Structure, Morphology, Composition of the CMBC
XRD technology was firstly used to analyze the structure of the CMBC. There are no diffraction peaks in the XRD pattern of the CMBC obtained from 800 ℃ with the duration time of 60 min (Fig. 1). The XRD characterization shows that the CMBC consists of amorphous structure. The amorphous structure is similar to that reported by different literatures [26−28].
SEM observation shows that the CMBC sample (Figs. 2a and 2b) exhibits irregular particle morphology and size of less than 10 μm which is similar to that reported by different literatures [29−32]. Element mapping of the CMBC (Fig. 3) indicates that the CMBC sample is comprised of element C.
Dye Adsorption Performance of the CMBC
Point of Zero Charge (pHPZC)
The relationship of zeta potential against the solution pH value of the CMBC in dyes (RhB or MB) solution is shown in Fig. 4. The surface charge of the CMBC adsorbent is negative when the pH value is higher than the pHPZC [33]. The adsorption of dye (RhB or MB) using the CMBC absorbent improves when pH is higher than 7. When solution pH value of dye (RhB or MB) solution is less than pH value of 7, the charge on the CMBC is positive. And the repulsion is produced between the dye (RhB or MB) and adsorbent CMBC. Therefore, the dye (RhB or MB) adsorption efficiency decreases obviously. The interaction between the dye (RhB or MB) and negatively charged surface of the CMBC is the strongest when the pH value is higher than pHPZC. When the pH value is lower than pHPZC, dye (RhB or MB) adsorption efficiency decreases obviously. The dye (RhB or MB) repels the surface of the CMBC which possesses same charges as the dye. Therefore, the adsorption process of the dye (RhB or MB) on the CMBC can be explained by an ion exchange mechanism [34].
Influence of the Adsorption Time, Dose and pH value
Fig. 5a shows the role of the adsorption time on the dye removal efficiency using the CMBC. The dye concentration is 10 mg·L−1. CMBC dose is 1.25 mg·mL−1 dye solution. Obviously, the adsorption efficiency of the dyes increases with increasing adsorption time. CMBC adsorbent can totally adsorb the dyes RhB and MB when the adsorption time is 12 min and 15 min, respectively. Thus, CMBC has excellent adsorption ability for organic pollutants removal. Fig. 5b shows dye adsorption efficiency against the CMBC dose using the CMBC. The dye concentration is 10 mg·L−1. The dye adsorption efficiency of the CMBC is significantly improved with prolonging the dose of the CMBC. The RhB adsorption efficiency increases from 52.7% to 91.2% with increasing the CMBC dose from 0.25 to 1.0 mg·mL−1. And MB adsorption efficiency increases from 44.8% to 88.9% with increasing the CMBC dose from 0.25 to 1.0 mg·mL−1. The dye (RhB or MB) can be totally adsorbed when the dose of the CMBC is higher than 1.25 mg·mL−1. Therefore, the optimum CMBC dose is 1.25 mg·mL−1.
The surface charge state of the CMBC can be changed by adjusting dye solution pH which has an important influence on dye removal efficiency of the CMBC. Fig. 6 shows the relationship between the pH value and dye removal efficiency using the CMBC. Obviously, the dye removal efficiency improves with increasing the pH from 2 to 12. The dye concentration is 10 mg·L−1. CMBC dose is 1.25 mg·mL−1. The result shows that the CMBC has the highest dye adsorption efficiency.
CV and EIS of CMBC-modified Electrode
CMBC-modified electrode was firstly applied for electrochemical oxidation of catechol using CV technology. There is no current response at the bare GCE in 0.1 M KCl solution with 1 mM catechol at 50 mV·s-1 scan rate (Fig. 7). The result is consistent to that reported by Krishnamoorthy et al. [14]. There is also no current signal of the CMBC-modified electrode in KCl solution. Compared with above CVs, CMBC-modified electrode shows strong current response in 0.1 M KCl solution with 1 mM catechol at 50 mV·s-1 scan rate. A pair of quasi-reversible redox CV peak are located at +0.38 V and +0.28 V with the current of 28.2 μA and 15.1 μA, respectively. The observed high current response of the CMBC-modified electrode towards electrocatalytic oxidation and reduction of catechol is contributed to the electrocatalytic activity of CMBC.
Electrochemical Sensing Performance of the CMBC-modified Electrode for Catechol Detection
Electrochemical Response of Catechol on the CMBC-modified Electrode
SWV technology is applied for quantitative electrochemical analysis of catechol in water environment owing to higher sensitivity than CV technology using same electrolyte [35, 36]. Fig. 8 shows SWV electrochemical properties of bare GCE, CMBC-modified electrode in 0.1 M KCl solution with or without 1 mM catechol by applying a potential range from −0.3 V ~ +0.9 V with a step increment of 4 mV and pulse period of 0.2 s. No SWV peaks are observed on the bare GCE with or without 1 mM catechol, CMBC-modified electrode in KClsolution. Different from above results, the CMBC-modified electrode has a strong and well-defined SWV peak at the potential of +0.34 V with peak current of 34.3μA. The produced anodic SWV peak at +0.34 V only exists in 0.1 M KCl and 1 mM catechol solution showing that SWV peak signal is caused from CMBC. The CMBC possesses high conductivity, good adsorption performance and large specific surface area, which provides a large amount of available adsorption and electro-catalytic active adsorption sites for the catechol. High SWV peak current originates from strong adsorption ability and electrostatic interaction between CMBC and catechol.
During electrochemical detection of catechol at CMBC-modified electrode, catechol molecules are adsorbed and diffused to modified electrode owing to strong adsorption activity of CMBC. Adsorbed catechol is oxidized to be benzoquinone by electro-catalytic role of the CMBC. And the SWV anodic peak is produced. The possible catechol electrocalytic detection mechanism of the CMBC-modified electrode is demonstrated in Fig. 9. Large number of adsorption and electro-catalytic active sites, large specific surface area, high conductivity are essential for the enrichment and electrocatalytic reaction of the catechol.
Catechol Detection
The catechol detection properties of the CMBC-modified electrode were carried out under above optimized measurement parameters. Fig. 10 shows SWV response of different concentrations of catechol in 0.001−1000 μM in 0.1 M KCl solution. The catechol concentration-dependent results show that the anodic SWV peak current of the catechol at the potential of +0.34 V is proportional to the catechol concentration. The linear range of the catechol is 0.001−1000 μM (Correlation coefficient (R2) = 0.998). The linearization equation is Ip (μA) = 9.683 + 0.076C (nM), where Ip and C represent anodic SWV peak current at +0.34 V and catechol concentration. Limit of detection (LOD) is 0.88 nM according to signal to noise of 3. Comparison of the proposed CMBC-modified electrode with other methods and electrodes for catechol detection is listed in Table 1. CMBC-modified electrode shows low detection range and wide LOD. Comparing with the LaNiO3 [14], N-doping carbon nanotube film [38], In-ZnO nanosheet–modified carbon nanotube–polyimide film [39], carbon nanotubes and silica nanoparticle-based laccase [42], Mg-doped ZnO nanoparticlesmodified electrodes by electrochemical methods [45], the CMBC-modified electrode shows lower LOD. Although CuS-based micro-flower loaded with carbon dots/laccase by colorimetric method [38], Langmuir–Blodgett film with phospholipid and phthalocyanines [40], clay-modified electrodes [43] and phosphate-modified TiO2 nanoparticles by fluorescence method [44] possess lower LOD, the proposed CMBC-modified electrode exhibits wider linear range.
Interference Role, Reproducibility and Stability
Some common interference species, such as Cr3+, Fe3+, Ni2+ and citric acid were used for analyzing selectivity of CMBC-modified electrode for catechol detection. As shown in Fig. S5, it is found that the SWV peak potential is same under optimum measurement parameters. And there is only a slight variation of the SWV peak response to catechol using the CMBC-modified electrode and different interference species. CMBC-modified electrode exhibits good anti-interference ability for catechol determination.
The reproducibility of the CMBC-modified electrode for catechol detection was evaluated at five independent electrodes which were fabricated under same conditions. The anodic peak potential is similar. There is no obvious reduction of the anodic peak current response towards catechol (Fig. S6). The stability of CMBC-modified electrode for catechol detection was examined by measuring the electrochemical response to 1 mM catechol solution for twenty successive measurements. Anodic SWV peak current is slightly reduced for initial current (Fig. S7). The low relative standard deviation (RSD) is 1.31%. Therefore, CMBC-modified electrode is promising for catechol detection with acceptable anti-interference ability, reproducibility and stability.
Real Sample Analysis
For further estimation of the application of CMBC-modified electrode, tap water and lake water samples were applied for quantitative analysis in real water environment. Catechol was not found in the samples. Recovery experiments were carried out by measuring SWV response to the samples in which the known catechol concentrations were added. The concentration of the catechol in the real water samples is estimated by calibration method and corresponding results are listed in Table 2. Recoveries for catechol detection are 95.8−102.4% at the CMBC-modified electrode. The result confirms the practical applicability of CMBC-modified electrode for accurate detection of catechol in practical water samples.