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Differentiating Zr/Hf IV Aqueous Polyoxocation Chemistry with Peroxide Ligation
Not provided.
Restricted Partition Function Semiclassical Transition State Theory (RPF-SCTST): Applications to Reactions Involving Hydrogen Cyanide, Hydrogen Peroxide, and Formaldehyde Oxide
We demonstrate the efficiency of the numerical calculation of thermal semiclassical transition state theory (SCTST) rates across several representative chemical reactions using the restricted partition function (RPF)─viz a function that depends only on the imaginary action associated with a reaction. Here, we treat the potential energy surfaces (PESs) through fourth order expansions around the saddle point and integrate the Hamiltonian up to second order in employing vibrational perturbation theory. We apply this formalism to uni- and bimolecular reactions with different─though relatively high─barrier heights to uncover the influence of the barrier properties, minimal energies, and separability of the rotational motion on rate constants and tunneling corrections. Although all modes are coupled within the RPF, we found in our numerical examples that the rotational component in the absence of significant rotational distortions can be separated from the vibrational contributions. Moreover, a classical treatment of the rotational contribution is adequate over the temperature range from approximately 100 to 1000 K. We also found that the choice of DFT basis set can lead to variations in rate constants of up to an order of magnitude. Lastly, different schemes for counting eligible energy levels result in rate constants that differ by no more than a factor of 2, with the remaining discrepancies attributed to the treatment of near-convergent levels in perturbation theory.
In Situ Strain Evolution on Pt Nanoparticles during Hydrogen Peroxide Decomposition
Fundamental understanding of structural changes during catalytic reactions is crucial to understanding the underlying mechanisms and optimizing efficiencies. Surface energy and related catalytic mechanisms are widely studied. However, the catalyst lattice deformation induced by catalytic processes is not well understood. Here, we study the strain in an individual platinum (Pt) nanoparticle (NP) using Bragg coherent diffraction imaging under in situ oxidation and reduction reactions. When Pt NPs are exposed to H 2 O 2 , a typical oxidizer and an intermediate during the oxygen reduction reaction process, alternating overall strain distribution near the surface and inside the NP is observed at the (111) Bragg reflection. In contrast, relatively insignificant changes appear in the (200) reflection. Density functional theory calculations are employed to rationalize the anisotropic lattice strain in terms of induced stress by H 2 O 2 adsorption and decomposition on the Pt NP surface. Our study provides deeper insight into the activity-structure relationship in this system.
Highly Selective Oxygen Reduction to Hydrogen Peroxide on a Carbon-Supported Single-Atom Pd Electrocatalyst
Selective electrochemical two-electron oxygen reduction is a promising route for renewable and on-site H 2 O 2 generation as an alternative to the anthraquinone process. In this study, we report a high-performance nitrogen-coordinated single-atom Pd electrocatalyst, which is derived from Pd-doped zeolitic imidazolate frameworks (ZIFs) through one-step thermolysis. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) combined with X-ray absorption spectroscopy verifies atomically dispersed Pd atoms on nitrogen-doped carbon (Pd-NC). The single-atom Pd-NC catalyst exhibits excellent electrocatalytic performance for two-electron oxygen reduction to H 2 O 2 , which shows ~95% selectivity toward H 2 O 2 and an unprecedented onset potential of ~0.8 V versus revisable hydrogen electrode (RHE) in 0.1 M KOH. Density functional theory (DFT) calculations demonstrate that the Pd-N 4 catalytic sites thermodynamically prefer *–O bond breaking to O–O bond breaking, corresponding to a high selectivity for H 2 O 2 production. This work provides a deep insight into the understanding of the catalytic process and design of high-performance 2e– ORR catalysts.
On-Line Raman Measurement of the Radiation-Enhanced Reaction of Cellobiose with Hydrogen Peroxide
Not Available
Dissolved Oxygen Redox as the Source of Hydrogen Peroxide and Hydroxyl Radical in Sonicated Emulsive Water Microdroplets
Sonicated emulsive water microdroplets (SEWMs) accelerate and enable a variety of catalyst-free chemical transformations. However, significant unanswered questions remain regarding the chemical intermediates they form and their possible redox origin. In this study, we identified dissolved O 2 as the primary originator of reactive oxygen species (ROS) such as OH• and H 2 O 2. We uncovered the role of dissolved O 2 redox by using a combination of microelectrochemical methods to detect H 2 O 2 , isotopic methods to identify the source of H 2 O 2 , and a combination of electron spin resonance and the DMPO spin trap to detect radicals such as OH•. Notably, we found that H 2 O 2 production is correlated with O 2 content via a reduction pathway enabled by a sufficiently large reducing power that can additionally generate H 2 and even perform Pb electroless deposition on Au and Cu metal substrates. Building on our findings, continuous O 2 bubbling of SEWMs showed accumulation of H 2 O 2 up to ∼88 mM in the aqueous phase within 1 h of sonication, demonstrating the scale-up promise of this method. Distinct to sonochemistry of a single phase, this study advances our understanding of the confluence of redox and chemical reaction mechanisms within SEWMs as a biphasic system. This insight paves the way for improving their reaction kinetics, yield, and selectivity, positioning these attractive redox microreactors as alternatives to traditional electrolyzers.
Hydrogen peroxide sensor HPCA1 is an LRR receptor kinase in Arabidopsis
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Production of hydrogen peroxide in an intra-meander hyporheic zone at East River, Colorado.
The traditionally held assumption that photo-dependent processes are the predominant source of H 2 O 2 in natural waters has been recently questioned by an increasing body of evidence showing the ubiquitiousness of H 2 O 2 in dark water bodies and in groundwater. In this study, we conducted field measurement of H 2 O 2 in an intra-meander hyporheic zone and in surface water at East River, CO. On-site detection using a sensitive chemiluminescence method suggests H 2 O 2 concentrations in groundwater ranging from 6 nM (at the most reduced region) to ~ 80 nM (in a locally oxygen-rich area) along the intra-meander transect with a maxima of 186 nM detected in the surface water in an early afternoon, lagging the maximum solar irradiance by ~1.5 h. Our results suggest that the dark profile of H 2 O 2 in the hyporheic zone is closely correlated to local redox gradients, indicating that interactions between various redox sensitive elements could play an essential role. Due to its transient nature, the widespread presence of H 2 O 2 in the hyporheic zone indicates the existence of a sustained balance between H 2 O 2 production and consumption, which potentially involves a relatively rapid succession of various biogeochemically important processes (such as organic matter turnover, metal cycling and contaminant mobilization). More importantly, this study confirmed the occurrence of reactive oxygen species at a subsurface redox transition zone and further support our understanding of redox boundaries on reactive oxygen species generation and as key locations of biogeochemical activity.