A density functional theory study of methanol dehydrogenation on the PtPd 3 (111) surface

Methanol oxidation on the PtPd(111) alloy surface: A density functional theory study

“…According to our calculations, both the PtPd‐bridge and Pt 2 Pd‐fcc sites are the second favorable sites with the CH 3 O adsorption energy of −1.65 eV. This situation is similar to Pt(111) and PtPd 3 (111) with the most preferred Pt‐top site for CH 3 O adsorption; however, different from Pd(111), where the most stable CH 3 O adsorption site is the fcc site (see Supporting Information Table S1) . Formaldehyde (CH 2 O) is apt to get adsorbed at Pt 2 ‐bridge site via a η 1 (C)η 1 (O) mode with the PtC and PtO distances of 2.147 and 2.081 Å, respectively.…”

“…For the comprehensive understanding of the catalytic mechanism of metal catalysts toward CH 3 OH oxidation, the computational chemistry methodology has been extensively used as a powerful tool . By using the density functional theory (DFT, PW91‐GGA) method, Greeley and Mavrikakis explored the competitive pathways for CH 3 OH decomposition on Pt(111), while CH 3 OH decomposition to CO on Pd(111) was studied in detail by Jiang et al Furthermore, the CH 3 OH dehydrogenation pathways have also been studied on the surface of alloy catalysts such as Pt 3 Pd(111) and Pt 3 Sn(111) . To further understand the influence of the second metal on CH 3 OH oxidation, Koper et al investigated the CO adsorption on PtRu alloy surfaces, and found that addition of Ru into Pt could help to weaken the adsorption energy of CO at Pt sites; however, the CO adsorption was strengthened at Ru sites .…”

“…2018;118:e25491.All the first-principle calculations were carried out by the periodic DFT method using the PW91 form of the general gradient approximation (GGA) functional in the DMol [3] package. [39][40][41][42][43] This computational strategy has been successfully employed to study the adsorption and reaction mechanisms of CH 3 OH on Pt(111), [31] Pd (111), [33] PtAu (111), [36] PdZn (111), [30] PtRu (111), [37] and PtRu/Pt(111) catalytic surfaces. [38] Notably, the PW91 functional does not take the van der Waals (vdW) contribution into consideration.…”

“…[24][25][26][27][28][29] By using the density functional theory (DFT, PW91-GGA) method, Greeley and Mavrikakis explored the competitive pathways for CH 3 OH decomposition on Pt(111), [30,31] while CH 3 OH decomposition to CO on Pd(111) was studied in detail by Jiang et al [32] Furthermore, the CH 3 OH dehydrogenation pathways have also been studied on the surface of alloy catalysts such as Pt 3 Pd(111) and Pt 3 Sn(111). [24,33] To further understand the influence of the second metal on CH 3 OH oxidation, Koper et al investigated the CO adsorption on PtRu alloy surfaces, and found that addition of Ru into Pt could help to weaken the adsorption energy of CO at Pt sites; however, the CO adsorption was strengthened at Ru sites. [34] Interestingly, periodic DFT calculations indicated that the principal channel of CH 3 OH oxidation was altered from the CO path on the Pt(111) surface to the non-CO path on the PtAu(111) alloy surface, and thus the formation of CO was inhibited.…”

Boron, nitrogen co-doped graphene: a superior electrocatalyst support and enhancing mechanism for methanol electrooxidation

“…Methanol is a polar molecule with negative charge accumulated on oxygen atoms and tends to adsorb on metal surface via lone-pair electrons of oxygen atoms [23]. However, the doping of nitrogen with high electronegativity into graphene decreases the electron density of its supported Pt, increasing the adsorption energy and reducing adsorption rate of methanol on Pt surface at low potentials [24]. Meanwhile, nitrogen doped graphene increases the d-band center of Pt, which enhances the adsorption of CO intermediate on Pt surface according to the d-band center theory from Nørskov [25], slowing down the oxidation removal of methanol at high potentials.…”