Formic acid dehydrogenation on Ni(111) and comparison with Pd(111) and Pt(111)

Qiquan Luo, Gang Feng, Matthias Beller, Haijun Jiao

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118 Scopus citations

Abstract

Spin-polarized density functional theory calculations have been performed to investigate formic acid dehydrogenation into carbon dioxide and hydrogen (HCO 2H → CO 2 + H 2) on Ni(111). It is found that formic acid prefers the O (O=C) atop adsorption on nickel surface and the H (H-O) atom bridging two neighboring nickel atoms, and formate prefers the bidentate adsorption with O atop on nickel surface. The computed stretching frequencies for deuterated formic acid (DCO 2H) and deuterated formate (DCO 2) on Ni(111) agree well with the experimentally observed IR spectra. Formic acid dehydrogenation into surface formate and hydrogen atom (HCO 2H → HCO 2 + H) has barrier of 0.41 eV and is exothermic by 0.35 eV. Formate dehydrogenation into carbon dioxide and hydrogen atom (HCO 2 → CO 2 + H) has an effective barrier of about 1.0 eV and is the rate-determining step. Our computed adsorption configurations and energetic data for formic acid dehydrogenation on Ni(111) are very close to the reported results for Pt(111), but in sharp contrast to the previously reported results for Pd(111). Our recalculated adsorption configurations and energetic data for formic acid dehydrogenation on Pd(111) are similar to those on Ni(111) and Pt(111), demonstrating the high similarities of these metals. These computed data show that Pd-catalyzed formic acid dehydrogenation has the lowest effective barrier (0.76 eV), followed by Ni (1.03 eV) and Pt (1.56 eV).

Original languageEnglish
Pages (from-to)4149-4156
Number of pages8
JournalJournal of Physical Chemistry C
Volume116
Issue number6
DOIs
StatePublished - 16 Feb 2012
Externally publishedYes

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