In this work, we pioneered the preparation of diamond-containing flexible electrodes using 3D printing technology. The herein developed procedure involves a unique integration of boron-doped diamond (BDD) microparticles and multi-walled carbon nanotubes (CNTs) within a flexible polymer, thermoplastic polyurethane (TPU). Initially, the process for the preparation of homogeneous filaments with optimal printability was addressed, leading to the development of two TPU/CNT/BDD composite electrodes with different CNT:BDD weight ratios (1:1 and 1:2), which were benchmarked against a TPU/CNT electrode. Scanning electron microscopy revealed a uniform distribution of conductive fillers within the composite materials with no signs of clustering or aggregation. Notably, increasing the proportion of BDD particles led to a 10-fold improvement in conductivity, from 0.12 S m-1 for TPU/CNT to 1.2 S m-1 for TPU/CNT/BDD (1:2). Cyclic voltammetry of the inorganic redox markers, [Ru(NH3)6]3+/2+ and [Fe(CN)6]3-/4-, also revealed a reduction in peak-to-peak separation (ΔE p) with a higher BDD content, indicating enhanced electron transfer kinetics. This was further confirmed by the highest apparent heterogeneous electron transfer rate constants (k 0 app) of 1 × 10-3 cm s-1 obtained for both markers for the TPU/CNT/BDD (1:2) electrode. Additionally, the functionality of the flexible TPU/CNT/BDD electrodes was successfully validated by the electrochemical detection of dopamine, a complex organic molecule, at millimolar concentrations by using differential pulse voltammetry. This proof-of-concept may accelerate development of highly desirable diamond-based flexible devices with customizable geometries and dimensions and pave the way for various applications where flexibility is mandated, such as neuroscience, biomedical fields, health, and food monitoring.

Department of Aerospace Structures and Materials Faculty of Aerospace Engineering Delft University of Technology Kluyverweg 1 2629 HS Delft The Netherlands

Department of Analytical Chemistry Faculty of Science Charles University Albertov 6 128 00 Prague Czech Republic

Department of Precision and Microsystems Engineering Faculty of Mechanical Engineering Delft University of Technology Mekelweg 2 2628 CD Delft The Netherlands

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