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Phys Chem Chem Phys ; 2020 Jul 29.
Artigo em Inglês | MEDLINE | ID: mdl-32724948


Ethylene glycol (EG) has been considered as a promising alcohol for direct alcohol fuel cells, however, our atomistic understanding of its interaction with doped transition-metal (TM) substrates is not well established. Here, we employed density functional theory calculations within the additive van der Waals D3 correction to improve our atomistic understanding of the role of TM dopants on the adsorption properties of EG on undoped and doped Pt(100) surfaces, namely, Pt8TM1/Pt9/Pt(100) and Pt9/Pt8TM1/Pt(100), where substitutional TM dopants (Fe, Co, Ni, Ru, Rh and Pd) are located within the topmost or subsurface Pt(100) layers, respectively. Except for Pd, all the studied TM dopants showed strong energetic preference for the subsurface layer, which can be explained by the segregation energy and charge effects, and it is not affected by the EG adsorption. In the lowest energy configurations of the undoped and doped substrates, EG binds via one OH group, with the anionic O atom located close to the on-top cationic TM site and the H atom parallel to the surface and pointing towards the bridge site. However, at slightly higher energy configurations, EG adsorbs via one OH with the C-C bond almost perpendicular to the surface, or via both OH groups. As expected, the adsorption is stronger on Pt8TM1/Pt9/Pt(100) with EG (OH group) bound to the cationic TM site and a O-TM distance of about 2 Å. Furthermore, doping enhanced the adsorption energy, and hence, decreased the distance between EG and the surface. For all substrates, adsorption induces a reduction of the work function, which is larger for the adsorption of EG via two OH groups.

Phys Chem Chem Phys ; 2020 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-32293626


Adsorption is a crucial preliminary step for the conversion of CO2 into higher-value chemicals, nonetheless, the atomistic understanding of how substrate particle size affects this step is still incomplete. In this study, we employed density functional theory to investigate the effects of particle size on the adsorption of model molecules involved in the CO2 transformations (CO2, CO, H2O and H2) on Con, Nin and Cun particles with different sizes (n = 13, 55, 147) and on the respective close-packed surfaces. We found significant size-dependence of the adsorption properties for physisorbed (linear) and chemisorbed (bent) CO2 on the substrates and distinct (symmetric or asymmetric) stretching of the C-O bonds, which can play a crucial role to understand the CO2 dissociation pathways. For CO and H2, some properties showed small oscillations, due to size effects that induced alternation of the adsorption site preference for different particle sizes; for H2O, the adsorption properties were almost independent of particle size. The presence of low-coordinated adsorption sites resulted in a trend for stronger adsorption and greater charge transfer for smaller clusters. Fixing the size-independent factors (e.g., type of metal), our results show that CO2 adsorption on transition-metal clusters is significantly affected by particle size, suggesting that substrate particle size could be a key factor to understand and control the catalytic transformations of CO2.

Phys Chem Chem Phys ; 21(16): 8434-8444, 2019 Apr 17.
Artigo em Inglês | MEDLINE | ID: mdl-30949640


Experimentally, steric and inductive effects have been suggested as key parameters in the adsorption and reactivity of alcohols on transition-metal (TM) surfaces, however, our atomistic understanding of the behavior of alcohols in catalysis is far from satisfactory, in particular, due to the role of hydroxy groups in the adsorption properties of C3 alcohols on TM surfaces. In this study, we investigated those effects through ab initio calculations based on density functional theory employing a semilocal exchange-correlation functional within van der Waals corrections (the D3 framework) for the adsorption of C3 alcohols with different numbers and positions of OH groups, namely, propane, 1-propanol, 2-propanol, 1,2-propanediol, 1,3-propanediol and glycerol, on the compact Ni(111), Pd(111) and Pt(111) surfaces. As expected, we found that the adsorption energy is affected by the number of hydroxy groups with similar values for each pair of regioisomers, which clearly indicates the effect of the number of OH groups. Based on Bader charge analysis, we found an effective charge transfer from the C3 molecules to the substrates, which can explain the reduction in the work function due to adsorption. Upon adsorption, the alpha carbon to the OH group closest to the surface and the central carbon are the most positively charged atoms, which increases the lability of their bonded H atoms. In addition, the depletion of electron density between the C-H and O-H bonds closer to the surfaces corroborated their stretching, suggesting that the proximity of the adsorbates to the surfaces affects the acidity of these H atoms, as well as inductive effects within the molecules.