Interfacial proton-coupled electron transfer (I-PCET) is typically viewed as a single elementary reaction despite the accepted recognition that analogous solution-phase reactivity requires proton donor/acceptor pre association. Herein, we examine role of pre-association in I-PCET to molecularly well-defined graphite-conjugated carboxylic acid (GC-COOH) surface site. We quantify electrolyte activity and I PCET kinetics acidic, acetate-buffered, alkaline electrolytes function NaClO4...

Programmable catalysis-the purposeful oscillation of catalytic potential energy surfaces (PES)-has emerged as a promising method for the acceleration catalyzed reaction rates. However, theoretical study programmable catalysis has been limited by onerous computational demands integrating stiff differential equations that describe periodic cycling between PESs. This work details methods reduce cost finding limit cycle ≳10

Significance The kinetic assessment of catalytic reactions is essential to the design and application thermochemical processes useful in petrochemical synthesis, energy conversion, environmental remediation. We demonstrate that ubiquitously used Langmuir–Hinshelwood formalism incomplete fails correctly describe even simple (e.g., A + → 2 ). An accurate description requires explicit rate equations for multisite configurations A*–A* pairs) account nonrandom clustering/isolation surface...

Mathematical relations prescribing unidirectional forward and reverse rates originally derived based on single-path reaction sequences do not apply to interconnected networks. The presence of branches in networks, leading alternative stable products, decreases reference those calculated by functional forms, as shown simulated isotopic exchange rates, but impacts the equally such that form effective reversibility remains unchanged. Regardless stoichiometric numbers network connectivity,...

Catalyst surfaces in contact with liquid media are subject to spontaneous charge transfer reactions that electrically polarize the solid-liquid interface. Consequently, electrochemical potential, Ecat, of surface is a critical parameter defines free-energy landscape catalysis. Ecat can be readily measured for catalyst supported on conductive material and wired an external circuit but difficult quantify vast majority thermochemical catalysts electrical insulators. This measurement gap has...

A group-contribution method based on scaled-particle theory was developed to predict Henry's constants for six families of persistent organic pollutants: polychlorinated benzenes, biphenyls, dibenzodioxins, dibenzofurans, naphthalenes, and polybrominated diphenyl ethers. The model uses limited experimental data obtain group-interaction parameters an easy-to-use systems where reliable are scarce. By using obtained from reduction, gives the partial molar Gibbs energy dissolution, Δg̅2,...

Dynamic catalysis—the forced oscillation of catalytic reaction coordinate potential energy surfaces (PES)—has recently emerged as a promising method for the acceleration heterogeneously-catalyzed reactions. Theoretical study enhancement rates and supra-equilibrium product yield via dynamic catalysis has, to-date, been severely limited by onerous computational demands forward integration stiff, coupled ordinary differential equations (ODEs) that are necessary to quantitatively describe...

Dynamic catalysis proffers a new strategy for leveraging linear free energy (LFE) relationships in to increase reaction rate, conversion, and selectivity by high-frequency, forced kinetic oscillations. This work explicates two dynamic mechanisms—“resonance” quasi-static, characterized finite frequency bands high limits, respectively—and details the necessary LFE parameters each phenomena arise. Detailed analytical numerical analyses reveal that under quasi-static mechanisms, Sabatier limits...

Many key energy conversion reactions are proton-coupled electron transfer (PCET) that consume or generate protons at electrode surfaces. Thus, catalytic turnover can non-equilibrium local pH environments the surface differ substantially from of bulk. Quantitative insight into magnitude this interfacial swing is a prerequisite for understanding and designing efficient systems conversion, but difficult to measure, particularly under high current density operation; with complex gas diffusion...

Catalyst surfaces in contact with liquid media are subject to spontaneous charge transfer reactions that electrically polarize the solid-liquid interface. Consequently, electrochemical potential, Ecat, of surface is a critical parameter defines free-energy landscape catalysis. Ecat can be readily measured for catalyst supported on conductive material and wired an external circuit but difficult quantify vast majority thermochemical catalysts electrical insulators. This measurement gap has...

Interfacial proton-coupled electron transfer (I-PCET) reactions are typically viewed as single elementary reaction steps even though analogous solution-phase reactivity is known to require pre-association of proton donor and acceptor. Herein, we examine the role in I-PCET a molecularly well-defined graphite-conjugated carboxylic acid (GC-COOH) surface site. We quantify electrolyte activity I PCET kinetics acidic, acetate buffered, alkaline electrolytes function NaClO4 concentration, ranging...

Interfacial proton-coupled electron transfer (I-PCET) reactions are typically viewed as single elementary reaction steps even though analogous solution-phase reactivity is known to require pre-association of proton donor and acceptor. Herein, we examine the role in I-PCET a molecularly well-defined graphite-conjugated carboxylic acid (GC-COOH) surface site. We quantify electrolyte activity I PCET kinetics acidic, acetate buffered, alkaline electrolytes function NaClO4 concentration, ranging...