While high internal phase emulsions (HIPEs) show significant potential for 3D printing applications, their widespread adoption is currently limited by issues such as emulsion instability and insufficient self-supporting capabilities. This study systematically investigates the effects of the coordination types of metal-phenolic networks (MPNs) on the formation and stabilization mechanisms, rheology, and printability of soy protein isolate (SPI)-based HIPEs. The results of two-dimensional (2D) correlation Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) indicate that the predominant interactions between SPI and MPNs are hydrogen bonds, electrostatic interactions, and hydrophobic interactions. Confocal laser scanning microscopy and backscattering variation analysis demonstrate that the SPI-MPNs significantly enhance the emulsion stability, which mainly originates from the rigid interfacial layer and the finer network structure reinforced by MPNs, especially the tris-complexes formed at pH 9. In terms of rheological evaluation, SPI-MPNs-stabilized HIPEs enhance apparent viscosity, creep-recovery performance, and viscoelastic properties with a clear concentration dependence, contributing to better spatial architecture and printing stability. Compared to HIPEs prepared with pure SPI, those stabilized by MPNs exhibited greater 3D printing fidelity than SPI-only HIPEs. Notably, the HIPEs containing tris-coordinated MPNs exhibited optimal texture properties, with significant improvements in hardness (from 166.76 ± 12.24 g to 238.66 ± 18.18 g) and springiness (from 0.19 ± 0.04 g to 0.52 ± 0.07 g). This study provides valuable insights into the design of HIPEs stabilizers for food formulations, especially for emerging technologies such as 3D food printing.
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