Despite the various synthesis methods to obtain carbon dots (CDs), the bottom-up methods are still the most widely administrated route to afford large-scale and low-cost synthesis. However, as CDs are developed with increasing reports involved in producing many CDs, the structure and property features have changed enormously compared with the first generation of CDs, raising classification concerns. To this end, a new classification of CDs, named carbonized polymer dots (CPDs), is summarized according to the analysis of structure and property features. Here, CPDs are revealed as an emerging class of CDs with distinctive polymer/carbon hybrid structures and properties. Furthermore, deep insights into the effects of synthesis on the structure/property features of CDs are provided. Herein, the synthesis methods of CDs are also summarized in detail, and the effects of synthesis conditions of the bottom-up methods in terms of the structures and properties of CPDs are discussed and analyzed comprehensively. Insights into formation process and nucleation mechanism of CPDs are also offered. Finally, a perspective of the future development of CDs is proposed with critical insights into facilitating their potential in various application fields.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/advs.201901316

Evolution and Synthesis of Carbon Dots: From Carbon Dots to Carbonized Polymer Dots

Carbon dots (CDs), as a new type of carbon-based nanomaterial, have attracted broad research interest for years, because of their diverse physicochemical properties and favorable attributes like good biocompatibility, unique optical properties, low cost, ecofriendliness, abundant functional groups (e.g., amino, hydroxyl, carboxyl), high stability, and electron mobility. In this Outlook, we comprehensively summarize the classification of CDs based on the analysis of their formation mechanism, micro-/nanostructure and property features, and describe their synthetic methods and optical properties including strong absorption, photoluminescence, and phosphorescence. Furthermore, the recent significant advances in diverse applications, including optical (sensor, anticounterfeiting), energy (light-emitting diodes, catalysis, photovoltaics, supercapacitors), and promising biomedicine, are systematically highlighted. Finally, we envisage the key issues to be challenged, future research directions, and perspectives to show a full picture of CDs-based materials.

Carbon Dots: A New Type of Carbon-Based Nanomaterial with Wide Applications

Electronic structure greatly determines the band structures and the charge carrier transport properties of semiconducting photocatalysts and consequently their photocatalytic activities. Here, by simply calcining the mixture of graphitic carbon nitride (g-C3 N4 ) and sodium borohydride in an inert atmosphere, boron dopants and nitrogen defects are simultaneously introduced into g-C3 N4 . The resultant boron-doped and nitrogen-deficient g-C3 N4 exhibits excellent activity for photocatalytic oxygen evolution, with highest oxygen evolution rate reaching 561.2 µmol h-1 g-1 , much higher than previously reported g-C3 N4 . It is well evidenced that with conduction and valence band positions substantially and continuously tuned by the simultaneous introduction of boron dopants and nitrogen defects into g-C3 N4 , the band structures are exceptionally modulated for both effective optical absorption in visible light and much increased driving force for water oxidation. Moreover, the engineered electronic structure creates abundant unsaturated sites and induces strong interlayer C-N interaction, leading to efficient electron excitation and accelerated charge transport. In the present work, a facile approach is successfully demonstrated to engineer the electronic structures and the band structures of g-C3 N4 with simultaneous introduction of dopants and defects for high-performance photocatalytic oxygen evolution, which can provide informative principles for the design of efficient photocatalysis systems for solar energy conversion.

Synergy of Dopants and Defects in Graphitic Carbon Nitride with Exceptionally Modulated Band Structures for Efficient Photocatalytic Oxygen Evolution.

The emergence of carbon dots (CDs) has opened up an exciting new field in the science and technology of carbon nanomaterials and has attracted increasing interest in recent years. Due to their diverse physicochemical properties and favourable attributes, such as quantum confinement effects and abundant surface defects, CDs and their derived hybrids have shown exciting and indispensable prospects in the energy conversion and storage fields. Considering the latest developments, in this review, we comprehensively summarize the classification and structure of CDs. Three strategies for structural engineering of CDs are presented and analyzed, in terms of the tuning of size and crystallinity, and the methodologies for surface modification and heteroatom doping, with a focus on the relationship among the synthesis methods, structure and properties of the concerned CDs. More importantly, the recent advances in energy-oriented applications of CDs, including photo- and electro-catalysis, light-emitting diodes, photovoltaic cells, lithium/sodium ion batteries and supercapacitors, will be systematically highlighted. Finally, we discuss and outline the remaining major challenges and opportunities for CDs in the future.

Design and fabrication of carbon dots for energy conversion and storage

Stimuli-responsive optical materials have received tremendous interest in the last several decades due to their numerous promising applications. Here, fluorescence emissive polymer carbon dots (F-CDs), prepared with a simple heating treatment from ethylenediamine and phosphoric acid, are found to produce unexpected ultralong room-temperature phosphorescence (URTP), which lasts for about 10 s with a lifetime of 1.39 s. This is the first example to achieve the conversion of a fluorescence material to URTP by means of an external heating stimulus. Further investigations reveal that the doping of N and P elements and self-immobilization of the excited triplet species are likely mainly responsible for the observed URTP after the heating treatment, due to the facilitation of the intersystem crossing and formation of more compact cores for effective intraparticle hydrogen bonds, respectively. Importantly, this study also demonstrates the potential for aqueous dispersion of the F-CDs as an advanced security ink for information encryption and anticounterfeiting; this is a feature that has not been reported before. This study is believed to open possibilities to extend stimuli-responsive optical materials to rarely exploited phosphorescence-relevant systems and applications, and also to provide a novel strategy to easily prepare URTP materials.

Conversion of Carbon Dots from Fluorescence to Ultralong Room-Temperature Phosphorescence by Heating for Security Applications

Multiple-color-emissive carbon dots (CDots) have potential applications in various fields such as bioimaging, light-emitting devices, and photocatalysis. The majority of the current CDots to date exhibit excitation-wavelength-dependent emissions with their maximum emission limited at the blue-light region. Here, a synthesis of multiple-color-emission CDots by controlled graphitization and surface function is reported. The CDots are synthesized through controlled thermal pyrolysis of citric acid and urea. By regulating the thermal-pyrolysis temperature and ratio of reactants, the maximum emission of the resulting CDots gradually shifts from blue to red light, covering the entire light spectrum. Specifically, the emission position of the CDots can be tuned from 430 to 630 nm through controlling the extent of graphitization and the amount of surface functional groups, COOH. The relative photoluminescence quantum yields of the CDots with blue, green, and red emission reach up to 52.6%, 35.1%, and 12.9%, respectively. Furthermore, it is demonstrated that the CDots can be uniformly dispersed into epoxy resins and be fabricated as transparent CDots/epoxy composites for multiple-color- and white-light-emitting devices. This research opens a door for developing low-cost CDots as alternative phosphors for light-emitting devices.

Synthesis of Carbon Dots with Multiple Color Emission by Controlled Graphitization and Surface Functionalization.

Defects play a significant part in promoting photocatalytic activity for H2 production. Various methods such as chemical reduction have been performed to metal oxide based photocatalysts. Herein, we present the NaBH4 reduction route to introduce the defects into the graphitic carbon nitride (g-C3N4) to enhance photocatalytic activity. A new −C≡N group is observed in the FTIR spectra of treated g-C3N4 nanosheets indicating the presence of structural defects. At the same time, the B signal appears in the X-ray photoelectron spectroscopy analysis, suggesting that B is doped in the g-C3N4 during the treatment. All these results manifested that multiple types of defects are introduced in the g-C3N4 during the NaBH4 treatment. The UV–vis spectra illustrate that the absorption band edge of g-C3N4 is extended from 420 to 450 nm after NaBH4 treatment. This demonstrates that the band gap of g-C3N4 turns narrow owing to the introduction of defects. Photocatalytic H2 production of defective g-C3N4 is ∼5-fold better t...

Defective g-C3N4 Prepared by the NaBH4 Reduction for High-Performance H2 Production

Carbon dots (CDs) have been demonstrated to be fluorescent materials for the new phosphor-free white light-emitting diodes (WLEDs). Herein, we synthesized a novel white CDs (WCDs). The spectrum hig...

White Emissive Carbon Dots Actuated by the H-/J-Aggregates and Förster Resonance Energy Transfer.

https://www.onlinelibrary.wiley.com/doi/epdf/10.1002/adma.201870002

Photoluminescence: Synthesis of Carbon Dots with Multiple Color Emission by Controlled Graphitization and Surface Functionalization (Adv. Mater. 1/2018)

Dongxue Yang

Papers

Synthesis of Carbon Dots with Multiple Color Emission by Controlled Graphitization and Surface Functionalization.

Defective g-C3N4 Prepared by the NaBH4 Reduction for High-Performance H2 Production

White Emissive Carbon Dots Actuated by the H-/J-Aggregates and Förster Resonance Energy Transfer.

Photoluminescence: Synthesis of Carbon Dots with Multiple Color Emission by Controlled Graphitization and Surface Functionalization (Adv. Mater. 1/2018)

A metal-free carbon dots for wastewater treatment by visible light active photo-Fenton-like reaction in the broad pH range