Lewis acidic Fe3+-driven catalytic active Ni3+ formation in Fe-free metal-organic framework for enhanced electrochemical glucose sensing.

Manipulating metal valence states and porosity in the metal-organic framework (MOF) by alloying has been a unique tool for creating high-valent metal sites and pore environments in a structure that are inaccessible by other methods, favorable for accelerating the catalytic activity towards sensing applications. Herein, we report Fe3+-driven formation of catalytic active Ni3+ species in the amine-crafted benzene-dicarboxylate (BDC-NH2)-based MOF as a high-performance electrocatalyst for glucose sensing. This work took the benefit of different bonding stability between BDC-NH2 ligand, and Fe3+ and Ni2+ metal precursor ions in the heterometallic NixFe(1-x)-BDC-NH2 MOF. The FeCl3 that interacts weakly with ligand, oxidizes the Ni2+ precursor to Ni3+-based MOF owing to its Lewis acidic behavior and was subsequently removed from the structure supported by Ni atoms, during solvothermal synthesis. This enables to create mesopores within a highly stable Ni-MOF structure with optimal feed composition of Ni0.7Fe0.3-BDC-NH2. The Ni3+-based Ni0.7Fe0.3-BDC-NH2 demonstrates superior catalytic properties towards glucose sensing with a high sensitivity of 13,435 µA mM-1 cm-2 compared to the parent Ni2+-based Ni-BDC-NH2 (10897 µA mM-1cm-2), along with low detection limit (0.9 µM), short response time (≤5 s), excellent selectivity, and higher stability. This presented approach for fabricating high-valent nickel species, with a controlled quantity of Fe3+ integrated into the structure allowing pore engineering of MOFs, opens new avenues for designing high-performing MOF catalysts with porous framework for sensing applications.

Atypical performance of CoO-accelerated interface tweaking in hierarchical cobalt phosphide/oxide@P-doped rGO heterostructures for hybrid supercapacitors.

Designing two-dimensional (2D) heterostructures based on suitable energy materials is a promising strategy to achieve high-performance supercapacitors with hybridized transition metal and carbonaceous-based electrodes. The influence of each component and its content on the capacitor performance necessitates deeper insights. In this study, a 2D/2D heterostructure made of hierarchical pseudocapacitive cobalt phosphide/oxide and P-doped reduced graphene oxide (PrGO) nanosheets (CoP/CoO@PrGO) was fabricated using porous zeolitic-imidazolate framework precursor. The decoration of 2D leaf-like CoP/CoO hybrid onto PrGO could create a unique interface with a large number of active sites, CoO-driven creation of pseudocapacitive surface POx species, and high P content (∼3 at.%) in PrGO, thus promoting the Faradaic reaction, electrical conductivity, and overall charge storage. This framework yields a high specific capacitance of 405 F g-1 at 5 A g-1 and excellent cycling stability (over 100 % after 10,000 cycles), superior to those of pristine CoP@PrGO (300 F g-1 at 5 A g-1). Furthermore, the fabricated asymmetric supercapacitor delivers reasonable energy density of 4.2 Wh kg-1 at a power density of 785 W kg-1 and cycling stability of âˆ¼100 % after 10,000 cycles. Therefore, CoP/CoO@PrGO with its unique interfacial properties can promote the development of heterostructure electrode for high-performance supercapacitors.