bluuebunny/crossref_metadata_2025_split huggingface dataset:
Hydroformylation of Alkenes by Supported Ionic Liquid Phase (SILP) Catalysis
Authors: Fehrmann Rasmus , Riisager Anders , Garcia-Suarez Eduardo Jose , Thang Le Minh 
Published: December 2024

Hydroformylation of olefins forms aldehydes which are valuable final products as well as intermediates in synthesizing bulk chemicals like alcohols, amines, and esters with a yearly world production of about 12 Mt. Industrial hydroformylation processes are essentially homogeneously catalyzed systems with an economic incitement for improvement by easy separation of products and reuse of catalysts, high reactivity and selectivity by using new catalysts, novel processes and alternative methodologies.
One such potential candidate for an alternative catalyst is a Supported Ionic Liquid- Phase (SILP) catalyst comprising “heterogenized” homogeneous ionic liquid (IL) catalyst systems on a porous support. Such catalysts make it possible to apply the much preferred fixed bed continuous flow process design which overcomes the troublesome and energy demanding separation of the products from the reaction mixture obtained in the traditional homogenous batch process.In our previous and very recent studies [1-2], we have prepared SILP catalysts containing immobilized Rh-complexes of TPPTS-Cs3 in 1-butyl-3-methylimidazolium octylsulfate ([BMIM][n-C8H17OSO3]) on SiO2 support and investigated the influence of IL loading on the catalytic activity. The influence of other supports : SBA-15, MCM-41, Al2O3, ZrO2 and TiO2 has also been studied and the catalytic activity compared to the SiO2 SILP catalyst. Finaly we will report on a comparison on the catalytic activity of the SiO2 SILP catalyst by use of the ligand precurser TPPTS-Cs3 and the much cheaper TPPTS-Na3 salt.

References.

H. N. T. Ha, D. T. Duc, T. V. Dao, M. T. Le, A. Riisager, R. Fehrmann. Catal. Commun. 25, 136-141 (2012)

Nguyen, V. C., Do, V. H., Truong, D. D., Pham, T. T., Dinh, P. K., Vu, T. L., Garcia-Suarez, E. J., Riisager, A., Fehrmann, R., Le, M. T. Res. Chem. Int..49, 6, 2383-2398 (2023).
(Invited) Hydrogen Consortium: Advancements in Renewable Hydrogen Production
Authors: Dinh Huyen N 
Published: December 2024

HydroGEN Energy Materials Network (EMN) is an U.S. Department of Energy (DOE) EERE Hydrogen and Fuel Cell Technologies Office (HFTO)-funded consortium that aims to accelerate the discovery and development of advanced water splitting materials (AWSM) for clean, low-cost hydrogen production. Materials innovations are key to enhancing performance, durability, and cost of hydrogen generation technologies.
HydroGEN is focused on low technology readiness level AWS technologies, including low- (alkaline exchanged membrane electrolysis) and high-temperature electrolysis (proton-conducting solid oxide electrolysis), photoelectrochecmical (PEC) and solar thermochemical (STCH) water splitting. This presentation will provide an overview of the HydroGEN EMN and technical highlights of a few lab-led and FOA-awarded R&D projects. HydroGEN continues to grow its community of industry, university, and national laboratories, forming a national innovation ecosystem focused on renewable hydrogen production.
(Invited) TiO2/MWCNT Composite Photoelectrodes for Water-Splitting Reaction Prepared Via Sol–Gel Electrophoretic Deposition
Authors: Matsunaga Mariko , Yu Yuhei 
Published: December 2024

TiO2 is a representative photocatalyst used in practical applications. To improve its catalytic activity, an increase in the active surface area and electroconductivity is a promising approach. For this purpose, various composite structures have been investigated by many researchers. We investigated the composition of TiO2 with multi-walled carbon nanotubes (MWCNT) using various approaches. Recently, we have developed on environmentally-friendly sol–gel electrophoretic deposition (sol–gel EPD) to find the best composite structures of TiO2 and MWCNT as a photoanode.[1] Consequently, it was demonstrated that sol–gel EPD produces various film structures by changing the deposition conditions. For example, it was confirmed that the solute composition, that is, the proportion of TiO2 sol to MWCNT in the electrophoresis bath, linearly changed the thickness and Ti/C composition of the film. Excellent photoelectrochemical activity for the water-splitting reaction was confirmed with a TiO2 film by combining MWCNT in an appropriate manner via sol–gel EPD to improve the film conductivity and UV adsorption by TiO2. In this presentation, several conditions including solvent as well as solute composition of sol–gel EPD significantly influencing film structures of TiO2/MWCNT composite films will be introduced, and the as-prepared film structures that show the best photoelectrochemical activity are also discussed.
[1] Matsunaga, Y. Yu, K.Takahashi, “Photoelectrochemical Activity of TiO2/MWCNT Thin-Film Electrodes with Different Film Structures Prepared by Combining Electrophoretic Deposition and Sol–Gel Method,” Electrochemistry, 92(4), 047004 (2024).
Utilization of Waste Melamine Formaldehyde Resin As an Enhancer in g-C3N4 Photocatalyst and Photoelectrochemical Applications
Authors: Kang Myung Jong 
Published: December 2024

Melamine Formaldehyde resin (MF), one of the thermoset plastic frequently used for cook wares, adhesive, insulator and coatings because of its thermostability, mechanical strength, electronic insulation and ease of manufacture. However, because of above properties of MF resin, it is hard to recycle after used, which causes serious environmental contamination. To overcome this drawback of after-used MF resin, we introduce a method on utilizing after-used MF resin for an enhancer of g-C3N4 photocatalyst, inspired by pristine methodologies to synthesize g-C3N4 photocatalyst.
The pristine g-C3N4 photocatalyst is synthesized by heat polymerization of urea, dicyandiamide(DCDA) and melamine and it utilize widely as a photocatalytst because it has a suitable band gap for visible light absorption, high chemical stability, and high thermal stability. However, high electron-hole recombination rate of g-C3N4 photocatalyst regarded as the reason decreases photocatalytic activity of g-C3N4 photocatalyst.
Therefore, in this study, after-used MF resin as an enhancer during g-C3N4 photocatalyst syntehsis process, to improve photocatalytic activity of g-C3N4. The pure g-C3N4 photocatalyst was synthesized by heat polyemrization of urea and MF resin added g-C3N4 photocatalyst (MR X, X is the amount of added MF resin) was synthesized by adding certain amount of MF resin during g-C3N4 synthesis process. Comparing photocatalytic activity between pure g-C3N4 and MR photocatalyst was carried out by Methyl Orange (MO) degradation under 1 sun illumination. Finally, pure g-C3N4 and MR photocatalyst was fabricated as an photoelectrode and their oxygen evolution reaction(OER) activity was analyzed by electrochemical analysis techniques.
(Invited) Operando visualization of Li Metal Anodes: From Liquid to Solid Electrolytes
Authors: Dasgupta Neil P. 
Published: December 2024

In recent years, there has been an explosion of research into Li metal anodes for high-energy-density batteries. However, despite tremendous progress in the field, the reversible plating and stripping of Li has been hindered by the complex interplay between electrode morphology, surface chemistry, and mechanics. This has led to many empirical observations of improved performance, but our ability to rationally design solutions to solve the challenges of reversibility remain limited by our fundamental understanding of the complex electrodeposition and dissolution processes involved [1]. Moreover, the emergence of solid-state batteries has created new opportunities to enable Li metal anodes, but the unique chemo-mechanical coupling at solid-solid interfaces also brings new challenges for Li metal anodes.
To address these challenges, in situ/operando analyses are of paramount importance to the community. However, given the dynamic nature of Li plating and stripping, challenges arise with respect to tradeoffs in spatial and temporal resolution. To address these challenges, we have recently integrated our optical visualization cells with a digital microscope capable of focus variation microscopy. This enables 3-D visualization of the electrode morphology with high temporal resolution, allowing for video capture of Li plating and stripping [2].
In this talk, I will discuss the application of operando 3-D microscopy for visualization of Li metal anodes using both liquid and solid-state electrolytes. In the case of Li metal anodes, we observe significant anisotropy in the geometric shape of individual pits during stripping [2]. The nucleation density and anisotropy are shown to be strongly influenced by the surface microstructure and underlying crystallographic texture of the Li metal surface. As a results, pits can exhibit strong faceting, which influences the nature of nucleation at pit edges in subsequent cycles [3].
The dynamic morphological evolution of Li metal anodes for solid-state batteries will also be demonstrated using 3-D microscopy. This enables visualization of nucleation and growth in anode-free architectures, where the Li metal anode is formed in situ at a solid electrolyte/current collector interface [4]. The similarities and differences between liquid and solid systems will be discussed in the context of electro-chemo-mechanical coupling, pointing towards new opportunities to enable reversible plating and stripping.
References
[1] A. J. Sanchez, N. P. Dasgupta, J. Am. Chem. Soc.
146, 4282 (2024).
[2] A. J. Sanchez, E. Kazyak, Y. Chen, J. Lasso, N. P. Dasgupta, J. Mater Chem. A.
9, 21013 (2021).
[3] A. J. Sanchez, E. Kazyak, Y. Chen, K.-H. Chen, E. R. Pattison, N. P. Dasgupta,
ACS Energy Lett.
5, 994 (2020).
[4] E. Kazyak, E., M. Wang, K. Lee, K, S. Yadavalli, A. J. Sanchez, M. D. Thouless, J. Sakamoto, N. P. Dasgupta, Matter
5, 3912 (2022).
Lignin-Derived Carbons for Electrocatalytic Oxygen Reduction Reaction in Alkaline Media
Authors: Rzeznicka Izabela Irena , Horino Hideyuki 
Published: December 2024

With the Paris agreement, many countries around the world have set ambitious decarbonization goals. Due to high abundance and greenhouse gas emitting index, there is a growing interest toward conversion of lignocellulosic biomass into materials used in the production of electrodes for batteries, fuel cells and supercapacitors. Lignin-derived carbons could substitute fossil fuel-based acetylene black. However, there are many challenges facing production of electrode-grade carbon from lignin. They include, control of inorganic impurities such as SiO2, porosity and conductivity. Lignin source and extraction processes also lead to many undesired impurities and batch to batch variability.
Carbon black alone is known to catalyze the oxygen reduction reaction (ORR), a key catalytic reaction controlling performance of metal-O2 batteries and fuel cells. The ORR can proceed via sequential 2-electron (2e) or a more desirable direct 4-electrons (4e) reduction pathway depending on the chemical identity of the active material.1-2)

In this presentation, we will report on the physio-chemical properties of kraft lignin-derived carbons and their application in formulation of catalytic inks for electrocatalytic applications. In particular, we will discuss the effect of lignin source and pyrolysis parameters on the ORR performance in alkaline media.
Lignin-derived carbons were characterized by powder X-ray diffraction, SEM-EDX, Raman spectroscopy and electrochemical methods. The catalytic activities of the electrodes prepared using lignin-derived carbons were studied by linear swept voltammetry (LSV) and rotating disk electrode (RDE) methods. Fig. 1 shows LSV of commercial acetylene black and pine-wood derived carbon, after three-steps pyrolysis. The ORR onset potential and a half-wave potential is 0.81 and 0.72 V vs. RHE, for the lignin carbon, which is closer to the half-wave potential of the widely-used 40% Pt/C catalyst. The electron transfer number, obtained from the Koutecky-Levich analysis, was 1.5, suggesting 2e reduction process.
References
1) Donghui Guo et al., Active Sites of Nitrogen-doped Carbon Materials for Oxygen Reduction Reaction Clarified using Model Catalysts.Science351,361-365 (2016).
2) R.P. Putra, Y. Samejima, S. Nakabayashi, H. Horino, I.I. Rzeznicka, Copper-based Electrocatalyst Derived from a Copper Chelate Polymer for Oxygen Reduction Reaction in Alkaline Solutions, Catalysis Today, (2020).
Acknowledgements
This work was supported by JST Strategic International Collaborative Research Program (SICORP), Grant Number JPMJSC2302, Japan.

Fig 1. LSV in the ORR region in 1 M KOH for acetylene black and lignin-derived carbon.

Figure 1
(Keynote) Key Intermediates and Cu Active Sites for the Electrocatalytic Reduction of CO2 to Ethylene and Ethanol
Authors: Roldan Cuenya Beatriz , Herzog Antonia 
Published: December 2024

Electrocatalytic reduction of CO2 (CO2RR) to multi-carbon products is a promising technology to store intermittent renewable electricity into high added value chemicals and close the carbon cycle. Its industrial scalability requires electrocatalysts to be highly selective to certain products, such as ethylene or ethanol. However, a substantial knowledge gap prevents the design of tailor-made materials, as the properties ruling the catalysts selectivity remain elusive. Here, I will describe how the findings from a combined in-situ surface-enhanced Raman spectroscopy and density functional theory study on electrochemically-roughened Cu foil electrocatalysts can be used to unveil the reaction scheme for CO2RR to C2+ products under potentiostatic conditions. In particular, ethylene generation occurs when *OC-CO(H) dimers form via CO coupling on undercoordinated Cu sites. The ethanol route opens up only in the presence of highly compressed and distorted Cu domains via the crucial intermediate *OCHCH2.
Moreover, although it is known that subjecting copper to short anodic pulses during CO2RR improves both, the activity and the selectivity towards hydrocarbons and alcohols, the nature of the active sites is still unclear. To address this issue, the final state of an electrochemically treated Cu(100) surface was resolved by a combination of spectroscopy, microscopy and diffraction methods applied concurrently. The evolution of the morphology, chemical state and crystal structure of Cu(100) exposed to potential pulses during CO2RR has served to shed light into the nature of the active sites formed under dynamic reaction conditions. In particular, anodic pulses, which enhance the ethylene and ethanol production, favor the formation of (n10) facets. Furthermore, pulsing between specific anodic and cathodic potentials during CO2RR also leads to the stabilization of Cu oxide species that are located either at the surface or directly below ultrathin metallic Cu layers, depending on the nature of the pulse potential. The latter is key for the enhanced C2+ product selectivity obtained during pulsed CO2RR.
Finally, by identifying and tracking the critical intermediates and specific actives sites, our work provides guidelines to selectively decouple different products on rationally designed catalysts.
Application of Molecular Silver Complexes for Efficient Electrochemical CO2 Reduction in Zero-Gap Electrolyzers
Authors: Wiesner Wiebke , Maldonado Arias Jenny Yurley , Siegmund Daniel , Apfel Ulf-Peter 
Published: December 2024

Powered by renewable sources the electrochemical conversion of CO2 can be a sustainable opportunity to generate fuels. In the past various molecular complexes have been studied in homogeneous, lab-scale systems for the electrochemical CO2 reduction. Lately the field of incorporating molecular metal complexes in heterogenous electrocatalysis emerged. This approach offers distinct advantages, such as well-defined and easily tunable environments around the active metal centers and enabling a deeper understanding of the structural features necessary for efficient catalysis. Factors like the presence of donor atoms and hydrophobicity play pivotal roles in influencing catalytic activity. Another advantage of using molecular complexes is the possibility of lower metal loadings per square centimeter compared to the usage of i.e. nanoparticles while maintaining the same activity level.[1] In recent years, our group has been focused on the integration and optimization of silver-based complexes in heterogenized systems and gas diffusion electrodes. Herein, we present our progress across two readily synthesized silver-based complexes: the Ag(tetraphenylporphyrin) and Ag(dithiacyclam)[2] complex. Although these complexes exhibited low to moderate performance in homogeneous electrocatalytic CO2 reduction, their integration into gas diffusion electrodes with a carbon black support led to a remarkable increase in faradaic efficiency for CO formation when used in scalable zero-gap electrolyzers. Performing lab scale screenings at current densities of 100 mA/cm2 with catalyst loadings of 0.5 mg/cm2 every complex exhibited a faradaic efficiency for CO formation above 90 %. Remarkably, even at a tenfold reduction in catalytic loading to 0.05 mg/cm2 the complexes’ performance was not decreased significantly. Further, these complexes also showed a high activity towards the formation of CO at elevated current densities of 300 mA/cm2, opening the gate towards electrolysis in application-orientated relevant conditions namely: even higher current densities over 500 mA/cm2, elevated temperatures of 60 °C and long-term measurements up to 100 hours.
[1] Pellumbi, K.; Krisch, D.; Rettenmaier, C.; Awada, H.; Sun, H.; Song, L.; Sanden, S.; Hoof, L.; Messing, L.; junge Puring, K.; Siegmund, D.; Roldán Cuenya, B.; Schöfberger, W.; Apfel, U.-P Cell Reports Physical Science 4
2023, 101746.
[2] Johnson, A.; Iffland, L.; Singh, K.; Apfel, U.-P.; Suntharalingam, K. A Dalton transactions
2021, 50 (17), 5779–5783.

Figure 1
Enhancing the Output Performance of Triboelectric Nanogenerators By Inserting CdS into Dielectric Layer
Authors: Mao Jianbin , Seo Soonmin 
Published: December 2024

Triboelectric nanogenerators (TENGs) have emerged as promising devices for harvesting mechanical energy from various environmental sources. In this study, we focus on enhancing the performance of TENGs by inserting nano-sized cadmium sulfide (CdS) into a polydimethylsiloxane (PDMS) material. The synthesis of CdS nanomaterials was achieved through an ultrasonication method, resulting in a significant reduction in particle size compared to commercial CdS. The fabrication process of the TENG involved dispersing CdS nanoparticles into PDMS and depositing the composite thin film onto a polyethylene terephthalate (PET) substrate. Characterization studies using field emission scanning electron microscopy (FE-SEM) and UV-visible spectroscopy confirmed the successful transformation of micron-level CdS into nano-level CdS with improved optical and morphological properties.
The TENG device was assembled employing a two-electrode configuration, comprising copper foils as electrodes and the CdS/PDMS composite thin film as the friction layer. Subsequent electrical measurements were conducted to assess the TENG's performance, encompassing evaluations of open circuit voltage, short circuit current, and charge transfer density. The findings revealed that the integration of CdS nanoparticles into PDMS significantly augmented the TENG's output, manifesting in notable increases in both voltage and current in comparison to PDMS-based TENGs. Moreover, a comparison between TENGs incorporating nano-scale CdS and those utilizing micro-scale CdS exhibited superior performance of the former, attributed to the enhanced charge transfer properties facilitated by the nanoparticles. Specifically, these findings indicate a threefold enhancement in output voltage and a 2.5-fold enhancement in current compared to the initial PDMS-based TENG.
Additionally, a comprehensive study on the impact of external load resistance on the TENG's output energy density demonstrated its potential for practical applications, with the device capable of powering LEDs continuously. Rectification of the TENG's output voltage using a full bridge rectifier showcased efficient conversion of mechanical energy into electrical energy without a significant performance decline. Stability tests conducted over multiple days confirmed the reliability of the TENG based on CdS/PDMS, suggesting its suitability for long-term applications.
In conclusion, the integration of nano-level CdS into PDMS material presents a promising approach to enhance the TENG performance for mechanical energy harvesting. Despite challenges such as CdS agglomeration in the polymer matrix, our findings highlight the potential of CdS-based TENGs for various energy harvesting applications and pave the way for future research in optimizing their performance and stability.
Kinetic Analysis of Lithium Titanium Oxide by Applying the Diluted Electrode Method to Various Electrochemical Measurements
Authors: Tsuchida Kamma , Ariyoshi Kingo 
Published: December 2024

Elucidating the diffusion phenomenon of Li ions in lithium insertion electrodes used in lithium-ion batteries is important for improving power capability of the batteries. However, it is extremely difficult to identify the rate-determining process of the reaction because there are various mass transport processes in the lithium insertion electrode. In our laboratory, by using a diluted electrode in which part of the active material is replaced with an electrochemically inactive material, the rate-determining step can be controlled by varying the active material content; the rate-determining step is Li-ion diffusion in the electrolyte within electrode pore for the conventional electrode with high active material content versus Li-ion transportation in the solid active material for the diluted electrode with quite low content. Thus, we have succeeded in measuring the inherent electrochemical properties of lithium insertion material via diluted electrode method.
In this study, we applied this diluted electrode method to various electrochemical measurements such as chronopotentiometry, chronoamperometry, and cyclic voltammetry, and analyzed the results in a complementary manner to understand the electrode kinetics of lithium insertion electrodes. In the experiment, lithium titanium oxide (Li[Li1/3Ti5/3]O4; LTO) was used as the active material and aluminum oxide (Al2O3) as the inactive material. The diluted LTO electrode consisted of (LTO+Al2O3):AB:PVdF = 88:6:6.
According to the results on chronopotentiometry (Fig. a), the capacity retention in the oxidation reaction was significantly higher than that in the reduction reaction. This means that the inherent reaction kinetics of LTO is asymmetric between oxidation and reduction. Chronoamperometric results at various applied voltages (Fig. b) also showed that the capacity increased more rapidly in the oxidation reaction than in the reduction reaction at the diluted LTO electrode. In the cyclic voltammograms of the diluted LTO electrode (Fig. c), the oxidation and reduction peaks were symmetrical, suggesting that there was almost no difference in reaction rate between the oxidation and reduction reactions.
In this presentation, we will analyze these measurement results using equations related to diffusion phenomena (Cottrell equation, Sand equation, etc.), and compare the independently obtained kinetic parameters from each measurement, we will discuss the validity of applying these analytical formulas to lithium insertion electrodes.

Figure 1