Incorporating enzymes with three-dimensional (3D) printing is an exciting new field of convergence research that holds infinite potential for creating highly customizable components with diverse and efficient biocatalytic properties. Enzymes, nature’s nanoscale protein-based catalysts, perform crucial functions in biological systems and play increasingly important roles in modern chemical processing methods, cascade reactions, and sensor technologies. Immobilizing enzymes on solid carriers facilitates their recovery and reuse, improves stability and longevity, broadens applicability, and reduces overall processing and chemical conversion costs. Three-dimensional printing offers extraordinary flexibility for creating high-resolution complex structures that enable completely new reactor designs with versatile sub-micron functional features in macroscale objects. Immobilizing enzymes on or in 3D printed structures makes it possible to precisely control their spatial location for the optimal catalytic reaction. Combining the rapid advances in these two technologies is leading to completely new levels of control and precision in fabricating immobilized enzyme catalysts. The goal of this review is to promote further research by providing a critical discussion of 3D printed enzyme immobilization methods encompassing both post-printing immobilization and immobilization by physical entrapment during 3D printing. Especially, 3D printed gel matrix techniques offer mild single-step entrapment mechanisms that produce ideal environments for enzymes with high retention of catalytic function and unparalleled fabrication control. Examples from the literature, comparisons of the benefits and challenges of different combinations of the two technologies, novel approaches employed to enhance printed hydrogel physical properties, and an outlook on future directions are included to provide inspiration and insights for pursuing work in this promising field.

Silicon is one of the most promising anode materials for lithium-ion batteries because of its highest known theoretical charge capacity (4,200 mAh g⁻¹). However, it has found limited application in commercial batteries because of the significant volume change (up to 400%) of silicon during cycling, which results in pulverization and capacity fading. Here, we present a new method to develop a silicon - carbon nanotube (CNT) hybrid anode architecture using CNT-polymer nanofiber hybridization method. The anode material is produced by electrospinning PMMA-Si nanofibers onto aligned CNT sheets, which are drawn on a grounded, rotating take-up roller, and then subsequently decomposing the PMMA electrospun fibers at elevated temperature to create a uniform distribution of Si particles within the CNT sheets. The whole structure is then coated with pyrolytic carbon via chemical vapor deposition (CVD). The architecture provides sufficient space to accommodate the volume expansion of the Si nanoparticles. The CVD pyrolytic carbon coating helps to anchor the Si nanoparticles within CNT sheets and stabilize solid-electrolyte-interface (SEI) formation. The novel freestanding, binder free CNT-Si-C sheet hybrid exhibited improved performance in terms of excellent cycling capacity (1470 mAh g⁻¹), high coulombic efficiency (98%), and good capacity retention of 88% after 150 cycles.