Coupling of BiOCl Ultrathin Nanosheets with Carbon Quantum Dots for Enhanced Photocatalytic Performance

Over the past few decades,photocatalysis technology has received extensive attention because of its potential to mitigate or solve energy and environmental pollution problems.Designing novel materials with outstanding photocatalytic activities has become a research hotspot in this field.In this study,we prepared a series of photocatalysts in which BiOCl nanosheets were modified with carbon quantum dots(CQDs)to form CQDs/BiOCl composites by using a simple solvothermal method.The photocatalytic performance of the resulting CQDs/BiOCl composite photocatalysts was assessed by rhodamine B and tetracycline degradation under visible-light irradiation.Compared with bare BiOCl,the photocatalytic activity of the CQDs/BiOCl composites was significantly enhanced,and the 5 wt%CQDs/BiOCl composite exhibited the highest photocatalytic activity with a degradation efficiency of 94.5%after 30 min of irradiation.Moreover,photocatalytic N_(2)reduction performance was significantly improved after introducing CQDs.The 5 wt%CQDs/BiOCl composite displayed the highest photocatalytic N_(2)reduction performance to yield NH_3(346.25μmol/(g h)),which is significantly higher than those of 3 wt%CQDs/BiOCl(256.04μmol/(g h)),7 wt%CQDs/BiOCl(254.07μmol/(g h)),and bare BiOCl(240.19μmol/(g h)).Our systematic characterizations revealed that the key role of CQDs in improving photocatalytic performance is due to their increased light harvesting capacity,remarkable electron transfer ability,and higher photocatalytic activity sites.

Small but mighty:Empowering sodium/potassium-ion battery performance with S-doped SnO_(2) quantum dots embedded in N,S codoped carbon fiber network

SnO_(2) has been extensively investigated as an anode material for sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)due to its high Na/K storage capacity,high abundance,and low toxicity.However,the sluggish reaction kinetics,low electronic conductivity,and large volume changes during charge and discharge hinder the practical applications of SnO_(2)-based electrodes for SIBs and PIBs.Engineering rational structures with fast charge/ion transfer and robust stability is important to overcoming these challenges.Herein,S-doped SnO_(2)(S-SnO_(2))quantum dots(QDs)(≈3 nm)encapsulated in an N,S codoped carbon fiber networks(S-SnO_(2)-CFN)are rationally fabricated using a sequential freeze-drying,calcination,and S-doping strategy.Experimental analysis and density functional theory calculations reveal that the integration of S-SnO_(2) QDs with N,S codoped carbon fiber network remarkably decreases the adsorption energies of Na/K atoms in the interlayer of SnO_(2)-CFN,and the S doping can increase the conductivity of SnO_(2),thereby enhancing the ion transfer kinetics.The synergistic interaction between S-SnO_(2) QDs and N,S codoped carbon fiber network results in a composite with fast Na+/K+storage and extraordinary long-term cyclability.Specifically,the S-SnO_(2)-CFN delivers high rate capacities of 141.0 mAh g^(−1) at 20 A g^(−1) in SIBs and 102.8 mAh g^(−1) at 10 A g^(−1) in PIBs.Impressively,it delivers ultra-stable sodium storage up to 10,000 cycles at 5 A g^(−1) and potassium storage up to 5000 cycles at 2 A g^(−1).This study provides insights into constructing metal oxide-based carbon fiber network structures for high-performance electrochemical energy storage and conversion devices.

Effective Activation of Melamine for Synchronous Synthesis of Catalytically Active Nanosheets and Fluorescence-Responsive Quantum Dots

Because of the low reactivity of cyclic nitrides,liquid-phase synthesis of carbon nitride introduces challenges despite its favorable potential for energy-efficient preparation and superior applications.In this study,we demonstrate a strong interaction between citric acid and melamine through experimental observation and theoretical simulation,which eff ectively activates melamine-condensation activity and produces carbon-rich carbon nitride nanosheets(CCN NSs)during hydrothermal reaction.Under a large specific surface area and increased light absorption,these CCN NSs demonstrate significantly enhanced photocatalytic activity in CO_(2) reduction,increasing the CO production rate by approximately tenfold compared with hexagonal melamine(h-Me).Moreover,the product selectivity of CCN NSs reaches up to 93.5%to generate CO from CO_(2).Furthermore,the annealed CCN NSs exhibit a CO conversion rate of up to 95.30μmol/(g h),which indicates an 18-fold increase compared with traditional carbon nitride.During the CCN NS synthesis,nitrogen-doped carbon quantum dots(NDC QDs)are simultaneously produced and remain suspended in the supernatant after centrifugation.These QDs disperse well in water and exhibit excellent luminescent properties(QY=67.2%),allowing their application in the design of selective and sensitive sensors to detect pollutants such as pesticide 2,4-dichlorophenol with a detection limit of as low as 0.04μmol/L.Notably,the simultaneous synthesis of CCN NSs and NDC QDs provides a cost-eff ective and highly efficient process,yielding products with superior capabilities for catalytic conversion of CO_(2) and pollutant detection,respectively.

Carbon Nitride Quantum Dots:A Novel Fluorescent Probe for Non-Enzymatic Hydrogen Peroxide and Mercury Detection

The mercury species in the ocean(MeHg,Hg^(2+))will be enriched in marine organisms and threaten human health through the food chain.While the excessive H_(2)O_(2)in the metabolic process will produce hydroxyl radicals and accelerate the aging of human cells,causing a series of diseases.Hence,the cost-effective and rapid detection of mercury and H_(2)O_(2)is of urgent requirement and significance.Here,we synthesized emerging graphitic carbon nitride quantum dots(g-CNQDs)with high fluorescence quantum yield(FLQY)of 42.69%via a bottom-up strategy by a facile one-step hydrothermal method.The g-CNQDs can detect the H_(2)O_(2)and Hg^(2+)through the fluorescence quenching effect between g-CNQDs and detected substances.With the presence of KI,g-CNQDs show concentration-dependent fluorescence toward H_(2)O_(2),with a wide detection range of 1–1000μmolL^(-1)and a low detection limit of 0.23μmolL^(-1).The g-CNQDs also show sensitivity toward Hg^(2+)with a detection range of 0–0.1μmolL^(-1)and a detection limit of 0.038μmolL^(-1).This dual-function detection of g-CNQDs has better practical application capability compared to other quantum dot detection.This study may provide a new strategy for g-CNQDs preparation and construct a fluorescence probe that can be used in various systems involving H_(2)O_(2)and Hg^(2+),providing better support for future bifunctional or multifunction studies.

Energy Transfer Dynamics between Carbon Quantum Dots and Molybdenum Disulfide Revealed by Transient Absorption Spectroscopy

Zero-dimensional environmentally friendly carbon quantum dots(CQDs)combined with two-di-mensional materials have a wide range of applications in optoelec-tronic devices.We combined steady-state and transient absorp-tion spectroscopies to study the energy transfer dynamics between CQDs and molybdenum disulfide(MoS_(2)).Transient absorption plots showed photoinduced absorption and stimulated emission features,which involved the intrinsic and defect states of CQDs.Adding MoS_(2)to CQDs solution,the lowest unoccupied molecular orbital of CQDs transferred energy to MoS_(2),which quenched the intrinsic emission at 390 nm.With addition of MoS_(2),CQD-MoS_(2)composites quenched defect emission at 490 nm and upward absorption,which originated from another energy transfer from the defect state.Two energy transfer paths between CQDs and MoS_(2)were efficiently manipulated by changing the concentration of MoS_(2),which laid a foundation for improving device performance.

Graphitic Carbon Quantum Dots Modified Nickel Cobalt Sulfide as Cathode Materials for Alkaline Aqueous Batteries

Carbon quantum dots(CQDs)as a new class of emerging materials have gradually drawn researchers’concern in recent years.In this work,the graphitic CQDs are prepared through a scalable approach,achieving a high yield with more than 50%.The obtained CQDs are further used as structure-directing and conductive agents to synthesize novel N,S-CQDs/NiCo2S4 composite cathode materials,manifesting the enhanced electrochemical properties resulted from the synergistic effect of highly conductive N,S-codoped CQDs offering fast electronic transport and unique micro-/nanostructured NiCo2S4 microspheres with Faradaic redox characteristic contributing large capacity.Moreover,the nitrogen-doped reduced graphene oxide(N-rGO)/Fe2O3 composite anode materials exhibit ultrahigh specific capacity as well as significantly improved rate property and cycle performance originating from the high-capacity prism-like Fe2O3 hexahedrons tightly wrapped by highly conductive N-rGO.A novel alkaline aqueous battery assembled by these materials displays a specific energy(50.2 Wh kg^−1),ultrahigh specific power(9.7 kW kg^−1)and excellent cycling performance with 91.5%of capacity retention at 3 A g^−1 for 5000 cycles.The present research offers a valuable guidance for the exploitation of advanced energy storage devices by the rational design and selection of battery/capacitive composite materials.

Carbon quantum dots for advanced electrocatalysis

Zero-dimensional(0D)carbon quantum dots(CQDs),as a nanocarbon material in the carbon family,have garnered increasing attention in recent years due to their outstanding features of low cost,nontoxicity,large surface area,high electrical conductivity,and rich surface functional groups.By virtue of their rapid electron transfer and large surface area,CQDs also emerge as promising functional materials for the applications in energy-conversion sectors through electrocatalysis.Besides,the rich functional groups on the surface of CQDs offer abundant anchoring sites and active sites for the engineering of multicomponent and high-performance composite materials.More importantly,the heteroatom in the CQDs could effectively tailor the charge distribution to promote the electron transfer via internal interactions,which is crucial to the enhancement of electrocatalytic performance.Herein,an overview about recent progress in preparing CQDs-based composites and employing them as promising electrode materials to promote the catalytic activity and stability for electrocatalysis is provided.The introduced CQDs could enhance the conductivity,modify the morphology and crystal phase,optimize the electronic structure,and provide more active centers and defect sites of composites.After establishing a deep understanding of the relationship between CQDs and electrocatalytic performances,the issues and challenges for the development of CQDs-based composites are discussed.

Multifarious roles of carbon quantum dots in heterogeneous photocatalysis

As a new member of carbon material family, carbon quantum dots (CQDs) have attracted tremendous attentions for their potentials in the heterogeneous photocatalysis applications. Due to the unique microstructure and optical properties, the roles of CQDs played in the CQDs-based photocatalytic systems have been found to be diverse with the continuous researches in this regard. Herein, we provide a concise minireview to elaborate the multifarious roles of CQDs in photocatalysis, including photoelectron mediator and acceptor, photosensitizer, photocatalyst, reducing agent for metal salt, enhancing adsorption capacity and spectral converter. In addition, the perspectives on future research trends and challenges are proposed, which are anticipated to stimulate further research into this promising field on designing a variety of efficient CQDs-based photocatalysts for solar energy conversion. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B. V. and Science Press. All rights reserved.

Synthesis of Fluorescent Carbon Quantum Dots and Their Application in the Plant Cell Imaging

Carbon quantum dots(CQDs) exhibit tremendous advantages for plant growth study due to its strong fluorescence and good biocompatibility. The fluorescent CQDs were synthesized by the onestep microwave method with the raw materials of citric acid(CA) and urea(UR), and expressed a unique green fluorescence with the optimal excitation wavelength of over 400 nm through adjusting the doping of N elements. It is demonstrated that CQDs can act as deliver media in plant and fluorescent probes for plant cell imaging through directly cultivated in the seedlings of melon and wheat, respectively. Based on the effects of the fluorescent CQDs on plants growth, we can further study the mechanisms of the ions transport in plants.

Curtailing Carbon Usage with Addition of Functionalized NiFe2O4 Quantum Dots:Toward More Practical S Cathodes for Li-S Cells

Smartcombination of manifold carbonaceous materials with admirable functionalities(like full of pores/functional groups,high specific surface area) is still a mainstream/preferential way to address knotty issues of polysulfides dissolution/shuttling and poor electrical conductivity for S-based cathodes.However,extensive use of conductive carbon fillers in cell designs/technology would induce electrolytic overconsumption and thereby shelve high-energy-density promise of Li-S cells.To cut down carbon usage,we propose the incorporation of multi-functionalized NiFe2O4 quantum dots(QDs) as affordable additive substitutes.The total carbon content can be greatly curtailed from 26%(in traditional S/C cathodes) to a low/commercial mass ratio(~5%).Particularly,note that NiFe2O4 QDs additives own superb chemisorption interactions with soluble Li2Sn molecules and proper catalytic features facilitating polysulfide phase conversions and can also strengthen charge-transfer capability/redox kinetics of overall cathode systems.Benefiting from these intrinsic properties,such hybrid cathodes demonstrate prominent rate behaviors(decent capacity retention with ~526 mAh g^-1 even at 5 A g^-1) and stable cyclic performance in LiNO3-free electrolytes(only ~0.08% capacity decay per cycle in 500 cycles at 0.2 A g^-1).This work may arouse tremendous research interest in seeking other alternative QDs and offer an economical/more applicable methodology to construct low-carbon-content electrodes for practical usage.

Amperometric Hydrogen Peroxide Biosensor Based on Multiwall Carbon Nanotubes and Cadmium Sulfide Quantum Dots

A novel third-generation hydrogen peroxide（H2O2） biosensor（Hb/CdS/MWNTs/GCE） was fabricated through hemoglobin（Hb） adsorbed onto the mercaptoacetic acid modified CdS QDs/carboxyl multiwall carbon nanotubes＇（MWNTs） films. Cyclic voltammogram of Hb/CdS/MWNTs/GCE showed a pair of well-defined and quasi-reversible redox peaks with a formal potential（E^0） of-0.230 V（vs. Ag/AgCl） in 0.1 mol/L pH=8.0 phosphate buffer solution（PBS）, which was the characteristic of the Hb heme Fe（Ⅲ）/Fe（Ⅱ） redox couple. The biosensor shows an excellent electrocatalytic activity to the reduction of H2O2. The response time of the designed biosensor to H202 at a potential of-0.30 V was less than 2 s and linear relationships were obtained in the concentration ranges of 2.0×10^-6-2.7×10^-3 mol/L and 2.7×10^-3-7.7×10^-3 mol/L with a detection limit of 3.0×10^-7 mol/L（S/N=3）. The apparent Michaelis-Menten constant Km was estimated to be 1.324 mmol/L that illustrated the excellent biological activity of the fixed Hb.

Photocatalytic degradation of organic pollutants using green oil palm frond-derived carbon quantum dots/titanium dioxide as multifunctional photocatalysts under visible light radiation

The present work suggested the use of waste oil palm frond as an alternative precursor for nitrogendoped carbon quantum dots(NCQDs)and proposed a straightforward in-situ hydrothermal method for the preparation of NCQDs/TiO_(2)nanocomposites.The elemental composition,morphological,structural and optical characteristics of NCQDs/TiO_(2)nanocomposites have been comprehensively investigated.The successful grafting of NCQDs on TiO_(2)matrix was confirmed by the formation of Ti AOAC bond and the electronic coupling between theπ-states of NCQDs and the conduction band of TiO_(2).For the first time,the oil palm frond-derived NCQDs/TiO_(2)was adopted in the photodegradation of methylene blue(MB)under visible-light irradiation.As a result,the photocatalytic efficiency of NCQDs/TiO_(2)nanocomposites(86.16%)was 2.85 times higher than its counterpart TiO_(2)(30.18%).The enhanced performance of nanocomposites was attributed to the pivotal roles of NCQDs serving as electron mediator and visiblelight harvester.Besides,the optimal NCQDs loading was determined at 4 ml while the removal efficiency of NCQDs/TiO_(2)-4 was the highest at a catalyst dosage of 1 g.L^(-1)under alkaline condition.This research work is important as it proposed a new insight to the preparation of biomass-based NCQDs/TiO_(2)using a facile synthetic method,which offers a green and sustainable water remediation technology.

Alcohol Solvent Effect on Fluorescence Properties in the Solvothermal Synthesis of Carbon Quantum Dots

Highly monodisperse carbon quantum dots(CQDs)were synthesized by a solvothermal method using L-ascorbic acid as carbon source and different simple alcohols(methanol,ethanol,ethylene glycol,and isopropanol)as reaction solvents at 180℃for 4 hours.The performance of CQDs was characterized by transmission electron microscope(TEM),Fourier infrared spectrometer(FTIR),UV-visible spectrophotometer,and fluorescence spectrophotometer.The results show that the prepared CQDs are wavelength-dependent,and have good hydrophilicity and similar surface compositions.However,there are more carbon and oxygen-containing functional groups on the surface of CQDs prepared with ethanol(CQDs-ET),and the type and number of functional groups will directly affect the fluorescence emission of CQDs.Also,it is found that the luminescence mechanisms of CQDs prepared by this solvothermal method are mainly based on the defect state of the oxygen group surface.And alcohol solvents do not directly participate in the formation of carbon nuclei during the reaction process,but it will affect the number and type of surface groups.Therefore,the influence of surface groups on the CQDs performance is greater than that of carbon nuclei in this experiment.

Surface defect-rich ceria quantum dots anchored on sulfur-doped carbon nitride nanotubes with enhanced charge separation for solar hydrogen production

Designing defect-engineered semiconductor heterojunctions can effectively promote the charge carrier separation.Herein,novel ceria(CeO2) quantum dots(QDs) decorated sulfur-doped carbon nitride nanotubes(SCN NTs) were synthesized via a thermal polycondensation coupled in situ depositionprecipitation method without use of template or surfactant.The structure and morphology studies indicate that ultrafine CeO2 QDs are well distributed inside and outside of SCN NTs offering highly dispersed active sites and a large contact interface between two components.This leads to the promoted formation of rich Ce^(3+) ion and oxygen vacancies as confirmed by XPS.The photocatalytic performance can be facilely modulated by the content of CeO2 QDs introduced in SCN matrix while bare CeO2 does not show activity of hydrogen production.The optimal catalyst with 10% of CeO2 loading yields a hydrogen evolution rate of 2923.8 μmol h-1 g-1 under visible light,remarkably higher than that of bare SCN and their physical mixtures.Further studies reveal that the abundant surface defects and the created 0 D/1 D junctions play a critical role in improving the separation and transfer of charge carriers,leading to superior solar hydrogen production and good stability.

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.

Highly conjugated water soluble CdSe quantum dots to multiwalled carbon nanotubes

Highly conjugated multiwalled carbon nanotube-quantum dot heterojunctions were synthesized by ethylene carbodiimide coupling procedure. The functional multiwalled carbon nanotube with carboxylic groups on sidewall could react with the amino group of L-cysteine capped CdSe quantum dots and then resulted in nanotube-quantum dot heterojunctions. Scanning electron microscopy was used to characterize the heterojunctions.

Synthesis of Humin-based Carbon Quantum Dots and Luminescent Properties

The unique properties of carbon quantum dots(CQDs) make them promising materials in many fields. Herein, we present a facile method for the preparation of photo-luminescent CQDs using humins as the carbon precursor for the purpose of providing a high value-added solution for this "biomass conversion process waste". The structure of the CQDs was analyzed, and the effects of reaction temperature and time on the CQDs' fluorescence were investigated. The results showed that humins were effectively carbonized during the reaction. The fluorescence intensity of humin-based CQDs initially increased with reaction temperature and time, and subsequently decreased beyond 200℃ and 4 h. Polyaromatic structures and hydrophilic groups such as O—H, C—O, —COOH and C==O groups exist in the CQDs. The huminbased CQDs have the dimension of 3～7 nm with an average size of about 5.5 nm. The highest emission intensity of blue/cyan fluorescence light at 440 nm is achieved on the excitation with UV light at the wavelength of 330 nm.

Intrinsic pentagon defect engineering in multiple spatial-scale carbon frameworks for efficient triiodide reduction

Intrinsic topological defect engineering has been proven as a promising strategy to elevate the electrocatalytic activity of carbon materials.However,the controllable construction of high-density and specific topological defects in carbon frameworks to reveal the relationship between reactivity and defect structure remains a challenging task.Herein,the intrinsic pentagon carbon sites that can favor electron overflow and enhance their binding affinity towards the intermediates of catalytic reaction are firstly presented by the work function and the p-band center calculations.To experimentally verify this,the cage-opening reaction of fullerene is proposed and utilized for synthesizing carbon quantum dots with specific pentagon configuration(CQDs-P),subsequently utilizing CQDs-P to modulate the micro-scale defect density of three-dimensional reduced graphene oxide(rGO)viaπ-πinteractions.The multiple spatial-scale rGO-conjugated CQDs-P structure simultaneously possesses abundant pentagon and edge defects as catalytic active sites and long-range-orderedπelectron delocalization system as conductive network.The defects-rich CQDs-P/rGO-4 all-carbon-based catalyst exhibits superb catalytic activity for triiodide reduction reaction with a high photoelectric conversion efficiency of 8.40%,superior to the Pt reference(7.97%).Theoretical calculations suggest that pentagon defects in the carbon frameworks can promote charge transfer and modulate the adsorption/dissociation behavior of the reaction intermediates,thus enhancing the electrocatalytic activity of the catalyst.This work confirms the role of intrinsic pentagon defects in catalytic reactions and provides a new insight into the synthesis of defects-rich carbon catalysts.

The resistance switching performance of the memristor improved effectively by inserting carbon quantum dots(CQDs)for digital information processing

As an emerging information device that adapts to development of the big data era,memristor has attracted much attention due to its advantage in processing massive data.However,the nucleation and growth of conductive filaments often exhibit randomness and instability,which undoubtedly leads to a wide and discrete range of switching parameters,damaging the electrical performance of device.In this work,a strategy of inserting carbon quantum dots(CQDs)into graphene oxide(GO)resistance layer is utilized to improve the stability of the switching parameters and the reliability of the device is improved.Compared with GO-based devices,GO/CQDs/GO-based devices exhibit a more stable resistance switching curve,low power,lower and more concentrated threshold voltage parameters with lower variation coefficient,faster switching speed,and more stable retention and endurance.The cause-inducing performance improvement may be attributed to the local electric field generated by CQDs in resistance switching that effectively guides the formation and rupture of conductive filaments,which optimizes the effective migration distance of Ag^(+),thereby improving the uniformity of resistance switching.Additionally,a convolutional neural network model is constructed to identify the CIFAR-10 data set,showing the high recognition accuracy of online and offline learning.The cross-kernel structure is used to further implement convolutional image processing through multiplication and accumulation operations.This work provides a solution to improve the performance of memristors,which can contribute to developing digital information processing.

Enhanced photocatalytic hydrogen production from Co-MOF/CN by nitrogen and sulfur co-doped coal-based carbon quantum dots

A novel composite photocatalyst for photocatalytic decomposition of water for hydrogen evolution was successfully synthesized by in-situ growth of nitrogen and sulfur co-doped coal-based carbon quantum dots(NSCQDs)nanoparticles on the surface of sheet cobalt-based metal-organic framework(Co-MOF)and graphitic carbon nitride(g-C_(3)N_(4),CN).The structure and properties of the obtained catalysts were systematically analyzed.NSCQDs effectively broaden the absorption of Co-MOF and CN in the visible region.The new composite photocatalyst has high hydrogen production activity and the hydrogen production rate reaches 6254μmol/(g·h)at pH=9.At the same time,NSCQDs synergy Co-MOF/CN composites have good stability.After four cycles of hydrogen production,the performance remains relatively stable.The tran sient photocurrent response and Nyquist plot experimental results further demonstrate the improvement of carrier separation efficiency in composite catalysts.The semiconductor type(n-type semico nductor)of the single-phase catalyst was determined by the Mott-Schottky test,and the band structure was analyzed.The conductive and valence bands of CN are-0.99 and 1.72 eV,respectively,and the conduction and valence bands of Co-MOF are-1.85 and 1.33 eV,respectively.Th e mechanism of the photocatalytic reaction can be inferred,that is,Z-type heterojunction is formed between CN an d Co-MOF,and NSCQDs was used as cocatalyst.