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PtRuC offers the opportunity to electrochemically convert bio-oils to drop-in biofuels and platform chemicals. Here we demonstrate the concept using phenol to cyclohexane as a model reaction.
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Abstract Lithium‐ion battery (LIB) electrodes are typically produced with n‐methyl‐2‐pyrrolidone, a toxic solvent that is a known carcinogen and reproductive hazard. Accordingly, aqueous processing has been an expanding area of research interest in the field of LIB manufacturing. Although aqueous processing has been widely successful in anode processing, serious challenges remain in processing the cathode. In this work, the drying mechanics of cathode processed with both solvents is investigated though implementation of a chemical‐engineering‐based model to better understand the utilization of heat provided by experimentally determining the heat and mass transfer coefficients. Electrochemical performance is also evaluated to determine the impact of drying temperature on cycling performance. Binder distribution is determined via various methods to confirm differences in binder homogeneity as a function of both solvent and drying temperature. Identified is the large difference in the efficiency in which the heat is used as well as an ideal drying temperature for both aqueous and non‐aqueous processed cathodes. Also identified is the increased sensitivity to processing temperature for aqueous processed electrodes compared to non‐aqueous processed counterparts, pointing to the possibility of tuned drying regimes which would capitalize on the potential cost savings of aqueous processing for cathodes.
Classical electric double layer (EDL) models have been widely used to describe ion distributions at charged solid-water interfaces in dilute electrolytes. However, the chemistry of EDLs remains poorly constrained at high ionic strength where ion-ion correlations control non-classical behavior such as overcharging, i. e., the accumulation of counter-ions in amounts exceeding the substrate's surface charge. Here, we provide direct experimental observations of correlated cation and anion distributions adsorbed at the muscovite (001)-aqueous electrolyte interface as a function of dissolved RbBr concentration ([RbBr]=0.01–5.8 M) using resonant anomalous X-ray reflectivity. Our results show alternating cation-anion layers in the EDL when [RbBr]≳100 mM, whose spatial extension (i. e., ~20 Å from the surface) far exceeds the dimension of the classical Stern layer. Comparison to RbCl and RbI electrolytes indicates that these behaviors are sensitive to the choice of co-ion. This new in-depth molecular-scale understanding of the EDL structure during transition from classical to non-classical regimes supports the development of realistic EDL models for technologies operating at high salinity such as water purification applications or modern electrochemical storage.
Here, the move toward nonfluorinated hydrocarbon ionomers for fuel cells and electrolyzers is driven by potential restrictions on polyfluoroalkyl substances such as Nafion. This study examines the key limitations of hydrocarbon ionomers through half- and single-cell experiments with model hydrocarbon ionomers. Half-cell tests reveal three major performance barriers: undesirable adsorption, electrochemical oxidation, and low gas permeability. Competitive sulfate adsorption helps counteract ionomer adsorption and oxidation. These findings align with single-cell performance data, which further reveal additional oxygen mass transport limitations likely caused by localized electrode flooding. Together, these findings offer valuable insights to guide the development of high-performance, fluorine-free hydrocarbon ionomers for next-generation fuel cells and electrolyzers.
The potential for extracellular electron transfer (EET) is a prevailing genomic feature of humic lake bacterioplankton. However, there has been little evidence for the substantial ecological contribution predicted by genetics. We hypothesized that anoxygenic phototrophic electrotrophs and accompanying heterotrophic electrogens cycle dissolved organic matter (DOM) between oxidized and reduced states. We predicted that such bacterioplankton would exhibit diel-scale oscillations due to the light dependency of photosynthesis. Using Trout Bog Lake in Wisconsin, USA, as our model ecosystem, we profiled the water column with depth-discrete metagenomic, physiochemical, and electrochemical analyses. We observed variation in oxidation reduction potential (ORP) in response to sunlight, initiating at depths populated by anoxygenic phototrophs with EET genes. We developed an automated buoy to measure electric current flow between many pairs of electrodes simultaneously, observing correlation in electron consumption to sunlight. Our results, combined with published metatranscriptomic analysis, indicate the occurrence of electron cycling between phototrophic oxidation (electrotrophic metabolism) by Chlorobium and anaerobic respiration (electrogenic metabolism) by Geothrix, involving DOM. We also repeatedly observed gradual seasonal increases in hypolimnion ORP throughout summer. These diel and seasonal patterns imply that electroactive DOM mediates the ecology of electroactive bacteria in lakes, controlling humic lake methane emissions.IMPORTANCEWe investigated the physical, chemical, and redox characteristics of a bog lake and electrodes hung therein to test the hypothesis that dissolved organic matter is being cycled between oxidized and reduced states by electroactive bacterioplankton powered by phototrophy. To do so, we performed field-based analyses on multiple timescales using both established and novel instrumentation. We paired these analyses with recently developed bioinformatics pipelines for metagenomics data to investigate genes that enable electroactive metabolism and accompanying metabolisms. Our results are consistent with our hypothesis and yet upend some of our other expectations. Our findings have implications for understanding greenhouse gas emissions from lakes, including electroactivity as an integral part of lake metabolism throughout more of the anoxic parts of lakes and for a longer portion of the summer than expected. Our results also give a sense of what electroactivity occurs at given depths and provide a strong basis for future studies.
Designing electrolytes based on mixture of different organic redox active molecules brings the opportunity of enhancing the volumetric energy density of flow batteries and removes the requirement of high solubility for individual organic species in the mixture. Here, in the present work, we conduct computational and experimental analysis to investigate the electrochemical performance of mixed redox-active organic molecules. A zero-dimensional transient model is employed to investigate the changes in the half-cell potential and the concentrations and partial currents of individual redox reactions in a mixture of organic molecules over time. The model demonstrates the effects of individual properties of species such as kinetic rate constants, mass transfer coefficients, concentration ratios and standard redox potentials and reports the effect of energy-losing homogenous chemical redox reaction on the voltage efficiency and concentration ratios of the mixed species. Pairs of anthraquinone negolyte species were selected for an experimental case study. A mixture of 2,6-N-TSAQ and 2,6-DHAQ showed 40% increase in the volumetric energy density compared to the performance of 2,6-DHAQ alone. Based on the results of the experimental and computational analysis, we propose guidelines for the design of suitable mixed redox-active organic species.
Tandem catalysis involves two or more catalysts arranged in proximity within a single reaction vessel, with the aim of synergistically aligning the catalysts’ reaction pathways to maximize overall system performance. This study presents a proof of concept showing the integration of continuum transport modeling with design optimization in a simplified two-dimensional flow reactor setup for electrochemical CO 2 reduction. Ag catalysts provide the CO 2 ⟶ CO reaction capability, and Cu catalysts provide the CO ⟶ high-value products reaction capability. Given a set of input parameters, the optimization algorithm uses adjoint methods to modify the Ag/Cu surface patterning in order to maximize the current density toward high-value products, such as ethylene. The optimized designs yield significant performance enhancement especially at more negative applied voltages (i.e., stronger surface reactions) and for larger numbers of patterning sections. For an applied voltage of −1.7 V vs. SHE, the 12-section optimized design increases the current density toward ethylene by up to 65% compared to the unoptimized 2-section design. For the optimized cases, observed differences in the production and consumption of CO (the key intermediate species) and minimized zones of low CO reactant surface concentration on Cu sections explain the improved reactor performance.
Siloxanes, as a type of impurity in biogas, can poison the Ni-YSZ anode of SOFCs. However, the influence of individual components of the anode, such as Ni, ZrO 2 , and Y 2 O 3 , on the siloxane deposition process has not been investigated extensively. In this study, Ni, ZrO 2 , and Y 2 O 3 pellets were exposed to H 2 + N 2 + H 2 O + D4 (octamethylcyclotetrasiloxane, 2.5 ppmv) and H 2 + N 2 + D4 (2.5 ppmv siloxane) gas mixtures at 750 °C to investigate their affinity and tolerance for siloxane degradation. Surface morphology analysis and electrochemical analysis including electrochemical impedance spectroscopy (EIS), related distribution of relaxation times (DRT) analysis and equivalent circuit modeling with complex nonlinear least square (CNLS) fitting were conducted. Here, a microstructure parameter—tortuosity factor to porosity ratio $\tau /\varepsilon $ calculated by diffusion polarization resistance was utilized for siloxane deposition evaluation. After comparing pellets surface morphology changes before and after experiments and $\tau /\varepsilon $ change following the contamination, Ni is considered as a major factor in siloxane deposition reactions in Ni-YSZ anode.
X-ray computed tomography (CT) is a non-destructive imaging technique in which contrast originates from the materials' absorption coefficient. The recent development of laboratory nanoscale CT (nano-CT) systems has pushed the spatial resolution for battery material imaging to voxel sizes of 50 nm, a limit previously achievable only with synchrotron facilities. Given the non-destructive nature of CT, in situ and operando studies have emerged as powerful methods to quantify morphological parameters, such as tortuosity factor, porosity, surface area and volume expansion, during battery operation or cycling. Combined with artificial intelligence and machine learning analysis techniques, nano-CT has enabled the development of predictive models to analyse the impact of the electrode microstructure on cell performances or the influence of material heterogeneities on electrochemical responses. In this Review, we discuss the role of X-ray CT and nano-CT experimentation in the battery field, discuss the incorporation of artificial intelligence and machine learning analyses and provide a perspective on how the combination of multiscale CT imaging techniques can expand the development of predictive multiscale battery behavioural models.
The phase-out of long-chain PFAS has led to the proliferation of highly recalcitrant short-chain analogs, and mineralization technologies for these short-chain PFAS are needed to mitigate their deleterious effects on environmental and human health. In this study, we utilize a statistical design of experiments, specifically, response surface methodology, to rapidly evaluate the electrochemical degradation of the short-chain PFAS, perfluorobutane sulfonate (PFBS). We evaluate the impacts of the three primary electrochemical parameters (concentration of PFBS, concentration of supporting electrolyte, and applied current) over multiple orders of magnitude on the three primary reaction outcomes of electrochemical PFBS degradation (incomplete PFBS decomposition, complete PFBS mineralization as fluorine, and anodic energy consumption). Our results correspond with literature and clearly identify the well-known tradeoff between energy consumption and complete mineralization. Intriguingly, partial PFBS decomposition and energy consumption demonstrate nonlinear dependencies in the current/supporting electrolyte concentration space and the current/PFBS concentration space, respectively. These findings highlight the utility of the response surface methodology model to efficiently interrogate a large parameter space, identifying both common results and less-obvious interactions between electrochemical parameters and their influences on reaction outcomes.
Engineering the interfacial distribution of electrolytic ions can aid in modulating the electrocatalyst performance and efficiency. Using a hybrid quantum-classical modeling approach, we describe how predictive tuning of the solution microenvironment on copper can enhance the efficiency of CO 2 reduction (CO 2 R) to C 2 products. We elucidate how competing electrolyte constituents in mixed electrolyte solutions stimulate restructuring of the electrochemical double layer (EDL) and stabilize the OCCO* dimer (* denotes surface adsorbed), with predictions validated in flow reactors using copper gas diffusion electrodes (Cu-GDEs). Furthermore, our findings highlight how molecular-scale electrolyte engineering with informed models of the EDL can be leveraged to tailor CO 2 R activity and selectivity toward C 2 products.
The ability for bipolar membranes (BPMs) to interconvert voltage and pH makes them attractive materials for use in energy conversion and storage. Reverse-biased BPMs, which use electrical voltage to dissociate water into acid and base, have become increasingly well studied. However, forward-biased BPMs (FB-BPMs), in which voltage is extracted from pH gradients through recombination, require further study. Here physics-based modeling elucidates how the complex coupling of transport and kinetics dictates the performance of FB-BPMs in electrochemical devices. Simulations reveal that the open-circuit potential of FB-BPMs is dictated by the balance of ion recombination and crossover, where recombination of buffering counter-ions attenuates the open-circuit potential. Counter-ion mass-transport limitations and uptake of ionic impurities limit achievable current densities by reducing the applied pH gradient or the available fixed-charge sites that mediate recombination. Further, the model highlights the importance of selective ion management in mitigating energy losses and provides insight into the rational material design of FB-BPMs for energy applications.
Single-ion conducting polymer blends (SICPBs) have demonstrated exceptional electrochemical performance as solid-state battery electrolytes; however, their nanoscale morphology and thermodynamic behavior remain unexplored. In this work, we investigate blends composed of deuterated poly(ethylene oxide) and poly[lithium sulfonyl(trifluoromethane sulfonyl)imide methacrylate], dPEO/P(LiMTFSI), and report the first experimental study of the nanostructures of charge-neutral polymer blends using small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS). Despite the macroscopic miscibility indicated by a single glass-transition temperature, SANS and SAXS results reveal disordered, charge-correlated nanostructures that are strongly influenced by blend composition and temperature. At low concentrations of charge polymer, the scattering is dominated by concentration fluctuations, and the random phase approximation is applied to extract values of the Flory–Huggins interaction parameter, χ SC . At higher charged polymer content, concentration fluctuations are suppressed, and a correlation model is used to characterize the nanostructures of the charge correlations. We find that the structures of the charge correlations are highly dependent on blend composition─consistent with predictions from Sing’s self-consistent field theory-liquid state models. Understanding these features is essential for uncovering the ion transport mechanism that leads to improved electrochemical performance previously reported in SICPB systems.
Titanium disulfide (TiS 2 ) with high electric conductivity, fast rate capability, and good cycling performance is a promising candidate for electrode material in sodium (Na)-ion batteries. Despite the well-studied electrochemical behaviors of TiS 2 in Li-ion batteries, the detailed reaction mechanism of TiS 2 in Na-ion batteries is not yet fully understood due to a more complex multi-phase conversion process. In this work, reactions of TiS 2 in Na-ion batteries are investigated via a multi-modal synchrotron approach: operando X-ray Absorption Spectroscopy (XAS) – including X-ray Absorption Near-Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) – and ex situ X-ray Powder Diffraction (XPD), coupled with computational modeling. Operando XANES spectra indicate that the redox reactions occur in both Ti and S during the electrochemically driven phase transformation. Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) analysis of XAS suggests that different numbers of components are involved in the lithiation and sodiation of TiS 2 , with the sodiation including at least one intermediate phase in addition to the starting material and the final sodiation product. Ex situ XPD and Rietveld refinement further determined and quantified the unknown phases, showing that three phases, TiS 2 , Na 0.55 TiS 2 , and NaTiS 2 , participate in the sodiation of TiS 2 . Operando EXAFS results show the changes in the Ti–Ti coordination number and interatomic distance. This explains the coulombic efficiency decay due to the incomplete recovery of the coordination number of Ti after cycling. Overall, this work reveals the reaction mechanism occurring in Na–TiS 2 batteries with a greater quantitative understanding of the structural evolution. By combining the multi-modal synchrotron approach and computational work, this study provides a framework for studying a broader range of electrochemically driven phase-transformation systems towards advanced energy storage and conversion applications.
High-valent Pd complexes are potent agents for the oxidative functionalization of inert C-H bonds, and it was previously shown that rapid electrocatalytic methane monofunctionalization could be achieved by electro-oxidation of Pd II to a critical dinuclear Pd III intermediate in concentrated or fuming sulfuric acid. However, the structure of this highly reactive, unisolable intermediate, as well as the structural basis for its mechanism of electrochemical formation, remained elusive. Herein, we use X-ray absorption and Raman spectroscopies to assemble a structural model of the potent methane-activating intermediate as a Pd III dimer with a Pd-Pd bond and a 5-fold O atom coordination by H x SO 4 (x-2) ligands at each Pd center. We further use EPR spectroscopy to identify a mixed-valent M-M bonded Pd 2 II,III species as a key intermediate during the Pd II -to-Pd III 2 oxidation. Combining EPR and electrochemical data, we quantify the free energy of Pd dimerization as <-4.5 kcal/mol for Pd 2 II,III and <-9.1 kcal/mol for Pd III 2 . The structural and thermochemical data suggest that the aggregate effect of metal-metal and axial metal-ligand bond formation drives the critical Pd dimerization reaction in between electrochemical oxidation steps. This work establishes a structural basis for the facile electrochemical oxidation of Pd II to a M-M bonded Pd III dimer and provides a foundation for understanding its rapid methane functionalization reactivity.
This model applies the Dusty Gas Model simulate multi-component species transport in SOFC (solid oxide fuel cell) anodes which considers the pressure gradient across the fuel electrode. This studyhas been verified with the analytical solution for different fuel electrode thicknesses and with literature values. The model was developed using the VoronoiFVM platform in Julia which is a built in implicit and semi implicit solver that integrates electrochemical behavior, microstructural effects, and transient analysis for accurate prediction of species transport under varying conditions.
Charge heterogeneity is a prevalent feature in many electrochemical systems. In a commercial cathode of Li-ion batteries, the composite is hierarchically structured across multiple length scales including the sub-micron single-crystal primary-particle domains up to the macroscopic particle ensembles. The redox kinetics of charge transfer and mass transport strongly couples with mechanical stresses. This interplay catalyzes substantial heterogeneity in the charge (re)distribution, stresses, and mechanical damage in the composite electrode during charging and discharging. We assess the heterogeneous electrochemistry and mechanics in a LiNi x Mn y Co z O 2 (NMC) cathode using a fully coupled electro-chemo-mechanics model at the cell level. A microstructure-resolved model is constructed based on the synchrotron X-ray tomography data. We calculate the stress field in the composite and then quantitatively evaluate the kinetics of surface charge transfer and Li transport biased by mechanical stresses. We further model the cyclic behavior of the cell. The repetitive deformation of the active particles and the weakening of the interfacial strength cause gradual increase of the interfacial debonding. The mechanical damage impedes electron transfer, incurs more charge heterogeneity, and results in the capacity degradation in batteries over cycles.