal stability of synthesized nanocomposites while enhanced dielectric properties were also observed. The maximum dielectric constant value for PVA/WPPy/GQDs nanocomposite films was observed to be ε = 6,311.85 (50 Hz, 150°C). The electromagnetic interference (EMI) shielding effectiveness (SE) of nanocomposite films was determined in the X-band (8–12 GHz) and Ku-band (12–18 GHz) frequency region. The EMI SE was found to be increased from 0.8 dB for the pure PVA film to 9.8 dB for the PVA/WPPy/GQDs nanocomposite film containing 10 wt% GQDs loading. The enhanced EMI shielding efficiency of nanocomposite films has resulted from the homogenous dispersion of GQDs in PVA/WPPy blend nanocomposites. Thus, the prepared nanocomposites are envisioned to utilize as a lightweight, flexible, and low-cost material for EMI shielding applications.     

Spray-deposited kesterite Cu2ZnSnS4 (CZTS): Optical,structural, and electrical investigations for solar cell applications

Kesterite Cu₂ZnSnS₄ (CZTS)-based solar devices have become a popular alternative to copper indium gallium selenide (CIGS) due to its outstanding properties such as high efficiency, non-toxicity, cost-effectiveness, suitable optoelectrical properties, and earth-abundancy. In this study, we directly fabricated CZTS films via a single-step spray pyrolysis technique, in contrast to conventional techniques where post sulfurization is required. The spray deposited CZTS films are investigated for their optical, structural, and electrical properties. The X-ray diffraction (XRD) and Raman analysis study revealed the synthesis of the phase-pure kesterite CZTS films without impurity phases. Large crystallites of CZTS are obtained at a deposition temperature of 400 °C, exhibiting a porous granular morphology with different grain sizes upon temperature variation. The size-dependent optical properties revealed that the CZTS films exhibited admirable visible light absorption of 10⁵ cm^?1 and an electronic bandgap ranging between 1.42 and 1.58 eV. The minimum dielectric loss obtained for optimized CZTS due to fewer intrinsic defects confirmed the materials’ applicability. Thus, the study provides a simple, viable route to fabricate CZTS without post-treatment to build affordable solar cells.