Effects of Coal Rank and High Organic Sulfur on the Structure and Optical Properties of Coal-based Graphene Quantum Dots

Coal-based graphene quantum dots(GQDs) were successfully produced via a one-step chemical synthesis from six different coal ranks, from which two superhigh organic sulfur(SHOS) coals were selected as natural S-doped carbon sources for the preparation of S-doped GQDs. The effects of coal properties on coal-based GQDs were analyzed by means of high-resolution transmission electron microscopy(HRTEM), X-ray diffraction(XRD), Fourier transform infrared(FTIR) spectroscopy, X-ray photoelectron spectroscopy(XPS), ultraviolet-visible(UV-Vis) absorption spectroscopy, and fluorescence emission spectra. It was shown that all coal samples can be used to prepare GQDs, which emit bluegreen and blue fluorescence under ultraviolet light. Anthracite-based GQDs have a hexagonal crystal structure without defects, the largest size, and densely arranged carbon rings in their lamellae; the highrank bituminous coal-based GQDs are relatively reduced in size, with their hexagonal crystal structure being only faintly visible; the low-rank bituminous coal-based GQDs are the smallest, with sparse lattice fringes and visible internal defects. As the metamorphism of raw coals increases, the yield decreases and the fluorescence quantum yield(QY) initially increases and then decreases. Additionally, the surface of GQDs that were prepared using high-rank SHOS coal(high-rank bituminous coal) preserves rich sulfur content even after strong oxidation, which effectively adjusts the bandgap and improves the fluorescence QY. Thus, high-rank bituminous coal with SHOS content can be used as a natural S-doped carbon source to prepare S-doped GQDs, extending the clean utilization of low-grade coal.

N-doped graphene quantum dot-decorated N-TiO2/P-doped porous hollow g-C_(3)N_(4) nanotube composite photocatalysts for antibiotic photodegradation and H2 production

Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.

Synergistically coupling of graphene quantum dots with Zn-intercalated MnO2 cathode for high-performance aqueous Zn-ion batteries

Cost-effective,safe,and highly performing energy storage devices require rechargeable batteries,and among various options,aqueous zinc-ion batteries(ZIBs)have shown high promise in this regard.As a cathode material for the aqueous ZIBs,manganese dioxide(MnO_(2))has been found to be promising,but certain drawbacks of this cathode material are slow charge-transfer capability and poor cycling performance.Herein,a novel design of graphene quantum dots(GQDs)integrated with Zn-intercalated MnO_(2)nanosheets is put forward to construct a 3D nanoflower-like GQDs@ZnxMnO_(2)composite cathode for aqueous ZIBs.The synergistic coupling of GQDs modification with Zn intercalation provides abundant active sites and conductive medium to facilitate the ion/electron transmission,as well as ensure the GQDs@ZnxMnO_(2)composite cathode with enhanced charge-transfer capability and high electrochemical reversibility,which are elucidated by experiment results and in-situ Raman investigation.These impressive properties endow the GQDs@ZnxMnO_(2)composite cathode with superior aqueous Zn^(2+) storage capacity(~403.6 mAh·g^(−1)),excellent electrochemical kinetics,and good structural stability.For actual applications,the fabricated aqueous ZIBs can deliver a substantial energy density(226.8 W·h·kg^(−1)),a remarkable power density(650 W·kg^(−1)),and long-term cycle performance,further stimulating their potential application as efficient electrochemical storage devices for various energy-related fields.

Graphene quantum dots as sulfiphilic and lithiophilic mediator toward high stability and durable life lithium-sulfur batteries

The development of lithium-sulfur(Li-S) battery as one of the most attractive energy storage systems among lithium metal batteries is seriously hindered by low sulfur utilization, poor cycle stability and uneven redeposition of Li anode. It is necessary to propose strategies to address the problems as well as improve the electrochemical performance. One of the effective solutions is to improve the sulfiphilicity of sulfur cathode and the lithiophilicity of the Li anode. Herein, we reported that a synergistic functional separator(graphene quantum dots(GQDs)-polyacrylonitrile(PAN) @polypropylene(PP) separator)improved the electrochemical activity of sulfur cathode as well as the stability of Li anode. GQDs induced uniform Li^(+)nucleation and deposition, which slowed down the passivation of Li anode and avoided shortcircuit. Further, three-dimensional network constructed by electrospinning nanofibers and the polar functional groups of GQDs could both effectively inhibit the shuttle of LiPSs and improve the sulfur utilization. The stability of Li-S battery was improved by the synergistic effect. In addition, GQDs and electrospinning nanofibers protector increased lifetime of separators. Benefiting from the unique design strategy, Li//Li symmetric battery with GQDs-PAN@PP separators exhibited stably cycling for over 600 h. More importantly, the Li-S full batteries based GQDs-PAN@PP separators enabled high stability and desirable sulfur electrochemistry, including high reversibility of 558.09 mA h g^(-1)for 200 cycles and durable life with a low fading rate of 0.075% per cycle after 500 cycles at 0.5 C. Moreover, an impressive areal capacity of 3.23 mA h cm^(-2)was maintained under high sulfur loading of 5.10 mg cm^(-2). This work provides a new insight for modification separator to improve the electrochemical performance of Li-S/Li metal batteries.

Graphene quantum dots doped poly(vinyl alcohol)hybrid membranes for desalination via pervaporation

Pervaporation desalination by highly hydrophilic materials such as poly(vinyl alcohol)(PVA)based separation membrane is a burgeoning technology of late years.However,the improvement of membrane flux in pervaporation desalination has been a difficult task.Here,a novel hybrid membrane with doped graphene oxide quantum dots(GOQDs)which is rich in hydrophilic groups and small size into the matrix of PVA was prepared to improve the membrane flux.The membranes structures were described by field emission scanning electron microscopy(FESEM),atomic force microscopy(AFM),Fourier transform infrared(FT-IR),differential scanning calorimetry(DSC),thermogravimetric analysis(TGA)and X-ray diffraction(XRD).And more,Water contact angle,swelling degree,and pervaporation properties were carried out to explore the effect of GOQDs in PVA matrix.In addition,GOQDs content in the hybrid membrane,NaCl concentration,and feed temperature were investigated accordingly.Moreover,the hydrogen bonds between PVA chains were weakened by the interaction between GOQDs and PVA chains.Significantly,the hybrid membrane with optimized doped GOQDs content,200 mg·L^(-1),displays a high membrane flux of 17.09 kg·m^(-2)·h^(-1)and the salt rejection is consistently greater than 99.6%.

One-pot facile synthesis of highly photoluminescent graphene quantum dots with oxygen-rich groups

To achieve a new type of carbon-based quantum dots with unique photoluminescence PL a simple approach for fabrication of graphene quantum dots GQDs with oxygen-rich groups was developed via the hydrothermal reaction by using graphene oxides GOs as a precursor. Transmission electron microscope TEM and atomic force microscope AFM characterizations confirmed that the sizes and heights of GQDs were 5.02±0.92 nm and 0.6 nm respectively.A strong PL emission exhibited unique excitation wavelength dependent features.Also the carbene-like free zigzag edge sites were proposed to be the origin of the strong PL emission.The GQDs were demonstrated to be a superior probe for Fe3＋ detection in aqueous solution with a high sensitivity and feasibility due to the special coordinate interaction between Fe3＋and the phenolic hydroxyl group at GQDs.

Graphene Quantum Dot‑Mediated Atom‑Layer Semiconductor Electrocatalyst for Hydrogen Evolution

The hydrogen evolution reaction performance of semiconducting 2H-phase molybdenum disulfide(2H-MoS_(2))presents a significant hurdle in realizing its full potential applications.Here,we utilize theoretical calculations to predict possible functionalized graphene quantum dots(GQDs),which can enhance HER activity of bulk MoS_(2).Subsequently,we design a functionalized GQD-induced in-situ bottom-up strategy to fabricate near atom-layer 2H-MoS_(2) nanosheets mediated with GQDs(ALQD)by modulating the concentration of electron withdrawing/donating functional groups.Experimental results reveal that the introduction of a series of functionalized GQDs during the synthesis of ALQD plays a crucial role.Notably,the higher the concentration and strength of electron-withdrawing functional groups on GQDs,the thinner and more active the resulting ALQD are.Remarkably,the synthesized near atom-layer ALQD-SO_(3)demonstrate significantly improved HER performance.Our GQD-induced strategy provides a simple and efficient approach for expanding the catalytic application of MoS_(2).Furthermore,it holds substantial potential for developing nanosheets in other transition-metal dichalcogenide materials.

Toxicity of Graphene Quantum Dots in Zebrafish Embryo

Objective To evaluate the bio-safety of graphene quantum dots （GQDs）, we studied its effects on the embryonic development of zebrafish. Methods In vivo, biodistribution and the developmental toxicity of GQDs were investigated in embryonic zebrafish at exposure concentrations ranging from 12.5-200μg/mL for 4-96 h post-fertilization （hpf）. The mortality, hatch rate, malformation, heart rate, GQDs uptake, spontaneous movement, and larval behavior were examined. Results The fluorescence of GQDs was mainly localized in the intestines and heart. As the exposure concentration increased, the hatch and heart rate decreased, accompanied by an increase in mortality. Exposure to a high level of GQDs （200μg/mL） resulted in various embryonic malformations including pericardial edema, vitelline cyst, bent spine, and bent tail. The spontaneous movement significantly decreased after exposure to GQDs at concentrations of 50, 100, and 200μg/mL. The larval behavior testing （visible light test） showed that the total swimming distance and speed decreased dose-dependently. Embryos exposed to 12.5 μg/mL showed hyperactivity while exposure to higher concentrations （25, 50, 100, and 200μg/mL） caused remarkable hypoactivity in the light-dark test. Conclusion Low concentrations of GODs were relatively non-toxic. However, GQDs disrupt the progression of embryonic development at concentrations exceeding 50 μg/mL.

Enhanced visible-light photocatalytic degradation and disinfection performance of oxidized nanoporous g-C3N4 via decoration with graphene oxide quantum dots

Oxidized nanoporous g-C3N4(PCNO)decorated with graphene oxide quantum dots(ox-GQDs)was successfully prepared by a facile self-assembly method.As co-catalysts,the ultrasmall zero-dimensional(0 D)ox-GQDs can achieve uniform dispersion on the surface/inner channels of PCNO,as well as intimate contact with PCNO through hydrogen bonding,π-π,and chemical bonding interactions.In contrast with PCNO,the ox-GQDs/PCNO composite photocatalysts possessed improved light-harvesting ability,higher charge-transfer efficiency,enhanced photooxidation capacity,and increased amounts of reactive species due to the upconversion properties,strong electron capturing ability,and peroxidase-like activity of the ox-GQDs.Therefore,the visible-light photocatalytic degradation and disinfection performances of the ox-GQDs/PCNO composite were significantly enhanced.Remarkably,the composite with a 0.2 wt.% deposited amount of ox-GQDs(ox-GQDs-0.2%/PCNO)exhibited optimum amaranth photodegradation activity,with a corresponding rate about 3.1 times as high as that of PCNO.In addition,ox-GQDs-0.2%/PCNO could inactivate about 99.6%of Escherichia coli(E.coli)cells after 4 h of visible light irradiation,whereas only^31.9% of E.coli cells were killed by PCNO.Furthermore,h+,·O2-,and·OH were determined to be the reactive species generated in the photocatalytic process of the ox-GQDs/PCNO system;these species can thoroughly mineralize azo dyes and effectively inactivate pathogenic bacteria.

Modulation of magnetic and electrical properties of bilayer graphene quantum dots using rotational stacking faults

Bilayer graphene quantum dots with rotational stacking faults(RSFs) having different rotational angles were studied.Using the first-principles calculation, we determined that these stacking faults could quantitatively modulate the magnetism and the distribution of spin and energy levels in the electronic structures of the dots.In addition, by examining the spatial distribution of unpaired spins and Bader charge analysis, we found that the main source of magnetic moment originated from the edge atoms of the quantum dots.Our research results can potentially provide a new path for producing all-carbon nanodevices with different electrical and magnetic properties.

Hydroxylated graphene quantum dots as fluorescent probes for sensitive detection of metal ions

Highly sensitive methods are important for monitoring the concentration of metal ions in industrial wastewater.Here,we developed a new probe for the determination of metal ions by fluorescence quenching.The probe consists of hydroxylated graphene quantum dots(H-GQDs),prepared from GQDs by electrochemical method followed by surface hydroxylation.It is a non-reactive indicator with high sensitivity and detection limits of 0.01μM for Cu2+,0.005μM for Al3+,0.04μM for Fe3+,and 0.02μM for Cr3+.In addition,the low biotoxicity and excellent solubility of H-GQDs make them promising for application in wastewater metal ion detection.

High-Performance Photo-Modulated Thin-Film Transistor Based on Quantum dots/Reduced Graphene Oxide Fragment-Decorated ZnO Nanowires

In this paper, a photo-modulated transistor based on the thin-film transistor structure was fabricated on the flexible substrate by spin-coating and magnetron sputtering. A novel hybrid material that composed of Cd Se quantum dots and reduced graphene oxide(RGO) fragment-decorated ZnO nanowires was synthesized to overcome the narrow optical sensitive waveband and enhance the photo-responsivity. Due to the enrichment of the interface and heterostructure by RGO fragments being utilized, the photo-responsivity of the transistor was improved to 2000 AW^(-1) and the photo-sensitive wavelength was extended from ultraviolet to visible. In addition, a positive back-gate voltage was employed to reduce the Schottky barrier width of RGO fragments and ZnO nanowires. As a result, the amount of carriers was increased by 10 folds via the modulation of back-gate voltage. With these inherent properties, such as integrated circuit capability and wide optical sensitive waveband, the transistor will manifest great potential in the future applications in photodetectors.

Construction of nitrogen and phosphorus co-doped graphene quantum dots/Bi5O7I composites for accelerated charge separation and enhanced photocatalytic degradation performance

Nitrogen and phosphorus co-doped graphene quantum dot-modified Bi5O7 I(NPG/Bi5O7 I)nanorods were fabricated via a simple solvothermal method.The morphology,structure,and optical properties of the as-prepared samples were investigated by X-ray diffraction,scanning electron microscopy,high-resolution transmission electron microscopy,X-ray photoelectron spectroscopy(XPS),and diffused reflectance spectroscopy.The photocatalytic performance was estimated by degrading the broad-spectrum antibiotics tetracycline and enrofloxacin under visible light irradiation.The photodegradation activity of Bi5O7 I improved after its surface was modified with NPGs,which was attributed to an increase in the photogenerated charge transport rate and a decrease in the electron-hole pair recombination efficiency.From the electron spin resonance spectra,XPS valence band data,and free radical trapping experiment results,the main active substances involved in the photocatalytic degradation process were determined to be photogenerated holes and superoxide radicals.A possible photocatalytic degradation mechanism for NPG/Bi5O7 I nanorods was proposed.

Photocatalytic degradation of Brilliant Green dye using CdSe quantum dots hybridized with graphene oxide under sunlight irradiation

CdSe quantum dots(QDs)hybridized with graphene oxide(GO)are synthesized by a facile chemical precipitation method.The absorption of the CdSe/GO nanocomposite is increased with a significantblue shift with respect to CdSe QDs.The specific surface area of the CdSe/GO nanocomposite is10.4m2/g,which is higher than that of CdSe QDs(5m2/g).The PL intensity of the CdSe/GO nanocomposite is lower than that of the CdSe QDs owing to the inhibition of the recombination of electron‐hole pairs in the composite.In Raman analysis,the two bands of the CdSe/GO nanocomposite are shifted to higher wavenumbers with respect to graphene oxide,which is attributed to electron injection that is induced by CdSe QDs into graphene oxide.Using the Brilliant Green dye,the photocatalytic reduction efficiency of CdSe QDs and the CdSe/GO nanocomposite under sunlight irradiation for90min are approximately81.9%and95.5%,respectively.The calculated photodegradation rate constants for CdSe QDs and the CdSe/GO nanocomposite are0.0190min–1and0.0345min–1,respectively.The enhanced photocatalytic activity of the CdSe/GO nanocomposite can be attributed to the high specific surface area and the reduction of electron‐hole pair recombination because of the introduction of graphene oxide.

Quantum computation with two-dimensional graphene quantum dots

We study an array of graphene nano sheets that form a two-dimensional S = 1/2 Kagome spin lattice used for quantum computation. The edge states of the graphene nano sheets are used to form quantum dots to confine electrons and perform the computation. We propose two schemes of bang-bang control to combat decoherence and realize gate operations on this array of quantum dots. It is shown that both schemes contain a great amount of information for quantum computation. The corresponding gate operations are also proposed.

Recent Advances on Graphene Quantum Dots for Electrochemical Energy Storage Devices

Graphene quantum dots(GQDs)which are nanofragments of graphene with an average size between 2 and 50 nm have attracted much attention due to their outstanding properties such as high conductivity,high surface area,and good solubility in various solvents.GQDs combine the quantum confinement and edges effects and the properties of graphene.Therefore,GQDs offers a broad range of applications in various fields(medicine,energy conversion,and energy storage devices).This review will present the recent research based on the introduction of GQDs in batteries,supercapacitors,and microsupercapacitors as electrodes materials or mixed with an active material as an auxiliary agent.Tables,discussed on selected examples,summarize the electrochemical performances and finally,challenges and perspectives are recalled for the subsequent optimization strategy of electrode materials.This review is expected to appeal a broad interest on functional GQDs materials and promote the further development of high-performance energy storage device.

An approach to controlling the fluorescence of graphene quantum dots: From surface oxidation to fluorescent mechanism

We report a facile method of synthesizing graphene quantum dots（GQDs） with tunable emission. The as-prepared GQDs each with a uniform lateral dimension of ca. 6 nm have fine solubility and high stability. The photoluminescence mechanism is further investigated based on the surfacestructure and the photoluminescence behaviors. Based on our discussion, the green fluorescence emission can be attributed to the oxygen functional groups, which could possess broad emission bands within the π –π ＊ gap. This work is helpful to explain the vague fluorescent mechanism of GQDs, and the reported synthetic method is useful to prepare GQDs with controllable fluorescent colors.

Graphene quantum dots for tumor optical diagnosis and treatment

Graphene quantum dots(GQDs)are two-dimensional carbon nano-material with excellent physicochemical properties,including biocompatibility,high photoluminescence,water-solubility,hypotoxicity and so on.Owing to bigπ-conjugated structure and oxygen-containing functional groups,GQDs have the ability to absorb various chemical drugs viaπ-πstacking and electrostatic interaction.On the other hand,owning to photoluminescence,GQDs also have potential to serve as fluorescence probe for bioimaging,especially for optical diagnostics.In addition,GQDs have the ability to generate reactive oxygen species(ROS)including singlet oxygen upon photoexcitation.Therefore,GQDs are likely to be used for photodynamic therapy.This article aims to review the frontier researches about GQDs in the field of fluorescence probe,photodynamic therapy and anti-tumor drug delivery system.

Ionic polymer metal composites actuators with enhanced driving performance by incorporating graphene quantum dots

In order to further improve the driving performance of ionic polymer metal composites(IPMCs),Nafion/graphene quantum dots(GQDs)hybrid membranes incorporating GQDs with various contents of 0,0.1 wt.%,0.5 wt.%,1.0 wt.%,2.0 wt.%and 4.0 wt.%were fabricated by solution casting,and then IPMCs were manufactured by electroless plating.The water contents and elastic moduli of the hybrid membranes were tested.The morphology characteristics of the hybrid membranes and the IPMCs were observed,and the current,AC impedance,blocking force and displacement of the IPMCs were measured.The results show that the elastic modulus of the hybrid membranes decreases,the water content increases,and the actuation performance of the IPMCs improves significantly after the addition of GQDs.IPMC with 1.0 wt.%GQDs exhibits the best driving property.Compared with the IPMC without GQDs,the working current,ion conductivity,blocking force,and tip displacement increase by 94.67%,311.11%,53.66%,and 66.07%,respectively.These results lay a solid foundation for the preparation of IPMCs with high performance,and further broaden their applications in biomedical devices and bionic robots.

Graphene Quantum Dots Derived from Carbon Fibers for Oxidation of Dopamine

We demonstrated a facile method to prepare photoluminescent graphene quantum dots using commercial polyacrylonitrile（PAN） based carbon fibers（CFs） as the raw material by facile chemical oxidation and exfoliation method. The as-prepared GQDs with uniform size exhibit an excitation-independent photoluminescence behavior, which is similar to other semiconductor quantum dots. Moreover, when acting as catalyst the uniform GQDs have better activity for electrochemical oxidation of dopamine（DA） than graphene oxides（GOs）. The square wave voltammogram（SWV） peak values of GQDs are in good correspondence with DA concentrations and can act as a sensor of DA.