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...多相催化领域已投入大量精力，用于识别介导催化反应活性的**活性位点（active sites）**，若能掌握此类位点的相关信息，便可令基于第一性原理的预测理论在合理催化剂设计中发挥实用价值。当前存在一项核心挑战：能够催化加速反应的活性结构，往往仅在高温高压的反应条件下才会形成。这使得此前在超高真空、低温环境中被证实可有效识别活性位点的实验工具，其适用性变得存疑。本研究中，我们针对钯（Pd）表面的催化氢氧化反应，在宽表面浓度范围与高温条件下开展了**速度分辨动力学（velocity-resolved kinetics, VRK）**测试。反应速率对氧覆盖度与台阶密度呈现出复杂的依赖关系，唯有当考虑至少三个（原文截断）的协同稳定构型时，结合**密度泛函理论（density functional theory, DFT）**与**过渡态理论（transition-state theory, TST）**构建的动力学模型，才能解释这一现象。# 协同氧原子结合形成高温催化氢氧化中OH生成的活性构型 [https://doi.org/10.5061/dryad.x3ffbg7vb](https://doi.org/10.5061/dryad.x3ffbg7vb) ## 数据与文件结构说明 本次提供了两个压缩文件： 1. 名为`dft_structures`的压缩包：内含论文**补充材料（supplementary information, SI）**中提及的所有结构的几何构型文件，文件命名遵循补充材料中的编号规则（S1至S29）。 2. 名为`experimental_data`的压缩包：包含本研究测得的动力学轨迹数据。本次提供了四个文件夹，分别对应Pd(332)与Pd(111)晶面在富氧、贫氧条件下的测试数据。 ### 文件与变量说明 #### 压缩包：dft_structures.zip **说明：** 该压缩包内含论文补充材料中提及的所有结构的几何构型文件，文件命名遵循补充材料中的编号规则（S1至S29）。 #### 压缩包：experiment...