Continuous addition kinetic elucidation: catalyst and reactant order, rate constant, and poisoning from a single experiment.

Kinetic analysis of catalytic reactions is a powerful tool for mechanistic elucidation but is often challenging to perform, limiting understanding and therefore development of these reactions. Establishing order in a catalyst is usually achieved by running several reactions at different loadings, which is both time-consuming and complicated by the challenge of maintaining consistent run-to-run experimental conditions. Continuous addition kinetic elucidation (CAKE) was developed to circumvent these issues by continuously injecting a catalyst into a reaction, while monitoring reaction progress over time. For reactions that are mth order in a single yield-limiting reactant and nth order in catalyst, a plot of reactant concentration against time has a shape dependent only on the orders m and n. Therefore, fitting experimental CAKE data (using open access code or a convenient web tool) allows the reactant and catalyst orders, rate constant, and the amount of complete catalyst inhibition to be determined from a single experiment. Kinetic information obtained from CAKE experiments showed good agreement with the literature.

Anodic and Cathodic Platinum Dissolution Processes Involve Different Oxide Species.

The degradation of Pt-containing oxygen reduction catalysts for fuel cell applications is strongly linked to the electrochemical surface oxidation and reduction of Pt. Here, we study the surface restructuring and Pt dissolution mechanisms during oxidation/reduction for the case of Pt(100) in 0.1 M HClO4 by combining operando high-energy surface X-ray diffraction, online mass spectrometry, and density functional theory. Our atomic-scale structural studies reveal that anodic dissolution, detected during oxidation, and cathodic dissolution, observed during the subsequent reduction, are linked to two different oxide phases. Anodic dissolution occurs predominantly during nucleation and growth of the first, stripe-like oxide. Cathodic dissolution is linked to a second, amorphous Pt oxide phase that resembles bulk PtO2 and starts to grow when the coverage of the stripe-like oxide saturates. In addition, we find the amount of surface restructuring after an oxidation/reduction cycle to be potential-independent after the stripe-like oxide has reached its saturation coverage.

Driving Force of the Initial Step in Electrochemical Pt(111) Oxidation.

The first step of electrochemical surface oxidation is extraction of a metal atom from its lattice site to a location in a growing oxide. Here we show by fast simultaneous electrochemical and in situ high-energy surface X-ray diffraction measurements that the initial extraction of Pt atoms from Pt(111) is a fast, potential-driven process, whereas charge transfer for the related formation of adsorbed oxygen-containing species occurs on a much slower time scale and is evidently uncoupled from the extraction process. It is concluded that potential plays a key independent role in electrochemical surface oxidation.

An Overview of Glycerol Electrooxidation Mechanisms on Pt, Pd and Au.

In the most recent decade, glycerol electrooxidation (GEOR) has attracted extensive research interest for valorization of glycerol: the conversion of glycerol to value-added products. These reactions at platinum, palladium, and gold electrodes have a lot of uncertainty in their reaction mechanisms, which has generated some controversies. This review gathers many reported experimental results, observations and proposed reaction mechanisms in order to draw a full picture of GEOR. A particular focus is the clarification of two propositions: Pd is inferior to Pt in cleaving the C-C bonds of glycerol during the electrooxidation and the massive production of CO2 at high overpotentials is due to the oxidation of the already-oxidized carboxylate products. It is concluded that the inferior C-C bond cleavability with Pd electrodes, as compared with Pt electrodes, is due to the inefficiency of deprotonation, and the massive generation of CO2 as well as other C1/C2 side products is partially caused by the consumption of OH- at the anodes, as a lower pH reduces the amount of carboxylates and favors the C-C bond scission. A reaction mechanism is proposed in this review, in which the generation of side products are directly from glycerol ("competition" between each side product) rather than from the further oxidation of C2/C3 products. Additionally, GEOR results and associated interpretations for Ni electrodes are presented, as well as a brief review on the performances of multi-metallic electrocatalysts (most of which are nanocatalysts) as an introduction to these future research hotpots.

Structural Reorganization of Pt(111) Electrodes by Electrochemical Oxidation and Reduction.

The surface restructuring of Pt(111) electrodes upon electrochemical oxidation/reduction in 0.1 M HClO4 was studied by in situ grazing-incidence small-angle X-ray scattering and complementary scanning tunneling microscopy measurements. These methods allow quantitative determination of the formation and structural evolution of nanoscale Pt islands during potential cycles into the oxidation region. A characteristic ripening behavior is observed, where these islands become more prominent and homogeneous in size with increasing number of cycles. Their characteristic lateral dimensions primarily depend on the upper potential limit of the cycle and only slightly increase with cycle number. The structural evolution of the Pt surface morphology strongly resembles that found in studies of Pt(111) homoepitaxial growth and ion erosion in ultrahigh vacuum. It can be fully explained by a microscopic model based on the known surface dynamic behavior under vacuum conditions, indicating that the same dynamics also describe the structural evolution of Pt in the electrochemical environment.

The role of available sites in the activity of lattice gases with geometric constraints.

The activity in lattice-gas systems with geometric constraints is shown to be the ratio of the number of particles to the number of available sites. The key role of sites available for occupation is emphasized. Available sites may be different for different species and are not necessarily just unoccupied sites. Location-specific or non-local constraints are allowed. An analytical expression for the number of available sites is given for the hard-hexagon model. The utility of an expression for available sites is illustrated for the non-trivial case of a mixed Langmuir/hard-hexagon adsorption system, where the influence of the Langmuir adsorbates on the hard-hexagon phase transition is investigated. The dependence on available sites indicates how to extend these results to the kinetic regime and simulations of kinetic voltammograms for the hard-hexagon model are given as an example.

A microfluidic fuel cell with flow-through porous electrodes.

A microfluidic fuel cell architecture incorporating flow-through porous electrodes is demonstrated. The design is based on cross-flow of aqueous vanadium redox species through the electrodes into an orthogonally arranged co-laminar exit channel, where the waste solutions provide ionic charge transfer in a membraneless configuration. This flow-through architecture enables improved utilization of the three-dimensional active area inside the porous electrodes and provides enhanced rates of convective/diffusive transport without increasing the parasitic loss required to drive the flow. Prototype fuel cells are fabricated by rapid prototyping with total material cost estimated at 2 USD/unit. Improved performance as compared to previous microfluidic fuel cells is demonstrated, including power densities at room temperature up to 131 mW cm-2. In addition, high overall energy conversion efficiency is obtained through a combination of relatively high levels of fuel utilization and cell voltage. When operated at 1 microL min-1 flow rate, the fuel cell produced 20 mW cm-2 at 0.8 V combined with an active fuel utilization of 94%. Finally, we demonstrate in situ fuel and oxidant regeneration by running the flow-through architecture fuel cell in reverse.