Search

Addressing the challenge of sluggish kinetics and limited stability in alkaline oxygen evolution reactions, recent exploration of novel electrochemical catalysts offers improved prospects. To expedite the assessment of these catalysts, a half-cell rotating disk electrode is often favored for its simplicity. However, the actual catalyst performance strongly depends on the fabricated catalyst layers, which encounter mass transport overpotentials. We systematically investigate the role and sequence of electrode drop-casting methods onto a glassy carbon electrode regarding the efficiency of the oxygen evolution reaction. The catalyst layer without Nafion experiences nearly 50% activity loss post stability test, while those with Nafion exhibit less than 5% activity loss. Additionally, the sequence of application of the catalyst and Nafion also shows a significant effect on catalyst stability. The catalyst activity increases by roughly 20% after the stability test when the catalyst layer is coated first with an ionomer layer, followed by drop-casting the catalysts. Based on the half-cell results, the Nafion ionomer not only acts as a binder in the catalyst layer but also enhances the interfacial interaction between the catalyst and electrolyte, promoting performance and stability. This study provides new insights into the efficient and accurate evaluation of electrocatalyst performance and stability as well as the role of Nafion ionomer in the catalyst layer.

Many people around the world rely on groundwater for drinking and sanitation, however, they are exposed to various health risks from the naturally occurring groundwater arsenic (As). Air-cathode Assisted Iron Electrocoagulation (ACAIE) using Carbon Black Pearls 2000® cathode was previously shown catalyse the removal of groundwater As by producing hydrogen peroxide (H2O2). This work explored Vulcan® XC-72, and Printex® L6 Carbon as alternative cathodes for iron electrocoagulation which are more selective towards the 2-electron oxygen reduction reaction into H2O2 compared to Carbon Black Pearls®. The cathodes were tested in an ACAIE set-up to treat synthetic groundwater spiked with 1,500 μg/L of As at different charge dosage rates (CDR) from 1.56 C/L-min to 100 C/L-min with a total charge dosage of 600 C/L for all set-ups. Although the electrocoagulation energies among the cathodes were similar, the use of Printex® cathode for ACAIE remediated the groundwater for all CDR with final As levels below 10 μg/L. This is in contrast with the less selective Carbon Black Pearls® at low CDR, and the less active Vulcan® Carbon at high CDR where the treated groundwater may still have As levels above 10 μg/L. Future research would explore modifications in the carbon materials and reactor configuration to further optimize ACAIE in removing groundwater As.

The increasing demand for batteries’ application in grid-balancing, electric vehicles, and portable electronics has prompted research efforts on improving their performance and safety features. The improvement of batteries involves the comparison of multiple battery designs and the determination of electrochemical and thermal property distributions at the continuum scale. This is achieved by using multiphysics modeling for investigatory battery research, as conventional experimental approaches would be costly and impractical. The fundamental electrochemical models for these batteries have been established, hence, new models are being developed for specific applications, such as thermal runaway and battery degradation in lithium-ion batteries, gas evolution in lead-acid batteries, and vanadium crossover in vanadium redox flow batteries. The inclusion of new concepts in multiphysics modeling, however, necessitates the consideration of phenomena beyond the continuum scale. This work presents a comprehensive review on the multiphysics models of lithium-ion, lead-acid, and vanadium redox flow batteries. The electrochemical models of these chemistries are discussed along with their physical interpretations and common applications. Modifications of these multiphysics models for adaptation and matching to end applications are outlined. Lastly, we comment on the direction of future work with regards to the interaction of multiphysics modeling with modeling techniques in other length and time scales. Molecular-scale models such as density functional theory and kinetic Monte Carlo can be used to create new multiphysics models and predict transport property correlations from first principles. Nanostructures and pore-level geometries can be optimized and integrated into continuum-scale models. The reduction of multiphysics models via machine learning, mathematical simplification, or regression enables their application in battery management systems and energy systems modeling.

Density functional theory was used to investigate the effects of doping alkaline earth metal atoms (beryllium, magnesium, calcium and strontium) on graphene. Electron transfer from the dopant atom to the graphene substrate was observed and was further probed by a combined electron localization function/non-covalent interaction (ELF/NCI) approach. This approach demonstrates that predominantly ionic bonding occurs between the alkaline earth dopants and the substrate, with beryllium doping having a variant characteristic as a consequence of electronegativity equalization attributed to its lower atomic number relative to carbon. The ionic bonding induces spin-polarized electronic structures and lower workfunctions for Mg-, Ca-, and Sr-doped graphene systems as compared to the pristine graphene. However, due to its variant bonding characteristic, Be-doped graphene exhibits non-spin-polarized p-type semiconductor behavior, which is consistent with previous works, and an increase in workfunction relative to pristine graphene. Dirac half-metal-like behavior was predicted for magnesium doped graphene while calcium doped and strontium doped graphene were predicted to have bipolar magnetic semiconductor behavior. These changes in the electronic and magnetic properties of alkaline earth doped graphene may be of importance for spintronic and other electronic device applications.

Traditional understanding of electrocatalytic reactions generally focuses on either covalent interactions between adsorbates and the reaction interface (i.e., electrical double layer, EDL) or electrostatic interactions between electrolyte ions. Here, our work provides valuable insights into interfacial structure and ionic interactions during alkaline oxygen evolution reaction (OER). The importance of inner-sphere OH- adsorption is demonstrated as the IrOx activity in 4.0 M KOH is 6.5 times higher than that in 0.1 M KOH. Adding NaNO3 as a supporting electrolyte, which is found to be inert for long-term stability, complicates the electrocatalytic reaction in a half cell. The nonspecially adsorbed Na+ in the outer compact interfacial layer is suggested to form a stronger noncovalent interaction with OH- through hydrogen bond than adsorbed K+, leading to the decrease of interfacial OH- mobility. This hypothesis highlights the importance of outer-sphere adsorption for the OER, which is generally recognized as a pure inner-sphere process. Meanwhile, based on our experimental observations, the pseudocapacitive behavior of solid-state redox might be more reliable in quantifying active sites for OER than that measured from the conventional EDL charging capacitive process. The interfacial oxygen transport is observed to improve with increasing electrolyte conductivity, ascribing to the increased accessible active sites. The durability results in a liquid alkaline electrolyzer which shows that adding NaNO3 into KOH solution leads to additional degradation of OER activity and long-term stability. These findings provide an improved understanding of the mechanistic details and structural motifs required for efficient and robust electrocatalysis.

Traditional understanding of electrocatalytic reactions generally focuses on either covalent interactions between adsorbates and the reaction interface (i.e., electrical double layer, EDL) or electrostatic interactions between electrolyte ions. Here, our work provides valuable insights into interfacial structure and ionic interactions during alkaline oxygen evolution reaction (OER). The importance of inner-sphere OH- adsorption is demonstrated as the IrOx activity in 4.0 M KOH is 6.5 times higher than that in 0.1 M KOH. Adding NaNO3 as a supporting electrolyte, which is found to be inert for long-term stability, complicates the electrocatalytic reaction in a half cell. The nonspecially adsorbed Na+ in the outer compact interfacial layer is suggested to form a stronger noncovalent interaction with OH- through hydrogen bond than adsorbed K+, leading to the decrease of interfacial OH- mobility. This hypothesis highlights the importance of outer-sphere adsorption for the OER, which is generally recognized as a pure inner-sphere process. Meanwhile, based on our experimental observations, the pseudocapacitive behavior of solid-state redox might be more reliable in quantifying active sites for OER than that measured from the conventional EDL charging capacitive process. The interfacial oxygen transport is observed to improve with increasing electrolyte conductivity, ascribing to the increased accessible active sites. The durability results in a liquid alkaline electrolyzer which shows that adding NaNO3 into KOH solution leads to additional degradation of OER activity and long-term stability. These findings provide an improved understanding of the mechanistic details and structural motifs required for efficient and robust electrocatalysis.

A majority of individuals infected with human immunodeficiency virus (HIV) have inadequate access to antiretroviral therapy and ultimately develop debilitating oral infections that often correlate with disease progression. Due to the impracticalities of conducting host-microbe systems-based studies in HIV infected patients, we have evaluated the potential of simian immunodeficiency virus (SIV) infected rhesus macaques to serve as a non-human primate model for oral manifestations of HIV disease. We present the first description of the rhesus macaque oral microbiota and show that a mixture of human commensal bacteria and "macaque versions" of human commensals colonize the tongue dorsum and dental plaque. Our findings indicate that SIV infection results in chronic activation of antiviral and inflammatory responses in the tongue mucosa that may collectively lead to repression of epithelial development and impact the microbiome. In addition, we show that dysbiosis of the lingual microbiome in SIV infection is characterized by outgrowth of Gemella morbillorum that may result from impaired macrophage function. Finally, we provide evidence that the increased capacity of opportunistic pathogens (e.g. E. coli) to colonize the microbiome is associated with reduced production of antimicrobial peptides.

A majority of individuals infected with human immunodeficiency virus (HIV) have inadequate access to antiretroviral therapy and ultimately develop debilitating oral infections that often correlate with disease progression. Due to the impracticalities of conducting host-microbe systems-based studies in HIV infected patients, we have evaluated the potential of simian immunodeficiency virus (SIV) infected rhesus macaques to serve as a non-human primate model for oral manifestations of HIV disease. We present the first description of the rhesus macaque oral microbiota and show that a mixture of human commensal bacteria and "macaque versions" of human commensals colonize the tongue dorsum and dental plaque. Our findings indicate that SIV infection results in chronic activation of antiviral and inflammatory responses in the tongue mucosa that may collectively lead to repression of epithelial development and impact the microbiome. In addition, we show that dysbiosis of the lingual microbiome in SIV infection is characterized by outgrowth of Gemella morbillorum that may result from impaired macrophage function. Finally, we provide evidence that the increased capacity of opportunistic pathogens (e.g. E. coli) to colonize the microbiome is associated with reduced production of antimicrobial peptides.