Mechanism of methanol decomposition on the Pd/WC(0001) surface unveiled by first-principles calculations

doi:10.1007/s11705-019-1908-y

Front. Chem. Sci. Eng.

2020, Vol. 14

Issue (6) : 1052-1064 https://doi.org/10.1007/s11705-019-1908-y

RESEARCH ARTICLE

Mechanism of methanol decomposition on the Pd/WC(0001) surface unveiled by first-principles calculations

Jinhua Zhang^1,², Yuanbin She¹(

)

¹. College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China
². School of Materials and Environmental Engineering, Chizhou University, Chizhou 247000, China

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Abstract

In this study, the decomposition of methanol into the CO and H species on the Pd/tungsten carbide (WC)(0001) surface is systematically investigated using periodic density functional theory (DFT) calculations. The possible reaction pathways and intermediates are determined. The results reveal that saturated molecules, i.e., methanol and formaldehyde, adsorb weakly on the Pd/ WC(0001) surface. Both CO and H prefer three-fold sites, with adsorption energies of −1.51 and −2.67 eV, respectively. On the other hand, CH₃O stably binds at three-fold and bridge sites, with an adsorption energy of −2.58 eV. However, most of the other intermediates tend to adsorb to the surface with the carbon and oxygen atoms in their sp³ and hydroxyl-like configurations, respectively. Hence, the C atom of CH₂OH preferentially attaches to the top sites, CHOH and CH₂O adsorb at the bridge sites, while COH and CHO occupy the three-fold sites. The DFT calculations indicate that the rupture of the initial C–H bond promotes the decomposition of CH₃OH and CH₂OH, whereas in the case of CHOH, O–H bond scission is favored over the C–H bond rupture. Thus, the most probable methanol decomposition pathway on the Pd/WC(0001) surface is CH₃OH → CH₂OH → trans-CHOH → CHO → CO. The present study demonstrates that the synergistic effect of WC (as carrier) and Pd (as catalyst) alters the CH₃OH decomposition pathway and reduces the noble metal utilization.

Keywords density functional theory methanol direct methanol fuel cells WC(0001)-supported Pd monolayer decomposition mechanism

Corresponding Author(s): Yuanbin She

Online First Date: 23 March 2020 Issue Date: 11 September 2020

Cite this article:

Jinhua Zhang,Yuanbin She. Mechanism of methanol decomposition on the Pd/WC(0001) surface unveiled by first-principles calculations[J]. Front. Chem. Sci. Eng., 2020, 14(6): 1052-1064.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-019-1908-y
https://academic.hep.com.cn/fcse/EN/Y2020/V14/I6/1052

Tab.1 Most stable adsorption sites, adsorption energies and key structural parameters of different intermediates of CH₃OH decomposition on the Pd/WC(0001) surface

Fig.1 Structures and electronic distributions of methanol decomposition intermediates on the Pd/WC(0001) surface. The upper part of each panel shows a top view of the most stable adsorption configuration of the different reaction intermediates (with side views shown in the top-right corner) involved in the CH₃OH decomposition on Pd/WC(0001), whereas the bottom part displays a side view of the electron density difference map of the corresponding intermediate. Red, orange, blue, gray and white spheres represent O, Pd, W, C and H atoms, respectively.

Fig.2 Top views of the most stable co-adsorption structures for CH₃OH decomposition on the Pd/WC(0001) surface, with side views displayed in the top-right corner of each panel (top). Side views of electron density difference maps of the corresponding co-adsorption structures (bottom).

Tab.2 Most stable co-adsorption structures and corresponding co-adsorption energies for CH₃OH decomposition on the Pd/WC(0001) surface

Fig.3 Structures and electronic distributions of TS formed during methanol decomposition on the Pd/WC(0001) surface. The upper panels of each figure represent top views of the TS structure during the CH₃OH decomposition reaction on Pd/WC(0001), with side views displayed in the top-right corner of each panel. The bottom panels of each figure show side views of the corresponding electron density difference map.

Tab.3 Energy barrier and reaction energy for CH₃OH decomposition on the Pd/WC(0001) surface

Fig.4 Reaction network of CH₃OH decomposition on Pd/WC(0001) surface; the proposed reaction pathway is marked with red arrows.

Fig.5 Potential energy profiles for CH₃OH and CH₂OH decomposition on the Pd/WC(0001) surface.

Fig.6 Potential energy profiles for CH₃O, CH₂O, and CHOH decomposition on the Pd/WC(0001) surface.

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