bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Electrocatalysts and Processes for Carbon Dioxide Reduction
Authors: Mueller Astrid M 
Published: February 2024

Efficient and robust electrocatalytic processes that convert climate-damaging carbon dioxide into useful fuels and chemicals are essential to decarbonize our economy. The accelerated discovery of effective catalysts critically depends on rational materials design, predicated on mechanistic and structural understanding of catalysts, electrode–electrolyte interfaces, and mass transport and catalytic processes. New synthetic methods are needed that enable the preparation of tailored multimetallic nanomaterials with precisely controlled properties, for which pulsed laser in liquids synthesis is an ideal tool. Laser-made catalysts are intrinsically more active than analogs made by conventional equilibrium methods.[1] For electrolyzer devices, nanoparticulate catalysts must be immobilized on inert, high surface area carbon substrates for electrocatalysis in aqueous electrolytes. We solved this challenge by preparing carbon fiber paper with intact mesostructures and long-lasting hydrophilicity by a green chemistry process.[2] We developed novel copper-free trimetallic electrocatalysts for aqueous carbon dioxide reduction [3] that produced C–C-coupled products. Systematic variation of metal ratios revealed trends in product distributions. We also assessed gold nanoparticle–hydrophilic carbon fiber paper assemblies with ionomer overlayers for clean syngas generation. Our laser-made catalysts together with the newly developed ability to use them on high surface area electrode supports provide the foundation towards the realization of viable successor technologies.
References:
[1] R.C. Forsythe, C.P. Cox, M.K. Wilsey, A.M. Müller. Pulsed Laser in Liquids Made Nanomaterials for Catalysis. Chem. Rev.
2021, 121, 7568-7637.
[2] M.K. Wilsey, K.R. Watson, O.C. Fasusi, B.P. Yegela, C.P. Cox, P.R. Raffaelle, L. Cai, A.M. Müller. Selective Hydroxylation of Carbon Fiber Paper for Long-Lasting Hydrophilicity by a Green Chemistry Process. Adv. Mater. Interfaces
2023, 10, 2201684.
[3] M.K. Wilsey, C.P. Cox, R.C. Forsythe, L.R. McCarney, A.M. Müller. Selective CO2 reduction towards a single upgraded product: a minireview on multi-elemental copper-free electrocatalysts. Catal. Sci. Technol.
2021, 11, 416-424.
Carbon Dioxide Reduction on Alloyed Galinstan
Authors: Mohamed Aya , Bogdanoff Peter 
Published: February 2024

Solar powered electrochemical CO₂ reduction to disposable products is presently being developed as one of negative carbon emission technologies1. State-of-the-art electrocatalysts are mainly developed for the CO2 reduction to hydrogen rich products or chemical feedstock materials while for the above-mentioned application solid carbon-rich products are desired (best pure carbon). Even though the formation of solid products is sometimes observed on catalysts (coking effect), this usually leads to an undesirable irreversible deactivation of their solid interfaces.
Thus, the development of next generation CO2 electrocatalysts is demanded based on liquid metal alloys such as galinstan (GaInSn). The advantage of using liquid phase electrodes is to eliminate coking and coarsening limitations that are associated with solid catalysts. For example, it has been reported that ceria-supported liquid galinstan can electrochemically produce carbonaceous materials from CO2 gas2. This shows, that doping with additional active elements can change the CO2 reduction activity of GaInSn in the direction of other desired products.
Our work investigates the activity of galinstan for the electroreduction of CO2 depending on alloying with additional metals (such as Ce, Ag, Pb). While pure GaInSn shows a predominant activity for the formation of C1 products (CO, HCOOH) in DMF/H2O electrolyte, we are mainly interested in the formation of solid carbon or oxalate. Therefore, our investigations aim at finding suitable modifications of GaInSn that achieve high selectivity for these products. Electrochemical analysis coupled with in-line gas chromatography and in-line mass spectroscopy are used to characterize the reactivity. Furthermore, the influence of the water content of the organic electrolyte on the product selectivity will be investigated. In particular, to suppress the observed low hydrogen evolution as a by-product even more efficiently.

May, M. M.; Rehfeld, K., Negative Emissions as the New Frontier of Photoelectrochemical CO2 Reduction. Advanced Energy Materials
2022, 2103801.

Esrafilzadeh, D.; Zavabeti, A.; Jalili, R.; Atkin, P.; Choi, J.; Carey, B. J.; Brkljača, R.; O’Mullane, A. P.; Dickey, M. D.; Officer, D. L.; MacFarlane, D. R.; Daeneke, T.; Kalantar-Zadeh, K., Room Temperature CO2 Reduction to Solid Carbon Species on Liquid Metals Featuring Atomically Thin Ceria Interfaces. Nature Communications
2019,
10 (1), 865.

Figure 1
(Invited) Energy Materials Development at Ceres: From Nanometers to Megawatts
Authors: Leah Robert , Hjalmarsson Per , Lankin Mike , De Vero Jeffrey , Donatus Uyime , Srivastara Raghav , Ray Santanu , McKenna Fiona-Mairead , Macauley Chandra , Mukerjee Subhasish , Hargrove Caroline , Selby Mark 
Published: February 2024

Ceres’ unique metal supported SteelCell® SOC technology is increasingly establishing itself as the global standard for SOC, combining robustness, efficiency and low manufacturing cost. The technology is rapidly moving from demonstration to true volume production, with Robert Bosch GmbH in Germany and Doosan Fuel Cell in South Korea both having licenses to manufacture Ceres SteelCell® cells and stacks at the hundreds of MW per year scale with factories under construction. Ceres acts as design authority to licensees who manufacture Ceres-developed technology at scale. As such Ceres specifies the raw materials required for cell manufacture and has ultimate responsibility for the validation of any new suppliers of raw materials proposed by licensees.
In addition to supporting the high-volume scale up of current generations of SteelCell technology, Ceres has an extensive R&D program to develop future technology generations which offer improved performance, lower cost and/or lower degradation. A very detailed understanding of the behavior of the materials used in cells, stacks and systems is required to enable future optimization and/or the development of novel materials. This particularly includes the challenges of understanding degradation phenomena, which due to the extended timescales involved are poorly characterized in academic literature. To enhance this understanding Ceres has a number of academic collaborations, most notably with Imperial College London to use leading-edge experimental and computational techniques to understand material behavior affecting initial performance, degradation (particularly changes at interfaces) and corrosion of metallic components. Information gained from these collaborations is used to enable reliable lifetime prediction for current-generation stacks and systems to be undertaken using computer models to predict performance through-life using degradation models derived from theoretical understanding. Theoretical understanding of materials behavior also drives innovation in new generations of materials offering enhanced performance and/or durability, enabling Ceres to maintain its competitive advantage in SOC technology.
Electrochemistry and Organic Synthesis: New Adventures with Olefin Coupling Reactions and Electrode Surfaces
Authors: Moeller Kevin D , Feng Enqi , Krueger Ruby , Medcalf Zachary , Barzova Polina , Wagner Sarah 
Published: February 2024

Electrochemistry has long offered opportunities to explore new modes of reactivity, new approaches for introducing selectivity into synthetic reactions, and new strategies for the synthesis of everything from complex molecules to complex, addressable molecular surfaces. In the talk to be given, two aspects of our efforts along these lines will be detailed.
In the first, we will take a look at recent efforts to use anodically-generated reactive intermediates to convert readily available small molecules into functionalized synthetic building blocks and natural product derivatives. Key to these efforts are oxidation reactions that generate reactive radical cation and radical intermediates. In one application, newly available chiral lactols synthesized using methodology developed by the Lin (Cornell) and Miller (Yale) groups are being transformed into C-glycoside and aza-C-glycoside derivatives. The reactions take advantage of oxidation reactions of either enol ether or vinylsulfide groups. The cyclization reactions and the subsequent deprotection strategy needed for converting the cyclization products into a useful synthetic building block will be highlighted.
In a second application of an anodic cyclization, the role of thioamides in reactions targeting the chrysosoporazine family of natural products will be discussed. The reactions seek to provide an efficient method for converting lignin derived building blocks into molecules that reduce the efflux of anticancer drugs from cells. Initial cyclization attempts utilizing amide based N-radicals and anodic olefin coupling reactions were not successful. Those reactions consistently led to over-oxidation of the products that contain a highly electron-rich aryl ring. The use of thio-amide derived radicals provides a method to circumvent this problem.
In the second topic to be discussed, the question of how one might begin to induce asymmetry into such electrochemical cyclizations will be highlighted. The chemistry focuses on efforts to influence the course of both electrochemical oxidation and reduction reaction and non-redox based transition metal catalyzed reactions with the surface of an electrode.
(Invited) Insights into Processes at the Electrode/Electrolyte Interface of Battery Electrodes Via Scanning (Electrochemical) Probe Microscopy
Authors: Daboss Sven , Philipp Tom , Palanisamy Krishnaveni , Romer Jan , Kranz Christine 
Published: February 2024

Scanning (electrochemical) probe microscopy (SEPM) techniques such as atomic force microscopy (AFM), scanning electrochemical microscopy (SECM), nano-pipette derived scanning probe methods like scanning electrochemical cell microscopy (SECCM) and hybrid methods have recently been used to study interfacial processes occurring at solid/electrolyte interfaces of battery electrodes [1]. So far, mainly Lithium-ion battery (LIB) electrodes have been studied, such as the solid-electrolyte interphase formation at graphite anodes [2,3]. Next generation battery chemistries, using earth abundant elements like sodium (Na), potassium (K), aluminum (Al) improving sustainability still suffer from insufficient knowledge of processes occurring during cycling at the electrode/electrolyte interface such as interphase formation, as gained insights from Li batteries cannot simply be transferred to post-Li chemistries.
In this contribution, an overview of the potential of SEPM techniques to gain insight in interfacial process of post-Li battery chemistries will be given, focusing mainly on the SEI formation on hard carbon composite anodes for Na-ion batteries (SIBs) [4]. The influence of the electrolyte composition along with the effects of additives on the SEI formation and the nanomechanical properties of the electrode will be presented. In addition, given the abundance of Al and the high theoretical volumetric capacity, makes Al a highly attractive battery chemistry [5]. Despite these advantages, there are several challenges like the Al2O3 passivating layer and the mostly used acidic ionic liquid (IL)-based electrolyte AlCl3/1-ethyl-3-methylimidazolium chloride [EMIm]Cl that leads to corrosion, which determines the plating and stripping efficiency and therefore the overall performance. First correlative SECCM/EDX/EBSD studies on Al anodes will be presented.

Acknowledgement

This work contributes to the research performed at CELEST (Center for Electrochemical Energy Storage Ulm - Karlsruhe) and was funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany's Excellence Strategy – EXC 2154 – Project number 390874152 (POLiS Cluster of Excellence).

References

[1] S. Daboss, F. Rahmanian, H. S. Stein, C. Kranz, Electrochem. Sci. Adv. 2, e2100122 (2021).
[2] H. Bülter, F. Peters, J. Schwenzel, G. Wittstock, Angew. Chemie Int. Ed. 53 10531 (2014).
[3] G. Zampardi, S. Klink, V. Kuznetsov, T. Erichsen, A. Maljusch, F. LaMantia, W. Schuhmann, E. Ventosa, ChemElectroChem 2 1607 (2015).
[4] S. Daboss T. Philipp, K. Palanisamy, J. Flowers, H.S. Stein, C. Kranz, Electrochim. Acta ahead of print, (2023)
[5] H. Yang et al., Angew. Chem. Int. Ed. 58, 11978 (2019).
Continuum and Equivalent Circuit Modelling of Porous Electrode Charging
Authors: Janssen Mathijs , Pedersen Christian , Aslyamov Timur 
Published: February 2024

The flow of electrolytes through pores is important in various fields of science and technology. Examples range from axons in the brain and plasmodesmata in plant cells to energy storage in batteries and supercapacitors. In the porous carbon electrodes of supercapacitors, ions move over micrometers through macropores until they arrive at nanopores, forming so-called electrical double layers. In this presentation, I discuss several models for this multi-scale charging process. First, I present analytical [1] and finite-element solutions [2,3] to the Poisson-Nernst-Planck (PNP) equation for the charging of cylindrical electrolyte-filled pores [Figure (a)]. With these methods, I will delineate the validity of the famous “transmission line” circuit model developed by de Levie in the 1960s [4,5] [Figure (b)]. The TL model assumes equipotential lines in a pore to be straight, which is not the case at a pore’s entrance and end, see Figure (a). As a result, the TL model does not accurately describe short-pore charging. Related, the impedance of short pores deviates from the impedance of the TL circuit (the “Warburg open” impedance Wo), especially at high frequencies, see Figure (c).
Figure Caption: (a) The electrostatic potential in a cylindrical pore next to an electrolyte reservoir of resistance Rb
shortly after applying a potential step. The data represent numerical solutions to the Poisson-Nernst-Planck (PNP) equations, which we solved with finite elements using a Newton solver from the FEniCS library. (b) The transmission line circuit is an equivalent circuit that describes the charging of pores such as the one shown in panel (a). In the circuit, the resistance R and capacitance C of the pore are cut into small pieces r and c. (c) The impedance of the TL circuit is given by Rb
+Wo
(blue dotted line), where Wo
is the Warburg open impedance. Also shown is the impedance of a pore whose length is five times its diameter, as obtained from numerical PNP simulations (black).

T. Aslyamov and M. Janssen, Electrochim. Acta 424, (2022)

J. Yang, M. Janssen, C. Lian, R. van Roij, J. Chem. Phys. 156, (2022)

C. Pedersen, T. Aslyamov, M. Janssen, in preparation

R. de Levie, Electrochim. Acta 8, (1963)

M. Janssen, Phys. Rev. Lett. 126, (2021)

Figure 1
Li-Ion Cell in Operando Monitoring and Prognostication Using CMUT Devices
Authors: Cannon Andrew 
Published: February 2024

Capacitive micromachined ultrasonic transducer (CMUT) devices are ideal solutions for in operando battery monitoring applications especially for consumer electronics. Their minute size (2mm x 1mm x 0.5mm) allows direct placement on the battery without affecting the form factor of the device, the volume production techniques used for their manufacture allow for a very low-cost device, and they can be easily integrated with front-end integrated circuits either in a single device or in a discrete multichip form. Together with industry partners we have developed CMUT devices that we use to continuously monitor the behavior of a battery while it is cycling.
For this work we used CMUTs (close-up shown in Fig. 1(a)) developed to operate with a low bias voltage (less than 30 V) which reduces the complexity of the driving hardware. The impulse response and its frequency content are shown in Fig. 1(b). In collapse mode, the peak frequency is 4.0 MHz and the one-way –3 dB BW is 76%, which allows flexibility in setting the drive conditions to interrogate the battery. Our testing also shows that the CMUTs show good device-to-device uniformity and they have a very stable performance in variable temperature environments (e.g. 0℃ - 60℃ ).
The cell is interrogated in pulse-echo mode. The CMUT is excited by a wide-band unipolar pulse and the returned analog signal is filtered and amplified. The signal is then digitized and processed to extract features that allow us to quantify the state of the battery. Figure 1(c) depicts such signal features change under baseline cell cycling conditions (three cycles at a charge rate of C/4). These changes are the result of mechanical material property changes in the cell e.g., electrode stiffness and density [1] which directly affect the acoustic wave propagation inside the cell. Figure 1(d) depicts signal feature change due cell overcharge (red line). Ultrasound is especially sensitive to gas generation which occurs as the cell voltage extends beyond normal operating range [2]. Signal features provide early warning notice that cell is outside of normal operating conditions.
Figure 1. a) Close-up image of CMUT device. b) CMUT impulse response and corresponding frequency content. c) Signal features (RMS and Time of Flight (ToF)) and thickness change during C/4 charge and discharge. d) Signal features during cell constant current overcharge. Cell overcharged after 4.4V (red line).

Chang, W. et al. Measuring effective stiffness of Li-ion batteries via acoustic signal processing. Mater. Chem. A
8, 16624–16635 (2020).

Appleberry, M. C. et al. Avoiding thermal runaway in lithium-ion batteries using ultrasound detection of early failure mechanisms. Journal of Power Sources
535, 231423 (2022).

Figure 1
Detection of Covid-19 with Dual-Signal Probes in Paper Microfluidics
Authors: Xiong Helen , Hang Yingjie , Wu Nianqiang 
Published: February 2024

Current Covid-19 detection methods commercialized today that use colorimetric probes have
the advantage of short response time but the issue of low sensitivity. Other methods consider
fluorescent probes that increase sensitivity but lead to longer response times. In this work,
both fluorescence probes and colorimetric probes are integrated into a microfluidic paper strip.
Both probes are incorporated into a single microfluidic paper strip to optimize sensitivity and
efficiency. As a result, the use of colorimetric probes allows for the advantages of antibody
absorption to be utilized for a short response time to detect antigens without need an extra
excitation source while fluorescent probes increase detection sensitivity and compensate for
the low sensitivity of colorimetric probes. The dual-signal probe displays capacity for greatly
improving the accuracy and timeliness of standard Covid-19 detection in test kits.
Fast Screening of Fentanyl Illicit Drug By the Electrochemical Enhancement of Raman Intensity
Authors: Ibáñez David , González-García María Begoña , Hernández-Santos David , Fanjul Pablo 
Published: February 2024

Fentanyl is a potent opioid drug used as an analgesic and anesthetic because it is approximately 100 times more potent than morphine and 50 times more potent than heroin as an analgesic. However, the overdose of fentanyl requires small dose and can cause stupor, changes in pupil size, clammy skin, cyanosis, coma, and respiratory failure leading to death. During the last years the illicit fentanyl and its analogues have been responsible for most drug overdose deaths in different countries and for that reason, the development of identification and detection methods is mandatory.
Spectroelectrochemical methods are currently proposed for the screening of this drug [1]. For instance, the combination of electrochemistry (EC) and surface-enhanced Raman scattering (SERS) has received growing attention due to the enhancement of Raman intensity associated with EC-SERS effect. However, the generation of reproducible SERS substrates is a traditional limitation of this effect. In that way, activation of metallic screen-printed electrodes (SPEs) by electrochemical routes allows to obtain reproducible nanostructures with excellent SERS properties [2], opening new gates for analytical applications.
In this work, the development of a fentanyl detection method based on EC-SERS effect is achieved. Spectroelectrochemical screening of this drug with metallic SPEs consists of two consecutive steps performed in a single experiment: (1) electrochemical generation of metallic NPs with SERS effect and (2) Raman detection of fentanyl present in solution.
Metallic SPEs provide interesting results being not only useful in the characterization of fentanyl, but also for analytical purposes. The proposed EC-SERS method with gold SPEs allows the detection of 0.33 ug/ml fentanyl and offers a rapid, efficient, and accurate approach for the detection of this drug.

References

[1] C.E. Ott, M. Perez-Estebanez, S. Hernandez, K. Kelly, K.A. Dalzell, M.J. Arcos-Martinez, A. Heras, A. Colina, L.E. Arroyo, Frontiers in Analytical Science, 2 (2022) 1-12.
[2] D. Ibáñez, M. B. González-García, D. Hernández-Santos, P. Fanjul-Bolado, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 248 (2021) 119174.
Highly Stable and Active Ru Clusters Supported on Boron Carbon Nitride for Acidic Water Oxidation
Authors: Bai Xiaofang , Zhang Xiuping , Sun Yujiao , Huang Mingcheng , Fan Jiantao , Xu Shaoyi , Li Hui 
Published: February 2024

In recent years, metal oxides, such as IrO2, have been widely used in proton exchange membrane water electrolysis (PEMWE) because of their excellent catalytic activity and long-term stability [1]. However the high price and scarcity of these catalysts were not enough to meet the requirements of PEMWE [2]. Therefore, it is significant to explore novel electrochemically active, stable, and low-cost catalysts.
In this paper, a uniformly dispersed Ru confined on boron carbon nitride support was synthesized and studied. The surface chemical states of Ru were tuned by the interaction between Ru and the active N in boron carbon nitrogen (BCN), forming a highly stable Ru-N bond. Benefiting from a graphene-like structure, the BCN-0.5Ru catalyst exhibited greater conductivity than RuO2. The strong interaction between Ru and the BCN support also allowed for accelerated charge transfer at the electrode interface.
Transmission electron microscopy (TEM) investigations revealed that Ru clusters were uniformly dispersed on BCN (Figure 1a), and the particle size distributions (Figure 1b) showed that the Ru clusters possessed an average particle size of 4 nm. It suggests that the Ru nanoclusters on the BCN support had small particle sizes and a narrow particle size distribution. These results demonstrated that the BCN support helped disperse the Ru metal nanoclusters more homogeneously than what occurred when RuO2 was prepared via direct RuCl3 annealing. The electrochemical performance of oxygen evolution reaction (OER) for BCN-xRu catalysts in O2-saturated 0.5 M H2SO4 solution was evaluated. The BCN-0.5Ru catalyst demonstrates a low overpotential of 164 mV at a current density of 10 mA cm–2 and remains stable for 12 h in acidic electrolyte (Figure 1c). In contrast, RuO2 without any support fails in only 1 h (Figure 1c). We propose that the surface chemical states of Ru supported by BCN may play an important role in enhancing stability. This study provides insights into designing and synthesizing high-performance electrocatalysts for acidic OER.
References
[1] An L, Wei C, Lu M, et al. Recent Development of Oxygen Evolution Electrocatalysts in Acidic Environment[J]. Advanced Materials, 2021, 33: 2006328.
[2] Gao J, Tao H, Liu B. Progress of Nonprecious-Metal-Based Electrocatalysts for Oxygen Evolution in Acidic Media[J]. Advanced Materials, 2021, 33: 2003786.
Figure 1 (a) TEM, (b) Particle size distributions, and (c) Chronopotentiometry tests at 10 mA cm–2 of BCN-0.5Ru

Figure 1