RESUMO
Preparation of the NC-Cu@Ti electrode involved electrochemical deposition of nanocrystalline copper on the surface of titanium foil using a constant potential method, intended for high stability anode-free zinc ion battery (ZIB) anode material applications. This paper examines the effect of Cu2+ concentration in the electrodeposition solution on the structure and morphology of copper crystals on the NC-Cu@Ti electrode surface. The study also assesses how the interfacial properties of the NC-Cu@Ti electrode affect the process of anodic zinc deposition without anodic ZIBs. Our data suggest that with a voltage setting of -0.95 V and a copper ion concentration of 0.5 M in the solution, the deposition rate of copper crystals on the NC-Cu@Ti-0.5 electrode remains consistent. The resultant crystal phase surface appears smooth with a fine grain size. The NC-Cu@Ti-0.5 electrodes have increased hydrogen potentials and superior corrosion resistance; noting zinc nucleation sites at a mere 21.4 mV, it can provide stable electrochemical conditions for the zinc deposition interface of ZIBs and accelerate the process of zinc desolvation and nucleation. The constructed Zn//NC-Cu@Ti-0.5 asymmetric cell displays swift zinc deposition/stripping kinetics, elevated Coulombic efficiency, and prolonged stability (maintaining nearly 99% after 200 cycles). This performance significantly extends the service life relative to the Zn//Zn symmetric cell, which operates stably for 400 h at 1 mA/cm2. Moreover, the NC-Cu@Ti-0.5//MnO2 ZIBs offer enhanced conductivity and magnification performance to the pure zinc anode ZIBs. This study presents a novel approach for the low-cost and rapid preparation of anode materials for high-performance free-anode ZIBs.
RESUMO
A novel metal-organic framework (MOF)/covalent-organic framework (COF) heterostructure hybrid composite (NH2-UiO-66/TpPa-1-COF) with excellent photoactivity was developed, which further acted as the photoelectrochemical sensitized layer of a molecularly imprinted photoelectrochemical (MIP-PEC) sensor for extremely sensitive and selective determination of dibutyl phthalate (DBP). The NH2-UiO-66/TpPa-1-COF was synthesized using a simple one-step solvothermal method, which showed improved photocurrent response owing to heterojunction formation, favorable energy-band configuration and strong light absorption capacity. To improve the sensing performance, molecularly imprinted polymer (MIP) was developed by sol-gel polymerization method as the recognition component of PEC sensor. The specific binding of imprinting sites towards DBP could block the electron transfer, causing decreased photocurrent response of the MIP-PEC sensor. The MIP-PEC sensor showed a wide detection range from 0.1 nmol L-1 to 100 µmol L-1 with a limit of detection of 3.0 × 10-11 mol L-1 under optimal conditions. Meanwhile, the proposed MIP-PEC sensor showed good stability, selectivity, reproducibility, and applicability in real samples. This is the first attempt to apply MOF/COF heterostructure hybrid composite for MIP-PEC sensor construction, providing new insight into the potential applications of microporous crystalline framework heterostructure hybrid composite in the sensing field.