Fluorescent carbon nanoparticles or carbon quantum dots (CQDs) are a new class of carbon nanomaterials that have emerged recently and have garnered much interest as potential competitors to conventional semiconductor quantum dots. In addition to their comparable optical properties, CQDs have the desired advantages of low toxicity, environmental friendliness low cost and simple synthetic routes. Moreover, surface passivation and functionalization of CQDs allow for the control of their physicochemical properties. Since their discovery, CQDs have found many applications in the fields of chemical sensing, biosensing, bioimaging, nanomedicine, photocatalysis and electrocatalysis. This article reviews the progress in the research and development of CQDs with an emphasis on their synthesis, functionalization and technical applications along with some discussion on challenges and perspectives in this exciting and promising field.

Carbon quantum dots and their applications

Fluorescent carbon-based materials have drawn increasing attention in recent years owing to exceptional advantages such as high optical absorptivity, chemical stability, biocompatibility, and low toxicity. These materials primarily include carbon dots (CDs), nanodiamonds, carbon nanotubes, fullerene, and fluorescent graphene. The superior properties of fluorescent carbon-based materials distinguish them from traditional fluorescent materials, and make them promising candidates for numerous exciting applications, such as bioimaging, medical diagnosis, catalysis, and photovoltaic devices. Among all of these materials, CDs have drawn the most extensive notice, owing to their early discovery and adjustable parameters. However, many scientific issues with CDs still await further investigation. Currently, a broad series of methods for obtaining CD-based materials have been developed, but efficient one-step strategies for the fabrication of CDs on a large scale are still a challenge in this field. Current synthetic methods are mainly deficient in accurate control of lateral dimensions and the resulting surface chemistry, as well as in obtaining fluorescent materials with high quantum yields (QY). Moreover, it is important to expand these kinds of materials to novel applications. Herein, a facile and highoutput strategy for the fabrication of CDs, which is suitable for industrial-scale production (yield is ca. 58%), is discussed. The QY was as high as ca. 80%, which is the highest value recorded for fluorescent carbon-based materials, and is almost equal to fluorescent dyes. The polymer-like CDs were converted into carbogenic CDs by a change from low to high synthesis temperature. The photoluminescence (PL) mechanism (high QY/PL quenching) was investigated in detail by ultrafast spectroscopy. The CDs were applied as printing ink on the macro/micro scale and nanocomposites were also prepared by polymerizing CDs with certain polymers. Additionally, the CDs could be utilized as a biosensor reagent for the detection of Fe in biosystems. The CDs were prepared by a hydrothermal method, which is described in the Supporting Information (Figure 1a; see also the Supporting Information, Figure S1). The reaction was conducted by first condensing citric acid and ethylenediamine, whereupon they formed polymer-like CDs, which were then carbonized to form the CDs. The morphology and structure of CDs were confirmed by analysis. Figure 1b shows transmission electron microscopy (TEM) images of the CDs, which can be seen to have a uniform dispersion without apparent aggregation and particle diameters of 2–6 nm. The sizes of CDs were also measured by atomic force microscopy (AFM; Figure S2), and the average height was 2.81 nm. From the high-resolution TEM, most particles are observed to be amorphous carbon particles without any lattices; rare particles possess well-resolved lattice fringes. With such a low carbon-lattice-structure content, no obvious D or G bands were detected in the Raman spectra of the CDs (Figure S3). The XRD patterns of the CDs (Figure 1c) also displayed a broad peak centered at 258 (0.34 nm), which is also attributed to highly disordered carbon atoms. Moreover, NMR spectroscopy (H and C) was employed to distinguish sp-hybridized carbon atoms from sp-hybridized carbon atoms (Figure S4). In the H NMR spectrum, sp carbons were detected. In the C NMR spectrum, signals in the range of 30–45 ppm, which correspond to aliphatic (sp) carbon atoms, and signals from 100–185 ppm, which are indicative of sp carbon atoms, were observed. Signals in the range of 170– 185 ppm, which correspond to carboxyl/amide groups, were also present. In the FTIR analysis of CDs, the following were observed: stretching vibrations of C OH at 3430 cm 1 and C H at 2923 cm 1 and 2850 cm , asymmetric stretching vibrations of C-NH-C at 1126 cm , bending vibrations of N H at 1570 cm , and the vibrational absorption band of C=O at 1635 cm 1 (Figure S5). Moreover, the surface groups were also investigated by XPS analysis (Figure 1d). C1s analysis revealed three different types of carbon atoms: graphitic or aliphatic (C=C and C C), oxygenated, and nitrous (Table S1). In the UV/Vis spectra, the peak was focused on 344 nm in an aqueous solution of CDs. In the fluorescence spectra, CDs have optimal excitation and emission wavelengths at 360 nm and 443 nm, and show a blue color under a hand-held UV lamp (Figure 2a). Excitation-dependent PL behavior was [*] S. Zhu, Q. Meng, Prof. J. Zhang, Y. Song, Prof. K. Zhang, Prof. B. Yang State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University Changchun, 130012 (P. R. China) E-mail: byangchem@jlu.edu.cn

Highly Photoluminescent Carbon Dots for Multicolor Patterning, Sensors, and Bioimaging

Carbon nanodots (C-dots) have generated enormous excitement because of their superiority in water solubility, chemical inertness, low toxicity, ease of functionalization and resistance to photobleaching. In this review, by introducing the synthesis and photo- and electron-properties of C-dots, we hope to provide further insight into their controversial emission origin (particularly the upconverted photoluminescence) and to stimulate further research into their potential applications, especially in photocatalysis, energy conversion, optoelectronics, and sensing.

Carbon nanodots: synthesis, properties and applications

At present, the actual mechanism of the photoluminescence (PL) of fluorescent carbon dots (CDs) is still an open debate among researchers. Because of the variety of CDs, it is highly important to summarize the PL mechanism for these kinds of carbon materials; doing so can guide the development of effective synthesis routes and novel applications. This review will focus on the PL mechanism of CDs. Three types of fluorescent CDs were involved: graphene quantum dots (GQDs), carbon nanodots (CNDs), and polymer dots (PDs). Four reasonable PL mechanisms have been confirmed: the quantum confinement effect or conjugated π-domains, which are determined by the carbon core; the surface state, which is determined by hybridization of the carbon backbone and the connected chemical groups; the molecule state, which is determined solely by the fluorescent molecules connected on the surface or interior of the CDs; and the crosslink-enhanced emission (CEE) effect. To give a thorough summary, the category and synthesis routes, as well as the chemical/physical properties for the CDs, are briefly introduced in advance.

The photoluminescence mechanism in carbon dots (graphene quantum dots, carbon nanodots, and polymer dots): current state and future perspective

5. In Situ Polymerization 3907 5.1. General Polymerization 3907 5.2. Photopolymerization 3910 5.3. Surface-Initiated Polymerization 3912 5.4. Other Methods 3913 6. Colloidal Nanocomposites 3913 6.1. Sol-Gel Process 3914 6.2. In Situ Polymerization 3916 6.2.1. Emulsion Polymerization 3917 6.2.2. Emulsifier-Free Emulsion Polymerization 3919 6.2.3. Miniemulsion Polymerization 3920 6.2.4. Dispersion Polymerization 3921 6.2.5. Other Polymerization Methods 3923 6.2.6. Conducting Nanocomposites 3924 6.3. Self Assembly 3926 7. Other Preparative Methods 3926 8. Characterization and Properties 3928 8.1. Chemical Structure 3928 8.2. Microstructure and Morphology 3929 8.3. Mechanical Properties 3933 8.3.1. Tensile, Impact, and Flexural Properties 3933 8.3.2. Hardness 3936 8.3.3. Fracture Toughness 3937 8.3.4. Friction and Wear Properties 3937 8.4. Thermal Properties 3938 8.5. Flame-Retardant Properties 3941 8.6. Optical Properties 3942 8.7. Gas Transport Properties 3943 8.8. Rheological Properties 3945 8.9. Electrical Properties 3945 8.10. Other Characterization Techniques 3946 9. Applications 3947 9.1. Coatings 3947 9.2. Proton Exchange Membranes 3948 9.3. Pervaporation Membranes 3948 9.4. Encapsulation of Organic Light-Emitting Devices 3948

Polymer/Silica Nanocomposites: Preparation, Characterization, Properties, and Applications

Carbon-based photoluminescent nanoparticles have recently received increased interest, owing to their favorable optical properties along with their biocompatibility and low toxicity. Such nascent nanomaterials, the so-called carbon dots (CDs or C-dots), are a promising alternative to more toxic metal-based semiconductor quantum dots (QDs) for applications such as bioimaging. Recent advances in the synthesis of CDs allow them to be formed from fine carbon structures (like graphene and multi-wall carbon nanotubes) by topdown methods, or from chemical precursors (like ammonium citrate and ethylenediaminetetraacetic acid) by bottom-up approaches. Typically, these CDs require surface oxidation and/or further passivation to emit fluorescence, which also makes them hydrophilic. Alternatively, some one-step strategies to fabricate surface-passivated CDs have also been shown. We reported a one-step synthesis of multicolor CDs from pyrolysis of epoxy-enriched polystyrene photonic crystals and their potential for use in light-emitting diodes. Herein, we present a simple and rapid strategy to fabricate CDs from cheap and natural carbon sources and further extend their application as printing “inks”. The fluorescent CDs developed herein have the following notable characteristics: 1) one-step generation in minutes from low-cost, natural, edible chicken eggs by plasma-induced pyrolysis; 2) good amphiphilicity with high solubility in a broad range of aqueous and organic solvents; 3) resistance to acids and bases; 4) versatile applications as fluorescent carbon inks for luminescent patterns. Figure 1 shows the fabrication of egg-derived fluorescent CDs and their application as “inks” for luminescent patterns using inkjet or silk-screen printing. We chose chicken eggs as the starting material to maintain low toxicity and affordability of the final product. Low-temperature plasma with highenergy, inherently charged particles (electrons or cations) and excited neutral species was used to create an active chemical environment for the synthesis of the nanostructures. As shown in Figure 1, the egg was separated into egg white and egg yolk, using an egg-separator, prior to use. A glass dish filled with egg white or yolk was placed between two quartz slides (height= 1.5 cm) of the plasma generator. Subsequently, intense and uniform plasma beams generated from the upper electrode (voltage= 50 V, current= 2.4 A) irradiated the egg samples for 3 min to yield dark black products, referred to as CDpew and CDpey for the plasma-treated egg white and yolk, respectively. The yield of CDs from the egg sample was calculated to be approximately 5.96%. Elemental analysis showed an increase in the carbon content of the products (62.42% for CDpey and 56.75% for CDpew) in comparison to that of the starting material (57.55% for egg yolk and 43.50% for egg white), implying carbonization occurs during the plasma treatment (Supporting Information, Table S1). Significantly, solutions of CDpew and CDpey display bright blue fluorescence under UV light (lex= 302 nm). Figure 2 shows high-resolution transmission electron microscope (HRTEM) images of the CDs. CDpey had uniform dispersion without apparent aggregation and a mean particle diameter (Dp) of 2.15 nm (Figure 2a and Figure S2). Detectable rings in the selected-area electron-diffraction (SAED) pattern revealed the crystalline structure of CDpey (Figure 2a inset). Well-resolved lattice fringes with an interplanar spacing of 0.208 nm were observed (Figure 2b), which is close to the (100) facet of graphite. On the other hand, CDpew was well distributed (Dp= 3.39 nm) and appeared Figure 1. Digital photographs of plasma-induced fabrication of eggderived CDs and their application as fluorescent carbon inks. Egg white or yolk, after a few minutes of plasma treatment under ambient conditions, were transformed into well-defined CDs with bright blue emission under UV light. The CD solutions can also be used as inks for making luminescent patterns by inkjet or silk-screen printing.

Amphiphilic Egg-Derived Carbon Dots: Rapid Plasma Fabrication, Pyrolysis Process, and Multicolor Printing Patterns

https://www.rsc.org/suppdata/cc/c2/c2cc17769b/c2cc17769b.pdf

Facile access to versatile fluorescent carbon dots toward light-emitting diodes

electrophoretic displays, [ 4 , 5 ] self-assembly of multidimensional ordered structures, [ 6 ] and sensors. [ 7 ] A variety of Janus particles with complex shapes, anisotropic nature, and diverse functionalities have been developed by using elegant methods including electrifi ed co-jetting, [ 8 ] the spinning disks technique, [ 9 ] surface modifi cation, [ 10 ] microcontact printing, [ 11 ] the microfl uidic technique, [ 12 ] and others. [ 13 ] Particularly, Janus particles with magnetic, electric, or optical characteristics have aroused special interest because of their ability to undergo switching in response to a stimulus (e.g., magnetic or electric fi elds or light). In this respect, Yang et al. developed a light-curing technology to generate magnetoresponsive Janus microparticles for remotecontrolled locomotion. [ 2 ] Doyle and co-workers reported the preparation of Janus hydrogel particles with anisotropic superparamagnetism and demonstrated that these particles could be aligned and assembled by an external magnetic fi eld. [ 14 ]

Versatile bifunctional magnetic-fluorescent responsive Janus supraballs towards the flexible bead display

We report a simple, low-cost and green route for fabrication of fluorescent carbon dots (CDs), and demonstrate their applications in sensing, patterning, and coding. Pyrolysis of various plant leaves yielded bright blue-emitting CDs, providing a one-step way for large-scale production of CDs without surface passivation treatment or the use of toxic/expensive solvents and starting materials. Also, further improvement in the fluorescence intensity of CDs was achieved after treatment using plasma and microwave-assisted techniques. The obtained CDs were applied as a fluorescent sensing platform for sensitive and selective detection of Fe3+ ions, and as fluorescent inks for printing luminescent patterns useful in anti-counterfeit and optoelectronic applications. Moreover, uniform fluorescent microbeads of polymer-encapsulated CDs, CD/QD nanocomposites, and CD/organic fluorescent dye nanocomposites were prepared via a microfluidic process, which may expand the potential applications of CDs in coding, bioimaging, and drug delivery.

Plant leaf-derived fluorescent carbon dots for sensing, patterning and coding

However, it is stilla great challenge to mount or shape CPCs into a desiredmorphology (e.g., spheres, Janus, ellipsoids, and dumbbell-like supaparticles); efficient pathways are needed to selec-tively endow CPCs with versatile functions whilst preservingtheir original optical properties.Herein, we developed a triphase microfluidic-directedself-assembly to construct CPC supraparticles with control-lable and predictable shape, and selectively introducedadvanced functions to them. The triphase microfluidictechnique is a co-flowing system that produces continuousmicrodroplets comprising two immiscible phases. By adjust-ing the interfacial tension of each phase in the microfluidicsystem, CPC supraparticles with tunable shape, varying fromcrescent, meniscus, and ellipsoid to spherical were preparedbytheself-assemblyofthemonodispersecolloidalparticlesinthese microdroplet templates. Importantly, studying theinterfacechemistryindicatedthatthestructureofthebiphasicmicrodroplets and the resulting CPCs might be predicted inour strategy. The further introduction of photoinducedconsolidation into the triphase microfluidic system yieldedcore–shell or Janus CPC superstructures. The encapsulationof magnetic nanoparticles created Janus CPC supraparticleswith superparamagnetism and a photonic bandgap in twodistincthemispheres.ThesemultifunctionalJanusCPCsupra-particles exhibit “Dark” and “Light” switchable behaviorsunder an external magnetic field, and thus can be processedinto rewritable and color-tunable photonic patterns. To ourknowledge, this is the first example of the utilization of thetriphase microfluidic technique for the design of anisotropicCPCs. This facile strategy can be extended to build up aseriesofnovelmultidimensionalcolloidalstructures,withtheaimofcollecting colloidal particles and orgnizing them into func-tional materials for pratical application.Figure 1a illustrates the fabrication of shape-controllableCPC supraparticles in a triphase microfluidic flow-focusingdevice composed of a cylindrical polydimethylsiloxane(PDMS) capillary and a pair of inner cylindrical 25G steelneedles. We chose three immiscible fluids, an aqueoussolution of monodisperse polystyrene (PS) microspheres in

Su Chen

Papers

Amphiphilic Egg-Derived Carbon Dots: Rapid Plasma Fabrication, Pyrolysis Process, and Multicolor Printing Patterns

Facile access to versatile fluorescent carbon dots toward light-emitting diodes

Versatile bifunctional magnetic-fluorescent responsive Janus supraballs towards the flexible bead display

Plant leaf-derived fluorescent carbon dots for sensing, patterning and coding

Triphase Microfluidic-Directed Self-Assembly: Anisotropic Colloidal Photonic Crystal Supraparticles and Multicolor Patterns Made Easy