bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Europe Section Heinz Gerischer Award) Endeavours in the Electro-Solar World of Schottky, Mott and Gerischer
Authors: Schmuki Patrik 
Published: February 2024

The origins of semiconductor electrochemistry lies in the early 20th century with the pioneering work of scientists like Walter H. Schottky, Nevill Mott, and Heinz Gerischer. Schottky and Mott made significant contributions to the understanding of semiconductor physics, while Gerischer is often credited with laying the groundwork for the field of semiconductor electrochemistry. Particularly Gerischer's studies on the kinetics of electron transfer reactions at semiconductor-electrolyte interfaces have been fundamental to our understanding of semiconductor chemistry and photoelectrochemistry. His early work has conceptually created strong links between electrochemistry and solid state physics, has created a close connection to photochemistry, and has profoundly improved the understanding of interfacial reactions. It allowed to exploit the feature of semiconductors to conduct electricity under certain conditions and their conductivity being strongly altered by doping or by the application of an electric field or a photon flux.
These findings have stimulated a work in a wide range of science and led to the foundations towards tremendous success of applications across diverse fields such as Photovoltaics (Solar Cells), Photoelectrochemical Cells, Sensors, Catalysis, Batteries and Fuel Cells, Corrosion Protection, Electrochromic Devices or Water Treatment.
The presentation will give a personal perception of the principles, their use in the last 20 years. It is focused on TiO2 based semiconductor electrochemistry and its applications. It involves the growth and use of titania nanotubes their properties and applications, as well as – in recent years – the use of single atoms as co-catalysts in the field of semiconductor electrochemistry.
(Invited)The Role of the Catalyst Microenvironment in the Electrochemical Reduction of Carbon Monoxide
Authors: Endrődi Balázs , Kormanyos Attila , Drágity Deján , Galbicsek Noémi , Janaky Csaba 
Published: February 2024

Carbon monoxide is already an important raw material for the synthesis of different bulk chemicals (e.g., phosgene and different products thereof). Considering that it can be a building block for the synthesis of virtually any organic compound, carbon monoxide might play an important role in the production of synthetic fuels and other typical petrochemical products. This can be performed under high temperature and pressure conditions in the Fischer-Tropsch process, but electrochemical methods also offer a possible way of forming different chemicals from carbon monoxide.
Because of the low solubility of carbon monoxide in water, instead of the routinely used H-cells, its reduction must be performed in gas-fed electrolyzer cells, ensuring a short diffusion length for the reactant. However, even in such devices the surface of the catalyst (nano)particles is typically surrounded by a thin water shell under operating conditions, caused by various effects such as electrowetting, or wetting by the formed products. The practical insolubility of carbon monoxide (that is ca. 30 times lower compared to the solubility of CO2) makes it vital to ensure that the thickness of this hydration layer is minimized, hence the reactant can reach the catalysts' surface in gas phase, meanwhile just enough amount of a proton source – water – is in the immediate vicinity.
The phase boundary between the catalyst particles, the liquid phase and the gas reactant can be engineered by using functional catalyst layer additives. Here we will demonstrate a commercial pore sealer for this purpose, ensuring the formation of C2+ products in CORR with high selectivity and rate.1 As no specific interaction between the polymer and the CO reactant was found, we assumed that the most important role of this polymer is to increase the hydrophobicity of the catalyst layer. To challenge this theory, various, systematically chosen polymeric materials were tested as catalyst binders to reveal any possible further contribution of certain motifs (e.g., functional groups, fluorinated backbone etc.), present in these polymers. The electrochemical results are contrasted with the detailed characterization of the structure, wetting and gas adsorption properties of the catalyst layer.

Reference

Kormányos, B. Endrődi, Z. Zhang, A. Samu, L. Mérai, G. F. Samu, L. Janovák, & C. Janáky (2023). EES Catalysis. https://doi.org/10.1039/D3EY00006K
(Keynote) Competition of Oxygen and Chlorine Evolution on Oxide Surfaces – a Soft X-Ray and Dems Approach to Identification of Active Site
Authors: Krtil Petr , Minhova Macounova Katerina , Astudillo Catalina , Sakata Kaoruho , Amemiya Kenta 
Published: February 2024

Anodic gas evolving reactions, e.g. oxygen evolution and chlorine evolution, are of fundamental importance both in energy storage as well as in electrolytic production of chemicals. Both reactions are of electrocatalytic nature, proceed in the same potential range and are catalyzed by the same types of electrode materials. While the oxygen evolution is thermodynamically favored the two electron chlorine evolution is kinetically preferred, namely at acid and neutral pH. This kinetic preference is industrially explored in chlor-alkali processes as well in chlorate electrolysis. The growing interest in electrolytic hydrogen production fueled by the popularity of the hydrogen as the likely replacement of fossil fuels brings up the question of the tolerance of the industrial anodes to presence of chlorides in the water intended for electrolytic hydrogen production. Such a tolerance can be best achieved by steering the selectivity of the anode between oxygen and chlorine evolution aiming eventually at the possibility of the sea water use in hydrogen producing water electrolysis. So far existing attempts at control the anode selectivity in presence of chlorides explore two principal approaches – pH control and surface engineering. While the pH related approach is rationalized by different pH sensitivity of each of the competing reaction the surface engineering related activities so far rely on trial and error approach. Qualitatively the selectivity may be controlled by either selectively promoting/suppressing each of the contributing reactions. While the literature lists attempts when the overall selectivity towards OER is apparently achieved by selective suppression of CER [1] more recent reports suggest that the actual selectivity is in fact controlled by the ability of the catalysts to support a lattice oxygen activating mechanism of the oxygen evolution process [2]. While these assignments are based on correlation of selectivity measurements with local structure and DFT modelling and a direct evidence of such a behavior is so far missing. This paper will document here the capability of the real-time and operando soft X-ray absorption spectroscopy [3] to provide this missing evidence. Anodic behavior of two type of ruthenium oxide electrodes in chloride free and chloride containing solutions will be documented by comparison of the nature and potential dependent population of the oxygen related intermediates formed at anode surface in the potential range of oxygen and chlorine evolution in acid media (pH=1) and combined with DEMS data to identify the active sites for each contributing electrode reaction.
References:

V Petrykin, K Macounova, O.A Shlyakhtin, P. Krtil, Angew. Chem., 122, 4923-4925

K. Minhová Macounová, R. K. Pittkowski, R. Nebel, A. Zitolo, P. Krtil, Electrochim. Acta, 427, 140878

K. Amemiya, K. Sakata, M. Suzuki-Sakamaki, Rev. Sci. Instrum. 91, 093104
(Invited) Tuning the Activity of Iron Phosphide Electrocatalysts for Sustainable Energy Conversion
Authors: Emin Saim , Chouki Takwa , Machreki Manel , Stefanov Plamen , Rutkowska Iwona A. , Rytelewska Beata , Kulesza Pawel , Tyuliev Georgi , Harb Moussab , Azofra Luis 
Published: February 2024

Electrocatalysis is a promising approach for the sustainable conversion of renewable energy sources, such as solar and wind power, into chemical energy that can be stored and used on demand. By harnessing renewable electricity to drive electrochemical reactions, we can produce fuels and chemicals in a way that is both clean and cost-effective. As we continue to develop new electrocatalytic materials and improve the efficiency of existing processes, the potential for electrocatalysis to transform our energy system will only continue to grow.
We report the use of iron phosphide (Fe2P, FeP) in several electrocatalytic applications, such as reduction of nitrate ions (NO3), hydrogen and oxygen evolution studies. The electrochemical reduction of the nitrate ion (NO3), a widespread water pollutant, to valuable ammonia (NH3) is a promising approach to achieving green energy conservation. Particularly, FeP and Fe2P phases were successfully demonstrated as efficient catalysts for NH3 generation. Detection of the in-situ formed product using a bi-potentiostat was achieved by electrooxidation of NH3 to nitrogen (N2) on a Pt electrode. The Fe2P catalyst exhibits the highest Faradaic efficiency (96%) for NH3 generation with a yield (0.25 mmol h−1 cm-−2 or 2.10 mg h−1 cm−2) at −0.55 V vs. reversible hydrogen electrode (RHE). To get relevant information about the reaction mechanisms and the fundamental origins behind the better performance of Fe2P, density functional theory (DFT) calculations were performed.
In addition to NH3 synthesis, the iron phosphide catalyst was used in electrocatalytic hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) studies. To enhance the catalytic activities of the obtained iron phosphide particles, heat-treatments were carried out at elevated temperatures. Heat-treatment at 500°C under a reductive atmosphere induced structural changes in the samples: (i) Fe2P yielded a pure Fe3P phase (Fe3P−500°C) and (ii) FeP transformed into a mixture of iron phosphide phases (Fe2P/FeP−500°C). The electrocatalytic activities of heat-treated Fe3P−500°C, and Fe2P/FeP−500°C catalysts were studied for hydrogen evolution reaction (HER) in 0.5 M H2SO4. The lowest HER electrode potential of 110 mV vs. a reversible hydrogen electrode (RHE) at 10 mA cm−2 was achieved with a Fe2P/FeP−500°C catalyst. The intrinsic activity of FeP catalysts was also tuned and studied for OER.
Investigation of Pd Based Metal-Carbon As Bifunctional Electrocatalyst for OER and ORR
Authors: Vashishth Surishi , Eswaramoorthy Muthusamy 
Published: February 2024

Developing oxygen reduction/ evolution reaction (ORR/OER) bifunctional electrocatalysts has great significance for promoting the sustainable energy conversion. Herein, Pd (5wt% only) based bimetallic catalyst adhered well on heteroatom doped conducting carbon substrate is designed and constructed. Rich defects, multiple active centers and strong synergistic effect with rapid ion/electron transport ability allow the electrocatalyst to exhibit superior performance (Li et al., 2019). Owing to its more active metal-Pd sites due to high surface area conducting carbon matrix an ultralow overpotential of 240 mV at 10 mA/cm2 for OER was obtained. It outperforms state of art RuO2 and Pt/C electrocatalyst. High half-wave potential (E1/2) of 0.821 V for ORR is comparable to commercial Pt/C (E1/2 =0.819 V) electrocatalysts was attained. The catalyst exhibits a prolonged stability in alkaline medium at 20 mA cm-2 for 24 h for OER and a small 20 mV shift in linear sweep voltammetry scan after accelerated durability test for 5000 cycles at 50mV/s for ORR. In-situ Raman analysis exhibits surface oxidation of electrocatalyst on OER in highly alkaline (1M KOH) conditions.
Reference:
Li, S., Hao, X., Abudula, A., & Guan, G. (2019). Nanostructured Co-based bifunctional electrocatalysts for energy conversion and storage: current status and perspectives. Journal of Materials Chemistry A, 7(32), 18674–18707. https://doi.org/10.1039/C9TA04949E
Metal-Oxygen Covalency Competition of Unsymmetrical Metal Pairs for Enhanced Bifunctional Oxygen Electrocatalysis
Authors: Zhou Tao , Guo Zheng Xiao 
Published: February 2024

Rechargeable zinc-air batteries are considered promising energy conversion devices due to their inherent safety and high energy-to-cost ratio. However, the sluggish kinetics of oxygen evolution reaction and oxygen reduction reaction during the charging-discharging process lead to low round trip efficiency and power density. The synthesis of efficient and stable bifunctional oxygen electrocatalysts constitutes the bottleneck to construct applicable ZABs.
Here, we report an Mn-doped ruthenium oxide electrocatalyst that exhibits remarkable ORR/OER activity, with a low potential gap of 0.62V between the half-wave potential of ORR and the OER potential at 10mA cm-2. The Mn-RuO2 assembled ZABs present a high power density of 179 mW cm-2 and long lifespans of 800 h. Metal covalency competition induces surface Mn atoms shows more favorable adsorption behavior for ORR and Ru atoms shows more favorable adsorption behavior for OER. The charge redistribution between asymmetrical Ru-O-Mn pairs results in dual actives sites towards OER/ORR. The surface ruthenium stabilizes the O* intermediate due to the weaker hybridization of the lattice Ru-O bond. The upshift of the dz2 orbital relieves the over-binding of the critical intermediates OH* on the Mn atom. Such dual Ru-Mn sites minimized the OER/ORR activity gap restricted by scaling relationships. Our findings rationalize the double active sites mechanism in Mn-RuO2 electrocatalyst and provide a strategy to enhance bifunctional catalytic performance.

Figure 1
Unraveling the Crystal Facet and Support Effects on the Oxygen Evolution Activity of Cobalt Oxide Using Single Nanoparticle Electrocatalysis
Authors: Amin Hatem M.A. , Liu Zhibin , Peng Yuman , Corva Manuel , Hosseini Yazdeli Seyed Pouya , Pentcheva Rossitza , Tschulik Kristina 
Published: February 2024

Transition metal oxide catalysts have recently gained special interest in alkaline water electrolysis due to their relatively high abundancy and high catalytic activity. However, their catalytic performance has typically been evaluated based on measurements at composite electrodes, that is by immobilizing a large number of these nanoparticles together with inactive binders and additives on a current collector/support and measuring only their integral activity. In such studies, it is challenging to deconvolute the catalyst intrinsic properties from matrix effects. For example, the measured catalytic trends can be influenced by blocking of catalyst active sites by the additives or by non-optimal iR compensation or by different porosity within the composite, impeding a direct comparison of nanocatalysts.[1] Alternatively, single-particle electrocatalysis by the “nano impact” approach has been applied to assess the intrinsic activity of nanoparticles (NPs) at the individual particle level.[2] Exploiting this method, we demonstrate how the catalyst’s crystal facet/shape influences the OER activity by comparing the activity of cubes and spheres of Co3O4.[3] In contrast to the tentative differences in OER activity recorded on ensembles, the single particle studies unambiguously reveal that Co3O4 cubes are more active than spheres when both NPs have otherwise identical parameters. We also can link our experimental data to theory data obtained from DTU+U calculations. Furthermore, we investigate catalyst-support effects and show the higher activity of Pt support than carbon.[4]. This approach enables the identification of highly active facets to guide shape-selective syntheses of improved metal oxide nanocatalysts for water oxidation.

References

[1] N. Blanc, C. Rurainsky, K. Tschulik, J. Electroanal. Chem. 872(2020)114345
[2] A. El Arrassi, Z. Liu, M. V. Evers, N. Blanc, G. Bendt, S. Saddeler, D. Tetzlaff, D. Pohl, C. Damm, S. Schulz, K. Tschulik, J. Am. Chem. Soc. 141 (2019) 9197
[3] Z. Liu, H. M.A. Amin, Y. Peng, M. Corva, R. Pentcheva, K. Tschulik, Adv. Funct. Mater. 33 (2023) 2210945
[4] Z. Liu, M. Corva, H.M.A. Amin, N. Blanc, J. Linnemann, K. Tschulik, Int. J. Mol. Sci. 22 (2021)13137.
Figure: Single particle electrochemistry illustrating the higher OER activity of Co3O4 cubes than spheres.

Figure 1
LiPON/Multilayer-Graphene Interface Enables High-Rate Charging and Discharging
Authors: Yamamoto Satoshi , Sakakibara Ryotaro , Motoyama Munekazu , Ishigaki Norikazu , Norimatsu Wataru , Iriyama Yasutoshi 
Published: February 2024

Graphite is the anode-active material commonly used in LIBs. In LIB, solid electrolyte interphase (SEI) is formed by the reduction of the liquid electrolyte, and the SEI plays a role as a passive film. In the charging process, Li ions transport in the liquid electrolyte and SEI, desolvation reactions of Li ions occur, and then Li ions insert into the graphite anode. It has been reported that the desolvation reaction of Li ions is the rate-limiting process[1].
Lithium phosphorous oxynitride glass (LiPON) is a well-known material as a solid electrolyte. However, it has been reported that the electrochemical window of LiPON ranges from 0.68 V to 2.63 V[2]. Therefore, it is possible that the decomposition reaction of LiPON occurs when the electrochemical cell is charged. Since the decomposition products can be a resistance, LiPON that is not easily reduced is required.
In this study, we focused on the lithium phosphorus oxynitride glass (LiPON) electrolyte/multilayered graphene (MGr) film interface as an example without the desolvation process. In addition, we have investigated the relationship between LiPON composition ratio, electronic properties, and interfacial resistance by changing the sputtering conditions for LiPON film. Consequently, we found that the charge-transfer resistance at the MGr/LiPON interface was significantly small, although the MGr/LiPON interface was supposed to have inorganic solid electrolyte interphase resulting from the LiPON reduction decomposition. The figure shows a schematic illustration of the Liquid Electrolyte/MGr interface and the LiPON/MGr interface.

Figure 1
Stabilizing of Lithium-Solid-Electrolyte Interfaces by Atomic Layer Deposition Prepared Nano-Interlayers for a Model All-Solid-State Battery
Authors: Götz Rainer , Ahaliabadeh Zahra , Llanos Princess Stephanie , Bandarenka Aliaksandr S. , Kallio Tanja 
Published: February 2024

To understand the electrochemistry of all-solid-state batteries (ASSBs), the use of electrochemical equivalent circuits with a physical meaning is essential. A model battery is needed whose characterization is independent of the influence of the complex battery assembly.
Therefore, LICGC©, a model solid electrolyte is chosen that shows stability in air, but on the other hand is also well-known for its instability against metallic lithium upon direct contact. As a first step towards a model ASSB, the interface between lithium and the solid electrolyte (SE) is stabilized with thin (5 nm and 10 nm) coatings of titanium oxide (TO). Impedance data shows that symmetric cells with the TO coatings are protected from rapid SE surface degradation due to reducing lithium. Titanium oxide nano-interlayers can hence serve as a protective interlayer on the anode side of a model ASSB. Additionally, the formation of space charge layers (SCLs), which have been already documented for LICGC alone, appear once again at the interface between metal oxide interlayer and the solid electrolyte. The observed SCL thickness can reach up to ∼ 5 µm (cf. figure).

Figure 1
(Invited) Combining Constant Potential Molecular Dynamics and Experiments to Study Electrolyte Effects at Solid/Liquid Interfaces
Authors: Serva Alessandra , Salanne Mathieu 
Published: February 2024

Liquid electrolytes are at the heart of many devices in energy storage and conversion applications. Bringing an atomistic picture of the composition-properties relation is essential to understand how their reactivity can be tuned, both in the bulk and at interfaces, by variation of their composition.
In this talk, I will present some recent works where we elucidated the role of the electrolyte, by using state-of-the-art constant potential classical Molecular Dynamics [1] in combination with experiments. I will first introduce some developments that we did for treating metallic surfaces within the constant potential approach, which allows computing interfacial properties, e.g. capacitance, in good agreement with experiments.[2] Then, I will show a study about the insertion process of Li+ into LiFePO4 and K+ into Prussian blue for Li-ion and K-ion batteries, in aqueous vs non-aqueous electrolytes. I will describe the molecular aspects of the electrode-electrolyte interface that dictate ion transport and insertion processes, which strongly depend on the nature of the electrolyte.[3]
I will finally illustrate some exciting perspectives for the design of more complex electrolytes, where water and an organic solvent are mixed, to control the reactivity of water at a solid/liquid interface. This finds direct applications in practical devices such as Li-ion batteries, multivalent batteries, or even electrolyzers. Our strategy was to confine the reactive species, i.e. water, in a non-reactive organic matrix and different salts. Modifying the nature of the salt as well as the salt/water ratio can be used to fine tune the water reactivity at the interface by controlling its coordination environment at both short- and long-range.[4,5]

References

[1] A. Marin-Laflèche et al., J. Open Source Softw., 5, 2373, 2020.
[2] A. Serva, L. Scalfi, B. Rotenberg, M. Salanne, J. Chem. Phys., 155, 044703, 2021.
[3] P. Lemaire, A. Serva et al., ACS Appl. Mater. Interfaces, 14, 20835, 2022.
[4] N. Dubouis, A. Serva et al., Nat. Catal., 3, 656, 2020.
[5] A. Serva, N. Dubuois, A. Grimaud, M. Salanne, Acc. Chem. Res., 54, 1034, 2021.
Pinnwall: Heterogeneous Electrode Models from Integrating Machine Learning and Atomistic Simulation
Authors: Knijff Lisanne , Dufils Thomas , Shao Yunqi , Zhang Chao 
Published: February 2024

Electrochemical energy storage always involves the capacitive process. The prevailing electrode model used to study such polarizable electrode-electrolyte systems is the Siepmann-Sprik model, which has been recently extended to study the metallicity in the electrode model by including the Thomas-Fermi screening length. Nevertheless, a further extension to heterogeneous electrode models is required. Here, we address this challenge by integrating the atomistic machine learning code (PiNN) [1] for generating the base charge [2] and response kernel [3] and the classical molecular dynamics code (MetalWalls). This leads to the development of the PiNNwall [4] interface. Apart from the cases of chemically doped graphene and graphene oxide electrodes as shown in this study, the PiNNwall interface also allows us to probe polarized oxide surfaces in which both the proton charge and the electronic charge can coexist. Therefore, this work opens the door for modelling heterogeneous and complex electrode materials often found in energy storage systems.
[1] Shao, Y.; Hellström, M.; Mitev, P. D.; Knijff, L.; Zhang, C. PiNN: A python library for building atomic neural networks of molecules and materials. J. Chem. Inf. Model.
2020, 60, 1184.
[2] Knijff, L.; Zhang, C. Machine learning inference of molecular dipole moment in liquid water. Mach. Learn.: Sci. Technol.
2021, 2, 03LT03.
[3] Shao, Y.; Andersson, L.; Knijff, L.; Zhang, C. Finite-field coupling via learning the charge response kernel. Electron. Struct.
2022, 4, 014012.
[4] Dufils, T., Knijff, L., Shao, Y. and Zhang, C. PiNNwall: heterogeneous electrode models from integrating machine learning and atomistic simulation. arXiv preprint arXiv:2303.15307. 2023.
*This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Programme (Grant Agreement No. 949012). We also acknowledge the support from the Centre for Interdisciplinary Mathematics (CIM) and the AI4Research initiative at Uppsala University.