石墨烯量子点的制备及在生物传感器中的应用研究进展

石墨烯是由一层碳原子以sp~2杂化轨道按蜂巢晶格排列构成的二维碳纳米材料,由于其超大的平面共轭结构,石墨烯中的π电子具有显著的离域效应。石墨烯具有许多令人惊奇的电子或电学性质,比如室温量子霍尔效应、自选传输性质、极高的载流子迁移率和超低的电阻率以及优异的光学性质和力学性质。然而,与其他绝大多数二维材料不同,较大二维尺寸的石墨烯还具有零带隙的半金属材料特性,限制了石墨烯在光电器件和半导体等领域的应用。因此,如何打开石墨烯的带隙,将其从半金属材料转变为半导体材料,引起了人们的广泛兴趣。目前,已知打开石墨烯带隙的方法主要有两种:一种是对石墨烯进行化学掺杂以破坏其π电子共轭体系;另外一种是基于量子效应,将石墨烯切割成纳米带、纳米筛或量子点。石墨烯量子点(GQDs)是二维平面尺寸小于100 nm的石墨烯片段,因其具有量子限域效应和边界效应而呈现出特殊的物理化学性质,是一种具有带隙的半导体材料。与传统半导体量子点相比,GQDs具有毒性低、水溶性好、化学活性低、生物相容性好以及荧光性质稳定等突出优点。此外,GQDs具有单原子层平面共轭结构和较大的比表面积,同时表面的含氧基团可以为外来分子与之结合提供活性位点,在太阳能电池、光电子器件、生物医药等领域具有广泛的应用前景。GQDs的制备方法主要分为自上而下和自下而上两种方法。自上而下法主要包括强酸氧化法,水热/溶剂热法,电化学氧化法等。该方法的优点是原料来源丰富、制备过程相对简单,制备所得的GQDs表面含有丰富的含氧基团,具有良好的水溶性,易于表面功能化。自下而上方法主要分为可控有机合成和碳化反应。前者可以制备出具有精确碳原子数、大小和形状均一的GQDs,但是制备过程复杂繁琐、反应耗时长且产率较低,而后者所制备的GQDs,其尺寸和结构难以控制,产物具有多分散性。本文全面介绍了石墨烯量子点的各种制备方法,对这些方法的特点进行了评论,同时对重要或新颖方法的反应机理进行了阐述,并且重点介绍了GQDs在生物传感器方面的应用,最后对GQDs的未来研究和发展前景进行了展望。     

荧光石墨烯量子点的制备及其荧光机理分析

石墨烯量子点(GQDs)因其潜在的全光谱荧光可调控性和稳定性,在环境化学、物理器件、生物医药等诸多领域被认为是最有前景的纳米材料之一。探索GQDs的荧光发光机理,调控荧光能谱,进一步开发可控性合成与生长途径和工艺,尤其可批量及规模化生产方式,是GQDs器件应用中亟待解决的关键问题。从自上而下(Top-down)法、自下而上(Bottom-up)法和表面修饰等3个方面介绍了荧光GQDs的制备及调控,比较了GQDs与其它量子点材料荧光性质的异同,并重点综述了GQDs的量子限域效应以及边缘态和表面态对其光致荧光性质的影响。     

纳米氧化锌-石墨烯量子点复合材料制备及光催化性能研究

采用溶剂热法在醋酸锌的乙醇溶液中制备出了纳米氧化锌(ZnO);然后利用葡萄糖为原料,通过热裂解的方法制备石墨烯量子点(GQDs);再将二者混合制备不同比例的ZnO-GQDs复合材料,对材料的形貌、晶相结构和光谱特性进行表征,并以罗丹明B为目标降解物考察了其光催化性能。结果表明:以汞灯光照120min,纳米ZnO、GQDs和ZnOGQDs-0.3复合材料对罗丹明B的降解率分别达到81.91%、43.26%和90.24%。复合材料光催化活性的提高,主要归因于适量引入GQDs可以更好地吸附有机染料,同时促进ZnO光生载流子的有效分离,降低其复合率。     

热解柠檬酸制备石墨烯量子点及其光学性质研究

通过热解柠檬酸制备发蓝光的石墨烯量子点(GQDs),并进一步水热处理得到蓝绿色荧光量子点(gGQDs)。通过紫外-可见吸收光谱、荧光光谱、傅里叶变换红外光谱、X射线光电子能谱和X射线衍射对制备的GQDs的结构和光学性质进行了表征和测试;同时,讨论了不同裂解温度和裂解时间及水热处理过程的温度和时间对GQDs荧光性能的影响。     

模板法及其在纳米材料制备领域的应用研究进展

纳米材料的量子尺寸效应、小尺寸效应、表面效应和宏观量子隧道效应使其展现出许多特有的性质,在电子、环境保护、生物医药等领域具有广阔的应用前景.模板法组装纳米材料是一种简单有效的途径.系统介绍了氧化铝、多孔硅、生物大分子、表面活性剂等6种常见模板的特点及制备机理,给出了各类方法制备纳米材料的最新进展,并展望了模板法制备纳米材料的前景.     

石墨烯量子点在分离膜材料中的应用研究进展

在传统分离膜中引入纳米材料,有望解决选择性与渗透性之间存在的Trade-off效应、膜污染、化学稳定性等关键共性技术难题.零维石墨烯量子点(GQDs)纳米材料具有尺寸小、比表面积大、亲水性强等突出优点,在分离膜材料领域具有潜在的应用前景.本文归纳了基于界面聚合、相转化、表面改性等常规制膜方法,将GQDs或改性GQDs引入活性层(表层)、中间层或支撑层(亚层)等膜基质中,实现调控与优化分离膜结构与性能的最新研究进展.探讨了GQDs与改性GQDs对界面聚合"反应-扩散"过程、铸膜液热力学与相转化动力学过程以及层状膜层间距的影响机制,并阐述了引入GQDs或改性GQDs赋予分离膜抑菌、自清洁、荧光检测等新功能的原因.最后,展望了基于GQDs开发新型膜材料所面临的机遇和挑战.     

N掺杂石墨烯量子点的制备及其光催化降解性能

石墨烯量子点(GQDs)作为绿色、经济的新型碳质纳米材料在有机污染物的降解、能源利用方面有着广泛的应用前景。以柠檬酸为碳源,尿素作为氮源,通过水热法制备出尺寸均匀、高荧光的N掺杂石墨烯量子点(N-GQDs)。通过X射线衍射、拉曼光谱、透射电子显微镜、荧光光谱、紫外可见吸收光谱等手段对N-GQDs的晶型结构、微观形貌、表面官能团分布和光物理性能进行表征。通过MTT法对N-GQDs的毒性进行检测,又通过对亚甲基蓝(MB)的光催化降解考察样品的光催化性能。结果表明,制备的N-GQDs尺寸均匀、荧光强度高且毒性低。由于N原子的成功掺杂,N-GQDs作为光催化剂在可见光下对MB进行光催化降解比MB的自身降解更快,在短时间内(120 min)降解率可以达到82.5%。     

多枝CdS纳米晶粒的溶剂热法制备及光学性能研究

本文以溶剂热法在乙二醇溶剂里制备了小尺寸的多枝权CdS纳米晶粒,通过溶剂、硫源的选择,使其直径接近激子的玻尔半径(6nm),分析硫源和溶剂对CdS粒子晶体结构、形貌和尺寸的控制作用.对多枝权粒子的形成机理进行探讨,初步得到一种可能的两相共存的生长机制.光学性能的测试显示样品具有良好的量子尺寸效应和发光性能.选择合适的反应源和溶剂可调整半导体纳米粒子的形貌和尺寸,对制备满足不同应用需要的纳米结构,尤其是复杂形貌的纳米量子器件的应用具有重要的意义.     

石墨烯量子点修饰TiO_2复合纳米材料的制备及其光电性能研究

传统的二氧化钛(TiO_2)存在一些问题,如能隙值过大只可响应紫外波段,光生电子与空穴极易在体内和表面复合。针对目前TiO_2在光催化应用中存在的不足,提出了有效提升其光催化性能的实验方案。以高比率(001)面纳米TiO_2粒子为研究对象,采用热裂解柠檬酸制备的石墨烯量子点(GQDs),在强碱水热条件下制备出GQDs修饰的海胆状TiO_2。对所制样品的形貌与结构进行表征,并利用构建好的电化学平台,分析改性修饰对TiO_2光催化性能的影响。结果表明,GQDs敏化的TiO_2显示出优异的光催化性能。     

石墨烯的制备技术研究进展

石墨烯以其高强度、高导电性、极轻薄等优势,使其在电子、航天、军工、生物、新能源、半导体等领域具有广阔的应用潜力,成为国际上的研究热点和竞争焦点。石墨烯的制备是石墨烯走向应用的关键,如何大规模制备高质量、大尺寸、低成本的石墨烯是产业化亟待解决的问题。本文对近些年在石墨烯的制备方法方面取得的进展及优缺点进行了综述。     

Glowing Graphene Quantum Dots and Carbon Dots: Properties,Syntheses, and Biological Applications

The emerging graphene quantum dots (GQDs) and carbon dots (C‐dots) have gained tremendous attention for their enormous potentials for biomedical applications, owing to their unique and tunable photoluminescence properties, exceptional physicochemical properties, high photostability, biocompatibility, and small size. This article aims to update the latest results in this rapidly evolving field and to provide critical insights to inspire more exciting developments. We comparatively review the properties and synthesis methods of these carbon nanodots and place emphasis on their biological (both fundamental and theranostic) applications.     

Graphene Quantum Dots for Optical Bioimaging

Graphene quantum dots (GQDs) have shown great potential in bioimaging applications due to their excellent biocompatibility, low cytotoxicity, feasibility for surface functionalization, physiological stability, and tunable fluorescence properties. This Review first introduces the intriguing optical properties of GQDs that are suitable for biological imaging, and is followed by the GQDs' synthetic strategies. The emergent and latest development methods for tuning GQDs' optical properties are further described in detail. The recent advanced applications of GQDs in vitro, particularly in cell imaging, targeted imaging, and theranostic nanoplatform fabrication, are included. The applications of GQDs for in vivo bioimaging are also covered. Finally, the Review is concluded with the challenges and prospectives that face this nascent yet exciting field.     

Graphene quantum dots derived from carbon fibers

Graphene quantum dots (GQDs), which are edge-bound nanometer-size graphene pieces, have fascinating optical and electronic properties. These have been synthesized either by nanolithography or from starting materials such as graphene oxide (GO) by the chemical breakdown of their extended planar structure, both of which are multistep tedious processes. Here, we report that during the acid treatment and chemical exfoliation of traditional pitch-based carbon fibers, that are both cheap and commercially available, the stacked graphitic submicrometer domains of the fibers are easily broken down, leading to the creation of GQDs with different size distribution in scalable amounts. The as-produced GQDs, in the size range of 1-4 nm, show two-dimensional morphology, most of which present zigzag edge structure, and are 1-3 atomic layers thick. The photoluminescence of the GQDs can be tailored through varying the size of the GQDs by changing process parameters. Due to the luminescence stability, nanosecond lifetime, biocompatibility, low toxicity, and high water solubility, these GQDs are demonstrated to be excellent probes for high contrast bioimaging and biosensing applications.     

Dual-mode emission of single-layered graphene quantum dots in confined nanospace: Anti-counterfeiting and sensor applications

Nano Research - Engineering of the luminescent properties for graphene quantum dots (GQDs) presents two enormous challenges: 1) The bandgap of GQDs is mainly determined by structural defects (size,...     

Preparation of graphene quantum dots for bioimaging application

In this communication, preparation of graphene quantum dots (GQDs) with size about 10 nm by vigorous oxidation of graphite is reported. Thus obtained GQDs exhibit good physiological solubility, high photostability, low cytotoxicity, and yellow-green fluorescence with quantum yield about 7%. Furthermore, the feasibility of the GQDs for cell imaging application is demosntrated.     

Specific Oxygenated Groups Enriched Graphene Quantum Dots as Highly Efficient Enzyme Mimics

Significant progress is achieved for the utilization of graphene quantum dots as enzyme mimics in various biomedical fields recently. Although promising, the biocatalytic performance is far from satisfactory. Here, the rational design and synthesis of specific oxygenated groups enriched graphene quantum dots (o‐GQDs) via a facile oxidation reflux route is reported. These well‐prepared o‐GQDs with uniform size exhibit an ultrahigh peroxidase‐like activity in a wide range of pH values, and their superior performance is verified by using glucose detection as a typical model. Compared with classical nanozymes, these o‐GQDs show multiple times higher enzymatic activity. It is believed that the super facile synthesis strategy can greatly facilitate the practical use of o‐GQDs as enzyme mimics in the future.     

Preparation and gas-sensing properties of SnO<Subscript>2</Subscript>/graphene quantum dots composites via solvothermal method

SnO₂/graphene quantum dots (GQDs) nano-composites were prepared via solvothermal method (160 °C, 10 h), in which graphene quantum dots were synthesized from graphene oxide by one-step solvothermal method. The nano-composites were characterized by means of HRTEM, XRD, SEM, FTIR, XPS and N₂ adsorption–desorption, respectively. The sensor devices were fabricated using SnO₂/GQDs nano-composites as sensing materials. The effect of the GQDs content on the gas-sensing responses and the gas-sensing selectivity was investigated. The experimental results showed that the sensor based on SnO₂/GQDs nano-composite (S-2) exhibited good response and good selectivity to acetone vapor. When operating at 275 °C, the responses of the sensor based on SnO₂/GQDs nano-composite (S-2) to 1000 and 0.1 ppm acetone reached 120.6 and 1.3, respectively; the response time and the recovery time for 1000 ppm acetone were 17 and 13 s, respectively.     

Carbon Dots,Unconventional Preparation Strategies,and Applications Beyond Photoluminescence

Carbon dots (C‐dots) are generally separated into graphene quantum dots (GQDs) and carbon nanodots (CNDs) based on their respective top‐down and bottom‐up preparation processes. However, GQDs can be prepared by carbonization of small‐molecule precursors as revealed with unconventional preparation strategies. Thus, it is their structures rather than their precursors and preparation strategy that govern whether C‐dots are GQDs or CNDs. Here, the composites, structure, and electronic properties of C‐dots are discussed. C‐dots generally consist of a graphite‐like core and amorphous oxygen‐containing shell. When graphite becomes C‐dots, its conduction and valence bands are separated, and the quantum confinement effect appears. Combined with the light‐harvesting ability inherited from graphite, electrons in the core of C‐dots are transferred from conduction to valence bands, leading to electron–hole pair formation upon light excitation. The photoexcitation activities, such as photovoltaic conversion, photocatalysis, and photodynamic therapy, are influenced by the electronic properties of the core. Different to the semiconductor properties of core, the C‐dot shell is electrochemically active, leading to electrochemiluminescence (ECL). The oxygen‐containing groups in shell can conjugate to functional species for use in imaging and therapy. The applications of C‐dots beyond photoluminescence, including ECL, solar photovoltaics, photocatalysis, and theranostics, are reviewed.     

Sensitive determination of uric acid by using graphene quantum dots as a new substrate for immobilisation of uric oxidase

A novel strategy for highly sensitive electrochemical detection of uric acid (UA) was proposed based on graphene quantum dots (GQDs), GQDs were introduced as a suitable substrate for enzyme immobilisation. Uric oxidase (UOx) was immobilised on GQDs modified glassy carbon electrode (GCE). Transmission electron microscope, scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy techniques were used for characterising the electrochemical biosensor. The developed biosensor responds efficiently to UA presence over the concentration linear range 1–800 μM with the detection limit 0.3 μM. This novel biosensing platform based on UOx/GQDs electrode responded even more sensitively than that based on GCE modified by UOx alone. The inexpensive, reliable and sensitive sensing platform based on UOx/GQDs electrode provides wide potential applications in clinical.Inspec keywords: organic compounds, graphene devices, quantum dots, enzymes, biosensors, biochemistry, electrochemical electrodes, electrochemical sensors, transmission electron microscopy, scanning electron microscopy, voltammetry (chemical analysis), electrochemical impedance spectroscopy, nanomedicine, molecular biophysicsOther keywords: sensitive uric acid determination, graphene quantum dots, uric oxidase immobilisation, electrochemical detection, GQD, enzyme immobilisation, glassy carbon electrode, GCE, transmission electron microscope, scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectroscopy, electrochemical biosensor, C     

石墨烯量子点/CdS/CdSe共敏化太阳能电池

以三维锐钛矿TiO₂微球为上层光散射层材料, 以商业纳米TiO₂为下层连接材料, 采用刮刀法制备了一种新颖的双层TiO₂薄膜, 并应用于量子点敏化太阳能电池(QDSSC)。其中, 石墨烯量子点(GQDs)采用滴液法引入, CdS/CdSe量子点采用连续离子层吸附法(SILAR)制备。采用场发射扫描电镜、透射电镜、X射线衍射、紫外-可见漫反射光谱及荧光光谱对样品进行表征。实验还制备了CdS/CdSe量子点敏化及石墨烯量子点/CdS/CdSe共敏化太阳能电池, 并研究了石墨烯量子点及CdS不同敏化周期及对电池性能影响。研究结果表明, 石墨烯量子点及CdS不同敏化周期对薄膜的光学性质、电子传输及载流子复合均有较大影响。优选条件下, TiO₂/QGDs/CdS(4)/CdSe电池的光电转换效率为1.24%, 光电流密度为9.47 mA/cm², 显著高于TiO₂/CdS(4)/CdSe电池的这些参数(0.59%与6.22 mA/cm²)。这主要是由于TiO₂表层吸附石墨烯量子点后增强了电子的传输, 减少了载流子的复合。