bluuebunny/crossref_metadata_2025_split huggingface dataset:
Biomimetic Supported Lipid Bilayer on Thylakoid Membrane-Based Photobioelectrochemical System for Stability Enhancement
Authors: Yun JaeHyoung , Kim Seon Il , Ryu Wonhyoung 
Published: July 2022

Light-induced charge separation in photosynthetic reaction centers has a very high quantum yield. Due to this high quantum yield, bioenergy harvesting using photosynthesis of plant has been studied extensively. In the studies using algal cells or chloroplasts, their lipid membranes interfere with electron extraction. Therefore, most of studies are underway by using extracted photosynthetic organelles such as photosystems (PS I, II) and thylakoid membranes (TMs). However, without lipid membrane, the stability of photosynthetic organelles cannot be maintained. This is because photosynthesis generates reactive oxygen species (ROS) and protons that cause the degradation of photosynthetic organelles along with the production of high-energy electrons. On the other hand, chloroplasts have the internal environment separated by the lipid membrane to maintain homeostasis, which controls the level of ROS and pH within the chloroplasts.
In this study, by mimicking chloroplast, we propose to form a biomimetic supported lipid bilayer (SLB) to maintain stability while constructing a TM-based photobioelectrochemical system. Alginate was used as a synthetic extracellular matrix (ECM), and SLB was formed with 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) through vesicle fusion. The swelling of the alginate prevents direct contact of TM-alginate composite film with the electrode and prevents separation of inside of the biomimetic protochloroplast from outside environment. To solve this problem, crosslink alginate with CaCl2 water solutions containing 20% ethanol to prevent warping of composite film and amino groups were created through silanization on ITO electrode to improve adhesion with film. Thereafter, SLB formation conditions were analyzed through confocal microscopy. With the formed DOPC SLB, it was verified by the dye release test whether the inside of protochloroplast was separated from the outside environment. Under the SLB-encapsulating environment, pH and ROS were controlled by ADP, ascorbate and glutathione. To confirm the improvement of the stability of TM, the long-term photocurrent was measured in the presence or absence of SLB and stability-maintaining materials. Moreover, SLB can act as a separator in electrochemical circuits due to its high electrical resistance. Electrical insulation property of SLB was confirmed using electrochemical impedance spectroscopy (EIS).

References

[1] Kosumi, Daisuke, et al. Journal of Photochemistry and Photobiology A: Chemistry
358 (2018): 374-378.
[2] Pankratov, Dmitry, Galina Pankratova, and Lo Gorton. Current Opinion in Electrochemistry
19 (2020): 49-54.
[3] Kluzek, Monika, et al. Soft matter
14.28 (2018): 5800-5810.
[4] Blokhina, Olga, Eija Virolainen, and Kurt V. Fagerstedt. Annals of botany
91.2 (2003): 179-194.
[5] Vockenroth, Inga K., et al. Biointerphases
3.2 (2008): FA68-FA73.
Autonomous Image Analysis to Accelerate the Discovery and Integration of Energy Materials
Authors: Eslamibidgoli Mohammad J. , Malek Kourosh , Eikerling Michael 
Published: July 2022

Accelerating the development of electrochemical energy devices (e.g., batteries, fuel cells, electrolysis cells) is pivotal for the transition towards a green and sustainable energy economy. A significant proportion of development efforts in this realm is relying on new functional materials as electrocatalytically active media, ionic media, porous transport media, or multi-functional electrodes. Experimental materials research harnesses a broad spectrum of imaging and visualization methods, based on modern spectroscopy, microscopy, and scattering techniques. These techniques are utilized to quantify structural characteristics of materials and to detect and monitor structural changes during fabrication and normal operating cycles of the device. The extreme diversity and the complexity of materials leave the applications of conventional methods for image processing often empirical and indiscriminate. Recently, deep learning (DL) models based on deep convolutional neural networks (ConvNets) have been transforming the field of computer vision by outperforming the classical algorithms in various problems such as image recognition, reconstruction, synthesis, style transfer, and other tasks. To leverage the advancements in DL-based approaches in materials research, ConvNet models are employed for various analysis tasks like segmentation, object detection, denoising, or super-resolution microscopy. Here, we will present DL-based methodical pipelines to automate the particle size distribution analysis of Pt nanoparticles in catalyst layers [1] and for high-throughput screening of catalyst layer inks [2] in polymer electrolyte fuel cells.

References:
[1] Colliard-Granero, André, Mariah Batool, Jasna Jankovic, Jenia Jitsev, Michael Eikerling, Kourosh Malek, and Mohammad Javad Eslamibidgoli. "Deep learning for the automation of particle analysis in catalyst layers for polymer electrolyte fuel cells." Nanoscale (2021) DOI: 10.1039/d1nr06435e
[2] Eslamibidgoli, Mohammad J., Fabian P. Tipp, Jenia Jitsev, Jasna Jankovic, Michael H. Eikerling, and Kourosh Malek. "Convolutional neural networks for high throughput screening of catalyst layer inks for polymer electrolyte fuel cells." RSC Advances 11, no. 51 (2021): 32126-32134.
Microstructural Engineering of Li7La3Zr2O12 Solid Electrolytes for Enhanced Stability in H2O/CO2
Authors: Lee Jong-Won , Lee Jong-Won 
Published: July 2022

Solid-state batteries with nonflammable inorganic solid electrolytes provide a fundamental solution for resolving safety concerns. Moreover, mechanically robust solid electrolytes can physically block the penetration of Li dendrites, and thus, Li metal can be applied as an anode (negative electrode), boosting the energy density of the batteries. Garnet-type cubic Li7La3Zr2O12 (LLZO) has been considered as a promising candidate for solid electrolytes, due to its high Li+ conductivity and chemical/electrochemical compatibility with Li metal. When exposed to the ambient air, however, LLZO electrolytes are known to react with H2O and CO2 to form Li2CO3. Li2CO3 also grows along the grain boundaries, resulting in the significant degradation in Li+-conducting properties.
In an effort to develop LLZO electrolytes with enhanced interfacial stability, here, we investigate the composition–microstructure–stability relationship of LLZO modified with aliovalent elements (Ta and Ga) under controlled H2O and CO2 atmospheres. Dense LLZO electrolytes doped with Ta (LLZTO) and Ta/Ga (Ga-LLZTO) are synthesized via a sol-gel process, followed by high-temperature sintering (1100 °C). Microstructural analyses show that the elemental doping has a crucial role in the grain growth behavior during the sintering process, thereby modifying the density, morphology, and atomic structure of grain boundaries. The interfacial stability of doped LLZO electrolytes is examined under accelerated durability test (ADT) conditions, where the concentration of O2/H2O/CO2 is precisely controlled to promote the interfacial reaction. During the ADTs, the degradation kinetics of Li+-conducting properties is quantitatively determined using in situ AC-impedance measurements combined with ex situ surface characterizations. The Li+ conductivity of Ga-LLZTO is almost retained during the ADT, while LLZTO shows only 27% of its initial conductivity value after 24 h of ADT. The significant degradation of LLZTO is caused by the formation of Li2CO3, which is further verified by Raman mapping and X-ray photoelectron spectroscopy analysis. On the other hand, the compositional and structural characterizations suggest that the enhanced interfacial stability of Ga-LLZTO is attributed to the reduced grain boundary density with enlarged grains and the segregation of H2O/CO2-tolerant Li–Ga–O species in the grain boundaries. The findings of this study would be essential in understanding the degradation of Li+-conducting properties and in developing highly conductive and stable LLZO solid electrolytes.
References
[1] H.-S. Shin, W. Jeong, M.-H. Ryu, S. W. Lee, K.-N. Jung J.-W. Lee, Chem. Eng. J, published online.
[2] X. Huang, J. M. Su, Z. Song, T. P. Xiu, J. Jin, M. E. Badding, Z. Wen, Ceram. Int., 47(2) (2021) 2123-2130.
Ta-LLZO Garnet Processed By Spark Plasma Sintering for All Solid State Batteries
Authors: Charrad Ghassen , Taberna Pierre-Louis , Simon Patrice , Rozier Patrick 
Published: July 2022

All Solid State Lithium based Batteries (ASSLB) using a stable inorganic solid state electrolyte are envisaged as the most promising answer to solve the safety issues of Li-ion batteries using inflammable organic liquid electrolyte. Garnet Li7La3Zr2O7 showing high ionic conductivity and high stability versus metallic lithium is currently the most appealing solid electrolyte to be used in oxide based ASSLB. However, its high reactivity with moisture and sensitivity to all energetic process lead to strong difficulties in obtaining stable fully dense pellets while mandatory to ensure its role as mechanical barrier to avoid the short-circuit caused by Li-dendrites [1-2]. In this work, Spark Plasma Sintering is used as both a characterization and a fast sintering techniques to determine the influence of side products and efficiency of applied processes to remove them in reaching dense pellets with high ionic conductivity.
Commercial Ta-doped LLZO powder is fully characterized using conventional techniques to identify chemical and thermal stability. SPS experiments are conducted to determine the influence of the side products on the sintering. The efficiency of powder pretreatment designed to remove side products is determined based on data collected during SPS experiments. SPS parameters (applied pressure, temperature ramping, densification dwell ...) are then optimized allowing reaching in a reproducible way pellets with high density (>97 %) and high mechanical strength. Analysis using XPS, SEM and XRD of obtained pellets shows that decomposition occurs only at the surface while the core of the pellet is made of pure cubic phase Ta-doped LLZO. Impedance spectroscopy is used to evidence the influence of side products on the electrical properties and confirms high ionic conductivity (0.5 mS/cm) and very low electronic conductivity of optimized electrolyte. The sintering temperature and dwell time are then optimized by advanced sintering techniques (high pressure, Flash SPS) allowing to prevent the chemical instability usually observed between LLZO and active materials (LiCoO2 or Li[Ni1-x-yCoxMny]O2 (NCM)) and to obtain a cathodic half-cell (LLZO/positive electrode) in one step.

References :

[1] H. Yamada, T. Ito, R. Basappa, Electrochimica Acta 222 (2016) 648–656.
[2] M. Kotobuki, M.Koishi, Journal of Alloys and Compounds 826 (2020) 15421.
Redox Flow: How Low Can You Go? High-Throughput Battery Lifetime Characterization for Grid-Scale Energy Storage
Authors: Fell Eric M. , Aziz Michael J. 
Published: July 2022

Aqueous Organic Redox Flow Batteries (AORFBs) have emerged as potentially disruptive technologies for the storage of electrical energy from intermittent renewable sources. With the goal of cost-effective, safe, and scalable stationary electricity storage systems, AORFBs could eclipse Li-ion batteries due to their inherent non-flammability, lack of materials scarcity fluctuations, and intrinsic decoupling of energy and power capacities. We have previously demonstrated that calendar life, rather than cycle life, limits molecular lifetimes in AORFBs due to various molecular instabilities that lead to side reactions, thus inhibiting performance [1]. The continued synthetic effort to produce stable redox-active organics has improved molecular design strategies to the point that the most stable chemistries now degrade at less than 1% per year [2].
With further lifetime increases, the measurement of lower capacity fade rates now necessitates higher precision coulometry methods [3] and the use of thermally accelerated decomposition protocols [4,5] to determine which stabilizing approaches are most effective without waiting for multi-month cycling tests to quantify capacity fade.
In this presentation, I highlight a high-throughput setup we have recently developed for the electrochemical screening of candidate molecules in AORFBs. We demonstrate the effect that cycling protocols can have on measured capacity fade rates and propose figures of merit for cell-to-cell variability. Finally, we explore accelerated decomposition protocols to expedite the screening process of candidate molecules for long lifetime AORFBs, which may enable massive grid penetration of intermittent renewable energy.
[1] M.-A. Goulet and M. J. Aziz, “Flow Battery Molecular Reactant Stability Determined by Symmetric Cell Cycling Methods,” Journal of The Electrochemical Society
,
165, A1466 (2018).
[2] M. Wu, Y. Jing, A. A. Wong, E. M. Fell, S. Jin, Z. Tang, R. G. Gordon, M. J. Aziz, “Extremely Stable Anthraquinone Negolytes Synthesized from Common Precursors,” Chem, 6, 1432 (2020).
[3] T. M. Bond, J. C. Burns, D. A. Stevens, H. M. Dahn, and J. R. Dahn, "Improving Precision and Accuracy in Coulombic Efficiency Measurements of Li-Ion Batteries,” Journal of The Electrochemical Society, 160, A521 (2013).
[4] D. G. Kwabi, K. Lin, Y. Ji, E. F. Kerr, M.-A. Goulet, D. De Porcellinis, D. P. Tabor, D. A. Pollack, A. Aspuru-Guzik, R. G. Gordon, and M. J. Aziz, “Alkaline Quinone Flow Battery with Long Lifetime at pH 12,” Joule, 2, 1894 (2018).
[5] D. A. Stevens, R. Y. Ying, R. Fathi, J. N. Reimers, J. E. Harlow, and J. R. Dahn, "Using High Precision Coulometry Measurements to Compare the Degradation Mechanisms of NMC/LMO and NMC-Only Automotive Scale Pouch Cells,” Journal of The Electrochemical Society, 161, A1364 (2014).
(Keynote) Opportunities and Challenges of Organic Redox Flow Batteries
Authors: Liu Tianbiao 
Published: July 2022

Aqueous organic redox flow batteries (AORFBs) represent a promising energy storage technology for the integration of renewable energy and balancing electricity grids because of their technical merits of decoupled energy and power, sustainable and tunable redox active materials, and non-flammable and low cost aqueous supporting electrolytes. This presentation will review recent efforts in developing new flow battery chemistries, including viologen (anolyte), quinone (anolyte), TEMPO (catholyte), ferrocene (catholyte), and ferrocyanide (catholyte). The merits and drawbacks of representative acidic, pH neutral, and alkaline AORFBs will be discussed and compared. A number of research strategies will be discussed to develop high-performance redox active electrolytes to enable energy dense, durable, low-cost flow battery technologies. Particularly, this presentation emphasizes that in-depth mechanistic understandings of redox active electrolytes play crucial roles in developing advanced organic redox flow batteries towards sustainable, long-duration energy storage.

References:
(1) Luo, J.; Hu, B.; Hu, M.; Liu, T. L. "Status and Prospects of Organic Redox Flow Batteries towards Renewable Energy Storage", ACS Energy Lett. 2019, 4, 2220-2240.
(2) Wu, W.; Luo, J.; Wang, F.; Yuan, B.; Liu, T. L. "A Self-Trapping, Bipolar Viologen Bromide Electrolyte for Aqueous Redox Flow Batteries", ACS Energy Lett. 2021, 6, 2891-2897.
(3) Luo, J.; Hu, B.; DeBruler C. Zhao, Y.; Yuan B;. Hu, M.; Wu, W.; Liu, T. L. "Unprecedented Capacity and Stability of Ammonium Ferrocyanide Catholyte in pH Neutral Aqueous Redox Flow Batteries", Joule 2019, 4, 149-163.
(4) Hu, B.; Luo, J.; Hu, M.; Yuan B.; Liu, T. L.* "A Neutral, Metal Free Aqueous Organic Redox Flow Battery Employing an Ammonium Anthraquinone Anolyte", Angew. Chem. 2019, 58, 16629-16636.
(5) DeBruler C.; Hu, B.; Moss, J.; Liu, X. Luo, J.; Sun, Y; Liu, T. L. "Designer Two Electron Storage Viologen Anolyte Materials for Aqueous Organic Redox Flow Batteries", Chem 2017, 3, 961-978.
(6) Hu, B.; DeBruler C., Rhodes, Z.; Liu, T. L. "Long Cycling Aqueous Organic Redox Flow Battery for Sustainable and Safe Energy Storage", J. Amer. Chem. Soc. 2017, 139, 1207-1214.
(7) Liu, T.; Hu, B.; DeBruler, C.; and Luo, J. "Materials for Use in Aqueous Organic Redox Flow Batteries", US patent No., 10,934,258, 2021.
(8) Liu, T.; Wei, X.; Sprenkle, V.; Wang, W. "Aqueous electrolytes for redox flow battery systems", US patent No. 14,690,224, 2016.
Revealing the Role of Mo Doping in Promoting Oxygen Reduction Reaction Performance of Pt3Co Nanowires
Authors: Deng Zhiping , Wang Xiaolei 
Published: July 2022

Highly active and durable electrocatalysts towards oxygen reduction reaction (ORR) are imperative for the commercialization application of proton exchange membrane fuel cells. By manipulating ligand effect, structural control, and strain effect, we report here the precise preparation of Mo-doped Pt3Co alloy nanowires (Pt3Co-Mo NWs) as the efficient catalyst towards ORR. The as-prepared Pt3Co-Mo NWs deliver high specific activity (0.596 mA cm-2) and mass activity (MA, 0.84 A mg
-1Pt), much higher than those of undoped counterparts. Besides activity, Pt3Co-Mo NWs also demonstrate excellent structural stability and cyclic durability even after 50,000 cycles (76% MA retain), again surpassing control samples without Mo dopants. The superior catalytic performance can be attributed to several structural advantages. First, both ultrafine nanowire morphology and controlled growth ensure the exposure of abundant highly active high-index facets, resulting in increased electrochemical active surface area (ECSA, 141 m2 g−1
Pt). Second, one dimensional (1D) Pt nanostructure, particularly ultrafine Pt nanowires, are less subject to dissolution, aggregation, and even Ostwald ripening than nanoparticles, leading to much-improved durability. Third and most importantly, the Mo doping directly changes the local electronic structure of both element Pt and Co, not only effectively endowing the Pt3Co electrocatalysts with an enhanced activity but also efficiently preventing element Co from leaching leading to improved durability.
The geometric phase analysis (GPA) strain maps and the density function theory (DFT)calculations were conducted to further analyze the role of Mo dopants. GPA strain maps reveal that Mo dopants are inclined to be the tensile strain cores, generating local lattice expansion to adjust the excessively compressive strain effect introduced by Co alloying. Benefiting from the optimized d-band center, the oxygen binding energy (Eo) on Pt3Co-Mo slabs is closest to the optimal value compared with those of undoped counterparts. Moreover, the energy required to remove Co atoms from Pt3Co slab with Mo doping is increased by 0.195 eV compared to the slab without Mo doping, indicating the electronic effect of Mo dopants to stabilize Co. This work provides not only a facile methodology but also an in-depth investigation of the relationship between structure and properties to provide general guidance for future design and optimization.
Stepping Beyond Cyclic Voltammetry: Obtaining the Electronic Properties of Electrified Solid-Liquid Interfaces
Authors: Wong Raymond , Yokota Yasuyuki , Wakisaka Mitsuru , Inukai Junji , Kim Yousoo 
Published: July 2022

Organically tailorable monolayers of ferrocene-terminated alkanethiol self-assembled monolayers (Fc SAM, Fig. 1a) on Au surfaces are attractive model systems to elucidate the molecular-level physicochemical properties of solid-liquid electrochemical (EC) interfaces [1]. In particular, Fc SAM has been shown to be an attractive spectroscopic molecular probe for photoelectron spectroscopy because the Fe heteroatom is at a fixed position above the electrode surface. Thus, this allows photoelectron spectroscopy to ascertain the electronic and structural properties at a fixed position above the electrode surface [2-3]. The ability to obtain molecular-level structure-function-property relationships with Fc SAM has relevance to bio(chemical) sensors, micro-actuators, and molecular electronics.
Here, we use X-ray and ultraviolet photoelectron spectroscopy combined with an electrochemical cell (EC-XPS/UPS) to electrochemically control the Fc SAM and spectroscopically probe the corresponding electronic and structural changes [2-3]. To perform our experiments, electrochemical (EC) measurements are performed in a separate and dedicated EC chamber in a solution environment under Ar atmosphere, followed by evacuation and finally transfer to the XPS/UPS analysis chamber [2-3]. The EC chamber contains a retractable PTFE (polytetrafluorethylene) cell and utilizes a hanging meniscus setup. I will discuss the merits and challenges of EC-XPS/UPS methodology in the context of other approaches.
Using EC-XPS/UPS, we are able to discriminate anion dependencies (Fig. 1b-d) with respect to the Fe oxidation state, monolayer thickness, and changes to the valence structure regarding the highest occupied molecular orbital (HOMO. Lastly, we are able to spectroscopically probe the changes relating to the interfacial potential distribution across the electrode-monolayer-electrolyte interface or so-called “potential drop” in the form of systematic potential-induced binding energy shifts in the XPS/UPS spectra. Further details will be provided at the presentation.

Fig. 1

(a) Ferrocene-terminated alkanethiol SAM on Au. Schematic of electrode-monolayer-electrolyte interface and interfacial potential distribution. (b) Cyclic voltammograms at 50 mV s-1 in 0.1 M NaTFSI or NaPF6 (c-d) Fe 2p3/2 spectra of Fc SAM, pristine and after anodic/cathodic polarization at 0.625 and 0 V, respectively.

References
[1] K. Uosaki, Electrochemistry
12, 1105-1113 (1999).
[2] R. A. Wong, Y. Yokota, M. Wakisaka, J. Inukai, Y. Kim, J. Am. Chem. Soc.
140, 13672-13679 (2018).
[3] R. A. Wong, Y. Yokota, M. Wakisaka, J. Inukai, Y. Kim, Nat. Commun.
11, 1-9 (2020).

Figure 1
(Digital Presentation) OER Catalysts Supported on Layered Zirconium Phosphate Nanomaterials
Authors: Colon Jorge L 
Published: July 2022

Learning from nature, instead of using expensive catalysts such as platinum for splitting water, cheaper alternatives (such as cobalt, iron, or nickel) could be used for the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). Hydrogen solar fuel produced in artificial photosynthesis schemes for water splitting could be used in fuel cells. However, obtaining efficient catalysts based on earth-abundant materials is still difficult, particularly for the OER. Recent theory has shown that nanoscopic confinement of catalysts increases the stability and efficiency of catalysts for OER. We have designed and develop earth-abundant electrocatalysts for oxygen reduction and water splitting using nanostructured layered inorganic materials of zirconium phosphate (ZrP). We have demonstrated improved electrocatalytic activity of ZrP nanomaterials loaded with metal ions suitable for the OER of water splitting. Adsorbing Co or Ni catalysts on the ZrP nanoparticles surface proved to improved OER activity compared to intercalated catalysts. A comparison between adsorbed Co or Ni catalysts and those catalysts on exfoliated ZrP hexagonal nanoplatelets proved that those on exfoliated nanoplatelets were more active, with diminished overpotentials and reduced Tafel plot slopes as well as higher mass activities. More recently, comparison between Co and Ni catalyst on ZrP particles with different morphologies (hexagonal platelets, rods, cubes, and spheres) revealed that the more active Co catalysts are those on hexagonal ZrP platelets, whereas the best Ni catalysts are those on ZrP spheres. Finally, encouraging recent results with a cobalt porphyrin catalyst and bimetal catalysts will be presented, as well as recent XAS operando results. These results demonstrate that ZrP nanoparticles are suitable supports for electrocatalysis of the OER and water splitting.
Sponsored by the NSF-PREM Center for Interfacial Electrochemistry for Energy Materials (CIE2M) grant DMR-1827622.