Gas reactions under intrapore condensation regime within tailored metal\u2013organic framework catalysts

Iker Agirrezabal-Telleria,Mustapha Soukri,Iñaki Gandarias,Manuel A Ortuño,Marty A Lail,Núria López,Mikel Oregui-Bengoechea,Ignacio Luz

doi:10.1038/s41467-019-10013-6

Abstract

Production of 1-butene, a major monomer in polymer industry, is dominated by homogeneous protocols via ethylene dimerization. Homogeneous catalysts can achieve high selectivity but require large amounts of activators and solvents, and exhibit poor recyclability; in turn, heterogeneous systems are robust but lack selectivity. Here we show how the precise engineering of metal–organic frameworks (MOFs) holds promise for a sustainable process. The key to the (Ru)HKUST-1 MOF activity is the intrapore reactant condensation that enhances ethylene dimerization with high selectivity (> 99% 1-butene) and high stability (> 120 h) in the absence of activators and solvents. According to spectroscopy, kinetics, and modeling, the engineering of defective nodes via controlled thermal approaches rules the activity, while intrapore ethylene condensation accounts for selectivity and stability. The combination of well-defined actives sites with the concentration effect arising from condensation regimes paves the way toward the development of robust MOF catalysts for diverse gas-phase reactions.

Highlights

Production of 1-butene, a major monomer in polymer industry, is dominated by homogeneous protocols via ethylene dimerization
Metal–organic frameworks (MOFs)[3] hold promise to get the best ingredients from both worlds, i.e., selective and well-defined catalytic sites distributed on porous solids[4,5,6]
We propose a new experimental set up where such defective metal–organic frameworks (MOFs) can efficiently catalyze ethylene dimerization in the absence of activators

Summary

Introduction

Production of 1-butene, a major monomer in polymer industry, is dominated by homogeneous protocols via ethylene dimerization. The thermal engineering of defects yields catalytically active species with remarkable activity in the absence of activators, high selectivity to 1-butene (>99% selectivity), and long-time stability (>120 h) under intrapore ethylene condensation regime.

Results

Conclusion