bluuebunny/crossref_metadata_2025 huggingface dataset:
Proton Activity and Pathway in Aqueous Organic Redox Flow Battery Electrolyte
Authors: Wang Wei
Published: August 2024

Aqueous soluble organic (ASO) redox-active materials have recently shown great promise as alternatives to transition metal ions employed as energy-bearing active materials in redox flow batteries for large-scale energy storage because of their structural tunability, cost-effectiveness, availability, and safety features. However, development so far has been limited to a small palette of organics that are aqueous soluble. This presentation will use fluorenone as an example to showcase how a natively redox-inactive molecule can be tuned to possess two-electron redox reversibility through hydrogenation and dehydrogenation. The modified fluorenone molecules demonstrated high energy density and recorded stable cycling. Furthermore, research has shown the unique chemical-electrochemical coupled redox reactions mechanism; thus, the system rate capabilities can be improved by incorporating suitable hydrogen acceptors that regulate the proton pathway for faster kinetics.

Reference:

Feng et al., Science 372, 836–840, 2021

Feng et al., Joule 7, 1–14, 2023
Ecofriendly K-Ion Batteries Relying on Abundant Chemical Elements and Water-Based Processes
Authors: Dautain Nicolas , Peralta David , Martin Jean-Frédéric , Sotta Dane , Azaïs Philippe
Published: August 2024

Current Li-ion batteries are mainly composed of a graphite anode and a cathode based on either NMC (LiNixMnyCozO2) or LFP (LiFePO4) materials. However, the rapid growth of the electric car market will generate significant stress on key chemical elements (nickel, cobalt, copper, lithium). Moreover, the production of NMC and LFP materials turns out to be very energy intensive (multiple calcinations) and uses toxic solvents (NMP, ammonia). Because of that, Li-ion batteries are quite expensive and their ecological footprint is relatively high.

The scope of our work is to develop a potassium-ion battery which does not require any critical element and whose production significantly reduces the ecological footprint of the system. Such a battery technology could find its place either in low-cost electric cars or in large-scale-energy-storage devices.

We focused our efforts on the development of a Prussian White cathode material based on potassium, manganese and iron (K2Mn[Fe(CN)6) showing a theoretical capacity of 155 mAh/g with a potential close to 4 V vs K+/K. The synthesis of this material takes place in water at ambient temperature and it does not involve any calcination. First we optimized the synthesis via a chelating route: tuning the morphology of the Prussian White particles allowed us to come closer to the theoretical capacity of the material. Then we developed water-based coating slurries for our material. We were able to obtain electrodes containing 90 wt% of active material by optimizing both carbon additive and binder. These electrodes showed similar performances compared to electrodes obtained with literature-standard conditions (70 wt% active material, NMP-based slurries). Finally, we tested our Prussian White in full cells versus graphite in coin cells and pouch cells.

Figure 1
Development of Binderless Graphite Compact for Bipolar Plate Production
Authors: Paradis Linsea , Mena-Garcia Javier , Rajagopalan Ramakrishnan
Published: August 2024

Bipolar plates account for almost 29% of the fuel cell stack costs and hence cost-effective manufacturing methods for making the bipolar plates are of paramount importance. Current manufacturing technologies for graphite bipolar plates require consolidation of graphite precursor materials using compression or injection molding followed by high temperature treatment for baking and graphitization. In contrast, in this investigation, we demonstrate direct consolidation of graphite powders without the use of any coal, petroleum or polymer binders resulting in significant reduction of time during compression molding as well as elimination of the need for additional heat treatment. Graphite particles were electrolessly coated with copper particles and subject to uniaxial compression at 100°C to produce a highly dense compact with relative density of ~ 98%, The process resulted in improving the flexural strength of the compact by almost ~50%. TEM investigation of the graphite particle interfaces revealed that copper undergoes creep deformation that aids in strengthening the compacts. The paper will describe the underlying mechanisms for the binderless production of graphite compacts which could be potentially useful for energy and cost-effective production of bipolar plates for fuel cells and flow batteries.
Interrelationship between Different Aspect of Materials for Low Temperature Water Splitting Technologies
Authors: Ogitsu Tadashi
Published: August 2024

One of challenging aspects of developing novel functional materials for water splitting technologies (or computational materials design in general) is that there are usually correlation between different aspect of material properties that are both relevant for the device performance, such as activity of catalyst and its stability, therefore focusing only on one (or limited number of) aspect does not necessary lead to satisfactory outcome as such a correlation tend to be detrimental in nature with small number of exception [1,2,3]. In this presentation, we will review our effort in understanding various cases of such conflicting conditions, in screening catalyst (stability vs activity[4]), in identifying materials synthesis condition (presence of competing phases[5,6]), in understanding the effect of operation conditions (ex. reaction vs diffusion of intermediates[7,8]/operation condition vs transport[9,10]). We will discuss possible strategies that could help us deconvoluting such correlating factors so as to accelerating materials discovery/development for low temperature water splitting technologies and beyond [11].

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N. Gaillard et al., Mater. Adv. 2, 5752 (2021)

J.A. Trindell et al., Chem. Mater. 34, 7712 (2022)

J.C. Fornaciari et al., Electrochimica Acta 405, 139810 (2022)

Z. Zou et al., ACS App. Ener. Mater. DOI:10.1021/acsaem.3c02136 (2023)

A.J.E. Rowberg et al., Mater. Adv. 4, 6233 (2023)

A.J.E. Rowberg et al., Phys. Rev. Mater. 7, 015402 (2023)

M.D. Witman et al., Nature Comp. Sci. 3, 675 (2023)
Intrinsically Microporous Ion-Pair Membranes for HT-PEMFCs
Authors: Lee Albert S
Published: August 2024

Fuel cells are electrochemical devices with high energy efficiency expected to be applied economically and eco-friendly across various energy sectors. Low-temperature polymer electrolyte membrane fuel cells (LT-PEMFCs) using Nafion operates at a relatively low operating temperature (60-80°C) and fully hydration condition. HT-PEMFC is operable at high temperatures (140-180°C), but requires anhydrous conditions to avoid loss of doped phosphoric acid (PA). In this presentation, polymer membranes designed through with intrinsic microporosity were synthesized through super acid polycondensation. We demonstrated that high proton conductivity (106.33 mS cm-1 at 180℃) is obtained by forming phosphoric acid filled ion-channels within the interconnected microporous structure. Moreover, ion-pair coordinated PIMs are fabricated by methylation of PIMs to improve PA retention even under humidified conditions. It is suggested that the water tolerance of ion-pair coordinated PIMs is improved and can be operated under various conditions regardless of humidification and operating temperature and exceptional membrane electrode assembly performance and durability achieved even under humidified reformate gas conditions.
(Invited) Electrolyte Design for Wide-Temperature Lithium Batteries
Authors: Chen Zheng
Published: August 2024

Improving the wide temperature performance of rechargeable batteries is vital to the operation of electronics and vehicles in extreme environments, where systems capable of higher energy, high-rate discharge and long cycling are in short supply. In this talk, we will show electrolyte designs to achieve high-energy density and stable cycling performance in wide temperature range, especially in extremely low-temperature environment. We will use a few examples, including ester- and ether-based electrolyte with different concentrations to showcase the critical role of solvation and desolvation in determining the charge-transfer kinetics at low-temperature. We will also discuss the role of solvation structure in shaping interfacial stability in different cathode and anode systems. These fundamental understanding may provide viable design strategies for high energy density and long-life batteries for both high and extremely low temperatures such as rechargeable Li metal batteries using both high-Ni oxide and sulfur cathodes.
Mechanistic Insights on Direct Ammonia Solid Fuel Cell Using Ni-YSZ Anode: Experimental and Density Functional Theory Studies
Authors: Elmutasim Omer , Dhawale Dattatray S , Giddey Sarbjit , Paul Gary , Bhattacharya Sankar
Published: August 2024

While Ni-Yttria-stabilized zirconia (Ni-YSZ) cermet exhibits a great potential to realize high-efficiency ammonia to power using direct ammonia solid oxide fuel cell (DA-SOFC), the mechanisms of NH3 cracking and H2 oxidation reactions as well as direct electro-oxidation of ammonia are still unclear. In this context, with the motivation, the DA-SOFC performance of fuel electrode (Ni-YSZ) using conventional anode-supported cell (Ni-YSZ|YSZ|GDC-LSCF) is studied through microscale observation coupled with density functional theory (DFT) calculations to unravel the reaction mechanisms on Ni-YSZ(111) anode. The performance of DA-SOFC is examined using NH3, H2 and N2/H2 mixture as fuel at the temperature range of 700-800℃. In addition to XRD and SEM-EDX characterizations, the electrochemical characterization is performed using the impedance spectroscopy (EIS) measurements at three different temperatures of 700, 750 and 800 °C. Interestingly, the experimentally observed trend in Open-circuit voltage (OCV) implies that direct electro-oxidation of ammonia is the dominant reaction mechanism. Notably, polarization resistance is primarily contributed by ammonia anodic reaction and secondarily by the gas diffusion impedance. DFT results revealed that ammonia adsorbs favorably on the Ni cluster, and hydrogen follows a dissociative mode of adsorption on the Ni cluster. The activation barriers of elementary steps involved in the proposed mechanisms for fuel cracking and oxidation reactions are computed. This work is anticipated to provide valuable insights into the rational design of Ni-YSZ-based fuel electrodes.

Keywords: ammonia, hydrogen, SOFC, fuel cells, DFT, reaction mechanism
Controlled Catalyst Layer Architectures for Fuel Cell Applications
Authors: Ghosh Arpita , Walrand Gilles , Rozière Jacques , Jones Deborah J. , Cavaliere Sara
Published: August 2024

The catalyst layer composition and architecture play a pivotal role in bridging the gaps between ex situ and in situ catalyst activities in fuel cells.1 The catalyst-support architecture strongly influences the catalyst distribution, ionomer distribution and mass transport losses, occurring at high current density.2 Herein, a novel architecture based on self-standing fiber-network has been fabricated and characterized.3 The resulting porous structure of such catalyst layer is expected to control mass transport limitation across both the interface of catalyst layer by increasing the number of Triple Phase Boundaries. Further platinum catalyst is deposited onto this fibrous support as well as the ionomer. The full electrode is characterized for its morphology and electrochemically verified in both ex situ as well as in situ configurations.

References

(1) Jiantao Fan, Ming Chen, Zhiliang Zhao, Zhen Zhang, Siyu Ye, Shaoyi Xu, Haijiang Wang & Hui Li, “Bridging the Gap between Highly Active Oxygen Reduction Reaction Catalysts and Effective Catalyst Layers for Proton Exchange Membrane Fuel Cells”,
Nature Energy,

6, 475–486, (2021).

(2) Nagappan Ramaswamy, Wenbin Gu, Joseph M. Ziegelbauer and Swami Kumaraguru, “Carbon Support Microstructure Impact on High Current Density Transport Resistances in PEMFC Cathode”,
Journal of The Electrochemical Society
,167, 064515, 2020.

(3) Giorgio Ercolano, Filippo Farina, Sara Cavaliere, Deborah J. Jones and Jacques Rozière, “Towards Ultrathin Pt Films on Nanofibers by Surface-Limited Electrodeposition for Electrocatalytic Applications”,

Journal of Materials Chemistry A

,
5, 3974–3980, 2017.
Long Time Dynamics for Platinum Surface Area Loss in PEM Fuel Cells
Authors: Van-Brunt Alexander John , Beck Victor , Braaten Jonathan , Cheng Lei , Mehrazi Shirin , Stewart Sarah , Stuhmeier Bjorn Marcel , Mojica Felipe
Published: August 2024

Proton exchange membrane (PEM) fuel cells may emerge as a dominant clean energy source for heavy duty transport vehicles. Amongst other considerations, the lifetime performance of the fuel cell cathode catalyst layer is a key component of their future viability and a focus in the development of many proposed membrane electrode assemblies (MEAs). Typical targets of the lifetime of a PEMFC stack are on the order of thousands of hours of operation. However, running degradation tests spanning those long timescales is often impractical; and consequently, extensive work has been done developing and implementing accelerated stress tests (AST's) in order to screen proposed cathode catalyst materials for fuel cells.

Much value is obtained by accurate and robust lifetime prediction models which are able bridge the gap between degradation from AST's in differential cells, and degradation of the catalyst layer in a fuel cell stack under realistic operating conditions. In other words, by parameterizing a model on short-time, subscale ASTs and extrapolating to a stack after tens of thousands of hours of operation. Commonly in such models, the electrochemically active surface area (ECSA) of platinum is used as the primary state-of-health parameter and predicted using either data-driven models or physics-based models. On one hand, data-driven models may be well suited to utilize large sets of stack data, but offer weaker extrapolation potential, conversely fitting physics-based models on global measurements of stack data is rarely a well-conditioned inverse problem.

In this talk we present a scaling law on the long-time behavior of the ECSA obtained from analysis of governing physics equations from the literature. It is assumed that the primary loss mechanism is the coarsening of platinum particles, and the chief technique used is the method of averaging, which allows for the separation of two timescales: the short timescale of platinum oxide formation and dissolution, and the longer timescale over which the particle size distribution changes and a performance loss can be detected. The physics-derived asymptote for the ECSA evolution is then applied to several experiments and found to be in good agreement, allowing for a simple, streamlined lifetime prediction method for PEM fuel cells.
Regulation of Transition Metal Doping into Double Perovskite Structure as for a Electrocatalyst in Water Electrolysis
Authors: Han Kyeongwon , Kim Hyungjin , Song Jeongeun , Park Hyeonji , Jeon Yukwon
Published: August 2024

Applying and combining of transition metals to perovskite structure is significantly dealt for improving the electrochemical property. The introduction of transition metals in the active B-site is considered as a useful pathway to regulate the chemical and electronic properties of the perovskites. In this study, a double perovskite structure (A2BB’O6) is designed to apply large ionic radius elements such as tungsten(W) that can not be doped into the general single perovskite structure(ABO3). Tungsten is normally equilibrium in the metallic phase, but tungsten ions rapidly move from 4+ state to the 6+ state in the oxide phase, boosting the electrochemical property. The W-based double perovskite materials are synthesized by a high temperature solid-state method. With a combination of Calcium (Ca) doped in the B-site for structural stabilization, transition metals (Ni, Co, etc.) are doped together as an active site to enhance the electrochemical performance. To analyze the physical and chemical structural characteristics, XRD with Rietveld refinement, XPS and XANES/EXAFS measurements are used. Rotating Disk Electrode (RDE) system is utilized to confirm the electrochemical performance of the prepared samples. Through cyclic voltammetry (CV) and linear sweep voltammetry (LSV) measurements, oxygen involved reactions are carried out to prove possibility on our W-based double perovskite materials as a high performance oxygen electrocatalyst with low-price.
Optimization of Pd–Co–M (M= Cu, Au, Ni) Catalysts for the Oxidation of Formic Acid Using Scanning Electrochemical Microscopy
Authors: Weng Yu-Ching , Chiang Chieh-Lin
Published: August 2024

Formic acid, a versatile substance with applications as both a fuel and hydrogen storage material, emerges as a promising energy source. When utilized as a hydrogen storage material, a single liter of formic acid yields an impressive 590 liters of hydrogen gas under ambient conditions. Furthermore, as a fuel, the Direct Formic Acid Fuel Cell (DFAFC) stands out as a potential energy solution due to its elevated open-circuit voltage, low toxicity, and reduced permeability of high molecular weight membranes. Efficient catalysts play a pivotal role in enhancing the formic acid oxidation reaction, thereby diminishing the anode overpotential and amplifying the hydrogen production efficiency of DFAFC. The conventional method of manually testing each catalyst for optimal formic acid oxidation performance is both time-consuming and resource-intensive. Consequently, this study employs a substrate collection method based on a scanning electrochemical microscope (SECM) microelectrode for catalyst screening. A ternary catalyst array, primarily comprising PdCo with supplementary elements (Au, Cu, Ni), was crafted using the innovative concept of compositional assembly. The SECM facilitated the determination of the catalyst's surface morphology, energy-dispersive spectroscopy gauged the catalyst composition, and X-ray diffraction, along with X-ray photoelectron spectroscopy, confirmed the crystalline structure composition. To delve into the kinetic aspects of the catalyst for formic acid oxidation, a comprehensive analysis was carried out using cyclic voltammetry, stripping voltammetry, electrochemical impedance spectroscopy, and Tafel slope analysis. The outcomes unveiled that the optimal proportions for the ternary catalysts were Pd2Co6Au2, Pd2Co6Cu2, and Pd2Co6Ni2, with Pd2Co6Au2 exhibiting superior attributes such as lower overpotential, heightened resistance to CO poisoning, and enhanced catalytic activity for formic acid oxidation.
Lunar Electrochemistry Enabling Microgrid Energy Storage on the Moon
Authors: Li Yifan
Published: August 2024

This talk will cover an atypical paradigm of large scale energy storage technology - the need for scalable energy storage using resources available at the point of use for sustained human presence in space exploration. For Lunar surface power reliability, large scale energy storage enables increased safety factor for power generation downtime, but the launch mass of energy storage makes scalable storage to the level of microgrids or grids unappealing. This is compounded by a central paradox of safe energy storage, that achieving high energy density intrinsically carries greater safety risk in storing greater energy in a smaller mass or volume. In situ resource utilization aims to solve both these problems, enabling safe and scalable energy storage to be deployed for Lunar surface power reliability. However, a long road remains between the nascent field of ISRU energy storage as it exists today and its needed destination to enable future sustained human presence on the Moon and Mars.

This talk will survey applications of electrochemical energy storage technologies and concepts with a focus on how Lunar resources can principally drive the electrochemistry. Brief mention will be given to non-electrochemical technologies such as thermal or mechanical methods, but the emphasis will be on electrochemistry owing to rapid advances in electrochemical state-of-the-art on Earth. Examples will include beyond Li-ion intercalation chemistry, metal-air cells, redox flow batteries, and regenerative fuel cells, using Lunar regolith and water as primary resources. For each technology, the talk will highlight where the study of “Lunar electrochemistry” must deviate from current terrestrial research to enable energy storage optimized for ISRU, rather than a simple transplant of Earth technology to Lunar application.
(Industrial Electrochemistry and Electrochemical Engineering Division H. H. Dow Memorial Student Achievement Award) Tailoring Electrode-Electrolyte Interfaces through Non-Covalent Interactions for Electrochemical Energy Storage and Conversion
Authors: Zhang Yirui Arlene , Wang Tao , Fraggedakis Dimitrios , Huang Botao , Stephens Ryan , Bazant Martin Z. , Shao-Horn Yang
Published: August 2024

Li-ion batteries and fuel cells play essential roles in electrifying transportation. Central to the electrochemical systems is the electrode-electrolyte interface, where (electro)chemical surface reactions or intercalation occur, and its thermodynamic and kinetic properties determine the energy density, power density, and lifetime of the electrochemical devices. However, the molecular structures at the electrical double layer and reaction mechanisms remain poorly understood, hindering the rational material design for more efficient electrochemical devices. This talk focuses on the mechanisms of (electro)chemical reactions and charges transfer kinetics at the electrode-electrolyte interface, providing design principles based on non-covalent interactions in electrolytes.

First, an in situ Fourier-transform infrared spectroscopy (FTIR) method was developed for Li-ion batteries, which revealed unique evidence for dehydrogenation of carbonate electrolytes on Ni-rich lithium nickel, manganese and cobalt oxides (NMC), accounting for interface impedance build-up and battery capacity fading. Based on the proposed mechanism, strategies on suppressing electrode and electrolyte reactivity were demonstrated to improve battery cycling. Next, the kinetic mechanism for ion intercalation at the electrode-electrolyte interface will be discussed. Li-ion concentration-dependent intercalation kinetics was demonstrated from charge-adjusted electrochemical experiments and fit into a coupled ion-electron transfer mechanism, which governed the current-dependent maximum capacity and power density of intercalation batteries. Finally, for electrocatalytic reactions central to fuel cell technologies, we demonstrated tuning interfacial hydrogen bonding through protic ionic liquids with different acid dissociation constants and organic solvents with different donor numbers to tailor oxygen-reduction reaction (ORR) and hydrogen evolution reaction (HER). Strengthening hydrogen bonding between ORR products and ionic liquids, or between interfacial water molecules facilitated proton-coupled electron transfer kinetics, revealed by in situ surface-enhanced infrared absorption spectroscopy and density functional theory (DFT) calculations. The study can pave the way for the electrolyte and electrode design of electrochemical storage devices with improved energy and power density and cycle life.
(Invited) Scalable Synthesis of Low Carbon Fuels via CO2 Electrolysis
Authors: Ma Sichao , Zhao Shuai
Published: August 2024

Over three trillion tons of greenhouse gasses have been emitted since the start of the industrial revolution, with dire consequences for our climate, including an increase in the regularity of natural disasters such as heatwaves, wildfires, and hurricanes. Cost-effective, industrial-scale CO2 recycling using renewable energy sources could form the basis of an artificial carbon cycle to produce the same products that are currently derived from fossil resources while mitigating greenhouse gas emissions. Towards this end, Twelve is developing a highly efficient and scalable electrochemical reactor that converts CO2 into valuable building blocks for chemicals and fuels such as carbon monoxide (CO). The resulting CO can be blended with green hydrogen from water electrolyzers to form syngas, enabling an ultra-low carbon pathway to sustainable aviation fuel (SAF) via the Fischer-Tropsch process. At scale, this technology could eliminate the aviation industry’s dependence on fossil resources by providing an alternative source of carbon-based compounds for jet fuel. Twelve is presently scaling up the technology to reduce production costs and achieve industrially relevant production rates. This talk will present Twelve’s CO2 electrolysis technology and highlight collaborative development efforts towards our commercialization goals.
(Invited) Tailored Electrochemical Interfaces for Renewable Fuels Production
Authors: Escudero-Escribano Maria
Published: August 2024

Tailoring the structure of the electrified interface and the electrocatalytically active sites at the atomic and molecular levels is key to elucidating the design principles to develop advanced materials for sustainable energy conversion and storage. This talk will focus on recent strategies to tune the structure-activity-selectivity relationships for oxygen, carbon dioxide/carbon monoxide and methane electrocatalysis to produce renewable fuels.

First, I will present our work toward understanding and tuning the structure-property relations for oxygen evolution for the production of green hydrogen in proton exchange membrane water electrolysers. Then, I will show our model studies on well-defined Cu-based surfaces to understand structure-properties relations for the electrochemcial CO2 reduction reaction. We have investigated the effect of electrolyte, pH, and potential dependence for CO reduction on Cu single crystals as well as methods to evaluate the facet distribution on Cu-based catalysts. Finally, I will discuss some strategies for selective oxidation reactions such as partial oxidation of methane to produce liquid fuels such as methanol.
Fe-Single-Atom Catalysts on Nitrogen-Doped Carbon Nanosheets for Electrochemical Conversion of Nitrogen to Ammonia
Authors: K. Allam Nageh
Published: August 2024

Electrochemical nitrogen reduction reaction (NRR) has been established as a promising and sustainable alternative to the Haber–Bosch process, which requires intensive energy to produce ammonia. Unfortunately, NRR is constrained by the high adsorption/activation of the N2 energy barrier and the competing hydrogen evolution reaction, resulting in low faradic efficiency. Herein, a well-dispersed iron single-atom catalyst was successfully immobilized on nitrogen-doped carbon nanosheets (FeSAC-N-C) synthesized from pre-hydrothermally derived Fe-doped carbon quantum dots with an average particle size of 2.36 nm and used for efficient electrochemical N2 fixation at ambient conditions. The as-synthesized FeSAC-N-C catalyst records an onset potential of 0.12 VRHE, exhibiting a considerable faradic efficiency of 23.7% and an NH3 yield rate of 3.47 μg h–1 cm–2 in aqueous 0.1 M KOH electrolyte at a potential of −0.1 VRHE under continuous N2 feeding conditions. The control experiments assert that the produced NH3 molecules only emerge from the dissolved N2-gas, reflecting the remarkable stability of the nitrogen–carbon framework during electrolysis. The DFT calculations showed the FeSAC-N-C catalyst to demonstrate a lower energy barrier during the rate-limiting step of the NRR process, consistent with the observed high activity of the catalyst. This study highlights the exceptional potential of single-atom catalysts for electrochemical NRR and offers a comprehensive understanding of the catalytic mechanisms involved. Ultimately, this work provides a facile synthesis strategy of FeSAC-N-C nano-sheets with high atomic-dispersion, creating a novel design avenue of FeSAC-N-C that can vividly have a potential applicability in the large spectrum of electrocatalytic applications.
Electrocatalytic Upgrading of Biomass-Derived Compounds for Biofuel Production
Authors: Lam Jason Chun-Ho
Published: August 2024

Biomass fast pyrolysis liquid (also known as bio-oil) is considered to be one of the most promising renewable carbon feedstocks. However, fresh pyrolyzed bio-oil is acidic and corrosive and contains large amounts of carbonyl and phenolic compounds produced by polymerization under acidic conditions. This work primarily utilizes an electrochemical conversion strategy using only earth-abundant metal catalysts to achieve the carbonyl hydrogenation process. The results show that upgrading this process produces biofuels with greater stability and higher specific energy. In addition to analyzing the chemical implications of this conversion strategy, this work will also discuss why electrocatalytic conversion is a promising technology path for biofuels and fine chemicals.

Reference

Huang, S., Lam, C. H.* et al. (2022). "The Structural Phase Effect of MoS2 in Controlling the Reaction Selectivity between Electrocatalytic Hydrogenation and Dimerization of Furfural." ACS Catalysis 12(18): 11340-11354.

Huang, S., Lam, C. H.* et al. (2022). "MoS2-Catalyzed Selective Electrocatalytic Hydrogenation of Aromatic Aldehydes in an Aqueous Environment." Green Chemistry.

Tu, Q., Lam, C. H.* et al. (2021). "Electrocatalysis for Chemical and Fuel Production: Investigating Climate Change Mitigation Potential and Economic Feasibility." Environmental Science & Technology 55(5): 3240-3249.

Garedew, M., Lam, C. H.* et al. (2020). "Greener Routes to Biomass Waste Valorization: Lignin Transformation Through Electrocatalysis for Renewable Chemicals and Fuels Production." ChemSusChem 13(17): 4214-4237.

Lam, C. H., et al. (2017). "Towards sustainable hydrocarbon fuels with biomass fast pyrolysis oil and electrocatalytic upgrading." Sustainable Energy & Fuels 1(2): 258-266.

Figure 1
Electrochemical Ammonia Recovery from Manure Wastewater Integrated with Electrochemical Carbon Dioxide Reduction
Authors: Moeller Anneke , Wang Rui , Jin Song
Published: August 2024

There were 40 million cows in the US in 2020 which provide necessary protein-rich food and are integral to the US economy. However, . Currently manure is managed simply by storing and spreading to nearby cropland as a fertilizer to reuse nutrients. Given the high water content and low nutrient concentration of manure, effective approaches to recover nutrients from manure wastewater and reduce greenhouse gas emissions are needed. Our group has recently developed ammonia (potassium) recovery from manure wastewater and co-production of chemicals using nutrient-selective redox material1. I will report my progress toward developing a new electrochemical strategy to achieve integrated ammonium (and potassium) nutrient recovery from manure wastewater and simultaneous biogas upgrading by electrochemically reducing carbon dioxide to formate and other locally useful products. This project will effectively mitigate CO2 emissions in traditional manure processing and provide a sustainable strategy for resource recovery, distributed electrosynthesis of fertilizers and other value-added chemicals, paving the way to carbon-neutral agriculture.

Wang, R., Yang, K., Wong, C. et al. Electrochemical ammonia recovery and co-production of chemicals from manure wastewater. Nat Sustain (2023). https://doi.org/10.1038/s41893-023-01252-z
Multi-Physics Modeling and the Sensitivity Analysis for the Critical Factors in Solid Oxide CO2-Steam Co-Electrolysis System Performances
Authors: Wang Dewei , Bao Jie , Coyle Christopher , Marina Olga A
Published: August 2024

A multi-physics modeling framework, which includes electrochemical and chemical reactions, mass transfer, and energy balance, has been developed and validated against experiment measurements to investigate the performance of solid oxide CO2-steam co-electrolysis (SOEC) under various operating conditions and cell designs. However, multi-physics modeling for complex SOEC systems can be computationally expensive and not tractable for general system design and optimization. Reduced-order models (ROMs) have been proven as a powerful tool for reducing computational costs, closely mimic the high-fidelity SOEC stack models and identify the operational condition parameters to which the SOEC stack is sensitive and needs appropriate controls for stable operation. In this study, the deep neural networks (DNN) algorithm is employed to construct ROMs according to multi-physics simulations for SOECs to systematically investigate the SOECs’ electrochemical performance and rank the contributions of operational condition parameters for both 2 cm2 button cell and 300 cm2 planar cells. Sensitivity analysis reveals that cell voltage, fuel composition (denoted by CO2/H2O ratio), and the operating temperature impact the cell performance most. The product ratio ΔCO/ΔH2 has a stronger dependence on the CO2/H2O ratio in the fuel compositions than on other operating condition parameters. The large 300 cm2 planar cells were modeled under both adiabatic and furnace environment. The simulation and sensitivity analysis indicate that the large cell operating in adiabatic environment usually provides relatively lower performances than the one in furnace environment. Additionally, the adiabatic environment also causes the cell’s performances are more sensitive to the operation conditions, such as external voltage, fuel flow rate, and fuel compositions. The large cell in adiabatic environment also leads to higher internal temperature variation, which may impact the structure reliability.
(Invited) Durability of Solid Oxide Electrolysis Cells Via Accelerated Stress Testing
Authors: Marina Olga A , Le Long , Coyle Chris , Springer Renaldo , Karki Surendra , Liu Tian
Published: August 2024

In this work, we will present a systematic study of state-of-the-art SOEC cells for hydrogen production using Ni-YSZ and LSCF electrodes. SOEC cells were tested in a broad range of experimental conditions, while varying temperature, steam concentration, steam utilization, current, voltage, operating pressure, potential Cr and S contaminants as well as under dynamic operation. Accelerated stress testing was performed to map potential degradations in a shorter period of time and compare to testing under standard operating conditions. Following each test termination, extensive post-test characterization of Ni-YSZ and LSCF microstructures using SEM/EDS and TEM was performed to assess the extent of degradations, if new degradations were imposed, and to predict conditions where cell failure might occur.
Designing Stable Nanoparticles for Deforming Silicon Anodes in Lithium Ion Batteries
Authors: Joshi Shaunak , Tartakovsky Daniel , Tchelepi Hamdi
Published: August 2024

Silicon anodes in lithium-ion batteries are a promising next-generation battery technology offering ten times higher theoretical capacity than commercial graphite anodes. However, substantial volume changes (around 300%) associated with silicon anodes pose a significant challenge to the cycle life of these batteries. To understand the effect of the interaction between lithiation (diffusion) and mechanics (volume expansion, stress generation) on cycle life, a theoretical chemo-mechanical model of an isolated deforming silicon anode nanospherical particle is proposed in this study. Existing models, designed for low-capacity electrode materials, ignore the effect of deforming volume in the model formulation. Deforming volume, critical for high-capacity electrodes like silicon, is accounted for in the proposed model. Galvanostatic and potentiostatic operating conditions are considered. Simulations of the model help explain the importance of smaller particle sizes in observed longer cycle lives of silicon anodes. These enable mathematically accurate calibration of the partial molar volume of the material and determination of the developed mechanical stresses. Simulations of the proposed model help us optimize design parameters like particle size, particle thickness, and the charge rate/ applied voltage for elastic operation to ensure longer cycle lives of these batteries.

Figure 1
(Invited) Overcoming Electro-Chemo-Mechanical Limitations of Solid-State Battery Li-Metal and Na-Metal Anodes through 3D Architecture and Tailored Materials/Interfaces
Authors: Wachsman Eric D
Published: August 2024

Electro-chemo-mechanical expansion at metal/electrolyte interfaces is a rate limiting factor in solid-state lithium (SSLiBs) and sodium (SSNaBs) batteries. In this presentation we will explain the roles of composition, structure, and interfaces in achieving extremely high current densities for SSNaBs and SSLiBs of 30 mA/cm2 and 100 mA/cm2, respectively, without dendrites at room temperature and no applied pressure.
(Energy Technology Division Supramaniam Srinivasan Young Investigator Award) CO2 as a Building Block for Electrosynthetic Coupling to N- and S- Based Reactants
Authors: Kornienko Nikolay
Published: August 2024

Energy-intensive thermochemical processes within chemical manufacturing are a major contributor to global CO2 emissions. With the increasing push for sustainability, the scientific community is striving to develop renewable energy-powered electrochemical technologies in lieu of CO2-emitting fossil-fuel-driven methods. However, to fully electrify chemical manufacturing, it is imperative to expand the scope of electrosynthetic technologies, particularly through the innovation of reactions involving nitrogen- and sulfur- based reactants as products from water/CO2 electrolysis do not cover the full scope of industrial needs.

To this end, this talk focuses on my lab’s efforts not only in CO2 conversion in the use of this molecule as a building block. This entails the co-electrolysis of CO2 with additional small molecule reactants (N2, NO3
-, SO3
2-...) in generating products with C-N and C-S bonds like amides, urea, and sulfonates that are important as commodity and fine chemicals in the chemical industry. In particular, I will discuss several new reaction pathways discovered towards several of the above-mentioned products and the application of operando techniques to understand the key C-N/C-S coupling steps in the reaction process.

Figure 1
(Invited) Fundamentals of Single Atom Alloy Catalysts for Electrochemical Nitrate Reduction to Ammonia
Authors: Rivera Daniel , Gupta Srishti , Muhich Christopher L
Published: August 2024

Electrochemical conversion of toxic nitrate into useful ammonia provides a route to remediating the most frequent water pollutant while simultaneously generating one of the most produced bulk chemicals. While highly desirable, this conversion is plagued by complications including a highly branching reaction pathway - which can produce highly toxic undesirable products, the need to reduce a negatively charged species, a relatively low nitrate concentration, and competition for electrons between nitrate reduction and parasitic hydrogen evolution. Therefore, electrocatalysts must be developed which are highly selective not only for nitrate over other species in the water matrix, but also selective to the desired ammonia product. Single atom alloy catalysts, where a single atom of one element is embedded in a solvating phase of a secondary element, provides an opportunity to engineer catalysts with atomic level precision. In this presentation, we will outline the fundamental behavior of single atom alloy for nitrate reduction. We explore this topic through density functional theory calculations of the reaction mechanisms, including thermodynamics and kinetic aspects. Particularly, we will discuss the effect of single atom identity, effect of matrix element, and pH and potential. We show that the ability of the single atom to localize the N* species drives the reduction towards ammonia formation, as exemplified by Ru in Cu, while facile exchange of N* between the single atom site and the matrix leads to the formation of N2 or other undesirable products, as exemplified by Pd in Cu and Au in Cu, respectively. We also discuss the importance of the selection of the solvating element; for example, Cu is a good solvating metal because it is a good conductor, while minimizing the hydrogen evolution reaction. Further, we discuss the limits of pH and potential on the performance. In general, higher pH and more moderately negative potentials favor nitrate reduction to NH3 or N2, while lower pH and more negative potentials drive H2 evolution, and generation of NOx species.
A Strategy to Enhance Photo-Algal Hydrogen Production Using External H+ Ions in a Dual Photobioreactor
Authors: Hwang Jae-Hoon , Lee Woo Hyoung
Published: August 2024

The use of microalgae for direct biohydrogen energy generation exhibits significant promise as an alternative to traditional bio-energy production due to zero-emission of CO2. It is known that during photolysis, algae are capable of producing hydrogen (H2) gas instead of oxygen (O2) under enriched acetate conditions by algal fermentative metabolisms [1]. The utilization of acetate as a practical oxygen regulator in photosystem II (PSII), but the algal hydrogen production was relatively low due to the insufficient H+ ions available in the photobioreactor (PBR) [2]. Therefore, given that hydrogen ions from acetate contribute to H2 production, it is still unclear whether supplying additional external H+ ions can enhance H2 production.

Here, we demonstrate a feasibility study on improving algal H2 production using a dual PBR system. This system enables the continuous transfer of H+ ions generated from photolysis to an algal H2 PBR through a proton exchange membrane (PEM), thereby enhancing photo-algal hydrogen production. The maximum H2 production of 108 µmol L-1 was obtained for Chlamydomonas reinhardtii in a single PBR for 15 days at a light intensity of 100 µmol m-2 s-1 [3]. However, by leveraging the external H+ ions supply, the dual PBR system increased photo-algal hydrogen production from 108 up to 760 µmol L-1 for the same period, which is 7 times greater compared to single chamber operation. This indicates that supplying external H+ ions in the operation of the dual PBR is one of the important parameters for improving biohydrogen production. Our findings contribute to the ongoing development of high-performance algal H2 production, offering valuable insights into optimizing the amount of H+ ions for enhanced hydrogen production.

[1] Clemens KL, Force DA, Britt RD. Acetate binding at the photosystem II oxygen evolving complex: an S2-state multiline signal ESEEM study. J Am Chem Soc. 2002;124(36):10921-33.

[2] Hwang J-H, Church J, Lim J, Lee WH. Photosynthetic biohydrogen production in a wastewater environment and its potential as renewable energy. Energy. 2018;149:222-9.

[3] Hwang J-H, Lee WH. Continuous photosynthetic biohydrogen production from acetate-rich wastewater: Influence of light intensity. Int J Hydrogen Energy. 2021;46(42):21812-21.
Concepts for Sustainable Organic Electrosynthesis
Authors: Francke Robert
Published: August 2024

Organic electrosynthesis is frequently presented as an intrinsically sustainable, safe, and efficient method [1]. While this is indeed often the case, this assessment cannot be easily generalized, since several challenges need to be addressed on the way to more efficient and truly sustainable processes. These challenges comprise the necessity for employing large amounts of supporting electrolyte additives along with concomitant separation and waste issues [2]. Another separation problem arises when mediators have to be employed for controlling the selectivity [3]. In addition, highly flammable and toxic solvents are often used.

The present contribution will provide an overview of our recent work on the development of new approaches toward improving the practicality and sustainability of electro-organic reactions. Several concepts will be discussed, including polymediator-guided electrosynthesis [4], multi-functional supporting electrolytes [5], and electrolysis in sustainable solvents [6].

References:

a) M. Yan, Y. Kawamata, P. S. Baran, Chem.
Rev.
2017, 117, 13230. b) A. Wiebe, T. Gieshoff, S. Möhle, E. Rodrigo, M. Zirbes, S. R. Waldvogel, Angew.
Chem.
2018, 57, 5594.

a) R. Francke, Chimia
2020, 74, 49. b) R. Francke, Curr. Opin. Electrochem.
2022, 36, 101111.

a) R. Francke, R. D. Little, Chem. Soc. Rev.
2014, 43, 2492. b) R. Francke, B. Schille, M. Roemelt, Chem. Rev.
2018, 118, 4631.

A. Prudlik, N. Mohebbati, L. Hildebrandt, A. Heck, L. Nuhn, R. Francke, Chem. Eur. J.
2023, 29, e202202730. b) N. Mohebbati, A. Prudlik, A. Scherkus, A. Gudkova, R. Francke, ChemElectroChem
2021, 8, 3837. c) B. Schille, N. O. Giltzau, R. Francke, Angew. Chem. Int. Ed.
2018, 57, 422.

a) A. F. Roesel, T. Broese, M. Májek, R. Francke, ChemElectroChem.
2019, 6, 4229. b) O. Koleda, T. Broese, J. Noetzel, M. Roemelt, E. Suna, R. Francke, J. Org. Chem.
2017, 82, 11669. c) T. Broese, R. Francke, Org.
Lett.
2016, 18, 5896.

A. Prudlik, A. Matei, S. Beil, R. Francke, 2024, manuscript in preparation.
Reusable Cyclodextrin-Mediated Electrochemical Sensor in Automated Flow Cell for Cortisol Detection
Authors: Sajedi Ferdows , Halpern Jeffrey M.
Published: August 2024

Our focus is on using beta cyclodextrin (βCD) to electrochemically detect cortisol; cortisol is a hydrophobic molecule that is a vital hormone, and cortisol is involved in the immune system, metabolism, heart health, and overall body balance. Cyclodextrins, characterized by a hydrophobic inner cavity and a hydrophilic outer surface, emerge as promising molecular receptors for detecting hydrophobic molecules. Notably, βCD and cortisol can form host/guest inclusion complexes. Building on our success in detecting cortisol with βCD in previous static cell experiments [1], herein we introduce innovations to further improve our methodology by employing an automated flow cell system. The transition to automation offers advantages such as repeated runs for obtaining more reproducible data and the elimination of human interactions and considerations, leading to an increased number of experiments. Our efforts, including the utilization of a ten-way multi-position valve and a pump for solution transfer, were crucial for enhancing the accuracy, stability, and reproducibility of cyclodextrin-mediated biosensors in automated flow cell systems. The automation process did encounter challenges, particularly with pump control, necessitating manual pauses before electrochemical measurements. Additionally, issues related to bubbles arose, prompting the search for the optimal flow rate and the utilization of a degasser. The ultimate goal is to optimize sensor stability, sensitivity, and reproducibility, contributing to the advancement of cortisol detection with the automated cyclodextrin-mediated biosensors.

Research supported by New Hampshire- INBRE through an Institutional Development Award (IDeA), P20GM103506, from the National Institute of General Medical Sciences of the NIH. Support was also provided by a National Science Foundation EPSCoR award (#2119237), BIO-SENS.

[1] Z. Panahi, T. Ren, and J. M. Halpern, “Nanostructured Cyclodextrin-Mediated Surface for Capacitive Determination of Cortisol in Multiple Biofluids,” ACS Appl. Mater. Interfaces, vol. 14, no. 37, pp. 42374–42387, Sep. 2022, doi: 10.1021/acsami.2c07701.