Metal–organic frameworks (MOFs) based on Ti-oxo clusters (Ti-MOFs) represent a naturally self-assembled superlattice of TiO₂ nanoparticles separated by designable organic linkers as antenna chromophores, epitomizing a promising platform for solar energy conversion. However, despite the vast, diverse, and well-developed Ti-cluster chemistry, only a scarce number of Ti-MOFs have been documented. The synthetic conditions of most Ti-based clusters are incompatible with those required for MOF crystallization, which has severely limited the development of Ti-MOFs. This challenge has been met herein by the discovery of the [Ti₈Zr₂O₁₂(COO)₁₆] cluster as a nearly ideal building unit for photoactive MOFs. A family of isoreticular photoactive MOFs were assembled, and their orbital alignments were fine-tuned by rational functionalization of organic linkers under computational guidance. These MOFs demonstrate high porosity, excellent chemical stability, tunable photoresponse, and good activity toward photocatalytic hydrogen evolution reactions. The discovery of the [Ti₈Zr₂O₁₂(COO)₁₆] cluster and the facile construction of photoactive MOFs from this cluster shall pave the way for the development of future Ti-MOF-based photocatalysts.

The oxygen reduction reaction (ORR) is central in carbon-neutral energy devices. While platinum group materials have shown high activities for ORR, their practical uses are hampered by concerns over deactivation, slow kinetics, exorbitant cost, and scarce nature reserve. The low-cost yet high tunablility of metal-organic frameworks (MOFs) provide a unique platform for tailoring their characteristic properties as new electrocatalysts. Herein, we report a new concept of design and present stable Zr-chain-based MOFs as efficient electrocatalysts for ORR. The strategy is based on using Zr-chains to promote high chemical and redox stability, and more importantly, tailor the immobilization and packing of redox active-sites at an ideal density to improve the reaction kinetics. The obtained new electrocatalyst, PCN-226, thereby shows high ORR activity. We further demonstrate PCN-226 as a promising electrode material for practical applications in rechargeable Zn-air batteries, with a high peak power density of 133 mW cm−2. Being one of the very few electrocatalytic MOFs for ORR, this work provides a new concept by designing chain-based structures to enrich the diversity of efficient electrocatalysts and MOFs.