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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_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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electrolysis_01 | 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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electrolysis_01 | 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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electrolysis_01 | The 100-%-level for optical transmittance was taken as the value recorded with nothing but electrolyte in the cell. | [
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electrolysis_01 | 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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electrolysis_01 | 3. Results | [
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electrolysis_01 | 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_01 | 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 | 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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electrolysis_01 | These films exhibited a slightly lower HER performance, as observed by close inspection of Fig. S1 in SI. | [
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electrolysis_01 | These films will not be discussed further below. | [
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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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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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electrolysis_01 | 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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electrolysis_01 | The effect of sputtering power was negligible, as depicted in Fig. S1a in SI. | [
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electrolysis_01 | 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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electrolysis_01 | 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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electrolysis_01 | 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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electrolysis_01 | The values of the Tafel slope could not be correlated to the sputter parameters. | [
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electrolysis_01 | 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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electrolysis_01 | 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 | 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 | 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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electrolysis_01 | 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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electrolysis_01 | 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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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 | 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 | 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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electrolysis_01 | STH efficiency was investigated for a solar water splitting system | [
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electrolysis_01 | Table 1 Ga/(Ga+In) ratio and Eg of A-CIGS. | [
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electrolysis_01 | consisting of a PV–electrolyzer with WO3 as an electrocatalytic cathodic material. | [
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electrolysis_01 | 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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electrolysis_01 | j– | [
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electrolysis_01 | 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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electrolysis_01 | 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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electrolysis_01 | 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_01 | 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 | 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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electrolysis_01 | The effect of band gap changes are seen in the j–V characteristics of the A-CIGS module. | [
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electrolysis_01 | 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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electrolysis_01 | 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_01 | 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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electrolysis_01 | 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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electrolysis_01 | Thus, | [
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electrolysis_01 | Fig. 3. | [
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electrolysis_01 | 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 | 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 | 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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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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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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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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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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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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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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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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electrolysis_01 | EIS measurements were done on WO3 thin films deposited on Ni foam and ITO coated glass substrates. | [
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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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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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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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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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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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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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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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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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electrolysis_01 | The EIS data were fitted with an equivalent circuit model, embedded in Fig. 6a [42]. | [
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electrolysis_01 | 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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electrolysis_01 | 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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electrolysis_01 | 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 | 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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electrolysis_01 | Uniform deposition of WO3 thin films on ITO at 30 mTorr, 200 W and | [
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electrolysis_01 | 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_01 | Experimental data are shown by symbols and impedance fits to the model are by lines. | [
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Subsets and Splits