bluuebunny/crossref_metadata_2025_split huggingface dataset:
Localized Surface Oxygen Ion Transport in Sto and YSZ Observed Via Quasi in Situ Scanning Probe Microscopy
Authors: Kang Hung-Sen , Garcia ThomasJae , Li Haoyu , Liu Ziqi , Lee Min Hwan 
Published: November 2022

Ionic transport in solid oxides lays the fundamentals of solid-state electrochemical energy and sensor devices. While ionic transport in polycrystalline oxides has been studied for decades, most studies are reliant upon macro-scale observations where direct revelation of localized transport behavior is not feasible. In this presentation, we report a direct quasi in situ observation of oxygen ion transport in SrTiO3 (STO) and Y2O3-stabilized ZrO2 (YSZ) by leveraging scanning probe microscopy variants.
First, a cluster of oxygen vacancies formed by an electrical bias at a tip-sample contact. Then, we exposed the sample to an elevated temperature to allow a facilitated ionic diffusion. The resultant lateral distribution of oxygen vacancies was obtained by Kelvin probe force microscopy (KPFM). Depth-wise distribution of oxygen vacancies were acquired by a combination of in situ etching with a diamond-coated probe and KPFM scans, which enabled an observation of ionic charge transport in a highly localized fashion in both lateral and depth-wise directions.
From 3D spatial charge imaging, the activation energies of surface ionic diffusion in the lateral direction (Esurf) and those of bulk diffusion in the depth-wise direction (Ebulk) were quantified; for YSZ, Esurf = 0.34 eV and Ebulk = 1.13 eV, and for STO, Esurf = 0.50 eV and Ebulk = 1.30 eV. It was also found that the surface ion diffusivity of YSZ (1.68 × 10-8 cm2/s) is more than 3 orders of magnitude higher than that of STO (4.86 × 10-12 cm2/s), and that bulk diffusivity of YSZ (1.70 × 10-11 cm2/s) is more than 7 orders of magnitude higher than that of STO (7.61 × 10-19 cm2/s). To the best of our knowledge, this is the first study where the ionic diffusivities along the surface and into the bulk are separately quantified by direct localized observations of 3D distribution of ionic species, as opposed to a bulk measurement from which diffusivities were indirectly deduced.
The authors acknowledge the support by National Science Foundation (DMR 1753383).
Development of SOEC Performance Model Based on Cell Performance
Authors: Mugikura Yoshihiro , Imabayashi Takumi , Asano Koichi 
Published: November 2022

Central Research Institute of electric Power Industry (CRCIEPI) has developed original SOFC performance evaluation method and applied to a wide variety of cells. Based on the SOFC performance evaluation method, a new SOEC performance evaluation method has been developed this time. By this evaluation method, the difference between the open circuit voltage and the cell voltage can be expressed by the internal resistance loss (measured value), the fuel electrode overvoltage, the oxygen electrode overvoltage, and the Nernst loss.
In this study, cell performance before and after the CO2 direct electrolysis test was compared by SOFC and SOEC evaluation methods and clarification of cell degradation factor by CO2 direct electrolysis.
(Invited) Hot Electron Generation and Photocatalysis with Plasmonic Nanocrystals and Metastructures
Authors: Govorov Alexander 
Published: November 2022

The generation of energetic (hot) electrons and the photoheating are intrinsic properties of any optically excited plasmonic nanocrystal [1,2]. In addition, high-energy hot electrons and phototemperature contribute to the kinetic processes observed in plasmonic photodetectors, colloidal nanocrystals, and metastructures [1,2]. In this talk, we will focus on the theory of hot electron generation and present related applications for plasmonic photochemistry and plasmonic photocatalysis [3,4,5,6].
[1] L. Chang, L. V. Besteiro, J. Sun, E. Y. Santiago, S. K. Gray, Z. Wang, A. O. Govorov, ACS Energy Lett., 4, 10, 2552-2568 (2019).
[2] L. V. Besteiro, P. Yu, Z. Wang, A. W. Holleitner, G. V. Hartland, A. O. Govorov, Nano Today, 27, 120-145 (2019).
[3] T. Liu, L.V. Besteiro, T. Liedl, M.A. Correa-Duarte, Z. Wang, A. Govorov, Nano Letters, 19, 1395–1407 (2019).
[4] L. Khosravi Khorashad, L. V. Besteiro, M. A. Correa-Duarte, S. Burger, Z. M. Wang, A.O. Govorov, J. Am. Chem. Soc., 142, 9, 4193–4205 (2020).
[5] O. Ávalos-Ovando, L.V. Besteiro, A. Movsesyan, G. Markovich, T. Liedl, K. Martens, Zh. Wang, M.A.Correa-Duarte, and A.O. Govorov, Nano Letters (2021); DOI: 10.1021/acs.nanolett.1c02479.
[6] A. Movsesyan, E. Y. Santiago, S. Burger, M. A. Correa-Duarte, L. V. Besteiro, Zh. Wang,andA.O.Govorov, Advanced Optical Materials (2022); https://doi.org/10.1002/adom.202102663.
(Invited) Transient Absorption and Compressive Sensing for Understanding Dynamics in Photocatalytic Nanoparticles and Energy Conversion Materials
Authors: Wiederrecht Gary P. 
Published: November 2022

Transient absorption (TA) is a well-known tool for understanding the dynamical response of materials following the absorption of a photon. TA allows the dynamics of photoinduced energy flow and energy conversion to be monitored, along with other competing dissipative processes. With current technologies, TA can provide dynamical information over the ultraviolet, visible, near-infrared, mid-infrared, and terahertz spectral ranges, which allows the study of a concomitant range of photoinduced processes of relevance to photocatalysis. However, since TA usually involves very small changes in absorption, the approach can be quite time consuming and, as a result, signal averaging for hours is not uncommon. In addition to time limitations, long signal averages are challenging for many materials, including photocatalytic systems, because many materials degrade under long periods of laser illumination. Longer experiments also place greater demands on the stability of lasers, usually leading to the need for environmental controls, which adds cost and complexity to TA spectroscopies. Thus, there are several important reasons to increase the speed of TA as long as accuracy and sensitivity can be maintained.
In this talk, I present recent efforts to dramatically decrease the time needed to perform TA through compressive sensing, whereby a smaller number of data points are randomly collected over the chosed dynamical range of the TA experiment.[1] The general principle works well when the transformation of the optical signal to another domain has a low density of TA features. Studies and applications to colloidal plasmonic nanoparticles, such as nanostructures made of refractory materials, and energy conversion materials are shown. I also present imaging efforts using femtosecond optical pulses in scattering environments where conventional imaging is difficult.[2] By utilizing enhanced second harmonic generation from high peak-power ultrashort pulses, combined with compressive sensing approaches, successful reconstruction of optical images can be undertaken.
Work performed at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, was supported by the U.S. DOE, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. This material is based on work supported by Laboratory Directed Research and Development (LDRD) funding from Argonne National Laboratory, provided by the Director, Office of Science, of the U.S. Department of Energy under Contract No. DE-AC02-06CH11357.

References

Adhikari, S., Cortes, C. L., Wen X., Panuganti, S., Gosztola, D. J., Schaller, R. D., Wiederrecht, G. P., Gray, S. K., “Accelerating ultrafast spectroscopy with compressive sensing,” Phys. Rev. Appl., Vol. 15, 024032, 2021.

Wen, X., Adhikari, S., Cortes, C. L., Gosztola, D. J., Gray, S. K., Wiederrecht, G. P., “Ghost imaging second harmonic generation microscopy,” Appl. Phys. Lett., Vol. 116, 191101, 2020.
(Invited) Water Splitting and Carbon Dioxide Conversion By Mixed-Anion Materials
Authors: Maeda Kazuhiko 
Published: November 2022

Mixed-anion materials that consist more than one anionic species in a single-phase have attracted attention for various applications. Oxynitrides containing d0- or d10-metal cations are typical example of visible-light-driven photocatalysts for water splitting and CO2conversion. In this presentation, recent progress on the development of mixed-anion materials for water splitting and CO2 conversion made by our group will be given.
While two-dimensional (2D) undoped layered oxynitrides are potential candidates as high performance visible-light photocatalysts, synthesis of 2D layered oxynitrides is generally difficult because most of them are metastable phases and are not chemically very stable. We found an exceptional example of a 2D layered oxynitride, K2LaTa2O6N (more specifically, K2LaTa2O6N·1.6H2O), which is a Ruddlesden-Popper phase two-layer perovskite analogous to Li2LaTa2O6N and has a band gap of 2.5 eV. This material undergoes in situH+/K+ exchange in aqueous solution while keeping its visible light absorption capability. The protonated, Ir-modified K2LaTa2O6N exhibited photocatalytic activity for H2 evolution from aqueous NaI solution under visible light, outperforming Pt/ZrO2/TaON and Pt/SrTiO3:Rh, which are one of the best-performing oxynitride and oxide photocatalysts for H2 evolution, respectively.
The use of mixed-anion materials is of interest not only for photocatalysts but also for catalysts promoting water oxidation and CO2reduction. For example, we found that certain oxyfluorides work as electrocatalysts for water oxidation. A 2D perovskite oxyfluoride Pb3Fe2O5F2 exhibits activity for electrochemical water oxidation to O2, which is 8 times more active than a 3D bulk PbFeO2F.
(Invited) Controlling Hydrogen Evolution and Oxygen Reduction Electrocatalysis By Tuning Interfacial Hydrogen Bonds
Authors: Zhang Yirui , Wang Tao , Huang Botao , Shao-Horn Yang 
Published: November 2022

Designing electrochemical water splitting and its reverse process is crucial for fuel cells to achieve high efficiency. Conventional design of catalysts has focused on tuning the surface electronic structures and binding strength of intermediates, while recent studies show that changing electrolyte compositions, such as cations and pH [1], can also significantly alter catalytic activity, highlighting new opportunities in tuning noncovalent interactions in the electrolytes to control activities.
In the first part of this talk, we use an interfacial layer of protic ionic liquids on platinum and gold to tune the oxygen-reduction reaction (ORR) kinetics, where altering the proton activity of ionic liquids increases the intrinsic ORR activity by up to five times [2]. The maximum enhancement of kinetics is achieved when the pKa of the ionic liquid is comparable to that of the reaction intermediate, which is attributed to the most strengthened hydrogen bonding between the ionic liquid and ORR products, as supported by surface-enhanced infrared absorption spectroscopy (SEIRAS). In the second part, we confine water in an organic matrix and tune the hydrogen-bonding networks as well as hydrogen evolution and oxidation reactions (HER/HOR) kinetics by changing the water concentration (1% - 50% molar ratio) and altering the physical properties (donor number) of organic solvents. Decreasing the water-to-organic ratio, the OH stretching frequency of water shifts to higher wavenumbers, indicating more isolated water, while the water reduction has more negative onset potentials. The shifts in onset potentials are solvent-dependent, highlighting the role of interfacial hydrogen bonds between solvents and water in controlling HER/HOR kinetics. SEIRAS measurements provide further support to the changes in interfacial hydrogen bonding during the reactions.
These findings open up immense opportunities for using noncovalent hydrogen bonding interactions at the electrified interface to control the kinetics of ORR, HER, and beyond. The understanding would also be impactful across other reactions crucial to improving decarbonizing efforts in energy storage, such as CO2 reduction and aqueous batteries.

References

[1] Huang, B., Rao, R.R., You, S., Hpone Myint, K., Song, Y., Wang, Y., Ding, W., Giordano, L., Zhang, Y., Wang, T. and Muy, S., 2021. Cation-and pH-Dependent Hydrogen Evolution and Oxidation Reaction Kinetics. JACS Au, 1(10), pp.1674-1687.
[2] Wang, T. ‡, Zhang, Y. ‡, Huang, B., Cai, B., Rao, R.R., Giordano, L., Sun, S.G. and Shao-Horn, Y., 2021. Enhancing oxygen reduction electrocatalysis by tuning interfacial hydrogen bonds. Nature Catalysis, 4(9), pp.753-762.
Effect of Substrate Microstructure and Hydrophobicity on Ag Gas Diffusion Electrodes for Electrochemical CO2 Reduction
Authors: Senocrate Alessandro , Bernasconi Francesco , Battaglia Corsin 
Published: November 2022

Electrochemical CO2 reduction (CO2RR) is a very promising way to convert detrimental CO2 emissions into sustainable fuels and chemicals, and move us closer to a circular economy.1 To compete with traditional fuel/chemical production routes, we need to develop electrocatalysts that are highly active, selectivity towards a desired product, and stable. Thanks to the use of gas diffusion electrodes (GDEs) that provide gaseous CO2 close to the catalyst, high activities can be achieved.2,3 However, product selectivity and stability must still be improved before practical application. An emerging strategy in this regard is to control the local environment surrounding a catalyst, i.e. the concentration of the various products and reagents therein.4 In this work, we achieve such control by varying the microstructure of substrates later used to fabricate GDEs by Ag deposition. By systematically studying the CO2RR performance, we observe a clear correlation between the pore size of the GDEs and their product selectivity, stability, and even resilience to Cu impurities.5 We rationalize it with the different effective hydrophobicity of the GDEs, which control the extent of electrolyte penetration within the electrode and depends on both substrate chemistry and pore size. We show that a higher effective hydrophobicity correlates with higher Faradaic efficiency towards carbon monoxide production (FECO up to 95 % at 100 mA/cm2) and longer stability (~100 % retention after a 1 hour electrolysis at 100 mA/cm2). These results show the importance of the substrate's microstructural properties in GDE for CO2RR, and highlight a new strategy to achieve control over selectivity and stability of these electrodes.
References:
(1) Senocrate, A.; Battaglia, C. J. Energy Storage
2021, 36, 102373.
(2) Verma, S.; Hamasaki, Y.; Kim, C.; Huang, W.; Lu, S.; Jhong, H. R. M.; Gewirth, A. A.; Fujigaya, T.; Nakashima, N.; Kenis, P. J. A. ACS Energy Lett.
2018, 3 (1), 193–198.
(3) García de Arquer, F. P.; Dinh, C.-T.; Ozden, A.; Wicks, J.; McCallum, C.; Kirmani, A. R.; Nam, D.-H.; Gabardo, C.; Seifitokaldani, A.; Wang, X.; Li, Y. C.; Li, F.; Edwards, J.; Richter, L. J.; Thorpe, S. J.; Sinton, D.; Sargent, E. H. Science (80-. ).
2020, 367 (6478), 661–666.
(4) Veenstra, F. L. P.; Ackerl, N.; Martín, A. J.; Pérez-Ramírez, J. Chem
2020, 1–16.
(5) Senocrate, A.; Bernasconi, F.; Battaglia, C. et al.
Submitted
2022.
(Invited) Understanding and Mitigating Chemo-Mechanical Degradation in Solid Oxide Cells
Authors: Lim Hyung-Tae 
Published: November 2022

Solid-state electrochemical cells may undergo significant chemical potential changes in the electrolyte region near the electrodes, depending on operating conditions. Lithium dendrite growth, which may eventually induce mechanical stresses and short circuit in all-solid-state batteries (SSBs) in the charging process, is one of the well-known examples representing chemo-mechanical failure in solid-state electrochemical cells [1, 2]. A similar phenomenon has been observed in solid oxide cells (SOCs) operated in electrolysis mode and also in fuel cell mode with a negative voltage [3, 4]. Contrary to lithium precipitation in SSBs, high partial pressure of oxygen is developed in SOCs, resulting in electrode/electrolyte delamination. In the present study, we investigated the mechanism of delamination growth in SOCs with respect to operating conditions, based on which we determined a critical factor correlated to mechanical failure. This study provides basic understanding and critical insights into the chemo-mechanical failure mechanism of SOCs with respect to operating conditions.

References

[1] S. Ohno, R. Koerver, G. Dewald, C. Rosenbach, P. Titscher, D. Steckermeier, A. Kwade, J. Janek, W.G. Zeier, Chem. Mater., 31 (8) (2019), pp. 2930-2940
[2] M. Otoyama, M. Suyama, C. Hotehama, H. Kowada, Y. Takeda, K. Ito, A. Sakuda, M. Tatsumisago, A. Hayashi, ACS Appl. Mater. Interfaces, 13 (4) (2021), pp. 5000-5007
[3] H.-T. Lim, A.V. Virkar, J. Power Sources, 185 (2008), pp. 790-800
[4] B.-K. Park, Q. Zhang, P.W. Voorhees, S.A. Barnett, Energy Environ. Sci., 12 (2019), pp. 3053-3062
A Highly Performing Electrode with in-Situ Exsolved Nanoparticles for Direct Electrolysis of CO2
Authors: Park Ka-Young , Lee Taehee , Wang Wanhua , Li Haixia , Chen Fanglin (Frank) 
Published: November 2022

Carbon dioxide (CO2) emissions have increased continuously and rapidly since the industrial revolution, contributing to the serious greenhouse effect and leading to global warming. To minimize this effect, more attentions have been devoted to convert CO2 into useful chemicals such as carbon monoxide (CO), methane, methanol and dimethyl ether through sustainable, renewable, and alternative energy sources while lowering the dependence on fossil fuels. Although various technologies for CO2 conversion have been employed, such as thermocatalytic, electrochemical, and photochemical reductions, the conversion of CO2 to valuable products is relatively difficult due to its remarkably stable C=O bonds. Among them, the electrochemical reaction has a better possibility than the others because the electrochemical reaction is controllable and can utilize alternative energy sources for CO2 conversion, potentially achieving a carbon-neutral energy cycle.
As an efficient energy storage method, several types of electrolysis cells have been studied to reduce CO2 electrochemically. Due to the advantages of high energy efficiency, good stability, and high faradaic efficiency, solid oxide electrolysis cells (SOECs) are more promising for practical applications in the future than the other electrolysis cells. One challenge is to develop high-performance CO2 conversion electrode, which should possess high catalytic activity, electronic and ionic conductivity, chemical stability in the CO2 atmosphere, and good resistivity against carbon deposition. Cermets (e.g., Ni-YSZ) have been utilized as a traditional CO2 conversion electrode for SOECs because Ni metal serves as not only the electrocatalyst but also the electronic conductor. However, the cermets have issues for CO2 electrolysis due to the oxidation of Ni metal and carbon coking when exposed to a pure or concentrated CO2 atmosphere. Therefore, mixed ionic-electronic conducting (MIEC) perovskites have been investigated as the potential cathode materials for CO2 electrolysis, which should have high enough electrical conductivity and chemical stability in the CO2 atmosphere.
Perovskites have been considered attractive catalytic materials in the fields of solid oxide fuel cells due to their acceptable electrical conductivity and coking resistance. However, these perovskites have shown relatively low catalytic activity compared to Ni-YSZ cermet. In this work, a novel perovskite has been developed by introducing active nanoparticles via an in situ exsolution process, which showed high performance for the conversion of CO2 to CO. Its electrical conductivity and chemical stability in operating conditions for CO2 electrolysis have been systematically evaluated.

Acknowledgements

Financial support from the U.S. Department of Energy (DE-EE0009427) is greatly appreciated.
Effects of Electronic and Ionic Conductivities of Layered Perovskites on Solid Oxide Electrolyser Performances
Authors: Jang Inyoung , Kelsall Geoff H 
Published: November 2022

The climate change crisis is causing an exponentially increase in demand for green hydrogen. When run in electrolysis mode, solid oxide electrochemical reactors (SOERs) are one of the systems that can generate green hydrogen with high efficiencies, due to their high operating temperatures. In SOERs, the rate-determining steps for the overall reaction come from oxygen reduction (ORR) in fuel cell mode and oxygen evolution (OER) in electrolyser mode. For the enhancement of catalytic activity for ORR/OER, recent studies have been focused on layer perovskite materials for positive electrodes to increase SOER performances. The distinctive arrangement of cations in their structures leads to higher oxygen vacancy concentrations, thereby promoting catalytic activity for ORR/OER.
We shall report OER kinetics of two layered perovskites: PrBaCo1.6Fe0.4O5+δ (PBCF) and NdBaCo1.6Fe0.4O5+δ (NBCF) which have been studied as materials exhibiting major differences in oxide ion and electronic conductivities. Electrolyser performances were determined of both water vapour (→2H2 + O2) and CO2 (→2CO + O2), on which the effects were investigated of those differences in ionic / electronic conductivities. For water vapour electrolysis at the thermoneutral potential difference of 1.285 V, the current density was 144 mA cm-2 at 700 ℃ for the cell with a PBCF positive electrode, which exhibited current densities 1.42 times higher than for the cell with a NBCF positive electrode, for reasons we shall explain.
Molecular (photo)Electrochemical Reduction of CO2 to C1 Products with 2, 4, 6 and 8 Electrons from Mechanistic Studies to Hybrid Systems and Devices
Authors: Robert Marc 
Published: November 2022

Reduction of carbon dioxide has as main objective the production of useful organic compounds and fuels - renewable fuels - in which solar energy would be stored. Molecular catalysts can be employed to reach this goal, either in photochemical or electrochemical (or combined) contexts. They may in particular provide excellent selectivity thanks to easy tuning of the electronic properties at the metal and of the ligand second and third coordination sphere. Recently it has been shown that such molecular catalysts may also be tuned for generating highly reduced products such as methanol and methane, leading to new exciting advancements.
Hybridization of these catalysts with conductive or semi-conductive materials may lead to enhance stability and new catalytic properties, as well as inclusion of molecular catalysts in devices for applications. This approach bridges between homogeneous and heterogeneous, and it raises new fundamental questions that may further lead to breakthrough in CO2 reduction chemistry.
Our recent results in these various areas will be discussed, using earth abundant metal (Fe, Co) porphyrins and phthalocyanines as well as related complexes as catalysts.
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E. Boutin, M. Wang, J. C. Lin, M. Mesnage, D. Mendoza, B. Lassalle-Kaiser, C. Hahn, T. F. Jaramillo, M. Robert, Angew. Chem. Int. Ed.
2019, 58, 16172-16176.

Z. Guo, C. Cometto, G. Chen, L. Chen, B. Ma, H. Fan, T. Groizard, W-L. Man,S-M. Yiu, K-C. Lau, T-C. Lau, M. Robert, Nat. Catal. 2019, 2, 801-808.

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