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Then, a 10 nm NaF layer was deposited by evaporation.
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electrolysis_01
train3
electrolysis
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The CdS layer was deposited by wet chemical bath deposition, using 1.2 M ammonia, 3.2 mM cadmium acetate, and 0.1 M Thiourea.
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train3
electrolysis
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The samples were immersed in a beaker with 175 mL solution, which was heated in a 60 ◦C water bath for 10 min, of which the first 6 min were without Thiourea.
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electrolysis_01
train3
electrolysis
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After the process, the samples were rinsed and dried with nitrogen.
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train3
electrolysis
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A double layer of undoped ZnO (70 nm) and a layer of aluminum-doped ZnO (210 nm) were deposited as a transparent conducting layer by rf magnetron sputtering.
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train3
electrolysis
electrolysis_01
A Ni-Al-Ni grid was evaporated through a shadow mask by electron gun evapora- tion (about 2.5% area coverage) as the top electrode.
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electrolysis
electrolysis_01
The A-CIGS layer was deposited by vacuum co-evaporation using a process dedicated to give high-quality material and with an in-depth grading of the Ga/(Ga+In) ratio through the film thickness obtained by using a high Ga/(Ga+In) evaporation rate in the beginning of the process and a lower one in the rest of the evaporation.
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train3
electrolysis
electrolysis_01
The Ag/(Ag+Cu) ratio was 0.2.
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electrolysis_01
train3
electrolysis
electrolysis_01
The Ga/(Ga+In) ratio and band gap energy (Eg) of the samples are listed in Table 1.
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electrolysis_01
train3
electrolysis
electrolysis_01
After the A-CIGS deposition, the surface was modified by deposition of 5–10 nm of KF at a substrate temperature of 350 ◦C.
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electrolysis_01
train3
electrolysis
electrolysis_01
Separation of cells was approached by mechanical scribing as described previously [9,17].
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16,018
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electrolysis_01
train3
electrolysis
electrolysis_01
2.2. Characterization techniques
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['Heading']
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electrolysis_01
train3
electrolysis
electrolysis_01
Scanning electron microscopy (SEM)-Energy–dispersive X-ray spec- troscopy (EDS) measurements were performed on a Zeiss 1530 instru- ment using 10 kV electron accelerating voltage.
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MEASUREMENT
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electrolysis_01
train3
electrolysis
electrolysis_01
X-ray mapping and elemental analysis were done within the Aztec software.
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16,232
16,305
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MEASUREMENT
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electrolysis_01
train3
electrolysis
electrolysis_01
X-ray photo- electron spectroscopy (XPS) studies were carried out on a PHI Quantera II spectrometer with Al Kα radiation with the energy of 1453 eV.
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16,306
16,454
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MEASUREMENT
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electrolysis_01
train3
electrolysis
electrolysis_01
All spectra were calibrated to the adventitious C 1s peak (284.8 eV).
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16,524
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QUAL_MEASUREMENT
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electrolysis_01
train3
electrolysis
electrolysis_01
The films were not sputtered prior to measurement since preferential sput- tering of elements can lead to deviation from real chemical composition and state [39].
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The XPS spectra were analyzed using the CasaXPS soft- ware.
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The analysis of the O 1s peak was not included in this work to avoid misinterpretation of the oxygen composition and state, which could be due to the exposure of the surface to the atmosphere, adven- titious contamination, oxidation or water.
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electrolysis
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X-ray diffraction (XRD) of the films deposited on glass substrates was recorded with 1◦ of grazing angle using a grazing-incidence Siemens D5000 diffractometer with CuKα1 radiation at 1.5406 Å, 45 kV, and 40 mA.
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Half-cell and full-cell reactions were characterized by linear sweep voltametry (LSV) measurements performed using a CH Instrument model 760C workstation with a scan rate of 5 mV s− 1 for hydrogen evolution of WO3 thin films.
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The electrolyte was 0.5 M H2SO4 (pH 0), which was purged by nitrogen flow for 5 min before the measurements.
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The half-cell measurements were performed with a three-electrode configuration at room temperature.
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An Ag/AgCl electrode (E0 = 0.235 V at 25 ◦C) and a Pt wire were used as reference and counter electrode, respectively.
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Electrochemical impedance spectroscopy (EIS) measurements of the WO3 films were performed using a computer-controlled BioLogic Sci- ence Instruments SP-200 electrochemical interface.
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The measurements were done in the frequency range of 0.01 Hz–0.1 MHz using a 10 mV amplitude AC potential at − 0.4 V (where HER occurs) and 0 V (where no HER occurs) vs. RHE.
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The optical transmittance of the WO3 film was recorded in situ in the visible range with a setup that has a light-emitting diode (LED) and a photodiode sensor.
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The LED emitted light peaking at a wavelength of 528 nm, which is close to the middle of the luminous spectrum, and with a full width at half maximum of 33 nm for the intensity distribution.
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The 100-%-level for optical transmittance was taken as the value recorded with nothing but electrolyte in the cell.
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The current density-potential (j–V) characteristics of the A-CIGS cells were recorded under simulated AM 1.5G sunlight in a set-up with a halogen lamp (ELH).
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The cells were kept at 25 ◦C during measurement.
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3. Results
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WO3 thin films were deposited by sputtering onto Ni foam, and ITO coated glass, as detailed in the Experimental section.
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electrolysis
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In order to assess the optimum sputtering parameters of WO3 thin films for HER applica- tion, WO3 thin films were sputtered using 32 different sputtering con- ditions (pressure, O2/Ar gas ratio, and power) in a relevant region of parameters that could show electrochromic activity.
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electrolysis_01
train3
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Sputter parameters of all the WO3 thin films are shown in Table S1.
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electrolysis_01
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A number of films deposited at low pressures and low O2/Ar ratios were dark as-deposited and displayed poor electrochromism (see Supplementary Information (SI)).
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['Results']
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electrolysis_01
train3
electrolysis
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These films exhibited a slightly lower HER performance, as observed by close inspection of Fig. S1 in SI.
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['Results']
QUAL_MEASUREMENT
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electrolysis_01
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These films will not be discussed further below.
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19,587
['Results']
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electrolysis_01
train3
electrolysis
electrolysis_01
To quantify the effects of the sputtering pa- rameters on HER performance, LSV measurements were performed in the potential region from 0 to − 0.7 V vs. RHE.
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MEASUREMENT
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electrolysis_01
train3
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Current density (j) of WO3 thin films coated on Ni foam substrate versus potential (V) is shown in Fig. 3 for selected films in order to show the effect of (a) different sputter pressures and (b) different O2/Ar ratios.
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['Results']
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electrolysis_01
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electrolysis
electrolysis_01
All HER measurements that were performed for WO3 thin films on Ni foam are shown in Fig. S2a in SI.
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['Results']
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The overpotential (OVP) varied between 182 and 322 mV vs. RHE at 10 mA cm− 2 where it was 610 mV for bare Ni foam (Fig. S2b).
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The effect of sputtering power was negligible, as depicted in Fig. S1a in SI.
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There was not any observable trend connecting the j − V characteristics of the thin films with the O2/Ar ratio and pressure (Fig. 3a and b) during sputtering, as well.
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The Tafel slope of the WO3 thin film on Ni foam showed a considerable variation between 45 and 110 mV dec− 1 (Fig. 3c and d).
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This indicates that the HER follows a rate-determining Volmer or Heyrovsky step for different sputtering conditions without any order [40,41].
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The values of the Tafel slope could not be correlated to the sputter parameters.
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WO3-based electrolyzers were built using WO3 thin films coated on Ni foam as cathodic and uncoated Ni foam as anodic parts of the system.
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The performance of the electrolyzers was tested in 0.5 M H2SO4 from 0 to 2 V for the different WO3 thin films.
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electrolysis_01
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The load curves for the WO3 (HER)-Ni foam (oxygen evolution reaction (OER)) electrolyzers are shown in Fig. 4 for some selected sputtering conditions.
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electrolysis_01
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The load curves were similar for the electrolyzers with different WO3 thin films and the lowest potential needed for 10 mA cm− 2 in the overall reaction was 1.77 V.
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In order to further quantify the performance of the WO3 films as cathodic electrocatalytic materials under acidic conditions, the results were compared with a known electrocatalyst configuration for hydrogen production.
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j–V characteristics of NiMo coated on Ni foam (HER) com- bined with NiO on Ni foam (OER) electrolysis in 1 M KOH are shown in Fig. 4
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21,573
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electrolysis_01
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electrolysis
electrolysis_01
The measurements were done in a 5 mL cylindrical electro- chemical cell without membrane and with a 1 cm interdistance between the electrodes.
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electrolysis_01
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It is seen that j–V characteristics of the different systems are very similar in the operation range of a solar cell.
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electrolysis_01
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electrolysis
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Therefore, it can be concluded that WO3 under acidic conditions is able to compete with known alkaline electrocatalysts for hydrogen production, where higher current densities naturally can be obtained upon further nano- structuring and by increasing the total internal surface area for either WO3, NiMo, or NiO.
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['Conclusion']
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electrolysis_01
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electrolysis
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STH efficiency was investigated for a solar water splitting system
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electrolysis_01
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electrolysis
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Table 1 Ga/(Ga+In) ratio and Eg of A-CIGS.
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electrolysis_01
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consisting of a PV–electrolyzer with WO3 as an electrocatalytic cathodic material.
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['Experiment']
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electrolysis_01
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In order to find an optimum efficiency of the PV–electrolysis, different combinations of the electrolyzer with A-CIGS-based thin film solar cell modules with different band gaps of the cell were examined.
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j–
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V measurements were done for the electrolyzer and the cells, as well as extended to 3–cell A-CIGS modules to generate a photovoltage large enough to fulfill the energy need of the electrolyzer.
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STH was estimated from the intersection of the j–V curves for the same area of the modules and the electrodes of the electrolyzer.
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The electrolyzer load curve can be shifted to the left and provide higher catalytic current at a given potential up to the current plateau but is here kept at the same area as the PV-module to more easily compare with previously published PV/photoelectrochemical approaches.
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electrolysis
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This also allows comparison with STH found from direct photocatalysis, naturally sharing the same area of the photoabsorber and the area available for catalysis.
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electrolysis_01
train3
electrolysis
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Current densities versus the potential for 3–cell A-CIGS mod- ules with different band gap energies and an electrolyzer with a WO3 on Ni foam (HER) and Ni foam (OER) are shown in Fig. 5.
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The effect of band gap changes are seen in the j–V characteristics of the A-CIGS module.
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train3
electrolysis
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An increase in the STH efficiency from 12% to 13% resulted from lowering the bandgap from 1.25 eV to lower values in order to increase the photocurrent while still having a sufficient photovoltage to perform the full water splitting reaction (Fig. S3).
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train3
electrolysis
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A similar situation could be ob- tained by using slightly concentrated solar light but with increase of the likely cost of the system quite substantially.
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electrolysis
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However, in order to ach- ieve a more robust system, with less sensitivity to the sputtering pa- rameters of the WO3 films and allowing for variation in the active area and solar illumination conditions, the A-CIGS module with 1.25 eV band gap a cell would be preferred.
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This module was chosen for further study in order to reduce the effect of the module voltage on the STH since the intersection is in the plateau region of the j–V curve of the module.
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Thus,
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electrolysis_01
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electrolysis
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Fig. 3.
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electrolysis_01
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electrolysis
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Linear sweep voltammetry recorded in 0.5 M H2SO4 with 5 mV s− 1 scan rate, showing the effect of varying (a) O2/Ar ratio with 30 mTorr pressure and 200 W power, (b) sputter pressure with 0.90 O2/Ar ratio and 200 W power, and (c, d) Tafel plots of (a, b) for electrocatalytic HER of WO3 thin films on Ni foam.
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electrolysis_01
train3
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Fig. 4. Potential dependence of current density of overall water splitting recorded with 5 mV s− 1 scan rate for the WO3 (HER)-Ni foam (OER) electro- lyzers in 0.5 M H2SO4 and a NiMo (HER)-NiO (OER) electrolyzer in 1 M KOH.
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electrolysis_01
train3
electrolysis
electrolysis_01
the variation of the STH came mainly from the j–V characteristic of the electrolyzer and varied between 12.35% and 12.49% for the different sputtering conditions used to deposit WO3 films.
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25,133
25,321
['Results']
O
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electrolysis_01
train3
electrolysis
electrolysis_01
The results showed that the sputtering parameters of WO3 films are less significant for achieving a high STH efficiency of the A-CIGS-Ni foam-WO3 system (1% unit variance in STH) if a suitable band gap matching is done.
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25,322
25,541
['Conclusion']
QUAL_MEASUREMENT
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electrolysis_01
train3
electrolysis
electrolysis_01
The above reported results are from a Ni foam supported approach where the electrochromic properties of the catalyst can be used to study the state or the health of the cathodic catalyst by viewing the surface color.
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25,542
25,758
['Explanation']
O
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electrolysis_01
train3
electrolysis
electrolysis_01
However, reflectance modulations are typically rather small, and a much better sensitivity would be achieved by using a transmitting substrate.
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25,759
25,902
['Background']
O
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electrolysis_01
train3
electrolysis
electrolysis_01
Furthermore, in order to thoroughly analyze the coloration efficiency and the electrochromic effect, a transparent electrode was also applied.
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25,903
26,045
['Exp_Characterization', 'Experiment']
O
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electrolysis_01
train3
electrolysis
electrolysis_01
In addition, for design of a combined electrochromic and electrocatalytic hydrogen evolution system where the transmission properties are in focus, Ni foam has to be replaced by other alternatives.
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26,046
26,243
['Background']
O
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electrolysis_01
train3
electrolysis
electrolysis_01
Here, we deposited a WO3 film onto a transparent and electrically conducting ITO coated glass electrode and analyzed the charge incor- poration, transmitted light, and coloration efficiency in a proof-of- concept for electrochromic HER.
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26,244
26,480
['Experiment']
O
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electrolysis_01
train3
electrolysis
electrolysis_01
Before studying the electrochromic HER performance of WO3, we investigated the role of the substrate on the catalytic activity by EIS and electrochemical real surface area (ECSA) analysis.
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26,481
26,669
['Exp_Characterization', 'Experiment']
MEASUREMENT
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electrolysis_01
train3
electrolysis
electrolysis_01
EIS measurements were done on WO3 thin films deposited on Ni foam and ITO coated glass substrates.
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26,670
26,768
['Exp_Characterization', 'Experiment']
MEASUREMENT
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electrolysis_01
train3
electrolysis
electrolysis_01
The measurements were performed at DC potentials of 0 and − 0.4 V vs. RHE which represented the non-reaction and reaction cases.
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26,769
26,897
['Exp_Characterization', 'Experiment']
MEASUREMENT
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electrolysis_01
train3
electrolysis
electrolysis_01
The Nyquist plots of the experimental data are shown in Fig. 6a and b for the films on Ni foam and ITO, respectively.
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26,898
27,015
['Results']
MEASUREMENT
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electrolysis_01
train3
electrolysis
electrolysis_01
It should be noted that the highest frequencies are at the left–hand side of the Nyquist plots and that frequencies decrease as one follows the curves towards the right.
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27,016
27,185
['Results']
O
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electrolysis_01
train3
electrolysis
electrolysis_01
For the WO3 films on Ni foam, the impedance response with a DC potential of 0 V vs. RHE where there was not any HER showed two almost over- lapping arcs, and was dominated by the second arc in the lower fre- quency range with higher impedance values.
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27,186
27,436
['Results']
QUAL_MEASUREMENT
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electrolysis_01
train3
electrolysis
electrolysis_01
Under HER condition (− 0.4 V vs. RHE), only one arc was seen, probably due to the su- premacy of the reaction impedance.
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27,437
27,557
['Results']
QUAL_MEASUREMENT
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electrolysis_01
train3
electrolysis
electrolysis_01
For WO3 on ITO, the high- –frequency arc was not complete due to the limit of the instrument at high-frequencies but was large enough to be clearly distinguished from the low–frequency behavior.
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27,558
27,752
['Results']
O
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electrolysis_01
train3
electrolysis
electrolysis_01
For both substrates, the lower abso- lute impedance in the low–frequency range was seen when HER occurred compared to the measurement at the non-reaction state.
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27,753
27,913
['Results']
QUAL_MEASUREMENT
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electrolysis_01
train3
electrolysis
electrolysis_01
Impedance values were noticeably higher for the films coated on ITO and underline that the substrate-catalyst interface also is important for the overall catalytic performance as recently highlighted [42].
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27,914
28,119
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The EIS data were fitted with an equivalent circuit model, embedded in Fig. 6a [42].
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The model consists of a series connection of a resistance (Rs) with a parallel connection of a high frequency resistance (R1) and a high frequency constant phase element (CPE1), and a parallel connec- tion of a low frequency resistance (R2) and a low frequency constant phase element (CPE2).
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The impedance function of a constant phase element is given as Z∗ CPE = [ T(iω)P ]− 1 (8) where ω is angular frequency, T is a parameter related to the electrode capacitance, and P is the constant phase exponent.
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The elements Rs is related to the electrolyte and electrical connections, the high frequency part is related to the surface geometry where R1 is the charge transfer resistance, and the low–frequency part is associated with the reaction kinetics with the reaction resistance of R2 that depends on the applied overpotential.
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electrolysis_01
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electrolysis
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The resistance values of the WO3 films on Ni foam and ITO substrates at potentials corresponding to non-HER and HER states are given in Table 2.
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Uniform deposition of WO3 thin films on ITO at 30 mTorr, 200 W and
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electrolysis
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Nyquist plots of WO3 thin films on Ni foam (a) and on ITO coated glass (b) substrates deposited at 30 mTorr, 200 W and 0.90 O2/Ar. EIS measurements were performed at the shown DC potentials in 0.5 M H2SO4.
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electrolysis
electrolysis_01
Experimental data are shown by symbols and impedance fits to the model are by lines.
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