Superior Micro‐Supercapacitors Based on Graphene Quantum Dots

Graphene quantum dots (GQDs) have attracted tremendous research interest due to the unique properties associated with both graphene and quantum dots. Here, a new application of GQDs as ideal electrode materials for supercapacitors is reported. To this end, a GQDs//GQDs symmetric micro‐supercapacitor is prepared using a simple electro‐deposition approach, and its electrochemical properties in aqueous electrolyte and ionic liquid electrolyte are systematically investigated. The results show that the as‐made GQDs micro‐supercapacitor has superior rate capability up to 1000 V s^?1, excellent power response with very short relaxation time constant (τ₀ = 103.6 μs in aqueous electrolyte and τ₀ = 53.8 μs in ionic liquid electrolyte), and excellent cycle stability. Additionally, another GQDs//MnO₂ asymmetric supercapacitor is also built using MnO₂ nanoneedles as the positive electrode and GQDs as the negative electrode in aqueous electrolyte. Its specific capacitance and energy density are both two times higher than those of GQDs//GQDs symmetric micro‐supercapacitor in the same electrolyte. The results presented here may pave the way for a new promising application of GQDs in micropower suppliers and microenergy storage devices.     

A Facile Microwave Avenue to Electrochemiluminescent Two‐Color Graphene Quantum Dots

With the assistance of microwave irradiation, greenish‐yellow luminescent graphene quantum dots (gGQDs) with a quantum yield (QY) up to 11.7% are successfully prepared via cleaving graphene oxide (GO) under acid conditions. The cleaving and reduction processes are accomplished simultaneously using microwave treatment without additional reducing agent. When the gGQDs are further reduced with NaBH₄, bright blue luminescent graphene quantum dots (bGQDs) are obtained with a QY as high as 22.9%. Both GQDs show well‐known excitation‐dependent PL behavior, which could be ascribed to the transition from the lowest unoccupied molecular orbital (LUMO) to the highest occupied molecular orbital (HOMO) with a carbene‐like triplet ground state. Electrochemiluminescence (ECL) is observed from the graphene quantum dots for the first time, suggesting promising applications in ECL biosensing and imaging. The ECL mechanism is investigated in detail. Furthermore, a novel sensor for Cd²⁺ is proposed based on Cd²⁺ induced ECL quenching with cysteine (Cys) as the masking agent.     

Facile Synthesis of Graphene Quantum Dots from 3D Graphene and their Application for Fe3+ Sensing

Owing to their small size, biocompatibility, unique and tunable photoluminescence, and physicochemical properties, graphene quantum dots (GQDs) are an emerging class of zero‐dimensional materials promising a wide spectrum of novel applications in bio‐imaging, optical, and electrochemical sensors, energy devices, and so forth. Their widespread use, however, is largely limited by the current lack of high yield synthesis methods of high‐quality GQDs. In this contribution, a facile method to electrochemically exfoliate GQDs from three‐dimensional graphene grown by chemical vapor deposition (CVD) is reported. Furthermore, the use of such GQDs for sensitive and specific detection of ferric ions is demonstrated.     

Microwave‐Assisted Preparation of White Fluorescent Graphene Quantum Dots as a Novel Phosphor for Enhanced White‐Light‐Emitting Diodes

Graphene quantum dots (GQDs) with white fluorescence are synthesized by a microwave‐assisted hydrothermal method using graphite as the precursor. A solution‐processed white‐light‐emitting diode (WLED) is fabricated using the as‐prepared white fluorescent GQDs (white‐light‐emitting graphene quantum dots, WGQDs) doped 4,4‐bis(carbazol‐9‐yl)biphenyl as the emissive layer. White‐light emission is obtained from the WLED with 10 wt% doping concentration of WGQDs, which shows a luminance of 200 cd m^?2 at the applied voltage of 11–14 V. Importantly, an external quantum efficiency of 0.2% is achieved, which is the highest among all the reported WLED based on GQDs or carbon dots. The results demonstrate that WGQDs as a novel phosphor may open up a new avenue to develop the environmentally friendly WLEDs for practical application in solid‐state lighting.     

CoS Quantum Dot Nanoclusters for High‐Energy Potassium‐Ion Batteries

Potassium‐ion batteries (PIBs) are a promising alternative to lithium‐ion batteries because potassium is an abundant natural resource. To date, PIBs are in the early stages of exploration and only a few anode materials have been investigated. This study reports a cobalt sulfide and graphene (CoS@G) composite as anode electrode for PIBs for the first time. The composite features interconnect quantum dots of CoS nanoclusters uniformly anchored on graphene nanosheets. The coexistence of CoS quantum dot nanoclusters and graphene nanosheets endows the composite with large surface area, highly conductive network, robust structural stability, and excellent electrochemical energy storage performance. An unprecedented capacity of 310.8 mA h g^?1 at 500 mA g^?1 is obtained after 100 cycles, with a rate capability better than an equivalent sodium‐ion batteries (SIBs). This work provides the evidence that PIBs can be a promising alternative to SIBs, especially at high charge–discharge rates. The development of the CoS@G anode material also provides the basis of expanding the library of suitable anode materials for PIBs.     

Evidence for Edge‐State Photoluminescence in Graphene Quantum Dots

For a practical realization of graphene‐based logic devices, the opening of a band gap in graphene is crucial and has proven challenging. To this end, several synthesis techniques, including unzipping of carbon nanotubes, chemical vapor deposition, and other bottom‐up fabrication techniques have been pursued for the bulk production of graphene nanoribbons (GNRs) and graphene quantum dots (GQDs). However, only limited progress has been made towards a fundamental understanding of the origin of strong photoluminescence (PL) in GQDs. Here, it is experimentally shown that the PL is independent of the functionalization scheme of the GQDs. Following a series of annealing experiments designed to passivate the free edges, the PL in GQDs originates from edge‐states, and an edge‐passivation subsequent to synthesis quenches the PL. The results of PL studies of GNRs and carbon nano‐onions are shown to be consistent with PL being generated at the edge sites of GQDs.     

Silver‐Adapted Diffusive Memristor Based on Organic Nitrogen‐Doped Graphene Oxide Quantum Dots (N‐GOQDs) for Artificial Biosynapse Applications

Carbon‐based electronic devices are suitable candidates for bioinspired electronics due to their low cost, eco‐friendliness, mechanical flexibility, and compatibility with complementary metal‐oxide‐semiconductor technology. New types of materials such as graphene quantum dots (GQDs) have attracted attention in the search for new applications beyond solar cells and energy harvesting due to their superior properties such as elevated photoluminescence, high chemical inertness, and excellent biocompatibility. In this paper, a biocompatible/organic electronic synapse based on nitrogen‐doped graphene oxide quantum dots (N‐GOQDs) is reported, which exhibits threshold resistive switching via silver cation (Ag⁺) migration dynamics. In analogy to the calcium (Ca²⁺) ion dynamics of biological synapses, important biological synapse functions such as short‐term potentiation (STP), paired‐pulse facilitation, and transition from STP to long‐term plasticity behaviors are replicated. Long‐term depression behavior is also evaluated and specific spike‐timing dependent plasticity is assessed. In addition, elaborated switching mechanism of biosimilar Ag⁺ migration dynamics provides the potential for using N‐GOQD‐based artificial synapse in future biocompatible neuromorphic systems.     

New Opportunities: Second Harmonic Generation of Boron‐Doped Graphene Quantum Dots for Stem Cells Imaging and Ultraprecise Tracking in Wound Healing

Second harmonic generation (SHG) has recently emerged, having the advantages of no bleaching, no blinking, and no signal saturation, as well as a high signal to‐noise ratio compared to fluorescence. Existing SHG probes are based on heavy metal or organic dye molecules, which have the shortcomings of toxicity, a large size, or photoinstability. To address the urgent need for long‐term tracking and imaging in organisms, boron‐doped graphene quantum dots (B‐GQDs), a highly biocompatible graphene based with a strong and photostable SHG signal is first synthesized and is further applied for stem cell imaging and tracking in wounds. The results demonstrate the possibility of stem cell internalization of B‐GQDs as a SHG probe and show no hindering of the stem cell's central physiological activities such as differentiation. Most importantly, B‐GQDs are successfully tracked in skin tissue in vivo after the labeled mouse mesenchymal stem cells being implanted over 35 days. This work will inspire the development of doped graphene quantum dot materials and promote the broad use of B‐GQDs in future molecular imaging, drug delivery, and stem cell therapy.     

Fabrication of Graphene–Quantum Dots Composites for Sensitive Electrogenerated Chemiluminescence Immunosensing

A novel strategy is reported for the fabrication of poly(diallyldimethylammonium chloride) (PDDA)‐protected graphene–CdSe (P‐GR‐CdSe) composites. An advanced electrogenerated chemiluminescence (ECL) immunosensor is proposed for the sensitive detection of human IgG (HIgG) by using the as‐prepared P‐GR‐CdSe composites. The P‐GR‐CdSe composite film shows high ECL intensity, good electronic conductivity, fast response, and satisfactory stability, all of which holds great promise for the fabrication of ECL biosensors with improved sensitivity. After two successive steps of amplification via the conjugation of PDDA and gold nanoparticles (GNPs) in the film, high ECL intensity is observed. The ECL immunosensor has an extremely sensitive response to HIgG in a linear range of 0.02–2000 pg mL^?1 with a detection limit of 0.005 pg mL^?1. The proposed sensor exhibits high specificity, good reproducibility, and long‐term stability, and may become a promising technique for protein detection.     

In Vitro Prostate Cancer Treatment via CRISPR-Cas9 Gene Editing Facilitated by Polyethyleneimine-Derived Graphene Quantum Dots

CRISPR (Clustered Regularly Interspaced Short Palindromic Repeats)-Cas9 (CRISPR associated protein 9) is a programmable gene editing tool with a promising potential for cancer gene therapy. This therapeutic function is enabled in the present study via the non-covalent delivery of CRISPR ribonucleic protein (RNP) by cationic glucosamine/PEI-derived graphene quantum dots (PEI-GQDs) that aid in overcoming physiological barriers and tracking genes of interest. PEI-GQD/RNP complex targeting the tumor protein 53 (TP53) gene mutation overexpressed in ∽50% of cancers successfully produces its double-stranded breaks in solution and in prostate cancer (PC-3) cells. Restoring this cancer “suicide” gene can promote cellular repair pathways and lead to cancer cell apoptosis. Its repair to the healthy form performed by simultaneous PEI-GQD delivery of CRISPR RNP and a gene repair template leads to a successful therapeutic outcome: 40% apoptotic cancer cell death, while having no effect on non-cancerous (HeK293) cells. The translocation of PEI-GQD/RNP complex into PC-3 cell cytoplasm is tracked via GQD intrinsic fluorescence, while enhanced green fluorescent protein (EGFP)-tagged RNP is detected in the cell nucleus, showing the successful detachment of the gene editing tool upon internalization. Using GQDs as non-viral delivery and imaging agents for CRISPR-Cas9 RNP sets the stage for image-guided cancer-specific gene therapy.     

Synthesis of blue light-emitting graphene quantum dots and their application in flexible nonvolatile memory

We presented a facile method to prepare graphene quantum dots (GQDs) from double-walled carbon nanotube with blue light emission in a chlorobenzene solution, which enabled the preparation of GQD–polymer hybrid nanocomposite. The wavelength-dependent fluorescent lifetime of the GQDs was investigated by using time-resolved photoluminescence technique. Significantly, nonvolatile rewritable memory effect was observed for the GQD-based nanocomposite, suggesting the promising applications of GQDs in data storage. Moreover, due to the easy solution process, we demonstrated the design and realization of flexible GQD-based memory device. This work may expand the application of GQDs to the portable electronic devices.     

Highly Brilliant Noniridescent Structural Colors Enabled by Graphene Nanosheets Containing Graphene Quantum Dots

The most important properties of noniridescent structural colors of amorphous photonic structures (APS) are sufficient color brightness and saturation, which are difficult to be optimized simultaneously. Herein, highly saturated and brilliant noniridescent structural colors are achieved by introducing graphene nanosheets, which contain a fraction of graphene quantum dots (GQDs), into the short‐range ordered APS. The effective modulation of the photoluminescence (PL) of GQDs by the selective enhancement of absorption at the blue pseudo photonic bandgap edges of the APS boosts the PL with wavelength matching that of the photonic bandgap and thus enables high structural color brightness; the uniform light absorption of graphene nanosheets in the whole visible spectra contributes to the high color saturation. Furthermore, by using APS films with short‐range order as templates, a brilliant colorful humidity sensor is demonstrated. Compared with the conventional sensing platform based on photonic crystals, the humidity sensor with brilliant noniridescent structural colors is more convenient by avoiding the confusing color dependence on the viewing angles. The improvement in the structural color brightness of the APS films by facile graphene doping will facilitate their practical applications in fields of decorations, packaging, pigments, sensors, displays, or other color‐related areas.     

Surface Chemistry Routes to Modulate the Photoluminescence of Graphene Quantum Dots: From Fluorescence Mechanism to Up‐Conversion Bioimaging Applications

The bandgap in graphene‐based materials can be tuned from 0 eV to that of benzene by changing size and/or surface chemistry, making it a rising carbon‐based fluorescent material. Here, the surface chemistry of small size graphene (graphene quantum dots, GQDs) is tuned programmably through modification or reduction and green luminescent GQDs are changed to blue luminescent GQDs. Several tools are employed to characterize the composition and morphology of resultants. More importantly, using this system, the luminescence mechanism (the competition between both the defect state emission and intrinsic state emission) is explored in detail. Experiments demonstrate that the chemical structure changes during modification or reduction suppresses non‐radiative recombination of localized electron‐hole pairs and/or enhances the integrity of surface π electron network. Therefore the intrinsic state emission plays a leading role, as opposed to defect state emission in GQDs. The results of time‐resolved measurements are consistent with the suggested PL mechanism. Up‐conversion PL of GQDs is successfully applied in near‐IR excitation for bioimaging.     

CsPbX3 Quantum Dots for Lighting and Displays: Room‐Temperature Synthesis,Photoluminescence Superiorities,Underlying Origins and White Light‐Emitting Diodes

Recently, Kovalenko and co‐workers and Li and co‐workers developed CsPbX₃ (X = Cl, Br, I) inorganic perovskite quantum dots (IPQDs), which exhibited ultrahigh photoluminescence (PL) quantum yields (QYs), low‐threshold lasing, and multicolor electroluminescence. However, the usual synthesis needs high temperature, inert gas protection, and localized injection operation, which are severely against applications. Moreover, the so unexpectedly high QYs are very confusing. Here, for the first time, the IPQDs' room‐temperature (RT) synthesis, superior PL, underlying origins and potentials in lighting and displays are reported. The synthesis is designed according to supersaturated recrystallization (SR), which is operated at RT, within few seconds, free from inert gas and injection operation. Although formed at RT, IPQDs' PLs have QYs of 80%, 95%, 70%, and FWHMs of 35, 20, and 18 nm for red, green, and blue emissions. As to the origins, the observed 40 meV exciton binding energy, halogen self‐passivation effect, and CsPbX₃@X quantum‐well band alignment are proposed to guarantee the excitons generation and high‐rate radiative recombination at RT. Moreover, such superior optical merits endow them with promising potentials in lighting and displays, which are primarily demonstrated by the white light‐emitting diodes with tunable color temperature and wide color gamut.     

Modulating the Photocatalytic Activity of Graphene Quantum Dots via Atomic Tailoring for Highly Enhanced Photocatalysis under Visible Light

Precise control over doping of photocatalysts is required to modulate their photocatalytic activity in visible light‐driven reactions. Here, a single precursor‐employing bottom‐up approach is developed to produce different heteroatom‐doped graphene quantum dots (GQDs) with unique photocatalytic activities. The solvothermal reaction of a norepinephrine precursor with redox active and condensable moieties effectively produces both nitrogen/sulfur codoped GQDs (NS‐GQDs) and nitrogen‐doped GQDs (N‐GQDs) by simply varying solvents (from dimethyl sulfoxide to water) under microwave irradiation. As‐prepared NS‐GQDs and N‐GQDs show similar lateral sizes (3–4 nm) and heights (1–2 nm), but they include different dopant types and doping constitution and content, which lead to changes in photocatalytic activity in aerobic oxidative coupling reactions of various amines. NS‐GQDs exhibit much higher photocatalytic activity in reactions under visible light than N‐GQDs and oxygen‐doped GQDs (O‐GQDs). The mechanism responsible for the outstanding photocatalytic activity of NS‐GQDs in visible light‐driven oxidative coupling reactions of amines is also fully investigated.     

Organometal Halide Perovskite Quantum Dot Light‐Emitting Diodes

Organometal halide perovskites quantum dots (OHP‐QDs) with bright, color‐tunable, and narrow‐band photoluminescence have significant advantages in display, lighting, and laser applications. Due to sparse concentrations and difficulties in the enrichment of OHP‐QDs, production of large‐area uniform films of OHP‐QDs is a challenging task, which largely impedes their use in electroluminescence devices. Here, a simple dip‐coating method has been reported to effectively fabricate large‐area uniform films of OHP‐QDs. Using this technique, multicolor OHP‐QDs light‐emitting diodes (OQ‐LEDs) emitting in blue, blue‐green, green, orange, and red color have been successfully produced by simply tuning the halide composition or size of QDs. The blue, green, and red OQ‐LEDs exhibited, respectively, a maximum luminance of 2673, 2398, and 986 cd m^?2 at a current efficiency of 4.01, 3.72, and 1.52 cd A^?1, and an external quantum efficiency of 1.38%, 1.06%, and 0.53%, which are much better than most LEDs based on OHP films. The packaged OQ‐LEDs show long‐term stability in air (humidity ≈50%) for at least 7 d. The results demonstrate the great potential of the dip‐coating method to fabricate large‐area uniform films for various QDs. The high‐efficiency OQ‐LEDs also demonstrate the promising potential of OHP‐QDs for low‐cost display, lighting, and optical communication applications.     

Integrative Self‐Assembly of Graphene Quantum Dots and Biopolymers into a Versatile Biosensing Toolkit

Hybrid self‐assembly has become a reliable approach to synthesize soft materials with multiple levels of structural complexity and synergistic functionality. In this work, photoluminescent graphene quantum dots (GQDs, 2–5 nm) are used for the first time as molecule‐like building blocks to construct self‐assembled hybrid materials for label‐free biosensors. Ionic self‐assembly of disc‐shaped GQDs and charged biopolymers is found to generate a series of hierarchical structures that exhibit aggregation‐induced fluorescence quenching of the GQDs and change the protein/polypeptide secondary structure. The integration of GQDs and biopolymers via self‐assembly offers a flexible toolkit for the design of label‐free biosensors in which the GQDs serve as a fluorescent probe and the biopolymers provide biological function. The versatility of this approach is demonstrated in the detection of glycosaminoglycans (GAGs), pH, and proteases using three strategies: 1) competitive binding of GAGs to biopolymers, 2) pH‐responsive structural changes of polypeptides, and 3) enzymatic hydrolysis of the protein backbone, respectively. It is anticipated that the integrative self‐assembly of biomolecules and GQDs will open up new avenues for the design of multifunctional biomaterials with combined optoelectronic properties and biological applications.     

Amorphous FeOOH Quantum Dots Assembled Mesoporous Film Anchored on Graphene Nanosheets with Superior Electrochemical Performance for Supercapacitors

Previous research on iron oxides/hydroxides has focused on the crystalline rather than the amorphous phase, despite that the latter could have superior electrochemical activity due to the disordered structure. In this work, a simple and scalable synthesis route is developed to prepare amorphous FeOOH quantum dots (QDs) and FeOOH QDs/graphene hybrid nanosheets. The hybrid nanosheets possess a unique heterostructure, comprising a continuous mesoporous FeOOH nanofilm tightly anchored on the graphene surface. The amorphous FeOOH/graphene hybrid nanosheets exhibit superior pseudocapacitive performance, which largely outperforms the crystalline iron oxides/hydroxides‐based materials. In the voltage range between ?0.8 and 0 V versus Ag/AgCl, the amorphous FeOOH/graphene composite electrode exhibits a large specific capacitance of about 365 F g^?1, outstanding cycle performance (89.7% capacitance retention after 20 000 cycles), and excellent rate capability (189 F g^?1 at a current density of 128 A g^?1). When the lower cutoff voltage is extended to ?1.0 and ?1.25 V, the specific capacitance of the amorphous FeOOH/graphene composite electrode can be increased to 403 and 1243 F g^?1, respectively, which, however, compromises the rate capability and cycle performance. This work brings new opportunities to design high‐performance electrode materials for supercapacitors, especially for amorphous oxides/hydroxides‐based materials.     

A Practical Guide to Prepare and Synthetically Modify Graphene Quantum Dots

Due to the favorable properties of graphene quantum dots (GQDs), there has been a rapid development of sensors, devices, and composite materials, which incorporate this 0D nanomaterial. GQDs provide a means to instill superior optical, electronic, mechanical, and adsorptive properties to various platforms and have found use as biosensors, photovoltaic devices, polymer composites, and drug delivery vehicles. One of the key factors to successfully integrating GQD technology is the intelligent choice of synthetic chemical pathways to fabricate, modify, and instill functionality in the developed platform. GQDs are decorated with a variety of functional groups that are amenable to traditional synthetic chemistry transformations; however, the technology for post‐synthetic modifications is only in its infancy. Herein, a comprehensive analysis of the chemistry available for modifying GQDs is provided; starting from methods for GQD fabrication and synthetic chemical pathways for producing functional GQDs, to the advantages, disadvantages, and challenges of specific chemistries, and finally techniques for the appropriate characterization of these functional materials. This review is meant for researchers considering entering the GQD field, as well as those more experienced, providing a practical guide on how to prepare, modify, and characterize GQDs for a broad range of applications.     

Facile method for the preparation of high-performance photodetectors with a GQDs/perovskite bilayer heterostructure

A high-performance nitrogen doped graphene quantum dots (GQDs)/all-inorganic (CsPbBr₃) perovskite nanocrystals (NCs) heterostructure photodetector was fabricated on a quartz substrate, using the low cost spin coating technique followed by hot plate annealing. The GQDs/CsPbBr₃ NCs heterostructure photodetector exhibits a high overall performance with a photoresponsivity of 0.24 AW⁻¹, on/off ratio of 7.2 × 10⁴, and specific detectivity of up to 2.5 × 10¹² Jones. The on/off ratio of the hybrid device was improved by almost ten orders of magnitude, and the photoresponsivity was enhanced almost three times compared to the single layer perovskite NCs photodetector. The performance enhancement of the hybrid device was due to its highly efficient carrier separation at the GQDs/CsPbBr₃ NCs interface. This results from the coupling of the GQDs layer, which efficiently extracts and transports the photogenerated carriers, with the CsPbBr₃ NCs layer, which has a large absorption coefficient and high quantum efficiency. The interfacial charge transfer from the CsPbBr₃ NCs to the GQDs layer was demonstrated by the quenching in the photoluminescence (PL) spectra, and the fast-average decay time in the time-resolved photoluminescence (Trpl) spectra of the hybrid photodetector. Moreover, the performance-enhancement mechanism of the hybrid GQDs/CsPbBr₃ photodetector was elucidated by analyzing the band alignment of the GQDs and CsPbBr₃ under laser illumination.