With
the advantages of on-demand customization, 3D-printing techniques
have elevated the horizon of various fields. The as-printed 3D structures
often require postmodification to enhance their properties. Here,
we describe the use of molecularly precise covalent framework modification
in combination with atomic layer deposition (ALD) to construct advanced
sensors. First, a high-stability electrode was obtained by covalent
modification of porous nanomaterial [covalent organic frameworks,
(COF)] on the activated 3D electrode for the first time. Subsequently,
the Al2O3 nanomaterial was coated on the COF-based
3D electrode by the ALD technique. The constructed sensor termed Al2O3/COF/3DE was chosen for the determination of
important biomarkers including ascorbic acid, catechol, and dopamine,
which showed a high sensitivity for detecting these biomarkers. This
work opens avenues for the covalent modification of porous materials
on 3D-printed electrodes and deposition of functional material using
the ALD technique on the modified 3D electrode surface.