Hydrogen generation from formic acid decomposition on Ni(2 1 1),Pd(2 1 1) and Pt(2 1 1)

Qiquan Luo, Tao Wang, Matthias Beller, Haijun Jiao

Research output: Contribution to journalArticlepeer-review

40 Scopus citations

Abstract

The catalytic decomposition of formic acid into carbon dioxide and hydrogen (HCO2H → CO2+ H2) onM(2 1 1) (M = Ni, Pd, Pt) was investigated by using spin-polarized plane-wave based density functionaltheory calculations. It is found that on M(2 1 1) formic acid prefers the O (O C) atom atop adsorption andthe H (H O) atom bridging two neighboring metal atoms, and formate prefers the bidentate adsorptionwith O atoms atop on metal surface. For M = Ni, Pd, Pt, formic acid has close adsorption energies (-0.69,-0.58, -0.61 eV) and also close dissociation barriers (0.42, 0.53, 0.51 eV), and the dissociation step isexothermic (-0.95, -0.44, -0.81 eV). Formate dissociation into surface CO2and H (HCOO → CO2+ H) isthe rate-determining step; and the effective barrier is higher on Ni(2 1 1) than on Pd(2 1 1) and Pt(2 1 1)(1.43 vs. 0.96 and 0.86 eV), and formate dissociation is endothermic (0.44 eV) on Ni(2 1 1), but exothermicon Pd(2 1 1) and Pt(2 1 1) (-0.09 vs. -0.19 eV). On M(2 1 1), CO2 has chemisorption (-0.32, -0.13, -0.27 eVfor M = Ni, Pd, Pt, respectively). For formate dissociation, detailed comparisons between M(2 1 1) andM(1 1 1) show that Pd(1 1 1) and Pt(2 1 1) have the smallest effective barriers, while Pt(1 1 1) and Ni(2 1 1)have the largest effective barriers.

Original languageEnglish
Pages (from-to)169-177
Number of pages9
JournalJournal of Molecular Catalysis A: Chemical
Volume379
DOIs
StatePublished - 15 Nov 2013
Externally publishedYes

Keywords

  • Dehydrogenation
  • Formic acid
  • Nickel
  • Palladium
  • Platinum

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