Preparation of GO-COOH/AuNPs/ZnAPTPP nanocomposites based on the π–π conjugation: Efficient interface for low-potential photoelectrochemical sensing of 4-nitrophenol
Graphical abstract
Introduction
Porphyrins widely exist in the natural world as chlorophyll in plants and hemoglobin in animals and have very good light absorption capacity because of their extended π–π conjugation. Because of their attractive optical properties, ultrafast electron injection ability and high absorption coefficient [1], [2], [3], [4], porphyrins have seen wide spread applications in many areas such as organic synthesis [5], analytical chemistry [6], medicine [7], [8], material science [9], energy sources [10], [11] and photoelectrochemical [12], [13].
Carboxylated graphene oxide (GO-COOH) is a derivative of graphene oxide (GO), which was reportedly prepared based on the nucleophilic substitution reaction between the hydroxyl groups of GO and ClCH2COOH in NaOH solution [14]. Thus, the –OH and epoxide groups of the GO were converted to –COOH groups, and then obtained COOH [15] functionalized GO. GO-COOH [16] not only shows excellent solubility (as much as 2 mg/mL−1) in water, and the solution has been stable for several months at room temperature, but also has a strong conductivity.
4-nitrophenol (4-NP) is flammable and toxic nitroaromatic compound. The toxic intensity of 4-NP is the highest compared to its homologues (2-NP and 3-NP), which often found in chemical industrial wastewaters as a pollutant [17], [18]. 4-NP is also the hydrolyzate for organophosphorus pesticides [19], which have been widely used for pest control [20]. The health will be damaged by high toxicity of 4-NP when accumulated in the body. Further causes headache, nausea, drowsiness and cyanosis, contact with eyes causes irritation. 4-NP is also existed in others environments [21], [22]. Hence, the detection of 4-NP has received much attention in analytical chemistry and has been widely reported to detect 4-NP with different analytical methods such as: chromatography with spectrophotometry [23], mass spectrometry [24], Fluorescence spectrometry [25] and electrochemical methods [22], [26], [27], [28], [29]. Compared with the traditional methods, a newly developed photoelectrochemical (PEC) [6], [11], [12], [20], [30] detection of biomolecules is the interesting approach in developing analytical method attributed to the efficient charge separation upon photoexcitation and result in highly sensitive photocurrent signal due to the low signal to noise ratio. PEC technique is inherited from the advantages such as remarkable sensitivity, inherent miniaturization, portability and easy integration. The general principal on which the PEC methods developed can be generalized as follows. The semiconductive materials are first irradiated to generate charge carriers. And the added biomolecule [31], [32] as an analyte capture the holes by donating electrons. So that the biomolecules can be oxidized at relatively lower oxidation potential compared to the direct electrochemical oxidation. This technique is highly sensitive to the excitation source and the detection signal due to the low background. A novel PEC biosensor for rapid, sensitive and selective monitoring of 4-NP was developed using functional nanocomposites which consists of ZnAPTPP and GO-COOH with AuNPs through π–π conjugation. Although there are many studies on the electrochemical detection of 4-NP using several modified electrodes, as far as we know, there is no report on the modification of indium tin oxide (ITO) electrode with ZnAPTPP and GO-COOH with AuNPs through π–π conjugation for PEC determination of 4-NP.
Section snippets
Materials and reagents
Benzaldehyde, 4-nitrophenol (4-NP), sodium phosphate monobasic dihydrate and disodium hydrogen phosphate were purchased from Aladdin Industrial Corporation (ShangHai, China). Pyrrole and DuPont Nafion solution were purchased from Shanghai Macklin Biochemical Co., Ltd and Shanghai Hesen Electric Co., Ltd (ShangHai, China) respectively. Chloroform and Petroleum ether were purchased from TianJin Chemical Reagent Factory (TianJin, China). The Carboxylated Graphene Oxide (GO-COOH), AuNPs, APTPP and
Characterization of GO, GO-COOH, GO-COOH/AuNPs, GO-COOH/APTPP, GO-COOH/ZnAPTPP, GO-COOH/AuNPs/APTPP and GO-COOH/AuNPs/ZnAPTPP nanocomposites
The evidence of the nanocomposites formation was confirmed by the scanning electron microscope (SEM). It can be seen that the GO (Fig. 1A) looks like a uniform laminar sheet with a compact texture. Morphology of GO-COOH (Fig. 1B) was the same as GO as a whole, but GO-COOH was appeared to be thinner than GO. Pristine AuNPs (about 15 nm, Fig. S8) and the AuNPs on the surface of GO-COOH are shown in Figs. 1C and D respectively. Well dispersion of the AuNPs in the nanocomposites GO-COOH/AuNPs/APTPP
Conclusions
In conclusion, we have successfully constructed a novel PEC sensor using GO-COOH/AuNPs/ZnAPTPP nanocomposites. Out of the two methods followed to prepare the nanocomposites, material prepared through π–π conjugation resulted in the better response than that prepared via amidaion reaction. GO-COOH/AuNPs/ZnAPTPP nanocomposites modified ITO exhibited good photocurrent response under xenon lamp illumination at −0.1 V in 0.1 M pH 7.0 PBS. The photocurrent response was significantly enhanced after
Acknowledgments
This work was supported by the National Natural Science Foundation of China (Nos. 21175108 and 21327005), the Program for Chang Jiang Scholars and Innovative Research Team, Ministry of Education, China (No. IRT1283), the Program of Innovation and Entrepreneurial for Talent, Lan Zhou, Gansu Province (No. 2014-RC-39).
Novelty Statement
We constructed a novel PEC sensor of GO–COOH/AuNPs/ZnAPTPP nanocomposites with Au nanoparticles (AuNPs) on the surface of carboxylated graphene oxide (GO–COOH) and 5-(4-aminophenyl)-10, 15, 20-triphenylporphinatozinc (ZnAPTPP) through π-π conjugation and exhibited an excellent photocurrent response on ITO electrode to 4-NP at -0.1 V in 0.1 M pH 7.0 PBS, this method was simple, high sensitivity, wide concentration range and low detection limit. The novel sensor has got great potential to detect
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