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

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.