ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Elucidation of Electrochemically Induced but Chemically Driven Pt Dissolution

Cite this: JACS Au 2023, 3, 1, 105–112
Publication Date (Web):January 12, 2023
https://doi.org/10.1021/jacsau.2c00474

Copyright © 2023 The Authors. Published by American Chemical Society. This publication is licensed under

CC-BY-NC-ND 4.0.
  • Open Access

Article Views

2435

Altmetric

-

Citations

LEARN ABOUT THESE METRICS
PDF (4 MB)
Supporting Info (1)»

Abstract

Securing the electrochemical durability of noble metal platinum is of central importance for the successful implementation of a proton exchange membrane fuel cell (PEMFC). Pt dissolution, a major cause of PEMFC degradation, is known to be a potential-dependent transient process, but its underlying mechanism is puzzling. Herein, we elucidate a chemical Pt dissolution process that can occur in various electrocatalytic conditions. This process intensively occurs during potential perturbations with a millisecond timescale, which has yet to be seriously considered. The open circuit potential profiles identify the dominant formation of metastable Pt species at such short timescales and their simultaneous dissolution. Considering on these findings, a proof-of-concept strategy for alleviating chemical Pt dissolution is further studied by tuning electric double layer charging. These results suggest that stable Pt electrocatalysis can be achieved if rational synthetic or systematic strategies are further developed.

This publication is licensed under

CC-BY-NC-ND 4.0.
  • cc licence
  • by licence
  • nc licence
  • nd licence

Introduction

ARTICLE SECTIONS
Jump To

Proton exchange membrane fuel cells (PEMFCs) have attracted significant attention for implementation in green and sustainable energy economies because they can generate electricity from clean hydrogen fuels. (1,2) Platinum is a core element of commercialized PEMFCs and exhibits superior activity toward both hydrogen oxidation (HOR) and oxygen reduction reactions (ORRs). (2−5) The initial catalytic performance of Pt electrocatalysts has recently reached a sufficient standard by alloying with other transition metals or modifying nanostructures and supporting substrates. (5−9) Consequently, securing their long-term durability is the next quest for successful PEMFC distribution since Pt electrocatalysts are often exposed to highly corrosive conditions. Especially PEMFC electrodes encounter potential excursions or spikes at highly anodic potentials, especially during fuel starvation and start-up/shut-down (SU/SD) events (up to 2.0 and 1.6 VRHE for fuel starvation and SU/SD, respectively), inducing severe degradation of Pt electrocatalysts (and carbon support) and ultimately deteriorating PEMFC performance. (10,11)
Therefore, a comprehensive understanding of Pt degradation is critical to achieve durable PEMFC operation. Despite significant efforts pioneered by Johnson et al. in 1970, (12) the insufficient resolution and sensitivity of spectroscopic analyses hinder a solid grasp of the detailed Pt degradation mechanism. Recently, great advances in operando spectroscopic analyses have enabled more detailed understanding of the degradation mechanisms of Pt electrocatalysts, particularly Pt dissolution. (13−16) For instance, online inductively coupled plasma-mass spectrometry coupled with an electrochemical flow cell (EFC/ICP-MS) successfully detects Pt dissolution during electrochemical operations, unveiling that Pt dissolution is a transient process accompanying substantial changes in the surface chemistry and structure of Pt (Figure 1a and Figure S1). (17−23) Moreover, it has been revealed that Pt dissolution can be influenced by various parameters such as facet, reactant, pH, temperature, etc. (16−18,21,22) Although previous studies have achieved a potential-resolved and quantitative understanding of Pt dissolution, the underlying Pt dissolution mechanisms during the transition process are highly vague. (23−25) For instance, a number of electrochemical and chemical Pt dissolution reactions have been proposed as possible Pt dissolution mechanisms, but their deconvolutions and even verifications of any reaction paths have yet to be clearly accomplished.

Figure 1

Figure 1. Pt degradation process. (a) Real-time Pt dissolution measured by an online EFC/ICP-MS during a cyclic voltammetry (CV), with a scan rate of 5 mV s–1 in a potential range of 0.05–1.5 VRHE in Ar-saturated 0.1 M HClO4 electrolyte. (b) Electrode potentials and potential perturbation durations observed during or used for describing the SU/SD and fuel starvation events in the literature. (26−33) For better identification, each event accelerating the PEMFC degradation is grouped and indicated with a shaded area. Previous Pt dissolution studies using the EFC/ICP-MS cover most conditions of the SU/SD and fuel starvation events, but unexplored conditions still remain, where the ringing effect possibly occurs when the electrical circuit is connected or applied potential is changed. (32,33)

Herein, we demonstrate that chemical corrosion occurs on electrochemically induced unstable Pt surfaces. This conclusion is supported by our Pt dissolution study using EFC/ICP-MS under multiple potential pulses with different pulse widths (t). In particular, an electrically disconnected condition immediately after the potential pulses allows the distinction of chemical dissolution from the complex convolution of unknown dissolution pathways during the transient process. By taking advantage of the open circuit potential (OCP), the formation of metastable Pt and its spontaneous dissolution can be identified as the origin of the chemical Pt dissolution process. We further confirm that chemical Pt dissolution, which has not been seriously considered as one of Pt dissolution pathways because this event occurs in electrochemical environments, is transposable to more practically relevant conditions. Combined with the knowledge of the electric double layer (EDL), we discuss a proof-of-concept strategy for alleviating chemical Pt dissolution during rapid potential disturbance.

Results and Discussion

ARTICLE SECTIONS
Jump To

Platinum dissolution on a polycrystalline Pt electrode was investigated in Ar-saturated 0.1 M HClO4 using online EFC/ICP-MS (Figure S2), during eight consecutive potential pulses. The potential pulses were set to 1.5 VRHE, and their t was varied from 0.2 ms to 1000 s. After the anodic polarization at 1.5 VRHE, the electrode potential dropped to 0.05 VRHE and held there for 7 min to stabilize the ICP-MS signals. This series of potential excursions is referred to as Protocol 1 (P1), and each pulse of the protocol is denoted as Pt1, depending on its t. It is worth noting that this protocol covers most of the potential perturbation durations of the detrimental processes of PEMFC operations, such as fuel starvation and SU/SD events during real PEMFC operations (Figure 1b). (26−33)
In Protocol 1, no distinct Pt dissolution is found at P0.2ms1 (Figure 2a). However, a trace amount of Pt (0.42 pg cm–2 s–1) starts to dissolve at P1ms1, and dissolution becomes intensified from 2.6 to 7.1 pg cm–2 s–1 as the t increased from 10 ms to 1000 s. This observation indicates that Pt dissolution can be initiated at a very short potential perturbation (i.e., 1 ms), which has not been rigorously addressed so far. For longer t of P100s1 and P1000s1, clear anodic and cathodic Pt dissolutions are distinguishable at a potential jump to 1.5 VRHE and a sequential potential drop to 0.05 VRHE, respectively. The cathodic dissolution is more pronounced than anodic dissolution, and negligible Pt dissolution is shown during the potential hold at 1.5 VRHE for P1000s1. This result is consistent with previous reports, verifying that Pt dissolution is a transient process. (14,16) However, the anodic and cathodic Pt dissolutions are hardly distinguishable at t below 10 s, probably due to the insufficient resolution of our EFC/ICP-MS system at a such short t, i.e., signal tailing.

Figure 2

Figure 2. Stability evaluation of the polycrystalline Pt during pulsed potential disturbances. Real-time Pt dissolution measured by an online EFC/ICP-MS during (a) Protocol 1 and (b) Protocol 2 in Ar-saturated 0.1 M HClO4 electrolyte. The pulse width, t, increases from 0.2 ms to 1000 s, and the lowest t, where the Pt dissolution is discernible, is highlighted with a hollow circle. (c) Dissolved Pt amount at each potential pulse. (d) OCP profiles just after potential pulses of the Protocol 2. Their inflection points are marked with hollow circles. As references, OCP values of PtO2 and metallic Pt with and without HUPD are also shown by dashed lines.

To investigate the Pt dissolution behavior more clearly, we performed an experiment analogous to Protocol 1, referred to as Protocol 2 (P2). In Protocol 2, after the potential jump and hold at 1.5 VRHE for t, the electrode potential was released to an OCP for 5 min, followed by a potential hold at 0.05 VRHE for 7 min. This additional OCP step was employed to deconvolute the contribution of anodic and cathodic dissolutions and further provided an opportunity to observe possible chemical dissolution processes. It is of note that a potential jump followed by the OCP is a practically feasible event for PEMFCs during SU/SD operations. (27−30)
Interestingly, during Protocol 2, the Pt dissolution rate for each potential pulse increases by approximately 1 order of magnitude at t below 10 s compared to that during Protocol 1 (Figure 2b, c). Pt redeposition and cathodic dissolution hardly govern the enhanced Pt dissolution rate because the dissolution increment in Protocol 2 occurs prior to the potential drop (from OCP to 0.05 VRHE). In addition, since Pt electrode experienced an identical potential excursion at the initial stage of all the potential pulses, i.e., the potential jump from 0.05 to 1.5 VRHE (the potential rising time is shorter than 2 μs, much shorter than t for P0.2ms2), increased anodic dissolution can also be ruled out as the cause of enhanced Pt dissolution during Protocol 2. For instance, for P100s2 and P1000s2, the anodic dissolution rates are almost identical, i.e., 2.2 ± 0.2 pg cm–2 s–1, the values of which are also comparable with those for P100s2 and P1000s1 of Protocol 1 (Figure S3). Surprisingly, the amount of such anodic dissolutions is quantitatively much lower than the Pt dissolution at short durations of potential pulses in Protocol 2, i.e., Pt2 for t = 10 ms–10 s. This cannot be adequately explained by electrochemical Pt dissolution alone, because the charge passed at P100s2 and P1000s2 (and also P100s1 and P1000s1) is much larger than that at Pt2 for t = 10 ms–10 s. Nevertheless, nonelectrochemically driven chemical Pt dissolution is clearly identified during the OCP step after the potential hold at 1.5 VRHE. Especially, a non-negligible amount of Pt (∼1.7 ng cm–2) was dissolved during the OCP step for P100s2. This Pt dissolution signal is not an artifact induced by the signal tailing of anodic Pt dissolution because anodic dissolution is undoubtedly distinguishable from a subsequent plateau, and is much lower even than that of chemical dissolution (max. ∼7 pg cm–2 s–1). For P1000s2, although it is relatively insignificant, the chemical Pt dissolution during OCP step is also discernible (∼0.4 pg cm–2 s–1), before which Pt dissolution signal converges to almost zero value (baseline) during a 1000 s potential hold at 1.5 VRHE. These findings allow us to conclude that chemical Pt dissolution indeed exists during the electrochemically driven transient process of Pt. Therefore, we can reasonably deduce that the origin of the unexpected larger Pt dissolution in Protocol 2 than in Protocol 1 at a relatively low t is attributed to chemical Pt dissolution. An identical conclusion was made from control experiments with an O2-saturated 0.1 M HClO4, which is a more realistic condition for the PEMFC cathode than the Ar-saturated one (Figures S4 and S5), and with an opposite order of potential pulses from 1000 s to 0.2 ms (Figure S6).
The OCP profiles during Protocol 2 further reveal that the slow kinetics of the stable Pt oxide formation results in different amounts of chemical Pt dissolution depending on t. In the literature, partially oxidized Pt species, e.g., PtOxHy, have been proposed as the main cause of chemical Pt dissolution (see the Supplementary Note for a detailed discussion). (34−36) Unfortunately, the exact chemical nature of metastable Pt species is not clearly understood (and even defined) owing to their unstable and short-lived characteristics, which are hardly measurable using typical ex situ analyses. Alternatively, the formation of metastable species on Pt can be electrochemically deduced from OCP profiles because it reflects the equilibrium potential between the electrode and the electrolyte and is very sensitive to the chemical nature of the electrode surface. (37)
Figure 2d shows considerable OCP changes of the Pt electrode for 300 s after its potential hold at 1.5 VRHE for different t. It is of note that, to avoid any interferences from redox-active O2 and H2 molecules, in this measurement the electrochemical cell and electrolyte were continuously purged with Ar, and the counter electrode was physically separated from the Pt working electrode using a Nafion membrane (Figure S2). This result is in contrast to the case of the potential perturbation-free metallic Pt and fully oxidized PtO2, which show OCP values of 0.12–0.58 VRHE (depending on the absence and presence of hydrogen underpotential deposition, HUPD) and ∼1.1 VRHE, respectively (Figure S7). For P1000s2, at which insignificant chemical Pt dissolution is observed (Figure S3), its OCP value is stabilized at ∼1.1 VRHE, indicating formation of a stable outer PtO2. On the other hand, for Pt2(t = 10 ms–10 s), the OCPs are quickly stabilized and reached a potential range of 0.7–0.9 VRHE within a few tens of seconds. Since these quasi-stabilized OCP values are located between those of metallic Pt and PtO2, the result implies the formation of partially oxidized Pt on the surface (i.e., PtOxHy) after the potential hold at 1.5 VRHE for 10 ms–10 s. Afterward, their OCP values converge to ∼0.3 VRHE, which is positioned between OCP values of HUPD and its free Pt surfaces. In addition, as t increases, the quasi-stabilized OCP values are anodically shifted, and their windows (defined here as the time at the inflection point of the OCP curves) become elongated. Hence, the results reveal that the inner metallic Pt is gradually exposed to the electrolyte through the continuous chemical dissolution of the outer PtOxHy species, the amount of which is magnified as the potential perturbation time, t, increases. We note that the chemical Pt dissolution is a dominant process under open circuit conditions since the OCP profile does not originate from the self-discharge of the polarized Pt via the Faradaic reactions (Figure S8). (38−40) Nevertheless, for Pt2(t < 10 ms), their OCP values quickly rebounded to ∼0.1 VRHE, probably due to insufficient time duration for desorbing all the HUPD generated during chronoamperometry (CA) at 0.05 VRHE prior to the potential perturbation.
To summarize our findings, the OCP step after the short duration of potential pulses enables the deconvolution of chemical Pt dissolution from the unclear and complex Pt dissolution process during electrochemical Pt transitions (Figure 3a), and the duration of the potential perturbation, t, is identified as a key parameter governing the extent of chemical Pt dissolution. For t less than 100 s, the chemical Pt dissolution is intensified as the t becomes longer owing to the increased formation of metastable PtOxHy. However, for t longer than 100 s, PtOxHy further transforms to stable Pt oxides, leading to a considerable suppression of chemical Pt dissolution. This turning point, predicted here by the decline of the chemical Pt dissolution, is well matched with previous results reported by Imai et al., who showed a partially oxidized Pt is fully converted to PtO2 after 100 s polarization at 1.4 VRHE through in situ X-ray absorption spectroscopy (XAS). (36)

Figure 3

Figure 3. Verification of the broad applicability of the chemical Pt dissolution in more realistic conditions. (a) Summary of this work identifying chemical Pt dissolution from unclear and complex Pt dissolution processes. Real-time Pt dissolution of Pt black, Pt/C, PtCo/C, and PtNi/C measured by an online EFC/ICP-MS during (b) Protocol 1 and (c) Protocol 2 (see Figures S9–12 for the data of all t of 0.2 ms–1000 s). (d) Real-time Pt dissolution of Pt black during 1000 potential pulses (t = 10 ms, E = 1–1.5 VRHE). For clear comparisons, a part of online EFC/ICP-MS signals was collected and shown at each potential. (e) Accumulated amounts of Pt dissolved during the 1000 potential pulses with and without the OCP steps.

We then studied the chemical Pt dissolution process under various electrochemical conditions to understand whether this event is only limited to the polycrystalline Pt electrode at the potential pulse of 1.5 VRHE. Pt dissolution rates were measured with Pt black nanoparticles during Protocols 1 and 2 (Figure 3b, c and Figure S9). Similar to the polycrystalline Pt, the results show much magnified Pt dissolution at t = 0.2 ms–10 s in Protocol 2 (rather than that in Protocol 1) and discernible Pt dissolution during OCP steps. For PEMFC-relevant catalysts (i.e., Pt/C, PtCo/C, and PtNi/C), such Pt dissolution behaviors were also found in Protocol 2 (Figure 3b, c and Figures S10–12), inferring that the chemical Pt dissolution also occurs for the conventional Pt-based catalysts as well as the polycrystalline Pt.
Online EFC/ICP-MS study of Pt black nanoparticles, analyzed during repeated 1000 potential pulses with t = 10 ms, further reveals that the chemical Pt dissolution could occur at much moderated potential pulses of 1–1.4 VRHE. With an OCP step immediately after each potential pulse (analogous to Protocol 2), considerably magnified Pt dissolution rates were recorded at all potential pulses of 1–1.5 VRHE compared to those without the OCP step (analogous to Protocol 1; Figure 3d, e). However, the dissolution rate is lowered as the potential decreases (Figures S13 and 14). These control experiments with various materials and potential conditions indicate that the chemical Pt dissolution would be a ubiquitous event, possibly occurring at a potential higher than 1 VRHE for conventional Pt-based catalysts.
The time constant (τ) is a key physical parameter describing the electrode–electrolyte interface properties, which basically represents the characteristic time required to charge a capacitor (Cdl) connected to a resistor (R) in series. (41) Once the potential changes, the non-Faradaic current first dominates the overall current flow for charging EDL, and afterward by the Faradaic process (Figure S15). We surmised that this well-known phenomenon might offer an opportunity to prevent undesirable chemical Pt dissolution by delaying the formation of metastable Pt species, if EDL charging process becomes a major event during potential perturbations with short durations. To confirm this hypothesis, we prepared a Pt black electrode, and its τ was sequentially tuned by mixing it with different amounts of the activated carbon (AC). The Pt black electrodes with low and high amounts of AC were denoted as “Pt black + AC-L” (mass ratio = 4:6) and “Pt black + AC-H” (1:9), respectively. It is of note that increasing R can also increase τ but this is not beneficial for efficient PEMFC operations.
Their CV profiles show an almost identical HUPD response with a similar electrochemical surface area (ECSA) value of 12.5 ± 1 m2 gPt–1 (Figure 4a), implying no chemical modifications of the Pt black after the physical mixing with AC. Nevertheless, a clear increase in the double layer capacitance is found in the presence of AC on the electrode. The estimated τ values for Pt black, Pt black + AC-L, and Pt black + AC-H are 0.2, 0.9, and 3 ms, respectively (Figure 4b), suggesting that their Faradaic processes can be postponed to the millisecond timescale. The effect of τ on the chemical Pt dissolution was then investigated during Protocol 2 (Figure 4c and Figure S16). AC-free Pt black reveals discernible Pt dissolution at P0.2ms2. However, this signal disappears for Pt black + AC-L, and more interestingly, Pt black + AC-H confirms negligible Pt dissolution even at P1ms2. The suppressed chemical Pt dissolution is not an artifact induced either by a decrease in the active Pt surface area, or by the increased diffusion path for Pt ions after the introduction of AC, as confirmed by the almost untouched HUPD values and Pt dissolution rates at each potential pulse with t longer than 10 ms (much longer than τ) for all samples (Figure 4a, d). Therefore, we identify a preceded non-Faradaic charging to be a critical process governing the extent of followed metastable Pt formation and consequent its dissolution.

Figure 4

Figure 4. Proof-of-concept strategy for mitigating the chemical Pt dissolution. (a) CVs and (b) calculated τ of the Pt black electrodes with different AC amounts in Ar-saturated 0.1 M HClO4 electrolyte. (c) Real-time Pt dissolution signals of the Pt black electrodes monitored by online EFC/ICP-MS during Protocol 2 (see Figure S16 for the data at t > 10 ms). The lowest t where the Pt dissolution is discernible is highlighted with a hollow circle. (d) Dissolved Pt amount at each potential pulse for the Pt black electrodes.

Outlook and Conclusions

ARTICLE SECTIONS
Jump To

We demonstrated the presence of chemical Pt dissolution process during its electrochemical excursion, which can become dominant under certain conditions that accompany a short duration of potential perturbations. The OCP profiles identified relatively slow Pt oxidation kinetics, which led to the formation of metastable Pt species, an origin of chemical Pt dissolution, at such a rapid potential perturbation. Along with the above understanding, our additional studies further unveiled the markedly accelerated chemical Pt dissolution even at t of 1000 s in the presence of methanol in acidic medium (Figure S17), and that chemical Pt dissolution can also be arisen in alkaline conditions (Figure S18). These findings highlight that chemical Pt dissolution does not occur in a limited manner under PEMFC conditions, but is likely to be a ubiquitous path of Pt degradation in various electrochemical devices, implying the need for further investigation under various experimental conditions reflecting a wide range of electrochemical energy conversion systems for durable electrocatalysis.
In addition, although we exemplified that mitigation of the chemical Pt dissolution is achievable by introducing AC to tune the EDL parameter τ, this strategy is not suitable for immediate implementation in PEMFCs. This limitation primarily originates from thickened catalyst layer, which strongly affects both the performance and durability of PEMFCs. As already well-understood by several previous experimental and theoretical reports, (3,4,42−44) the thickened catalyst layer not only governs Ohmic loss and mass transportation but also water flooding and even uniformity of potential distribution in PEMFCs. In addition, at relevant timescales of PEMFC operation, a practically nonfeasible amount of AC may be needed to prevent the chemical Pt dissolution (Figure S19). However, this proof-of-concept strategy will provide a fundamental principle for developing future rational strategies, for instance, tuning the internal or external PEMFC components (e.g., additional potential load) to buffer the unavoidable potential perturbations and to minimize the undesirable chemical Pt dissolution.

Supporting Information

ARTICLE SECTIONS
Jump To

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacsau.2c00474.

  • Experimental details; possible generation of the partially oxidized Pt species; CV result of Pt; schematic images of EFC connected to the ICP-MS; real-time Pt dissolution results of Pt black and Pt-based catalysts; OCP profiles of PtO2 and metallic Pt; modeling of Faradaic and non-Faradaic current responses of a simplified Randles circuit model (PDF)

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Author Information

ARTICLE SECTIONS
Jump To

  • Corresponding Authors
  • Authors
    • Junsic Cho - Department of Chemistry, Pohang University of Science and Technology (POSTECH), Pohang 37673, Republic of Korea
    • Hyung-Suk Oh - Clean Energy Research Center, Korea Institute of Science and Technology (KIST), Seoul 02792, Republic of KoreaOrcidhttps://orcid.org/0000-0002-0310-6666
  • Author Contributions

    CRediT: Junsic Cho formal analysis, investigation, methodology, writing-original draft, writing-review & editing; Haesol Kim conceptualization, formal analysis, investigation, project administration, writing-original draft, writing-review & editing; Hyung-Suk Oh methodology, resources; Chang Hyuck Choi conceptualization, project administration, resources, supervision, writing-original draft, writing-review & editing.

  • Notes
    The authors declare no competing financial interest.

Acknowledgments

ARTICLE SECTIONS
Jump To

This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT) (2019M3D1A1079309 and 2021R1A5A1030054) and by the KIST Institutional Program.

References

ARTICLE SECTIONS
Jump To

This article references 44 other publications.

  1. 1
    Eberle, U.; Müller, B.; von Helmolt, R. Fuel Cell Electric Vehicles and Hydrogen Infrastructure: Status 2012. Energy Environ. Sci. 2012, 5 (10), 87808798,  DOI: 10.1039/c2ee22596d
  2. 2
    Debe, M. K. Electrocatalyst Approaches and Challenges for Automotive Fuel Cells. Nature 2012, 486 (7401), 4351,  DOI: 10.1038/nature11115
  3. 3
    Fan, J.; Chen, M.; Zhao, Z.; Zhang, Z.; Ye, S.; Xu, S.; Wang, H.; Li, H. Bridging the Gap between Highly Active Oxygen Reduction Reaction Catalysts and Effective Catalyst Layers for Proton Exchange Membrane Fuel Cells. Nat. Energy 2021, 6 (5), 475486,  DOI: 10.1038/s41560-021-00824-7
  4. 4
    Chong, L.; Wen, J.; Kubal, J.; Sen, F. G.; Zou, J.; Greeley, J.; Chan, M.; Barkholtz, H.; Ding, W.; Liu, D.-J. Ultralow-Loading Platinum-Cobalt Fuel Cell Catalysts Derived from Imidazolate Frameworks. Science 2018, 362 (6420), 12761281,  DOI: 10.1126/science.aau0630
  5. 5
    Kodama, K.; Nagai, T.; Kuwaki, A.; Jinnouchi, R.; Morimoto, Y. Challenges in Applying Highly Active Pt-Based Nanostructured Catalysts for Oxygen Reduction Reactions to Fuel Cell Vehicles. Nat. Nanotechnol. 2021, 16 (2), 140147,  DOI: 10.1038/s41565-020-00824-w
  6. 6
    Chattot, R.; Le Bacq, O.; Beermann, V.; Kühl, S.; Herranz, J.; Henning, S.; Kühn, L.; Asset, T.; Guétaz, L.; Renou, G.; Drnec, J.; Bordet, P.; Pasturel, A.; Eychmüller, A.; Schmidt, T. J.; Strasser, P.; Dubau, L.; Maillard, F. Surface Distortion as a Unifying Concept and Descriptor in Oxygen Reduction Reaction Electrocatalysis. Nat. Mater. 2018, 17 (9), 827833,  DOI: 10.1038/s41563-018-0133-2
  7. 7
    Cui, C.; Gan, L.; Heggen, M.; Rudi, S.; Strasser, P. Compositional Segregation in Shaped Pt Alloy Nanoparticles and their Structural Behaviour during Electrocatalysis. Nat. Mater. 2013, 12 (8), 765771,  DOI: 10.1038/nmat3668
  8. 8
    Chen, C.; Kang, Y.; Huo, Z.; Zhu, Z.; Huang, W.; Xin, H. L.; Snyder, J. D.; Li, D.; Herron, J. A.; Mavrikakis, M.; Chi, M.; More, K. L.; Li, Y.; Markovic, N. M.; Somorjai, G. A.; Yang, P.; Stamenkovic, V. R. Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces. Science 2014, 343 (6177), 13391343,  DOI: 10.1126/science.1249061
  9. 9
    Huang, X.; Zhao, Z.; Cao, L.; Chen, Y.; Zhu, E.; Lin, Z.; Li, M.; Yan, A.; Zettl, A.; Wang, Y. M.; Duan, X.; Mueller, T.; Huang, Y. High-Performance Transition Metal–Doped Pt3Ni Octahedra for Oxygen Reduction Reaction. Science 2015, 348 (6240), 12301234,  DOI: 10.1126/science.aaa8765
  10. 10
    Jung, S.-M.; Yun, S.-W.; Kim, J.-H.; You, S.-H.; Park, J.; Lee, S.; Chang, S. H.; Chae, S. C.; Joo, S. H.; Jung, Y.; Lee, J.; Son, J.; Snyder, J.; Stamenkovic, V.; Markovic, N. M.; Kim, Y.-T. Selective Electrocatalysis Imparted by Metal–Insulator Transition for Durability Enhancement of Automotive Fuel Cells. Nat. Catal. 2020, 3 (8), 639648,  DOI: 10.1038/s41929-020-0475-4
  11. 11
    Kaspar, R. B.; Wittkopf, J. A.; Woodroof, M. D.; Armstrong, M. J.; Yan, Y. Reverse-Current Decay in Hydroxide Exchange Membrane Fuel Cells. J. Electrochem. Soc. 2016, 163 (5), F377F383,  DOI: 10.1149/2.041605jes
  12. 12
    Johnson, D. C.; Napp, D. T.; Bruckenstein, S. A Ring-Disk Electrode Study of the Current/Potential Behaviour of Platinum in 1.0 M Sulphuric and 0.1 M Perchloric Acids. Electrochim. Acta 1970, 15 (9), 14931509,  DOI: 10.1016/0013-4686(70)80070-6
  13. 13
    Ehelebe, K.; Knöppel, J.; Bierling, M.; Mayerhöfer, B.; Böhm, T.; Kulyk, N.; Thiele, S.; Mayrhofer, K. J. J.; Cherevko, S. Platinum Dissolution in Realistic Fuel Cell Catalyst Layers. Angew. Chem., Int. Ed. 2021, 60 (16), 88828888,  DOI: 10.1002/anie.202014711
  14. 14
    Topalov, A. A.; Katsounaros, I.; Auinger, M.; Cherevko, S.; Meier, J. C.; Klemm, S. O.; Mayrhofer, K. J. J. Dissolution of Platinum: Limits for the Deployment of Electrochemical Energy Conversion?. Angew. Chem., Int. Ed. 2012, 51 (50), 1261312615,  DOI: 10.1002/anie.201207256
  15. 15
    Sugawara, Y.; Okayasu, T.; Yadav, A. P.; Nishikata, A.; Tsuru, T. Dissolution Mechanism of Platinum in Sulfuric Acid Solution. J. Electrochem. Soc. 2012, 159 (11), F779F786,  DOI: 10.1149/2.017212jes
  16. 16
    Lopes, P. P.; Strmcnik, D.; Tripkovic, D.; Connell, J. G.; Stamenkovic, V.; Markovic, N. M. Relationships between Atomic Level Surface Structure and Stability/Activity of Platinum Surface Atoms in Aqueous Environments. ACS Catal. 2016, 6 (4), 25362544,  DOI: 10.1021/acscatal.5b02920
  17. 17
    Topalov, A. A.; Cherevko, S.; Zeradjanin, A. R.; Meier, J. C.; Katsounaros, I.; Mayrhofer, K. J. J. Towards a Comprehensive Understanding of Platinum Dissolution in Acidic Media. Chem. Sci. 2014, 5 (2), 631638,  DOI: 10.1039/C3SC52411F
  18. 18
    Topalov, A. A.; Zeradjanin, A. R.; Cherevko, S.; Mayrhofer, K. J. J. The Impact of Dissolved Reactive Gases on Platinum Dissolution in Acidic Media. Electrochem. Commun. 2014, 40, 4953,  DOI: 10.1016/j.elecom.2013.12.021
  19. 19
    Cherevko, S.; Zeradjanin, A. R.; Keeley, G. P.; Mayrhofer, K. J. J. A Comparative Study on Gold and Platinum Dissolution in Acidic and Alkaline Media. J. Electrochem. Soc. 2014, 161 (12), H822H830,  DOI: 10.1149/2.0881412jes
  20. 20
    Fuchs, T.; Drnec, J.; Calle-Vallejo, F.; Stubb, N.; Sandbeck, D. J. S.; Ruge, M.; Cherevko, S.; Harrington, D. A.; Magnussen, O. M. Structure Dependency of the Atomic-Scale Mechanisms of Platinum Electro-Oxidation and Dissolution. Nat. Catal. 2020, 3 (9), 754761,  DOI: 10.1038/s41929-020-0497-y
  21. 21
    Cherevko, S.; Topalov, A. A.; Zeradjanin, A. R.; Keeley, G. P.; Mayrhofer, K. J. J. Temperature-Dependent Dissolution of Polycrystalline Platinum in Sulfuric Acid Electrolyte. Electrocatalysis 2014, 5 (3), 235240,  DOI: 10.1007/s12678-014-0187-0
  22. 22
    Lopes, P. P.; Tripkovic, D.; Martins, P. F. B. D.; Strmcnik, D.; Ticianelli, E. A.; Stamenkovic, V. R.; Markovic, N. M. Dynamics of Electrochemical Pt Dissolution at Atomic and Molecular Levels. J. Electroanal. Chem. 2018, 819, 123129,  DOI: 10.1016/j.jelechem.2017.09.047
  23. 23
    Wang, Z.; Tada, E.; Nishikata, A. In-Situ Monitoring of Platinum Dissolution under Potential Cycling by a Channel Flow Double Electrode. J. Electrochem. Soc. 2014, 161 (4), F380F385,  DOI: 10.1149/2.012404jes
  24. 24
    Cherevko, S.; Kulyk, N.; Mayrhofer, K. J. J. Durability of Platinum-Based Fuel Cell Electrocatalysts: Dissolution of Bulk and Nanoscale Platinum. Nano Energy 2016, 29, 275298,  DOI: 10.1016/j.nanoen.2016.03.005
  25. 25
    Myers, D. J.; Wang, X.; Smith, M. C.; More, K. L. Potentiostatic and Potential Cycling Dissolution of Polycrystalline Platinum and Platinum Nano-Particle Fuel Cell Catalysts. J. Electrochem. Soc. 2018, 165 (6), F3178F3190,  DOI: 10.1149/2.0211806jes
  26. 26
    Liang, D.; Shen, Q.; Hou, M.; Shao, Z.; Yi, B. Study of the Cell Reversal Process of Large Area Proton Exchange Membrane Fuel Cells under Fuel Starvation. J. Power Sources 2009, 194 (2), 847853,  DOI: 10.1016/j.jpowsour.2009.06.059
  27. 27
    Bisello, A.; Colombo, E.; Baricci, A.; Rabissi, C.; Guetaz, L.; Gazdzicki, P.; Casalegno, A. Mitigated Start-Up of PEMFC in Real Automotive Conditions: Local Experimental Investigation and Development of a New Accelerated Stress Test Protocol. J. Electrochem. Soc. 2021, 168 (5), 054501,  DOI: 10.1149/1945-7111/abf77b
  28. 28
    Colombo, E.; Bisello, A.; Casalegno, A.; Baricci, A. Mitigating PEMFC Degradation during Start-Up: Locally Resolved Experimental Analysis and Transient Physical Modelling. J. Electrochem. Soc. 2021, 168 (5), 054508,  DOI: 10.1149/1945-7111/abf4eb
  29. 29
    Kim, J.; Lee, J.; Tak, Y. Relationship between Carbon Corrosion and Positive Electrode Potential in a Proton-Exchange Membrane Fuel Cell during Start/Stop Operation. J. Power Sources 2009, 192 (2), 674678,  DOI: 10.1016/j.jpowsour.2009.03.039
  30. 30
    Shen, Q.; Hou, M.; Liang, D.; Zhou, Z.; Li, X.; Shao, Z.; Yi, B. Study on the Processes of Start-Up and Shutdown in Proton Exchange Membrane Fuel Cells. J. Power Sources 2009, 189 (2), 11141119,  DOI: 10.1016/j.jpowsour.2008.12.075
  31. 31
    Taniguchi, A.; Akita, T.; Yasuda, K.; Miyazaki, Y. Analysis of Electrocatalyst Degradation in PEMFC Caused by Cell Reversal during Fuel Starvation. J. Power Sources 2004, 130 (1), 4249,  DOI: 10.1016/j.jpowsour.2003.12.035
  32. 32
    Cooper, K. R.; Smith, M. Electrical Test Methods for On-Line Fuel Cell Ohmic Resistance Measurement. J. Power Sources 2006, 160 (2), 10881095,  DOI: 10.1016/j.jpowsour.2006.02.086
  33. 33
    Huang, X.; Wang, X.; Nergaard, T.; Lai, J.-S.; Xu, X.; Zhu, L. Parasitic Ringing and Design Issues of Digitally Controlled High Power Interleaved Boost Converters. IEEE Trans. Power Electron. 2004, 19 (5), 13411352,  DOI: 10.1109/TPEL.2004.833434
  34. 34
    Cherevko, S.; Keeley, G. P.; Geiger, S.; Zeradjanin, A. R.; Hodnik, N.; Kulyk, N.; Mayrhofer, K. J. J. Dissolution of Platinum in the Operational Range of Fuel Cells. ChemElectroChem. 2015, 2 (10), 14711478,  DOI: 10.1002/celc.201500098
  35. 35
    Inzelt, G.; Berkes, B.; Kriston, Á. Temperature Dependence of Two Types of Dissolution of Platinum in Acid Media. An Electrochemical Nanogravimetric Study. Electrochim. Acta 2010, 55 (16), 47424749,  DOI: 10.1016/j.electacta.2010.03.074
  36. 36
    Imai, H.; Izumi, K.; Matsumoto, M.; Kubo, Y.; Kato, K.; Imai, Y. In Situ and Real-Time Monitoring of Oxide Growth in a Few Monolayers at Surfaces of Platinum Nanoparticles in Aqueous Media. J. Am. Chem. Soc. 2009, 131 (17), 62936300,  DOI: 10.1021/ja810036h
  37. 37
    Muller, A. W. J.; Maessen, F. J. M. J.; Davidson, C. L. The Corrosion Rates of Five Dental Ni-Cr-Mo Alloys Determined by Chemical Analysis of the Medium using ICP-AES, and by the Potentiostatic De-Aeration Method. Corros. Sci. 1990, 30 (6), 583601,  DOI: 10.1016/0010-938X(90)90025-Z
  38. 38
    Andreas, H. A. Self-Discharge in Electrochemical Capacitors: A Perspective Article. J. Electrochem. Soc. 2015, 162 (5), A5047A5053,  DOI: 10.1149/2.0081505jes
  39. 39
    Black, J.; Andreas, H. A. Effects of Charge Redistribution on Self-Discharge of Electrochemical Capacitors. Electrochim. Acta 2009, 54 (13), 35683574,  DOI: 10.1016/j.electacta.2009.01.019
  40. 40
    Harrington, D. A.; Conway, B. E. Kinetic Theory of the Open-Circuit Potential Decay Method for Evaluation of Behaviour of Adsorbed Intermediates: Analysis for the Case of the H2 Evolution Reaction. J. Electroanal. Chem. 1987, 221 (1), 121,  DOI: 10.1016/0022-0728(87)80242-5
  41. 41
    Bard, A. J.; Faulkner, R. L. Electrochemical Methods and Applications, 2nd ed.; Wiley: New York, 2001.
  42. 42
    Newman, J. S.; Tobias, C. W. Theoretical Analysis of Current Distribution in Porous Electrodes. J. Electrochem. Soc. 1962, 109 (12), 1183,  DOI: 10.1149/1.2425269
  43. 43
    Obut, S.; Alper, E. Numerical Assessment of Dependence of Polymer Electrolyte Membrane Fuel Cell Performance on Cathode Catalyst Layer Parameters. J. Power Sources 2011, 196 (4), 19201931,  DOI: 10.1016/j.jpowsour.2010.10.030
  44. 44
    Abedini, A.; Dabir, B.; Kalbasi, M. Experimental Verification for Simulation Study of Pt/CNT Nanostructured Cathode Catalyst Layer for PEM Fuel Cells. Int. J. Hydrog. Energy 2012, 37 (10), 84398450,  DOI: 10.1016/j.ijhydene.2012.02.093

Cited By

ARTICLE SECTIONS
Jump To

This article is cited by 1 publications.

  1. Koteswararao Vemula, Do Xuan Ha, Min Hwangbo, Tasmina Khandaker, Kyung Byung Yoon. Low-Overpotential Hydrogen Evolution Reaction Electrode Loaded with Very Small Amounts of PtPd Alloy Nanoparticles. ACS Applied Nano Materials 2023, 6 (22) , 20731-20745. https://doi.org/10.1021/acsanm.3c03044
  • Abstract

    Figure 1

    Figure 1. Pt degradation process. (a) Real-time Pt dissolution measured by an online EFC/ICP-MS during a cyclic voltammetry (CV), with a scan rate of 5 mV s–1 in a potential range of 0.05–1.5 VRHE in Ar-saturated 0.1 M HClO4 electrolyte. (b) Electrode potentials and potential perturbation durations observed during or used for describing the SU/SD and fuel starvation events in the literature. (26−33) For better identification, each event accelerating the PEMFC degradation is grouped and indicated with a shaded area. Previous Pt dissolution studies using the EFC/ICP-MS cover most conditions of the SU/SD and fuel starvation events, but unexplored conditions still remain, where the ringing effect possibly occurs when the electrical circuit is connected or applied potential is changed. (32,33)

    Figure 2

    Figure 2. Stability evaluation of the polycrystalline Pt during pulsed potential disturbances. Real-time Pt dissolution measured by an online EFC/ICP-MS during (a) Protocol 1 and (b) Protocol 2 in Ar-saturated 0.1 M HClO4 electrolyte. The pulse width, t, increases from 0.2 ms to 1000 s, and the lowest t, where the Pt dissolution is discernible, is highlighted with a hollow circle. (c) Dissolved Pt amount at each potential pulse. (d) OCP profiles just after potential pulses of the Protocol 2. Their inflection points are marked with hollow circles. As references, OCP values of PtO2 and metallic Pt with and without HUPD are also shown by dashed lines.

    Figure 3

    Figure 3. Verification of the broad applicability of the chemical Pt dissolution in more realistic conditions. (a) Summary of this work identifying chemical Pt dissolution from unclear and complex Pt dissolution processes. Real-time Pt dissolution of Pt black, Pt/C, PtCo/C, and PtNi/C measured by an online EFC/ICP-MS during (b) Protocol 1 and (c) Protocol 2 (see Figures S9–12 for the data of all t of 0.2 ms–1000 s). (d) Real-time Pt dissolution of Pt black during 1000 potential pulses (t = 10 ms, E = 1–1.5 VRHE). For clear comparisons, a part of online EFC/ICP-MS signals was collected and shown at each potential. (e) Accumulated amounts of Pt dissolved during the 1000 potential pulses with and without the OCP steps.

    Figure 4

    Figure 4. Proof-of-concept strategy for mitigating the chemical Pt dissolution. (a) CVs and (b) calculated τ of the Pt black electrodes with different AC amounts in Ar-saturated 0.1 M HClO4 electrolyte. (c) Real-time Pt dissolution signals of the Pt black electrodes monitored by online EFC/ICP-MS during Protocol 2 (see Figure S16 for the data at t > 10 ms). The lowest t where the Pt dissolution is discernible is highlighted with a hollow circle. (d) Dissolved Pt amount at each potential pulse for the Pt black electrodes.

  • References

    ARTICLE SECTIONS
    Jump To

    This article references 44 other publications.

    1. 1
      Eberle, U.; Müller, B.; von Helmolt, R. Fuel Cell Electric Vehicles and Hydrogen Infrastructure: Status 2012. Energy Environ. Sci. 2012, 5 (10), 87808798,  DOI: 10.1039/c2ee22596d
    2. 2
      Debe, M. K. Electrocatalyst Approaches and Challenges for Automotive Fuel Cells. Nature 2012, 486 (7401), 4351,  DOI: 10.1038/nature11115
    3. 3
      Fan, J.; Chen, M.; Zhao, Z.; Zhang, Z.; Ye, S.; Xu, S.; Wang, H.; Li, H. Bridging the Gap between Highly Active Oxygen Reduction Reaction Catalysts and Effective Catalyst Layers for Proton Exchange Membrane Fuel Cells. Nat. Energy 2021, 6 (5), 475486,  DOI: 10.1038/s41560-021-00824-7
    4. 4
      Chong, L.; Wen, J.; Kubal, J.; Sen, F. G.; Zou, J.; Greeley, J.; Chan, M.; Barkholtz, H.; Ding, W.; Liu, D.-J. Ultralow-Loading Platinum-Cobalt Fuel Cell Catalysts Derived from Imidazolate Frameworks. Science 2018, 362 (6420), 12761281,  DOI: 10.1126/science.aau0630
    5. 5
      Kodama, K.; Nagai, T.; Kuwaki, A.; Jinnouchi, R.; Morimoto, Y. Challenges in Applying Highly Active Pt-Based Nanostructured Catalysts for Oxygen Reduction Reactions to Fuel Cell Vehicles. Nat. Nanotechnol. 2021, 16 (2), 140147,  DOI: 10.1038/s41565-020-00824-w
    6. 6
      Chattot, R.; Le Bacq, O.; Beermann, V.; Kühl, S.; Herranz, J.; Henning, S.; Kühn, L.; Asset, T.; Guétaz, L.; Renou, G.; Drnec, J.; Bordet, P.; Pasturel, A.; Eychmüller, A.; Schmidt, T. J.; Strasser, P.; Dubau, L.; Maillard, F. Surface Distortion as a Unifying Concept and Descriptor in Oxygen Reduction Reaction Electrocatalysis. Nat. Mater. 2018, 17 (9), 827833,  DOI: 10.1038/s41563-018-0133-2
    7. 7
      Cui, C.; Gan, L.; Heggen, M.; Rudi, S.; Strasser, P. Compositional Segregation in Shaped Pt Alloy Nanoparticles and their Structural Behaviour during Electrocatalysis. Nat. Mater. 2013, 12 (8), 765771,  DOI: 10.1038/nmat3668
    8. 8
      Chen, C.; Kang, Y.; Huo, Z.; Zhu, Z.; Huang, W.; Xin, H. L.; Snyder, J. D.; Li, D.; Herron, J. A.; Mavrikakis, M.; Chi, M.; More, K. L.; Li, Y.; Markovic, N. M.; Somorjai, G. A.; Yang, P.; Stamenkovic, V. R. Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces. Science 2014, 343 (6177), 13391343,  DOI: 10.1126/science.1249061
    9. 9
      Huang, X.; Zhao, Z.; Cao, L.; Chen, Y.; Zhu, E.; Lin, Z.; Li, M.; Yan, A.; Zettl, A.; Wang, Y. M.; Duan, X.; Mueller, T.; Huang, Y. High-Performance Transition Metal–Doped Pt3Ni Octahedra for Oxygen Reduction Reaction. Science 2015, 348 (6240), 12301234,  DOI: 10.1126/science.aaa8765
    10. 10
      Jung, S.-M.; Yun, S.-W.; Kim, J.-H.; You, S.-H.; Park, J.; Lee, S.; Chang, S. H.; Chae, S. C.; Joo, S. H.; Jung, Y.; Lee, J.; Son, J.; Snyder, J.; Stamenkovic, V.; Markovic, N. M.; Kim, Y.-T. Selective Electrocatalysis Imparted by Metal–Insulator Transition for Durability Enhancement of Automotive Fuel Cells. Nat. Catal. 2020, 3 (8), 639648,  DOI: 10.1038/s41929-020-0475-4
    11. 11
      Kaspar, R. B.; Wittkopf, J. A.; Woodroof, M. D.; Armstrong, M. J.; Yan, Y. Reverse-Current Decay in Hydroxide Exchange Membrane Fuel Cells. J. Electrochem. Soc. 2016, 163 (5), F377F383,  DOI: 10.1149/2.041605jes
    12. 12
      Johnson, D. C.; Napp, D. T.; Bruckenstein, S. A Ring-Disk Electrode Study of the Current/Potential Behaviour of Platinum in 1.0 M Sulphuric and 0.1 M Perchloric Acids. Electrochim. Acta 1970, 15 (9), 14931509,  DOI: 10.1016/0013-4686(70)80070-6
    13. 13
      Ehelebe, K.; Knöppel, J.; Bierling, M.; Mayerhöfer, B.; Böhm, T.; Kulyk, N.; Thiele, S.; Mayrhofer, K. J. J.; Cherevko, S. Platinum Dissolution in Realistic Fuel Cell Catalyst Layers. Angew. Chem., Int. Ed. 2021, 60 (16), 88828888,  DOI: 10.1002/anie.202014711
    14. 14
      Topalov, A. A.; Katsounaros, I.; Auinger, M.; Cherevko, S.; Meier, J. C.; Klemm, S. O.; Mayrhofer, K. J. J. Dissolution of Platinum: Limits for the Deployment of Electrochemical Energy Conversion?. Angew. Chem., Int. Ed. 2012, 51 (50), 1261312615,  DOI: 10.1002/anie.201207256
    15. 15
      Sugawara, Y.; Okayasu, T.; Yadav, A. P.; Nishikata, A.; Tsuru, T. Dissolution Mechanism of Platinum in Sulfuric Acid Solution. J. Electrochem. Soc. 2012, 159 (11), F779F786,  DOI: 10.1149/2.017212jes
    16. 16
      Lopes, P. P.; Strmcnik, D.; Tripkovic, D.; Connell, J. G.; Stamenkovic, V.; Markovic, N. M. Relationships between Atomic Level Surface Structure and Stability/Activity of Platinum Surface Atoms in Aqueous Environments. ACS Catal. 2016, 6 (4), 25362544,  DOI: 10.1021/acscatal.5b02920
    17. 17
      Topalov, A. A.; Cherevko, S.; Zeradjanin, A. R.; Meier, J. C.; Katsounaros, I.; Mayrhofer, K. J. J. Towards a Comprehensive Understanding of Platinum Dissolution in Acidic Media. Chem. Sci. 2014, 5 (2), 631638,  DOI: 10.1039/C3SC52411F
    18. 18
      Topalov, A. A.; Zeradjanin, A. R.; Cherevko, S.; Mayrhofer, K. J. J. The Impact of Dissolved Reactive Gases on Platinum Dissolution in Acidic Media. Electrochem. Commun. 2014, 40, 4953,  DOI: 10.1016/j.elecom.2013.12.021
    19. 19
      Cherevko, S.; Zeradjanin, A. R.; Keeley, G. P.; Mayrhofer, K. J. J. A Comparative Study on Gold and Platinum Dissolution in Acidic and Alkaline Media. J. Electrochem. Soc. 2014, 161 (12), H822H830,  DOI: 10.1149/2.0881412jes
    20. 20
      Fuchs, T.; Drnec, J.; Calle-Vallejo, F.; Stubb, N.; Sandbeck, D. J. S.; Ruge, M.; Cherevko, S.; Harrington, D. A.; Magnussen, O. M. Structure Dependency of the Atomic-Scale Mechanisms of Platinum Electro-Oxidation and Dissolution. Nat. Catal. 2020, 3 (9), 754761,  DOI: 10.1038/s41929-020-0497-y
    21. 21
      Cherevko, S.; Topalov, A. A.; Zeradjanin, A. R.; Keeley, G. P.; Mayrhofer, K. J. J. Temperature-Dependent Dissolution of Polycrystalline Platinum in Sulfuric Acid Electrolyte. Electrocatalysis 2014, 5 (3), 235240,  DOI: 10.1007/s12678-014-0187-0
    22. 22
      Lopes, P. P.; Tripkovic, D.; Martins, P. F. B. D.; Strmcnik, D.; Ticianelli, E. A.; Stamenkovic, V. R.; Markovic, N. M. Dynamics of Electrochemical Pt Dissolution at Atomic and Molecular Levels. J. Electroanal. Chem. 2018, 819, 123129,  DOI: 10.1016/j.jelechem.2017.09.047
    23. 23
      Wang, Z.; Tada, E.; Nishikata, A. In-Situ Monitoring of Platinum Dissolution under Potential Cycling by a Channel Flow Double Electrode. J. Electrochem. Soc. 2014, 161 (4), F380F385,  DOI: 10.1149/2.012404jes
    24. 24
      Cherevko, S.; Kulyk, N.; Mayrhofer, K. J. J. Durability of Platinum-Based Fuel Cell Electrocatalysts: Dissolution of Bulk and Nanoscale Platinum. Nano Energy 2016, 29, 275298,  DOI: 10.1016/j.nanoen.2016.03.005
    25. 25
      Myers, D. J.; Wang, X.; Smith, M. C.; More, K. L. Potentiostatic and Potential Cycling Dissolution of Polycrystalline Platinum and Platinum Nano-Particle Fuel Cell Catalysts. J. Electrochem. Soc. 2018, 165 (6), F3178F3190,  DOI: 10.1149/2.0211806jes
    26. 26
      Liang, D.; Shen, Q.; Hou, M.; Shao, Z.; Yi, B. Study of the Cell Reversal Process of Large Area Proton Exchange Membrane Fuel Cells under Fuel Starvation. J. Power Sources 2009, 194 (2), 847853,  DOI: 10.1016/j.jpowsour.2009.06.059
    27. 27
      Bisello, A.; Colombo, E.; Baricci, A.; Rabissi, C.; Guetaz, L.; Gazdzicki, P.; Casalegno, A. Mitigated Start-Up of PEMFC in Real Automotive Conditions: Local Experimental Investigation and Development of a New Accelerated Stress Test Protocol. J. Electrochem. Soc. 2021, 168 (5), 054501,  DOI: 10.1149/1945-7111/abf77b
    28. 28
      Colombo, E.; Bisello, A.; Casalegno, A.; Baricci, A. Mitigating PEMFC Degradation during Start-Up: Locally Resolved Experimental Analysis and Transient Physical Modelling. J. Electrochem. Soc. 2021, 168 (5), 054508,  DOI: 10.1149/1945-7111/abf4eb
    29. 29
      Kim, J.; Lee, J.; Tak, Y. Relationship between Carbon Corrosion and Positive Electrode Potential in a Proton-Exchange Membrane Fuel Cell during Start/Stop Operation. J. Power Sources 2009, 192 (2), 674678,  DOI: 10.1016/j.jpowsour.2009.03.039
    30. 30
      Shen, Q.; Hou, M.; Liang, D.; Zhou, Z.; Li, X.; Shao, Z.; Yi, B. Study on the Processes of Start-Up and Shutdown in Proton Exchange Membrane Fuel Cells. J. Power Sources 2009, 189 (2), 11141119,  DOI: 10.1016/j.jpowsour.2008.12.075
    31. 31
      Taniguchi, A.; Akita, T.; Yasuda, K.; Miyazaki, Y. Analysis of Electrocatalyst Degradation in PEMFC Caused by Cell Reversal during Fuel Starvation. J. Power Sources 2004, 130 (1), 4249,  DOI: 10.1016/j.jpowsour.2003.12.035
    32. 32
      Cooper, K. R.; Smith, M. Electrical Test Methods for On-Line Fuel Cell Ohmic Resistance Measurement. J. Power Sources 2006, 160 (2), 10881095,  DOI: 10.1016/j.jpowsour.2006.02.086
    33. 33
      Huang, X.; Wang, X.; Nergaard, T.; Lai, J.-S.; Xu, X.; Zhu, L. Parasitic Ringing and Design Issues of Digitally Controlled High Power Interleaved Boost Converters. IEEE Trans. Power Electron. 2004, 19 (5), 13411352,  DOI: 10.1109/TPEL.2004.833434
    34. 34
      Cherevko, S.; Keeley, G. P.; Geiger, S.; Zeradjanin, A. R.; Hodnik, N.; Kulyk, N.; Mayrhofer, K. J. J. Dissolution of Platinum in the Operational Range of Fuel Cells. ChemElectroChem. 2015, 2 (10), 14711478,  DOI: 10.1002/celc.201500098
    35. 35
      Inzelt, G.; Berkes, B.; Kriston, Á. Temperature Dependence of Two Types of Dissolution of Platinum in Acid Media. An Electrochemical Nanogravimetric Study. Electrochim. Acta 2010, 55 (16), 47424749,  DOI: 10.1016/j.electacta.2010.03.074
    36. 36
      Imai, H.; Izumi, K.; Matsumoto, M.; Kubo, Y.; Kato, K.; Imai, Y. In Situ and Real-Time Monitoring of Oxide Growth in a Few Monolayers at Surfaces of Platinum Nanoparticles in Aqueous Media. J. Am. Chem. Soc. 2009, 131 (17), 62936300,  DOI: 10.1021/ja810036h
    37. 37
      Muller, A. W. J.; Maessen, F. J. M. J.; Davidson, C. L. The Corrosion Rates of Five Dental Ni-Cr-Mo Alloys Determined by Chemical Analysis of the Medium using ICP-AES, and by the Potentiostatic De-Aeration Method. Corros. Sci. 1990, 30 (6), 583601,  DOI: 10.1016/0010-938X(90)90025-Z
    38. 38
      Andreas, H. A. Self-Discharge in Electrochemical Capacitors: A Perspective Article. J. Electrochem. Soc. 2015, 162 (5), A5047A5053,  DOI: 10.1149/2.0081505jes
    39. 39
      Black, J.; Andreas, H. A. Effects of Charge Redistribution on Self-Discharge of Electrochemical Capacitors. Electrochim. Acta 2009, 54 (13), 35683574,  DOI: 10.1016/j.electacta.2009.01.019
    40. 40
      Harrington, D. A.; Conway, B. E. Kinetic Theory of the Open-Circuit Potential Decay Method for Evaluation of Behaviour of Adsorbed Intermediates: Analysis for the Case of the H2 Evolution Reaction. J. Electroanal. Chem. 1987, 221 (1), 121,  DOI: 10.1016/0022-0728(87)80242-5
    41. 41
      Bard, A. J.; Faulkner, R. L. Electrochemical Methods and Applications, 2nd ed.; Wiley: New York, 2001.
    42. 42
      Newman, J. S.; Tobias, C. W. Theoretical Analysis of Current Distribution in Porous Electrodes. J. Electrochem. Soc. 1962, 109 (12), 1183,  DOI: 10.1149/1.2425269
    43. 43
      Obut, S.; Alper, E. Numerical Assessment of Dependence of Polymer Electrolyte Membrane Fuel Cell Performance on Cathode Catalyst Layer Parameters. J. Power Sources 2011, 196 (4), 19201931,  DOI: 10.1016/j.jpowsour.2010.10.030
    44. 44
      Abedini, A.; Dabir, B.; Kalbasi, M. Experimental Verification for Simulation Study of Pt/CNT Nanostructured Cathode Catalyst Layer for PEM Fuel Cells. Int. J. Hydrog. Energy 2012, 37 (10), 84398450,  DOI: 10.1016/j.ijhydene.2012.02.093
  • Supporting Information

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacsau.2c00474.

    • Experimental details; possible generation of the partially oxidized Pt species; CV result of Pt; schematic images of EFC connected to the ICP-MS; real-time Pt dissolution results of Pt black and Pt-based catalysts; OCP profiles of PtO2 and metallic Pt; modeling of Faradaic and non-Faradaic current responses of a simplified Randles circuit model (PDF)


    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect