bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Impact of Nife-Based Metal Alloy on CO2 Conversion to CH4 and Carboxylic Acids in a Microbial Electrosynthesis Cell
Authors: Nwanebu Emmanuel , Tartakovsky Boris , Tanguay-Rioux Fabrice , Gharbi Rihab , Omanovic Sasha 
Published: August 2024

The goal of this study was to evaluate the impact of NiFe-based metal alloys on the CO2 conversion to carboxylic acids and methane (CH4) in CO2-fed Microbial Electrosynthesis (MES) cells. First, the impact of transition metal alloys on CO2 conversion and product specificity was studied in a MES cell with a conductive polymer cathode with electrodeposited NiFeBi alloy. It was found that the presence of the NiFeBi alloy significantly decreased production of CH4 from 0.5 to 0.1 L (Lc d) – 1, suggesting that methanogenic activity was suppressed in the presence of NiFeBi. On the other hand, the production of carboxylic acids consisting mainly of acetate, propionate and butyrate increased. Specifically, acetate production, which represented 80% of the total carboxylic acids in the cathode liquid increased by 70% to 1.0 g(Lc d)-1. This initial study demonstrated that product selectivity can be influenced by electrodeposition of transition metal alloys such as NiFeBi. It might be preferable to achieve selective production of high value long chain carboxylic acids such as valerate and caproate instead of acetate.
Accordingly, in the following experiments NiFeMn and NiFeSn alloys were electrodeposited on carbon felt cathodes and evaluated for enhanced CO2 conversion in MES cells. Both alloys enhanced CH4 production, which reached 0.8 L (Lc d)-1. However, there was no observable improvement in acetate production (0.2 – 0.5 g (Lc d)-1) or other higher chain carboxylic acids in comparison to NiFeBi – coated MES. It was suggested that by using a more biocompatible carbon-based support for alloy electrodeposition, it is possible to improve acetate, butyrate and caproate production. In addition, it is important to facilitate nutrient transport through the three-dimensional (3D) cathode. Limited transport of CO2, H2 and nutrients was identified as a potential rate-limiting factor when using carbon felt electrode. 3D-printed conductive polymer lattices were manufactured and electrodeposited with NiFeSn and NiFeMn alloys. The NiFeMn-coated lattice showed insignificant improvement in higher chain carbon production, however caproate concentration was increased five folds on NiFeSn-coated cathode. Also, electrochemical characterization demonstrated increased hydrogen evolution reaction rate over time. Nevertheless, the throughput of this product remained low at 0.1 g (Lc d)-1).
These results indicate that the presence of the NiFe-based metal alloys significantly influenced the electron transfer efficiency from the cathodes to microbial electroactive biofilms leading to increased formation of carboxylic acids in the cathode liquid. Therefore, the next step is to design more efficient 3D conductive polymer lattice electrodeposited with NiFeSn metal alloy to increase CO2 conversion to longer chain carboxylic acids.
The Best of Both Worlds: Stacked Catalytic Layers for the Electrocatalytic Generation of CO in Zero-Gap Electrolyzers
Authors: Pellumbi Kevinjeorjios , Hoof Lucas , Blaudzsun Dennis , junge Puring Kai , Apfel Ulf-Peter 
Published: August 2024

Tailoring the properties of the catalytic layer (CL) alongside its architecture is a key development towards ensuring both improve efficiency and selectivity for CO2 electrolyzers. Traditionally, CLs for the CO2R consist of a single binder-material or a combination of them overtaking both the ion-conductance and maintenance of a hydrophobic environment.
We herein decoupled these processes into two individual, stacked catalyst-containing layers. Specifically, a hydrophobic catalytic layer was herein placed on the GDL aiming to improve water management within the CL during CO2R in zero-gap electrolyzers, while A second catalytic layer bound by an ion-conducting binder allows for the conduction of OH- and HCO3-/CO3
2- during CO2R, improving both the ionic conductivity between the GDE and AEM as well as the mechanical adhesion between the different interfaces. Notably, we present the complete stepwise CL-optimization pathway, regarding both the single and segmented-CLs towards the CO2-CO conversion at current densities ≥ 300 mA cm2, highlighting the role of the operational parameters regarding scalability in different cell sizes and long-term stability > 100 h.
Electrochemical Hydrogen Pump Using CsH2PO4/SnO2 Composite Proton Conducting Membrane
Authors: Gupta Minal , Zhang Kangkang , Huang Kevin 
Published: August 2024

Liquid organic hydrogen carriers (LOHCs) are molecular compounds that have potential to be a promising class of hydrogen storage materials. Upon thermal treatment and in the presence of catalysts, H2-rich LOHCs can give off H2 without phase change. One immediate example is methylcyclohexane (C7H14) (MCH) conversion to toluene (C7H8) (TOL). The rate of H2 production of LOHC’s dehydrogenation reaction is kinetically limited. Therefore, adequate catalysts can help boost kinetics. An alternative approach to overcome the kinetic limitation is to shift the dehydrogenation reaction by removing H2 in the product via either a chemical or electrochemical route. Here we show an electrochemical H2 pump concept to promote the dehydrogenation reaction of MCH to TOL by pumping out H2 from the product line. We selected the super-protonic conductor CsH2PO4 (CDP) as the electrolyte for the pump due to the operating temperature of the dehydrogenation reaction (250-350 oC). However, CDP would not be stable if there is an insufficient amount of H2O (<38%) in the working environment, irreversibly dehydrated into a low-conductivity phase. On the other hand, too much H2O in MCH stream would negatively affect the catalytic performance of MCH-to-TOL conversion. Therefore, it is critical to limit the H2O content in MCH stream without affecting H2 pump performance.
Here, we report the use of SnO2 to stabilize the super-protonic conducting phase in CDP. SnO2 is a super-hydrophilic material. We first show the ionic conductivity stabilization over a broad H2O content to demonstrate the effectiveness of SnO2 in stabilizing CDP conductivity. We then show the performance of H2 pump based on the composite CDP-SnO2 protonic conductor. We also show materials characterization results including XRD, SEM and Raman to facilitate our understanding of the observed improvement and degradation. Overall, this study provides a supporting method to accelerate the production of green hydrogen with LOHCs.
Electrochemical Approaches for Enhanced Phosphorus Recovery from Synthetic Animal Wastewater: A Comparative Analysis of Response Surface Methodology and Artificial Neural Networks
Authors: Ojoawo Babatunde IBRAHIM , Trembly Jason , Daramola Damilola 
Published: August 2024

Electrochemical recovery from animal wastewater is a novel and comprehensive strategy needed in the effort to develop sustainable technology and nutrient delivery solutions, with an emphasis on nitrogen (N) and phosphorus (P) components. This research study addresses critical global environmental sustainability challenges associated with waste by contributing to the evolving conversation on nutrient recovery by using synthetic animal wastewater (SAW) as a substrate. This approach presents a viable solution for wastewater treatment and aligns with the sustainable management of water and energy resources.
This research utilized a Box-Behnken experimental design framework formulated with the aid of Minitab Statistical Software. The constructed design laid out a series of experimental runs (comprising 12 distinct conditions, each replicated twice, along with five central points) to explore the influence of three different variables (Mg:Ca molar ratio, N:P molar ratio, and temperature), each at three distinct levels, on phosphorus removal efficiency. The relationship between these three variables and the removal efficiency was then investigated using two distinct modeling methods: Artificial Neural Networks (ANN) and Response Surface Methodology (RSM). ANN, part of machine learning, involves developing a model that learns from experimental data using a network of neurons for training and validation. This allows the ANN to address complex, nonlinear relationships between variables effectively. Conversely, based on statistical analysis, RSM focused on understanding the interactions between the multiple factors, using designed experiments to build a model. Employing both methods leveraged ANN's prowess in handling nonlinearity and RSM's strength in experimental design and optimization, offering a comprehensive approach to enhance P removal efficiency from SAW. The combination of these approaches provided a deep insight into the dynamics of the process, aiding in the effective optimization of the removal response.
However, at optimal conditions, the ANN model predicted a higher P removal efficiency (66%) than RSM (45%). The precision of the ANN predictions was reflected in the minimal error margins with Root Mean Squared Error (RMSE) of 2.4, suggesting the robustness of this model in predicting the optimal conditions for P removal compared to the RSM, with an RMSE of 4.7. These findings underscore the potential of employing ANN and RSM to enhance the phosphorus removal process in wastewater treatment applications and show how ANN gives better predictions than RSM. Additional details will be presented at the meeting, including experimental data, regression models, and neural networks.
Pt/C and PtRu/C Catalysts Prepared by Modified Sulfite Complex Routes for Fuel Cell Applications
Authors: Lo Vecchio Carmelo , Mosca Erminia , Dollenz Riccardo , Mondello Angelo , Baglio Vincenzo 
Published: August 2024

In-house 30 wt.% Pt and 50 wt.% Pt1Ru1 catalysts supported on high-surface area carbon (Ketjenblack, abbreviated as KB) were synthesized by the sulfite complex route. Two different procedures involving either a direct mixing of Pt-sulfite and Ru-sulfite complexes or Pt-sulfite preparation and subsequent impregnation of Ru precursor were adopted for the bimetallic species. In both cases, an impregnation of the formed metal oxides onto KB was adopted to increase the electronic conductivity of the samples. Finally, a carbothermal treatment at 600°C in He atmosphere was carried out for the reduction of the metal oxides to metallic PtRu/C compounds. The Pt1Ru1 ratio was calculated and revealed by X-ray fluorescence (XRF) analysis whereas the carbon percentage was calculated by weight loss. 50 mg of sample was treated in air at 550°C for 2 h and, after cooling, the weight corresponded to 25 mg, confirming a carbonaceous matrix percentage of 50 wt.%. In a similar way, the 30 wt.% Pt/C was determined. X-ray diffraction (XRD) revealed that the samples showed face centered cubic (fcc) structure for Pt nanoparticles. It appears that two distinct crystallographic phases of Pt and Ru nanoparticles were encountered after the synthesis conducted by Ru impregnation. In contrast, only a single fcc phase is visible when the Pt and Ru sulfite precursors were mixed, confirming the formation of an alloy. Furthermore, Scanning Transmission Electron Microscopy-Energy dispersive X-ray spectroscopy (S/TEM-EDX) and X-ray Photoelectron Spectroscopy (XPS) were used to characterize the differences in morphology and surface characteristics of the catalysts.
For the electrochemical measurements, rotating disc electrode (RDE) technique under acid and alkaline conditions was employed to investigate the half cell reactions. The catalysts were also deposited at the anode and cathode of fuel cells to evaluate the activity, performance, and short-term durability.

Acknowledgement

“This research was funded by the European Union – EIT Raw Materials in the framework of the following project: LYDIA- Recycling Critical Metals from Fuel Cells (G.A. 22019)”
Nanoparticles for Active and Sustainable Fuel Cell Cathodes
Authors: Kazimova Nargiz , Romero Nuria , Cavaliere Sara , Cavarroc Marjorie , Philippot Karine 
Published: August 2024

Depletion of fossil fuels and environmental pollution raised interest in new technologies for sustainable energy production, conversion, and storage, among which fuel cell technology is greatly studied, in both academia and industry. Proton exchange membrane fuel cells (PEMFCs) are reputed energy devices, due to their high conversion efficiency and low environmental pollution.1 Nowadays, Pt-based catalysts exhibit the best electrocatalytic activity towards oxygen reduction reaction (ORR), but enhancing their catalytic efficiency and reducing costs are essential for commercializing fuel cell technology.2

Our interest relies with the development of Pt-based nanoalloys2,4 via solution organometallic chemistry approach.3 This approach allows control over the composition, structure, and morphology of metal nanoparticles, and could lead to increased catalytic activity and long-term stability by revealing more active sites of the catalyst. Additionally, the ability to alloy with a range of metals for producing bimetallic compounds is one of the key advantages of this approach.
In this communication, the synthesis of Pt-based nanoparticles and their characterization by state-of-the-art techniques such as ICP, EA, IR, TEM and HR-TEM will be described. The influence of the Pt complexes used as precursors and of the reaction conditions on the morphology of the Pt nanoparticles will be shown. The obtained nanostructures offer interesting starting materials to incorporate other metals, such as transition or rare earth metals, in order to have nanoalloys and study their performance in ORR in comparison to pure Pt catalysts.
References
[1] X. Tang, D. Fang, L. Qu, D. Xu, X. Qin, B. Qin, W. Song, Z. Shao, B. Yi, Chin. J. Catal. 2019, 40, 504–514.
[2] X. Ren, Q. Lv, L. Liu, B. Liu, Y. Wang, A. Liu, G. Wu, Sustain. Energy Fuels 2019, 4, 15–30.
[3] C. Amiens, B. Chaudret, D. Ciuculescu-Pradines, V. Collière, K. Fajerwerg, P. Fau, M. Kahn, A. Maisonnat, K. Soulantica, K. Philippot, New J. Chem. 2013, 37, 3374–3401.
[4] J. Greeley, I.E.L Stephens, A. S Bondarenko, T. P. Johansson, H.A. Hansen, T. F Jaramillo, J. Rossmeisl, I. Chorkendorff, J.K. Nørskov, Nat. Chem. 2009, 1, 552–556.
Electropolymerization of Various Aromatic Monomers Using Streaming Potentials
Authors: Iwai Suguru , Sato Kosuke , Hasegawa George , Ishizuka Norio , Matsukawa Kimihiro , Tomita Ikuyoshi , Inagi Shinsuke 
Published: August 2024

Bipolar electrodes, i.e., wireless electrodes driven by an external electric field, have been paying more and more attention1. Electrolysis using bipolar electrodes is an eco-friendly electrolysis system because they work with a low concentration of supporting electrolytes, which become waste after reactions. Indeed, we achieved the electrochemical fluorination on the bipolar electrodes, reducing the amount of supporting electrolyte to 1/100 compared to a conventional electrolysis2. However, in bipolar electrolysis, driving electrodes are necessary to generate an external electric field, which creates concern regarding the side reaction occurring on the driving electrode. Streaming potentials can be promising candidates to solve this problem. Streaming potentials are the potential differences between an inlet and an outlet of a narrow channel, which is generated when low-concentrated electrolytes are fed into the channel3. In the previous work, we developed a bipolar electrode system using the streaming potential4. The streaming potential was successfully generated by filling the cotton into a narrow channel to conduct the electropolymerization of pyrrole and 3,4-ethylenedioxythiophene. Yet, a large pressure drop of about 10 MPa is needed in this case. Moreover, the value of streaming potential is still low and the monomer scope was limited to pyrrole and 3,4-ethylenedioxythiophene.
In this study, we aimed to investigate the condition with a low-pressure drop and a high-streaming potential, which enabled to expand the scope of electropolymerization. The screening of the filling declared that a polymer monolith, a porous material having continuous pores, was the best filling material for electrolysis. Then, the electropolymerization of thiophene and the ruthenium monomer, which could not be polymerized with the cotton-filled channel because of a low-streaming potential, was successfully carried out to obtain the corresponding polymers. The details of the streaming potential measurement and electropolymerization will be presented in the talk.
References

N. Shida, Y. Zhou, S. Inagi, Acc. Chem. Res., 2019,52, 2598–2608.

K. Miyamoto, H. Nishiyama, I. Tomita, S. Inagi, ChemElectroChem, 2019, 6, 97–100.

A. V. Delgado, F. González-Caballero, R. J. Hunter, L. K. Koopal, J. Lyklema, J. Colloid Interface. Sci., 2007, 309, 194–224.

S. Iwai, T. Suzuki, H. Sakagami, K. Miyamoto, Z. Chen, M. Konishi, E. Villani, N. Shida, I. Tomita, S. Inagi, Commun. Chem., 2022, 5, 66.

Figure 1
(Invited) Understanding the Nano-Biointerface to Improve Biorecognition in Electrochemical Biosensing
Authors: Cardoso Costa Clara , Silveira Toldo Gustavo , Cancino-Bernardi Juliana 
Published: August 2024

Nano-biointerface knowledge inspire both diagnostic and therapeutic functions in the nanomedicine area with remarkable progress. Biomimicking nanoparticles with cell membranes are one of the most innovative approaches to enhance performance, selectivity, and functionality for biomedical applications1,2. The cell membrane coating provides several advantages such as enhanced biocompatibility, improved stability, and specific targeting capabilities due to inherit properties of the source cells3. These advantages can be transferred to the biosensing scenario. For examples, to improve the specificity and selectivity of SARS-CoV-2 biosensors, the angiotensin-converting enzyme 2 (ACE-2) transmembrane receptor, that are overexpressed in respiratory model cells, was used as biorecognition element. In this new SARS-CoV-2 detection platform, cellular membranes from VeroCCL81 (mVero) and Calu-3 (mCalu) cells (which overexpress the ACE-2 transmembrane receptors) were extracted and immobilized as vesicles on an indium tin oxide electrode (ITO). Electrochemical impedance spectroscopy was used to optimize the performance of the developed devices for SARS-CoV-2 detection. The membrane biosensors showed limit of detection of 10.0 pg/mL and 7.25 pg/mL and limit of quantification of 30.4 pg/mL and 21.9 pg/mL were achieved with satisfactory accuracy for ITO-APTES-mVero and ITO-APTES-mCalu, respectively. Selectivity studies revealed that this platform was able to differentiate the target spike proteins from NS1 proteins from dengue and Zika viruses. The use of biorecognition between cell membranes that express the ACE-2 receptors and the virus spike protein may be a new and efficient way to diagnose SARS-CoV-2, especially in terms of the cost of production and isolation, when compared to other targets.
References:
1 J. Cancino-Bernardi, E. J. Comparetti, N. N. Ferreira, R. R. Miranda, M. M. Tuesta, I. Sampaio, P. I. Costa and V. Zucolotto, Talanta,
2023, 253, 124008.
2 N. F. Noronha, J. Cancino-Bernardi, V. M. O. Cardoso, E. J. Comparetti, R. R. Miranda, L. M. B. Ferreira, V. Zucolotto. Chapter 13. In: Smart nanomaterials for bioencapsulation. Ed. Amsterdam: Elsevier, 2022, 223-232.
3 J. Cancino-Bernardi. Innovation in Nanomedicine - Nanomaterials Camouflaged with Cellular Membrane for Application in Therapies. Bio. J. Sci. & Tech. Res., 2018, 8, 1-3.
(Invited) Scanning Gel Electrochemical Microscopy: Towards Biological Applications?
Authors: Liu Liang , Brites Helu Mariela , Dang Ning , Echeveste Salazar Gustavo Adrian , Zammali Marouen , Etienne Mathieu , Walcarius Alain 
Published: August 2024

Scanning electrochemical probe techniques have been developed in the last 30 years for measuring spatially localized electrochemistry at micro and nano scale. Here, we will present a recently developed tool, namely Scanning Gel Electrochemical Microscopy, for imaging the electrochemical reactivity of surfaces and patterning surfaces by local electrodeposition. The concept is based on a gel probe that is in soft contact with the sample, allowing electrochemical measurements to be spatially localized in the contact area with gel as electrolyte.1 The physical resolution, or the pixel size, can thus be tuned by pressing or pulling the probe after touching the sample.2 So far, two types of gel probes have been developed: Type I by electrodeposition of chitosan on micro-disk electrodes,1-3 and Type II by “electrodeposition + pulling” on sharpened metal wires.4 Local chronoamperometry, potentiometry and cyclic voltammetry have been carried out, either for imaging or for patterning (complex-shaped) surfaces.1-4

The gel has an advantage of localizing and immobilizing the electrolyte, which “frees” the sample from solution in scanning electrochemical microscopy (SECM) and reduces the wetting in scanning electrochemical cell microscopy (SECCM) as supported by quartz crystal microbalance (QCM) measurements in our recent work.5 Moreover, the excellent biocompatibility of the chitosan-based gel (which can easily immobilize drugs, proteins or bacteria) and the soft contact make SGECM a promising technique for biological applications. In this presentation, we will discuss about the feasibility of measuring different possible responses when a gel probe is in contact with a bio-entity (bacteria, bio-film, etc.) in-situ in its culture media: (1) Transport of redox species through the bio-entity, either from the gel to the culture media or the opposite way; (2) Production of redox mediators by the bio-entity that would be captured by the gel probe; (3) Physical and chemical response of the bio-entity induced by the gel probe. These possibilities will be examined by electrochemical modelling. The recent development on polyvinylalcohol-based gel probes will also be introduced. The work is partially supported by ANR-NRF project MEACT (ANR-20-CE09-0028).
References:
1. L. Liu, M. Etienne, A. Walcarius, Anal.
Chem., 2018, 90, 8889-8895.
2. N. Dang, M. Etienne, A. Walcarius, L. Liu, Anal. Chem., 2020,92, 6415-6422.
3. N. Dang, M. Etienne, A. Walcarius, L. Liu, Electrochem. Commun., 2018, 97, 64-67.
4. M. A. Brites Helú, L. Liu, Chem. Eng. J., 2021, 416, 129029.
5. G. A. Echeveste Salazar, M.A. Brites Helú, A. Walcarius, L. Liu, Electrochim. Acta,
2023, 437, 141455.

Figure 1