3.1. Characterization of the prepared materials
The morphologies of obtained UiO-66-NH2 and UiO-66-NH2@PPy were observed by SEM and TEM. As shown in Fig. 1 (A) and 1 (C), the highly crystalline UiO-66-NH2 has a traditional octahedral structure: the particle size of UiO-66-NH2 ranges from 122 nm to 243 nm, and the statistical average particle size was 178 ± 30 nm (n = 100). Compared with UiO-66-NH2, UiO-66-NH2@PPy has the same regular octahedral structure except for a slight difference in size. As can be seen from Figs. 1B and 1D, PPy nanoparticles were uniformly distributed around UiO-66-NH2.
The XRD patterns of UiO-66-NH2, PPy, and UiO-66-NH2@PPy are shown in Fig. 2 (A). The obvious diffraction peaks of UiO-66-NH2 at 2θ = 7.38°, 8.51°, 12.02°, 14.13°, 17.03°, 25.66°, 30.03°, 33.14°, 35.53°,and 43.20° match well with those reported in the literature (Gomes Silva et al. 2010), indicating that UiO-66-NH2 was successfully prepared and had good crystallinity. For the PPy, broad amorphous diffraction peaks were found at 2θ = 25° in the XRD pattern of PPy (Fig. 2 (A), inset), which was consistent with the conclusions in the literature (Sanches et al. 2015). The PPy diffraction peak was not observed in XRD patterns of UiO-66-NH2@PPy, which may be owing to the weak diffraction signal of PPy, and the other characteristic diffraction peaks were similar to those of UiO-66-NH2, suggesting that the added PPy did not affect the crystallinity of UiO-66-NH2.
As shown in Fig. 2B, the characteristic fingerprint peaks of UiO-66-NH2 were 657 cm− 1,767 cm− 1,1260 cm− 1,1386 cm− 1,1573 cm− 1 and 3373 cm− 1. The fingerprint spectra at 657 cm− 1 and 767 cm− 1 were caused by the Zr-O bond (Yang et al. 2019); the peaks at1260 cm− 1 and 1386 cm− 1 were contributed by the C–N stretching vibration (Ghobakhloo et al. 2022); the bond of -COOH and Zr4+ showed obvious absorption peaks at 1659 cm− 1 and 1573 cm− 1 (Jiang et al. 2019); the peaks in the range of 3350–3450 cm− 1 were due to the vibration of the N–H bonds (Du et al. 2017; Zhang et al. 2022). For UiO-66-NH2@PPy, the FT-IR characteristic fingerprint spectrum was similar to that of UiO-66-NH2 due to the relatively low content of PPy.
In order to further verify the successful preparation of UiO-66-NH2@PPy nanocomposites, an XPS experiment was performed to study the surface information. As exhibited in Fig. 3 (A), the XPS spectra of UiO-66-NH2@PPy were similar to the XPS spectra of UiO-66-NH2 except for slightly different N1s intensity. The characteristic fingerprint peaks of Zr 3d, C 1s, N 1s, and O 1s were all observed. Compared with UiO-66-NH2, the C 1s and Zr 3d spectra of UiO-66-NH2@PPy have no significant change as shown in Fig. 3 (B) and 3 (C). However, the O 1s and N 1s spectra of UiO-66-NH2@PPy all appeared as new peaks compared with UiO-66-NH2. The new peak at 533.4 eV in the O 1s spectra (Fig. 3 (D)) of UiO-66-NH2@PPy was attributed to C = O, and the new peak at 398.7 eV in N 1s spectra (Fig. 3(E)) of UiO-66-NH2@PPy was ascribed to -N = segments in the backbone of PPy chains (Zhou et al. 2020).
Materials with large specific surface areas and stability play a huge role in the field of electrochemical sensors. The larger the specific surface area, the more adsorption sites can be provided. As shown in Fig. S1A, the isotherm of UiO-66-NH2 and UiO-66-NH2@PPy is similar to that of the type I adsorption isotherm, confirming the typical microporous structure (LuDengLuoLvLiXuChen and Wang 2019). As shown in Table 1, the surface area of UiO-66-NH2@PPy are up to 964.86 m2 g− 1 with an average pore diameter of 2.50 nm and a total pore volume of 0.604 cm3 g− 1, which is conducive to the capture and binding of analytes on the sensor surface. Moreover, TGA curves (Fig. S1B) demonstrated that UiO-66-NH2@PPy possess good thermal stability, which is crucial for the stability of electrochemical sensors.
Table 1
The textural properties of UiO-66-NH2 and UiO-66-NH2@PPy composites.
Sample
|
BET
(m2 g− 1)
|
total pore volume
(cm3 g− 1)
|
pore diameter
(nm)
|
UiO-66-NH2
|
1124.55
|
0.595
|
2.11
|
UiO-66-NH2@PPy
|
964.86
|
0.604
|
2.50
|
3.2. Electrochemical behavior
The performance of the fabricated electrochemical sensor was investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in a mixed solution containing 5.0 mmol/L [Fe (CN)6]3−/4− and 0.1 mol/L KCl. As shown in Fig. 4 (A), the signal value of the UiO-66-NH2 modified electrode is the smallest, which may be because the weak conductivity of UiO-66-NH2 limits the electron transfer, while the signal value of the PPy and the UiO-66-NH2@PPy modified electrode all increased, which is the result of the combined effect of the exceedingly good electrical conductivity of PPy and the higher specific surface area and rich functional groups of UiO-66-NH2. To further demonstrate the excellent electrochemical performance of the fabricated electrochemical sensor, EIS was adopted to study the interface properties and impedance information. The Nyquist diagrams of bare GCE, UiO-66-NH2, PPy, and UiO-66-NH2@PPy modified electrodes are shown in Fig. 4 (B). The electron transfer resistance (Ret) of GCE increased after modification of UiO-66-NH2. However, the Ret of the PPy and UiO-66-NH2@PPy modified electrodes was reduced compared with bare GCE, indicating that the participation of PPy can accelerate the transfer of electrons on the electrode surface.
Examining the UiO-66-NH2@PPy modified electrode's CV curve changes at various scan rates allowed for the study of the mass transfer process. As shown in Fig. 4 (C) and 4 (D), the peak currents correspondingly increased in the range of 20–150 mV s− 1. There is a good linear relationship between the peak current and the square root of the scanning rate, with a linear correlation coefficient greater than 0.999, which is in accordance with the Randles-Sevcik equation, suggesting that the mass transfer process occurring on the electrode surface was controlled by diffusion.
The pH value of the solution, deposition voltage, and deposition time are three very important parameters in the differential pulse stripping voltammetry (DPSV) technique. Under different pH conditions, the peak current variation of the electrode was first studied. As shown in Fig. 5 (A), the highest peak current occurred when the pH was 5, which was explained by the protonation of the amino group in UiO-66-NH2 due to the too-low pH environment (Zou et al. 2021), and the lead ions were combined with the hydroxide ion when the pH was too high (Li et al. 2020).
The deposition potential is another key factor that affects the sensitivity of the electrochemical analysis. The trend between peak current value and deposition potential within the range of -0.9 to -1.4 V was studied. As shown in Fig. 5 (B), the peak current reaches its maximum when the deposition potential is -1.2 V. This is because the negative deposition potential accelerates the reduction of lead ions, while the excessively large negative potential leads to the produce of the hydrogen evolution reaction and prevents further reduction of lead ions (Wang et al. 2020).
In addition, the variation between deposition time and peak current was also studied. As shown in Fig. 5 (C), with the increase in deposition time, more lead ions were reduced on the electrode surface, thus increasing the peak current. When the deposition time increases 200 s, the peak current reached its maximum. When the time is extended further, the peak current is almost unchanged, which may be because the binding sites on the electrode surface are all bound by lead ions and reach saturation (Hanif et al. 2019).
3.3. Analytical performance of the UiO-66-NH2@PPy/GCE
Under optimal experimental conditions, the DPSV method was employed to investigate the analytical performance of the prepared electrochemical device in buffer solutions containing different concentrations of lead ions. Figure 5 (D) shows that the peak value of the electrochemical signal appears near − 0.55 V, and the signal value increases with the increase of lead ion concentration. Figure 5 (E) shows that the fitted linear equation is y = 0.177x -0.638, and the linear range is 0.1–256 µg/L. According to the suggestion of signal-to-noise ratio (S/N = 3), the limit of detection (LOD) was obtained as 0.05 µg/L (liquid) and 0.0025 mg/kg (solid), which is far lower than the 1 mg/Kg stipulated by China National Food Safety Standard. Compared with other sensors in the literature on electrochemical detection of lead ions (Table S2), the electrochemical sensor has excellent performance, mainly due to the higher specific surface area and abundant amino groups of UiO-66-NH2 contributing to the bond of lead ions on the electrode interface, and the excellent conductivity of polypyrrole accelerates the transfer of lead ions on the electrode interface.
3.4. Interference, reproducibility, repeatability and stability of the prepared sensor
During the actual sample testing process, the possibility of only the presence of lead ions in the sample is relatively small, and there are often other interfering ions. As shown in Fig. S2A, in the presence of interfering ions (Zn2+, K+, Ca2+, Na+, Al3+, Mn2+, and Cd2+) with 5 times the concentration of lead ions, the electrical signal value of the sensor to lead ions has no obvious change, and there are no other interfering peaks near the − 0.55V potential in the DPSV graph.
The reproducibility experiment was studied by monitoring the response values of the five sensors prepared at the same time to lead ions with a concentration of 100 µg/L. The relative standard deviation (RSD) of the five current signal values was calculated to be 5.3% (Fig. S2B), which proved that the reproducibility was good. In addition, the repeatability of the sensor was studied by monitoring the response values of the same electrode to the same concentration of lead ions for 7 times, and the RSD was 4.1% (Fig. S2C), which proved that the repeatability was good. Finally, the signal value of the sensor changed by only 6.2% (Fig. S2D) after 2 weeks of storage, indicating that the sensor has good stability.
3.5. Determination of lead ion in real samples
The sensor's practicability (UiO-66-NH2@PPy) was evaluated to analyze the lead ions in pig liver power and the certified reference material (GBW08551). Before detection, all samples were digested into clear and transparent solutions by microwave. In short, 0.5 g of sample and 6 mL of nitric acid were added to the digestion tank and then transferred to the microwave digestion instrument after capping. The microwave power was 1200 W, and the digestion program was as follows: hold 120°C for 5 minutes, 150°C for 5 minutes, and 180°C for 20 minutes. After digestion, the solution was transferred to the heating plate and volatilized until about 1 mL of solution remained. Then the digestion solution was loaded into a 25 mL volumetric bottle, and the buffer solution of pH = 5 was used to maintain a constant volume of 25 mL. The content of lead ions in real samples is very low, so the standard addition method and ICP-MS method are used for recovery evaluation and comparative verification. The calculation results are listed in Table S3. The RSD was less than 4.10%, the recovery was within the range of 95.2–118.0%, the content of lead in the certified reference material is 0.12 mg/Kg, and the result analyzed by our electrochemical sensor is 0.11 mg/kg. All the results show that the prepared sensor can be used for the detection of actual samples with reliable and sensitive characteristics.