Junwei Dinga,
Tianjiao Liua,
Wei Xua,
Hang Liaoa,
Jingfeng Lib,
Gang Wei*b and
Zhiqiang Su*a
aState Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, 100029 Beijing, China. E-mail: suzq@mail.buct.edu.cn
bHybrid Materials Interface Group, Faculty of Production Engineering, University of Bremen, D-28359 Bremen, Germany. E-mail: wei@uni-bremen.de
First published on 16th September 2015
Sulfur-doped γ-MnOOH rods were successfully prepared by employing a one-step hydrothermal process based on thioacetamide (TAA), and their structure was directly confirmed and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray powder diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) techniques. The mechanism for the TAA assisted hydrothermal synthesis of γ-MnOOH rods has been preliminarily presented. Furthermore, the synthesized sulfur-doped γ-MnOOH rods were immobilized onto a glassy carbon electrode and applied to construct an electrochemical hydrazine sensor, which exhibited a wide linear range (0.1 μM–1.15 mM and 1.15–45.75 mM), low detection limit (0.079 μM), high selectivity, and long-term stability.
Hydrazine (N2H4) is applied as intermediate in chemical industry to synthesize pesticides and herbicides as well as to produce anti-tuberculosis and anti-diabetes medicines.23 However, N2H4 is quite toxic.24 Therefore, the development of a sensitive way to detect N2H4 is critical.25 Until now many methods have been developed for N2H4 determination, such as spectrophotometric method,26 fluorimetric method,27 and potentiometry.28 However, these methods are usually expensive and time-consuming. Among them, electrochemical method attracts more and more attention, due to its higher sensitivity and reliability and less expensive.29,30
Though 1D γ-MnOOH have been successfully synthesized by different synthetic methods,7,15,16,19,31,32 most of them are as intermediates to prepare other types of manganese oxide, and are not with uniform rod morphology. In this work, we report the fabrication of sulfur (S)-doped γ-MnOOH rods based on a one-step hydrothermal reaction between KMnO4 and MnSO4 in the presence of thioacetamide (TAA). We utilized TAA as S source and reductant. To the best of our knowledge, the synthesis of γ-MnOOH using TAA has not been reported to date. The additional studies were carried out to study the properties and performances of the fabricated electrochemical N2H4 sensor. It is also the first time to fabricate the electrochemical sensor by using MnOOH for detecting N2H4.
To investigate the effects of different reaction parameters, such as temperature, the amount of TAA, and the reaction period, on the formation of S doped γ-MnOOH, the temperature was set from 140 to 160, 180 and 200 °C; the amount of TAA was kept from 0.1 to 0.2, 0.4 and 0.8 g; the reaction period was adjusted from 8 to 16, 24 and 36 h.
Furthermore, in order to study the effect of different reactants in reaction system, three sets of control experiment without KMnO4, TAA and MnSO4·H2O respectively were studied, while keeping all other experimental parameters as in the typical run.
The GCE was polished with 1 and 0.3 μm alumina powder and washed with distilled water, followed by sonication in ethanol solution and distilled water, respectively. Then, the cleaned GCE was dried with a high-purity nitrogen steam for next modification. A total of 5 μL of active materials solution (1.0 mg mL−1) was dropped on the GCE surface and dried at room temperature. Finally, 5 μL Nafion solution (0.1%, diluted with ethanol) was cast onto the electrode to avoid the leakage of modified GCE.
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Fig. 1 SEM images of the obtained materials at 200 °C for 24 h: (a) without MnSO4, (b) without TAA, (c) 0.1 g TAA, (d) 0.2 g TAA, (e) 0.4 g TAA, and (f) 0.8 g TAA. |
To identify the structure and composition of the products (Fig. 1) synthesized with different experimental parameters, XRD was applied, and the result is shown in Fig. 2. It is clear that the XRD patterns indicate these products have different compositions. Without the addition of TAA into the reaction system, all the diffraction peaks can be indexed to α-MnO2 (JCPDS 44-0141),33 which is formed by the following redox reaction between MnO4− and Mn2+: 2MnO4− + 3Mn2+ + 2H2O = 5MnO2 + 4H+ (1). When the amount of TAA increases to 0.1 g, all the diffraction peaks can also be indexed to α-MnO2 (JCPDS 44-0141). As KMnO4 is excessive, so at this time another redox reaction between MnO4− and TAA, 2MnO4− + 3CH3CS(NH2) + H2O = 2MnO2 + 3S + 3CH3CO(NH2) + 2OH− (2), will happen. Further increasing TAA to 0.2 g, all observed reflections are perfectly indexed γ-MnOOH (JCPDS 41-1379). When the amount of TAA increases to 0.4 g, all the diffraction peaks can be indexed to Mn3O4 (JCPDS 24-0734).34 Because TAA is a reductant, with the increasing of TAA, the reducing ability also increases, Mn3O4 was prepared with lower valence compared to γ-MnOOH. Meanwhile, when the amount of TAA increases to 0.8 g, all the diffraction peaks can be indexed to alabandite (MnS, JCPDS 06-0518). At this time, relative to MnSO4 and TAA, KMnO4 is not excessive, and TAA is excessive. So at this time the following reactions, CH3CS(NH2) + H2O = CH3CO(NH2) + H2S (3) and Mn2+ + H2S = MnS + 2H+ (4), will happen. Being consistent with SEM results, the XRD results also indicate that an optimal the amount of TAA is favorable for the formation of γ-MnOOH, and the optimized amount of TAA is about 0.2 g. Furthermore, without the addition of MnSO4 into the reaction system, all observed reflections are perfectly indexed γ-MnOOH (JCPDS 41-1379) but without uniform rod morphology. Therefore, the effect of the hydrothermal treatment temperature on the morphology of the obtained materials is studied at 0.2 g TAA for 24 h, and the SEM images of the obtained materials at different hydrothermal temperatures are shown in Fig. 3.
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Fig. 2 XRD patterns of the obtained materials at 200 °C for 24 h: (a) without TAA, (b) 0.1 g TAA, (c) 0.2 g TAA, (d) 0.4 g TAA, (e) 0.8 g TAA, and (f) without MnSO4. |
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Fig. 3 SEM images of the obtained materials at different hydrothermal temperatures for 24 h: (a) 140 °C, (b) 160 °C, (c) 180 °C, and (d) 200 °C. |
It can be seen that the morphology, size, and uniformity of the as-prepared materials are connected with the hydrothermal treatment temperature. γ-MnOOH with random rod and wire shape are obtained at 140 °C (Fig. 3a). On the other hand, γ-MnOOH with rod and wire morphology are also obtained when the hydrothermal treatment temperatures are 160 °C and 180 °C (Fig. 3b and c). It should be noted that, relative to material obtained at 140 °C, rod-shaped morphology product has smaller diameter while wire-shaped morphology product has bigger diameter at 160 °C and 180 °C. Upon further raising the hydrothermal treatment temperature to 200 °C, γ-MnOOH with uniform rod morphology is obtained (Fig. 3d).
Although the morphology of the as-prepared products obviously changes in accompany with the increase of the hydrothermal treatment temperature from 140 to 200 °C, the phase structure does not change and all ascribed to γ-MnOOH. The XRD patterns of the obtained products at different hydrothermal treatment temperatures are shown in Fig. 4. The overall diffraction peaks of the obtained materials are completely indexed to γ-MnOOH. With the hydrothermal treatment temperature from 140 to 160, 180, and 200 °C, the phase structure ascribed to γ-MnOOH does not change, while only the crystallinity of the obtained materials increases. The above results clearly show that the optimum preparation temperature of γ-MnOOH with uniform rod morphology is 200 °C.
To further understand the formation process of γ-MnOOH with uniform rod morphology, the systematic time-dependent experiments illustrating the evolution of the morphology and structure are performed at 200 °C when the amount of TAA is studied at 0.2 g. The SEM images of the obtained products for different hydrothermal treatment times are shown in Fig. 5. γ-MnOOH with random rod and wire shape are obtained when the reaction system is hydrothermally treated at 200 °C for 8 h (Fig. 5a). Only prolonging the hydrothermal treatment time to 16 h, γ-MnOOH with random rod and wire shape are also obtained (Fig. 5b). Continuing increase the hydrothermal treatment time to 24 h, γ-MnOOH with uniform rod morphology and a mean lateral size of 500 nm is obtained (Fig. 5c). Further prolonging the hydrothermal treatment time from 24 to 36 h, uniform rod was destroyed and the irregular morphology appeared (Fig. 5d).
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Fig. 5 SEM images of the obtained materials at 200 °C for different hydrothermal times: (a) 8 h, (b) 16 h, (c) 24 h, and (d) 36 h. |
Although the morphology of them changes with the increasing of the hydrothermal treatment time from 8 to 36 h, the phase structure does not change (all ascribed to γ-MnOOH). The XRD patterns of the products obtained at different hydrothermal treatment times are shown in Fig. 6. The overall diffraction peaks of the obtained materials are completely indexed to γ-MnOOH, indicating that γ-MnOOH can be obtained by hydrothermal treatment at 200 °C for 8 h. Further prolonging the hydrothermal treatment time from 8 to 16, 24, and 36 h, the phase structure ascribed to γ-MnOOH does not change, while only the crystallinity of the obtained materials changes a little. On the basis of the SEM images and XRD patterns, it can be concluded that γ-MnOOH with uniform rod morphology can be prepared under hydrothermal treatment at 200 °C for 24 h.
The morphology changes of γ-MnOOH obtained at different hydrothermal treatment times support the occurrence of the growth process. TEM images of γ-MnOOH obtained at different hydrothermal stages further indicate the existence of the growth process (Fig. 7).
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Fig. 7 TEM images of the obtained materials at 200 °C for different hydrothermal times: (a) 8 h, (b) 16 h, (c) 24 h, and (d) 36 h. |
In brief, firstly, large amount of nuclei form rapidly in a short time and then self-assembly to form amorphous small nanoparticles. During the hydrothermal process, an Ostwald ripening process is carried out,35 in which smaller nanoparticles dissolve while the bigger ones grow into sphere-like particles. It has been reported that MnO2 nanowires/nanorods tended to assemble along lateral surface and form thick nanorods through an oriented attachment mechanism under the hydrothermal condition since the formation of bundles could reduce the surface-to-volume ratio and the surface energy.36–38 As different crystal planes of the crystals have different energy potentials, the growth rates along different crystal planes are different. Therefore, we conceive that (−111) crystal plane of γ-MnOOH has a maximal energy in solution. Through oriented attachment, the crystal plane can reduce energy to promote the crystal growth along the surface orderly. As the surface energy of the crystal plane decreases, the growth rate gradually slows down. We believe that two mechanisms are responsible for the formation of the rods: (a) a dissolution–crystallization process that converts less ordered precursors into sphere-like particles and converts smaller diameter wires into bigger diameter rods; (b) an oriented attachment process that aggregates wires along the lateral faces to form rods.
The formation process can be described as follows: first, according to the previous report,39 as the concentration of reactants is comparatively high in the beginning; therefore, some nuclei can be formed very fast resulting in the occurrence of small nanoparticles. Meanwhile, some small nanoparticles tended to attachment, and this attachment might be attributed to the destruction of the stabilization layer around each nanoparticle.40 In addition, the aspect ratios of those small nanoparticles make us believe that those nanoparticles just began to grow into sphere-like particles. Second, sphere-like particles had grown into wire-shaped anisotropic nanostructures with the assistance of TAA. The sphere-like particles orient to form one dimensional wires and grow fast along the (−111) direction to form small diameter 1D wires. Once the nuclei had been formed, the morphology of the sphere-like particles changed very quickly from particles to wires and wire aggregates. In this period, we think the source of the γ-MnOOH molecules for the growth of the wires come from two aspects: the reactants of the solution on one side, and the dissolution of the sphere-like particles on the other side. With the rapid growth of wires and wire aggregates, the concentration of the reactants decreased, and then the dissolution process became dominant. Third, as the reaction proceeded, meanwhile, some wires tended to assemble along their side surfaces to reduce the surface energy. The small gaps between wires were filled rapidly due to coarsening during aging, which led to reconstruction of boundaries and smoothing of the surfaces. That is the reason why the rods show a single-crystalline nature. That is to say, at this stage, wire aggregates began to evolve its morphology into rods, and then the wire-like intermediate transformed into the rod structure after continuous growth through a dissolution–recrystallization process. At last, the rods were formed due to the hydrothermal process providing sufficient energy for the dissolution and recrystallization of those wire-like crystals. In addition, the transition of wires into rods indicates that the wires and wire aggregates are intermediate states between small nanoparticles and rod states, but they are not in a metastable state, as this transformation happens only in the reaction solution. On the basis of the above discussions, it sounds reasonable to conclude that the reactions follow a nucleation–dissolution anisotropic growth–recrystallization mechanism. A similar mechanism of nucleation–dissolution–recrystallization, suggested by Qian and co-workers,41 has been accounted for the formation of Te nanotube. It is necessary to note that the dissolution–crystallization and oriented attachment are two simultaneous processes in the crystal growth,42 the separated stages in Fig. 8 are illustrated just for the convenience of explanation.
In our experiments, the introduction of TAA is important and ingenious. On the one hand, the TAA itself could serve as an appropriate reducing agent. On the other hand, a part of TAA would hydrolyze in the aqueous solution, generate H2S and provide a weak acidic reaction circumstance, which was believed good for the formation and growth of γ-MnOOH rods. Meanwhile, the S element of TAA is also entered into the crystal lattice of γ-MnOOH, thus formed S-doped γ-MnOOH. Certainly, this mechanism needs to be confirmed by further studies.
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Fig. 9 (a) XRD pattern, (b) Raman spectrum, (c) XPS spectrum, (d) XPS spectrum of Mn2p, (e) XPS spectrum of O1s, and (f) XPS spectrum of S2p of the γ-MnOOH. |
Raman spectroscopy is a powerful experimental technique for the identification and characterization of the local manganese environment. It further confirms our product as γ-MnOOH. As reported in the literature,43,44 γ-MnOOH shows well resolved and sharp Raman bands with the main peaks at 142, 352, 384, 528, 552 and 615 cm−1 together with another four minor peaks, which reflect good crystallinity. The Raman spectrum of our as-prepared γ-MnOOH is shown in Fig. 9b, well resolved peaks can be seen at 145, 254, 356, 384, 527, 554 and 623 cm−1, which agrees well with the previous data in the literature.43,44
Fig. 9c presents the XPS spectrum of γ-MnOOH. XPS is best known for its capability in disclosing the chemical states of a surface, and it also further confirms our product as γ-MnOOH. The XPS results show photoelectron peaks of Mn, O, the contaminant C, and the Auger peaks of Mn LMM and O KLL. The Mn2p spectrum exhibits two major peaks with binding energy values at 653.8 and 642.2 eV, corresponding to the Mn2p1/2 and Mn2p3/2 peaks (Fig. 9d).17 The observed binding energies of the Mn2p3/2 and Mn2p1/2 for the γ-MnOOH rods are in good agreement with data on γ-MnOOH. The XPS spectrum of O1s (Fig. 9e) consists of two peaks, which correspond to lattice oxygen and adsorption oxygen on the sample surface.45 The O1s spectrum has its maximum near 530 eV and a distinct shoulder with a pronounced tail on the high energy side of the peak. The separation of the O1s peak was deconvoluted by Gaussian fits. The peak at 530.8 eV corresponds to the lattice oxygen species (O2−, OH−), which reflect the redox behavior of the metal. The peak at 532.5 eV corresponds to the adsorption oxygen species (O2−, O22−), whose content reflects the concentration of oxygen vacancy in the compound. By trapping electrons, adsorption oxygen becomes the active center for the oxidation, which leads to the formation of O2−.45 It was confirmed by XPS that there are no obvious impurity such as K (from the KMnO4) detected in the samples. It was also confirmed by XPS that there is S element detected in the samples (Fig. 9f).
Furthermore, the elemental analysis by SEM-EDS also confirms the presence of Mn, O, and S elements (Fig. 10a–d). The crystal structure is further characterized by HRTEM and selected area electron diffraction (SAED) pattern analyses in Fig. 10e and f. The HRTEM image enables a clear view of lattice fringes, which are shown in Fig. 10e. The well-resolved lattice fringes give an inter-planar spacing of 0.34 nm, corresponding with the distance of the (−111) plane of γ-MnOOH.7 This indicates that the growth of the microrods is along the [−111] direction and the results agree well with the XRD result. Moreover, the corresponding SAED pattern performed on an individual rod in Fig. 10f indicates that the rod is of single crystal and can be indexed as the monoclinic MnOOH phase, which is in accordance with the XRD result in Fig. 9a. These results indicate γ-MnOOH with high crystallinity and uniform rod morphology can be prepared at 200 °C for 24 h in the typical experiment.
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Fig. 10 (a–d) Multi-element EDS mapping images, (e) HRTEM image, and (f) SAED pattern of the γ-MnOOH. |
According to the previous report,30 a possible electrochemical reaction for the N2H4 is proposed to be N2H4 + 5/2OH− → 1/2N3− + 1/2NH3 + 5/2H2O + 2e−. As faster electron transfer leads to a sharper and more well-defined peak, the substantial increase in the peak current reflects a faster electron transfer reaction and the increase of reversibility of the electron transfer process. Therefore, N2H4 can be effectively detected by oxidation on the modified GCE. The pH of the solution is important to obtain efficient electrocatalytic oxidation of N2H4, and it was reported that the electrocatalytic oxidation of N2H4 can be improved by increasing the pH value of the solution (pH > 7).30 Therefore, we maintained pH 7.4 for all the electrochemical experiments. Fig. 11b and c present the current–time (I–T) plot of the modified GCE with successive adding N2H4. As the N2H4 is injected, the steady-state currents reach another steady-state value (98% of the maximum) in less than 2 s. The linear relationship between the catalytic current and the concentration is shown in Fig. 11d–f. Our electrochemical N2H4 sensor has wide linear range 0.1 μM–1.15 mM (correlation coefficient: 0.998) and 1.15–45.75 mM (correlation coefficient: 0.999), and a detection limit of 0.079 μM at a signal-to-noise ratio of 3. As can be seen from Table 1, our sensor has larger linear range and lower detection limit compared to the previous N2H4 sensors.
Electrode materials | Potential (V) | Linear range (mM) | LOD (mM) | Ref. |
---|---|---|---|---|
ZnO–carbon nanotube | 0.4 | 6 × 10−4 to 0.25 | 1.8 × 10−4 | 46 |
ZnO nanonails | −0.5–0.4 | 1 × 10−4 to 1.2 × 10−3 | 2 × 10−4 | 30 |
MnO2–carbon nanotube | 0.3 | 5 × 10−4 to 1 | 2 × 10−4 | 47 |
Au–TiO2 | 0.2 | 2.5 × 10−3 to 0.5 | 5 × 10−4 | 48 |
Micro/nano ZnO | 0.1 | 8 × 10−4 to 0.2 | 2.5 × 10−4 | 49 |
S Doped γ-MnOOH | 0.55 | 1 × 10−4 to 1.15 | 7.9 × 10−5 | This work |
1.15–45.75 |
The wide linear range and low detection limit may be due to the unique structure of S-doped γ-MnOOH microrods. The presence of the S-doped γ-MnOOH microrods in GCE with high surface area provides the platform for the N2H4 oxidation by contributing excess electroactive sites, which effectively enhanced the catalytic activity for N2H4 oxidation. In addition, their good crystalline structure and facile accessibility of enormous nanoscale transport channels resulted from the micromaterial structure can also cause efficient electron transportation, greatly enhanced adsorption and the rate of electron transfer from N2H4 to electrode. Thus, the S-doped γ-MnOOH microrods can be used as modification layer to improve the sensitivity of the N2H4 oxidative detection.
The selectivity of the modified GCE towards N2H4 was studied for a number of potential interferents, and the result is shown in Fig. 12a. Here, we defined the tolerance limit as the molar ratio of potential interfering substance/N2H4 that caused the change of peak current less than 5% for the determination of 0.01 mM N2H4. It was found that 5-fold hydroxylamine(NH2OH), 12-fold NH3, 18-fold H2O2, dopamine, and glucose, 30-fold Zn2+, Cu2+, Ca2+, NO3−, Cl−, SO42− have no obvious interfere on the determination of N2H4. The reproducibility of the modified GCE was examined by repetitive detection of 0.01 mM N2H4, there was about 4.59% decrease in the response towards 0.01 mM N2H4 after 60 times, demonstrating high antifouling ability of our N2H4 sensor (Fig. 12b). The storage stability measured every 2–3 days over a 21-days period. When not in use, the modified electrode was stored in air at room temperature. There was about 3.69% decrease in the response towards 0.01 mM N2H4 after 21 days, indicating that our S doped γ-MnOOH modified GCE maintained its catalytic activity very well and could be used for a long time (Fig. 12c).
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