@article{15114,
  abstract     = {As a key liquid organic hydrogen carrier, investigating the decomposition of formic acid (HCOOH) on the Pd (1 1 1) transition metal surface is imperative for harnessing hydrogen energy. Despite a multitude of studies, the major mechanisms and key intermediates involved in the dehydrogenation process of formic acid remain a great topic of debate due to ambiguous adsorbate interactions. In this research, we develop an advanced microkinetic model based on first-principles calculations, accounting for adsorbate–adsorbate interactions. Our study unveils a comprehensive mechanism for the Pd (1 1 1) surface, highlighting the significance of coverage effects in formic acid dehydrogenation. Our findings unequivocally demonstrate that H coverage on the Pd (1 1 1) surface renders formic acid more susceptible to decompose into H2 and CO2 through COOH intermediates. Consistent with experimental results, the selectivity of H2 in the decomposition of formic acid on the Pd (1 1 1) surface approaches 100 %. Considering the influence of H coverage, our kinetic analysis aligns perfectly with experimental values at a temperature of 373 K.},
  author       = {Yao, Zihao and Liu, Xu and Bunting, Rhys and Wang, Jianguo},
  issn         = {0009-2509},
  journal      = {Chemical Engineering Science},
  publisher    = {Elsevier},
  title        = {{Unravelling the reaction mechanism for H2 production via formic acid decomposition over Pd: Coverage-dependent microkinetic modeling}},
  doi          = {10.1016/j.ces.2024.119959},
  volume       = {291},
  year         = {2024},
}

@article{15356,
  abstract     = {Identifying efficient active sites for the direct synthesis of hydrogen peroxide over Pd-based catalysts has been a subject of considerable debate. In this study, we employ particle swarm optimization method and density functional theory to explore the H2O2 synthesis mechanism on Pd, PdO, and the partially oxidized surface (Pd9OX). A comprehensive mechanism for Pd9OX is elucidated, and subsequent coverage-dependent kinetic analysis allows for a quantitative assessment of catalytic performance at the interphase. Our findings conclusively establish that the interphase between Pd and PdO represents the optimal active site. Phase diagram analysis further aids in determining stable structures under reaction conditions. At 298.15 K and under oxygen balance, the Pd9O6 surface remains stable throughout the reaction, demonstrating high activity and selectivity. This work underscores the significance of the interphase in comprehending catalytic performance and unveils promising avenues for optimizing catalyst performance by controlling reaction conditions and surface composition.},
  author       = {Zhao, Jinyan and Yao, Zihao and Bunting, Rhys and Wang, Yaqiu and Wang, Jianguo},
  issn         = {0009-2509},
  journal      = {Chemical Engineering Science},
  publisher    = {Elsevier},
  title        = {{Identifying Pd9OX as the optimum catalyst for the direct synthesis of H2O2 through microkinetic modeling with coverage effects}},
  doi          = {10.1016/j.ces.2024.120199},
  volume       = {295},
  year         = {2024},
}