Project description:Varying the solution pH not only changes the reactant concentrations in bulk solution but also the local reaction environment (LRE) that is shaped furthermore by macroscopic mass transport and microscopic electric double layer (EDL) effects. Understanding ubiquitous pH effects in electrocatalysis requires disentangling these interwoven factors, which is a difficult, if not impossible, task without physical modeling. Herein, we demonstrate how a hierarchical model that integrates microkinetics, double-layer charging, and macroscopic mass transport can help understand pH effects of the formic acid oxidation reaction (FAOR). In terms of the relation between the peak activity and the solution pH, intrinsic pH effects without consideration of changes in the LRE would lead to a bell-shaped curve with a peak at pH = 6. Adding only macroscopic mass transport, we can already reproduce qualitatively the experimentally observed trapezoidal shape with a plateau between pH 5 and 10 in perchlorate and sulfate solutions. A quantitative agreement with experimental data requires consideration of EDL effects beyond Frumkin correlations. Specifically, the peculiar nonmonotonic surface charging relation affects the free energies of adsorbed intermediates. We further discuss pH effects of FAOR in phosphate and chloride-containing solutions, for which anion adsorption becomes important. This study underpins the importance of a full consideration of multiple interrelated factors for the interpretation of pH effects in electrocatalysis.
Project description:A surface-driven flow is generated during the electrocatalytic reaction of a platinum-gold bielectrode within hydrogen peroxide. This flow can be experimentally visualized and quantified using micrometer-sized particles that are transported by a flow field. Tracer particles, which possess an inherent surface charge, also interact with the induced electric field and exhibit a collective behavior at the surface of the electrodes where they accumulate. The underlying mechanism for the accumulation dynamics demonstrated by these catalytic pump systems has so far been lacking. In this work, the accumulation dynamics and kinetics were experimentally investigated. With use of numerical simulations, we demonstrate that the self-driven particle accumulation is controlled by a positive dielectrophoretic force, mediated by the reaction-induced electric and flow field. These results contribute to the fundamental knowledge on immobilized bimetallic systems.
Project description:Hot electrons generated on metal catalysts influence atomic and molecular processes, leading to hot electron-driven catalytic reactions. Here, we show the acceleration of electrocatalytic hydrogen evolution caused by internal injection of hot electrons on Pt/Si metal-semiconductor electrodes. When a forward bias voltage is applied to the Pt/Si contact, hot electrons are injected. The excess energy of these electrons allows them to reach the Pt/electrolyte interface and reduce the adsorbed hydrogen ions to form H2 (2H+ + 2e-→H2). We show that the onset potential of the hydrogen evolution reaction shifts positively by 160 mV while the cathodic current exhibits an 8-fold increase in the presence of hot electrons. The effect disappears when the thickness of the Pt film exceeds the mean free path of the hot electrons. The concept of a hot electron-driven reaction can lead to the development of a novel mechanism for controlling reactivity at liquid-solid interfaces.
Project description:To simulate the effects of shear stress in regions of the vasculature prone to developing atherosclerosis, we subjected human umbilical vein endothelial cells to reversing shear stress to mimic the hemodynamic conditions at the wall of the carotid sinus, a site of complex, reversing blood flow and commonly observed atherosclerosis. We compared the effects of reversing shear stress (time-average: 1 dyn/cm(2), maximum: +11 dyn/cm(2), minimum: -11 dyn/cm(2), 1 Hz), arterial steady shear stress (15 dyn/cm(2)), and low steady shear stress (1 dyn/cm(2)) on gene expression, cell proliferation, and monocyte adhesiveness. Microarray analysis revealed that most differentially expressed genes were similarly regulated by all three shear stress regimens compared with static culture. Comparisons of the three shear stress regimens to each other identified 138 genes regulated by low average shear stress and 22 genes regulated by fluid reversal. Low average shear stress induced increased cell proliferation compared with high shear stress. Only reversing shear stress exposure induced monocyte adhesion. The adhesion of monocytes was partially inhibited by the incubation of endothelial cells with ICAM-1 blocking antibody. Increased heparan sulfate proteoglycan expression was observed on the surface of cells exposed to reversing shear stress. Heparinase III treatment significantly reduced monocyte adhesion. Our results suggest that low steady shear stress is the major impetus for differential gene expression and cell proliferation, whereas reversing flow regulates monocyte adhesion.
Project description:Amyloid fibril polymorphism is not well understood despite its potential importance for biological activity and associated toxicity. Controlling the polymorphism of mature fibrils including their morphology and supramolecular chirality by postfibrillation changes in the local environment is the subject of this study. Specifically, the effect of pH on the stability and dynamics of HET-s (218-289) prion fibrils has been determined through the use of vibrational circular dichroism (VCD), deep UV resonance Raman, and fluorescence spectroscopies. It was found that a change in solution pH causes deprotonation of Asp and Glu amino acid residues on the surface of HET-s (218-289) prion fibrils and triggers rapid transformation of one supramolecular chiral polymorph into another. This process involves changes in higher order arrangements like lateral filament and fibril association and their supramolecular chirality, while the fibril cross-β core remains intact. This work suggests a hypothetical mechanism for HET-s (218-289) prion fibril refolding and proposes that the interconversion between fibril polymorphs driven by the solution environment change is a general property of amyloid fibrils.
Project description:The pressure-driven growth model that describes the two-dimensional (2-D) propagation of a foam through an oil reservoir is considered as a model for surfactant-alternating-gas improved oil recovery. The model assumes a region of low mobility, finely textured foam at the foam front where injected gas meets liquid. The net pressure driving the foam is assumed to reduce suddenly at a specific time. Parts of the foam front, deep down near the bottom of the front, must then backtrack, reversing their flow direction. Equations for one-dimensional fractional flow, underlying 2-D pressure-driven growth, are solved via the method of characteristics. In a diagram of position versus time, the backtracking front has a complex double fan structure, with two distinct characteristic fans interacting. One of these characteristic fans is a reflection of a fan already present in forward flow mode. The second fan however only appears upon flow reversal. Both fans contribute to the flow's Darcy pressure drop, the balance of the pressure drop shifting over time from the first fan to the second. The implications for 2-D pressure-driven growth are that the foam front has even lower mobility in reverse flow mode than it had in the original forward flow case.
Project description:Conventional food production is restricted by energy conversion efficiency of natural photosynthesis and demand for natural resources. Solar-driven artificial food synthesis from CO2 provides an intriguing approach to overcome the limitations of natural photosynthesis while promoting carbon-neutral economy, however, it remains very challenging. Here, we report the design of a hybrid electrocatalytic-biocatalytic flow system, coupling photovoltaics-powered electrocatalysis (CO2 to formate) with five-enzyme cascade platform (formate to sugar) engineered via genetic mutation and bioinformatics, which achieves conversion of CO2 to C6 sugar (L-sorbose) with a solar-to-food energy conversion efficiency of 3.5%, outperforming natural photosynthesis by over three-fold. This flow system can in principle be programmed by coupling with diverse enzymes toward production of multifarious food from CO2. This work opens a promising avenue for artificial food synthesis from CO2 under confined environments.
Project description:Herein, we show that the performance of mesostructured cobalt oxide electrocatalyst for oxygen evolution reaction (OER) can be significantly enhanced by coupling of silver species. Various analysis techniques including pair distribution function and Rietveld refinement, X-ray absorption spectroscopy at synchrotron as well as advanced electron microscopy revealed that silver exists as metallic Ag particles and well-dispersed Ag2 O nanoclusters within the mesostructure. The benefits of this synergy are twofold for OER: highly conductive metallic Ag improves the charge transfer ability of the electrocatalysts while ultra-small Ag2 O clusters provide the centers that can uptake Fe impurities from KOH electrolyte and boost the catalytic efficiency of Co-Ag oxides. The current density of mesostructured Co3 O4 at 1.7 VRHE is increased from 102 to 211 mA cm-2 with incorporation of silver spices. This work presents the dual role of silver moieties and demonstrates a simple method to increase the OER activity of Co3 O4 .
Project description:We report observations of a striking reversal in the direction of electroosmotic flow (EOF) outside a conical glass nanopore as a function of salt concentration. At high ionic strengths (>100 mM), we observe EOF in the expected direction as predicted by classical electrokinetic theory, while at low salt concentrations (<1 mM) the direction of the flow is reversed. The critical crossover salt concentration depends on the pore diameter. Finite-element simulations indicate a competition between the EOF generated from the inner and outer walls of the pore, which drives flows in opposite directions. We have developed a simple analytical model which reveals that, as the salt concentration is reduced, the flow rates inside the pore are geometrically constrained, whereas there is no such limit for flows outside the pore. This model captures all of the essential physics of the system and explains the observed data, highlighting the key role the external environment plays in determining the overall electroosmotic behavior.
Project description:Monolayer nanosheets have gained significant attention as functional materials and also in photo/electrocatalysis due to their unique physical/chemical properties, abundance of highly exposed coordination sites, edges, and corner sites, motivating the pursuit of highly active monolayer nanosheets. NiFe-based layered double hydroxide (NiFe-LDH) nanosheets have been regarded as the most efficient electrocatalysis for oxygen evolution. However, the limited catalytic active site and the stacking layer limited the performance. Therefore, by introducing highly electroactive Co ions into monolayer NiFe-LDH, the obtained ternary NiFeCo-LDH monolayer structure possessed an increased concentration of defect (oxygen and metal vacancies), providing enough unsaturated coordination sites, benefitting the electrocatalytic water oxidation, as also explained by the density functional theory (DFT). This work reported an efficient strategy for the synthesis of ternary monolayer LDH in the application of energy conversion and storage.