A hybrid of ultrathin metal-organic framework sheet and ultrasmall copper nanoparticles for detection of hydrogen peroxide with enhanced activity

Here, we design and synthesize a novel 2D Cu-tetrakis(4-carboxyphenyl)porphyrin (TCPP) metal–organic framework (MOF) sheet and ultrasmall Cu5.4O nanoparticle (Cu5.4O USNP) hybrid (Cu-TCPP MOF/Cu5.4O nanocomposite). The graphene-like ultrathin Cu-TCPP MOF sheets offer high surface-to-volume atom ratios and many active sites, which is beneficial for loading more Cu5.4O USNPs. The Cu5.4O USNPs with ultrasmall size (<5 nm) have promising conductivity and excellent enzymatic ability for H2O2. The successfully prepared nanocomposites are characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and Fourier transform infrared (FT-IR) techniques. The 2D graphene-like ultrathin Cu-TCPP MOF sheets show no H2O2-sensing signals, whereas Cu5.4O USNPs exhibit a clear reduction peak for detection of H2O2. Interestingly, the combination of two kinds of nanomaterials improved the H2O2 sensing ability due to their synergistic effect. The properties of the unmodified electrodes and the Cu-TCPP MOF/Cu5.4O nanocomposite-modified electrodes were systemically studied by cyclic voltammetry (CV), current-time (i-t) response, and square-wave voltammetry (SWV) techniques. The electrochemical sensor for the detection of H2O2 based on the Cu-TCPP MOF/Cu5.4O nanocomposite has a lower detection limit of 0.13 μmol·L−1 and wider linear range of 0.1 × 10−6 ~ 0.59 × 10−3 mol·L−1 and 1.59 × 10−3 ~ 20.59 × 10−3 mol·L−1 when compared with the Cu5.4O USNPs-modified electrode. The electrochemical sensor can be further used to detect H2O2 produced by cells.