bluuebunny/crossref_metadata_2025_split huggingface dataset:
Gas-Phase Pd Clusters-Modified Mesoporous Copper Oxide Hollow Spheres As Electrocatalysts for CO2 Reduction to Ethylene
Authors: Nguyen Thi Hong Trang , Sanchez Oriol Gutiérrez , Chinnabathini Vana Chinnappa , Papamichail Dimitra , Pant Deepak , Grandjean Didier , Nguyen Trang 
Published: February 2024

Renewable energy-driven electrochemical CO2 conversion to value-added chemicals is a prospective strategy for addressing global carbon emission and energy consumption issues worldwide. Until today, only copper-based electrocatalysts can successfully transform CO2 into C2H4 or other desirable C2+ products, but their stability and product selectivity remain insufficient.1 Oxide-derived Cu mesoporous foam catalysts currently show the best selectivity toward C2+ product formation at particularly low overpotentials due to the availability of specific surface sites for C−C coupling in their structure and to the temporal trapping of gaseous intermediates inside the mesoporous catalyst material during CO2 electrolysis.2 To further improve their stability and product selectivity their surface can be modified with metallic clusters that can promote the adsorption of CO2 and the subsequent formation of intermediates. In particular, Pd clusters provide a favorable surface for the initial adsorption of CO2,3 while inducing a continuous restructuring of the Cu surface that maintains its catalytic properties for CO2 reduction to hydrocarbons.4

Herein, we report a novel highly efficient electrocatalyst for CO2 conversion in C2+ products based on mesoporous oxygen-rich copper hollow spheres prepared by a colloid templating method, whose surface is uniformly modified by the deposition of different loadings of well-defined Pd clusters of ca. 3 nm diameter using the laser ablation cluster beam deposition (CBD) technology.5

Primary electrochemical results show that these electrodes are able to reduce CO2 to ethylene with a faradaic efficiency of more than three times higher than that of commercial Cu2O nanoparticles under the same reaction conditions. A clear phase transition from CuO to Cu2O and metallic Cu is occurring under CO2 electro-reduction conditions as highlighted by XRD.
These remarkable performances are likely originating from the facile gas charge transport via the mesoporous structure of the oxygen-rich copper spheres as imaged by SEM (Figure 1) as well as from their high surface area, which allows a high catalytic activity and a uniform accommodation of the metallic clusters.
As CBD is a versatile technique that allows the deposition of virtually any type of well-defined cluster on a large variety of support, this work provides an attractive avenue to achieve stable selective multicarbon products via rational electrode design. References

Kuhl KP, et al., Energy and Environmental Science, 2012;5 (5):7050-7059.

Abhijit Dutta, et al., ACS Catal. 2016, 6, 3804−3814

Sichao Ma, et al., J. Am. Soc. 2017, 139, 47−50

Zhe Weng, et al., Angew. Int. Ed. 2017, 56, 13135 –13139

Chinnabathini V. C., et al., Nanoscale, 2023, DOI: 10.1039/D2NR07287D.

Figure 1
Formation of Pores on Pure Ti in Highly Concentrated Sulfuric Acids
Authors: Tsuchiya Hiroaki , Sato Ryoma , Fujimoto Shinji 
Published: February 2024

TiO2 nanotubes formed by anodization in fluoride-containing electrolytes have been extensively examined due to their wide rage of applications. It is reported that fluoride ions move faster to the interface between anodic oxide layer and underlying Ti substrate, forming a fluoride-rich layer at the interface as the ionic radius of fluoride ion is smaller compared to that of oxygen ion. The fluoride-rich layer is also reported to decrease the adhesion of the anodic oxide layer to the substrate. Therefore, the formation of nanotubular oxide layer in fluoride-free electrolytes is highly desired. In the present work, we examined the formation of nanotubular oxide layers on pure Ti in highly concentrated sulfuric acids.
Specimens with the dimension of 5 mm x 80 mm x 0.6 mm were prepared from pure Ti sheet (purity ; 99.5%). Prior to anodization, the specimens were cleaned in acetone, methanol and deionized water, successively. Anodization was carried out in highly concentrated sulfuric acids at elevated temperatures using two-electrode configuration cell with platinum counter electrode. The applied voltage was increased with the sweep rate of 1 V/s to desired voltages and then kept at the voltages for various durations. After the anodization, the surface of the specimens was cleaned with deionized water and dried. The structure of the surface was evaluated using FE-SEM.
In a highly concentrated sulfuric acid, the anodic current increased with increasing the applied voltage and after switching constant voltage, decreased with time. The formation of oxide layer was confirmed at the surface, but no porous structure was visible. However, a porous structure was observed on the specimen above the electrolyte surface, indicating that the anodization occurred under the meniscus consisting of highly concentrated sulfuric acids. The optimization of water concentration in sulfuric acid and temperature led to the formation of porous structure on pure Ti. This indicates that porous oxide layers can be formed in fluoride-free electrolytes although further optimization is required to improve the ordering of pores.
A Density Potential Functional Approach for Mesoscopic Metal-Solution Interfaces
Authors: Huang Jun 
Published: February 2024

Mesoscopic metal-solution interfaces (MSI) are found at nanostructured electrodes in myriad electrochemical devices. Resolving the local reaction environment for electrochemical reactions occurring in mesoscopic MSIs requires a constant-potential, computationally economic method that properly treat both quantum mechanical metal electrons and almost classical electrolyte components. We have been developing a density potential functional theory (DPFT) to meet these harsh requirements [1-4]. Our DPFT method combines an orbital-free density functional theory of quantum mechanical metal electrons, a statistical field theoretic description of classical electrolyte ions and solvent, and Morse potentials describing short-range interactions between the two parts that are parameterized using first-principles based computations. In this talk, I will introduce the theoretical framework, its relationship to other similar methods including the jellium model and implicit solvation model, its parameterization and benchmark with experimental and ab initio simulation data, and recent applications to understand solvent effects on potential of zero charge, mechanoelectrochemistry of MSIs, and supported nanoparticle catalysts. The emerging opportunities, future development needs, and important caveats of the DPFT method will be discussed.
Reference

Huang J, Zhang Y, Li M, Groß A, Sakong S. Comparing Ab Initio Molecular Dynamics and a Semiclassical Grand Canonical Scheme for the Electric Double Layer of the Pt (111)/Water Interface. The Journal of Physical Chemistry Letters. 2023 Feb 27;14:2354-63.

Huang J. Density-Potential Functional Theory of Electrochemical Double Layers: Calibration on the Ag (111)-KPF6 System and Parametric Analysis. Journal of Chemical Theory and Computation. 2023 Jan 18.

Huang J, Chen S, Eikerling M. Grand-canonical model of electrochemical double layers from a hybrid density–potential functional. Journal of chemical theory and computation. 2021 Mar 31;17(4):2417-30.

Huang J. Hybrid density-potential functional theory of electric double layers. Electrochimica Acta. 2021 Sep 1;389:138720.

J.H. is supported by the Helmholtz Young Investigators Group Leader Program.
Developing Cu-Co-Based Catalysts for Enhanced OER in Alkaline Water Electrolysis
Authors: Saei Worawee , Pasel Joachim , Scheepers Fabian , Korte Carsten 
Published: February 2024

Copper, Cobalt-based (CuCo-based) catalysts are promising candidates for the anodes of alkaline water electrolyzers due to their high electrical conductivity, variable chemical state, and the potential for cost-effective large-scale production. However, the effective chemical composition and structure of these catalysts are still being explored. In this work, the focus is on the proposal CuCo-based catalysts for the oxygen evolution reaction (OER) in alkaline water electrolysis, with significant advantages for their use in anion exchange membrane (AEM) electrolyzer systems. CuCo-based catalysts with varying Cu:Co ratios were synthesized using a co-precipitation method and heat treatment, resulting in spinel type (oxides), CuCo-O, or brucite type structures (hydroxides), CuCo-OH. The catalysts were characterized using XRD, SEM, EDX, TEM and ICP-OES to confirm their morphology and composition. The OER catalytic performance of the catalysts was evaluated using rotating disk electrode (RDE) measurements with a 3-electrode system and 1 M KOH as the electrolyte.
Our results show that CuCo-OH provides lower overpotentials than CuCo-O at a current density of 10 mA/cm2. Nevertheless, CuCo-O exhibits a more consistent performance than CuCo-OH, indicating its superior properties in terms of reproducibility and reliability. Additionally, we propose a promising Cu:Co mol ratio of CuCo-OH and CuCo-O. These findings highlight the importance of the chemical composition and provides insight into the structure design of OER catalysts for alkaline water electrolysis. The results suggest a synergistic effect of Cu and Co in the catalyst composition, which could be further explored in future research.
Single-Impact Electrochemistry of Redox Liposomes for the Detection of Virulence Factors
Authors: Langlard Arthur , Thobie-Gautier Christine , Boujtita Mohammed , Lebegue Estelle 
Published: February 2024

Early detection of pathogens is a key factor for the successful therapy of infectious diseases. Some of the pathogenic bacteria involved in diseases interact with the host by producing compounds that are toxic or disruptive to the cells. As these virulence factors can be easier to spot than the pathogen, strategies of detection can be focused on these released compounds to identify the pathogenic bacterium.[1]

Liposomes are vesicles composed of a lipid bilayer membrane, and as such are often used to mimic living cells. Here, the strategy consists in making redox liposomes by encapsulating an electroactive probe in their inner cavity, which will be detected at the electrode.[2] Virulence factors interacting with the vesicles increase the permeability of the lipid membrane and the contents of the liposomes are released over time. This redox probe is then detected with an electrode polarized at the appropriate potential. This work aims to study the single-impact electrochemistry of redox liposomes in different conditions. Previous results indicate that the addition of a surfactant to a liposomal suspension leads to their rupture when they stochastically collide with an ultramicroelectrode.[3] Similarly, virulence factors increase their release or electrolysis of contents upon impact with an ultramicroelectrode.[4] Chronoamperometry measurements recorded at the ultramicroelectrode polarized at the redox potential of the electrochemical probe show impact events (vesicle blocking) and opening events (vesicle reactor) when the encapsulated redox probe is released by the liposome, which are traced back to the presence of pathogenic bacteria.
References:

Smida, H.; Langlard, A.; Ameline, D.; Thobie-Gautier, C.; Boujtita, M.; Lebègue, E.; Anal. Bioanal. Chem.
2023, doi.org/10.1007/s00216-023-04568-z.

Smida, H.; Thobie-Gautier, C.; Boujtita, M.; Lebègue, E.; Curr. Opin. Electrochem.
2022, 36, 101141.

Lebègue, E.; Anderson, C. M.; Dick, J. E.; Webb, L. J.; Bard, A. J.; Langmuir
2015, 31 (42), 11734- 11739.

Luy, J.; Ameline, D.; Thobie-Gautier, C.; Boujtita, M.; Lebègue, E.; Angew.
Chem. Int. Ed.
2022, 134 (6), e202111416.

Figure 1
Fast and Facile Microwave Synthesis of Cubic CuFe2O4 Nanoparticles for Electrochemical CO2 Reduction
Authors: Zander Judith , Marschall Roland 
Published: February 2024

Electrochemical CO2 reduction is a promising strategy for the sustainable synthesis of carbon-based chemicals or fuels such as CO, or CH4.[1] Copper-based materials are of special interest due to their broad substrate scope. While copper itself is the first known metal catalyst able to directly yield CH4, CO, methanol, or C2+ products such as ethanol can also be obtained, e.g. from oxide derived catalysts.[2][3] Another interesting copper oxide is the spinel CuFe2O4, due to its versatile electronic and magnetic properties. Those can be tuned via variations in the cation distribution between octahedral and tetrahedral sites.[4] Changes in the cation distribution, or degree of inversion, can additionally lead to a structural transformation between the cubic and tetragonal form, due to the strong Jahn-Teller effect of Cu2+. Both degree of inversion and structure are strongly dependant on the synthesis conditions.[4]
In this contribution we introduce a fast microwave-assisted solvothermal synthesis of cubic CuFe2O4. Very short synthesis times of 1 min and low temperatures of 120 °C in ethylene-glycol/water mixtures could be realised, without a loss of phase-purity and no necessity for subsequent thermal treatment.[5] The degree of inversion was found to decrease with increasing synthesis time, whereas the particle size and crystallinity was almost independent of the synthesis conditions. The influence of the synthesis conditions – and thus material properties – on the activity in electrochemical CO2 reduction to CO in 0.1 M KHCO3 was investigated. The best activity was obtained for CuFe2O4 with an intermediate degree of inversion of approx. 0.75, together with a large crystallite size and micro-strain. Since hydrogen was produced as the only side-product, CuFe2O4 can be an interesting candidate for the production of syngas.
References:
[1] Q. Lu, F. Jiao, Nano Energy
2016, 29, 439
[2] S. Nitopi, E. Bertheussen, S. B. Scott, X. Liu, A. K. Engstfeld, S. Horch, B. Seger, I. E. L. Stephens, K. Chan, C. Hahn, J. K. Nørskov, T. F. Jaramillo, I. Chorkendorff, Chem. Rev. 2019, 119, 7610
[3] D. Raciti, C. Wang, ACS Energy Lett.
2018, 3, 1545
[4] R. Zhang, Q. Yuan, R. Ma, X. Liu, C. Gao, M. Liu, C.-L. Jia, H. Wang, RSC Adv.
2017, 7, 21926
[5] J. Zander, M. Weiss, R. Marschall, Adv. Energy Sustainability Res.
2023, 2200184
High Areal Capacity Cycling of Three-Electrode Sodium/NBA/Sodium Cells
Authors: Larson Karl , Carmona Eric A , Albertus Paul 
Published: February 2024

The cycling stability of Li and Na metal electrodes is influenced by the interface with the solid electrolyte. Study of the cycling behavior at areal capacities >>0.5 mAh/cm2 are uncommon, and plating and stripping behaviors remain relatively unknown for the individual electrode/electrolyte interfaces because of the difficulty of separating the individual interfaces in a two-electrode cell configuration. Because areal capacities of practical cells target >5 mAh/cm2, it is important to cycle at much higher areal capacities than typically studied. Here, we utilize a three-electrode symmetric cell of sodium metal with sodium beta alumina (NBA) electrolyte and cycled areal capacities ranging from 0.5 to 5 mAh cm-2 and achieved current densities >10 mA cm-2 at 1.0 mAh cm-2. We find that polarization increases most at the stripping electrode, and that during current density ramps the polarizations are greatly affected by the areal capacity, affecting the maximum current density that can be reached prior to either cell shorting or impedance rise that drives the voltage magnitude to well over 1 V. Additionally, we found resistance rise occurring at the Na/NBA interface during plate (reduction) as well as strip (oxidation) for the same electrode, potentially indicating voiding on plate at sufficiently high current densities and areal capacities (5 mAh cm-2, >2 mA cm-2). For two-electrode studies, the voltage evolution on the plating electrode we observe must be considered for the assumption that the plating electrode is a pseudo reference electrode. We also use our three-electrode cell configuration to study several other experimental conditions, including cycling to failure at a fixed current density and areal capacity, as well as a uni-directional current flow experiment to determine the maximum amount of plating / stripping that can be achieved in the absence of cycling. These findings will help direct future experiments and interpretation of data to quantify the limits and improve the engineering of Li and Na metal / solid electrolytes interfaces.
Jolly, D. S.; Ning, Z.; Darnbrough, J. E.; Kasemchainan, J.; Hartley, G. O.; Adamson, P.; Armstrong, D. E. J.; Marrow, J.; Bruce, P. G. Sodium/Na Β″ Alumina Interface: Effect of Pressure on Voids. ACS Appl Mater Interfaces
2019, 12 (1), 678–685. https://doi.org/10.1021/ACSAMI.9B17786.
Krauskopf, T.; Hartmann, H.; Zeier, W. G.; Janek, J. Toward a Fundamental Understanding of the Lithium Metal Anode in Solid-State Batteries - An Electrochemo-Mechanical Study on the Garnet-Type Solid Electrolyte Li 6.25 Al 0.25 La 3 Zr 2 O 12. ACS Appl Mater Interfaces
2019, 11 (15), 14463–14477. https://doi.org/10.1021/ACSAMI.9B02537/SUPPL_FILE/AM9B02537_SI_001.PDF.
(Invited) The Electric Double Layer Revisited from an Atomistic Perspective
Authors: Gross Axel 
Published: February 2024

At the interface between two conducting phases, an electric double layer (EDL) forms. In interfacial electrochemistry, such an EDL is present at the interface between the electrode and the electrolyte. The structure of the EDL can be crucial for all processes that occur at such interfaces, for example in electrochemical energy conversion and storage. Yet, it is fair to say that our understanding of the structure of the EDL is still limited and mainly based on concepts that are more than one hundred years old. In this contribution, I will focus on relatively simple interfaces between metallic electrodes and aqueous electrolytes [1] from a conceptual and from a quantum chemical atomistic perspective. I will discuss how elecrochemically control parameter such as the electrode potential and pH values can enter a first-principles description of electrochemical interfaces. Furthermore, I will present examples in which the explicit consideration of the electrochemical environment is not necessary in order to faithfully reproduce adsorbate structures on metal electrodes as a function of the electrochemical control parameters [2]. In addition, I will critically discuss the properties of electrochemical interfaces that correspond to observables from an atomistic perspective.
[1] A. Groß and S. Sakong, Ab initio simulations of water/metal interfaces, Chem. Rev. 2022, 122, 10746.
[2] A. Groß, Reversible vs. standard hydrogen electrode scale in interfacial electrochemistry from a theoretician's atomistic point of view, J. Phys. Chem. C 2022, 126, 11439.
Improving Lithium Intercalation Kinetics at Nanoconfined Electrochemical Interfaces
Authors: Fleischmann Simon 
Published: February 2024

Improving the performance of lithium-ion batteries (LIBs), as well as establishing alternative cell chemistries such as sodium- or multivalent-ion batteries, requires detailed understanding of ion transport processes across the electrochemical interface and within the solid-state structure of the host electrodes.To enhance the kinetics of the charge storage processes, reducing charge transfer resistance at the interface and/or reducing ion diffusion-limitations in the solid-state are required. This can be achieved, for example, by active material design, electrolyte formulation, or electrode-electrolyte matching.
In this contribution, our team’s efforts in improving the kinetics of electrochemical Li+ intercalation reactions are addressed from the electrode material side. Using layered transition metal oxides and two-dimensional transition metal dichalcogenides, we employ an interlayer-functionalization approach with organic pillar molecules to tailor the interlayer micro-environment. Changes in interlayer geometry, realized by organic pillars with different lengths, will cause changes in solid-state Li+ transport properties, with larger interlayer distance favoring Li+ diffusivity. Manipulating interlayer chemical environment is accomplished via organic pillars with different chemical backbone compositions. This can lead to changes in electrode-electrolyte/solvent interaction, impacting the charge transfer resistance. The talk will cover synthesis approaches and (electrochemical) characterization of the systems, highlighting mechanistic insights and pointing out opportunities of interlayer-functionalized materials for ion intercalation applications.
(Invited) Study of Electrochemical Interfaces Using DFT and the Classical Liquid Theory Hybrid Simulations
Authors: Otani Minoru 
Published: February 2024

Understanding the properties of electrochemical interfaces leads to improving the efficiency and durability of energy and structural materials such as secondary batteries, fuel cells, catalysts, and corrosion. First-principles calculations based on the density functional theory (DFT) are useful simulation technique to those materials and are widely used to understand physicochemical phenomena such as charge and electron transfer and reaction kinetics. However, the simulation costs for the full DFT calculation are quite large. Thus, we need to reduce it to obtain as many results as possible within the limited calculation resources. Combining the DFT and the classical liquid theory is one of a possible way to reduce the costs. We have been developed a series of simulation techniques to hybridize the DFT and the reference interaction site model (RISM) [1-4]. In the presentation, after providing a brief introduction of our simulation technique, we will show the simulation results for electrolyte decompositions and battery degradation [5], a confined effect of water molecule in the MXene electrode [6], and a water dissociation reaction on Cu surface using an automated reaction path search method [7,8].
References:

Otani and O. Sugino, Phys. Rev. B, 73, 115407 (2006).

Bonnet, T. Morishita, O. Sugino, and M. Otani, Phys. Rev. Lett., 109, 266101, (2012).

Nishihara and M. Otani, Phys. Rev. B, 96, 115429 (2017).

Haruyama, T. Ikeshoji, and M. Otani, Phys. Rev. Mater., 2, 095801 (2018).

Hagiwara, J. Haruyama, M. Otani, Y. Umemura, T. Takeuchi and H. Sakaebe, Electrochemistry, 90, 107002 (2022).

Sugahara, Y. Ando, S. Kajiyama, K. Yazawa, K. Gotoh, M. Otani, M. Okubo, A. Yamada, Nat. Commun., 10 850, (2019).

S. Maeda, K. Ohio, and K. Morokuma, Phys. Chem. Chem. Phys. 15, 3683 (2013)

Hasegawa, S. Hagiwara, M. Otani, and S. Maeda, submitted to J. Phys. Chem. Lett.