Hierarchical molybdenum disulfide on carbon nanotube–reduced graphene oxide composite paper as efficient catalysts for hydrogen evolution reaction

Journal Pre-proof Hierarchical molybdenum disulfide on carbon nanotube–reduced graphene oxide composite paper as efficient catalysts for hydrogen evolution reaction Mahider Asmare Tekalgne, Khiem Van Nguyen, Dang Le Tri Nguyen, Van-Huy Nguyen, Thang Phan Nguyen, Dai-Viet N. Vo, Quang Thang Trinh, Amirhossein Hasani, Ha Huu Do, Tae Hyung Lee, Ho Won Jang, Hoang Sinh Le, Quyet Van Le, Soo Young Kim PII:

S0925-8388(20)30260-7

DOI:

https://doi.org/10.1016/j.jallcom.2020.153897

Reference:

JALCOM 153897

To appear in:

Journal of Alloys and Compounds

Received Date: 4 September 2019 Revised Date:

7 January 2020

Accepted Date: 16 January 2020

Please cite this article as: M.A. Tekalgne, K. Van Nguyen, D. Le Tri Nguyen, V.-H. Nguyen, T.P. Nguyen, D.-V.N. Vo, Q.T. Trinh, A. Hasani, H.H. Do, T.H. Lee, H.W. Jang, H.S. Le, Q. Van Le, S.Y. Kim, Hierarchical molybdenum disulfide on carbon nanotube–reduced graphene oxide composite paper as efficient catalysts for hydrogen evolution reaction, Journal of Alloys and Compounds (2020), doi: https:// doi.org/10.1016/j.jallcom.2020.153897. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2020 Published by Elsevier B.V.

Graphical Abstract

Hierarchical molybdenum disulfide on carbon nanotube– reduced graphene oxide composite paper as efficient catalysts for hydrogen evolution reaction Mahider Asmare Tekalgne,a,† Khiem Van Nguyen,b,† Dang Le Tri Nguyen,b,† Van-Huy Nguyen,c Thang Phan Nguyen,d,e Dai-Viet N. Vo,f Quang Thang Trinh,g Amirhossein Hasani,a Ha Huu Do,a Tae Hyung Lee,h Ho Won Jang,h Hoang Sinh Le, b,* Quyet Van Le,b,* Soo Young Kim,i,* a

School of Chemical Engineering and Materials Science, Chung-Ang University, Seoul 06974, Republic of Korea b

Institute of Research and Development, Duy Tan University, Da Nang 550000, Vietnam

c

Key Laboratory of Advanced Materials for Energy and Environmental Applications, Lac Hong University, Bien Hoa, Vietnam d

Laboratory of Advanced Materials Chemistry, Advanced Institute of Materials Science, Ton Duc Thang University, Ho Chi Minh City, Vietnam; [email protected]

e

Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City, Vietnam

f

Center of Excellence for Green Energy and Environmental Nanomaterials (CE@GrEEN), Nguyen Tat Thanh University, 300A Nguyen Tat Thanh, District 4, Ho Chi Minh City 755414, Vietnam

g

Cambridge Centre for Advanced Research and Education in Singapore (CARES), Campus for Research Excellence and Technological Enterprise (CREATE), 1 Create Way, 138602 Singapore

h

Department of Materials Science and Engineering, Research Institute of Advanced Materials, Seoul National University, Seoul 08826, Republic of Korea

i

Department of Materials Science and Engineering, Korea University 145, Anam-ro Seongbuk-gu, Seoul 02841, Republic of Korea Keywords: MoSx, vertical alignment, rGO, CNT, traditional paper

1

Abstract

Herein, we report a composite structure composed of vertically grown molybdenum disulfide (MoSx) nanosheets supported by conductive carbon nanotube–reduced graphene oxide (CNT–rGO) on Vietnamese traditional paper (MoSx/CNT–rGO/VTP) for a highperformance electrochemical hydrogen evolution reaction (HER). In the fabrication, CNT– rGO is first prepared on VTP by roll coating, following which the vertically aligned MoS2 nanosheets are synthesized on the surface of CNT–rGO/VTP through a simple hydrothermal reaction. The catalyst exhibits excellent HER electrocatalytic activity including a low onset potential of 190 mV, Tafel slope of 59 mV dec−1, and excellent stability in an acidic electrolyte solution. The excellent catalytic performance can be attributed to the abundant active edges provided by the vertically aligned MoSx nanosheets, as well as the effective electron transport provided by the CNT–rGO conductive substrate. Therefore, our study demonstrates an inexpensive and simple method to facilitate the large-scale application of non-noble catalysts. In addition, the method can be extended to the development of other transition metal dichalcogenide composite structures for electrochemical applications.

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1. Introduction With increasing industrialization and modernization, concerns for environmental pollution have heightened due to the high consumption of carbon-releasing fossil fuels [1]. Therefore, a clean and sustainable energy source is required to address this issue [2, 3]. Hydrogen, a clean energy carrier with zero carbon content, has attracted wide attention since the past few decades as a substitute for fossil fuels. Though there are different methods to produce hydrogen such as steam reforming [4], and natural gas oxidization [5], electrochemical and photoelectrochemical hydrogen production via water splitting is a promising and sustainable method for production [6, 7]. Noble metals such as platinum and their alloys are the most efficient catalysts for electrocatalytic water splitting [8, 9]. However, owing to their high cost and scarcity, it is difficult to employ such catalysts on a large scale. Hence, an inexpensive and high-performance catalyst is desirable. Two-dimensional dichalcogenides (TMDs) such as molybdenum disulfide (MoS2) and WS2 have shown immense potential in the electrocatalytic hydrogen evolution reaction (HER) and other applications because of their unique properties, such as high thermal conductivity, charge carrier mobility, and tunable bandgap [10-14]. Among them, MoS2 has gained widespread interest for hydrogen production via electrocatalysis. Both DFT and experimental investigation have shown that the edges of MoS2 are more catalytically active than the basal surface for the HER [15-19]. Along with the development of nanostructured crystalline MoS2 nanosheets (NSs), amorphous MoSx has also been discovered to be very active toward the HER owing to the unsaturated sulfur atom [20, 21]. However, MoSx exhibits poor electrical conductivity, which could result in inefficient electron transfer during the electrochemical process [22]. Therefore, to improve the catalytic activity, the incorporation of MoSx on a conductive template is important [23]. Thang et al. investigated the growth of vertically aligned amorphous MeSx on the surface of conductive 1T MeS2 NSs, and reported a

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significantly higher catalytic activity for the HER by increasing the active sites and conductivity of the catalysts [24]. In addition, to improve the conductivity of MoSx, carbonbased materials, such as carbon nanotubes (CNTs) and graphene were employed as templates to accelerate the transport of electrons between the active sites and the electrode [22, 25-28]. However, there still remain challenges to be addressed to achieve higher efficiency and stability. In this work, CNT–reduced graphene oxide (rGO) was first embedded onto Vietnamese traditional paper (VTP) and used as a substrate for the growth of the catalyst. The VTP is an insulator; however, it can be used as support for improving the stability and mechanical properties of rGO-CNT network for realizing the practical application. The CNTs are known for their high surface area and excellent electrical conductivity thus can be used as electrodes for HER. The addition of rGO is a key for enhancing the toughness and stability of the substrate [29]. A facile hydrothermal method was adopted to obtain vertically aligned MoS2 on the CNT–rGO paper. The vertical alignment increased the surface area, thereby providing more exposed active edges. Moreover, the electron transfer efficiency improved by the conductive CNT–rGO, enabling electron transfer to the vertically aligned MoSx. To ensure a desirable connection between MoSx/CNT–rGO and the electrolyte, the as-prepared catalyst was further twisted on Ni and Ti wires and used as the working electrode. Owing to the synergetic effect of MoS2 and the CNT–rGO paper, the MoSx/CNT–rGO twisted on the conductive wires exhibited superior electrochemical performance with a low onset overpotential and Tafel slope. This strategy can enhance the stability, and increase the surface area as well as conductivity of the catalyst. This study provides a route to achieving a lowcost and efficient HER electrocatalyst by a one-step hydrothermal process.

2. Experiment details

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2.1. Chemical materials Graphite was obtained from Graphene Supermarket and CNTs were provided by OCSiAl Company. Vietnamese traditional paper was purchased from the local market. Sodium dodecylbenzenesulfonate

(SDSB),

ascorbic

acid,

ammonium

tetrathiomolybdate

((NH4)2MoS4), hydrazine hydrate, and 5% Nafion solution were purchased from Sigma Aldrich. Dimethylformamide (DMF) was provided by Daihan Chemical Co. Ltd and deionized (DI) water was obtained from Millipore Mili-Q at 18.3 MUcm-1. 2.2. Synthesis of GO GO was prepared from graphite powder using a modified Hummers’ method. First, 1 g of graphite and 1 g of NaNO3 were vigorously stirred in a flask containing 46 mL of concentrated H2SO4 and 6 g KMnO4 in an ice bath for 2 h. Subsequently, the solution was heated up to 95 °C for 1 h. Finally, the obtained product was treated with H2O2, water, and collected using a centrifuge.

2.3. Deposition of CNT–rGO on Vietnamese traditional paper The CNT-GO solution was prepared by adding 4 mg of GO, 36 mg of CNT, and 20 mg of SDSB into 20 mL of DI water. The solution was then roll-coated onto the surface of the VTP and dried at 80 °C in an oven. The process was repeated thrice. The CNT-GO/VTP was then dipped into a solution of ascorbic acid for 24 h to obtain CNT–rGO/VTP. Reduction is very important to ensure that the materials are not peeled off upon the hydrothermal deposition of MoSx. Finally, the CNT–rGO/VTP was treated with UV-ozone for 15 min before the hydrothermal deposition of MoSx.

2.4. Synthesis of vertically grown MoSx on CNT–rGO paper

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Hierarchical MoSx was synthesized by a simple hydrothermal method on CNT–rGO paper [24]. In a typical procedure, 0.450 g of (NH4)2MoS4 was dissolved in 100 mL of DMF water under vigorous stirring to form a homogeneous solution. The CNT–rGO paper was carefully placed against the wall of the Teflon cell, following which the mixed solution was added. Subsequently, the Teflon-lined stainless steel autoclave was sealed and maintained at 200 °C for 10 h, and then allowed to cool to room temperature. The sample was taken out from the autoclave and subsequently rinsed with DI water and ethanol, and dried at room temperature. The MoSx/CNT-rGO/VTP was twisted onto Ni or Ti wires following a previous report [29].

2.5. Electrochemical measurement All electrochemical measurements were performed at room temperature on a standard three-electrode electrolytic system using an Ivium potentiostat V55630. The saturated calomel electrode (SCE), graphite rod, and vertically aligned MoSx/CNT–rGO twisted on Ni and Ti wire served as the reference, counter, and working electrodes, respectively. The HER activities were evaluated by linear sweep voltammetry (LSV) with a scan rate of 10 mV s−1. All measurements were performed in 0.5 M H2SO4 with iR compensation. The stability was tested by acquiring continuous cyclic voltammograms at a scan rate of 50 mV s−1 for 1000 cycles. In addition, electrochemical impedance spectroscopy (EIS) was performed at -250 mV potential versus a reversible hydrogen electrode (RHE) at a frequency ranging from 100 kHz to 0.1 Hz. All the potentials here were referenced to the RHE using the following equation: E (RHE) = E (SCE) + 0.2 V + 0.059 pH

2.6. Materials characterization

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The X-ray diffraction (XRD) patterns of the CNT-graphene paper and vertically aligned MoS2/CNT–rGO paper were recorded on a powder X-ray diffractometer (Bruker New D8Advance, Seoul, Korea) using Cu Kα radiation (λ = 0.154 nm). Field-emission scanning electron microscopy (FE-SEM, Zeiss 300 VP, Seoul, Korea) images were obtained at an acceleration voltage of 10 kV and transmission electron microscopy (TEM, JEM-2100F, JEOL) was performed to study the morphology. X-ray photoelectron spectroscopy (XPS, Thermo Fisher, K-Alpha, Seoul, Korea) was performed under vacuum exceeding 1 × 10−5 mbar using Mg Kα radiation (1250 eV) and a constant pass energy of 40 eV to verify the presence of Mo and S. Raman spectroscopy was performed to measure the structures and sizes of the synthesized sample.

3. Results and discussion Figure 1 shows the procedure for preparing the vertically aligned MoSx on the CNT–rGO (9:1) paper. Vietnamese traditional paper was used as the substrate for preparing the CNT– rGO paper. A flexible vertically aligned MoSx/CNT–rGO paper hybrid could be easily fabricated through a simple hydrothermal method. Figure 2 (a-d) shows the morphology of the as-prepared CNT–rGO paper and vertically aligned MoSx/CNT–rGO paper observed by FE-SEM at high and low magnification. The bare CNT–rGO paper (Figure 2a and b) consists of fibers with a smooth surface, which are intertwined together as shown. Figure 2 (c, d) indicates the successful growth of vertically aligned MoSx on CNT–rGO, thereby confirming the uniform and dense deposition of MoSx with numerous active edges exposed at a large scale. In addition, the cross-sectional FESEM images of the MoSx/CNT–rGO paper twisted on Ti and Ni employed as a working electrode are shown in Figure S1. Abundant edges of MoSx were also confirmed by TEM images as shown in Figure 3a-b. From the selected area electron diffraction pattern (SAED) revealed that the structure of MoSx was amorphous. The

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material composition and crystal structure of the bare CNT–rGO and vertically aligned MoSx/CNT–rGO paper were further evaluated by XRD, the patterns of which are shown in Figure 3c. The (002) plane of MoSx is not clear, indicating that the synthesized MoSx is in an amorphous state. The Raman spectrum of the synthesized MoSx/CNT–rGO is shown in Figure 3d. After the hydrothermal process, the peaks at 381 cm-1 and 406 cm-1 appear, confirming the formation of amorphous MoSx on CNT/CNT–rGO/VTP [30, 31]. To study the interaction between MoSx and CNT–rGO paper in more detail, XPS measurements were performed. Overall, the XPS profiles in Figure 4 show that the MoSx/CNT–rGO composite is composed of C, O, Mo, and S elements. In the C1s spectrum of the composite (Figure 4a, b), the dominant peak at 284.6 eV is attributed to graphitic carbon (C-C), whereas the other peaks at 286.0 and 288.2 eV are related to C-OH and C=O configurations, respectively [32, 33]. The relatively low intensities of oxidized C (C-O bonds) reveal that most oxygen groups have been removed. As shown in Figure 4c, there are two peaks at 228.1 and 231.9 eV, which can be assigned to the Mo4+ (3d5/2) and Mo4+ (3d3/2) binding energies of MoSx, respectively. The higher energy peaks located at 232.2 and 235.8 eV are attributed to Mo6+ 3d5/2 and Mo6+ 3d3/2 (Mo-O bond), due to the formation of MoO3 during the preparation of the catalyst and air exposure [34, 35], whereas the lower energy peak at 226 eV can be attributed to S2s. The peaks centered at 163.6 and 165 eV in Figure 4d are assigned to S (2p3/2) and S (2p1/2), respectively, indicating the existence of sulfide ions in the MoS2/CNT–rGO composites [36], This implies that the formation of the MoSx/CNT–rGO composite is not just the result of simple mixing, but also improves the electron interactions in the composite to enhance the conductivity for better catalytic performance [33, 37, 38]. The performance of MoSx/CNT–rGO is summarized in Figure 5. As can be seen, the vertically aligned MoSx/CNT–rGO paper cannot be used directly as a working electrode due to its low conductivity upon soaking into electrolyte. Hence, a method to improve its

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performance is needed. Ni and Ti wires were used as a support, which further improved its catalytic activity. The successful preparation of vertically aligned MoSx/CNT–rGO twisted on Ni and Ti wires was confirmed by FESEM (Figure S1), and then employed as a working electrode. The electrochemical performance of MoSx/CNT–rGO was evaluated by LSV measurements at a scan rate of 10 mV/s. For comparison, we also tested bare Ni and Ti wires, MoS2/CNT–rGO paper, and Pt. According to Figure 5b, the Pt electrode shows the best HER activity with negligible onset overpotential, whereas the bare Ni and Ti wire MoS2/CNT–rGO exhibits high overpotential. The prepared MoSx/rGO-CNT/Ni or MoSx/rGO-CNT/Ti showed higher performance than MoSx/CNT-rGO. As shown in Fig 5(a), the MoSx/CNT-rGO has high overpotential than the MoSx/rGO-CNT/Ni or MoSx/rGO-CNT/Ti. For example, at a current density of 10 mA cm-2, the overpotential of bare MoS2/CNT–rGO is 260 mV, while, the overpotentials of MoSx/CNT–rGO twisted on Ni and Ti wires are much lower at 145 and 190 mV, respectively. The Ni and Ti wires act as a support for the synthesized catalyst and also increase the conductivity, which further improves the charge transfer from the electrolyte to the surface of the MoSx/CNT–rGO paper. Thus, MoSx/CNT–rGO twisted on Ni and Ti wires acts as a high-performance catalyst for hydrogen generation. The Tafel plots, recorded with the linear regions fitted into the Tafel equation, provided Tafel slopes of 33 mV per decade for Pt, 64 mV per decade for MoSx/CNT–rGO twisted on Ti wire, and 59 mV per decade for MoSx/CNT–rGO twisted on Ni wire, as shown in Figure 5c. In addition, a comparison of overpotential and Tafel slope is provided in Table S2. Apart from the polarization curves and Tafel slope analysis, Nyquist plots are also essential to verify efficient electron transfer, which is required for excellent HER performance. The Nyquist plots in Figure 5d reveal that the charge transfer resistances of MoSx/CNT–rGO twisted on Ni and Ti wires (5 Ω and 20 Ω, respectively) are much lower than that of bare MoSx/CNT–rGO (Table S1). This very low resistance corresponds to rapid charge transfer at the interface

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between the electrocatalyst and the electrolyte, resulting in excellent performance. This is ascribed to CNT–rGO, which serves as a highly conductive substrate to improve the conductivity of MoSx. Furthermore, due to the Ni and Ti wires, the generated electrons can be easily transferred directly and efficiently from CNT–rGO to the vertically aligned MoSx NS. It is important to measure the electrochemical capacitance surface area, in order to compare the active surface area of the catalyst film and estimate the density of electrochemically active sites [39]. The non-faradic capacitive currents associated with electrochemical double layer charging for MoSx/CNT–rGO twisted on Ni and Ti wires were measured (Figure S2). As is shown in Figure, the Cdl values (Figure S2 (c)) are obtained from the CV curves (a and b). It can be seen that the Cdl of MoS2-CNT-rGO/Ni is 320 µF cm−2, nearly 7 times larger than MoS2-CNT-rGO/Ti (50 µF cm−2). This phenomenon needs further investigation in the near future. The turnover frequencies (TOFs) of MoSx/CNT–rGO twisted on Ni and Ti were calculated according to a previous formula [40]. TOF=jA/4nF

(1)

where j is the current density (A cm−2), A is the surface area of the working electrode (cm2), n is the number of moles of the loaded catalyst onto the working electrode, and F is the Faraday constant (C mol−1). The TOF calculated for MoSx/CNT–rGO twisted on Ni is 0.322 s−1. Figure S3 shows the TOF plotted against the potential vs RHE. To assess the long-term durability of the MoSx/CNT–rGO twisted on Ni and Ti wires in an acidic medium, the continuous HER was assessed by conducting cyclic voltammetry at a scanning rate of 10 mV/s. Polarization curves after 1000 cycles almost overlap the curve of the initial cycle with negligible loss of the cathodic current, as shown in Figure 5e. In addition, the stability of the catalysts, i–t chronoamperometric curve (Figure S4) was recorded for MoS2/rGO-CNT/Ni at constant potentials of 150 mV in a 0.5 M H2SO4 solution over 25000 s.

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4. Conclusions In this work, a MoSx/CNT–rGO paper composite with high catalytic activity toward the HER was synthesized by a facile hydrothermal method, in which MoSx NSs were vertically grown on CNT–rGO paper. The vertically aligned MoSx/CNT–rGO paper provided numerous exposed active edge sites and high electrical conductivity, thus improving its catalytic activity. Due to the synergetic effect between MoSx and CNT–rGO paper with high flexibility, the as-synthesized catalyst exhibited a very low onset potential of 140 mV and a Tafel slope of 59 mV/decade, with excellent cyclic stability. This study shows that the synthesis of low-crystalline MoSx supported on inexpensive and conductive CNTs is feasible and promising for electrocatalytic hydrogen evolution.

Author information Corresponding Author * [email protected] (S. Y. Kim) * [email protected] (Q. V. Le) * [email protected] (H. S. Le) Author Contributions † M. A. Tekalgne, K. V. Nguyen, D. L. T. Nguyen contributed equally to this work. Notes The authors declare no competing financial interest Acknowledgments This work was funded by the Vietnam National Foundation for Science and Technology Development (NAFOSTED) (grant number 103.99-2016.95) and the Basic Research 11

Laboratory of the NRF funded by the Korean government (2018R1A4A1022647). Dr Q. T. Trinh would like to acknowledge the financial support by the Singapore National Research Foundation (NRF) under its Campus for Research Excellence and Technological Enterprise (CREATE) program through the Cambridge Center for Carbon Reduction in Chemical Technology (C4T) and eCO2EP programs.

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Figure 1. Fabrication of MoSx/CNT–rGO/VTP twisted on Ni or Ti wire

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Figure 2. FESEM images of (a) and (b) bare CNT-rGO paper, (c) and d) MoS2/CNT–rGO at different magnifications

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Figure 3. (a) and (b) TEM images of MoSx at different magnifications and SEAD pattern (inset), (c) XRD patterns of rGO and MoSx/CNT–rGO, (d) Raman spectra of rGO and MoSx/CNT–rGO

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Figure 4. XPS profiles of (a) C1s (CNT–rGO), (b) C1s (MoSx/CNT–rGO), (c) Mo 3d, and (d) S 2p

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Figure 5. (a) Schematic illustration of HER over MoSx/CNT-rGO/VTP/Ni/Ti electrode. Electrochemical measurements: (b) polarization curves (c) corresponding Tafel plots, (d) electrochemical impedance spectra, and (e) stability after 1000 cycles

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• • •

We successfully fabricated CNT-rGO composite papers using Vietnamese Traditional paper as templates. Hierarchical MoSx was uniformly grown on CNT-RGO paper using hydrothermal method. All the basic characterizations were carried out to confirm the structure of materials such as XRD, XPS, SEM and Raman.

•

We figure out that the use of Ni or Ti wire is necessary to improve the performance of MoSx on CNT/rGO paper as catalyst for HER.

•

Finally, binder-free with strong stability electrocatalysts for HER under working condition were demonstrated, showing good potential for practical applications.

Author contribution section Q. V. Le, H. S. Le, and S. Y. Kim conceived the idea and supervised the project. M. A. Tekalgne, K. V. Nguyen and D. L. T. Nguyen carried out the experiment and prepared the manuscript. V.-H. Nguyen, T. P. Nguyen, D.-V. N. Vo, Q. T. Trinh, A. Hasani, H. H. Do, T. H. Lee, and H. W. Jang contributed to the characterization of the materials and interpretation of the results. All authors discussed the results and commented on the manuscript.

Declaration of interests ☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.