# Facile Synthesis of Highly Dispersed WO3·H2O and WO3 Nanoplates for Electrocatalytic Hydrogen Evolution

Authors: Wen-Hui Hu; Guan-Qun Han; Bin Dong; Chen-Guang Liu
Journal: Journal of Nanomaterials
 (2015)

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## Abstract

The highly dispersed WO3·H2O nanoplates have been synthesized by a facile hydrothermal reaction assisted by citrate acid. WO3 nanoplates have been prepared by the calcination of as-prepared WO3·H2O at 450°C. XRD data show that WO3·H2O and WO3 have good crystal structure and high purity. SEM images show that WO3·H2O and WO3 have the uniform nanoplates morphology with the edge length of about 100–150 nm. The selective absorbance of citrate acid with many OH groups onto [010] facet of tungsten oxide precursors can result in the controlled growth of WO3·H2O, thus leading to the good dispersion and small size of WO3·H2O nanoplates. The electrocatalytic activity of WO3·H2O and WO3 for hydrogen evolution reaction (HER) has been investigated in detail. The good electrocatalytic activity for HER has been obtained, which may be attributed to the good dispersion and small size of nanoplates. And the growth mechanisms of WO3·H2O and WO3 nanoplates have been discussed.


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## Body

## 1. Introduction

Hydrogen evolution reaction has attracted the growing interest because hydrogen as a promising sustainable energy carrier could accelerate the transition from the hydrocarbon economy to sustainable energy economy [1]. One of the promising fashions of hydrogen production is to adopt electrochemical [2] route. Novel metals such as Pt are the highly active electrocatalysts for HER [3], but the disadvantages of Pt are high cost and limited reserve, preventing the utilization of novel metal electrocatalysts. Therefore, designing the earth-abundant elements as active electrocatalysts represents future development of the electrocatalysts for HER [4].As importantn-type semiconductors, tungsten oxide hydrates (WO3·nH2O) and tungsten oxides (WO3) have obtained more and more attention due to their polytypic structures and excellent physical/chemical properties [5]. Many applications have been extensively investigated such as lithium-ion batteries [6], supercapacitors [7], gas sensors [8], photocatalysts [9, 10], solar energy devices [11], and electrocatalyst in electrolysis of water for HER [12]. Furthermore, the monoclinic WO3 is more stable phase than any other WO3 structures owing to the structure consisting of a three-dimensional network of WO6 octahedrons [13, 14].Up to now, many approaches have been adopted to synthesize WO3 nanostructures with different morphologies including nanotubes [15], nanowires [16], nanorods [17], nanoplates [18], and hollow spheres [19]. Among the different morphologies, nanoplate-like structure displays excellent gas response and catalytic properties because of their high density of surface sites [20]. WO3·nH2O has been usually prepared through the liquid-phase synthesis routes, and WO3 has been synthesized by annealing WO3·nH2O to remove crystal water. The hydrothermal method can be used owing to some advantages in controlling the morphology, size, and homogeneity at the mild temperature for large-scale production [21]. However, developing a facile route for large-scale production of WO3 with high crystal phase and high purity is still a challenge.In our work, highly dispersed WO3·H2O nanoplates have been synthesized by a facile hydrothermal reaction assisted by citrate acid. WO3 nanoplates have also been prepared by the calcination of WO3·H2O at 450°C for 4 h. SEM images show that as-prepared WO3·H2O and WO3 samples have the uniform nanoplates morphology with the edge length of about 100–150 nm. The electrocatalytic activity of the two samples for HER properties has been investigated in detail. The good electrocatalytic activity for HER has been obtained, which may be attributed to the good dispersion and small size of nanoplates. And the growth mechanisms of highly dispersed WO3·H2O and WO3 nanoplates have been discussed.


## 2. Experimental

### 2.1. Preparation of WO3·H2O and WO3 Nanoplates

All chemical reagents were of analytic purity and used directly without further purification. WO3·H2O nanoplates have been prepared by dissolving 0.4 g citrate acid and 0.53 g Na2WO4·2H2O in 40 mL deionized water in order under stirring. The pH value of the solution was adjusted to about 1.0 by the addition of HCl. Then the mixture was transferred into a 50 mL Teflon-lined stainless steel autoclave and sealed, and the autoclave was placed in a preheated oven at 120°C for 3 h. After being naturally cooled down to room temperature, the yellow precipitates were collected by filtration and washed with deionized water and ethanol for several times and dried in oven at 80°C. The as-prepared WO3·H2O nanoplates have been calcined at 450°C for 4 h to prepare WO3 samples. The yellow WO3·H2O samples changed to white-yellow WO3 samples.


### 2.2. Characterization of Morphology and Structure

Crystallographic structure of all as-prepared samples was investigated with X-ray powder diffraction (XRD, X’Pert PRO MPD, Cu KR) at a scanning rate of 8°C min−1. XRD data were collected in the 2θ ranges from 10 to 60°. The morphology of the samples was examined with field-emission scanning electron microscopy (SEM, Hitachi, S-4800). Selected area electron diffraction (SAED) was used to examine samples’ crystallinity (TEM, JEM-2100UHR with an accelerating voltage of 200 kV).


### 2.3. Electrochemical Measurement

The glassy carbon electrode (geometric surface area of glassy carbon = 0.1256 cm2), Pt plate, and Ag/AgCl electrode were used as working, counter, and reference electrodes, respectively. 0.5 M H2SO4 solution was used as electrolyte for linear sweep voltammetry and electrochemical impedance spectra on the Gamry reference 600 electrochemical workstation. The working electrodes were prepared by catalytic ink-dispersing 20 mg catalyst in 1 mL ethanol and 0.01 mL of 5 wt% Nafion under 30 min ultrasonic radiation.


## 2.1. Preparation of WO3·H2O and WO3 Nanoplates

All chemical reagents were of analytic purity and used directly without further purification. WO3·H2O nanoplates have been prepared by dissolving 0.4 g citrate acid and 0.53 g Na2WO4·2H2O in 40 mL deionized water in order under stirring. The pH value of the solution was adjusted to about 1.0 by the addition of HCl. Then the mixture was transferred into a 50 mL Teflon-lined stainless steel autoclave and sealed, and the autoclave was placed in a preheated oven at 120°C for 3 h. After being naturally cooled down to room temperature, the yellow precipitates were collected by filtration and washed with deionized water and ethanol for several times and dried in oven at 80°C. The as-prepared WO3·H2O nanoplates have been calcined at 450°C for 4 h to prepare WO3 samples. The yellow WO3·H2O samples changed to white-yellow WO3 samples.


## 2.2. Characterization of Morphology and Structure

Crystallographic structure of all as-prepared samples was investigated with X-ray powder diffraction (XRD, X’Pert PRO MPD, Cu KR) at a scanning rate of 8°C min−1. XRD data were collected in the 2θ ranges from 10 to 60°. The morphology of the samples was examined with field-emission scanning electron microscopy (SEM, Hitachi, S-4800). Selected area electron diffraction (SAED) was used to examine samples’ crystallinity (TEM, JEM-2100UHR with an accelerating voltage of 200 kV).


## 2.3. Electrochemical Measurement

The glassy carbon electrode (geometric surface area of glassy carbon = 0.1256 cm2), Pt plate, and Ag/AgCl electrode were used as working, counter, and reference electrodes, respectively. 0.5 M H2SO4 solution was used as electrolyte for linear sweep voltammetry and electrochemical impedance spectra on the Gamry reference 600 electrochemical workstation. The working electrodes were prepared by catalytic ink-dispersing 20 mg catalyst in 1 mL ethanol and 0.01 mL of 5 wt% Nafion under 30 min ultrasonic radiation.


## 3. Results and Discussion

Figure1 displays XRD patterns and SAED patterns of WO3·H2O synthesized by hydrothermal route. As shown in Figure 1(a), all the peaks clearly demonstrate that the samples are the orthorhombic WO3·H2O crystal, corresponding to the (020), (111), and (002) diffraction at 2θ of 16.5°, 25.7°, and 35.1° (JCPDS number 43-0679 with lattice constants ofa = 0.5238 nm,b = 0.1070 nm, andc = 0.5120 nm). The high intensity and narrow peaks of (020) and (111) mean good crystallinity of WO3·H2O. No other impurity peaks can be observed from the patterns, indicating high purity of the sample. It can be concluded that the hydrothermal process assisted by citrate acid could produce the pure WO3·H2O with the orthorhombic phase. Figure 1(b) shows the corresponding SAED patterns of WO3·H2O, indicating that these nanoplates have a polycrystalline orthorhombic WO3·H2O phase.(a) XRD patterns of WO3·H2O as-prepared by hydrothermal method. (b) Selected area electron diffraction (SAED) patterns of WO3·H2O.
(a)
(b)To investigate the morphology and size of WO3·H2O, the as-prepared samples have been measured by SEM (in Figure 2). As shown in Figure 2(a), SEM images of WO3·H2O assisted by citrate acid show the uniform nanoplates morphology with the edge length of about 100–150 nm. With higher magnification, it can be seen from Figure 2(b) that the thickness of each WO3·H2O nanoplate is about 30 nm. The coarse surface and monodispersed structure of WO3·H2O nanoplates can also be clearly observed, which maybe indicate the lager specific surface area and more active sites for HER [12]. From Table 1, it can be seen that WO3·H2O nanoplates have much higher Brunauer-Emmett-Teller (BET) specific surface area of 23.28 m2·g−1 than WO3 nanoplates (11.99 m2·g−1), which implies that the BET area of WO3 nanoplates is decreased after the calcination.Table 1
BET area of WO3·H2O and WO3 nanoplates.
Materials
WO3·H2O
WO3
BET area (m2·g−1)
23.28
11.99SEM images of WO3·H2O nanoplates.
(a)
(b)XRD patterns of WO3 after calcination at 450°C are shown in Figure 3. It can be seen that all the diffraction peaks of WO3 samples are consistent with the monoclinic WO3 phase (JCPDS number 43-1035). No other peaks from XRD patterns were detected, indicating that WO3·H2O samples completely transform to the pure WO3 phase with three distinct diffraction peaks of (002), (020), and (200), respectively.Figure 3
XRD patterns of WO3 after being calcined in 450°C for 4 h.The SEM images of the calcined WO3 samples are shown in Figure 4. It can be found in Figure 4(a) that the similar nanoplates morphology has been maintained during the process of calcination at 450°C. However, the surface of WO3 nanoplates obviously becomes smooth, which may be attributed to the elimination of water molecules between the tungstite layers. Figure 4(b) shows that some aggregation growth of WO3 nanoplates appears with the slight increasing of thickness of WO3 nanoplates due to the effect of the calcination process at 450°C.SEM images of WO3 nanoplates.
(a)
(b)The transformation process from WO3·H2O nanoplates to WO3 nanoplates is illustrated in Figure 5. Firstly, H2WO4 phase formed when adding HCl into Na2WO4 solution (1) as follows:
(1)
Na
2
WO
4
+
2
HCl
⟶
H
2
WO
4
+
2
NaCl
(2)
H
2
WO
4
⟶
WO
(
OH
)
4
(
O
H
2
)Figure 5
Schematic illustration of the formation mechanism of WO3 nanoplates.Secondly, H2WO4 precursor changed to [WO(OH)4(OH2)] (2), with the sixfold coordinated W6+ including one oxygen atom and water molecule alongb-axis, two OH groups alonga-axis, and two OH groups alongc-axis, respectively (as shown in Figure 5(a)). Thirdly, during hydrothermal process, [WO(OH)4(OH2)] converted to the octahedral [WO5(OH2)] layer by oxolation, which is the structural unit of WO3·H2O with more OH on the [
010
] facets [9]. There are stable hydrogen bonds force-derived from the terminal oxygen atoms and coordinated water molecules between the neighbouring layers of WO3·H2O, thus leading to the formation of WO3·H2O with layers structure (Figure 5(b)). When being calcined at 450°C, the water molecules between the neighbouring layers of WO3·H2O have been released with keeping the layer structure. The dehydration process has been proved to be a topotactic process [22]. Finally, the structure of monoclinic WO3 is obtained in Figure 5(c). During the hydrothermal process, the growth of WO3·H2O nanoplates has largely been affected by the citrate acid as dispersant and control agent. Similar research has been reported that certain crystal faces of WO3 can be impeded by using that preferentially adsorbed to specific crystal faces with the assistance of malic acid [23]. In our work, citrate acid including many OH groups can be selectively absorbed onto [
010
] facet because there are many OH groups on the surface of [WO5(OH2)] layer. The selective absorbance may be attributed to the strong interaction between the OH groups (Figure 5(d)). Therefore, the stacking growth along (010) facet has been controlled by the adding of citrate acid. And the good dispersion and small size of WO3·H2O nanoplates could be obtained.The electrocatalytic activity for HER of WO3·H2O and WO3 nanoplates has been studied in 1 M H2SO4 solution over the potential range of −0.60 to +0.8 V at a scan rate of 50 mVs−1 by the linear sweep voltammetry (LSV), Tafel plots, and electrochemical impedance spectra. Figure 6 shows the LSV curves and Tafel plots of WO3·H2O and WO3 nanoplates. It can be seen from Figure 6(a) that WO3·H2O exhibits the electrocatalytic activity for HER with onset potential of −0.20 V (versus RHE) and the exchange current density of −4.5 mA cm−2 at overpotential of 300 mV. The onset potential for the HER of WO3 nanoplates is about −0.09 V. The exchange current density of WO3 sample is about −7.5 mA cm−2 at overpotential of 300 mV.(a) Linear sweep voltammogram curves of WO3·H2O and WO3 nanoplates. (b) Tafel plots of WO3·H2O and WO3 nanoplates.
(a)
(b)Figure6(b) shows Tafel slopes of 97 and 101 mV dec−1 for WO3·H2O and WO3 nanoplates, respectively. The ideal electrocatalysts should have low Tafel slopes and high cathodic current densities. For example, Pt has a high current density in the order of 10−3 A cm−2 and a Tafel slope of 30 mV dec−1 for HER. However, in our work, WO3 nanoplates have a higher current density but a higher Tafel slope than that of WO3·H2O. According to the previous report [24], which electrocatalyst is better depends on the targeted current density. For example, to obtain the targeted current density of 10 mA cm−2, WO3·H2O sample requires −390 mV of overpotential, while WO3 sample requires −340 mV. Therefore, WO3 is the better electrocatalyst for HER.The electrochemical impedance spectra of the two different samples can be shown in Figure7. WO3 sample shows the smaller charge-transfer resistance than WO3·H2O, which implies that WO3 has much faster electron transfer and improved efficiency for HER than WO3·H2O. The enhancement of conductivity also benefits from the compact structure of WO3 after calcination at high temperature. The poor HER activity of WO3·H2O may be attributed to the existence of crystal H2O. Firstly, the crystal H2O may occupy some active sites for HER, resulting in poor catalytic activity. Secondly, the poor conductivity of WO3·H2O impedes the transportation of the electrons between the active sites and the electrode. So WO3·H2O has the worse HER activity than WO3.Figure 7
Electrochemical impedance spectra of WO3·H2O and WO3 nanoplates.


## 4. Conclusions

The highly dispersed WO3·H2O and WO3 nanoplates have been synthesized by a facile process assisted by citrate acid. The as-prepared WO3·H2O and WO3 have the uniform nanoplates morphology with good crystal structure and high purity, which may be attributed to the adding of citrate acid. The selective absorbance of citrate acid onto [
010
] facet of [WO5(OH2)] layer may result in the good dispersion and small size of WO3·H2O nanoplates. The electrocatalytic activity of WO3·H2O and WO3 for HER has been studied. The poor electrocatalytic activity of WO3·H2O compared to WO3 may be attributed to the existence of crystal H2O.



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