Structure effects of Pt₁₅ clusters for the oxygen reduction reaction: first-principles calculations

Abstract

In the present work, the lowest energy structures and electronic properties of Pt15 clusters are investigated using first-principles calculations. The catalytic activity for the oxygen reduction reaction is analyzed and discussed.

On the structure and electronic properties of Ptn clusters: new most stable structures for n = 16–17

“…For example, we have recently found a new most stable structure for Pt 15 with a capped pyramid-like structure by performing simulated annealing based on molecular dynamics simulations. 24 The structure of this isomer is different to those of previously reported putative global minima. By means of a GA algorithm and the TPSS functional, we computed herein other low-lying isomer for Pt 15 ( 15.2 ) which is only 1.6 kcal mol −1 above the global minimum 15.1 reported in our previous work.…”

“…By means of a GA algorithm and the TPSS functional, we computed herein other low-lying isomer for Pt 15 ( 15.2 ) which is only 1.6 kcal mol −1 above the global minimum 15.1 reported in our previous work. 24 Moreover, we found that the structure of 15.2 is close to that put forward by Kumar et al 10 ( 15.3 ). The difference between the configurations of 15.2 and 15.3 lies in the position of a single Pt atom at the bottom of the structures shown in Fig.…”

“…These metrics have been previously used to characterize the geometrical structure of metallic clusters. 24,43 We can appreciate from Table 2 that the average distance for the isomers in the different clusters is very similar. The intervals of d av for Pt 15 , Pt 16 , and Pt 17 are 2.58–2.60 Å, 2.58–2.62 Å, and 2.55–2.58 Å respectively.…”

“…We have carried out a conformational search using genetic algorithms implemented in the Cluster program 25 in combination with the Orca suite of packages,. 26 We used previously reported structures 10,24 as starting points and produced a series of candidates using the xtb2 methodology. 27 We let the system evolve for at least 30 generations using the same methodology.…”

“…In this work, we performed a GA structure search procedure in combination with high-level DFT calculations to properly identify the most stable structures of Pt n ( n = 15–17) clusters using GGA (PBE), meta-GGA (TPSS) and hybrid (B3PW91, PBE0, PBEh-3c, M06-L) functionals in conjunction with the Def2-TZVP basis set. This procedure helped us to recognize the correct structures of the global minima of Pt clusters by comparing them with a number of reports available 20–24 and providing more definitive assignments of such structures. We computed electronic and energy properties of the most stable clusters as well.…”