Facile synthesis of tungsten oxide - Bismuth vanadate

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 6 ) 1 e8

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Facile synthesis of tungsten oxide e Bismuth vanadate nanoflakes as photoanode material for solar water splitting Akram A.M. Ibrahim a,b, Ibrahim Khan a,b, Naseer Iqbal a, Ahsanullhaq Qurashi a,b,* a

Center of Research Excellence in Nanotechnology, King Fahd University of Petroleum and Minerals, Dhahran, 31261, Saudi Arabia b Department of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran, 31261, Saudi Arabia

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abstract

Article history:

This research article describes the synthesis of hetero-structured WO3/BiVO4 nanoflakes as

Received 13 March 2016

photoanode material for photoelectrochemical water splitting. The heterojunction WO3/

Received in revised form

BiVO4 nanoflakes developed by facile hydrothermal method. WO3/BiVO4 uniform films

31 August 2016

fabricated simply by drop casting technique onto indium oxide tin oxide (ITO) coated glass

Accepted 14 September 2016

substrates. Detailed morphological, structural and compositional characterization of WO3/

Available online xxx

BiVO4 carried out by XRD, FE-SEM, and EDX techniques. Optical properties studied by Raman and UVeVIS spectroscopy, respectively. The band gap energy of WO3/BiVO4 hetero-junction

Keywords:

estimated to be about 2.00 eV. These WO3/BiVO4 heterojunction structures offered enhanced

WO3

photo-conversion efficiency and increased photo-corrosion stability. In addition, these

WO3/BiVO4 heterojunctions

nanoflakes films showed significantly enhanced photo-electrochemical properties due to

WO3/BiVO4 nanoflakes

their high surface-area and enhanced separation of the photo-generated charge at the WO3/

Solar water splitting

BiVO4 interface. The effect of calcination temperature on WO3/BiVO4 also investigated. © 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Introduction Water splitting for hydrogen generation in a photoelectrochemical reaction using TiO2 as photocatalyst under UV light credited to Fujishima [1]. Since then, research in fabrication of photocatalytic materials gained enormous attention [2e4]. Particularly metal oxides extensively investigated for their photo-electrochemical properties [5e7]. The solar spectrum generally consists of mixture of UV and visible light, thus it is preferred to develop a photocatalyst, which shows photoelectrochemical activity in the visible region of

light for effective photoelectrochemical hydrogen production from water. Despite of the fact that numerous metal oxide semiconducting materials have shown commendable photoelectrochemical properties, there are still some bottlenecks that need to be addressed comprehensively. These include photogenerated charge carrier separation, limited response to visible light where the most of solar energy lies [8], high charge recombination [9e11] and photocorrosion [12] etc. As far as the band gap is concerned, low band gap materials are active under visible light but usually they are tending to photocorrosion and charge recombination due to short bands

* Corresponding author. Center of Research Excellence in Nanotechnology, King Fahd University of Petroleum and Minerals, Dhahran, 31261, Saudi Arabia E-mail address: [email protected] (A. Qurashi). http://dx.doi.org/10.1016/j.ijhydene.2016.09.095 0360-3199/© 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved. Please cite this article in press as: Ibrahim AAM, et al., Facile synthesis of tungsten oxide e Bismuth vanadate nanoflakes as photoanode material for solar water splitting, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.09.095

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distance [13,14]. Whereas their larger band gap counterparts are not active to visible light [15]. Consequently, in order to avoid recombination of charge carriers, there is need to develop composite materials with suitable band gap energies [16,17]. Literature revealed various hetero-junction films, such as sulfur doped TiO2 [18], TiO2/CueTieO [19], WO3/Fe2O3 [20], BiVO4/Co3O4 [21] and WO3/BiVO4 [22], that have shown promising photoelectrochemical activity with efficient charge carrier separation in the hetero-junction films. Lately, various groups investigated WO3/BiVO4 as a photoactive material for solar water splitting [16,22e26]. BiVO4 showed a narrow band gap of ~2.40 eV as compared to WO3 and its conduction band is also more negative than that of WO3 [16]. Therefore, incorporation of photocorrosion resistant WO3, to develop WO3/ BiVO4 photoanodes could be good choice to overcome the aforementioned issues for efficient photoelectrochemical water splitting [23e25]. In the current effort, we have fabricated WO3/BiVO4 nanoflakes photoanode materials via a facile hydrothermal approach. These WO3/BiVO4 nanoflakes characterized by XRD, FE-SEM, EDS for structural and compositional analysis as well as their optical properties studied by UVeVIS and Raman spectroscopy. The hetero-junction films of WO3/BiVO4 nanoflakes were drop-casted onto indium oxide tin oxide glass coated (ITO) substrates. The WO3/BiVO4 nanoflakes offered large surface-area over which the minor charge carriers can diffuse. The photoelectrochemical (PEC) measurements showed enhance properties such as photogenerated charge carrier separation as well as high light to chemical (stored energy) conversion efficiencies.

oxide precursor solution was prepared by mixing 5 g from vanadium (V) oxide (V2O5) and bismuth (III) nitrate pentahydrate (Bi(NO3)3.5H2O) in 200 ml of 2 M Nitric acid (HNO3). Similarly, the tungsten oxide solution was prepared from a mixture of 2 g tungsten (VI) chloride WCl6 and 0.15 g of urea in 100 mL DI water. The two reaction mixtures containing WO3 and BiVO4 solutions were transferred into a Teflon vessel, sealed in a steeliness steel autoclave and maintained in an oven at 120 C for 24 h in order to proceed a hydrothermal reaction. The thin film of WO3/BiVO4 was fabricated by normal drop-casting of WO3/BiVO4 suspension on the ITO substrate and annealed at 200 C and 450 C, respectively for four hours.

Characterization X-ray diffraction spectroscopy The crystalline structure of both powder and thin film of WO3/ BiVO4 heterojunctions characterized by powder X-ray Diffractometer Rigaku RINT-2500 with radiation Cu Ka lamp: 1.54060, l ¼ 1.54056 A. The data was collected from 10 to 70 (2 q degree) at a scan rate of 3 /min.

FESEM, EDX analysis The structural morphology of WO3/BiVO4 heterojunctions evaluated by field emission scanning electron microscope (FESEM) TESCAN Lyra 3-Dual beam. The elemental composition and mapping of WO3/BiVO4 hetero-junctions were carried out by energy dispersive X-ray spectrometer (EDX) associated with the same machine. Powder samples and thin film mounted on circular aluminum standard sample studs using double-sided copper conductive tapes.

Experimental Optical measurements Materials and chemicals All the reagents, chemicals and solvents were purchased from sigma Aldrich and used as received without further purification unless otherwise stated e.g. Tungsten oxide targets (5 cm), indium oxide tin oxide glass coated substrate (ITO), Vanadium (V) oxide V2O5 (99.99%), Bismuth (III) nitrate pentahydrate Bi(NO3)3.5H2O (99.99%), Nitric acid (HNO3), Tungsten (VI) chloride WCl6 (99.99%, Sigma Aldrich) etc.

UVeVIS analysis investigated at room temperature by Cary series UVeVISeNIR spectrometer, Agilent technology. The Raman spectroscopy performed at room temperature using Yvon Jobin Horiba Raman spectrometer (iHR 320) model with charge-coupled detector (CCD). The laser source was of green type at 532 nm line and intensity was 45%. The spectrums obtained from the scattered light normal to the sample surface, with grating position 600 mm, slit width 96 cm, accumulation number 3 and exposure time 10 s.

Fabrication of tungsten oxide seeds

Photoelectrochemical (PEC) measurements and setup

Tungsten oxide seeds were fabricated by physical approach using automated sputter coater on indium oxide tin oxide glass coated substrate (ITO). WO3 magnetron target used for this purpose, whose diameter was 5 cm. During the sputtering operation, the base pressure was maintained at 9.1 106 Pa, whereas the working pressure was 2 103 Pa. The WO3 sputtering was carried out at 80 W for 40 min.

Synthesis of tungsten oxide e bismuth vanadate heterostructure Heterostructure of WO3/BiVO4 nanoflakes synthesized by hydrothermal approach as reported in literature [27,28] but with some modifications. In the first step, bismuth vanadium

The photoelectrochemical measurements carried out according to the standard photoelectrochemical parameters. Chronoamperometry (CA) and linear sweep voltammetry potentiostatic (LSVP) experiments conducted using a typical three-electrode setup. In which ITO/WO3/BiVO4 was used as photoanode, standard calomel electrode (Hg/Hg2Cl2) as reference and a platinum wire as a counter electrode, respectively in a 0.5 M Na2SO4 [pH ¼ 7] electrolyte solution. Metrohm autolab (B.V) Potentiostat/Galvanostat PGSTAT302N used to investigate the photocurrent at a scan rate of 0.0999 V/s. The PEC cell was exposed to chopped light (on/off) through oriel sol 3A class AAA solar simulator-Newport (100 mW/cm2, AM 1.5G filter (Oriel)) as a source of illumination. All photoelectrochemical analysis explained according to the normal hydrogen electrode (NHE).

Please cite this article in press as: Ibrahim AAM, et al., Facile synthesis of tungsten oxide e Bismuth vanadate nanoflakes as photoanode material for solar water splitting, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.09.095


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Results and discussions Formation of tungsten oxide seeds Tungsten oxide seeds deposited on the ITO substrate using automated sputter coater following a physical approach. Fig. 1(a), describes the powder XRD of ITO and WO3 seeds, it is evident that the entire substrate is covered by WO3 seeds, because all ITO diffraction peaks observed at 29.62, 30.19, 37.59, 40.49, 44.47, 48.31, 48.95 were corresponding to growth direction (003), (12e1), (220), (104), (303), (042) and (23e1) according to JCPDS #: 162144 have been disappeared. The peak indexes observed as (002), (020), (200), (120), (121), (022), (202) and (202), respectively belong to monoclinic phase of WO3 with JCPDS #: 00-043-1035. These indexes appeared at 23.12, 23.59, 24.38, 26.59, 29.14, 33.27, 33.57 and 34.15 in 2 q degree, respectively. The morphology of seeds layer investigated by FE-SEM and revealed the homogeneity of the seeds on the entire substrate with smooth surface and no grains observed. In addition, the size of the seeds was extremely small. Therefore, it was difficult to discriminate between bare ITO and WO3 seeds by naked eye as can be seen in Fig. 2(a and b). Furthermore, the elemental composition analyzed by EDX coupled with FE-SEM. The results confirmed the presence of W and O atoms in good agreement in the matrix quantitatively however, elemental composition of oxygen was higher as compared to tungsten. Fig. 2(a) and (b) shows FE-SEM images of bare ITO and WO3 seeds, respectively at high magnification.

Fabrication of tungsten oxide e bismuth vanadate heterostructure and their structural elucidation Tungsten oxide e bismuth vanadate heterostructure synthesized via hydrothermal approach. X-ray diffraction analysis conducted for structural analysis i.e. for purity and crystallinity and it revealed that the calcined material has polycrystalline structure with tetragonal phase. Their peak intensities were observed at 2 q angle 28.62, 32.64, 52.33, 55.06 which corresponding to (103), (110), (211), (213), respectively as growth directions (JCPDS #: 00-047-0478) with residual characteristic peaks of separated WO3 in the directions (002), (200), (202) (023) (004), corresponding to 23.28, 24.52, 34.22, 42.60, 47.62 (JCPDS #: 00-043-1035) and BiVO4 (002), (011), (004), which are related to 15.62, 19.18, 30.76 (JCPDS #: 01-083-1699) at 2 q degree, respectively, as can be seen in Fig. 1(b).

Fig. 1 e XRD patterns of (A) XRD of ITO (black) and WO3 seeds (red), (B) pure WO3 (black), pure BiVO4 (red) and WO3/ BiVO4 nanoflakes (blue). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

presences of W, Bi, V and O entities, and the atomic ratios of W and V were in good agreement to their stoichiometric ratios.

Tungsten oxide e bismuth vanadate optical characterization UVevis spectroscopy

Tungsten oxide e bismuth vanadate surface morphology and elemental composition analysis The morphology of the synthesized WO3/BiVO4 investigated using FE-SEM. Surface characterization showed the growth of nanoflakes, this morphology is due to an assembly of intertwined platelets radiating in all directions [29]. They have shown a smooth surface but no grains observed. Fig. 2(c and d) shows the FE-SEM Images of the WO3/BiVO4 heterostructure. The elemental compositional of WO3/BiVO4 hetero-structures determined by EDS and illustrated in Fig. 3(b). The elemental compositions confirmed for the

The optical properties of the WO3/BiVO4 nanoflakes like heterostructures were revealed using UVeVISeNIR spectrometer in Fig. 4. UVeVIS absorptions of pure WO3, BiVO4 and synthesized WO3/BiVO4 heterostructures depicted in Fig. 4. Small absorption onset observed at 473 nm for WO3 and the absorption onset of BiVO4 recorded at 575 nm. Incorporation of WO3 within BiVO4 nanostructure induced onset shift towards visible region at 590 nm for WO3/BiVO4 heterostructure in absorption spectrum as shown in Fig. 4(a). The absorption onset shift towards visible region indicates that WO3/BiVO4 heterostructure can harvest visible light of solar energy more appropriately and efficiently [23].


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Fig. 2 e FE-SEM micrographs of (A) bare ITO (B) ITO seeded with WO3 (C) low resolution WO3/BiVO4 nanoflakes (D) High resolution WO3/BiVO4 nanoflakes.

The band gap energy of WO3/BiVO4 heterostructure estimated from diffused reflectance spectroscopy and it was found to be ~2.00 eV. The band gap energies for each WO3, BiVO4 and WO3/BiVO4 presented in Fig. 4(b). A prominent difference in the band gap energies between WO3, BiVO4 and WO3/BiVO4 observed. This variation in band gap energies could be attributed to changing phase and crystal structure upon incorporation of WO3 to BiVO4 that we have discussed in XRD analysis of WO3, BiVO4 and WO3/BiVO4 heterostructures. In addition, several other factors such as morphology, variation in crystallographic phase, structure, particles size, annealing temperature etc. can influence the optical properties of semiconducting materials [30e32]. Either the optical band gap can vary with particle size variation, the red shift observed in optical band gap of metal oxide nanoparticle was attributed to change in morphology i.e. increase or variable particle sizes of the photocatalytic materials [31e33]. Literature revealed that the effect of annealing temperature on materials band gap is critical factor. An increase in annealing temperature resulted in the shift of bandeedge absorption at a larger wavelength. Increasing the annealing temperatures promote appearance of more defects in the material texture thus shifting band gap/edge absorption at a larger wave length or smaller energy value [33].

Raman spectroscopy For further structural elucidation Raman spectroscopy of calcined powders of each WO3, BiVO4 and WO3/BiVO4 was carried out. Fig. 5 shows the comparative analysis of Raman shifts of each powder material. The intensive Raman peaks at 809 and 720 cm1 were associated with stretching WeOeW bond while the bending modes of WeOeW bridging oxide ions were recorded at 273 and 329 cm1 in the pure WO3 [34], respectively. The Raman spectrum also showed the asymmetric and symmetric deformation modes of the (VO4)3 tetrahedron at 327 and 367 cm1. The characteristic Raman peak at 823 cm1 represented symmetric VeO bond [34,35]. The peaks slightly shifted with the appearance of new peaks at 137, 699.7 and 808.8 cm1, respectively in case of WO3/BiVO4. The appearance of these new Raman peaks provided strong evidence for the formation of WO3/BiVO4 heterostructure.

Photoelectrochemical (PEC) properties The photoelectrochemical measurements of the WO3/BiVO4 photoanode were investigated in three electrode setup i.e., a reference standard Calomel electrode, platinum counter electrode and WO3/BiVO4 heterojunction film photoanode served as working electrode, respectively in 0.5 M Na2SO4



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Fig. 3 e EDX spectrum showing corresponding elemental peaks of (A) ITO/WO3 (B) WO3/BiVO4 nanoflakes. [pH ¼ 7] electrolyte solution. The cell containing WO3/BiVO4 heterojunction photoanode was exposed to illumination source (1 SUN) in an on/off fashion with regular intervals of time to investigate the photoresponse of the material. Chrono-amperometry measurements (Jp) versus time (t) conducted to study the stability as well as the photocurrent generated by the WO3/BiVO4 heterojunction films at neutral pH of Na2SO4. At first, it was observed that WO3/BiVO4 photoanode showed a stable response upon exposure to light with no significant degradation noticed within given time span under continuous illumination (Fig. 6) [23]. Furthermore, the first Jp spike observed as the material was exposed to irradiation move to a higher value but later on relaxed to a stable plateau that explicit the significant stability of the WO3/BiVO4 semiconductor [22e24] with the passage of time. However, the Jpt profile gained shifted to its normal baseline when the illumination turned off hence showed a reversible response. Then linear sweep voltammetry (LSV) was carried out for further photoelectrochemical investigations using typical three electrode system under the same experimental conditions and setup as discussed earlier. The potential range was selected from 0 to 0.5 V versus normal hydrogen electrode (NHE) and the voltammogram is provided in Fig. 7. The WO3/ BiVO4 coated over an ITO substrate of dimensions (0.5 0.85 cm) by a normal drop e casting method. The ITO/ WO3/BiVO4 photoanode annealed at different temperatures

200 C and 450 C, respectively, in order to study the effect of annealing temperatures. It was observed from the photoelectrochemical measurements that all photoanodes were active towards oxygen evolution reaction. The photocurrent generated by WO3/BiVO4 photoanode enhanced slightly with increasing the annealing temperature and reached the maximum values of 0.078 and 0.080 mA/cm2 for 200 C and 450 C, respectively at bias voltage of 0.33 V in the absence of light as presented in Fig. 7. Upon exposing light to the WO3/ BiVO4 photoanode these photocurrents improved by a factor of 1.5, when compared with photocurrent produced in the dark. We achieved photocurrents of magnitude 0.106 and 0.109 mA/cm2 for 200 C and 450 C at the similar potential, respectively. Rao et al. synthesized core/shell WO3/BiVO4 NWs and achieved a photocurrent of >3.1 mA/cm2 under photosimulator at higher potential i.e. 1.23 V vs RHE. Their reported voltammogram suggested that the current density is ~0.1 mA/cm2 at 0.5 V, which is comparable with our reporting photocurrent value, provided that they used more complex flame-deposition technique, for their coreshell WO3/BiVO4 heterojunction synthesis [25]. In other study, researchers synthesized WO3 and BiVO4 separately by refluxing their precursors and then made their composite by depositing their layers on FTO. They achieved the same amount of current density at relative higher potential i.e. 1.0 V as compare to our potential, which was 0.5 V [16]. This rise in


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Fig. 5 e Raman spectrum of WO3 (black), BiVO4 (red) and WO3/BiVO4 (blue) materials. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

Fig. 4 e (A) UVeVIS, and (B) Diffused Reflectance Spectra for direct band gap estimation of Pure WO3 (black), pure BiVO4 (red) and WO3/BiVO4 nanoflakes (blue). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.) Fig. 6 e Chronoamperometry spectrum of WO3/BiVO4 coated on ITO glass substrate. photocurrent with increasing the annealing temperature is attributed to aggregation of the crystals, increase in grain size and defects in WO3/BiVO4 nanoflakes, in addition to creation of more oxygen vacancies in the material that lead to photogenerated electrons recombination. Therefore, incorporation of WO3 with BiVO4 enhances their photoelectrochemical properties. Otherwise, BiVO4 independently considered as good electron absorber but with poor electron transport properties. Furthermore, the conduction band of BiVO4 is more negative than that of WO3 [22] so when BiVO4 is coupled with photocorrosion resistant WO3 [28,36], more photocurrent would be expected as we observed. This WO3 insertion in BiVO4 overcome its low photocurrents and shorter photocarrier diffusion length [22,27]. The lifetime and quantity of photo-generated electrons are important parameters in understanding photoelectrochemical measurements. It is assumed that the photogenerated electrons in the crystallites transported to WO3 surface, thus the photoelectrochemical activity could

happens effectively. The possible charge transfer mechanism for WO3/BiVO4 nanoflakes coated on ITO glass under solar light (100 mWcm2AM 1.5G) is shown in Fig. 8. Consequently, the recombination of photo-generated electrons in the tungsten oxide influenced the photoelectrochemical behavior of WO3/BiVO4 [37]. The large surface area WO3/BiVO4 nanoflakes offered long distances and thus lead to better charge recombination of photo-generated electrons. Furthermore, enhanced oxygen vacancies and more defects in the material texture could consume the photo-generated electrons effectively, when annealed even at higher temperatures as reported by Gang Xin et al. [38]. Thus, the better photoelectrochemical properties are most significant feature of our WO3/BiVO4 experimental strategy that achieved by combing the light harvesting of BiVO4 and WO3 as efficient photo conversion materials that ultimately generated improved photocurrents by WO3/BiVO4 photoanode [39]. The



Fig. 7 e Linear Sweep Voltammogram of WO3/BiVO4 coated on ITO glass annealed at 200 C and 450 C.

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heterostructures were drop casted over WO3 seeded ITO substrates and annealed at 200 and 450 C, respectively. The WO3/BiVO4 morphology, structural and elemental composition were investigated via FE-SEM, EDX and XRD techniques. XRD pattern revealed a tetragonal crystal structure of WO3/ BiVO4 whereas, Raman spectroscopy further comprehend the structure elucidation by identifying characteristic fingerprint regions for specific functionalities in WO3/BiVO4. The comparative optical properties of each WO3, BiVO4 and WO3/ BiVO4 showed a variation in band gap energy and attributed to change in crystal phase of WO3/BiVO4 with respect to WO3 and BiVO4. The chrono-amperometry and LSV showed improved photocurrents due to visible response of the BiVO4 layer and the enhancement of charge separation in the WO3/BiVO4 hetero-structure. Moreover, effect of temperature on WO3/ BiVO4 was also revealed i.e., an increase in temperature also show increase in photocurrent and vice versa. The photocurrents recorded for WO3/BiVO4 at 200 C and 450 C were 0.106 and 0.109 mA/cm2, respectively. In summary, our results show that WO3/BiVO4 nanoflakes assimilated into a heterojunction structure stimulates charge-carrier separation, transfer, reduced charge recombination and photocorrosion stability have promising strategy for improving photoelectrochemical water splitting efficiencies.

Acknowledgment The National Plan funded this project for Science, Technology and Innovation (MAARIFAH) e King Abdulaziz City for Science and Technology e through the Science and Technology unit at King Fahd University of Petroleum and Minerals (KFUPM) e the Kingdom of Saudi Arabia, award number (13NAN1600-04).

references Fig. 8 e Energy diagram of WO3/BiVO4 heterostructure material coated on ITO glass showing probable charge transfer mechanism.

valence and conduction bands of WO3 are more positive in energy than those of BiVO4 thus facilitated enhanced charge separation from BiVO4 to WO3. Photo-generated holes from excited WO3 are transported into the valence band of BiVO4, which in turn improved charge separation at one end and decreases the recombination rate of Hþ and electrons (e) within BiVO4 [40,41]. Thus collectively better photoelectrochemical properties of the WO3/BiVO4 photocatalyst observed, that could be employed for reliable and effective photoelectrochemical applications under visible irradiation.

Conclusion WO3/BiVO4 nanoflakes as photoanode materials synthesized via hydrothermal method. The as prepared WO3/BiVO4

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