Carbon dots from natural‐product: applications as adsorbent and Sensing of Fe 3+ Ions

Carbon dots from natural‐product: applications as adsorbent and Sensing of Fe 3+ Ions | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Carbon dots from natural‐product: applications as adsorbent and Sensing of Fe 3+ Ions Hesam Salimi Shahraki, Anees Ahmad, Qurtulen Qurtulen, Sugandhi Gupta, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-2569839/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 16 Jun, 2023 Read the published version in Journal of Inorganic and Organometallic Polymers and Materials → Version 1 posted 7 You are reading this latest preprint version Abstract Freshwater contamination is a significant concern due to the increasing pollution by industrial activities. Dyes have a wide range of uses and are introduced at different stages of manufacture, raising the risk of unwanted human and environmental contact. Consequently, the demand for an effective method for removing dyes has become more important than before. In this context, Carbon dots have been synthesized by the green synthesis method from Coriander leaves (C-CDs) and used as a prospective adsorbent to remove (MB) methylene blue dye from aqueous solution. The as-synthesized C-CDs are characterized by HR-TEM, XRD, XPS, FTIR, Zeta potential, UV-visible, and Photoluminescence (PL). Effects of different controlling parameters such as adsorbent dosage, pH, contact time, and initial MB dye concentration were investigated. The highest adsorption efficiency (82.6%) and maximum adsorption capacity (96.05 mg/g) of MB were obtained at optimum conditions (303 K). The adsorption isotherm data could be fitted well by Freundlich model, and the experimental data fitted to the Pseudo-Second-Order kinetic model. It is worth noting that C-CDs exhibited excellent sensitivity and high fluorescence quenching effect on Fe 3+ ions. Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Introduction In recent years, the heightened awareness has emerged that by 2050, many countries will face significant problems related to the lack of freshwater [ 1 ]. The latest projections by the (UNESCO) United Nations Educational, Scientific and Cultural Organization suggest that the world population will reach 9.3 billion in 2050, and two-thirds of people will live under water stress [ 2 ]. The reuse and recycling of wastewater after contamination treatment is a serious issue in many areas to ensure water security at the national level. Contamination of water sources is increasing by many factors, such as climate, precipitation, population growth and related activities [ 3 ]. Wastewater contains a variety of pollutants, and Some wastewater often includes several classes of contaminants, such as anions, heavy metals, dyes, and different types of organic compounds [ 4 ]. Large quantities of dyes have been used as raw materials and produced as end products in textiles, clothing, food, etc. It has been estimated that the textile industries are consumed more than 7 x 10 5 tons of dyes, which makes them the top three pollutants [ 5 – 8 ]. The ingestion of water polluted with dyes poses a potential risk or threat to all forms of life and has negative effects on human health. Many different methods are available for removing dyes from wastewater, including ion exchange, adsorption, filtration, and chemical precipitation [ 9 , 10 ]. Among these methods, adsorption has significant advantages over other processes because of the flexibility and simplicity of design, cost savings, and ease of operation with adaptable designs [ 11 ]. Over recent years, a wide variety of adsorbent materials have been recommended for efficient dye removal, including graphene, activated carbon, metal oxides/hydroxides, polymers, and zeolites, but It should be noted these adsorbents have several problematic issues. In many cases, the adsorption capacity is quite low, with a long time taken to reach equilibrium [ 12 , 13 ]. Accordingly, the search for a high-capacity adsorbent with low toxicity and functional ability continues under the key condition of economic feasibility. Recently, Carbon Dots (CDs) have emerged as efficient absorbents for the removal of dyes from wastewater [ 14 ]. CDs can be generally synthesized using any carbon sources, such as chemicals, graphene, plants, and food wastes. Among all types of carbon sources, biomass and its derivatives, such as bagasse, fruit peel, tea residue, and leaves, received considerable attention due to renewability, low cost, and availability [ 15 – 17 ]. Taking into consideration the above, we report a green and novel synthesis of carbon dots derived from coriander leaves via a simple hydrothermal method. This approach is less time-consuming and uses water as a solvent without any additional surface passivating agent and have a high (QY) quantum yield of 12.0%. Coriander, known as Chinese parsley, is edible and rich in proteins and carbohydrates naturally, which is abundant in oxygen and carbon elements. The use of leaves as potential sources not only meets the urgent requirement for large-scale production of Carbon dots, but also improves the development of sustainable applications [ 18 – 20 ]. It is well known that the large amount of Fe 3+ in human body may cause severe diseases like Alzheimer’s disease, liver and kidney damage, and Parkinson’s disease [ 21 – 23 ]. In view of the above, the selective and sensitive detection of Fe 3+ is extremely important. The synthesized C-CDs have shown good sensitivity toward Fe 3+ over other metal ions. In this study, we have presented C-CDs that possess the following significant advantages; a) Eco-friendly adsorbent for removal of MB from wastewater, b) Synthesized through the hydrothermal method, c) Excellent sensitivity for Fe 3+ ions. Materials And Methods Chemicals and solutions Freshly harvested coriander leaves were bought from the local market of Aligarh and thoroughly washed before use. Methylene blue dye was purchased from Merck chemical Co. Figure. 1 exhibits the molecular structure of the MB (C 16 H 18 N 3 SCI). CaCl 2 , FeCl 3 , Zn(NO 3 ) 2 , NiCl 2 , KOH, NaOH, CrCl 3 , CdCl 2 , PbCl 2 , MnCl 2 , CuCl 2 , MgCl 2 , NaH 2 PO 4 and Na 2 HPO 4 were supplied from Industrial Research Laboratories, AMU. All chemicals were used as-received without further purifications. Synthesis of C-CDs. Briefly, 5 g of the fresh coriander leaves were finely crushed using a mortar and pestle and added to 50 mL of DDW by stirring at room temperature for 30 min. The solution was transferred to hydrothermal process for 5 h at 210°C. The mixture was allowed to cool at room temperature, and the large black insoluble portion was filtered through a 0.22µm filter membrane. The brownish-yellow C-CDs solution obtained then was kept at 4°C for further studies and characterizations [ 24 ]. Characterization The optical properties of the C-CDs were measured by using UV-Vis spectroscopy (Perkin Elmer LAMBDA-45) and PL spectra (HITACHI- F-2500 FL). The main functional groups of C-CDs were identified by Fourier transform spectroscopy (Perkin Elmer IR spectrometer) before and after adsorption. X-Ray diffraction or XRD (Rigaku TTRAX III) was used to determine the crystallographic structure of the adsorbent. X-ray photoelectron spectroscopy (XPS) (PHI 5000 Versa Probe III) is widely applied to determine the elemental composition. The surface charge of the C-CDs was determined by zeta potential (ZEECOM ZC-3000). Batch equilibrium studies The impact of adsorbent dose (0.01–0.05 g), pH (2–10), temperature (303-343K), and initial MB concentration (10–100 mg/L) for the removal of a basic dye (MB) onto C-CDs were studied. In each experiment, we added a desired amount of C-CDs to 50 mL of dye solution in a 100 mL conical flask under stirring to achieve equilibrium. At equilibrium, the concentration of MB was measured at 664 nm wavelength, using UV–vis Spectrophotometer. The adsorption efficiency (q%) and capacity (q e ) of the adsorbent can be calculated by the following equations: $${\text{q}}_{\text{e}}\left(\frac{\text{m}\text{g}}{\text{g}}\right)=\text{V}({\text{C}}_{\text{i}}-{\text{C}}_{\text{e}})/\text{M}$$ 1 $$\text{q}\text{%}=\frac{{\text{C}}_{\text{i}}-{\text{C}}_{\text{e}}}{{\text{C}}_{\text{i}}}\text{*}100$$ 2 Where, V and M are volume of solution (L) and mass of adsorbent used (g), respectively. C e is the equilibrium concentration (mg/L), and C i is the initial concentration of adsorbate in the solution (mg/L). Effect of temperature (thermodynamic and kinetics isotherms) The impact of temperature on MB dye uptake onto the surface of C-CDs, a series of experiments was performed at 303K, 313K, 323K, and 343K. Thermodynamic calculations were performed through the following equations: $${\text{K}}_{\text{d}}=\frac{{\text{q}}_{\text{e}}}{{\text{C}}_{\text{e}}}$$ 3 $${{\Delta }\text{G}}^{\text{o}}=-\text{R}\text{T}\text{l}\text{n}{\text{K}}_{\text{d}}$$ 4 $$\text{l}\text{n}{\text{K}}_{\text{d}}=\frac{{{\Delta }\text{S}}^{\text{o}}}{\text{R}}-\frac{{\varDelta \text{H}}^{\text{o}}}{\text{R}\text{T}}$$ 5 Where, 𝐾 𝑑 is distribution coefficient, Δ𝐺 o is Gibb’s free energy (kJ mol −1 ), ΔH o and ΔS o are obtained from the slope and intercept of Van't Hoff plot of ln K d versus 1/T, respectively. Values of K L can be determined from the relation ln q e /C e . The experimental data were analyzed with the Pseudo-First-Order (PFO) and (PSO) Pseudo-Second-Order models to improve understanding of kinetics adsorption process. The PFO model assumes that molecules of dye filled sites have linear relationship with rate of adsorption. The PFO equation can be expressed using Eq: $$\text{log}\left({\text{q}}_{\text{e}}-{\text{q}}_{\text{t}}\right)=\text{l}\text{o}\text{g}{\text{q}}_{\text{e}}-\frac{{\text{K}}_{1}}{2.303}\text{t}$$ 6 Where, k 1 is rate constant of PFO (1/h), q e is the equilibrium adsorption capacity (mg/g) and q t is quantity of adsorbate-adsorbed at time (mg/g). The PSO model is the most suitable for explaining the adsorption kinetics. The PSO equation is generally expressed as follows: $$\frac{\text{t}}{{\text{q}}_{\text{t}}}=\frac{1}{{\text{K}}_{2}{\text{q}}_{\text{e}}^{2}}+\frac{\text{t}}{{\text{q}}_{\text{e}}}$$ 7 The intercept and slope of linear plot of t/q t vs t can be calculated the values of q e and k 2 . Where, k 2 is rate constant of PSO. Adsorption isotherm studies Batch adsorption study was performed in 50 mL beaker having 0.04g C-CDs with different initial dye concentrations (10, 20, 40, 60, 80 and 100 mg/L). In this study, the Langmuir, Freundlich, and Temkin model is offered in the following Eqs: $$\frac{{\text{C}}_{\text{e}}}{{\text{q}}_{\text{e}}}=\frac{1}{{\text{q}}_{\text{m}}{\text{k}}_{\text{L}}}+\frac{{\text{C}}_{\text{e}}}{{\text{q}}_{\text{m}}}$$ 8 $$\text{l}\text{o}\text{g}{\text{q}}_{\text{e}}=\text{l}\text{o}\text{g}{\text{K}}_{\text{f}}+\frac{1}{{\text{n}}_{\text{f}}}\text{l}\text{o}\text{g}{\text{C}}_{\text{e}}$$ 9 $${\text{q}}_{\text{e}}=\text{B}\text{l}\text{n}{\text{K}}_{\text{T}}+\text{B}\text{l}\text{n}\text{C}$$ 10 Where, K L and K f are the Langmuir and Freundlich constant, respectively, q m is the maximum adsorption capacity, \(\frac{1}{{\text{n}}_{\text{f}}}\) is adsorption intensity, b T and K T are Temkin isotherm constant and equilibrium binding constant (L mol − 1 ), respectively. B = (R T /b T ) related to the heat of adsorption (J/mol). Calculation of quantum yield Quantum Yield (QY) of C-CDs can be measured by comparing (QY) quinine sulfate as a reference. C-CDs were dissolved in DDW, while quinine sulfate was dissolved in in 0.5 M H 2 SO 4 (QY = 0.54, η = 1.33). The QY of CQDs was obtained based on Eq: $${\text{Q}\text{Y}}_{\text{C}-\text{C}\text{D}\text{s}}= {\text{Q}\text{Y}}_{\text{R}}\left(\frac{{\text{A}}_{\text{R}}}{{\text{A}}_{\text{C}-\text{C}\text{D}\text{s}}} \right)\left(\frac{{\text{I}}_{\text{C}-\text{C}\text{D}\text{s}}}{{\text{I}}_{\text{R}}}\right)\left(\frac{{{\eta }}_{\text{C}-\text{C}\text{D}\text{s}}}{{{\eta }}_{\text{R}}}\right)$$ 11 Where, QY represents the Quantum yield, A represents the optical density at the excitation wavelength of 350 nm, ƞ (ƞ C−CDs = 1.33 and ƞ R = 1.76) represents the refractive index of solvent, and I represents the integrated fluorescence intensity. The subscript "C-CDs" and "R" refers to C-CDs sample and reference substance (Quinine sulfate), respectively. Sensing of Fe 3+ ion Fluorescent quenching of Fe 3+ ions was conducted in DDW at room temperature. For that, C-CDs solution (1ml in 300µM) reacted with 300µM concentration of various metal cations, include Mg 2+ , Pb 2+ , Na + , Ca 2+ , Mn 2+ , Cu 2+ , Zn 2+ , Ni 2+ , Co 2+ , K + , Cd 2+ , Cr 2+ , Fe 3+ and Sr 2+ . The resulting solution was lightly shaken and incubated at room temperature for 20 minutes. The quenching efficiency has been determined using a modified Stern–Volmer equation: $$\frac{\text{F}\text{o}}{\text{F}}=1+\text{K}\text{s}\text{v}\left[\text{Q}\right]$$ 12 The LOD (limit of detection) was calculated by the formula: $$LOD=3.3\left(\frac{\sigma }{S}\right)$$ 13 Where, Ksv is the Stern-Volmer constant, [Q] is Fe 3+ ion concentration, F and F o are the fluorescence intensities in the presence and absence of quencher, respectively. S and σ are the slope of curve and the standard deviation of the response, respectively. Detection of Fe 3+ in actual water sample To detection of Fe 3+ ions with C-CDs in the actual water sample, the concentration of Fe 3+ was studied by river water samples nearby our university campus. The first water sample was filtered through 0.22µM membrane and centrifuged at 8000 rpm for 20min for the removal of any suspended particles. The concentration of Fe 3+ in the actual water sample was calculated with the proposed method and then the fluorescence intensity of the solution was measured after adding different concentrations of Fe 3+ . The recovery rate of the samples was obtained from Equation: $$\text{R}\text{e}\text{c}\text{o}\text{v}\text{e}\text{r}\text{y}=\left(\frac{{\text{C}}_{2}-{\text{C}}_{1}}{{\text{C}}_{\text{o}}}\right)\times 100\text{%}$$ 14 Where, C o is the concentration of Fe 3+ added to the actual water sample, C 1 and C 2 are the concentration of Fe 3+ in the actual water sample before and after the addition of standard Fe 3+ . Result And Discussion Characterization of C-CDs To investigate the optical properties of the prepared C-CDs, UV-Vis and photoluminescence (PL) spectroscopy were recorded. The UV–vis absorbance curve shows two bands at 250 nm and 323 nm. The absorption peaks at 250 nm and 325 nm, which could be assigned to (π–π*) transitions of C = C bonds and (n–π*) transitions of C = O bonds, respectively (Fig. 2 a). The PL spectra of C-CDs under various excitation wavelengths (Fig. 2 b). The PL behaviour of C-CDs was dependent on the excitation wavelength when the excitation wavelength was changed from 300 to 390 nm in 10 nm increments. The emission peak toward a longer wavelength is due to the photoinduced electrons and holes present in C-CDs at different surfaces of energy traps. The maximum emission was noted at 460 nm (cyan colour), with an excitation wavelength of 370 nm. A smaller particle will have a visible PL effect at a lower wavelength, while a larger particle will exhibit PL at a higher wavelength [ 25 ]. FTIR spectra has been used to identify the functional groups of C-CDs before and after adsorption, as shown in Fig. 3 a. The peaks around 3440 cm − 1 (attributed to the O–H stretching vibrations), 2918cm − 1 (correspond to C–H stretching vibrations), 1610cm − 1 (corresponded to C = O stretching), 1321 cm − 1 (ascribed to C–O stretching vibrations of carboxylic ester group) and the peak observed around 1017cm − 1 (attributed to C = O vibrations). Figure. 3b displays the FTIR spectrum of C-CDs after the adsorption of MB at the surface of C-CDs. These minor peaks changes after MB dye adsorption are due to their involvement in the adsorption process through Van der Waals forces (weak electrostatic interaction) [ 26 ]. X-ray diffraction (XRD) pattern depicted a broad peak at 2θ = 21.5° and a weak peak at 2θ = 43.3° that are assigned to (002) and (101) diffraction patterns of graphitic carbon respectively, (Fig. 3 c). The former peak corresponds to interlayer spacing of 3.77 Å which is slightly more than the spacing between (002) planes in bulk graphite (3.44 Å). The XPS results showed that these C-CDs are composed of atomic C (282.8 eV) and O (529.4 eV), as can be seen in Fig. 4 a. The measured spectrum of C1s consisted of three noticeable peaks: 282.9 eV, 284.1 eV and 285.7 eV, which attributed to the C-H, C = C sp 2 and sp 3 C (C–OH), respectively (Fig. 4 b). In addition, the deconvolution spectrum of O1s showed three binding energy peaks: 529.1 eV, 529.7 eV and 531.9, which may be ascribed to the C-O, C–O–C and O-C = O/C = O, respectively (Fig. 4 c). HRTEM is used to study microporous materials at atomic scale. Figure. 5a shows the presence of spherical C-CDs ranging below 10 nm. The distribution curve displayed that nearly 15% C-CDs had diameter in the range of 4.5 nm, while 7.5% of the C-CDs had diameter in the range of 5.5 nm, as shown in Fig. 5 b. The zeta potential measurement of C-CDs exhibits that the C-CDs were negatively charged surface (-16.18 mV) due to the functionalization of the carboxylic group over the surface, as seen in Fig. 5 c. Effect of pH pH is a significant parameter determining the adsorption efficiency since it can control the adsorbent surface charge and the pollutants' ionization. Small amounts of dilute HCl or NaOH were applied to adjust the pH. The adsorption efficiency increases with increasing initial pH in the ranges of 2–10 (Fig. 6 a). The low adsorption efficiency observed at pH 2 is due to less number of negatively charged adsorbent sites and extra H + sites presented at the C-CDs surface. The presence of the excess H + ions competing for adsorption sites with the cations groups on the dye [ 27 , 28 ]. The maximum adsorption of the MB dye was observed at pH 10. Based on the results, pH = 10 was chosen as the desired pH for further studies. Effect of Adsorbent Dose and time In order to study the effect of C-CDs dose (g) on the removal of MB, the experimentation was carried out with an initial concentration of 100 mg L − 1 and pH 10 under the contact time between 30 to 120 min, while the amount of adsorbent added was varied. Figure. 6b illustrates the plot between the percent adsorption efficiency against the dose of adsorbent at a different time. It was observed that the adsorption efficiency % of MB was increased with increasing adsorbent dose up to 0.04 g, then increased slowly with a further increase of adsorbent dose and afterward remained unchanged. The increase in adsorption efficiency was because of the increase in the available absorption surface sites for C-CDs. Thus, to get a better percent of adsorption efficiency of MB and to not use more quantity of adsorbent, 0.04 g was selected as the best mass of the adsorbent in the following studies. Effect of temperature The effect of temperature on uptake of MB onto C-CDs was studied in the temperature range of 303 to 343 K at varying initial dye concentrations. As shown in Fig. 7 a, an increase in temperature (303K to 343K) leads to a gradual reduction in the MB adsorption efficiency at different initial concentrations. Thermodynamic behaviors are applied to understand better the effect of temperature on the removal of dyes on adsorbents. Table 1 displays the thermodynamic parameters for the adsorption of MB (initial dye concentration = 100 mg/L) onto C-CDs. The negative value of ΔH o showed that the process is exothermic in nature (Fig. 7 b). ∆G o values obtained are negative, suggesting that the adsorption process is spontaneous when the temperature changes from 303 K–343 K without external energy. The ΔS o value achieved is -0.0063 (J/Mol.K). The negative sign revealed an decreasing randomness at the solid/liquid interface during the adsorption process [ 29 ]. Table 1 Thermodynamic parameters for the MB adsorption on C-CDs Sample ΔS o ( J/mol.K) ΔH o ( kJ/mol) R 2 ΔG o ( kJ/mol) Temperature (K) C-CDs -0.00636 -7.03048 0.9777 -5.14538 303 -4.95520 313 -4.99636 323 -4.94110 333 -4.83710 343 Effects of initial MB concentration and isotherm studies The effect of initial MB concentration is closely related to the sites present on the adsorbent surface. The adsorption capacity of C-CDs was shown to increase with increasing initial MB concentration from 10 to 100 (mg/L) due to the adsorption sites on the surface of C-CDs becoming saturated (Fig. 8 ) [ 30 ]. The adsorption capacity of the C-CDs was expressively dependent on the initial dye concentrations in the solution. The adsorption isotherms describe how the molecules of the adsorbate are dispersed among the solid and liquid phases when the adsorption process reaches an equilibrium state. In this study, we employed Langmuir, Freundlich, and Temkin isotherm model to analyze isotherm data. (Fig. 9 a and b). The Langmuir isotherm is a simple type of adsorption equilibrium model for single-layer adsorption on a homogeneous surface when no interaction occurs between adjacent adsorbed molecules [ 31 ]. Freundlich isotherm is used to describe reversible and non-ideal adsorption systems on heterogeneous surfaces [ 32 ]. Temkin model is based on the assumption that the heat of adsorption decreases linearly because of interactions between adsorbent and adsorbate [ 33 ]. A summary of the isotherm parameters calculated for the Langmuir, Freundlich, and Temkin models for each temperature (303 − 343 K) is given in Table 2 . Based on the results, the value of R 2 according to the Freundlich model is higher than the Langmuir model. The slope range for the Freundlich isotherm model was determined between 0–1, showing the adsorption intensity and surface heterogeneity. If 𝑛 = 1, the adsorption is linear, 𝑛 1 a physical process [ 34 ]. The high K F value is favorable at 303K, which gives the adsorption of aggregated molecules. Therefore, experimental data for the adsorption of MB using C-CDs with respect to R 2 followed the order; Freundlich > Temkin > Langmuir. Table 2 Isotherm model parameters for MB uptake by C-CDs (initial dye concentration = 10 − 100 mg/L, dosage of adsorbent = 0.04 g, pH ~ 10, solvent temperature = 303 − 343 K) Isotherm model Temperature (K) 303 313 323 333 343 Langmuir R 2 q max ( mg/g) K L (L/mg) 0.9741 188.679 0.0110 0.9761 188.682 0.0104 0.8328 208.33 0.0075 0.6135 454.54 0.0024 0.5597 769.23 0.0012 Freundlich R 2 K f (mg.g − 1 ) 1/n 0.9803 0.2442 1.3557 0.9833 0.1862 1.3392 0.9892 0.0142 1.3118 0.9891 -0.8729 1.10132 0.9954 -2.647 1.0442 Temkin b T R 2 A T (L g − 1 ) 35.518 0.9853 0.15948 34.152 0.9856 0.15581 33.054 0.9658 0.1346 33.857 0.9559 0.1159 32.714 0.9386 0.1096 Kinetics of adsorption The experimental data were calculated based on the (PFO) Pseudo-First-Order and (PSO) Pseudo-Second-Order models to understand the kinetics of the adsorption process. Table 3 displays the parameters of the PFO and PSO models. The PSO model provided a better explanation of adsorption for MB from adsorbent. In this study, the R 2 value of PSO for every initial dye concentration was observed to be higher than 0.97. At PSO, dye concentration increased with increasing the value of qe might be due to the high competition for vacant sites, leading to higher adsorption rates. A plot between (t/qt) versus time was drawn to express the PSO kinetic model (Fig. 10 ). Table 3 Parameters of kinetics model for adsorption of MB onto C-CDs ( a ) Pseudo-First-Order and ( b ) Pseudo-Second-Order ( time = 30−120 min, initial dye concentration = 10−100 mg/L, Dosage of adsorbent = 0.04 g). 3.7. Sensing of Fe 3+ ions with C-CDs The fluorescence quenching effect of C-CDs upon the addition of different metal ions was investigated. It could be concluded from Fig. 11 a that there is a decrease in fluorescence intensity after the addition of C-CDs and Fe 3+ . At the same time, other metal ions show a slight change in fluorescence intensity compared to free C-CDs. According to the results, the synthesis of C-CDs was shown good selectivity towards Fe 3+ over other metal ions and could be used as an efficient fluorescence probe for Fe 3+ ions. It can be seen that no obvious interference was observed in detection of Fe 3+ in the occupancy of other metal ions. Figure. 11b shows the possible mechanism of fluorescence quenching and strong interaction between the Fe 3+ and the surface groups of C-CDs, which transfer the photoelectron from C-CDs to the metal ions. The Fe 3+ ions absorbed on the surface of C-CDs and coordinated with these hydroxyl groups was due to the presence of phenolic hydroxyl group on the edges of C-CDs. This coordination interaction, electrons are transferred from the excited state of C-CDs to the empty d orbital of Fe 3+ and the formation of non-radiative electron/ hole pair. The sensitive and selective response of C-CDs to Fe 3+ ions at different concentrations is depicted in Fig. 11 c. The concentration of Fe 3+ was gradually increased with increasing fluorescence intensity of C-CDs. This result revealed the change in fluorescence intensity of C-CDs solution by Fe 3+ (200µm) was clearly visible under UV light of 360nm. Hence blue emission disappeared after the addition of Fe 3+ to the C-CDs solution. Figure. 11d displays the plot of C-CDs at various concentrations of Fe3 + (F o /F versus concentration of Fe 3+ ion) where F o and F are the fluorescence intensity of C-CDs at λex = 330, λem = 420 in the presence and absence of Fe 3+ . The value of R 2 was 0.991 for a concentration ranging from 0.01 to 100 µM. The plot didn’t fit the linear equation over the entire concentration range of 0.01 to 200 µM, indicating that both dynamic and static quenching processes occur in this sensor system. The LOD value of this proposed sensor is about 0.16µM. Determination of Fe 3+ in river water samples Based on the high sensitivity and good selectivity, we calculated its potential application in determining Fe 3+ in river water samples. Table 4 shows the recovery results of all the samples were between 81.09–96.98%, and the value of relative standard deviation (RSDs) was very low (0.98–1.97%), which indicated that the proposed method had achieved high accuracy. Table 4 Determination of Fe 3+ in the environmental water sample. Sample Added(µM) Measured(µM) Recovery (%) RSD (%) (n = 3) River Water 0 2 6 10 20 50 1.33 3.47 7.87 10.95 20.97 50.98 90.02 81.09 92.96 96.98 94.99 1.20 1.97 0.98 1.34 0.99 1.67 Conclusion The novel carbon dots were successfully synthesized from coriander leaves through a facile hydrothermal method as a plausible adsorbent for the removal of a cationic dye (MB) from wastewater. The optical property, crystalline structure, surface morphology, and adsorption behavior of C-CDs are all analyzed. The amount of MB adsorbed was studied by varying initial MB concentration, C-CDs dose, pH, and contact time. It is evident that the percentage adsorption increased with an increase in initial concentration of dye, and pH values also increased with an increase in MB adsorption percentages. The adsorption isotherms and kinetic models were fitted well with Freundlich and PSO model. Moreover, thermodynamic parameters indicated that the adsorption process is exothermic in nature, spontaneous and feasible. It was validated that the obtained C-CDs had been utilized as an environmental-friendly adsorbent for removing MB in wastewater. Eventually, the low-toxicity C-CDs demonstrated high selectivity sensitivity towards Fe 3+ over other metal ions. Declarations Acknowledgments Authors acknowledge with thanks to the Department of Chemistry, AMU, Aligarh, for the financial support to carry out this work. Notes The authors declare no competing financial interest. 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Elsevier, pp 109–134 Hu J, Jia W, Yu X, et al (2022) Carbon dots improve the nutritional quality of coriander ( Coriandrum sativum L.) by promoting photosynthesis and nutrient uptake. Environ Sci Nano 9:1651–1661. https://doi.org/10.1039/D1EN01079D Meng W, Bai X, Wang B, et al (2019) Biomass‐Derived Carbon Dots and Their Applications. ENERGY Environ Mater 2:172–192. https://doi.org/10.1002/eem2.12038 Tejwan N, Saha SK, Das J (2020) Multifaceted applications of green carbon dots synthesized from renewable sources. Adv Colloid Interface Sci 275:102046. https://doi.org/10.1016/j.cis.2019.102046 Sarkar C, Chowdhuri AR, Kumar A, et al (2018) One pot synthesis of carbon dots decorated carboxymethyl cellulose- hydroxyapatite nanocomposite for drug delivery, tissue engineering and Fe3+ ion sensing. Carbohydr Polym 181:710–718. https://doi.org/10.1016/j.carbpol.2017.11.091 Chen Y, Sun X, Pan W, et al (2020) Fe3+-Sensitive Carbon Dots for Detection of Fe3+ in Aqueous Solution and Intracellular Imaging of Fe3+ Inside Fungal Cells. Front Chem 7:1–9. https://doi.org/10.3389/fchem.2019.00911 Liu W, Diao H, Chang H, et al (2017) Green synthesis of carbon dots from rose-heart radish and application for Fe3+ detection and cell imaging. Sensors Actuators, B Chem 241:190–198. https://doi.org/10.1016/j.snb.2016.10.068 Sachdev A, Gopinath P (2015) Green synthesis of multifunctional carbon dots from coriander leaves and their potential application as antioxidants, sensors and bioimaging agents. Analyst 140:4260–4269. https://doi.org/10.1039/c5an00454c Rani UA, Ng LY, Ng CY, Mahmoudi E (2020) A review of carbon quantum dots and their applications in wastewater treatment. Adv Colloid Interface Sci 278:102124. https://doi.org/10.1016/j.cis.2020.102124 Bedolla PO, Feldbauer G, Wolloch M, et al (2014) Effects of van der Waals Interactions in the Adsorption of Isooctane and Ethanol on Fe(100) Surfaces. J Phys Chem C 118:17608–17615. https://doi.org/10.1021/jp503829c Soltani A, Faramarzi M, Mousavi Parsa SA (2021) A review on adsorbent parameters for removal of dye products from industrial wastewater. Water Qual Res J 56:181–193. https://doi.org/10.2166/wqrj.2021.023 Banerjee S, Chattopadhyaya MC (2017) Adsorption characteristics for the removal of a toxic dye, tartrazine from aqueous solutions by a low cost agricultural by-product. Arab J Chem 10:S1629–S1638. https://doi.org/10.1016/j.arabjc.2013.06.005 Teymoorian T, Hashemi N, Mousazadeh MH, Entezarian Z (2021) N, S doped carbon quantum dots inside mesoporous silica for effective adsorption of methylene blue dye. SN Appl Sci 3:1–14. https://doi.org/10.1007/s42452-021-04287-z Rahman MA, Amin SMR, Alam AMS (2012) Removal of Methylene Blue from Waste Water Using Activated Carbon Prepared from Rice Husk. Dhaka Univ J Sci 60:185–189. https://doi.org/10.3329/dujs.v60i2.11491 Hasani N, Selimi T, Mele A, et al (2022) Theoretical, Equilibrium, Kinetics and Thermodynamic Investigations of Methylene Blue Adsorption onto Lignite Coal. Molecules 27:1856. https://doi.org/10.3390/molecules27061856 Ederer J, Ecorchard P, Slušná MŠ, et al (2022) A Study of Methylene Blue Dye Interaction and Adsorption by Monolayer Graphene Oxide. Adsorpt Sci Technol 2022:1–16. https://doi.org/10.1155/2022/7385541 Mohamed F, Shaban M, Zaki SK, et al (2022) Activated carbon derived from sugarcane and modified with natural zeolite for efficient adsorption of methylene blue dye: experimentally and theoretically approaches. Sci Rep 12:18031. https://doi.org/10.1038/s41598-022-22421-8 Momina, Mohammad S, Suzylawati I (2020) Study of the adsorption/desorption of MB dye solution using bentonite adsorbent coating. J Water Process Eng 34:101155. https://doi.org/10.1016/j.jwpe.2020.101155 Additional Declarations No competing interests reported. Supplementary Files GraphicalAbstract.png Graphical Abstract Cite Share Download PDF Status: Published Journal Publication published 16 Jun, 2023 Read the published version in Journal of Inorganic and Organometallic Polymers and Materials → Version 1 posted Editorial decision: Major revision 03 Apr, 2023 Reviews received at journal 07 Mar, 2023 Reviewers agreed at journal 11 Feb, 2023 Reviewers invited by journal 11 Feb, 2023 Editor assigned by journal 11 Feb, 2023 Submission checks completed at journal 10 Feb, 2023 First submitted to journal 09 Feb, 2023 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-2569839","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":175285907,"identity":"45ac7738-31b7-4133-a3d6-f710297366a1","order_by":0,"name":"Hesam Salimi Shahraki","email":"","orcid":"","institution":"Aligarh Muslim University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Hesam","middleName":"Salimi","lastName":"Shahraki","suffix":""},{"id":175285908,"identity":"ee914457-e9e9-43d6-bf84-991ee3bb941e","order_by":1,"name":"Anees Ahmad","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA2ElEQVRIiWNgGAWjYPCCA0CcfICBsYE0LWkJJGvJMSBOC//s5oMPf9TcieZvz/km8XOHjRwD++GjG/BpkbhzLNmY59iz3Bln3m6T7D2TZszAk5Z2A681N3LMpBnYDuc23MjdJsHbdjixQYLHDK8W+Rv533/++Hc4d/6NnGeSf4nRYnAjh40BaHjuBiBDmihbDG+kGUvz9h3O3XjmmbG1bFuaMRshv8jdSH748ce3w7nzjic/vPm2zUaOn/3wMfzeRwIsEiCSjVjlIMD8gRTVo2AUjIJRMHIAAI4qVPypwE71AAAAAElFTkSuQmCC","orcid":"","institution":"Aligarh Muslim University","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Anees","middleName":"","lastName":"Ahmad","suffix":""},{"id":175285909,"identity":"033a5c31-ab04-49f2-a4b9-b6277a99aa93","order_by":2,"name":"Qurtulen Qurtulen","email":"","orcid":"","institution":"Aligarh Muslim University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Qurtulen","middleName":"","lastName":"Qurtulen","suffix":""},{"id":175285910,"identity":"214c6400-e912-43ea-857f-8eb3d4449ffb","order_by":3,"name":"Sugandhi Gupta","email":"","orcid":"","institution":"Aligarh Muslim University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Sugandhi","middleName":"","lastName":"Gupta","suffix":""},{"id":175285912,"identity":"ae4876f9-5358-4b0b-bebb-359fb25ed36b","order_by":4,"name":"Uzma Meraj","email":"","orcid":"","institution":"Aligarh Muslim University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Uzma","middleName":"","lastName":"Meraj","suffix":""}],"badges":[],"createdAt":"2023-02-09 16:44:21","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-2569839/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-2569839/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s10904-023-02707-8","type":"published","date":"2023-06-16T21:11:17+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":32945470,"identity":"48d8fb7e-f2e2-491c-be2e-c2dede2dc29b","added_by":"auto","created_at":"2023-02-14 22:25:15","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":8654,"visible":true,"origin":"","legend":"\u003cp\u003eMolecular structure of MB (Molecular Weight = 319.85 g mol\u003csup\u003e−1\u003c/sup\u003e, λ\u003csub\u003emax\u003c/sub\u003e = 664 nm)\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-2569839/v1/4fe12e98b5459e6c4738d648.png"},{"id":32945471,"identity":"2fc2c4d8-af16-423a-ab09-00b4063f105d","added_by":"auto","created_at":"2023-02-14 22:25:15","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":139058,"visible":true,"origin":"","legend":"\u003cp\u003eUV-visible absorption spectrum (\u003cstrong\u003ea\u003c/strong\u003e) and PL spectra (\u003cstrong\u003eb\u003c/strong\u003e) of C-CDs\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-2569839/v1/5e95dcbb2523ec92e7ab9983.png"},{"id":32945734,"identity":"6c0e78a7-3e95-4282-b8f6-08900fe8a490","added_by":"auto","created_at":"2023-02-14 22:33:15","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":107642,"visible":true,"origin":"","legend":"\u003cp\u003eFTIR spectra of C-CDs (\u003cstrong\u003ea\u003c/strong\u003e) before MB adsorption (\u003cstrong\u003eb\u003c/strong\u003e) after MB adsorption and (\u003cstrong\u003ec\u003c/strong\u003e) XRD patterns of C-CDs\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-2569839/v1/bc3ed0444d1f270cc70a3692.png"},{"id":32945731,"identity":"893a1529-1f66-4b8b-95c9-a5db7021c1a2","added_by":"auto","created_at":"2023-02-14 22:33:15","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":77052,"visible":true,"origin":"","legend":"\u003cp\u003eXPS spectra of (\u003cstrong\u003ea\u003c/strong\u003e) C-CDs and high resolution XPS spectra of (\u003cstrong\u003eb\u003c/strong\u003e) C1s of C-CDs and (\u003cstrong\u003ec\u003c/strong\u003e) O1s of C-CDs\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-2569839/v1/34482c07af668469548ba52d.png"},{"id":32945475,"identity":"fa143984-4567-4a0e-946b-167ba072788a","added_by":"auto","created_at":"2023-02-14 22:25:15","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":323164,"visible":true,"origin":"","legend":"\u003cp\u003e(\u003cstrong\u003ea\u003c/strong\u003e) HRTEM image of C-CDs, (\u003cstrong\u003eb\u003c/strong\u003e) particle size distribution and (\u003cstrong\u003ec\u003c/strong\u003e) Zeta potential distributions of the C-CDs\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-2569839/v1/5efaa100ad0f25a94daa8448.png"},{"id":32945477,"identity":"8b46d7c0-612a-4c48-8d73-fa256b8c8c7e","added_by":"auto","created_at":"2023-02-14 22:25:15","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":60910,"visible":true,"origin":"","legend":"\u003cp\u003e(\u003cstrong\u003ea\u003c/strong\u003e) Effect of pH and (\u003cstrong\u003eb\u003c/strong\u003e) Effect of time and dosage on the adsorption of MB onto C-CDs (Initial concentration: 100 ppm, volume of adsorbate = 50 mL)\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-2569839/v1/59d44a00207ca2a21b2c4fca.png"},{"id":32945473,"identity":"4c281562-9d3d-4d77-8894-8559f703e370","added_by":"auto","created_at":"2023-02-14 22:25:15","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":98954,"visible":true,"origin":"","legend":"\u003cp\u003e(\u003cstrong\u003ea\u003c/strong\u003e) Effect of temperature on the MB adsorption by C-CDs, (\u003cstrong\u003eb\u003c/strong\u003e) Van't Hoff plot for MB adsorption\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-2569839/v1/49689bf5e837840360f9c764.png"},{"id":32945732,"identity":"5625a936-da0f-4c4d-9b45-bfe16ed6b703","added_by":"auto","created_at":"2023-02-14 22:33:15","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":64668,"visible":true,"origin":"","legend":"\u003cp\u003eEffect of initial MB concentration on adsorption capacity by C-CDs at different temperatures\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-2569839/v1/16a44f206faed513b9f4e200.png"},{"id":32946141,"identity":"f66acb4c-fc90-4b83-9b4e-806621a0f919","added_by":"auto","created_at":"2023-02-14 22:41:15","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":98036,"visible":true,"origin":"","legend":"\u003cp\u003eAdsorption isotherm models (\u003cstrong\u003ea\u003c/strong\u003e) Freundlich model and (\u003cstrong\u003eb\u003c/strong\u003e) Temkin model.\u003c/p\u003e","description":"","filename":"9.png","url":"https://assets-eu.researchsquare.com/files/rs-2569839/v1/e6e28295b5270c9e1f8a927e.png"},{"id":32945735,"identity":"97d9997b-d2dd-4d57-80b4-7ab720d91ac7","added_by":"auto","created_at":"2023-02-14 22:33:15","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":78157,"visible":true,"origin":"","legend":"\u003cp\u003ePSO kinetic plots for the MB adsorption by C-CDs (dose = 0.04 g, temperature = 303 K)\u003c/p\u003e","description":"","filename":"10.png","url":"https://assets-eu.researchsquare.com/files/rs-2569839/v1/04c6537a96682644a97cac60.png"},{"id":32945480,"identity":"c51f4b61-e9d9-4332-be00-34f62385e4c4","added_by":"auto","created_at":"2023-02-14 22:25:15","extension":"png","order_by":11,"title":"Figure 11","display":"","copyAsset":false,"role":"figure","size":209342,"visible":true,"origin":"","legend":"\u003cp\u003e(\u003cstrong\u003ea\u003c/strong\u003e) Quenching efficiency of the C-CDs to various heavy metal ion, (\u003cstrong\u003eb\u003c/strong\u003e) The mechanism of fluorescence quenching, (\u003cstrong\u003ec\u003c/strong\u003e) Fluorescent response of synthesized C-CDs to different concentration of Fe\u003csup\u003e3+\u003c/sup\u003e ion and (d) F\u003csub\u003eo\u003c/sub\u003e/F plot of various concentration of Fe\u003csup\u003e3+\u003c/sup\u003e ions.\u003c/p\u003e","description":"","filename":"11.png","url":"https://assets-eu.researchsquare.com/files/rs-2569839/v1/8cb4b97c90ebc1e3665d0339.png"},{"id":44731760,"identity":"ffc058a2-cd09-4f2d-bb01-d881c2bdb488","added_by":"auto","created_at":"2023-10-16 21:47:40","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1426006,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-2569839/v1/3f2f6784-0257-4b58-91ae-be9163e3eedc.pdf"},{"id":32945481,"identity":"3fcd1906-f39c-4a91-b44a-932c870a7b51","added_by":"auto","created_at":"2023-02-14 22:25:15","extension":"png","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":680570,"visible":true,"origin":"","legend":"\u003cp\u003eGraphical Abstract\u003c/p\u003e","description":"","filename":"GraphicalAbstract.png","url":"https://assets-eu.researchsquare.com/files/rs-2569839/v1/690a1c77ffde70021a24a3fc.png"}],"financialInterests":"No competing interests reported.","formattedTitle":"Carbon dots from natural‐product: applications as adsorbent and Sensing of Fe 3+ Ions","fulltext":[{"header":"Introduction","content":"\u003cp\u003eIn recent years, the heightened awareness has emerged that by 2050, many countries will face significant problems related to the lack of freshwater [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e]. The latest projections by the (UNESCO) United Nations Educational, Scientific and Cultural Organization suggest that the world population will reach 9.3\u0026nbsp;billion in 2050, and two-thirds of people will live under water stress [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. The reuse and recycling of wastewater after contamination treatment is a serious issue in many areas to ensure water security at the national level. Contamination of water sources is increasing by many factors, such as climate, precipitation, population growth and related activities [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. Wastewater contains a variety of pollutants, and Some wastewater often includes several classes of contaminants, such as anions, heavy metals, dyes, and different types of organic compounds [\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]. Large quantities of dyes have been used as raw materials and produced as end products in textiles, clothing, food, etc. It has been estimated that the textile industries are consumed more than 7 x 10\u003csup\u003e5\u003c/sup\u003e tons of dyes, which makes them the top three pollutants [\u003cspan additionalcitationids=\"CR6 CR7\" citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e]. The ingestion of water polluted with dyes poses a potential risk or threat to all forms of life and has negative effects on human health. Many different methods are available for removing dyes from wastewater, including ion exchange, adsorption, filtration, and chemical precipitation [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e, \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]. Among these methods, adsorption has significant advantages over other processes because of the flexibility and simplicity of design, cost savings, and ease of operation with adaptable designs [\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e]. Over recent years, a wide variety of adsorbent materials have been recommended for efficient dye removal, including graphene, activated carbon, metal oxides/hydroxides, polymers, and zeolites, but It should be noted these adsorbents have several problematic issues. In many cases, the adsorption capacity is quite low, with a long time taken to reach equilibrium [\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e, \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]. Accordingly, the search for a high-capacity adsorbent with low toxicity and functional ability continues under the key condition of economic feasibility. Recently, Carbon Dots (CDs) have emerged as efficient absorbents for the removal of dyes from wastewater [\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]. CDs can be generally synthesized using any carbon sources, such as chemicals, graphene, plants, and food wastes. Among all types of carbon sources, biomass and its derivatives, such as bagasse, fruit peel, tea residue, and leaves, received considerable attention due to renewability, low cost, and availability [\u003cspan additionalcitationids=\"CR16\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eTaking into consideration the above, we report a green and novel synthesis of carbon dots derived from coriander leaves via a simple hydrothermal method. This approach is less time-consuming and uses water as a solvent without any additional surface passivating agent and have a high (QY) quantum yield of 12.0%. Coriander, known as Chinese parsley, is edible and rich in proteins and carbohydrates naturally, which is abundant in oxygen and carbon elements. The use of leaves as potential sources not only meets the urgent requirement for large-scale production of Carbon dots, but also improves the development of sustainable applications [\u003cspan additionalcitationids=\"CR19\" citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eIt is well known that the large amount of Fe\u003csup\u003e3+\u003c/sup\u003e in human body may cause severe diseases like Alzheimer\u0026rsquo;s disease, liver and kidney damage, and Parkinson\u0026rsquo;s disease [\u003cspan additionalcitationids=\"CR22\" citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e]. In view of the above, the selective and sensitive detection of Fe\u003csup\u003e3+\u003c/sup\u003e is extremely important. The synthesized C-CDs have shown good sensitivity toward Fe\u003csup\u003e3+\u003c/sup\u003e over other metal ions. In this study, we have presented C-CDs that possess the following significant advantages; a) Eco-friendly adsorbent for removal of MB from wastewater, b) Synthesized through the hydrothermal method, c) Excellent sensitivity for Fe\u003csup\u003e3+\u003c/sup\u003e ions.\u003c/p\u003e"},{"header":"Materials And Methods","content":"\u003cp\u003eChemicals and solutions\u003c/p\u003e\n\u003cp\u003eFreshly harvested coriander leaves were bought from the local market of Aligarh and thoroughly washed before use. Methylene blue dye was purchased from Merck chemical Co. Figure. 1 exhibits the molecular structure of the MB (C\u003csub\u003e16\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003eN\u003csub\u003e3\u003c/sub\u003eSCI). CaCl\u003csub\u003e2\u003c/sub\u003e, FeCl\u003csub\u003e3\u003c/sub\u003e, Zn(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e, NiCl\u003csub\u003e2\u003c/sub\u003e, KOH, NaOH, CrCl\u003csub\u003e3\u003c/sub\u003e, CdCl\u003csub\u003e2\u003c/sub\u003e, PbCl\u003csub\u003e2\u003c/sub\u003e, MnCl\u003csub\u003e2\u003c/sub\u003e, CuCl\u003csub\u003e2\u003c/sub\u003e, MgCl\u003csub\u003e2\u003c/sub\u003e, NaH\u003csub\u003e2\u003c/sub\u003ePO\u003csub\u003e4\u003c/sub\u003e and Na\u003csub\u003e2\u003c/sub\u003eHPO\u003csub\u003e4\u003c/sub\u003e were supplied from Industrial Research Laboratories, AMU. All chemicals were used as-received without further purifications.\u003c/p\u003e\n\u003cp\u003eSynthesis of C-CDs.\u003c/p\u003e\n\u003cp\u003eBriefly, 5 g of the fresh coriander leaves were finely crushed using a mortar and pestle and added to 50 mL of DDW by stirring at room temperature for 30 min. The solution was transferred to hydrothermal process for 5 h at 210\u0026deg;C. The mixture was allowed to cool at room temperature, and the large black insoluble portion was filtered through a 0.22\u0026micro;m filter membrane. The brownish-yellow C-CDs solution obtained then was kept at 4\u0026deg;C for further studies and characterizations [\u003cspan class=\"CitationRef\"\u003e24\u003c/span\u003e].\u003c/p\u003e\n\u003cp\u003eCharacterization\u003c/p\u003e\n\u003cp\u003eThe optical properties of the C-CDs were measured by using UV-Vis spectroscopy (Perkin Elmer LAMBDA-45) and PL spectra (HITACHI- F-2500 FL). The main functional groups of C-CDs were identified by Fourier transform spectroscopy (Perkin Elmer IR spectrometer) before and after adsorption. X-Ray diffraction or XRD (Rigaku TTRAX III) was used to determine the crystallographic structure of the adsorbent. X-ray photoelectron spectroscopy (XPS) (PHI 5000 Versa Probe III) is widely applied to determine the elemental composition. The surface charge of the C-CDs was determined by zeta potential (ZEECOM ZC-3000).\u003c/p\u003e\n\u003cp\u003eBatch equilibrium studies\u003c/p\u003e\n\u003cp\u003eThe impact of adsorbent dose (0.01\u0026ndash;0.05 g), pH (2\u0026ndash;10), temperature (303-343K), and initial MB concentration (10\u0026ndash;100 mg/L) for the removal of a basic dye (MB) onto C-CDs were studied. In each experiment, we added a desired amount of C-CDs to 50 mL of dye solution in a 100 mL conical flask under stirring to achieve equilibrium. At equilibrium, the concentration of MB was measured at 664 nm wavelength, using UV\u0026ndash;vis Spectrophotometer. The adsorption efficiency (q%) and capacity (q\u003csub\u003ee\u003c/sub\u003e) of the adsorbent can be calculated by the following equations:\u003c/p\u003e\n\u003cdiv class=\"Equation\" id=\"Equ1\"\u003e\n \u003cdiv class=\"mathdisplay\" id=\"FileID_Equ1\" name=\"EquationSource\"\u003e$${\\text{q}}_{\\text{e}}\\left(\\frac{\\text{m}\\text{g}}{\\text{g}}\\right)=\\text{V}({\\text{C}}_{\\text{i}}-{\\text{C}}_{\\text{e}})/\\text{M}$$\u003c/div\u003e\n \u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Equation\" id=\"Equ2\"\u003e\n \u003cdiv class=\"mathdisplay\" id=\"FileID_Equ2\" name=\"EquationSource\"\u003e$$\\text{q}\\text{%}=\\frac{{\\text{C}}_{\\text{i}}-{\\text{C}}_{\\text{e}}}{{\\text{C}}_{\\text{i}}}\\text{*}100$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e2\u003c/div\u003e\u003c/div\u003e\u003cp\u003eWhere, V and M are volume of solution (L) and mass of adsorbent used (g), respectively. C\u003csub\u003ee\u003c/sub\u003e is the equilibrium concentration (mg/L), and C\u003csub\u003ei\u003c/sub\u003e is the initial concentration of adsorbate in the solution (mg/L).\u003c/p\u003e\u003cp\u003eEffect of temperature (thermodynamic and kinetics isotherms)\u003c/p\u003e\u003cp\u003eThe impact of temperature on MB dye uptake onto the surface of C-CDs, a series of experiments was performed at 303K, 313K, 323K, and 343K. Thermodynamic calculations were performed through the following equations:\u003c/p\u003e\u003cdiv class=\"Equation\" id=\"Equ3\"\u003e\u003cdiv class=\"mathdisplay\" id=\"FileID_Equ3\" name=\"EquationSource\"\u003e$${\\text{K}}_{\\text{d}}=\\frac{{\\text{q}}_{\\text{e}}}{{\\text{C}}_{\\text{e}}}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e3\u003c/div\u003e\u003c/div\u003e\u003cdiv class=\"Equation\" id=\"Equ4\"\u003e\u003cdiv class=\"mathdisplay\" id=\"FileID_Equ4\" name=\"EquationSource\"\u003e$${{\\Delta }\\text{G}}^{\\text{o}}=-\\text{R}\\text{T}\\text{l}\\text{n}{\\text{K}}_{\\text{d}}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e4\u003c/div\u003e\u003c/div\u003e\u003cdiv class=\"Equation\" id=\"Equ5\"\u003e\u003cdiv class=\"mathdisplay\" id=\"FileID_Equ5\" name=\"EquationSource\"\u003e$$\\text{l}\\text{n}{\\text{K}}_{\\text{d}}=\\frac{{{\\Delta }\\text{S}}^{\\text{o}}}{\\text{R}}-\\frac{{\\varDelta \\text{H}}^{\\text{o}}}{\\text{R}\\text{T}}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e5\u003c/div\u003e\u003c/div\u003e\u003cp\u003eWhere, 𝐾\u003csub\u003e𝑑\u003c/sub\u003e is distribution coefficient, \u0026Delta;𝐺\u003csup\u003eo\u003c/sup\u003e is Gibb\u0026rsquo;s free energy (kJ mol\u003csup\u003e\u0026minus;1\u003c/sup\u003e), \u0026Delta;H\u003csup\u003eo\u003c/sup\u003e and \u0026Delta;S\u003csup\u003eo\u003c/sup\u003e are obtained from the slope and intercept of Van\u0026apos;t Hoff plot of ln K\u003csub\u003ed\u003c/sub\u003e versus 1/T, respectively. Values of K\u003csub\u003eL\u003c/sub\u003e can be determined from the relation ln q\u003csub\u003ee\u003c/sub\u003e/C\u003csub\u003ee\u003c/sub\u003e.\u003c/p\u003e\u003cp\u003eThe experimental data were analyzed with the Pseudo-First-Order (PFO) and (PSO) Pseudo-Second-Order models to improve understanding of kinetics adsorption process. The PFO model assumes that molecules of dye filled sites have linear relationship with rate of adsorption. The PFO equation can be expressed using Eq:\u003c/p\u003e\u003cdiv class=\"Equation\" id=\"Equ6\"\u003e\u003cdiv class=\"mathdisplay\" id=\"FileID_Equ6\" name=\"EquationSource\"\u003e$$\\text{log}\\left({\\text{q}}_{\\text{e}}-{\\text{q}}_{\\text{t}}\\right)=\\text{l}\\text{o}\\text{g}{\\text{q}}_{\\text{e}}-\\frac{{\\text{K}}_{1}}{2.303}\\text{t}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e6\u003c/div\u003e\u003c/div\u003e\u003cp\u003eWhere, k\u003csub\u003e1\u003c/sub\u003e is rate constant of PFO (1/h), q\u003csub\u003ee\u003c/sub\u003e is the equilibrium adsorption capacity (mg/g) and q\u003csub\u003et\u003c/sub\u003e is quantity of adsorbate-adsorbed at time (mg/g).\u003c/p\u003e\u003cp\u003eThe PSO model is the most suitable for explaining the adsorption kinetics. The PSO equation is generally expressed as follows:\u003c/p\u003e\u003cdiv class=\"Equation\" id=\"Equ7\"\u003e\u003cdiv class=\"mathdisplay\" id=\"FileID_Equ7\" name=\"EquationSource\"\u003e$$\\frac{\\text{t}}{{\\text{q}}_{\\text{t}}}=\\frac{1}{{\\text{K}}_{2}{\\text{q}}_{\\text{e}}^{2}}+\\frac{\\text{t}}{{\\text{q}}_{\\text{e}}}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e7\u003c/div\u003e\u003c/div\u003e\u003cp\u003eThe intercept and slope of linear plot of t/q\u003csub\u003et\u003c/sub\u003e vs t can be calculated the values of q\u003csub\u003ee\u003c/sub\u003e and k\u003csub\u003e2\u003c/sub\u003e. Where, k\u003csub\u003e2\u003c/sub\u003e is rate constant of PSO.\u003c/p\u003e\u003cp\u003eAdsorption isotherm studies\u003c/p\u003e\u003cp\u003eBatch adsorption study was performed in 50 mL beaker having 0.04g C-CDs with different initial dye concentrations (10, 20, 40, 60, 80 and 100 mg/L). In this study, the Langmuir, Freundlich, and Temkin model is offered in the following Eqs:\u003c/p\u003e\u003cdiv class=\"Equation\" id=\"Equ8\"\u003e\u003cdiv class=\"mathdisplay\" id=\"FileID_Equ8\" name=\"EquationSource\"\u003e$$\\frac{{\\text{C}}_{\\text{e}}}{{\\text{q}}_{\\text{e}}}=\\frac{1}{{\\text{q}}_{\\text{m}}{\\text{k}}_{\\text{L}}}+\\frac{{\\text{C}}_{\\text{e}}}{{\\text{q}}_{\\text{m}}}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e8\u003c/div\u003e\u003c/div\u003e\u003cdiv class=\"Equation\" id=\"Equ9\"\u003e\u003cdiv class=\"mathdisplay\" id=\"FileID_Equ9\" name=\"EquationSource\"\u003e$$\\text{l}\\text{o}\\text{g}{\\text{q}}_{\\text{e}}=\\text{l}\\text{o}\\text{g}{\\text{K}}_{\\text{f}}+\\frac{1}{{\\text{n}}_{\\text{f}}}\\text{l}\\text{o}\\text{g}{\\text{C}}_{\\text{e}}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e9\u003c/div\u003e\u003c/div\u003e\u003cdiv class=\"Equation\" id=\"Equ10\"\u003e\u003cdiv class=\"mathdisplay\" id=\"FileID_Equ10\" name=\"EquationSource\"\u003e$${\\text{q}}_{\\text{e}}=\\text{B}\\text{l}\\text{n}{\\text{K}}_{\\text{T}}+\\text{B}\\text{l}\\text{n}\\text{C}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e10\u003c/div\u003e\u003c/div\u003e\u003cp\u003eWhere, K\u003csub\u003eL\u003c/sub\u003e and K\u003csub\u003ef\u003c/sub\u003e are the Langmuir and Freundlich constant, respectively, q\u003csub\u003em\u003c/sub\u003e is the maximum adsorption capacity, \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\frac{1}{{\\text{n}}_{\\text{f}}}\\)\u003c/span\u003e\u003c/span\u003e is adsorption intensity, b\u003csub\u003eT\u003c/sub\u003e and K\u003csub\u003eT\u003c/sub\u003e are Temkin isotherm constant and equilibrium binding constant (L mol\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), respectively. B = (R\u003csub\u003eT\u003c/sub\u003e/b\u003csub\u003eT\u003c/sub\u003e) related to the heat of adsorption (J/mol).\u003c/p\u003e\u003cp\u003eCalculation of quantum yield\u003c/p\u003e\u003cp\u003eQuantum Yield (QY) of C-CDs can be measured by comparing (QY) quinine sulfate as a reference. C-CDs were dissolved in DDW, while quinine sulfate was dissolved in in 0.5 M H\u003csub\u003e2\u003c/sub\u003eSO\u003csub\u003e4\u003c/sub\u003e (QY\u0026thinsp;=\u0026thinsp;0.54, \u0026eta;\u0026thinsp;=\u0026thinsp;1.33). The QY of CQDs was obtained based on Eq:\u003c/p\u003e\u003cdiv class=\"Equation\" id=\"Equ11\"\u003e\u003cdiv class=\"mathdisplay\" id=\"FileID_Equ11\" name=\"EquationSource\"\u003e$${\\text{Q}\\text{Y}}_{\\text{C}-\\text{C}\\text{D}\\text{s}}= {\\text{Q}\\text{Y}}_{\\text{R}}\\left(\\frac{{\\text{A}}_{\\text{R}}}{{\\text{A}}_{\\text{C}-\\text{C}\\text{D}\\text{s}}} \\right)\\left(\\frac{{\\text{I}}_{\\text{C}-\\text{C}\\text{D}\\text{s}}}{{\\text{I}}_{\\text{R}}}\\right)\\left(\\frac{{{\\eta }}_{\\text{C}-\\text{C}\\text{D}\\text{s}}}{{{\\eta }}_{\\text{R}}}\\right)$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e11\u003c/div\u003e\u003c/div\u003e\u003cp\u003eWhere, QY represents the Quantum yield, A represents the optical density at the excitation wavelength of 350 nm, ƞ (ƞ\u003csub\u003eC\u0026minus;CDs\u003c/sub\u003e = 1.33 and ƞ\u003csub\u003eR\u003c/sub\u003e = 1.76) represents the refractive index of solvent, and I represents the integrated fluorescence intensity. The subscript \u0026quot;C-CDs\u0026quot; and \u0026quot;R\u0026quot; refers to C-CDs sample and reference substance (Quinine sulfate), respectively.\u003c/p\u003e\u003cp\u003eSensing of Fe\u003csup\u003e3+\u003c/sup\u003e ion\u003c/p\u003e\u003cp\u003eFluorescent quenching of Fe\u003csup\u003e3+\u003c/sup\u003e ions was conducted in DDW at room temperature. For that, C-CDs solution (1ml in 300\u0026micro;M) reacted with 300\u0026micro;M concentration of various metal cations, include Mg\u003csup\u003e2+\u003c/sup\u003e, Pb\u003csup\u003e2+\u003c/sup\u003e, Na\u003csup\u003e+\u003c/sup\u003e, Ca\u003csup\u003e2+\u003c/sup\u003e, Mn\u003csup\u003e2+\u003c/sup\u003e, Cu\u003csup\u003e2+\u003c/sup\u003e, Zn\u003csup\u003e2+\u003c/sup\u003e, Ni\u003csup\u003e2+\u003c/sup\u003e, Co\u003csup\u003e2+\u003c/sup\u003e, K\u003csup\u003e+\u003c/sup\u003e, Cd\u003csup\u003e2+\u003c/sup\u003e, Cr\u003csup\u003e2+\u003c/sup\u003e, Fe\u003csup\u003e3+\u003c/sup\u003e and Sr\u003csup\u003e2+\u003c/sup\u003e. The resulting solution was lightly shaken and incubated at room temperature for 20 minutes. The quenching efficiency has been determined using a modified Stern\u0026ndash;Volmer equation:\u003c/p\u003e\u003cdiv class=\"Equation\" id=\"Equ12\"\u003e\u003cdiv class=\"mathdisplay\" id=\"FileID_Equ12\" name=\"EquationSource\"\u003e$$\\frac{\\text{F}\\text{o}}{\\text{F}}=1+\\text{K}\\text{s}\\text{v}\\left[\\text{Q}\\right]$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e12\u003c/div\u003e\u003c/div\u003e\u003cp\u003eThe LOD (limit of detection) was calculated by the formula:\u003c/p\u003e\u003cdiv class=\"Equation\" id=\"Equ13\"\u003e\u003cdiv class=\"mathdisplay\" id=\"FileID_Equ13\" name=\"EquationSource\"\u003e$$LOD=3.3\\left(\\frac{\\sigma }{S}\\right)$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e13\u003c/div\u003e\u003c/div\u003e\u003cp\u003eWhere, Ksv is the Stern-Volmer constant, [Q] is Fe\u003csup\u003e3+\u003c/sup\u003e ion concentration, F and F\u003csub\u003eo\u003c/sub\u003e are the fluorescence intensities in the presence and absence of quencher, respectively. S and \u0026sigma; are the slope of curve and the standard deviation of the response, respectively.\u003c/p\u003e\u003cp\u003eDetection of Fe\u003csup\u003e3+\u003c/sup\u003ein actual water sample\u003c/p\u003e\u003cp\u003eTo detection of Fe\u003csup\u003e3+\u003c/sup\u003e ions with C-CDs in the actual water sample, the concentration of Fe \u003csup\u003e3+\u003c/sup\u003e was studied by river water samples nearby our university campus. The first water sample was filtered through 0.22\u0026micro;M membrane and centrifuged at 8000 rpm for 20min for the removal of any suspended particles. The concentration of Fe\u003csup\u003e3+\u003c/sup\u003e in the actual water sample was calculated with the proposed method and then the fluorescence intensity of the solution was measured after adding different concentrations of Fe\u003csup\u003e3+\u003c/sup\u003e. The recovery rate of the samples was obtained from Equation:\u003c/p\u003e\u003cdiv class=\"Equation\" id=\"Equ14\"\u003e\u003cdiv class=\"mathdisplay\" id=\"FileID_Equ14\" name=\"EquationSource\"\u003e$$\\text{R}\\text{e}\\text{c}\\text{o}\\text{v}\\text{e}\\text{r}\\text{y}=\\left(\\frac{{\\text{C}}_{2}-{\\text{C}}_{1}}{{\\text{C}}_{\\text{o}}}\\right)\\times 100\\text{%}$$\u003c/div\u003e\n \u003cdiv class=\"EquationNumber\"\u003e14\u003c/div\u003e\n\u003c/div\u003e\n\u003cp\u003eWhere, C\u003csub\u003eo\u003c/sub\u003e is the concentration of Fe\u003csup\u003e3+\u003c/sup\u003e added to the actual water sample, C\u003csub\u003e1\u003c/sub\u003e and C\u003csub\u003e2\u003c/sub\u003e are the concentration of Fe\u003csup\u003e3+\u003c/sup\u003e in the actual water sample before and after the addition of standard Fe\u003csup\u003e3+\u003c/sup\u003e.\u003c/p\u003e"},{"header":"Result And Discussion","content":"\u003cp\u003eCharacterization of C-CDs\u003c/p\u003e \u003cp\u003eTo investigate the optical properties of the prepared C-CDs, UV-Vis and photoluminescence (PL) spectroscopy were recorded. The UV\u0026ndash;vis absorbance curve shows two bands at 250 nm and 323 nm. The absorption peaks at 250 nm and 325 nm, which could be assigned to (π\u0026ndash;π*) transitions of C\u0026thinsp;=\u0026thinsp;C bonds and (n\u0026ndash;π*) transitions of C\u0026thinsp;=\u0026thinsp;O bonds, respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea). The PL spectra of C-CDs under various excitation wavelengths (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb). The PL behaviour of C-CDs was dependent on the excitation wavelength when the excitation wavelength was changed from 300 to 390 nm in 10 nm increments. The emission peak toward a longer wavelength is due to the photoinduced electrons and holes present in C-CDs at different surfaces of energy traps. The maximum emission was noted at 460 nm (cyan colour), with an excitation wavelength of 370 nm. A smaller particle will have a visible PL effect at a lower wavelength, while a larger particle will exhibit PL at a higher wavelength [\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eFTIR spectra has been used to identify the functional groups of C-CDs before and after adsorption, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea. The peaks around 3440 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (attributed to the O\u0026ndash;H stretching vibrations), 2918cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (correspond to C\u0026ndash;H stretching vibrations), 1610cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (corresponded to C\u0026thinsp;=\u0026thinsp;O stretching), 1321 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (ascribed to C\u0026ndash;O stretching vibrations of carboxylic ester group) and the peak observed around 1017cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (attributed to C\u0026thinsp;=\u0026thinsp;O vibrations). Figure. 3b displays the FTIR spectrum of C-CDs after the adsorption of MB at the surface of C-CDs. These minor peaks changes after MB dye adsorption are due to their involvement in the adsorption process through Van der Waals forces (weak electrostatic interaction) [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e]. X-ray diffraction (XRD) pattern depicted a broad peak at 2θ\u0026thinsp;=\u0026thinsp;21.5\u0026deg; and a weak peak at 2θ\u0026thinsp;=\u0026thinsp;43.3\u0026deg; that are assigned to (002) and (101) diffraction patterns of graphitic carbon respectively, (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec). The former peak corresponds to interlayer spacing of 3.77 \u0026Aring; which is slightly more than the spacing between (002) planes in bulk graphite (3.44 \u0026Aring;). The XPS results showed that these C-CDs are composed of atomic C (282.8 eV) and O (529.4 eV), as can be seen in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea. The measured spectrum of C1s consisted of three noticeable peaks: 282.9 eV, 284.1 eV and 285.7 eV, which attributed to the C-H, C\u0026thinsp;=\u0026thinsp;C sp\u003csup\u003e2\u003c/sup\u003e and sp\u003csup\u003e3\u003c/sup\u003e C (C\u0026ndash;OH), respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb). In addition, the deconvolution spectrum of O1s showed three binding energy peaks: 529.1 eV, 529.7 eV and 531.9, which may be ascribed to the C-O, C\u0026ndash;O\u0026ndash;C and O-C\u0026thinsp;=\u0026thinsp;O/C\u0026thinsp;=\u0026thinsp;O, respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eHRTEM is used to study microporous materials at atomic scale. Figure. 5a shows the presence of spherical C-CDs ranging below 10 nm. The distribution curve displayed that nearly 15% C-CDs had diameter in the range of 4.5 nm, while 7.5% of the C-CDs had diameter in the range of 5.5 nm, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eb. The zeta potential measurement of C-CDs exhibits that the C-CDs were negatively charged surface (-16.18 mV) due to the functionalization of the carboxylic group over the surface, as seen in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eEffect of pH\u003c/p\u003e \u003cp\u003epH is a significant parameter determining the adsorption efficiency since it can control the adsorbent surface charge and the pollutants' ionization. Small amounts of dilute HCl or NaOH were applied to adjust the pH. The adsorption efficiency increases with increasing initial pH in the ranges of 2\u0026ndash;10 (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ea). The low adsorption efficiency observed at pH 2 is due to less number of negatively charged adsorbent sites and extra H\u003csup\u003e+\u003c/sup\u003e sites presented at the C-CDs surface. The presence of the excess H\u003csup\u003e+\u003c/sup\u003e ions competing for adsorption sites with the cations groups on the dye [\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e, \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]. The maximum adsorption of the MB dye was observed at pH 10. Based on the results, pH\u0026thinsp;=\u0026thinsp;10 was chosen as the desired pH for further studies.\u003c/p\u003e \u003cp\u003eEffect of Adsorbent Dose and time\u003c/p\u003e \u003cp\u003eIn order to study the effect of C-CDs dose (g) on the removal of MB, the experimentation was carried out with an initial concentration of 100 mg L\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and pH 10 under the contact time between 30 to 120 min, while the amount of adsorbent added was varied. Figure. 6b illustrates the plot between the percent adsorption efficiency against the dose of adsorbent at a different time. It was observed that the adsorption efficiency % of MB was increased with increasing adsorbent dose up to 0.04 g, then increased slowly with a further increase of adsorbent dose and afterward remained unchanged. The increase in adsorption efficiency was because of the increase in the available absorption surface sites for C-CDs. Thus, to get a better percent of adsorption efficiency of MB and to not use more quantity of adsorbent, 0.04 g was selected as the best mass of the adsorbent in the following studies.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eEffect of temperature\u003c/p\u003e \u003cp\u003eThe effect of temperature on uptake of MB onto C-CDs was studied in the temperature range of 303 to 343 K at varying initial dye concentrations. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ea, an increase in temperature (303K to 343K) leads to a gradual reduction in the MB adsorption efficiency at different initial concentrations. Thermodynamic behaviors are applied to understand better the effect of temperature on the removal of dyes on adsorbents. Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e displays the thermodynamic parameters for the adsorption of MB (initial dye concentration\u0026thinsp;=\u0026thinsp;100 mg/L) onto C-CDs. The negative value of ΔH\u003csup\u003eo\u003c/sup\u003e showed that the process is exothermic in nature (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003eb). ∆G\u003csup\u003eo\u003c/sup\u003e values obtained are negative, suggesting that the adsorption process is spontaneous when the temperature changes from 303 K\u0026ndash;343 K without external energy. The ΔS\u003csup\u003eo\u003c/sup\u003e value achieved is -0.0063 (J/Mol.K). The negative sign revealed an decreasing randomness at the solid/liquid interface during the adsorption process [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eThermodynamic parameters for the MB adsorption on C-CDs\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eΔS\u003csup\u003eo\u003c/sup\u003e ( J/mol.K)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eΔH\u003csup\u003eo\u003c/sup\u003e ( kJ/mol)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eR\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eΔG\u003csup\u003eo\u003c/sup\u003e ( kJ/mol)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eTemperature (K)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eC-CDs\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e-0.00636\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e-7.03048\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.9777\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-5.14538\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e303\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-4.95520\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e313\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-4.99636\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e323\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-4.94110\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e333\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-4.83710\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e343\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eEffects of initial MB concentration and isotherm studies\u003c/p\u003e \u003cp\u003eThe effect of initial MB concentration is closely related to the sites present on the adsorbent surface. The adsorption capacity of C-CDs was shown to increase with increasing initial MB concentration from 10 to 100 (mg/L) due to the adsorption sites on the surface of C-CDs becoming saturated (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e) [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]. The adsorption capacity of the C-CDs was expressively dependent on the initial dye concentrations in the solution.\u003c/p\u003e \u003cp\u003eThe adsorption isotherms describe how the molecules of the adsorbate are dispersed among the solid and liquid phases when the adsorption process reaches an equilibrium state. In this study, we employed Langmuir, Freundlich, and Temkin isotherm model to analyze isotherm data. (Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003ea and b). The Langmuir isotherm is a simple type of adsorption equilibrium model for single-layer adsorption on a homogeneous surface when no interaction occurs between adjacent adsorbed molecules [\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e]. Freundlich isotherm is used to describe reversible and non-ideal adsorption systems on heterogeneous surfaces [\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e]. Temkin model is based on the assumption that the heat of adsorption decreases linearly because of interactions between adsorbent and adsorbate [\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e]. A summary of the isotherm parameters calculated for the Langmuir, Freundlich, and Temkin models for each temperature (303\u0026thinsp;\u0026minus;\u0026thinsp;343 K) is given in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. Based on the results, the value of R\u003csup\u003e2\u003c/sup\u003e according to the Freundlich model is higher than the Langmuir model. The slope range for the Freundlich isotherm model was determined between 0\u0026ndash;1, showing the adsorption intensity and surface heterogeneity. If \u0026#119899; = 1, the adsorption is linear, \u0026#119899; \u0026lt; 1 a chemical process, or \u0026#119899; \u0026gt; 1 a physical process [\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e]. The high K\u003csub\u003eF\u003c/sub\u003e value is favorable at 303K, which gives the adsorption of aggregated molecules. Therefore, experimental data for the adsorption of MB using C-CDs with respect to R\u003csup\u003e2\u003c/sup\u003e followed the order; Freundlich\u0026thinsp;\u0026gt;\u0026thinsp;Temkin\u0026thinsp;\u0026gt;\u0026thinsp;Langmuir.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eIsotherm model parameters for MB uptake by C-CDs (initial dye concentration\u0026thinsp;=\u0026thinsp;10\u0026thinsp;\u0026minus;\u0026thinsp;100 mg/L, dosage of adsorbent\u0026thinsp;=\u0026thinsp;0.04 g, pH\u0026thinsp;~\u0026thinsp;10, solvent temperature\u0026thinsp;=\u0026thinsp;303\u0026thinsp;\u0026minus;\u0026thinsp;343 K)\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eIsotherm model\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTemperature (K)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e303\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e313\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e323\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e333\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e343\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eLangmuir\u003c/em\u003e\u003c/p\u003e \u003cp\u003eR\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eq\u003csub\u003emax (\u003c/sub\u003emg/g)\u003c/p\u003e \u003cp\u003eK\u003csub\u003eL\u003c/sub\u003e (L/mg)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.9741\u003c/p\u003e \u003cp\u003e188.679\u003c/p\u003e \u003cp\u003e0.0110\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.9761\u003c/p\u003e \u003cp\u003e188.682\u003c/p\u003e \u003cp\u003e0.0104\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.8328\u003c/p\u003e \u003cp\u003e208.33\u003c/p\u003e \u003cp\u003e0.0075\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.6135\u003c/p\u003e \u003cp\u003e454.54\u003c/p\u003e \u003cp\u003e0.0024\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.5597\u003c/p\u003e \u003cp\u003e769.23\u003c/p\u003e \u003cp\u003e0.0012\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eFreundlich\u003c/em\u003e\u003c/p\u003e \u003cp\u003eR\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eK\u003csub\u003ef\u003c/sub\u003e (mg.g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003cp\u003e1/n\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.9803\u003c/p\u003e \u003cp\u003e0.2442\u003c/p\u003e \u003cp\u003e1.3557\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.9833\u003c/p\u003e \u003cp\u003e0.1862\u003c/p\u003e \u003cp\u003e1.3392\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.9892\u003c/p\u003e \u003cp\u003e0.0142\u003c/p\u003e \u003cp\u003e1.3118\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.9891\u003c/p\u003e \u003cp\u003e-0.8729\u003c/p\u003e \u003cp\u003e1.10132\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.9954\u003c/p\u003e \u003cp\u003e-2.647\u003c/p\u003e \u003cp\u003e1.0442\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eTemkin\u003c/em\u003e\u003c/p\u003e \u003cp\u003eb\u003csub\u003eT\u003c/sub\u003e\u003c/p\u003e \u003cp\u003eR\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eA\u003csub\u003eT\u003c/sub\u003e (L g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e35.518\u003c/p\u003e \u003cp\u003e0.9853\u003c/p\u003e \u003cp\u003e0.15948\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e34.152\u003c/p\u003e \u003cp\u003e0.9856\u003c/p\u003e \u003cp\u003e0.15581\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e33.054\u003c/p\u003e \u003cp\u003e0.9658\u003c/p\u003e \u003cp\u003e0.1346\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e33.857\u003c/p\u003e \u003cp\u003e0.9559\u003c/p\u003e \u003cp\u003e0.1159\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e32.714\u003c/p\u003e \u003cp\u003e0.9386\u003c/p\u003e \u003cp\u003e0.1096\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eKinetics of adsorption\u003c/p\u003e \u003cp\u003eThe experimental data were calculated based on the (PFO) Pseudo-First-Order and (PSO) Pseudo-Second-Order models to understand the kinetics of the adsorption process. Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e displays the parameters of the PFO and PSO models. The PSO model provided a better explanation of adsorption for MB from adsorbent. In this study, the R\u003csup\u003e2\u003c/sup\u003e value of PSO for every initial dye concentration was observed to be higher than 0.97. At PSO, dye concentration increased with increasing the value of qe might be due to the high competition for vacant sites, leading to higher adsorption rates. A plot between (t/qt) versus time was drawn to express the PSO kinetic model (Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003e).\u003c/p\u003e\n\u003cp\u003eTable 3\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eParameters of kinetics model for adsorption of MB onto C-CDs (\u003cstrong\u003ea\u003c/strong\u003e) Pseudo-First-Order and (\u003cstrong\u003eb\u003c/strong\u003e) Pseudo-Second-Order\u003cstrong\u003e\u0026nbsp;(\u003c/strong\u003etime = 30\u0026minus;120 min, initial dye concentration = 10\u0026minus;100 mg/L, Dosage of adsorbent = 0.04 g).\u003c/p\u003e\n\u003cp\u003e\u003cimg 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\" style=\"width: 637px; height: 529.716px;\" width=\"637\" height=\"529.716\"\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cp\u003e3.7. Sensing of Fe\u003csup\u003e3+\u003c/sup\u003e ions with C-CDs\u003c/p\u003e \u003cp\u003eThe fluorescence quenching effect of C-CDs upon the addition of different metal ions was investigated. It could be concluded from Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e11\u003c/span\u003ea that there is a decrease in fluorescence intensity after the addition of C-CDs and Fe\u003csup\u003e3+\u003c/sup\u003e. At the same time, other metal ions show a slight change in fluorescence intensity compared to free C-CDs. According to the results, the synthesis of C-CDs was shown good selectivity towards Fe\u003csup\u003e3+\u003c/sup\u003e over other metal ions and could be used as an efficient fluorescence probe for Fe\u003csup\u003e3+\u003c/sup\u003e ions. It can be seen that no obvious interference was observed in detection of Fe\u003csup\u003e3+\u003c/sup\u003e in the occupancy of other metal ions. Figure. 11b shows the possible mechanism of fluorescence quenching and strong interaction between the Fe\u003csup\u003e3+\u003c/sup\u003e and the surface groups of C-CDs, which transfer the photoelectron from C-CDs to the metal ions. The Fe\u003csup\u003e3+\u003c/sup\u003e ions absorbed on the surface of C-CDs and coordinated with these hydroxyl groups was due to the presence of phenolic hydroxyl group on the edges of C-CDs. This coordination interaction, electrons are transferred from the excited state of C-CDs to the empty d orbital of Fe\u003csup\u003e3+\u003c/sup\u003e and the formation of non-radiative electron/ hole pair. The sensitive and selective response of C-CDs to Fe\u003csup\u003e3+\u003c/sup\u003e ions at different concentrations is depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e11\u003c/span\u003ec. The concentration of Fe\u003csup\u003e3+\u003c/sup\u003e was gradually increased with increasing fluorescence intensity of C-CDs. This result revealed the change in fluorescence intensity of C-CDs solution by Fe\u003csup\u003e3+\u003c/sup\u003e (200\u0026micro;m) was clearly visible under UV light of 360nm. Hence blue emission disappeared after the addition of Fe\u003csup\u003e3+\u003c/sup\u003e to the C-CDs solution. Figure. 11d displays the plot of C-CDs at various concentrations of Fe3\u003csup\u003e+\u003c/sup\u003e (F\u003csub\u003eo\u003c/sub\u003e/F versus concentration of Fe\u003csup\u003e3+\u003c/sup\u003e ion) where F\u003csub\u003eo\u003c/sub\u003e and F are the fluorescence intensity of C-CDs at λex\u0026thinsp;=\u0026thinsp;330, λem\u0026thinsp;=\u0026thinsp;420 in the presence and absence of Fe\u003csup\u003e3+\u003c/sup\u003e. The value of R\u003csup\u003e2\u003c/sup\u003e was 0.991 for a concentration ranging from 0.01 to 100 \u0026micro;M. The plot didn\u0026rsquo;t fit the linear equation over the entire concentration range of 0.01 to 200 \u0026micro;M, indicating that both dynamic and static quenching processes occur in this sensor system. The LOD value of this proposed sensor is about 0.16\u0026micro;M.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eDetermination of Fe\u003csup\u003e3+\u003c/sup\u003e in river water samples\u003c/p\u003e \u003cp\u003eBased on the high sensitivity and good selectivity, we calculated its potential application in determining Fe\u003csup\u003e3+\u003c/sup\u003e in river water samples. Table\u0026nbsp;\u003cspan refid=\"Tab4\" class=\"InternalRef\"\u003e4\u003c/span\u003e shows the recovery results of all the samples were between 81.09\u0026ndash;96.98%, and the value of relative standard deviation (RSDs) was very low (0.98\u0026ndash;1.97%), which indicated that the proposed method had achieved high accuracy.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab4\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eDetermination of Fe\u003csup\u003e3+\u003c/sup\u003e in the environmental water sample.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"5\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eAdded(\u0026micro;M)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMeasured(\u0026micro;M)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eRecovery (%)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eRSD (%) (n\u0026thinsp;=\u0026thinsp;3)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eRiver Water\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0\u003c/p\u003e \u003cp\u003e2\u003c/p\u003e \u003cp\u003e6\u003c/p\u003e \u003cp\u003e10\u003c/p\u003e \u003cp\u003e20\u003c/p\u003e \u003cp\u003e50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.33\u003c/p\u003e \u003cp\u003e3.47\u003c/p\u003e \u003cp\u003e7.87\u003c/p\u003e \u003cp\u003e10.95\u003c/p\u003e \u003cp\u003e20.97\u003c/p\u003e \u003cp\u003e50.98\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e90.02\u003c/p\u003e \u003cp\u003e81.09\u003c/p\u003e \u003cp\u003e92.96\u003c/p\u003e \u003cp\u003e96.98\u003c/p\u003e \u003cp\u003e94.99\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1.20\u003c/p\u003e \u003cp\u003e1.97\u003c/p\u003e \u003cp\u003e0.98\u003c/p\u003e \u003cp\u003e1.34\u003c/p\u003e \u003cp\u003e0.99\u003c/p\u003e \u003cp\u003e1.67\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eThe novel carbon dots were successfully synthesized from coriander leaves through a facile hydrothermal method as a plausible adsorbent for the removal of a cationic dye (MB) from wastewater. The optical property, crystalline structure, surface morphology, and adsorption behavior of C-CDs are all analyzed. The amount of MB adsorbed was studied by varying initial MB concentration, C-CDs dose, pH, and contact time. It is evident that the percentage adsorption increased with an increase in initial concentration of dye, and pH values also increased with an increase in MB adsorption percentages. The adsorption isotherms and kinetic models were fitted well with Freundlich and PSO model. Moreover, thermodynamic parameters indicated that the adsorption process is exothermic in nature, spontaneous and feasible. It was validated that the obtained C-CDs had been utilized as an environmental-friendly adsorbent for removing MB in wastewater. Eventually, the low-toxicity C-CDs demonstrated high selectivity sensitivity towards Fe\u003csup\u003e3+\u003c/sup\u003e over other metal ions.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgments\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAuthors acknowledge with thanks to the Department of Chemistry, AMU, Aligarh, for the financial support to carry out this work.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eNotes\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing financial interest.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eChapman D V., Sullivan T (2022) The role of water quality monitoring in the sustainable use of ambient waters. One Earth 5:132\u0026ndash;137. https://doi.org/10.1016/j.oneear.2022.01.008\u003c/li\u003e\n\u003cli\u003eAsamoah EF, Di Marco M, Watson JEM, et al (2022) Land-use and climate risk assessment for Earth\u0026rsquo;s remaining wilderness. 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J Water Process Eng 34:101155. https://doi.org/10.1016/j.jwpe.2020.101155\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"journal-of-inorganic-and-organometallic-polymers-and-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"joip","sideBox":"Learn more about [Journal of Inorganic and Organometallic Polymers and Materials](https://www.springer.com/journal/10904)","snPcode":"10904","submissionUrl":"https://submission.nature.com/new-submission/10904/3","title":"Journal of Inorganic and Organometallic Polymers and Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-2569839/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-2569839/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eFreshwater contamination is a significant concern due to the increasing pollution by industrial activities. Dyes have a wide range of uses and are introduced at different stages of manufacture, raising the risk of unwanted human and environmental contact. Consequently, the demand for an effective method for removing dyes has become more important than before. In this context, Carbon dots have been synthesized by the green synthesis method from Coriander leaves (C-CDs) and used as a prospective adsorbent to remove (MB) methylene blue dye from aqueous solution. The as-synthesized C-CDs are characterized by HR-TEM, XRD, XPS, FTIR, Zeta potential, UV-visible, and Photoluminescence (PL). Effects of different controlling parameters such as adsorbent dosage, pH, contact time, and initial MB dye concentration were investigated. The highest adsorption efficiency (82.6%) and maximum adsorption capacity (96.05 mg/g) of MB were obtained at optimum conditions (303 K). The adsorption isotherm data could be fitted well by Freundlich model, and the experimental data fitted to the Pseudo-Second-Order kinetic model. It is worth noting that C-CDs exhibited excellent sensitivity and high fluorescence quenching effect on Fe\u003csup\u003e3+ \u003c/sup\u003eions.\u003c/p\u003e","manuscriptTitle":"Carbon dots from natural‐product: applications as adsorbent and Sensing of Fe 3+ Ions","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2023-02-14 22:25:10","doi":"10.21203/rs.3.rs-2569839/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Major revision","date":"2023-04-03T20:51:54+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2023-03-08T03:35:21+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"a49ee697-9910-45e8-87bf-5a5f59903612","date":"2023-02-12T03:33:30+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2023-02-11T18:08:43+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2023-02-11T13:58:19+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2023-02-10T11:14:23+00:00","index":"","fulltext":""},{"type":"submitted","content":"Journal of Inorganic and Organometallic Polymers and Materials","date":"2023-02-09T16:39:31+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"journal-of-inorganic-and-organometallic-polymers-and-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"joip","sideBox":"Learn more about [Journal of Inorganic and Organometallic Polymers and Materials](https://www.springer.com/journal/10904)","snPcode":"10904","submissionUrl":"https://submission.nature.com/new-submission/10904/3","title":"Journal of Inorganic and Organometallic Polymers and Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"a1455700-f5de-4172-99ae-20e24ffcac3d","owner":[],"postedDate":"February 14th, 2023","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2023-10-16T21:31:32+00:00","versionOfRecord":{"articleIdentity":"rs-2569839","link":"https://doi.org/10.1007/s10904-023-02707-8","journal":{"identity":"journal-of-inorganic-and-organometallic-polymers-and-materials","isVorOnly":false,"title":"Journal of Inorganic and Organometallic Polymers and Materials"},"publishedOn":"2023-06-16 21:11:17","publishedOnDateReadable":"June 16th, 2023"},"versionCreatedAt":"2023-02-14 22:25:10","video":"","vorDoi":"10.1007/s10904-023-02707-8","vorDoiUrl":"https://doi.org/10.1007/s10904-023-02707-8","workflowStages":[]},"version":"v1","identity":"rs-2569839","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-2569839","identity":"rs-2569839","version":["v1"]},"buildId":"cBFmMYwuxLRRLfASyISRj","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}