There is wide interest in developing accurate theories for predicting rates of chemical reactions that occur at metal surfaces, especially for applications in industrial catalysis. Conventional methods contain many approximations that lack experimental validation. In practice, there are few reactions where sufficiently accurate experimental data exist to even allow meaningful comparisons to theory. Here, we present experimentally derived thermal rate constants for hydrogen atom recombination on platinum single-crystal surfaces, which are accurate enough to test established theoretical approximations. A quantum rate model is also presented, making possible a direct evaluation of the accuracy of commonly used approximations to adsorbate entropy. We find that neglecting the wave nature of adsorbed hydrogen atoms and their electronic spin degeneracy leads to a 10× to 1000× overestimation of the rate constant for temperatures relevant to heterogeneous catalysis. These quantum effects are also found to be important for nanoparticle catalysts.

We report accurate time-resolved measurements of NH 3 desorption from Pt(111) and Pt(332) and use these results to determine elementary rate constants for desorption from steps, from (111) terrace sites and for diffusion on (111) terraces. Modeling the extracted rate constants with transition state theory, we find that conventional models for partition functions, which rely on uncoupled degrees of freedom (DOFs), are not able to reproduce the experimental observations. The results can be reproduced using a more sophisticated partition function, which couples DOFs that are most sensitive to NH 3 translation parallel to the surface; this approach yields accurate values for the NH 3 binding energy to Pt(111) (1.13 ± 0.02 eV) and the diffusion barrier (0.71 ± 0.04 eV). In addition, we determine NH 3 ’s binding energy preference for steps over terraces on Pt (0.23 ± 0.03 eV). The ratio of the diffusion barrier to desorption energy is ∼0.65, in violation of the so-called 12% rule. Using our derived diffusion/desorption rates, we explain why established rate models of the Ostwald process incorrectly predict low selectivity and yields of NO under typical reactor operating conditions. Our results suggest that mean-field kinetics models have limited applicability for modeling the Ostwald process.

Up to now, methods for measuring rates of reactions on catalysts required long measurement times involving signal averaging over many experiments. This imposed a requirement that the catalyst return to its original state at the end of each experiment—a complete reversibility requirement. For real catalysts, fulfilling the reversibility requirement is often impossible—catalysts under reaction conditions may change their chemical composition and structure as they become activated or while they are being poisoned through use. It is therefore desirable to develop high-speed methods where transient rates can be quickly measured while catalysts are changing. In this work, we present velocity-resolved kinetics using high-repetition-rate pulsed laser ionization and high-speed ion imaging detection. The reaction is initiated by a single molecular beam pulse incident at the surface, and the product formation rate is observed by a sequence of pulses produced by a high-repetition-rate laser. Ion imaging provides the desorbing product flux (reaction rate) as a function of reaction time for each laser pulse. We demonstrate the principle of this approach by rate measurements on two simple reactions: CO desorption from and CO oxidation on the 332 facet of Pd. This approach overcomes the time-consuming scanning of the delay between CO and laser pulses needed in past experiments and delivers a data acquisition rate that is 10–1000 times higher. We are able to record kinetic traces of CO 2 formation while a CO beam titrates oxygen atoms from an O-saturated surface. This approach also allows measurements of reaction rates under diffusion-controlled conditions.

Understanding heterogeneous catalysis is based on knowing the energetic stability of adsorbed reactants, intermediates, and products as well as the energetic barriers separating them. We report an experimental determination of the barrier to CO2 functionalization to form bidentate formate on a hydrogenated Pt surface and the corresponding reaction energy. This determination was possible using velocity resolved kinetics, which simultaneously provides information about both the dynamics and rates of surface chemical reactions. In these experiments, a pulse of isotopically labeled formic acid (DCOOH) doses the Pt surface rapidly forming bidentate formate (DCO*O*). We then record the (much slower) rate of decomposition of DCO*O* to form adsorbed D* and gas phase CO2. We establish the reaction mechanism by dosing with O2 to form adsorbed O*, which efficiently converts H* or D* to gas phase water. H2O is formed immediately reflecting rapid loss of the acidic proton associated with formation of formate, while D2O formation proceeds more slowly and on the same time scale as the CO2 production. The temperature dependence of the reaction rate yields an activation energy that reflects the energy of the transition state with respect to DCO*O*. The derived heat of formation for DCO*O* on Pt(111) agrees well with results of microcalorimetry. The maximum release of translational energy of the formed CO2 provides a measure of the energy of the transition state with respect to the products and the barrier to the reverse process, functionalization of CO2. The comparison between the results on Pt(111) and Pt(332) shows that the barrier for CO2 functionalization is reduced by the presence of steps. The approach taken here could provide a method to optimize catalysts for CO2 functionalization.

We report nitric oxide (NO) desorption rates from Pd(111) and Pd(332) surfaces measured with velocity-resolved kinetics. The desorption rates at the surface temperatures from 620 to 800 K span more than 3 orders of magnitude, and competing processes, like dissociation, are absent. Applying transition state theory (TST) to model experimental data leads to the NO binding energy E 0 = 1.766 ± 0.024 eV and diffusion barrier D T = 0.29 ± 0.11 eV on the (111) terrace and the stabilization energy for (110)-steps Δ E ST = 0.060 –0.030 +0.015 eV. These parameters provide valuable benchmarks for theory.