Amorphous Carbon Dots Research Articles

Sensitive and rapid determination of tetracycline antibiotic by carrot juice-derived carbon dots as a fluorescent probe.

The antibiotic tetracycline can be efficiently used as medicine for the deterrence of bacterial infections in humans, animals, and plants. However, the unprecedented use of tetracycline is of great concern owing to its low biodegradability, extensive usage, and adverse impacts on the environment and water quality. In this study, a sensitive spectrofluorometric method was proposed for the direct determination of tetracycline, based on biocompatible fluorescent carbon dots (CDs). The synthesis of CDs was performed by adopting a green hydrothermal procedure from carrot juice without requiring surface passivation or outflowing any environmentally hazardous waste. X-ray diffraction analysis and transmission electron microscopy revealed amorphous spherical-shaped CDs that exhibited blue emission under blue illumination. The fabricated fluorescent probe directly detected tetracycline in the concentration range of 4.00 ×10-6 to 1.55 ×10-5mol L-1 with an LOD of 1.33 ×10-6mol L-1. The performance of the probe was assessed in a tap water sample, with recovery values between 80.70 and 103.60%. The method's greenness was evaluated using the Analytical Green metric approach (AGREE) and confirmed to be within the green range. The developed method is facile, rapid, cost-effective, and offers a wide linear range and satisfactory selectivity, making it potentially suitable for determining tetracycline in water applications.

Effect of carbon dots nanomaterial concentration on luminance spectral bandwidth via Kirchoff-Bunsen spectroscope

This study aims to determine the effect of the concentration of Carbon Dots on the bandwidth of the Carbon Dots luminescence spectrum. Carbon Dots are produced by ultrasonification method and characterized using UV-Vis spectroscopy, photoluminescence (PL) spectroscopy, scanning electron microscopy (SEM), electron dispersive X-Ray spectroscopy (EDX), X-ray diffraction (XRD), and particle size analyzer (PSA). Measurement of the bandwidth of the Carbon Dots fluorescence spectrum for various concentrations was carried out by irradiating the Carbon Dots sample using a laser with a wavelength of 405 nm and looking at the spectrum of light emitted using a Kirchoff-Bunsen spectroscope.The characterization results show that the resulting Carbon Dots have a light absorption peak at a wavelength of 303 nm, a light wave emission peak at a wavelength of 508.87 nm, the surface structure of the Carbon Dots is in the form of a porous layer, the presence of the dominance of carbon and oxygen atoms in Carbon Dots, an amorphous Carbon Dots structure is observed, and the smallest measured Carbon Dots particle size is 1.12 nm. The results show that increasing the concentration of Carbon Dots causes a tendency to increase the bandwidth of orange, green and blue light spectra emitted by the particles, and in the red color there was no significant effect of increasing the concentration of Carbon Dots on the spectrum. However, increasing the concentration of Carbon Dots actually causes a narrowing of the yellow and violet color spectra.

High S-doped amorphous carbon/carbon quantum dots coupled micro-frame for highly efficient potassium storage

Anode materials with excellent rate capability, capacity, and cycle life have been a challenge in obtaining cost-effective K-ion batteries (KIBs). Based on the concept of waste recycling, we prepared the S-doped (21.5%) amorphous carbon/carbon quantum dots coupled micro-frame (SCMF) by combining chemical exfoliation and S/Se-assisted carbonization. SCMF exhibited the advantages of integrating amorphous carbon and carbon quantum dots (CQDs). The CQDs serve as fast electron channels, while amorphous carbon can accommodate more large-size K-ions and mitigate volume expansion. In KIBs, SCMF maintained a high reversible capacity (414.0 mAh g−1, after 100 cycles at 100 mA g−1), a good rate capability (224.0 mAh g−1, 2000 mA g−1), and excellent capacity retention (208.9 mAh g−1, after 2000 cycles at 1000 mA g−1). The molecular dynamic simulation revealed that CQDs provided fast electron transport channels and that C, O and S atoms had suitable interactions with K, facilitating potassium storage. Moreover, the potassium-ion capacitor (PIC) assembled from SCMF and activated carbon exhibited stable electrochemical performance, proving its potential for application. The research provided valuable insights into the reuse of biomass waste in new secondary batteries.

Size-dependent activity of carbon dots for photocatalytic H2 generation in combination with a molecular Ni cocatalyst.

Carbon dots (CDs) are low-cost light-absorbers in photocatalytic multicomponent systems, but their wide size distribution has hampered rational design and the identification of the factors that lead to their best performance. To address this challenge, we report herein the use of gel filtration size exclusion chromatography to separate amorphous, graphitic, and graphitic N-doped CDs depending on their lateral size to study the effect of their size on photocatalytic H2 evolution with a DuBois-type Ni cocatalyst. Transmission electron microscopy and dynamic light scattering confirm the size-dependent separation of the CDs, whereas UV-vis and fluorescence spectroscopy of the more monodisperse fractions show a distinct response which computational modelling attributes to a complex interplay between CD size and optical properties. A size-dependent effect on the photocatalytic H2 evolution performance of the CDs in combination with a molecular Ni cocatalyst is demonstrated with a maximum activity at approximately 2-3 nm CD diameter. Overall, size separation leads to a two-fold increase in the specific photocatalytic activity for H2 evolution using the monodisperse CDs compared to the as synthesized polydisperse samples, highlighting the size-dependent effect on photocatalytic performance.

Synthesis Processes, Photoluminescence Mechanism, and the Toxicity of Amorphous or Polymeric Carbon Dots.

Fluorescence is the emission of light following photon absorption. This optical phenomenon has many applications in daily life, such as in LED lamps, forensics, and bioimaging. Traditionally, small-molecule fluorophores were most common, but the types of molecules and particles with compelling fluorescence properties have expanded. For example, green fluorescent protein (GFP) was isolated from jellyfish and won the Nobel prize in 2008 due to its significant utility as a fluorescent biomarker. Using the intrinsic fluorescence of GFP, many previously invisible biological processes and substances can now be observed and studied. Other fluorescent materials have also been developed, greatly expanding the potential applications. Semiconductor quantum dots (QDs), which have bright fluorescence and a narrow bandwidth, are a popular choice for display technologies. However, QDs are made of heavy metal elements such as Cd and Se, which pose potential safety concerns to the environment and human health. Thus, new fluorescent organic materials are being developed to mitigate the toxicological concerns while maintaining the QD advantages.One type of new material attracting great attention as an environmentally friendly substitute for semiconductor QDs is carbon dots (CDs). CDs have been developed with strong fluorescence, good photostability, and low toxicity using a variety of precursors, and some synthesis processes have good potential for scale-up. However, since they are made of a variety of materials and through different methods, the structure and properties of CDs can differ from preparation to preparation. There are three major types of CDs: graphene quantum dots (GQDs), carbon quantum dots (CQDs), and amorphous or polymeric carbon dots (PCDs). This Account focuses on PCDs and their unique properties by comparing it with other types of CDs. The synthesis processes, fluorescence properties, fluorescence mechanisms, and toxicity are discussed below with an emphasis on the distinct attributes of PCDs.PCDs can be synthesized from small molecules or polymers. They have an amorphous or cross-linked polymer structure with bright fluorescence. This fluorescence is possibly due to cross-link-enhanced emission or clusteroluminescence that arises from the through-space interactions of heteroatomic-rich functional groups. Other fluorescence mechanisms of CDs, including distinct contributions from the carbon core and surface states, may also contribute. The toxicological profiles of CDs are influenced by the chemical composition, surface functionalization, and light illumination. CDs are generally thought to be of low toxicity, and this can be further improved by removing toxic byproducts, functionalizing the surface, and reducing light exposure to minimize the generation of reactive oxygen species.

Engineering Electro- and Photocatalytic Carbon Materials for CO2 Reduction by Formate Dehydrogenase.

Semiartificial approaches to renewable fuel synthesis exploit the integration of enzymes with synthetic materials for kinetically efficient fuel production. Here, a CO2 reductase, formate dehydrogenase (FDH) from Desulfovibrio vulgaris Hildenborough, is interfaced with carbon nanotubes (CNTs) and amorphous carbon dots (a-CDs). Each carbon substrate, tailored for electro- and photocatalysis, is functionalized with positive (−NHMe2+) and negative (−COO–) chemical surface groups to understand and optimize the electrostatic effect of protein association and orientation on CO2 reduction. Immobilization of FDH on positively charged CNT electrodes results in efficient and reversible electrochemical CO2 reduction via direct electron transfer with >90% Faradaic efficiency and −250 μA cm–2 at −0.6 V vs SHE (pH 6.7 and 25 °C) for formate production. In contrast, negatively charged CNTs only result in marginal currents with immobilized FDH. Quartz crystal microbalance analysis and attenuated total reflection infrared spectroscopy confirm the high binding affinity of active FDH to CNTs. FDH has subsequently been coupled to a-CDs, where the benefits of the positive charge (−NHMe2+-terminated a-CDs) were translated to a functional CD-FDH hybrid photocatalyst. High rates of photocatalytic CO2 reduction (turnover frequency: 3.5 × 103 h–1; AM 1.5G) with dl-dithiothreitol as the sacrificial electron donor were obtained after 6 h, providing benchmark rates for homogeneous photocatalytic CO2 reduction with metal-free light absorbers. This work provides a rational basis to understand interfacial surface/enzyme interactions at electrodes and photosensitizers to guide improvements with catalytic biohybrid materials.

Bottom-up scalable temporally-shaped femtosecond laser deposition of hierarchical porous carbon for ultrahigh-rate micro-supercapacitor

With the accelerated development of electronic devices, micro-supercapacitors (MSCs), as energy storage devices that can charge and discharge quickly, have attracted considerable attention. To improve the rate capability of MSCs with consideration of the energy density remains a challenge. We demonstrated a facile method for the preparation of thin films through bottom-up femtosecond pulsed laser deposition. The femtosecond laser irradiated the polyimide film through a transparent substrate to uniformly sputter the electrode material onto the lower surface of the substrate. We successfully deposited porous amorphous carbon, graphene, and carbon quantum dots with controllable properties by temporally shaping the femtosecond laser. The resulting MSC exhibited an ultrahigh frequency response and good performance at scan rates up to 10,000 V s−1. The characteristic frequency f0 of the MSC was as high as 42,000 Hz, and the relaxation time constant τ0 was 0.0238 ms. The MSC reached an impedance phase angle of −82.6° at a frequency of 120 Hz, an ultrahigh power density of more than 30 kW cm−3, and an energy density of 0.068 W h cm−3. This method provides a novel perspective for the preparation of ultrahigh frequency filters for future miniaturized portable electronic devices.

Critical Optimization of Phosphorus Functionalized Carbon Nanomaterials for Metal‐Free Solar Hydrogen Production and Simultaneous Organic Transformation

AbstractComplete metal‐free P‐functionalized carbon nanomaterials are synthesized from a single molecular precursor, phytic acid, for photocatalytic solar H2 production and simultaneous organic transformation of 4‐methyl benzyl alcohol to 4‐methyl benzaldehyde by managing the complete redox cycle. It is observed that by increasing the carbonization time, P‐functionalized amorphous carbon dots convert to the highly defined 2D sheet‐like nanostructure with optimum P‐functionality, resulting in efficient light absorption, charge separation, and improved active sites for photocatalysis. Finally, the highly defined sheet‐like structure converts to a more defected aggregated form, resulting in the depletion of photocatalytic efficiency. The structural and elemental features are further correlated with the ongoing photophysics by means of steady‐state and time‐resolved fluorescence spectroscopy. Transient photocurrent responses and Mott‐Schottky plots directly support the optimization of P‐functionalized carbon nanostructure for efficient photocatalysis. Finally, the detailed computational studies are carried out to unveil the charge separation mechanism and the crucial role of P‐functionalities as active sites for better charge accumulation as well as H2O adsorption on the surface. Overall, the in‐depth structure–property correlation and critical optimization of the heteroatom functionalized carbon nanomaterials will open up new possibilities for further development of metal‐free photocatalysts for solar‐energy conversion devices.

A Hybrid Materials Approach for Fabricating Efficient WLEDs Based on Di‐Ureasils Doped with Carbon Dots and a Europium Complex

AbstractWhite light‐emitting diodes (WLEDs) revolutionized the lighting industry providing high energy efficiency and a long lifetime. The recent development of efficient ultraviolet (UV) LEDs pushed forward the development of WLEDs based on mixtures of down‐shifting phosphors and the current challenges are focused on the design of sustainable light converting materials with tunable correlated color temperature (CCT) and high color rendering index (CRI). Here the authors report a simple route to design sustainable WLEDs with tunable and enhanced color features through the assembly of a commercial LED chip (400 nm) and flexible films of a di‐ureasil hybrid comprising a mixture of a cyan component originating from amorphous carbon dots and a red one resulting from the Eu(tta)3(bpyO2) (tta−: 2‐thenoyltrifluoroacetonate and bpyO2: 2,2′‐dipyridyl‐1,1′‐dioxide) complex. This red emission is responsible for high CRI arising from an unprecedented efficient energy bridge between bpyO2 and tta− excited states mediated by the hybrid host, as modeled by theoretical calculations based on the density functional theory and intramolecular energy transfer. WLED prototypes were fabricated with a tunable CCT from cold (5796 K) to warm (4228 K) white‐light with high CRI values of 89 and 84, respectively, outperforming the state‐of‐the‐art of UV‐based WLEDs.

Symmetry-Breaking Charge-Transfer Chromophore Interactions Supported by Carbon Nanodots.

Carbon dots (CDs) and their derivatives are useful platforms for studying electron‐donor/acceptor interactions and dynamics therein. Herein, we couple amorphous CDs with phthalocyanines (Pcs) that act as electron donors with a large extended π‐surface and intense absorption across the visible range of the solar spectrum. Investigations of the intercomponent interactions by means of steady‐state and pump‐probe transient absorption spectroscopy reveal symmetry‐breaking charge transfer/separation and recombination dynamics within pairs of phthalocyanines. The CDs facilitate the electronic interactions between the phthalocyanines. Thus, our findings suggest that CDs could be used to support electronic couplings in multichromophoric systems and further increase their applicability in organic electronics, photonics, and artificial photosynthesis.

Amorphous carbon dot and chitosan based composites as fluorescent inks and luminescent films

A composite of self-passivated amorphous carbon dots (CDs) and chitosan has been developed and utilized to form fluorescent inks and luminescent films. The ink is invisible under visible light but glows brightly under external excitation. Cross-linking between the numerous surface groups present in the highly disordered CDs and chitosan, endow the inks and films with enhanced optical and mechanical properties. The amorphous CD based ink is capable of writing on nearly all types of surfaces and exhibits excellent anti-clogging and anti-smearing properties. The luminescent films on the other hand are characterized by good mechanical strength (σUTS ≈ 61.3 MPa) along with high luminescence efficiency. The luminescence yield, ultimate tensile stress, hydrophobicity and glass transition temperature of the films were found to scale similarly with the concentration of CDs in chitosan. All the parameters initially improved with increasing CD concentration but then deteriorated beyond some optimal CD loading due to agglomeration effect. We demonstrate that the amorphous carbon dot-based inks and films outperform all other carbon-based fluorescent inks and films prepared from the more expensive crystalline structures.

Precursor-Dependent Photocatalytic Activity of Carbon Dots.

This work systematically compares both structural features and photocatalytic performance of a series of graphitic and amorphous carbon dots (CDs) prepared in a bottom-up manner from fructose, glucose, and citric acid. We demonstrate that the carbon source and synthetic procedures diversely affect the structural and optical properties of the CDs, which in turn unpredictably influence their photo electron transfer ability. The latter was evaluated by studying the photo-reduction of methyl viologen. Overall, citric acid-CDs were found to provide the best photocatalytic performance followed by fructose- and glucose-CDs. However, while the graphitization of glucose- and citric acid-CDs favored the photo-reaction, a reverse structure–activity dependence was observed for fructose-CDs due to the formation of a large graphitic-like supramolecular assembly. This study highlights the complexity to design in advance photo-active bio-based carbon nanomaterials.

Electrostatically assembled construction of ternary TiO2-Cu@C hybrid with enhanced solar-to-hydrogen evolution employing amorphous carbon dots as electronic mediator

The huge demand for renewable hydrogen produced by water splitting has prompted people to conduct in-depth research on the hydrogen evolution reaction for the development of earth-abundant, non-precious, and multi-functional metal catalysts. Herein, a noble-metal-free ternary composite of TiO2-Cu@C was prepared by electrostatic self-assembly loaded copper nanoparticles and amorphous carbon dots (CDs) on porous TiO2 microrods. The good conductivity of the CDs was beneficial to promoting the charge transfer and separation, generating an enhanced solar-to-hydrogen performance on TiO2-Cu@C. The optimized TiO2-Cu@C reveals a stable and notable hydrogen evolution rate of 3911 μmol g−1h−1, which is 1.6 times that of TiO2-Cu and many times higher than that of TiO2. Instead of providing active sites for hydrogen production, the CDs act as an electronic mediator and provide another electron pathway to further enhance the activity of TiO2-Cu, where the photogenerated electrons on TiO2 could pass through the CDs to the copper cocatalyst and reduce water to hydrogen.

Pressure-triggered aggregation-induced emission enhancement in red emissive amorphous carbon dots

Red emissive carbon dots’ pressure-triggered aggregation-induced emission enhancement.

Ultra-small amorphous carbon dots: preparation, photoluminescence properties, and their application as TiO2 photosensitizers

Ultra-small carbon quantum dots (s-CQDs) with excitation wavelength-independent fluorescence had been obtained by hydrothermal-followed acid precipitation method and were characterized by FT-IR, TEM, XPS, UV–Vis and XRD. It was found that as-prepared s-CQDs were amorphous spherical particles with an average diameter of 1.51 nm, and there were abundant hydroxyl and carbonyl groups on their surfaces. Moreover, fluorescence emission study found that the luminescence of s-CQDs was aroused by oxygen group decorated on its surface, and the fluorescence properties of s-CQDs were much different from those of large CQDs (l-CQDs), which showed higher quantum yield and better photoluminescence (PL) property than that of l-CQDs. The PL of s-CQDs possessed two emission centers and was exhibited to be excitation independent. When s-CQDs was used as photosensitizer for TiO2 to photocatalytic degradation of methylene blue under visible light irradiation, it showed significantly improved photocatalytic activities compared with 1-CQDs, and the degradation efficiency of methylene blue reached up to 96.6%. The high degradation efficiency was attributed to the ultra-small particle size, abundant acidic groups, and excellent optical properties of s-CQDs.

Design of Carbon Dots for Metal-free Photoredox Catalysis.

The photoreduction potential of a set of four different carbon dots (CDs) was investigated. The CDs were synthesized by using two different preparation methods-hydrothermal and pyrolytic-and two sets of reagents-neat citric acid and citric acid doped with diethylenetriamine. The hydrothermal syntheses yielded amorphous CDs, which were either nondoped (a-CDs) or nitrogen-doped (a-N-CDs), whereas the pyrolytic treatment afforded graphitic CDs, either non-doped (g-CDs) or nitrogen-doped (g-N-CDs). The morphology, structure, and optical properties of four different types of CDs revealed significant differences depending on the synthetic pathway. The photocatalytic activities of the CDs were investigated as such, that is, in the absence of any other redox mediators, on the model photoreduction reaction of methyl viologen. The observed photocatalytic reaction rates:a-N-CDs ≥ g-CDs > a-CDs ≥ g-N-CDs were correlated with the presence/absence of fluorophores, to the graphitic core, and to quenching interactions between the two. The results indicate that nitrogen doping reverses the photoredox reactivity between amorphous and graphitic CDs and that amorphous N-doped CDs are the most photoredox active, a yet unknown fact that demonstrates the tunable potential of CDs for ad hoc applications.

Amorphous Carbon Dots and their Remarkable Ability to Detect 2,4,6-Trinitrophenol

Apparently mundane, amorphous nanostructures of carbon have optical properties which are as exotic as their crystalline counterparts. In this work we demonstrate a simple and inexpensive mechano-chemical method to prepare bulk quantities of self-passivated, amorphous carbon dots. Like the graphene quantum dots, the water soluble, amorphous carbon dots too, exhibit excitation-dependent photoluminescence with very high quantum yield (~40%). The origin and nature of luminescence in these high entropy nanostructures are well understood in terms of the abundant surface traps. The photoluminescence property of these carbon dots is exploited to detect trace amounts of the nitro-aromatic explosive — 2,4,6-trinitrophenol (TNP). The benign nanostructures can selectively detect TNP over a wide range of concentrations (0.5 to 200 µM) simply by visual inspection, with a detection limit of 0.2 µM, and consequently outperform nearly all reported TNP sensor materials.

Facile synthesis and versatile applications of amorphous carbon dot

A very simple facile method of preparation of carbon dots, by acid assisted ultrasonic chemical method has been demonstrated. Dextrose can be efficiently and simply synthesised into water-soluble photoluminescent carbon dot (CDs). The HRTEM confirms its size less than 15nm and its amorphous nature. We have tried to emphasized that even amorphous carbon dot has its own importance in the advance materials world by combinedly showing different possible applications of amorphous carbon dots. CDs were used in making fluorescent ink, flexible film and in sensing picric acid (TNP). The presence of surface states was shown by FTIR spectroscopy. The UV-Vis absorption spectra demonstrate the n-π∗ transition and the π-π∗ transition. The emission peak of PL spectra is near blue luminescent region. Significant changes were observed in the UV-Vis and PL spectra of CDs in the presence of TNP (Tri-Nitro phenol). The synthesized CDs has been showed as a source for direct applications in sensing explosives, as an invisible ink and as a flexible photo luminescent thin film.

Enhancing Light Absorption and Charge Transfer Efficiency in Carbon Dots through Graphitization and Core Nitrogen Doping.

Single-source precursor syntheses have been devised for the preparation of structurally similar graphitic carbon dots (CDs), with (g-N-CD) and without (g-CD) core nitrogen doping for artificial photosynthesis. An order of magnitude improvement has been realized in the rate of solar (AM1.5G) H2 evolution using g-N-CD (7950 μmolH2 (gCD )-1 h-1 ) compared to undoped CDs. All graphitized CDs show significantly enhanced light absorption compared to amorphous CDs (a-CD) yet undoped g-CD display limited photosensitizer ability due to low extraction of photogenerated charges. Transient absorption spectroscopy showed that nitrogen doping in g-N-CD increases the efficiency of hole scavenging by the electron donor and thereby significantly extends the lifetime of the photogenerated electrons. Thus, nitrogen doping allows the high absorption coefficient of graphitic CDs to be translated into high charge extraction for efficient photocatalysis.

Enhancing Light Absorption and Charge Transfer Efficiency in Carbon Dots through Graphitization and Core Nitrogen Doping

AbstractSingle‐source precursor syntheses have been devised for the preparation of structurally similar graphitic carbon dots (CDs), with (g‐N‐CD) and without (g‐CD) core nitrogen doping for artificial photosynthesis. An order of magnitude improvement has been realized in the rate of solar (AM1.5G) H2 evolution using g‐N‐CD (7950 μmolH2 (gCD)−1 h−1) compared to undoped CDs. All graphitized CDs show significantly enhanced light absorption compared to amorphous CDs (a‐CD) yet undoped g‐CD display limited photosensitizer ability due to low extraction of photogenerated charges. Transient absorption spectroscopy showed that nitrogen doping in g‐N‐CD increases the efficiency of hole scavenging by the electron donor and thereby significantly extends the lifetime of the photogenerated electrons. Thus, nitrogen doping allows the high absorption coefficient of graphitic CDs to be translated into high charge extraction for efficient photocatalysis.