Cooperation of Zr(IV)-N and Zr(IV)-O coordinate bonds of Zr(IV)-amide ensures the transparent and tough polyacrylamide hydrogels.

Developing advanced soft machines and tissue engineering for load-bearing cartilage or tendons requires tough hydrogels. However, the construction of double or triple crosslinked networks for these tough hydrogels, i.e., a strong network crosslinked by covalent bonds and one or two sacrificial networks built by hydrogen bonds or coordinate bonds, generally asks for multiple steps. It remains a challenge to develop hydrogels with a combination of excellent toughness and a high content of water through the time-saving one-pot process. This study demonstrates that this puzzle could be solved through engineering zirconium(IV)-amide coordinate bonds. To be specific, the combination of strong Zr(IV)-O and moderate Zr(IV)-N coordinate bonds in Zr-polyacrylamide (Zr-PAAm) hydrogels has the advantage that they are usually generated through multiple cross-linked networks. Compared to chemical crosslinked PAAm hydrogels, the highly transparent Zr-PAAm hydrogels crosslinked by Zr(NO3)4 displayed a 26-times increase in fracture stress, 4-times in fracture strain, 6-times in elastic modulus, and over 250-times in toughness. Besides, the mechanical properties of Zr-PAAm hydrogels could be altered over a wide range via changing the anion species, showing a dependence on the Hofmeister effect. The co-existence of Zr(IV)-N and Zr(IV)-O has been confirmed through XPS and FTIR characterizations. In particular, the effect of Zr(IV)-N in Zr-PAAm hydrogels has been verified by comparing the property changes of Zr-PAAm hydrogels before and after swelling in water, in which the Zr(IV)-N in the as-prepared hydrogels was replaced by Zr(IV)-O in the swollen gels. With ultra-stretchability and high transparency, the colorless Zr-PAAm hydrogels displayed rich interference colors under stretching, which brought great potential in anti-counterfeiting materials.