Tuning the selectivity for ring-opening reactions of methylcyclopentane over Pt catalysts: A mechanistic study from first-principles calculations

Abstract

Using density functional calculations, we studied the conversion of methylcyclopentane to its ring-opening products: branched hexanes [2-methylpentane (2MP), 3-methylpentane (3MP)], as well as unbranched n-hexane (nHx). We employed flat Pt(111) and stepped Pt(211) to describe terrace-rich large and defect-rich small Pt particles, respectively. On Pt(111), the barriers of all elementary steps for the paths leading to branched hexanes lie below 90kJmol−1, while the formation of nHx features a barrier of 116kJmol−1 in its C–C bond scission step. This higher barrier impedes the formation of nHx on Pt(111) and thus rationalizes the experimental observations that terrace-rich large Pt particles selectively produce branched hexanes. However, on Pt(211), the barrier of C–C scission for the formation of nHx decreases to 94kJmol−1, thus implying enhanced formation of nHx over the defects, in agreement with the essentially statistical product distribution observed with defect-rich small Pt particles.