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electrolysis_03 | The frequency of bubble removal from the catalyst layer (fb) can be scaled from the inertia capillary time scale τcap f 1 b ffiffiffiffiffiffiffiffiffiffiffiffiffiffi | [
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electrolysis_03 | ΔρV=γ p . | [
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electrolysis_03 | Thus, the frequency ratio of bubble removal can be fb;WP fb;PWP ¼ ffiffiffi 17 8 q 1:5, where the volume was considered from the critical volume for each structure (see details in Supplementary Note 2). | [
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electrolysis_03 | The second theoretical model calculated under the assumption of bubble size similar to or larger than pore channel size in the catalyst is consistent with the results of the SECM measurement data. | [
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electrolysis_03 | This implies that the bubbles having a size similar to or larger than that of the pores determines the frequency of bubble formation and removal from the catalyst layer. | [
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electrolysis_03 | We characterized and confirmed the larger bubbles that must be formed by the coalescence within the 3D catalyst layer via a dynamic light scattering (DLS, Fig. 4c) analysis on the electrolyte, where we conducted LSV once with different 3D geometries (WP 1200 and PWP1200). | [
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electrolysis_03 | The larger bubble size (2838 nm) from the PWP1200 structure was estimated to be 19% larger than that (2381 nm) of the bubbles from the more open and ordered WP1200 samples. | [
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electrolysis_03 | These results lead us to conclude that the bigger bubbles from PWP tend to have a larger size because of the longer residence time in the catalyst layer, which confirms the second hypothesis (B). | [
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electrolysis_03 | In addition, in the DLS spectra, it can be seen that relative intensity of the bigger bubbles from the PWP structure is relatively lower than that of the smaller bubbles (~150 nm diameter), while the tendency is reversed in the case of bubbles from the WP structure. | [
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electrolysis_03 | This can be attributed to the more facile escape of the larger bubbles in the WP structure before growing into much larger ones, which is consistent with the results of the SECM analysis and theoretical calculations. | [
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electrolysis_03 | These results suggest that coalescence of bubbles, which is driven by the reduction of the overall surface energy, should be prevented for higher OER activity. | [
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electrolysis_03 | As the coalesced gas bubbles within the catalyst layer hinder the approach of the reactant water to the catalytic surface, engineering 3D nanostructures can accelerate the rate of OER per unit ECSA by facilitating the removal of the generated gas bubbles. | [
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electrolysis_03 | There are further experimental results supporting that the ECSA-specific activities of the 3D WP catalysts are governed by the eases of gas bubble transport, which is controlled by the geometric parameters of the 3D catalysts. | [
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electrolysis_03 | When the stacking direction of three types of NW building block arrays were changed from perpendicular (WP) to parallel (PWP), the impact of decrease in the ECSA-specific activity (Fig. 3e and Supple- mentary Fig. 12) on the mass activity overwhelmed the that of ECSAs, which were maintained within a deviation of only 4.6% (Fig. 3c). | [
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electrolysis_03 | The reduction in the ECSA-specific activities resulted in a noticeably lower mass activity of PWP than that of the WP- structured catalysts (Fig. 3a and Supplementary Fig. 11b). | [
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electrolysis_03 | Furthermore, the decrease in mass activities resulting from the change of stacking direction of Ir NW arrays (from perpendicular to parallel) for the denser structures (P200 and P1200 in Fig. 4d, f) became relatively less significant than that for the more open NW building blocks (P400) (Fig. 4e). | [
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electrolysis_03 | The opening ratio (OR) of 3D catalysts (ratio of the spacing between NWs divided by NW width), which is in the order of P200 (OR= 0.250) > P1200 (OR = 0.208) > P400 (OR= 0.125), is thought to be inversely scaled with the ease of bubble transport. | [
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electrolysis_03 | This is consistent with the considerable loss of ECSA-specific activity by the structural change from WP to PWP in Fig. 3e (indicated with dotted red arrows). | [
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electrolysis_03 | In addition, the ECSA-specific activity increases less rapidly with increasing macropore size in the 3D WP samples (Fig. 3e), suggesting that there is an optimal macropore size. | [
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electrolysis_03 | For example, the change of building block from P200 to P400 resulted in a 31% increase of ECSA-specific activity, while there was only a 3% improvement by the change from P400 to P1200. | [
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electrolysis_03 | The ECSA-specific activity can be affected not only by the mass transport of the reactants/products of the reaction within the nanostructures but also by the conductivity of the electrons/ protons, which can be characterized by the Ohmic loss measured in the EIS analysis at the OER-occurring potential (1.55 V vs RHE) in Supplementary Fig. 10. | [
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electrolysis_03 | Regardless of the stacking directions, all NW stacks showed a comparable Ohmic resistance to that of the Ir black samples (Supplementary Table 6). | [
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electrolysis_03 | This suggests that in the 3D WP structures, the water inside the well- defined nanoscale pores can provide ionic conductance over a short distance even in the absence of ionomers38. | [
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electrolysis_03 | OER stability. | [
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electrolysis_03 | Figure 3f presents normalized current densities over the course of 500 repeating chronoamperometry for the three types of 4-layered 3D WP samples and an Ir black nano- particle electrode as a reference. | [
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electrolysis_03 | The normalized current densities (>0.8) after 500 cycles of the 3D WP samples are comparable to each other, but for the Ir black nanoparticles, the current density decreased by ~40%. | [
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electrolysis_03 | The trend of the superior stability of the WP samples was maintained for even more (1000) cycles of the OER (Supplementary Fig. 16a), which was also demonstrated with chronopotentiometry in Supplementary Fig. 17. | [
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electrolysis_03 | The decrease in the integrated surface charge during the 500 cycles (inset of Fig. 3f) can be attributed as the dominant factor in the OER stability of the samples. | [
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electrolysis_03 | To quantify ECSA, as an alternative for the estimation based on HUPD peaks, we exploited electric double-layer charge calculated from the CV data (Supplementary Fig. 8) and capacitances (Supplementary Fig. 9h) measured with another CV ranging 1.1–1.2 VRHE at various scan rates (Supple- mentary Fig. 9a–g). | [
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electrolysis_03 | In contrast to the significant degradation of the active surface area of the nanoparticle-type catalysts, the WP samples have more capability to sustain an active surface area. | [
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electrolysis_03 | It was reported that coalescence or detachment of Ir nanoparticles could lead to a severe loss of surface area (>50%)39–41. | [
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electrolysis_03 | Agglom- eration of Ir nanoparticles also could be expedited by ionomer degradation accelerated by the applied voltage42,43. | [
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electrolysis_03 | In contrast, the WP geometry was almost perfectly maintained even after 500 cycles of the degradation test, as shown in Supplementary Fig. 18, although they experienced similar amorphization and hydrated oxidation (Supplementary Fig. 16d–g) of the Ir-based OER catalysts in the acidic electrolyte. | [
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electrolysis_03 | This structural robustness suggests that the inherent dissolution of Ir44,45 is the main factor underlying the gradual OER performance degradation of the WP structure. | [
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electrolysis_03 | However, as shown in Supplementary Fig. 16c, the Ir dissolution rate was relatively smaller for the WP samples compared to Ir black. | [
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electrolysis_03 | Previous studies reported that there is an apparent tendency of | [
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electrolysis_03 | Ir dissolution in properly confined nanostructures11,46. | [
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electrolysis_03 | Also, for our WP samples, the 4-layer 3D geometry having more confined conditions improved the OER stability relative to the 2-layer structure (Supplementary Fig. 16b), suggesting that optimization of the 3D geometry may be able to provide a simultaneous influence on OER activity and stability. | [
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electrolysis_03 | Characterization of OER performance in PEMWE. | [
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electrolysis_03 | This can be understood by the linearly enlarging surfa- ce area along the number of stacking layers, as confirmed in the half-cell test (Supplementary Figs. 14a and 15). | [
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electrolysis_03 | The same ten- dency was observed for WP400 and WP200 samples (Supple- mentary Fig. 20). | [
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electrolysis_03 | The 30-layered P1200 sample recorded a maximum current density of 5.2 A cm−2 at 2.0 V, which is more than double of the conventionally reported maximum current densities of 1.0–3.0 A cm−2 at >1.8 V7. | [
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electrolysis_03 | In our setting of single-cell measurements, the WP 1200 30- layered sample showed the maximum current density with an Ir loading of ~45 μg cm−2, and the maximum current density was | [
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electrolysis_03 | Fig. 5 PEMWE performances of 3D WP catalysts. | [
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electrolysis_03 | Ir catalysts with those reported in previous studies5,17,47,48 based on both half-cell tests using a rotating disk electrode (RDE) and single-cell tests using a membrane electrode assembly (MEA). | [
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electrolysis_03 | 4.3-times higher than that of the cell based on Ir black nanoparticles (Fig. 5d) with comparable | [
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electrolysis_03 | In addition, the PEMWE equipped with 30-layer WP1200 sustained the advanced performance for longer than 45 h as shown in Supplementary Fig. 21. | [
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electrolysis_03 | Moreover, the best membrane electrode assembly (MEA) based on 10-layer P400 catalysts recorded a mass activity (40.6 A/mg) at 1.6 V, which corresponds to 25 times and 17 times the values of the Ir-black-based cells with a comparable | [
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electrolysis_03 | Ir loading amount (50 μg cm−2) and with the optimum Ir loading (=100 μg cm−2) measured in this study (Fig. 5e). | [
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electrolysis_03 | The mass activity is approximately four times greater than the highest previously reported value17 (9:94Amg 1 Ir , Fig. 5b) among those of Ir-based catalysts. | [
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electrolysis_03 | The correlation between the geometric properties of WP structures and the mass activity further validates the critical role of bubble transport in the catalyst. | [
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electrolysis_03 | Among the 10-layered WP catalysts, the mass activity was in the order of WP400 >WP1200 >WP200, which is consistent with the half-cell test performed with 4-layered samples. | [
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electrolysis_03 | A different trend, however, was observed for the larger number of stacking layers: WP1200 > WP400 >WP200 for 20- and 30-layered WP structures. | [
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electrolysis_03 | The decrease in mass activity accompanied with the addition of more layers was much less significant for P1200 compared to P400 and P200. | [
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electrolysis_03 | In the cases of P400 and P200, the mass activity decreased by ~50% from 10 layers to 20 layers and 10–15% from 20 layers to 30 layers at both 1.6 and 1.8 V. | [
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electrolysis_03 | In contrast, P1200 showed only a 10–20% decrease of the mass activity upon changing from 10 layers to 20 layers and with additional stacking from 20 to 30 layers. | [
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electrolysis_03 | As the path length for transport of O2 would be increased for a higher number of stacked layers, while increasing amount of bubbles, the decrease in mass activity accompanied with the addition of layers was much less significant for P1200 having larger channel size compared to P400 and P200. | [
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electrolysis_03 | These results indicate that well-defined macropore channels with appropriate size WP structures are critical for high-current density and mass activity, although the optimum structural parameters depend on the operation conditions and the total loading amount of Ir. | [
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electrolysis_03 | Discussion | [
"Discussion"
] | 33,862 | 33,872 | ['Heading'] | O | {
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electrolysis_03 | In this study, WP-structured | [
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electrolysis_03 | Ir catalysts were designed and successfully fabricated via a high-resolution printing process to enable extremely high mass activity in the OER, which is driven by both high ECSA and ECSA-specific activity. | [
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electrolysis_03 | A half-cell test demonstrates that the WP catalyst generated 4.8-times higher mass activity than the Ir black nanoparticles despite no dif- ference in the physiochemical properties. | [
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electrolysis_03 | More strikingly, when applied to a single-cell PEMWE device, the new catalyst achieved far more enhanced mass activity, up to 30 times that of Ir black. | [
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electrolysis_03 | Systematic tuning of the 3D geometry and NW building blocks revealed that O2 bubble transport, which was characterized with SECM, is a key parameter in improving the performance of the OER catalysts, providing practical design rules for more efficient OER catalysts. | [
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electrolysis_03 | We expect that these outcomes will provide a large step toward the development of highly feasible OER catalysts by simply controlling their 3D microstructures even without any change of physiochemical characteristics. | [
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electrolysis_03 | Therefore, there will be abundant room for further improving the OER performance of our WP-structured catalysts via synergistic combination with other approaches based on new elemental compositions. | [
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electrolysis_03 | Prior to the S-nTP process, we pre- pared three types of line-patterned master templates with periods of 200 nm, 400 nm, and 1 μm via photolithography and plasma etching. | [
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electrolysis_03 | A polydimethylsiloxane (PDMS) brush (PDMS-OH, molecular weight= 5 kg/mol) with a low surface energy was grafted on the surface of the master templates. | [
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electrolysis_03 | On top of the brush- treated mater template, a polymethylmethacrylate (PMMA) was spin-coated to produce a polymer replica, which was detached using a polyimide film. | [
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electrolysis_03 | On the PMMA replica, an oblique angle deposition process was employed through e-beam deposition to create discrete Ir NWs on the replica. | [
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electrolysis_03 | The NWs were transfer-printed onto a Cu receiver substrate, and then the polymer replica was removed by toluene washing. | [
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electrolysis_03 | Sequential printing of Ir NWs was then repeated, forming multilayer stacks of 3-dimensional structures, as illustrated in Fig. 2. | [
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electrolysis_03 | The NWs arrays were then transferred to a working electrode for the half cell test or the Nafion® membrane for the single-cell test. | [
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electrolysis_03 | To transfer Ir NWs from the receiver substrate onto a glassy carbon electrode or Nafion membrane, the Cu substrate was removed with a commercialized Cu etchant (Sigma Aldrich, Ammonium Persulfate). | [
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electrolysis_03 | After etching the Cu foil, the nanostructured | [
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electrolysis_03 | Ir samples floating on the surface of the Cu etchant were lifted up with the substrates for electrochemical measurements. | [
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electrolysis_03 | To measure the loaded amount of Ir in each sample, inductively coupled plasma-mass spectrometry (ICP-MS) measurements were performed at least five times. | [
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electrolysis_03 | Physiochemical characterization. | [
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electrolysis_03 | The physiochemical characteristics of the Ir OER catalysts were analyzed with various methods including XRD, TEM, XPS, and X-ray absorption fine structure (XAFS). | [
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electrolysis_03 | XRD measurements were performed on a SmartLab (RIGAKU) diffractomer in θ–2θ scan mode using Cu Ka1 radiation generated by high power (>9 kW) and a symmetric-cut curved crystal mono- chromator. | [
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electrolysis_03 | A TEM analysis was carried out using JEM-2100F (HR) (JEOL LTD., Japan)) with an acceleration voltage of 200 kV. | [
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electrolysis_03 | XPS measurements were performed using a K-alpha spectrometer (Thermo VG Scientific) with a microfocused monochromatic X-ray source. | [
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electrolysis_03 | The reference of the binding energies of the acquired spectra was the C 1 s line at 284.8 eV. | [
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electrolysis_03 | XANES and EXAFS were collected at the 1D XRD KIST_PAL beam line. | [
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electrolysis_03 | The incident beam was collimated with a mirror of Rh/ Pt, two Ag-coated strips, and monochromatized using a double crystal mono- chromator composed of in situ Si(111) and Si(311) exchange. | [
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electrolysis_03 | The mono- chromatized beam was refocused with a focusing mirror (Ag-coated strips, Si- cylindrical, and Rh/Pt coated). | [
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electrolysis_03 | The photon flux of the beam was measured with an ionization chamber equipped with a 1000 V-biased Ni electrode. | [
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electrolysis_03 | EXAFS data were calibrated with energy background subtraction and edge step normalization. | [
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