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

## TL;DR

A new acetic acid-based method creates single-crystal metal-oxo frameworks that act as highly efficient and stable catalysts for industrial fuel production.

## Contribution

A general acetic acid-based solvothermal protocol is introduced for engineering single-crystal 1D metal–oxo MOFs with high catalytic performance.

## Key findings

- The Zr–BTB-derived catalyst achieves a TOF of 1199.1 h−1, 99.0% selectivity, and long-term stability.
- Conventional Zr6O8 node-based catalysts show much lower performance with a TOF of 282.5 h−1 and 5.9% selectivity.
- The new protocol enables precise structure identification and large single-crystal formation.

## 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.

An unusual acetic acid-based synthetic protocol is proposed for generally engineering single-crystal metal-oxo-chain standing frameworks competent for industry-oriented performant heterogeneous catalysts with all-excellence in activity, selectivity, and durability.