Theoretical insights into the interaction between RunPt13-n (n = 4, 7 and 9) clusters and [BMIM]+ based ionic liquids: Effect of anion

Density functional theory has been performed to systematically study the interactions between Ru_nPt_13-n (n = 4, 7 and 9) clusters and [BMIM]⁺ based ionic liquids. Ionic liquids [BMIM][Br], [BMIM][BF₄], [BMIM][PF₆], [BMIM][CF₃SO₃], and [BMIM][NTf₂] have different effects on the stability of Ru₇Pt₆. Ionic liquids with median size anions of PF₆⁻ and CF₃SO₃⁻ can better improve the stability of Ru₇Pt₆ than those with the small anions of Br⁻ and BF₄⁻ and large anion of NTf₂⁻. Based on negative relaxation energies, the stabilities of Ru₄Pt₉, Ru₇Pt₆, and Ru₉Pt₄ are all enhanced after interacting with [BMIM][CF₃SO₃]. The stability enhanced degree is in agreement with the interaction strength. For Ru₇Pt₆–n{[BMIM][CF₃SO₃]} (n = 1, 2, 3, 4), the interaction between ionic liquid and cluster plays the primary role in stabilizing the cluster in Ru₇Pt₆–[BMIM][CF₃SO₃]. With the increase of the number of [BMIM][CF₃SO₃], the role of the interaction in stabilizing the cluster is getting weaker, while the role of steric protection is getting more important.