Porous {P₆Mo₁₈O₇₃}-type Poly(oxometalate) Metal–Organic Frameworks for Improved Pseudocapacitance and Electrochemical Sensing Performance

{P6Mo18} poly(oxometalate) (POM) clusters have huge steric hindrance and limited active oxygen atoms, which make them difficult to combine with metal–organic units to form three-dimensional (3D) porous structures. Therefore, functionalization of such POMs has always been a bottleneck that is difficult to break through. In this study, {P6Mo18} POM was successfully grafted on a lock-like metal–organic chain to generate a multiporous coordination polymer, [{Na(H2O)(H2btb)}{Cu4I(H2O)(pz)5Cl}{H2Sr⊂P6Mo2VMo16VIO73}]·3H2O (1) (pz = pyrazine; btb = 1,4-bis(1,2,4-triazole) butane). Meanwhile, a zero-dimensional (0-D) control compound with only btb ligands as counterions, (H4btb)[H4Sr⊂P6Mo2VMo16VIO73]·3H2O (2), was also obtained via a hydrothermal reaction. Compound 1 represents the first basket-type 3D poly(oxometalate) metal–organic framework (POMOF) assembly, which possesses interpenetrating pores and complex topology. 1-GO-CPE displays improved supercapacitor (SC) performance (the specific capacitance of 929.4 F g–1 at a current density of 3 A g–1 with 94.1% of cycle efficiency after 5000 cycles) compared with 2-GO-CPE and most reported POMOF electrode materials, which may be due to the outstanding redox capability of basket-POM, introduction of metal–organic chains, intersecting pores, and excellent conductivity of graphene. An asymmetric SC device with 1-GO-CPE as the negative electrode exhibits an energy density of 29.7 Wh kg–1 with a power density of 3148.2 W kg–1 and long-lasting cycling life. In addition, 1-GO-GCE as an electrochemical sensor responds to dopamine (DA) at a voltage of 0.40 V and shows lower detection limits (0.19 μM (signal-to-noise ratio (SNR) = 3)), higher selectivity, and good reproducibility in the linear range of 0.56 μM to 0.24 mM. The ability to accurately detect the content of DA in biological samples further proves the feasibility of the sensor in practical applications.