Cooperative O-atom binding produces the active configuration for OH formation in high-temperature catalytic hydrogen oxidation

Much effort in heterogeneous catalysis has gone into identifying “active sites” responsible for reactivity, knowledge of which could make predictive first principles theories useful for rational catalyst design. A major challenge arises since the structures that account for catalytic acceleration of reactivity may only form while reacting at high temperatures and pressures. This makes experimental tools that have proven useful in identifying active sites in ultrahigh vacuum and at low temperature of dubious utility. In this work, we present velocity-resolved kinetics (VRK) measurements for catalytic hydrogen oxidation on Pd over a wide range of surface concentrations and at high temperatures. The rates exhibit a complex dependence on oxygen coverage and step density, which can only be explained by a kinetic model derived from density functional theory (DFT) used in combination with transition-state theory (TST), when one includes a cooperatively stabilized configuration of at least thre..., , , # Cooperative O-atom binding produces the active configuration for OH formation in high-temperature catalytic hydrogen oxidation

[https://doi.org/10.5061/dryad.x3ffbg7vb](https://doi.org/10.5061/dryad.x3ffbg7vb)

## Description of the data and file structure

Two zip files are provided here.

The file named 'dft_structures' contains geometry files of the structures given in the supplementary information (SI) of the paper. The files are named after the nomenclature used in the SI (S1 to S29).

The file named 'experimental_data' contains the kinetic traces aquired in this work. Four folders are provided containing data for Pd(332) and Pd(111)  under oxygen rich and oxygen lean conditions.

### Files and variables

#### File: dft\_structures.zip

**Description:** The file named 'dft_structures.zip' contains geometry files of the structures given in the supplementary information (SI) of the paper. The files are named after the nomenclature used in the SI (S1 to S29).

#### File: experiment...