TiO₂ nanoparticle-Coated 3D-Printed porous monoliths enabling highly sensitive speciation of inorganic Cr, As, and Se

Post-printing functionalization can enhance the functionality and applicability of analytical devices manufactured using three-dimensional printing (3DP) technologies. In this study we developed a post-printing foaming-assisted coating scheme-through respective treatments with a formic acid (30%, v/v) solution and a sodium bicarbonate (0.5%, w/v) solution incorporating titanium dioxide nanoparticles (TiO₂ NPs; 1.0%, w/v)-for in situ fabrication of TiO₂ NP-coated porous polyamide monoliths in 3D-printed solid phase extraction columns, thereby enhancing the extraction efficiencies of Cr(III), Cr(VI), As(III), As(V), Se(IV), and Se(VI) for speciation of inorganic Cr, As, and Se species in high-salt-content samples when using inductively coupled plasma mass spectrometry. After optimizing the experimental conditions, the 3D-printed solid phase extraction columns with the TiO₂ NP-coated porous monoliths extracted these species with 5.0- to 21.9-fold enhancements, relative to those obtained with the uncoated monolith, with absolute extraction efficiencies ranging from 84.5 to 98.3% and method detection limits ranging from 0.7 to 32.3 ng L^-1. We validated the reliability of this multi-elemental speciation method through determination of these species in four reference materials [CASS-4 (nearshore seawater), SLRS-5 (river water), 1643f (fresh water), and Seronorm Trace Elements Urine L-2 (human urine); relative errors between certified and measured concentrations: 5.6 to +4.0%] and spike analyses of seawater, river water, agriculture waste, and human urine samples (spike recoveries: 96-104%; relative standard deviations of these measured concentrations all below 4.3%). Our results demonstrate that post-printing functionalization has great potential for future applicability in 3DP-enabling analytical methods.