A general protocol for engineering metal–oxo-chain standing frameworks

ABSTRACT Infinite metal–oxo metal–organic frameworks (MOFs) are recognized as promising platforms for developing all-round high-performance catalysts for both academic and industrial significance. Nevertheless, engineering infinite metal–oxo architectures typically requires harsh synthetic conditions, often yielding microcrystalline or even nanocrystalline products that hinder precise structure identifications. Herein, we propose a previously underestimated acetic acid-based solvothermal protocol for general engineering of 1D infinite metal–oxo (e.g. Zr, Hf, Ce) MOFs featuring large-size single crystals with well-identified crystallographic structures. As an example, the 1D Zr–BTB-derived catalyst exhibits a turnover frequency (TOF) of 1199.1 h−1, selectivity of 99.0% and long-term stability in the catalytic upgrading of natural feedstocks into high-value-added fuels. In comparison, the conventional Zr6O8 node-based counterpart only presents a TOF of 282.5 h−1, selectivity of 5.9% and poor recycling ability. This work opens the avenue to design industry-oriented performant heterogeneous catalysts for energy-critical transformations via rational engineering of versatile infinite metal–oxo units.