Fabrication, characterization and response surface method optimization for quantum efficiency of fluorescent nitrogen-doped carbon dots obtained from carboxymethylcellulose of oil palms empty fruit bunch

Bio based nitrogen doped carbon dots(N-CDs)were obtained from empty fruit bunch carboxymethylcellulose and ethylenediamine(EDA)through one-pot hydrothermal carbonization route.The optimum as-formed NCDs were thoroughly characterized via Transmission electron microscopy(TEM),high-resolution TEM(HRTEM),Fourier transform infrared(FTIR),X-ray photoelectron spectra(XPS),UV–vis spectra(UV–Vis)and Fluorescence spectra(PL).Response surface methodology was statistically used to assess three independent variables that have major influence on the fluorescence quantum yield(QY),including temperature(230–270℃),time(2–6 h)and EDA mass(10%–23.3%).Based on analysis of variance(ANOVA)results,synthesis temperature was found to be the most influential factor on the QY,followed by time and EDA mass.Higher temperature,long synthesis time and high amount of EDA were satisfactorily enough for efficient carbonization conversion rate and obtaining highest QY of N-CDs.The obtained quadratic model(R^2=0.9991)shows a good correlation between the experimental data and predicted values.The optimum synthetic parameters are of 270℃temperature,6 h reaction time and 23.3%of EDA mass.The optimized as-made N-CDs exhibited blue photoluminescence with both excitation dependent/independent phenomena and high nitrogen content.The maximum emission intensity was 426 nm at a maximum excitation wavelength of 320 nm,with a QY of up to 22.9%.XPS and FTIR data confirmed the existence of polar containing groups,such as carbonyl,carboxyl,hydroxyl and amino groups over the surface of N-CDs whereas nitrogen species in the form of(pyridinic and graphitic-N)were introduced in the aromatic carbon domains,which imparts the hydrophilic and photostability of N-CDs.Taking into account the low-cost and sustainable production of N-CDs,this method considered a feasible route for converting low quality waste into value-added nanomaterials and utilizing for different functionalization processes and analytical applications.

Preparation of Nitrogen-doped Carbon Dots from Coke Powder as a Fluorescent Chemosensor for Selective and Sensitive Detection of Cr (Ⅵ)

The nitrogen-doped carbon dots(N-CDs)were prepared by using coke powder as carbon source and one-step hydrothermal method.The N-CDs were studied as a fluorescent chemosensor for determining Cr(Ⅵ)in water.The selective,sensitive,reproducibility and stability of as-prepared N-CDs were investigated.The morphology,composition and properties of N-CDs were characterized by a series of methods.The fluorescence quenching of N-CDs by Cr(Ⅵ)was explored.The experimental results reveal that the obtained N-CDs have great hydrophilicity and strong luminescence properties,which demonstrates the successful doping of nitrogen into the CDs.The surface-active groups and emission wavelength range of CDs increase due to the electronegativity and electron donor effect of doping N atom.Furthermore,the N-CDs exhibit good photochemical properties for the detection of Cr(Ⅵ),including a wide linear range from 0.3 to 200μM(R^(2)=0.9935)and a low detection limit of 0.10μM at the signal-to-noise ratio of 3(S/N=3).Moreover,the N-CDs as a sensor was used successfully for Cr(Ⅵ)detection in real water samples with recovery rates of 99.9%-110.6%.This sensor also shows highly reproducibility and stability.The N-CDs fluorescent chemical sensor may be a potential candidate for applying in the field of other fluorescent chemical sensing,catalysis,photoelectric devices and other fields.

Nitrogen-doped carbon dots as efficient turn-on fluorescent probe for assay of organophosphorus pesticides

Concerns regarding human health and food safety have generated interest in developing simple,accurate,and cost-effective strategies for evaluating organophosphorus pesticide(OP)residues.In this study,nitrogen-doped carbon dots(N-CDs)were synthesized from a common low-cost precursor via a simple pyrolysis process.The fluorescence of the N-CDs can be suppressed by p-nitrophenol,which is the hydrolysis product of the p-nitrophenyl phosphate salt catalyzed by alkaline phosphatase(ALP).A fluorescent turn-on assay for the inhibitory effect of glyphosate was developed with a low detection limit and wide linear range.Moreover,the feasibility of visualizing OPs in vegetables was demonstrated by the fluorescence imaging of glyphosate on cabbage leaves.This research not only offers a facile method for the synthesis of highly fluorescent CDs but also inspires the development of effective multi-mode sensing platforms that include fluorescent testing and imaging for monitoring pesticide residues.

Nitrogen-doped carbon dots as photocatalysts for organic synthesis:Effect of nitrogen content on catalytic activity

Regulating the doping of carbon dots(CDs)and the generation of reactive oxygen species(ROS)is essential to selectively control their application in photocatalytic organic reactions.This study successfully synthesized five newly developed nitrogen-doped carbon dots(CDs 1-5)with varying nitrogen content,which have the ability to generate ROS when exposed to light radiation,specifically superoxide anion radicals(O_(2)•-)and singlet oxygen(^(1)O_(2)).The utilization of the aforementioned nitrogen-doped CDs as photocatalysts enables the realization of their potential in facilitating efficient photocatalytic organic conversion.Simultaneously,it was observed that the photocatalytic efficiency exhibited a gradual decrease when the nitrogen content in the CDs increased.In order to provide more evidence for this claim,we employed a set of five CDs in the context of photocatalytic dehalogenation ofα-bromoacetophenone,photocatalytic oxidative coupling reaction of amines to imines,photooxidation reaction of sulfides to sulfoxides,and cross-dehydrogenation coupling(CDC)reaction,in which it was further observed that there was a steady decrease in the yields of photocatalytic organic reactions as the nitrogen content in CDs increased.Notably,CDs 1 exhibited the best photocatalytic efficiency,thereby reinforcing the hypothesis that a higher nitrogen content corresponds to a decreased catalytic efficiency.This study not only investigates the impact of the nitrogen content on the catalytic performance of CDs,but also offers valuable insights for the future utilization of CDs for photocatalytic organic reactions in water.

Nitrogen-doped carbon dots-modified Prussian blue with sandwichlike structure as a high-performance electrochromic material

Prussian blue(PB),as a promising inorganic electrochromic material(ECM),has been widely used in smart windows,displays,sensors,etc.However,there are still many challenges for PB to achieve high electrochromic performance.Herein,we synthesized nitrogen-doped carbon dots-modified PB film(defined as PB@N-CDs)with a sandwich-like structure by a simple stepwise electrodeposition method.The carbon dots show an obvious advantage in ultrafast electron transfer ability,which can reduce charge loss during the transfer process,improve the electrochemical activity on both sides of PB,and thus facilitate a rapid electrochromic response.Furthermore,the surface of nitrogen-doped carbon dots contains multiple organic functional groups,which widen the movement path of K+ions under electrostatic adsorption.Impressively,the PB@N-CDs film exhibits a short bleaching/coloring time(0.5/0.9 s)and a superior optical modulation range(78.6%).Particularly,the coloring efficiency has been significantly improved to 137.71 cm^(2)/C(at 700 nm).All of these results open up new avenues for developing highperformance PB-based ECMs and promoting their applications in corresponding electrochromic devices(ECDs)and smart windows.

Synthesis of cell-penetrated nitrogen-doped carbon dots by hydrothermal treatment of eggplant sepals

Novel nitrogen doped carbon quantum dots were successfully fabricated by a hydrothermal method wxth eggplam sepals as carbon source. The carbon materials were characterized by transmission electron microscopy （TEM）, UV-Vis adsorption, Fourier-transformed infrared spectroscopy （FTIR）, fluorescence and the X-ray photoelectron spectroscopy （XPS） measurements, respectively. The carbon quantum dots showed excellent photoluminescence property with high stability in phosphate buffer solution with different pH values from 5 to 9, even in the cell culture medium supplied with the fetal bovine serum. Meanwhile, we also studied the interaction of carbon quantum dots with living HeLa cells with confocal microscopy. Our results indicated that the carbon quantum dots can enter the living HeLa cells by cellular penetration.

Nitrogen-doped Carbon Dots: Application of Hg Ions Detection in Rannasangpei

Nitrogen-doped carbon dots(N-CDs) were hydrothermally synthesized by folic acid, which revealed excited wavelengtli-dependent blue emission and the specific recognition ofHg ions by fluorescence quenching. A wide range response and a fitted linear relationsliip for Hg ions detection were established to show that tliese blue-emission N-CDs achieved a satisfying Hg ions detection in Chinese traditional herb, Rannasaiigpei(RSNP). Tlie results from the N-CDs FL quenching gave the similar outcomes with those from ICP-OES measurement, which exhibited the possibility of the simple FL method of Hg ions detection by N-CDs in Chinese traditional herbs.

Ultrafine VN nanodots induced generation of abundant cobalt single-atom active sites on nitrogen-doped carbon nanotube for efficient hydrogen evolution

Development of highly active and stable non-noble electrocatalysts with well-defined nanostructures is crucial for efficient hydrogen evolution reaction(HER). Herein, a novel three-dimensional(3D) selfsupported electrode consists of vanadium nitride(VN) nanodots and Co nanoparticles co-embedded and highly active single Co atoms anchored in N-doped carbon nanotubes supported on carbon cloth(VN-Co@CoSAs-NCNTs/CC) is fabricated via a one-step in situ nanoconfined pyrolysis strategy, which shows remarkable enhanced HER electrocatalytic activity in acidic medium. During pyrolysis, the formed VN nanodots induce the generation of atomic Co Nxsites in NCNTs, contributing to superior electrocatalytic activity. Experimental and density functional theory(DFT) calculation results reveal that the electrode has multiple accessible active sites, fast reaction kinetics, low charge/mass transfer resistances,high conductivity, as well as downshifted d-band center with a thermodynamically favorable hydrogen adsorption free energy(△G_(H·)), all of which greatly boost the HER performance. As a result, the VNCo@CoSAs-NCNTs/CC electrode displays superb catalytic performance toward HER with a low overpotential of 29 mV at 10 mA cm^(-2) in acidic medium, which could maintain for at least 60 h of stable performance. This work opens a facile avenue to explore low-cost, high performance, but inexpensive metals/nitrogen-doped carbon composite electrocatalysts for HER.

Electrochemical determination of paraquat using a glassy carbon electrode decorated with pillararene-coated nitrogen-doped carbon dots

An electrochemical sensor(carboxylatopillar[5]arene-coated nitrogen-doped carbon dots,namely CCDs)based on carboxylatopillar[5]arene(CP[5])functionalized nitrogen-doped carbon dots(N-CDs)has been developed in a facile and economic manner.To improve the performance of this electrochemical sensor in pesticide detection,the optimal solution pH(pH 7)and loading amount of CCDs on the electrode(0.50 mg/mL)have been determined.By virtue of the good conductivity of N-CDs and the molecular recognition property of CP[5],CCDs modified glassy carbon electrode,namely CCDs/GCE,shows excellent anti-interference capability,selectivity,stability,and reproducibility in the sensitive detection of paraquat.The peak currents are proportional to the paraquat concentration(from 0.1μmol/L to 10μmol/L)with a detection limit of 6.4 nmol/L(S/N=3),indicating a great potential in pesticide detection.In comparison with the electrochemical sensors that require expensive metal nanoparticles and complex preparation processes,CCDs/GCE exhibits excellent detection capability of paraquat with lower cost and simpler preparation processes.

Selenium–nitrogen-co-doped carbon dots increase rice seedling growth and salt resistance

Soil salinity seriously affects the utilization of farmland and threatens the crop production.Here,a selenium-nitrogen-co-doped carbon dots was developed,which increased rice seedling growth and alleviated its inhibition by salt stress by foliar spraying.The treatment activated Ca^(2+)and jasmonic acid signaling pathways and increased iron homeostasis,antioxidant defense,and cell wall development of rice seedlings.It could be used to increase crop resistance to environmental stress.

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.

Achieving high-efficient photocatalytic persulfate-activated degradation of tetracycline via carbon dots modified MIL-101(Fe)octahedrons

The synergistic reaction of photocatalysis and advanced oxidation is a valid strategy for the degradation of harmful antibiotic wastewater.Herein,carbon dots(CDs)modified MIL-101(Fe)octahedrons to form CDs/MIL-101(Fe)composite photocatalyst was synthesized for visible light-driven photocatalytic/persulfate(PS)-activated tetracycline(TC)degradation.The electron spin resonance(ESR)spectra,scavenging experiment and electrochemical analysis were carried out to reveal that the high visible light-driven photocatalytic degradation activity of TC over CDs/MIL-101(Fe)photocatalysts is not only ascribed to the production of free active radicals in the CDs/MIL-101(Fe)/PS system(·OH,·SO_(4-),^(1)O_(2),h^(+)and·O_(2)^(-))but also attributed to the consumption of electrons caused by the PS,which can suppress the recombination of photo-generated carriers as well as strong light scattering and electron trapping effects of CDs.Finally,the possible degradation pathways were proposed by analyzing intermediates via liquid chromatography-mass spectrometry technique.This research presents a rational design conception to construct a CDs/PS-based photocatalysis/advanced oxidation technology with high-efficient degradation activity for the remediation of organic antibiotic pollutant wastewater and for the improvement of carrier transport kinetics of photocatalysts.

High sensitivity detection of baicalein by N,S co⁃doped carbon dots and their application in biofluids

In this work,p⁃phenylenediamine and L⁃cysteine were used as raw materials,and water⁃soluble N,S co⁃doped carbon dots(N,S⁃CDs)with excellent performance were prepared through a one⁃step solvothermal method.The morphology and structure of N,S⁃CDs were characterized by transmission electron microscope,X⁃ray diffrac⁃tion,Fourier transform infrared spectroscopy,and X⁃ray photoelectron spectroscopy,and the basic photophysical properties were investigated via UV⁃Vis absorption spectra and fluorescence spectra.Meanwhile,the N,S⁃CDs have excellent luminescence stability with pH,ionic strength,radiation time,and storage time.Experimental results illus⁃trated the present sensor platform exhibited high sensitivity and selectivity in response to baicalein with a detection limit of 85 nmol·L-1.The quenching mechanism is proved to be the inner filter effect.In addition,this sensor can also detect baicalein in biofluids(serum and urine)with good accuracy and reproducibility.

High Colloidal Stable Carbon Dots Armored Liquid Metal Nano-Droplets for Versatile 3D/4D Printing Through Digital Light Processing(DLP)

Liquid metal(LM)and liquid metal alloys(LMs)possess unique physicochemical features,which have become emerging and functionalized materials that are attractive applicants in various fields.Herein,uniform LM nanodroplets armored by carbon dots(LMD@CDs)were prepared and exhibited high colloidal stability in various solvents,as well as water.After optimization,LMD@CDs can be applied as functional additives for the 3D/4D printing of hydrogel and cross-linked resin through digital light processing(DLP).The light absorption of LMD@CDs not only improved the printing accuracy,but also led to the cross-linking density differential during the post-curing process.Base on the cross-linking density differential of soft hydrogel and photothermal performance of the LM,the 3D printed objects can exhibit stimulus responses to both water and laser irradiation.Additionally,the CDs shell and LM core of LMD@CDs provide the printed objects interesting photoluminescence and electric conductivity capabilities,respectively.We deduce this versatile 3D/4D printing system would provide a new platform for the preparation of multi-functional and stimuli-responsive advance materials.

Accelerating H^(*)desorption of hollow Mo_(2)C nanoreactor via in-situ grown carbon dots for electrocatalytic hydrogen evolution

Molybdenum carbide(Mo_(2)C)is a promising non-noble metal electrocatalyst with electronic structures similar to Pt for hydrogen evolution reaction(HER).However,strong H^(*)adsorption at the Mo sites hinders the improvement of HER performance.Here,we synthesized monodisperse hollow Mo_(2)C nanoreactors,in which the carbon dots(CD)were in situ formed onto the surface of Mo_(2)C through carburization reactions.According to finite element simulation and analysis,the CD@Mo_(2)C possesses better mesoscale diffusion properties than Mo_(2)C alone.The optimized CD@Mo_(2)C nanoreactor demonstrates superior HER performance in alkaline electrolyte with a low overpotential of 57 mV at 10 mA cm^(−2),which is better than most Mo_(2)C-based electrocatalysts.Moreover,CD@Mo_(2)C exhibits excellent electrochemical stability during 240 h,confirmed by operando Raman and X-ray diffraction(XRD).Density functional theory(DFT)calculations show that carbon dots cause the d-band center of CD@Mo_(2)C to shift away from Fermi level,promoting water dissociation and the desorption of H^(*).This study provides a reasonable strategy towards high-activity Mo-based HER eletrocatalysts by modulating the strength of Mo–H bonds.

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.

Novel Formaldehyde Sensor based on Hydrogen Peroxide/Melamine Modulated Photoluminescence of Nitrogen-doped Graphene Quantum Dots

A modulated photoluminescence nanosensor was developed for the quantitative detection of formaldehyde with nitrogen-doped graphene quantum dots and melamine. The sensing system was based on the different activated effects of melamine and hydrogen peroxide on the photoluminescence intensity of nitrogendoped graphene quantum dots. Under the optimal conditions, the modulated photoluminescence sensing system can be used to detect formaldehyde with a good linear relationship between the nitrogen-doped graphene quantum dots photoluminescence difference and the concentration of formaldehyde. The novel sensing system provided new directions for the detection of formaldehyde with high selectivity and quick response.

High-performance Pt catalysts supported on hierarchical nitrogen-doped carbon nanocages for methanol electrooxidation

Hierarchical nitrogen-doped carbon nanocages （hNCNC） with large specific surface areas were used as a catalyst support to immobilize Pt nanoparticles by a microwave-assisted polyol method. The Pt/hNCNC catalyst with 20 wt% loading has a homogeneous dispersion of Pt nanoparticles with the average size of 3.3 nm, which is smaller than 4.3 and 4.9 nm for the control catalysts with the same loading supported on hierarchical carbon nanocages （hCNC） and commercial Vulcan XC-72, respec- tively. Accordingly, Pt/hNCNC has a larger electrochemical surface area than Pt/hCNC and Pt/XC-72. The Pt/hNCNC catalyst exhibited excellent electrocatalytic activity and stability for methanol oxidation, which was better than the control catalysts. This was attributed to the en- hanced interaction between Pt and hNCNC due to nitrogen participation in the anchoring function. By making use of the unique advantages of the hNCNC support, a heavy Pt loading up to 60 wt% was prepared without serious agglomeration, which gave a high peak-current density per unit mass of catalyst of 95.6 mA/mg for achieving a high power density. These results showed the potential of the Pt/hNCNC catalyst for methanol oxidation and of the new hNCNC support for wide applications.

Preparation of nitrogen-doped carbon nanoblocks with high electrocatalytic activity for oxygen reduction reaction in alkaline solution

The oxygen reduction reaction （ORR） is traditionally performed using noble‐metals catalysts, e.g. Pt. However, these metal‐based catalysts have the drawbacks of high costs, low selectivity, poor stabili‐ties, and detrimental environmental effects. Here, we describe metal‐free nitrogen‐doped carbon nanoblocks （NCNBs） with high nitrogen contents （4.11%）, which have good electrocatalytic proper‐ties for ORRs. This material was fabricated using a scalable, one‐step process involving the pyrolysis of tris（hydroxymethyl）aminomethane （Tris） at 800℃. Rotating ring disk electrode measurements show that the NCNBs give a high electrocatalytic performance and have good stability in ORRs. The onset potential of the catalyst for the ORR is-0.05 V （vs Ag/AgCl）, the ORR reduction peak potential is-0.20 V （vs Ag/AgCl）, and the electron transfer number is 3.4. The NCNBs showed pronounced electrocatalytic activity, improved long‐term stability, and better tolerance of the methanol crosso‐ver effect compared with a commercial 20 wt%Pt/C catalyst. The composition and structure of, and nitrogen species in, the NCNBs were investigated using Fourier‐transform infrared spectroscopy, scanning electron microscopy, X‐ray photoelectron spectroscopy, and X‐ray diffraction. The pyroly‐sis of Tris at high temperature increases the number of active nitrogen sites, especially pyridinic nitrogen, which creates a net positive charge on adjacent carbon atoms, and the high positive charge promotes oxygen adsorption and reduction. The results show that NCNBs prepared by pyrolysis of Tris as nitrogen and carbon sources are a promising ORR catalyst for fuel cells.

Controllable Synthesis of Fluorescent Carbon Dots and Their Detection Application as Nanoprobes

Carbon dots(CDs), as a new member of carbon nanomaterial family, have aroused great interest since their discovery in 2004. Because of their outstanding water solubility, high sensitivity and selectivity to target analytes, low toxicity, favorable biocompatibility, and excellent photostability, researchers from diverse disciplines have come together to further develop the fundamental properties of CDs. Many methods for the production of CDs have been reported, therein, hydrothermal and solvothermal technology needs simple equipments, and microwave synthesis needs less reaction time, hence these methods become current common synthesis methods, in which many precursors have been applied to produce CDs. Due to their excellent fluorescence, CDs have made impressive strides in sensitivity and selectivity to a diverse array of salt ions,organic/biological molecules and target gases. The development of CDs as nanoprobes is still in its infancy, but continued progress may lead to their integration into environmental and biological applications. Hydrothermal,solvothermal, and microwave synthesis of fluorescent carbon dots and their detection applications as nanoprobes in salt ions, organic/biological molecules, and target gases will be reviewed.