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electrolysis_01
0.90 O2/Ar was proven by SEM-EDS analysis (Fig. 7a).
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MEASUREMENT
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electrolysis_01
train3
electrolysis
electrolysis_01
The O/W ratio of the film deposited on ITO at 30 mTorr, 200 W and 0.90 O2/Ar was re- ported as 3.44 in a recent study, using Rutherford backscattering spec- troscopy (RBS) techniques [43].
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MEASUREMENT
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electrolysis_01
train3
electrolysis
electrolysis_01
Fig. 7b shows the high resolution tungsten (W 4f) peaks for the WO3 films deposited under the same conditions as the ones for the SEM-EDS and RBS measurements.
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30,175
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QUAL_MEASUREMENT
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electrolysis_01
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electrolysis_01
The doublet of W 4f was observed at the binding energies of 35.3 and 37.4 eV corresponding to W 4f7/2 and W 4f5/2, respectively.
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electrolysis_01
train3
electrolysis
electrolysis_01
The energy sepa- ration between the main peaks of W(4f7/2) and W (4f5/2) was 2.12 eV.
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electrolysis_01
train3
electrolysis
electrolysis_01
The results are in good agreement with those of WO3 and that the tungsten (W) in the WO3 film was present in the six-valence state (W6+) [44,45].
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electrolysis_01
train3
electrolysis
electrolysis_01
From the XRD analysis of the WO3 films on glass, the films were amorphous (Fig. 7c); which is preferable for electrochromic applications as crystalline electrochromic films have lower ionic mobility than amorphous films that lowers the switching speed.
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electrolysis_01
train3
electrolysis
electrolysis_01
Cyclic voltammetry measurements were performed (Fig. S4) to determine the ECSA of WO3 catalysts on Ni foam and ITO substrates.
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MEASUREMENT
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electrolysis_01
train3
electrolysis
electrolysis_01
The ECSAs of the WO3 catalyst on Ni foam was five times larger than that of ITO.
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['Results']
O
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electrolysis_01
train3
electrolysis
electrolysis_01
In principle, with neglect of changed recombination behavior, a catalyst with a larger ECSA is expected to provide an enhanced catalytic activity in correspondence with the increased exposed surface area.
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['Background']
O
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electrolysis_01
train3
electrolysis
electrolysis_01
The ratio of the current density of the WO3 thin films on Ni foam (− 34 mA cm− 2 , Fig. 3) and on ITO (− 5 mA cm− 2, Fig. 8) at − 0.4 V vs RHE was 6.8.
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31,203
31,354
['Results']
MEASUREMENT
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electrolysis_01
train3
electrolysis
electrolysis_01
Thus, the increased catalytic activity seen in the Ni-foam can be mainly (74%) be attributed to the surface area enhancement and a minor effect (26%) to the lower barrier formed in-between the catalyst and the conducting substrate [42].
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QUAL_MEASUREMENT
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electrolysis_01
train3
electrolysis
electrolysis_01
The electrocatalytic hydrogen evolution activity of the WO3 thin film coated on ITO was characterized by LSV at a scan rate of 5 mV s− 1 in aqueous 0.5 M H2SO4 (Fig. 8).
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In-situ optical transmittance measure- ments were performed at a wavelength of 528 nm with in-situ
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Table 2 Resistance elements from the fits of the experimental impedance data for WO3 thin films on Ni foam and ITO substrates at the shown potentials.
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Fig. 7. (a) SEM-EDS images with W and O distribution, (b) high resolution XPS spectra of the W 4f doublet core level, and (c) XRD pattern of a WO3 film deposited at 30 mTorr, 200 W and 0.90 O2/Ar on ITO-coated glass substrate.
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The WO3 film was deposited at 30 mTorr, 200 W and 0.90 O2/Ar on ITO.
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photographs of the colored (during HER) with evolving H2 gas and bleached state of the WO3 electrocatalyst shown in Fig. 8 (see Supple- mentary video 1 which shows coloration during LSV).
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The 100-%-level for the transmittance corresponded to the value recorded with nothing but electrolyte in the measurement cell.
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The WO3 thin films were in the bleached state without HER and in the colored state during HER.
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In the initial state, transmittance was 78% and decreased to ~10%, while delivering a current density of − 5 mA cm− 2 at an OVP of 400 mV, which was 0.014 mA cm− 2 for uncoated ITO (Fig. S5).
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We limited the LSV measurement at this potential because it was in the range for the application in solar water splitting.
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This limit is very close to the satu- ration level of H+ ion intercalation (Fig. S6).
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Integrating the current density from 0 to − 0.6 V vs Ag/AgCl and assuming that all electrons compensate the intercalated H+ ions, one reaches an ion insertion ratio of 0.72 H+ per W (Fig. 8).
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This value is of the same order and slightly higher than a saturated ion insertion ratio of 0.56 Li+ versus W recently reported [28].
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In the present situation, the saturation plateau is at a potential slightly higher than the voltage used in the water splitting and also at a higher insertion ratio due to the simultaneous consumption of electrons in the HER reaction.
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Using the data for the wider voltage range (Fig. S6), the apparent saturation of the H+ ion insertion occurs around a ratio of 0.8 H+/W, and assuming that H+ would have the same satura- tion ratio as Li+/W (0.56), it implies that 0.24 H+/W of the apparent ion saturation is related to the consumption of electrons in the HER.
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34,266
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['Results']
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With a fixed applied potential as in a normal application of alkaline electrolysis, however, there is creation of a steady-state situation for the coloration and the majority of the cathodic current will instead be consumed by the HER process with formation of a cathodic current plateau (Fig. 8).
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['Explanation']
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Recalling Eq. (6), the time-dependent intercalation level can be quantified by integrating the current density participating in the color- ation and obtain the number of charges inserted per unit area.
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34,890
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['Background']
O
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electrolysis_01
train3
electrolysis
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For [1- Rt(λ,x)] > Tt(λ,x) and a low variation in the total reflection Rt(λ,x) in Eq. (8), the differential coloration efficiency can be extracted with K(λ, x) = − 1 Tt(λ, x) dTt(λ, x) dq (9)
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35,092
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['Background']
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electrolysis_01
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electrolysis
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The corresponding coloration efficiency at a wavelength of 528 nm and the OVP of 400 mV was 40 cm2 C− 1.
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35,284
35,388
['Results']
MEASUREMENT
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electrolysis_01
train3
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A short demonstration of hydrogen evolution of the WO3 thin film at 400 mV OVP can be found in the Supplementary video 2.
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35,389
35,510
['Results']
O
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4. Discussion and concluding remarks
[ "4", ".", "Discussion", "and", "concluding", "remarks" ]
35,511
35,547
['Heading']
O
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electrolysis_01
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electrolysis_01
In this study, water electrolysis of WO3 thin films for hydrogen production in the potential range pertinent to electrochromic coloring was examined.
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['Motivation']
QUAL_MEASUREMENT
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train3
electrolysis
electrolysis_01
The results showed that WO3 under acidic conditions (0.5 M H2SO4) could compete with well-known non-precious catalysts for hydrogen production under alkaline conditions.
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35,698
35,867
['Conclusion']
QUAL_MEASUREMENT
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electrolysis_01
train3
electrolysis
electrolysis_01
Films of WO3 deposited on transparent substrates showed combined electrocatalytic and electrochromic properties, which were quantified and showed a change in transmission of visible light from 78% as an inactive elec- trocatalyst to 10% under the HER.
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35,868
36,119
['Results']
QUAL_MEASUREMENT
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The increased absorption in the film would be beneficial for increased heating of the catalyst area during operation if accessible by light or could be used for monitoring the charge state of the catalyst for process control.
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['Motivation']
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electrolysis_01
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Monitoring of the charge state and health of the cathodic WO3 catalyst film could also be carried out in reflection mode either by a simple low angle diode monitoring the reflected light or by utilization of reflection from a partly reflecting OER electrode.
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['Motivation']
O
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In transmission mode, solar heat and visible light through the thin film catalyst is modulated under operation, which can provide electrochromic functionality to water splitting devices for monitoring the state of HER or even pointing the way to possible future building integration.
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['Motivation']
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However, the latter option requires transparent electrodes to be also employed for the OER.
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['Background']
O
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electrolysis_01
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electrolysis_01
The highest STH efficiency obtained by combining A-CIGS materials with varying band gaps, with electrolyzer units using WO3 on Ni foam was about 13% for the range of WO3 thin films reported.
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36,981
37,171
['Conclusion']
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The lowest HER overpotential we find for the deposited WO3 films (182 mV@10 mA cm− 2) is in the same range or slightly higher compared to previously reported values for undoped WO3 [8] while being in the higher range of HER overpotentials reported for high surface area catalysts of iron-based phosphides (30–235 mV@10 mA cm− 2) [46] and FeNi-layered double hydroxides (down to 59 mV@10 mA cm− 2) [47].
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Hetero-atom doping and strate- gies to increase the active surface area of WO3, however, have resulted in HER overpotentials down to 38 mV@10 mA cm− 2 versus RHE [8] and show the promise for WO3-based catalyst systems that additionally al- lows electrochromic functionality.
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Utilization of a combined electro- chromic and water electrolytic effect can readily be utilized with monitoring capabilities, while a system for building integration and light flux control critically depends on transparent conducting elec- trodes for both HER and OER and requires more work on optimizing, for example, by increasing the surface area of transparent conducting electrodes, and at the same time minimize light scattering.
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This is indeed very challenging but would allow building-integrated hydrogen pro- duction with the added benefits of controlling the temperature or solar heat absorption by the tunable optical modulation of the electrochromic material.
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I.B.P. and G.A. performed the experimental work on the catalysts.
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L.S. and M.S. provided the (Ag,Cu)InGaSe2 solar cell and module manufacturing facilities.
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L.S., M.E., I.B.P., and T.E. provided the initial assessment of Ga variation and suitable band gap matching with the catalyst system.
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I.B-P and TE wrote the original draft and all authors participated in reviewing and editing the final manuscript.
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G.A.N. and T. E. provided instrumentation and participated in the analysis of the electrochemical characterization.
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I.B.P, L.S., M.S., and T.E. provided materials, access to characterization tools, and acquisition of the financial support for the project.
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Declaration of Competing Interest
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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.
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Acknowledgements
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We gratefully acknowledge financial support for the "PECSYS" proj- ect which has received funding from the Fuel Cells and Hydrogen 2 Joint Undertaking under grant agreement No 735218, supported by the Eu- ropean Union (Horizon 2020) and Hydrogen Europe and N. ERGHY, the Swedish energy agency, and the Swedish research council (Grant No 2015-03814).
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This work was supported by a pre-study funding from European Regional Development Fund.
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G.A. wants to thank the Scien- tific and Technological Research Council of Turkey (TÜBİTAK) for financial support to work at Uppsala University.
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Appendix
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A. Supporting information Supplementary data associated with this article can be found in the online version at doi:10.1016/j.nanoen.2020.105620.
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ARTICLE
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Highly efficient oxygen evolution reaction via facile bubble transport realized by three-dimensionally stack-printed catalysts
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Despite highly promising characteristics of three-dimensionally (3D) nanostructured cata- lysts for the oxygen evolution reaction (OER) in polymer electrolyte membrane water elec- trolyzers (PEMWEs), universal design rules for maximizing their performance have not been explored.
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Here we show that woodpile (WP)-structured
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Ir, consisting of 3D-printed, highly- ordered
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Ir nanowire building blocks, improve OER mass activity markedly.
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The WP structure secures the electrochemically active surface area (ECSA) through enhanced utilization effi- ciency of the extended surface area of 3D WP catalysts.
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Moreover, systematic control of the 3D geometry combined with theoretical calculations and various electrochemical analyses reveals that facile transport of evolved O2 gas bubbles is an important contributor to the improved ECSA-specific activity.
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The 3D nanostructuring-based improvement of ECSA and ECSA-specific activity enables our well-controlled geometry to afford a 30-fold higher mass activity of the OER catalyst when used in a single-cell PEMWE than conventional nanoparticle-based catalysts.
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Water electrolysis is a promising method to produce H2, a clean energy source, potentially serving as a central technology in the H2-based renewable energy cycle1.
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In particular, polymer electrolyte membrane water electrolyzers (PEMWEs) are attracting strong interest due to their compact- ness, superior energy efficiency, excellent purity of produced hydrogen, and high production rate2,3.
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However, one of the sig- nificant limitations for large-scale industrialization of PEMWEs is that high-cost noble metal catalysts are critical components for facilitating the extremely sluggish kinetics of the oxygen evolution reaction (OER) in an acidic environment4.
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Among various candidates, Ir-based oxides have been the most widely investigated as a potential catalyst material with high catalytic activity and moderate stability5,6.
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The generation of practical-level current density (>1–2 A cm−2) typically requires a high loading (0.5–3 mg cm−2) of Ir with a cost that is almost twice that of Pt7–9.
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Therefore, it is highly desirable to develop an innovative technology to raise the mass activity of Ir-based OER catalysts to the targeted level.
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The mass activity of electrochemical OER catalysts, where the current density normalized by the loa- ded amount of Ir, is determined by the electrochemically active surface area per loaded mass (ECSA) and ECSA-specific activity (mass activity per ECSA), both of which can be improved by engineering their nanostructures10–14.
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In particular, the formation of OER catalyst electrodes employing one-dimensional (1D) nanomaterials can be sub- stantially advantageous.
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electrolysis_03
train2
electrolysis
electrolysis_03
Long-range interconnectivity and low- tortuosity pore structures obtained by 1D nanostructures are expected to contribute to the enhancement of ECSA-specific activity by offering high electrical conductivity15 and highly efficient transport of evolved gas12–14.
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electrolysis_03
train2
electrolysis
electrolysis_03
This is because sufficiently long 1D metallic nanostructures can significantly reduce the number of electrically insulating junction points among catalyst particles15, and also can be designed to be beneficial for gas delivery due to the existence of more efficient gas-transporting channels compared to random aggregates of nanoparticles.
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electrolysis_03
train2
electrolysis
electrolysis_03
In previous research, random or vertically aligned nanowires (NWs) have been studied16–18, but to date the inter-catalyst space, where gas bubbles can be transmitted, has not been systematically engineered.
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electrolysis_03
train2
electrolysis
electrolysis_03
Gas bubble movement within well-defined transport pathway should be secured to reach a new level of OER electro- catalyst performance, as shown with the enhanced OER activity achieved by facile bubble detachment via transition from the Cassie state to the Wenzel state wetting of bubbles on 2- dimensionally patterned catalytic surfaces19–21.
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electrolysis
electrolysis_03
Aside from the bubble detachment, bubble coalescence before escaping the cat- alyst layer should be managed for control over bubble movement in nanostructured electrocatalysts, which was unattainable in previous studies without controllability over long-range 3D geometry.
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train2
electrolysis
electrolysis_03
For augmenting the ECSA of the OER catalysts, maximization of the two-phase contact area between water and catalyst is an essential condition for more effective interaction between the Ir surface, which serves as both catalytic active sites and pathways for the electrons, and an electrolyte22.
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electrolysis_03
train2
electrolysis
electrolysis_03
For this purpose, inter- catalyst space should secure the maximized utilization efficiency of the surface area, which is not easy to accomplish with Ir black nanoparticles (one of the state-of-the-art OER catalysts).
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electrolysis_03
train2
electrolysis
electrolysis_03
Fur- thermore, ionomers, which are typically mixed with Ir nano- particles for enhancing ionic conductivity in OER electrodes, may reduce the direct contact between the catalytic surface and reac- tants and also interfere with efficient transport of the generated gas23.
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electrolysis_03
train2
electrolysis
electrolysis_03
Taking all of these factors into account, to maximize catalytic performance, we hypothesize that an “ideal OER electrode” should simultaneously provide (1) efficient utilization of a large surface area per loading amount of catalytic material, (2) well- defined pore structures for highly efficient transport of evolved gas species, (3) long-range connectivity of building blocks for high electronic conductivity, and (4) capability of ionomer-free operation.
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['Explanation']
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electrolysis_03
train2
electrolysis
electrolysis_03
Although these requirements can be partially satisfied by the above-mentioned catalyst nanostructures, where the water electrolyte can contribute to ionic conductance over a short dis- tance even in the absence of ionomers24, it is difficult to find a prior art that demonstrates extensive 3D geometric controllability to deduce practical and universal design rules for high- performance OER catalysts.
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electrolysis_03
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electrolysis
electrolysis_03
Here, we report that 3D-geometry-controlled
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['Conclusion']
QUAL_MEASUREMENT
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electrolysis_03
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electrolysis
electrolysis_03
Ir catalysts with a woodpile (WP) structure suggest a new direction for the OER electrocatalysts to improve the PEMWE performance.
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['Conclusion']
O
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electrolysis_03
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electrolysis
electrolysis_03
The WP structure is attained by systematic engineering of NW building blocks and 3D geometry, which is carried out via ultrahigh- resolution nanotransfer printing.
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electrolysis_03
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The extensive controllability of the fabrication method enabled control of the NW-to-NW spa- cing and layer-to-layer alignment angles in the WP nanos- tructure.
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electrolysis_03
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With this capability, we reveal that the simultaneous improvements of ECSA and ECSA-specific activity result from uniform access of water reactants to the catalytic surface and easy transport and removal of evolved oxygen gas products through the well-defined pore channels, which is supported by the extensive control of 3D geometry and the scanning electro- chemical microscopy (SECM) analysis data combined with microfluidic calculations.
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Without any alteration of crystal- lographic structures or oxidation states, WP-structured
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electrolysis_03
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Ir cata- lysts achieve a high mass activity value of 140 A/mg (at 1.8 V) in a single-cell PEMWE, which is 30 times higher than that of the state-of-the-art commercial
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electrolysis_03
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Ir nanoparticle catalysts (Ir black).
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Results
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['Heading']
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Fabrication and characterization of WP-structured Ir catalysts.
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['Heading']
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We fabricated 3D WP-structured Ir electrocatalysts (Fig. 1a) with stacking 1D NW arrays processed by solvent-assisted nano- transfer printing (S-nTP), as illustrated in Fig. 1b.
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More detailed principles of S-nTP are described in our previous paper25.
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With the S-nTP process, highly ordered NW arrays can be printed on a macroscopic area with controlled size and orientation of NWs.
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