首页> 外文期刊>ACS catalysis >Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory study
【24h】

Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory study

机译:模型过渡金属表面上甲酸分解的趋势:密度泛函理论研究

获取原文
获取原文并翻译 | 示例
           

摘要

We present a first-principles, self-consistent periodic density functional theory (PW91-GGA) study of formic acid (HCOOH) decomposition on model (111) and (100) facets of eight fcc metals (Au, Ag, Cu, Pt, Pd, Ni, Ir, and Rh) and (0001) facets of four hcp (Co, Os, Ru, and Re) metals. The calculated binding energies of key formic acid decomposition intermediates including formate (HCOO), carboxyl (COOH), carbon monoxide (CO), water (H2O), carbon dioxide (CO2), hydroxyl (OH), carbon (C), oxygen (O), and hydrogen (H; H2) are presented. Using these energetics, we develop thermochemical potential energy diagrams for both the carboxylmediated and the formate-mediated dehydrogenation mechanisms on each surface. We evaluate the relative stability of COOH, HCOO, and other isomeric intermediates (i.e., CO + OH, CO2 + H, CO + O + H) on these surfaces. These results provide insights into formic acid decomposition selectivity (dehydrogenation versus dehydration), and in conjunction with calculated vibrational frequency modes, the results can assist with the experimental search for the elusive carboxyl (COOH) surface intermediate. Results are compared against experimental reports in the literature.
机译:我们提供了一种第一性原理,自洽周期密度泛函理论(PW91-GGA),研究了八种fcc金属(Au,Ag,Cu,Pt,四种hcp(Co,Os,Ru和Re)金属的Pd,Ni,Ir和Rh)和(0001)面。计算出的主要甲酸分解中间体的结合能包括甲酸(HCOO),羧基(COOH),一氧化碳(CO),水(H2O),二氧化碳(CO2),羟基(OH),碳(C),氧( O)和氢(H; H2)存在。使用这些能量,我们为每个表面上的羧基介导的和甲酸介导的脱氢机理建立了热化学势能图。我们评估了这些表面上COOH,HCOO和其他异构中间体(即CO + OH,CO2 + H,CO + O + H)的相对稳定性。这些结果提供了对甲酸分解选择性(脱氢与脱水)的认识,并结合计算出的振动频率模式,这些结果可帮助实验性地寻找难于解决的羧基(COOH)表面中间体。将结果与文献中的实验报告进行比较。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱:kefu@zhangqiaokeyan.com

京公网安备:11010802029741号 ICP备案号:京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有
  • 客服微信

  • 服务号