{BW₁₂O₄₀} Hybrids Modified by in Situ Synthesized Rigid Ligand with Supercapacitance and Photocatalytic Properties

Organic rigid ligand-modified polyoxometalate-based materials possess complex and diverse structures, promising electrochemical energy storage properties and outstanding photocatalytic capabilities. Hence, two new [BW₁₂O₄₀]^5-(abbreviated as {BW₁₂O₄₀})-based inorganic-organic hybrids [{Cu(en)₂(H₂O)}][{Cu(pdc)(en)}{Cu(en)₂}(BW₁₂O₄₀)]·2H₂O (1) and [{Cu^I₅(pz)₆(H₂O)₄}(BW₁₂O₄₀)] (2) (pdc = 2-picolinate, en = ethylenediamine, pz = pyrazine) were successfully synthesized through a hydrothermal method. Among them, pdc and pz were obtained by in situ transformation from 2,6-pyridinedicarboxylic acid (H₂ pydc) and 2,3-pyrazinedicarboxylic acid (H₂pzdc), respectively. In compound 1, the {BW₁₂O₄₀} clusters as an intermediate junction connect with {Cu(pdc)(en)}{Cu(en)₂} and {Cu(en)₂(H₂O)} to form monomers, which in turn form supramolecular chains, sheets, and space network via hydrogen bonding. The {BW₁₂O₄₀} clusters are packed into copper-pyrazine frameworks in compound 2, and a unique polyoxometalate-based metal organic frameworks (POMOFs) structure with a new topology of {12}₂{6.12³.14²}₂{6².12.14².18}{6².12³.16}{6}₆ is formed via covalent bonds. When used as electrode materials for supercapacitors, the values of specific capacitance are 651.56 F g^-1 for 1-GCE and 584.43 F g^-1 for 2-GCE at a current density of 2.16 A g^-1 and good cycling stability (90.94%, 94.81% of the initial capacity after 5000 cycles at 15.12 A g^-1, respectively). The kinetic analysis reveals that surface capacitance plays a major role. Furthermore, both compounds can effectively degrade Rhodamine B (RhB) and Methylene blue (MB), showing the outstanding photocatalytic performance.