bluuebunny/crossref_metadata_2025_split huggingface dataset:
Ni-Pt Core-Shell Formation via Spontaneous Galvanic Displacement Reaction at Boron Doped Diamond Electrodes for Ammonia Oxidation Reaction
Authors: Omoogun Abayomi , Cabrera Carlos R. 
Published: August 2024

Ammonia is a major environmental pollutant that is highly toxic and may cause unfavourable effects to the human body, even in low concentrations. As a result, the monitoring and elimination of NH3 has been an important topic worth exploring in depth. Moreover, ammonia can be a suitable fuel cell source because its theoretical electrical charge density is relatively high and it’s possible to take this advantage by converting ammonia to nitrogen and electrical energy via the ammonia oxidation reaction (AOR). This reaction requires a catalyst to decrease the energy barrier that prevents the molecule from reacting and transforming into nitrogen.
Ammonia electro-oxidation reaction has been paid much attention in recent years because it is widely used in various fields. However, the electro-oxidation of ammonia is a complex process, especially the reaction intermediate has a slow toxic effect on the electrode. To reduce the catalyst poisoning by the absorption of intermediate, the constituent and structure of the catalysts must be deeply researched.
Herein, a bimetallic Pt–Ni catalyst-modified boron-doped diamond (BDD) electrode was done via spontaneous galvanic displacement reaction for the ammonia oxidation reaction. The synergistic properties may include the promotion of low-temperature oxidation, improvement of the oxidation resistance, and increased catalytic efficiency. BDD was used as the electrode substrate in this work due to its excellent resistance to corrosion and good stability over time in a highly corrosive environment. First, nickel was electro-deposited through chronoamperometry on the BDD electrode surface at a potential of -1.1V vs Ag/AgCl in 0.1M KClO4 & 5mM Ni (NO3)2.6H2O aqueous solution. Second, platinum was deposited on the nickel particles on the BDD electrode surface through a spontaneous galvanic displacement reaction by a redox process which involves the nickel oxidation and Pt2+ reduction, using a K2PtCl4 precursor on the BDD surface while forming a core shell structure. Lastly, the Pt-Ni deposited on the BDD surface was then characterized through different techniques such as XPS, SEM, EDS, and Raman before and after the ammonia oxidation reaction.
Preliminary studies of the behaviour of BDD electrodes in the presence of Ni and Pt have been carried out to determine the electrochemical conditions at which the substrate works with these metal salts. The results found with these studies will show how Pt-Ni catalyst will improve AOR in alkaline media.
Iron Effects in Advanced Alkaline Electrolyzer
Authors: Rajeev Manasa , Kempler Paul A. , Boettcher Shannon W. 
Published: August 2024

Global warming, characterized by an alarming rise in the Earth’s temperature, is one of the serious impacts of industrialization. Transition towards a sustainable future requires the diversification of our energy sources by replacing fossil fuels with renewable energy such as green H2, to lower global CO2 emissions. Alkaline water electrolysis is one of the widely used affordable water splitting techniques that produces hydrogen gas. Since Fe contamination in this system is an unavoidable factor, it is important to understand the optimum Fe concentration for maximum performance. In this work, we are investigating the change in the total cell performance by spiking Fe2+ (0 to 140 ppm) solution at industrial standard conditions (6 M KOH, 80° C).
In this work, we are investigating the change in the total cell performance by spiking Fe2+ (0 to 140 ppm) solution at industrial standard conditions (6 M KOH, 80° C). The KOH was purified prior to the experiment making sure the Fe limits are below the ICP-MS detection limit. To fully understand how Fe activates/deactivates the electrode performance, we chose NixCoy(O)OH coated on Ni mesh anode, commercial AWE cathode and Zirfon-220 as separator and performed testing in both 3-electrode set up and zero-gap electrolyzer set up. Our initial results show that, Fe effect on the total cell performance follows a bell curve where the maximum contribution comes from the activation of the anode. It must be noted that by spiking 40 -50 ppm Fe in the electrolyte the total cell potential is reduced by over 1V which is a huge gain. As we spike over 60 ppm the performance starts to go down. This can be explained by the deposition of FeOx on the anode which is a bad OER catalyst in comparison with NixCoy(O)OH. Our anode has a high active surface area from the nano sheet composition along with high conductivity from CoOx. At 20 ppm Fe in the electrolyte, the anode over potential reduced by 49 mV at 10 mA and by ~110mV at 250mA at 80 °C. Unlike bare Ni electrode as cathode, commercial cathodes are very resistant to Fe fouling only leading to a few millivolts of change. It is important to understand that Fe has maximum effect at low temperature, where the total cell potential was reduced by 200mV by adding 40 ppm Fe solution. As we increase the temperature to 80 °C, reaction kinetics gets improved and the optimum Fe concentration for maximum performance decreases.
The activation in the anode performance at high Fe concentration has been verified by studying the surface morphology SEM imaging and by taking the EDX analysis. It has been seen that the anode gives maximum performance when we have sites of NixCoyFeO(OH) deposited on the anode catalyst. As our next step, we will be evaluating the changes in the surface morphology of the cathode along with the amount of Fe being deposited at each spiking. This will provide more information on how we should engineer the cell components to achieve the maximum output.

Figure 1
Rotating Disk Slurry Electrodeposition of Trimetallic Nickel-Cobalt-Iron Nanoparticles Electrocatalyst on Vulcan Xc-72R for the Oxygen Reduction Reaction in Alkaline Media
Authors: Chatterjee Suzatra , Cabrera Carlos R 
Published: August 2024

Although platinum and platinum group metals (PGMs) catalysts are the most efficient for oxygen reduction reaction, the cost and scarcity of the metals are the reason to look for alternative electrocatalysts. Transition metals, such as cobalt, iron, and nickel, have shown promise as an alternative catalyst to oxygen reduction reactions (ORR). In this work, we electrochemically synthesized nickel-cobalt-iron trimetallic alloy nanoparticles dispersed on carbon Vulcan using Rotating Disk Slurry Electrodeposition (RoDSE). This technique is an energy-efficient green method to synthesize well-dispersed catalysts on carbon and oxide supports for various applications including the oxygen reduction reaction (ORR) for fuel cell applications. Cobalt-nickel iron nanoparticles have been well dispersed in 20 mg carbon Vulcan XC-72R using a negative potential (-1.05V vs Ag/AgCl-sat KCl) in a saturated Argon environment. The electrodeposition potential was obtained from cyclic voltammetry analysis of the metal salts in 0.1m KClO4 solution with an electrochemically cleaned glassy carbon electrode. The starting material precursors were iron chloride, nickel acetate, and cobalt acetate in 0.1 M KClO4 aqueous solution. A 500 micromolar metal salt solution aliquot was added for the electrodeposition every 20 minutes, with a total of 12 aliquots.
Compared with commercially available 20% Pt/Vulcan, the synthesized catalyst shows comparable mass activity and durability with an onset potential of 0.78V vs RHE(@0.01mA/cm2), limiting current density of 5.56mA/cm2 and half wave potential of 0.66V vs RHE.
The X-ray diffraction (XRD) studies and transmission electron microscopy showed that trimetallic nanoparticles are formed and deposited on the carbon Vulcan support. Moreover, scanning electron microscopy, X-ray fluorescence studies, and transmission emission microscopy show the presence of trimetallic nanoparticles. The RDE and RRDE studies show that the synthesized material is active and may lead to a good and inexpensive catalyst for ORR.
Electrifying Chemistry: Characterizing TEMPO-Based Electrocatalysts for Isopropanol to Acetone Conversion in Novel Heat Pumps
Authors: Mishra Abhiroop , Kim Junyoung , Zorigt Michelle , Romo Adolfo I.B. , Gaddam Raghuram , Braun James , Ziviani Davide , Rodriguez Lopez Joaquin 
Published: August 2024

Heating, ventilation, and air conditioning (HVAC) systems account for more than 40% of the U.S. electricity usage, primarily utilizing vapor compression system (VCS) heat pumps, raising environmental concerns. The phase down of high GWP refrigerants, targeting an 85% reduction by 2035, prompts the exploration of novel heat pump technologies. Electrochemical looping heat pumps (ELHP) show promise by employing redox reactions for fluid compression to replace conventional compression technologies. However, energy-intensive redox interconversion necessitates catalysts to lower activation energy. Inspired by electrosynthesis principles, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) emerged as a successful homogeneous electrocatalyst for selective isopropanol oxidation to acetone for use in ELHP. HPLC and 13C NMR confirmed remarkable selectivity (~100%) at practical isopropanol concentrations.
To enhance TEMPO's catalytic activity, various electron-withdrawing and donating groups were explored. TEMPO-OCH3, among seven derivatives, exhibited superior efficiency with a notable rate constant (6 M-1s-1) and turnover frequency (3.1 s-1). This study innovatively applies concepts from molecular catalysis for the development of efficient catalyst materials.
Teaching Undergraduate Students Heterogeneous Electrocatalytic Water Oxidation Using Cyclic Voltammetry and Python Simulation
Authors: Qiu Jingjing , Moeller Anneke , Zhen Janet , Adelstein Nicole 
Published: August 2024

Undergraduate students are motivated and engaged to persist in STEM by learning skills to combat climate change and reduce carbon dioxide (CO2) generation. Water electrolysis is not only an important process to produce the clean energy source hydrogen (H2), but also a classical reaction discussed in the undergraduate chemistry curriculum.
In this talk, we will discuss our efforts of developing an upper division laboratory to teach undergraduate students basic concepts in electrochemistry via the heterogeneous anodic electrocatalytic water oxidation in water electrolysis.1Both experimental work and simulation practices with Python were implemented in this laboratory. Key concepts including chemical reversibility, electrochemical reversibility and kinetics of heterogeneous charge transfer were introduced to students in the learning outcomes. The integrated experience of mini lectures, hands-on experience of materials preparation and electrochemical characterizations along with the simulations helped enhance students’ learning. Additionally, the experience of using Python simulations motivates students to learn programming, which will help prepare them for the workforce and other STEM careers.

Chem. Educ. 2023, 100, 8, 3036–3043
Selective Recovery of Rare Earth Elements from Waste Magnets by Molten Salt Electrochemical Process
Authors: Nohira Toshiyuki , Kawaguchi Kenji 
Published: August 2024

Neodymium magnets are the strongest permanent magnets with Nd2Fe14B as the main phase. In applications where high temperature operation is expected, such as motors for electric vehicles (EVs) and hybrid electric vehicles (HEVs), Dy is added to prevent degradation of magnetic properties. Currently, the demand for EVs and HEVs is growing rapidly, and Dy-doped NdFeB magnets are used in these vehicles. Thus, a large amount of waste magnets will be generated in the future. Moreover, for heavy rare earths such as Dy, high-quality resources are extremely unevenly distributed in the world, and there are already concerns about their stable supply. Given the above background, there is a need to develop an efficient recycling process that can replace the conventional wet recycling process, which has a large environmental impact and energy consumption.
Our research group has proposed a process for the separation and recovery of rare earth elements (REEs) from the waste of neodymium magnet using molten salt electrolysis and alloy diaphragms [1,2]. The principle of this process is shown in Fig. 1. First, the Nd and Dy ions in the waste magnet used as the anode are dissolved into the molten salt by anodic dissolution. Next, the dissolved Nd or Dy ions are reduced on the surface of the diaphragm, which functions as a bipolar electrode, and only one of the ions is reduced to form an alloy. Furthermore, Nd or Dy diffuses through the alloy diaphragm and is dissolved into the molten salt by anodic dissolution on the cathode chamber side surface of the diaphragm. Finally, Nd and Dy are separated and recovered on the cathode.
So far, we have reported that selective permeation of Dy [2] and Nd [3] is possible using LiCl-KCl as the molten salt and a solid Ni-RE alloy as the diaphragm. In the present study, we selected LiF-CaF2 as a more practical fluoride-based molten salt and Hastelloy as a more durable diaphragm, and investigated the electrochemical permeation of RE. We also considered that liquid Fe-RE alloy is expected to be a more desirable diaphragm with higher durability and faster permeation. As a fundamental study, the formation behavior of liquid Fe-Nd and Fe-Dy alloys was investigated, and the results will also be reported.
[1] T. Oishi, H. Konishi, T. Nohira, M. Tanaka, and T. Usui, Kagaku Kogaku Ronbunshu, 36, 299 (2010). [in Japanese]
[2] T. Oishi, M. Yaguchi, Y. Katasho, H. Konishi, and T. Nohira, J. Electrochem. Soc., 167, 163505 (2020).
[3] T. Oishi, M. Yaguchi, Y. Katasho, and T. Nohira, J. Electrochem. Soc., 168, 103504 (2021).

Figure 1
A Sustainable Recycling Approach to Regenerate Graphite from Industrially Sourced Failed Anodes
Authors: Rica Brunilda , Briqueleur Elsa , Mankovsky Denis , Royer Ilona , Dolle Mickael , Waldron Karen 
Published: August 2024

Recycling graphite from Li-ion battery (LIB) waste plays an important role in increasing the accessibility of graphite resources and sustainable recovery. This presentation describes our work to purify graphite from failed (i.e., out-of-specification) anodes in LIB manufacturing by focusing on the most common contaminant: copper, used as the current collector in LIB anodes.
A new, three-step scalable and environmentally friendly approach was used to provide a cost-effective and sustainable method in industrial settings to recycle failed anodes during the early stages of battery manufacturing.
The study aimed to understand the differences between new, battery-grade graphite and recycled graphite from anode production waste. In particular, focus was placed on the effect of metallic Cu residues on electrochemical performance. The efficiency of Cu removal from graphite was quantified by Microwave Plasma – Atomic Emission Spectroscopy (MP-AES) analysis of leachates. The following experimental parameters were studied to maximize Cu leaching efficiency: solid-to-liquid ratio, temperature, acid concentration, time and stirring speed.
The surface morphology and elemental composition of leached and thermally treated purified graphite were analysed by Scanning Electron Microscopy – Energy Dispersive Spectroscopy (SEM-EDS) and Laser Induced Breakdown Spectroscopy (LIBS). The specific surface area and crystallographic parameters were measured by Braunauer–Emmett–Teller Analysis (BET) and X-Ray Diffraction (XRD), respectively. The electrochemical performance was evaluated by galvanostatic cycling with potential limitation versus Li+/Li. These five techniques were carried out on the solid residues after each stage of the regeneration procedure. The results were compared with battery-grade graphite to assess the effectiveness of our sustainable recycling approach to reuse graphite from failed anodes in LIBs.
CO2 Reduction in a Bio Mass-Paired Systems for the Production of e-Chemicals
Authors: Brueckner Sven , Hauke Philipp , Ju Wen , Strasser Peter 
Published: August 2024

The electrification of chemical manufacturing is an important pathway toward reduced CO2 emissions. Direct electrochemical CO2 reduction can thereby become a key technology. CO2 electrolyzers produce cathodically platform chemicals as CO, format, ethanol or ethylene. The state-of-the-art anode process is the oxygen electro evolution which suffers from high over potentials and moderate valorization. An alternative is the anodic oxidation of biomass to valorized carbonaceous products, such as the oxidation of hydroxymethylfurfural (HMF) to the biopolymer precursor 2.5-furandicarboxylic acid (FDCA).
In this work we report the design of electrolyzers flow cells with paired valorization of biomass and CO2. NiNC cathode GDEs are used for CO2 reduction to CO and NiFe-LDH anodes for the HMF oxidation in a zero-gap membrane electrolyzer flow cells. We used a bipolar membrane to separate and optimize either half-cell reactions. Inside the membrane, water is dissociated and the protons will neutralize carbonates on the cathode which is beneficial for a higher CO2 utilization and single pass. So, we can report close to 95% FE and 100% utilization efficiency towards CO.
On the other hand, the hydroxide will stabilize the anode pH and enable PGM-free anodes compared to AEM CO2 electrolyzer. State-of-the-art HMF oxidation is a semi-batch setup, in which the HMF containing anolyte is recycled to complete HMF depletion and utilization. This design suffered from severe mass limitations. Therefore, we modified the semi-batch process into a continuous process and made tradeoffs between faradaic efficiency and utilization. As HMF is not stable in alkaline solutions we decided that a high utilization is beneficial because the intermediates are stable and could be recycled. We can report a single pass conversion of around 70 % towards FDCA at 200 mA cm-2 at a total utilization of 90%.
Figure caption: Paired continuous HMF/CO2 electrolyzer with performance parameter.

Figure 1
Durability Assessment of Roll-to-Roll Coated PEM Water Electrolysis Anodes
Authors: Parrish Chance , Engtrakul Chaiwat , Iyer Radhika , Ware Sam , Blair Sarah J. , Padgett Elliot , Kominowski Andrew , Wrubel Jacob A , Schaffer Corey , Bender Guido , Mauger Scott A 
Published: August 2024

Widespread adoption of green hydrogen relies on the high-throughput production of key electrolyzer components in a manner yielding acceptable stack manufacturing costs. Roll-to-roll liquid coating methods, such as slot die and gravure coating, are particularly relevant means to produce key components (e.g., membranes and electrodes) at high throughput. In the case of proton exchange membrane water electrolysis (PEMWE), thrifting of expensive iridium-based catalysts poses additional challenges to the implementation of such high-throughput coating methods for iridium-based anode manufacture.
Herein, we investigate key challenges around roll-to-roll manufacture of low-loaded (<0.2 mgIr/cm2) iridium-based electrodes for PEMWE. In particular, we highlight fundamental limitations in coating the thin layers required to manufacture low-loaded electrodes, for which the improper choice of coating conditions may lead to macro- and micro-scale heterogeneity. By addressing causes of this heterogeneity, homogeneous slot-die coated iridium oxide anodes of varying iridium loading are produced on decal substrates. Catalyst coated membranes (CCMs) are subsequently produced from these anodes via hot-pressed decal transfer, and 1,000 hour constant current tests are conducted with intermediate diagnostics (polarization curves and impedance spectroscopy). Key effects of loading and homogeneity on electrode durability are highlighted, and future directions are discussed.
This work was authored by the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, LLC, for the U.S. Department of Energy (DOE) under Contract No. DE-AC36-08GO28308. Funding provided by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office and Advanced Manufacturing Office. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. The U.S. Government retains and the publisher, by accepting the article for publication, acknowledges that the U.S. Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this work, or allow others to do so, for U.S. Government purposes.
(Invited) Enabling Bio-Realistic Artificial Intelligence Hardware with Neuromorphic Nanoelectronics
Authors: Hersam Mark C 
Published: August 2024

The exponentially improving performance of digital computers has recently slowed due to the speed and power consumption issues resulting from the von Neumann bottleneck. In contrast, neuromorphic computing aims to circumvent these limitations by spatially co-locating logic and memory in a manner analogous to biological neuronal networks [1]. Beyond reducing power consumption, neuromorphic devices provide efficient architectures for image recognition, machine learning, and artificial intelligence [2]. This talk will explore how low-dimensional nanoelectronic materials enable gate-tunable neuromorphic devices [3]. For example, by utilizing self-aligned, atomically thin heterojunctions, dual-gated Gaussian transistors have been realized, which show tunable anti-ambipolarity for artificial neurons, competitive learning, spiking circuits, and mixed-kernel support vector machines [4,5]. In addition, field-driven defect motion in polycrystalline monolayer MoS2 enables gate-tunable memristive phenomena that serve as the basis of hybrid memristor/transistor devices (i.e., ‘memtransistors’) that concurrently provide logic and data storage functions [6]. The planar geometry of memtransistors further allows multiple contacts and dual gating that mimic the behavior of biological systems such as heterosynaptic responses [7]. Moreover, control over polycrystalline grain structure enhances the tunability of potentiation and depression, which enables unsupervised continuous learning in spiking neural networks [8]. Finally, the moiré potential in asymmetric twisted bilayer graphene/hexagonal boron nitride heterostructures gives rise to robust electronic ratchet states. The resulting hysteretic, non-volatile injection of charge carriers enables room-temperature operation of moiré synaptic transistors with diverse bio-realistic neuromorphic functionalities and efficient compute-in-memory designs for low-power artificial intelligence and machine learning hardware [9].
[1] V. K. Sangwan, et al., Matter, 5, 4133 (2022).
[2] V. K. Sangwan, et al., Nature Nanotechnology,
15, 517 (2020).
[3] M. E. Beck, et al., ACS Nano, 14, 6498 (2020).
[4] M. E. Beck, et al., Nature Communications, 11, 1565 (2020).
[5] X. Yan, et al., Nature Electronics, DOI: 10.1038/s41928-023-01042-7 (2023).
[6] X. Yan, et al., Advanced Materials, 34, 2108025 (2022).
[7] H.-S. Lee, et al., Advanced Functional Materials, 30, 2003683 (2020).
[8] J. Yuan, et al., Nano Letters, 21, 6432 (2021).
[9] X. Yan, et al., Nature, DOI: 10.1038/s41586-023-06791-1 (2023).