Project description:The Angstrom-scale space between graphene and its substrate provides an attractive playground for scientific exploration and can lead to breakthrough applications. Here, we report the energetics and kinetics of hydrogen electrosorption on a graphene-covered Pt(111) electrode using electrochemical experiments, in situ spectroscopy, and density functional theory calculations. The graphene overlayer influences the hydrogen adsorption on Pt(111) by shielding the ions from the interface and weakening the Pt-H bond energy. Analysis of the proton permeation resistance with controlled graphene defect density proves that the domain boundary defects and point defects are the pathways for proton permeation in the graphene layer, in agreement with density functional theory (DFT) calculations of the lowest energy proton permeation pathways. Although graphene blocks the interaction of anions with the Pt(111) surfaces, anions do adsorb near the defects: the rate constant for hydrogen permeation is sensitively dependent on anion identity and concentration.
Project description:Desolvation barriers are present for solute-solvent exchange events, such as ligand binding to an enzyme active site, during protein folding, and at battery electrodes. For solution-grown crystals, desolvation at kink sites can be the rate-limiting step for growth. However, desolvation and the associated kinetic barriers are poorly understood. In this work, we use rare-event simulation techniques to investigate attachment/detachment events at kink sites of a NaCl crystal in water. We elucidate the desolvation mechanism and present an optimized reaction coordinate, which involves one solute collective variable and one solvent collective variable. The attachment/detachment pathways for Na+ and Cl- are qualitatively similar, with quantitative differences that we attribute to different ion sizes and solvent coordination. The attachment barriers primarily result from kink site desolvation, while detachment barriers largely result from breaking ion-crystal bonds. We compute ion detachment rates from kink sites and compare with results from an independent study. We anticipate that the reaction coordinate and desolvation mechanism identified in this work may be applicable to other alkali halides.
Project description:The ultimate fate, over the course of millennia, of nearly all of the carbon dioxide formed by humankind is for it to react with calcium carbonate in the world's oceans. Although, this reaction is of global relevance, aspects of the calcite dissolution reaction remain poorly described with apparent contradictions present throughout the expansive literature. In this perspective we aim to evidence how a lack of appreciation of the role of mass-transport may have hampered developments in this area. These insights have important implications for both idealised experiments performed under laboratory conditions and for the measurement and modelling of oceanic calcite sediment dissolution.
Project description:Electrode dissolution was monitored in real-time during Kolbe electrolysis along with the characteristic products. The fast determination of appropriate reaction conditions in electro-organic chemistry enables the minimization of electrode degradation while keeping an eye on the optimal formation rate and distribution of products. Herein, essential parameters influencing the dissolution of the electrode material platinum in a Kolbe electrolysis were pinpointed. The formation of reaction products and soluble platinum species were monitored during potentiodynamic and potentiostatic experiments using an electroanalytical flow cell coupled to two different mass spectrometers. The approach opens new vistas in the field of electro-organic chemistry because it enables precise and quick quantification of dissolved metals during electrosynthesis, also involving electrode materials other than platinum. Furthermore, it draws attention to the vital topic of electrode stability in electro-organic synthesis, which becomes increasingly important for the implementation of green chemical processes utilizing renewable energy.
Project description:The enhanced electrochemical activity of nanostructured materials is readily exploited in energy devices, but their utility in scalable and human-compatible implantable neural interfaces can significantly advance the performance of clinical and research electrodes. We utilize low-temperature selective dealloying to develop scalable and biocompatible one-dimensional platinum nanorod (PtNR) arrays that exhibit superb electrochemical properties at various length scales, stability, and biocompatibility for high performance neurotechnologies. PtNR arrays record brain activity with cellular resolution from the cortical surfaces in birds and nonhuman primates. Significantly, strong modulation of surface recorded single unit activity by auditory stimuli is demonstrated in European Starling birds as well as the modulation of local field potentials in the visual cortex by light stimuli in a nonhuman primate and responses to electrical stimulation in mice. PtNRs record behaviorally and physiologically relevant neuronal dynamics from the surface of the brain with high spatiotemporal resolution, which paves the way for less invasive brain-machine interfaces.
Project description:Thermoset dissolution based on degradable bond or exchange reaction has been recently utilized to achieve thermosetting polymer dissolution and recycling. In this paper, an industrial grade epoxy thermoset was utilized as a model system to demonstrate the thermoset dissolution via solvent assisted transesterification (or alcoholysis) with high efficiency under mild conditions. The anhydride-cured epoxy thermoset was depolymerized by selective ester bond cleavage in 1,5,7-triazabicyclo[4,4,0]dec-5-ene (TBD)-alcohol solution below 180 °C at ordinary pressure in less than two hours. The epoxy dissolution proceeded in a surface erosion mode via transesterification that was coupled with catalyst-alcohol diffusion. Based on this observation, a surface layer model containing three layers, namely the gel layer, solid swollen layer and pure polymer layer was used to analyze the thermoset dissolution kinetics. The epoxy dissolution kinetics was derived from the surface layer model, which could be used to predict the dissolution rate during the diffusion-rate-controlled dissolution process well. The results show that alcohols with larger diffusivity and better solubility lead to a higher alcohol/catalyst concentration in the gel layer and promote faster erosion and dissolution of epoxy. This is the first work to show that it is possible to depolymerize industrial epoxy using the principle of dynamic bonds with fast dissolution rate at mild temperature under ordinary pressure.
Project description:This report is the first on heat-assisted transferable battery components, enabling manufacturing batteries on non-planer surfaces such as a curved surface and an edge. The transferrable battery components were composed of two layers: a cathode or an anode and a conductive heal-melt adhesive layer on a silicone-based flexible supporting paper. These mechanically-durable, flexible components enabled conformable adhesion even on curved surfaces and substrate edges. As a model battery, the manganese dioxide-zinc system was constructed on a curved surface using transfer techniques and showed a practical capacity of 1.8 mAh cm-2 per unit electrode area. These transferable electrodes allow arbitrary design of batteries according to the power consumption of IoT devices to be fabricated on unreported geometries where has been considered as a dead space.
Project description:Hydrogen gas is a promising, clean, and highly efficient energy source. However, to use combustible H2 gas safety, high-performance and safe gas leakage sensors are required. In this study, transparent and flexible platinum-catalyst-loaded tungsten trioxide (Pt/WO3) nanoparticle-dispersed membranes were prepared as H2 gas leakage sensors. The nanoparticle-dispersed membrane with a Pt:W compositional ratio of 1:13 was transparent and exhibited a sufficient color change in response to H2 gas. The membrane containing 0.75 wt.% of Pt/WO3 nanoparticles exhibited high transparency over a wide wavelength range and the largest transmittance change in response to H2 gas among the others. The heat treatment of the particles at 573 K provided sufficient crystallinity and an accessible area for a gasochromic reaction, resulting in a rapid and sensitive response to the presence of H2 gas. The lower limit of detection of the optimized Pt/WO3 nanoparticle-dispersed membrane by naked eye was 0.4%, which was one-tenth of the minimum explosive concentration. This novel membrane was transparent as well as flexible and exhibited a clear and rapid color response to H2. Therefore, it is an ideal candidate sensor for the safe and easy detection of H2 gas leakage.
Project description:Securing the electrochemical durability of noble metal platinum is of central importance for the successful implementation of a proton exchange membrane fuel cell (PEMFC). Pt dissolution, a major cause of PEMFC degradation, is known to be a potential-dependent transient process, but its underlying mechanism is puzzling. Herein, we elucidate a chemical Pt dissolution process that can occur in various electrocatalytic conditions. This process intensively occurs during potential perturbations with a millisecond timescale, which has yet to be seriously considered. The open circuit potential profiles identify the dominant formation of metastable Pt species at such short timescales and their simultaneous dissolution. Considering on these findings, a proof-of-concept strategy for alleviating chemical Pt dissolution is further studied by tuning electric double layer charging. These results suggest that stable Pt electrocatalysis can be achieved if rational synthetic or systematic strategies are further developed.