Ethylene Dimerization on Ni-Supported NU-1000: A Comprehensive Theoretical Study

Single-atom catalysts supported on metal–organic
frameworks
have attracted growing attention over the past few decades, as have
theoretical studies on these systems. While accurate predictions are
highly desirable for improved mechanistic understanding and catalyst
design, benchmarks on methodologies employed for such systems remain
limited. In this work, we present a comprehensive evaluation of computational
models and various density functionals for catalytic ethylene dimerization
on a Ni single-atom catalyst supported on NU-1000. We elucidate the
nature of the mononuclear Ni sites and their catalytic transformations
along the reaction pathway via the Cossee-Arlman mechanism. We assess
the adequacy of truncated cluster models and the accuracy of different
density functionals by comparing them with the highly accurate yet
computationally demanding periodic model and the DLPNO–CCSD­(T)
method, respectively.