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Zirconium-based metal-organic frameworks (Zr-MOFs) have been extensively studied due to their very rich structural chemistry. The combination of nearly unlimited carboxylic acid-based linkers and Zr 6 clusters with multiple connectivities has led to diverse structures and specific properties of resultant Zr-MOFs. Herein, we demonstrate the successful use of reticular chemistry to construct two novel Zr-MOFs, HIAM-4040 and HIAM-4040-OH, with zfu topology. Based on a thorough structural analysis of (4,4)-connected lvt-type Zr-tetracarboxylate frameworks and a judicious linker design, we have obtained the first example of a Zr-pentacarboxylate framework featuring unprecedented 5-connected organic linkers and 5-connected Zr 6 clusters. Compared with HIAM-4040, a larger Stokes shift is achieved in HIAM-4040-OH via hydroxyl group induced excited-state intramolecular proton transfer (ESIPT). HIAM-4040-OH exhibits high chemical and thermal stability and is used for HClO detection in aqueous solution with excellent sensitivity and selectivity., Competing Interests: The authors declare no competing financial interests., (This journal is © The Royal Society of Chemistry.)

Current Sn-based materials are ideal catalysts developed to drive the electrochemical conversion of CO 2 to formate, but competing proton reduction to hydrogen is an ever-present drain on catalytic selectivity. Herein, we report a reliable electrochemical exfoliation route, with the assistance of alternating voltage, for large-scale preparation of two-dimensional (2D) ultrathin tin monosulfide nanosheets (SnS NSs), which feature a large lateral size of 1.0 μm with a thickness of ∼5.0 nm. Systematic electrochemical studies demonstrated that the achieved SnS NSs exhibited an outstanding electrocatalytic activity towards the CO 2 reduction reaction (CO 2 RR) to the formate product, as evidenced by a considerable faradaic efficiency (F.E.) of 82.1%, a high partial current density of 18.9 mA cm -2 at -1.1 V, and a low Tafel slope of 180 mV dec -1 . Further, using an electrode prepared from the resulting SnS NSs by the particle transfer method, a remarkably high formate F.E. over 91% was achieved in a wide potential window. Such high performance renders the SnS NSs among the best reported tin sulfide-based CO 2 RR electrocatalysts. Theoretical calculations coupled with comprehensive experimental studies demonstrated that the synergistic effect between the ultrathin layered architecture and dominantly exposed (001) plane of SnS NSs accounted for the uniquely efficient catalytic activity for the CO 2 RR., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)