Facile Synthesis of WS<sub>2</sub>/WO<sub>3</sub> Materials in a Batch Reactor for the Hydrogen Evolution Reaction

Nguyen, Tuan Van; Huynh, Kim Anh; Le, Quyet Van; Ahn, Sang Hyun; Kim, Soo Young

doi:https://doi.org/10.1155/2024/4878549

International Journal of Energy Research

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Abstract Introduction Results and Discussion Conclusions Data Availability Conflicts of Interest Authors’ Contributions Acknowledgments Supplementary Materials References Copyright Related Articles

Research Article | Open Access

Volume 2024 | Article ID 4878549 | https://doi.org/10.1155/2024/4878549

Facile Synthesis of WS₂/WO₃ Materials in a Batch Reactor for the Hydrogen Evolution Reaction

Tuan Van Nguyen,¹Kim Anh Huynh,²Quyet Van Le,¹Sang Hyun Ahn,³and Soo Young Kim¹

Academic Editor: Semen Klyamkin

Received01 Nov 2023

Revised18 Dec 2023

Accepted29 Apr 2024

Published16 May 2024

Abstract

In this study, a new and facile process was developed for the preparation of composite catalysts based on tungsten oxide (WO₃) by batch reactor routes. The structures, morphologies, compositions, and characteristics of synthesized materials were investigated and confirmed. Using batch reactor processes, WO₃ nanorods (WO₃ NR), heterostructures of WS₂/WO₃ nanobricks (WS₂/WO₃ NB), and WS₂/WO₃ nanorods (WS₂/WO₃ NR) were successfully prepared. The prepared materials were then employed for hydrogen evolution reaction (HER) to investigate their catalytic performance. The results indicated that the electrocatalytic activities of WS₂/WO₃ NR are significantly improved compared to those of WO₃ NR and WS₂/WO₃ NB. This improvement could be attributed to the formation of heterostructure between WS₂ and WO₃ elements in highly uniform materials, which could create the synergistic effect and further improve the catalytic activities of the catalyst. The data shows that the Tafel slope of WS₂/WO₃ NR (82.7 mV dec⁻¹) is significantly lower than that of WO₃ NR (112.5 mV dec⁻¹) and WS₂/WO₃ NB (195.5 mV dec⁻¹). Furthermore, the resistance of WS₂/WO₃ NR (397.7 Ω) is markedly decreased compared to those of WO₃ NR (1816 Ω) and WS₂/WO₃ NB (3597 Ω). The results indicate that WS₂/WO₃ NR could be a great catalyst for electrochemical applications.

1. Introduction

Over the last decades, the excessive use of fossil fuels has become a critical issue that must be addressed because of greenhouse gas emissions and global warming [1–5]. New materials and breakthrough technologies are increasingly necessary to conserve energy and develop environmentally friendly energy sources. Tremendous efforts have been made to overcome the emerging environmental problems [6–13]. With the advent of cutting-edge technologies, hydrogen is one of the most prominent candidates as an ecosystem-friendly and reusable energy source [14–21]. Different materials have been investigated to enhance reaction performance and produce hydrogen gas [22–28]. Thus far, noble metals such as Pt group metals have demonstrated higher active electrocatalyst performances for the hydrogen evolution reaction (HER) than other materials [29–32]. However, the scarcity and high cost of those catalysts are their major drawbacks. Therefore, the design of abundant, low-cost materials with excellent catalytic performance for HER applications remains a considerable challenge for researchers. Transition metals and their compounds are promising candidates for the preparation of excellent catalytic materials for the HER. Recently, transition metals and their compounds have been extensively investigated for HER performance because of their benefits for electrocatalyst materials [33–35]. Among many materials, the well-known transition metal W and its derivatives have distinctive electronic characteristics [36–38]. In particular, WO₃ has been extensively investigated for various applications such as electrochromic devices [39–41], sensors [42, 43], solar cells [44, 45], photocatalysts [46, 47], and HER applications [48–51].

Catalysts based on WO₃ exhibit poor catalytic properties because the adsorption energy of atomic hydrogen on WO₃ molecules is inadequate, resulting in the low activity of WO₃ for the HER in the electrolyte [52, 53]. This can be attributed to the low conductivity and intrinsic inactivity of WO₃. In recent decades, several approaches have been developed to improve the HER performance of WO₃, including metallic and non-metallic doping to form hybrid materials [54, 55]. Noble metal doping or hybrid materials may create synergistic effects between different elements that can tune the electronic structure, increase the number of catalytic active sites, and enhance the HER activity. However, noble metal doping has several limitations, including complicated processes and expensive materials [56, 57]. Therefore, numerous studies have been conducted to develop facile, scalable, and low-cost processes for the synthesis of heterostructure catalysts based on WO₃ materials [58–60]. In previous researches, the performance of different catalysts based on various structures of WO₃ and/or WS₂ is listed in Table S1.

Herein, a simple, low-cost, and scalable method is introduced to synthesize different structures of WO₃ and its derivatives using a batch reactor. Various measurements were conducted to confirm the formation and morphology of the synthesized materials. Different materials including WO₃ nanorods (WO₃ NR) and heterostructures of WS₂/WO₃ nanobricks (WS₂/WO₃ NB) and WS₂/WO₃ nanorods (WS₂/WO₃ NR) were prepared. Electrochemical studies demonstrated that the HER activity of WS₂/WO₃ NR was higher than those of WO₃ NR and WS₂/WO₃ NB. The highly uniform and synergistic effect of WS₂ and WO₃ elements in the synthesized WS₂/WO₃ NR could be responsible for its excellent HER performance. Based on the catalytic performance, the synthesized WS₂/WO₃ NR is a promising material for electrochemical applications.

2. Experimental Section

The experiments were conducted in a closed batch reactor. The different mechanisms of procedures are briefly illustrated in Section 2.6.

2.1. Materials

All materials were used as received, without further purification. Ammonium metatungstate hydrate (NH₄)₆H₂W₁₂O₄₀.xH₂O) (AMT), thioacetamide (TAA) (C₂H₅NS, 99%), and hydrochloric acid (HCl, ACS reagent, 37%) were purchased from Sigma–Aldrich. Dimethylformamide (DMF) was supplied by Alfa Aesar. Deionized (DI) water (18.3 MΩ cm⁻¹) was obtained from Millipore Milli-Q.

2.2. Synthesis of WO₃ NR

TAA (3.75 g) was dissolved and stirred for 30 min in DI water (25 mL) in a 100 mL Teflon beaker. Subsequently, AMT (4 g) was added to the prepared solution, followed by stirring continuously for 30 min. Then, the Teflon beaker was placed in a batch reactor system and heated at 180°C for 24 h. After cooling to room temperature, the precipitate was formed at the bottom of the Teflon beaker, and it was collected and centrifuged thrice with DI water. The obtained powder, WO₃ NR, was dried in a vacuum dryer at 90°C for 12 h.

2.3. Synthesis of WS₂/WO₃ NB Composite

The WS₂/WO₃ NB composite was also synthesized via the process used for WO₃ NR, with slight modifications. Initially, TAA (3.75 g) was dissolved and stirred for 30 min in DMF (25 mL) in a 100 mL Teflon beaker. Subsequently, AMT (4 g) was added to the prepared solution, followed by stirring continuously for 30 min. Then, the Teflon beaker was placed in a batch reactor system and heated at 180°C for 24 h. After cooling to room temperature, the precipitate was formed at the bottom of the Teflon beaker, and it was collected and centrifuged thrice with DI water. The obtained powder, WS₂/WO₃ NB, was dried in a vacuum dryer at 90°C for 12 h.

2.4. Synthesis of WS₂/WO₃ NR Heterostructure

The WS₂/WO₃ NR heterostructure was also synthesized via the technique used for WO₃ NR and WS₂/WO₃ NB, with slight modifications. Firstly, TAA (3.75 g) was dissolved and stirred for 30 min in DI water (25 mL) in a 100 mL Teflon beaker. Subsequently, AMT (4 g) was added to the prepared solution, followed by stirring continuously for 30 min. After that, 37% HCl (3 mL) was added to the Teflon beaker, followed by stirring continuously for 30 min. Then, the Teflon beaker was placed in a batch reactor system and heated at 180°C for 24 h. After cooling to room temperature, the precipitate was formed at the bottom of the Teflon beaker, and it was collected and centrifuged thrice with DI water. The obtained powder, WS₂/WO₃ NR, was dried in a vacuum dryer at 90°C for 12 h.

2.5. Electrochemical Measurements

The HER performance of different materials was evaluated by a three-electrode system (Ivium potentiostat V55630) using 0.5 M H₂SO₄ electrolyte solution. Graphite rod, saturated calomel, and catalyst-coated glassy carbon electrodes with diameters of 3 mm were used as the counter, reference, and working electrodes, respectively. The catalyst inks were prepared by mixing 1 mg of each powder with 1 mL of DMF water and 50 μL of Nafion (5%) which works as the stabilizer. The prepared inks were then drop coated on glassy carbon, followed by drying at 90°C for 30 min. Linear sweep voltammetry (LSV) was conducted to measure the HER performance (scan rate of 10 mV s⁻¹). To calculate the double layer capacitance (), the cyclic voltammetry measurements were investigated from 0 to 0.2 V at various scan rates of 10, 20, 30, 40, and 50 mV s⁻¹. Electrochemical impedance spectroscopy (EIS) was studied at a potential of 280 mV and frequencies ranging from 100 kHz to 0.1 Hz.

2.6. Material Characterization

The crystallinity of the synthesized materials was confirmed using X-ray diffraction (XRD, D8-Advance/Bruker-AXS). Additionally, Raman spectroscopy (LabRAM HR, Horiba Jobin Yvon) was also studied to confirm the structures of prepared materials. After that, the morphologies, sizes, and shapes of the synthesized materials were analyzed using field-emission scanning electron microscopy (FE-SEM, SIGMA/Carl Zeiss). The chemical compositions as well as the oxidation states of the constituent elements of WO₃ NR, WS₂/WO₃ NB, and WS₂/WO₃ NR were then investigated by using X-ray photoelectron spectroscopy (XPS, Thermo Fisher Scientific, K-Alpha, USA).

2.7. Synthesis Process and Proposed Mechanisms

The proposed reaction mechanism of the synthesis process is shown in Figure 1. (1)Synthesis of WO₃ NR. Source materials (AMT, TAA, and ).(2)Synthesis of WS₂/WO₃ NB Composite. Source materials (AMT, TAA, and DMF).(3)Synthesis of WS₂/WO₃ NR Heterostructure. Source materials (AMT, TAA, HCl, and H₂O).

When hydrothermal or solvothermal processes are conducted to prepare materials in closed system, the reactions inside the batch reactor could take place and be highly complicated. Based on the source materials and their properties, the above-suggested mechanisms (1-13) could take place in batch reactor, depending on the source materials. Those processes take place in a closed system at a high temperature (180°C) for a long time (24 h). Using AMT, TAA, and different agents (H₂O, DMF, and H₂O+HCl), various gases could be released (H₂S, NH₃, SO₂, or even water vapour) in a small volume of reactor, which could significantly change the pH of the solution, the pressure inside of the batch reactor, and/or produce new ions. Those factors are the main reason which leads to the form of various structures and morphologies of synthesized materials [23, 61].

3. Results and Discussion

The crystallinity and structure of the synthesized materials were well investigated by using XRD measurement. In Figure 2, it is clear that all the peaks in the XRD pattern of WO₃ NR can be indexed to the monoclinic WO₃ (JCPDS Card No. 83-0950) and the hexagonal WO₃ (JCPDS Card No. 85-2460), as confirmed in a previous study [62, 63]. No other peaks could be observed in the XRD pattern of WO₃ NR which indicated that the high purity of WO₃ NR material was successfully synthesized. To confirm the appearance of WS₂ in WS₂/WO₃ NB and WS₂/WO₃ NR, the pure WS₂ was also synthesized by Teflon line autoclave as previous process [64]. The XRD pattern of pure WS₂ is provided in Figure S1. In the XRD pattern of WS₂/WO₃ NB, there are three peaks located at 29° (004), 32° (101), and 35° (102) which could be ascribed to the hexagonal phase of WS₂ (JCPDS Card No. 08-0237) [24]. The XRD intensity of WO₃ peaks in WS₂/WO₃ NB is lower than those of WO₃ NR, and those peaks could be ascribed to the orthorhombic phase of tungsten oxide hydrate WO₃.H₂O which was confirmed in the previous study [48]. The XRD result indicates the mixed phase of WS₂ and WO₃, suggesting the coexistence of WS₂ and WO₃ in WS₂/WO₃ NB. In the XRD pattern of WS₂/WO₃ NR, there are also various peaks of WO₃ which are in line with the peaks of WO₃ NR as mentioned above. Besides that, there are two peaks of WS₂ located at 29° (004) and 35° (102). The XRD data indicated the successful synthesis of different catalysts including WO₃ NR, WS₂/WO₃ NB, and WS₂/WO₃ NR.

Figure 3 shows the Raman spectra of the synthesized WO₃ NR, WS₂/WO₃ NB, and WS₂/WO₃ NR. In the Raman spectrum of WO₃ NR, the strongest peak centered at 786 cm⁻¹ corresponds to the stretching vibration of O–W–O bonds. The weak peak at 292 cm⁻¹ is attributed to the bending vibration of W–O–W bonds [65]. The vibrational modes centered at 103 cm⁻¹ correspond to the lattice modes of hexagonal WO₃ [66]. Furthermore, a shoulder peak appearing at 935 cm⁻¹ is attributed to the –W=O bonds of the hexagonal WO₃ crystal [67, 68]. The Raman spectra of WS₂/WO₃ NB and WS₂/WO₃ NR reveal that both materials exhibit characteristic peaks at 264, 350, 418, 705, and 805 cm⁻¹. The peaks located at 264 cm⁻¹ are assigned to the bending vibration of bridging oxygen of W–O–W bonds. The peaks located at approximately 705 and 805 cm⁻¹ correspond to the stretching vibrations of the O–W–O bonds. The Raman peaks of WS₂ appear in the spectra of WS₂/WO₃ NB and WS₂/WO₃ NR. The peak position of the in-plane mode is located at approximately 350 cm⁻¹. For the interlayer vibration mode A_1g, the peaks are located at approximately 418 cm⁻¹, as reported in previous studies [69, 70]. The Raman spectra indicate that all the materials, namely, WO₃ NR, WS₂/WO₃ NB, and WS₂/WO₃ NR, were effectively synthesized.

XPS was used to study the chemical compositions of the material surfaces. Figure 4(a) shows the wide XPS spectra of WO₃ NR, WS₂/WO₃ NB, and WS₂/WO₃ NR. Peaks of W, S, O, and N are observed in all the synthesized materials, except for the absence of the S peak in the WO₃ NR spectrum. This result confirms that WO₃ NR, WS₂/WO₃ NB, and WS₂/WO₃ NR were successfully synthesized. The coincident appearance of nitrogen elements could be caused by using of AMT as a source of W which contains nitrogen elements. The presence of in-situ doped N₂ elements in catalysts could increase the contact of catalysts with electrolyte and improve the intrinsic conductivity of materials [71]. Figures 4(b), 4(d), and 4(f) depict the high-resolution fitted peaks of W 4f in WO₃ NR, WS₂/WO₃ NB, and WS₂/WO₃ NR, respectively. In Figure 4(b), the XPS spectrum of W 4f in WO₃ NR is deconvoluted into two main states, namely, W 4f_7/2 and W 4f_5/2, located at approximately 35.2 and 37.4 eV, respectively. The XPS data indicates that pure WO₃ NR was synthesized. In contrast, the XPS spectra of W 4f in WS₂/WO₃ NB and WS₂/WO₃ NR can be fitted into four different peaks, as shown in Figures 4(d) and 4(f), respectively. The peaks centered at approximately 31.8 and 33.9 eV are assigned to W (IV) of W–S bonding (WS₂), whereas those located at approximately 35.7 and 38 eV can be indexed to W (VI) of W–O bonding (WO₃). In addition, S peaks are observed only for the synthesized WS₂/WO₃ NB and WS₂/WO₃ NR. The high-resolution XPS peaks of S in the synthesized WS₂/WO₃ NB and WS₂/WO₃ NR are presented in Figures 4(c) and 4(e), respectively. In Figures 4(c) and 4(e), the main doublet of the binding energies of 161.6 and 162.8 eV in the high-resolution XPS peaks of S 2p is ascribed to the S 2p_3/2 and S 2p_1/2 states of the W–S bond in WS₂, respectively. Moreover, the peak located at approximately 168.7 eV corresponds to the S–O bond (SO₂), which is attributed to the inevitable oxidation of the composite in air [72]. The presence of WO₃ and WS₂ in XPS data confirms the successful synthesis of WS₂/WO₃ NB and WS₂/WO₃ NR.

(a)

(b)

(c)

(d)

(e)

(f)

Figure S2 shows the high-resolution XPS peaks of O 1 s in the synthesized materials including WO₃ NR, WS₂/WO₃ NB, and WS₂/WO₃ NR. The deconvoluted peaks of O 1 s in the synthesized materials are considerably similar, with slightly shifted peaks after fitting, which could be assigned to the different synthesized structures. All the O 1 s peaks can be fitted to two main peaks, wherein the higher peaks are assigned to the W–O–W bonding and the lower peaks correspond to the –OH groups owing to contamination or crystal water [73]. All the XPS data confirm that different materials such as WO₃ NR, WS₂/WO₃ NB, and WS₂/WO₃ NR were successfully synthesized.

The morphologies, sizes, and shapes of the prepared materials were investigated using FE-SEM at various scales. Figure 5 presents the FE-SEM images of WO₃ NR, WS₂/WO₃ NB, and WS₂/WO₃ NR. The sizes, shapes, and morphologies of the synthesized materials are highly uniform. In Figures 5(a) and 5(b), the length of WO₃ NR is approximately 200–300 nm with a diameter of approximately 30–50 nm. In contrast, in Figures 5(c) and 5(d), the shape of WS₂/WO₃ NB appears in cubic shape, with dimensions of approximately . As can be seen from Figures 5(e) and 5(f), it seems that the WS₂ layer covers the surface of the WO₃ NR material. The synthesized WS₂/WO₃ NR is highly uniform, with a length range of approximately 100–200 nm and a diameter range of approximately 15–30 nm. The FE-SEM data indicate that different morphologies of catalysts based on WO₃ have been well prepared.

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(b)

(c)

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(e)

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During the HER, H₂ is released when protons (H⁺) in the electrolyte receive electrons from an applied voltage on the electrode surface. The HER in acidic media involves the following steps:

The efficiency of hydrogen evolution depends strongly on the electrode properties because hydrogen gas could be released on the cathode surface. Therefore, the more conductive and larger the active surface of the catalysts, the higher the catalytic performance. Figure 6 shows the electrochemical measurements of all samples with reference to the HER performance. The LSV data clearly indicate the poor catalytic behavior of WS₂/WO₃ NB. This could be explained by the big size of the WS₂/WO₃ NB particles, as revealed by the FE-SEM results. The large size of the WS₂/WO₃ NB is the primary reason for its low conductivity and small active surface. In contrast, the WO₃ NR and WS₂/WO₃ NR samples exhibit good HER activities and higher current densities at lower overpotentials. The WO₃ NR and WS₂/WO₃ NB samples achieve a current density of 10 mA cm⁻² at overpotentials of 284 and 394 mV, respectively. The WS₂/WO₃ NR sample attains the current density of 10 mA cm⁻² at an overpotential of 224 mV, implying that the HER activity of WS₂/WO₃ NR is enhanced compared with that of WO₃ NR and WS₂/WO₃ NB. These results suggest that the heterostructure of WS₂ and WO₃ could play a crucial role in improving the HER activity in acidic media. The binary structure of WS₂ and WO₃ in the sample may create a synergistic effect that consequently increases the number of active sites and enhances the conductivity, thereby improving the HER performance [64, 74–77].

(a)

(b)

(c)

(d)

The Tafel slope is another important parameter for evaluating the catalytic activity of catalysts and is strongly related to the catalytic activity of the materials. The reaction mechanism and exchange current density were interpreted based on the calculated Tafel slopes. Figure 6(b) depicts the Tafel slopes of the synthesized materials. The Tafel slope of WS₂/WO₃ NR (82.7 mV dec⁻¹) is considerably smaller than that of WO₃ NR (112.5 mV dec⁻¹) and WS₂/WO₃ NB (195.5 mV dec⁻¹), which suggests that the HER kinetics of WS₂/WO₃ NR are faster than those of WO₃ NR and WS₂/WO₃ NB. In Figure 6(c), the EIS results derived from the recorded Nyquist plots reveal that WS₂/WO₃ NR presents a smaller semicircle diameter than that of WS₂/WO₃ NB and WO₃ NR, indicating the higher conductivity and charge-transfer rate and consequently the faster HER kinetics of WS₂/WO₃ NR. The equivalent circuit in the inset is composed of constant-phase elements and charge-transfer resistances. The fitted values are listed in Table 1. Notably, the charge-transfer resistance of WS₂/WO₃ NR (397.7 Ω) is considerably lower than that of WS₂/WO₃ NB (3597 Ω) and WO₃ NR (1816 Ω). Therefore, the electron conduction on the surface of WS₂/WO₃ NR is superior to that on WS₂/WO₃ NB and WO₃ NR. of WS₂/WO₃ NR was also calculated by using cyclic voltammetry (CV) tests at different scan rates. The CV test results of WS₂/WO₃ NR at various scan rates are shown in the inset of Figure 6(d). is calculated to be approximately 1.327 mF cm⁻², which is comparable to that of WS₂ hollow spheres in a previous study [50]. The stability of WS₂/WO₃ NR was also investigated by i-t measurement for 12 h which is provided in Figure S3.

4. Conclusions

In summary, WO₃ NR, WS₂/WO₃ NB, and WS₂/WO₃ NR heterostructures were successfully synthesized using batch reactor routes. The structure, morphology, composition, and characteristics of the synthesized materials were completely confirmed. Subsequently, the HER performances of the prepared materials were thoroughly investigated. The catalytic activities of WS₂/WO₃ NR have been considerably improved compared with that of WO₃ NR and WS₂/WO₃ NB. The improved performance of WS₂/WO₃ NR heterostructures could be attributed to the coexistence of WS₂ and WO₃ materials, which could create a synergistic effect between the two materials and further improve the conductivity and intrinsic HER activity. The Tafel slope of the WS₂/WO₃ NR (82.7 mV dec⁻¹) is considerably lower than that of pure WO₃ NR (112.5 mV dec⁻¹) or WS₂/WO₃ NB (195.5 mV dec⁻¹). Besides that, the long-time stability of prepared WS₂/WO₃ NR heterostructures was also confirmed. This study provides a prominent strategy for designing heterostructures of transition-metal sulfides/oxides based on WO₃ and WS₂ to prepare an efficient catalyst for electrochemical processes or energy-storage applications.

Data Availability

The data used to support the findings of this study are included within the manuscript and the supplementary information files.

Conflicts of Interest

The authors declare that they have no conflicts of interest.

Authors’ Contributions

Tuan Van Nguyen and Kim Anh Huynh contributed equally to this work and co-first authors.

Acknowledgments

This research was supported by the NRF funded by the Korean government (2022M3H4A1A01012712 and 2022M3H4A1A04096380).

Supplementary Materials

Figure S1: XRD pattern of WS₂ material. Figure S2: (a) High-resolution XPS profiles of O 1 s in WO₃ NR, (b) WS₂/WO₃ NB, and (c) WS₂/WO₃ NR. Figure S3: stability test of WS₂/WO₃ nanorod catalyst by i-t measurement for 12 hours. Table S1: different catalysts based on WO₃ and/or WS₂ for HER. (Supplementary Materials)

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Copyright © 2024 Tuan Van Nguyen et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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International Journal of Energy Research

Facile Synthesis of WS2/WO3 Materials in a Batch Reactor for the Hydrogen Evolution Reaction

Abstract

1. Introduction

2. Experimental Section

2.1. Materials

2.2. Synthesis of WO3 NR

2.3. Synthesis of WS2/WO3 NB Composite

2.4. Synthesis of WS2/WO3 NR Heterostructure

2.5. Electrochemical Measurements

2.6. Material Characterization

2.7. Synthesis Process and Proposed Mechanisms

3. Results and Discussion

4. Conclusions

Data Availability

Conflicts of Interest

Authors’ Contributions

Acknowledgments

Supplementary Materials

References

Copyright

Facile Synthesis of WS₂/WO₃ Materials in a Batch Reactor for the Hydrogen Evolution Reaction

2.2. Synthesis of WO₃ NR

2.3. Synthesis of WS₂/WO₃ NB Composite

2.4. Synthesis of WS₂/WO₃ NR Heterostructure