Compartmentalization-Mediated Mineralization Via Spontaneous Adsorption Of Graphene Oxide On Polymeric Surfaces

Biological minerals exhibit various excellent properties due to their hierarchical ordered structure.The prismatic layer and nacreous layer of mollusk shells have been widely studied for their excellent mechanical properties in biological minerals.The mollusk shells grow prismatic layer and nacreous layer in the extrapallial space between the mantle and the periostracum,and the mantle can selectively permeate calcium ions,thus forming the reaction-diffusion system required for mineralization reaction in the extrapallial space,and then forming prismatic layer and nacreous layer.Biomimetic synthesis of prismatic layer is always a challenging topic.The reported nanoseed crystals overlayer mineralization method is based on two independent mineralization steps to synthesize prismatic-like structures,and the selection of polymer substrates is relatively limited.In this paper,we hope to construct an imitating mantle structure with calcium ion selective permeability,and accurately construct a prism-like structure in the compartment between the polymer substrates and the imitating extrapallial space,so as to simulate the formation process of prismatic layer in mollusk shells.In this paper,we first reported that graphene oxide can spontaneously adsorb on the surface of various polymer substrates,and then utilized the compartment between the GO layer and polymer substrates to biomimetic synthesis of prismatic-like calcium carbonate films.The spontaneous adsorption behavior of GO on the surface of polymer substrates was firstly studied.By statistical analysis of the discrepancy in the adsorption capacity of GO on different polymer substrates,it was found that although polarity,hydrogen bonding and dispersion force all contributed to the adsorption of GO,the main contribution came from the hydrogen bonding force.On this basis,we continue to explore the influence of hydrogen bonding force on the adsorption kinetics of GO,and further regulate the adsorption behavior of GO on the polymer substrate surface by changing the concentration of GO dispersion solution and the reduction degree of GO.In the second part of the work,we carried out biomimetic mineralization research on GO-covered polymer substrates and successfully synthesized the prismatic-like calcium carbonate film with continuous structure and vertical orientation.We put forward the following mechanism of biomimetic mineralization by the observation of the growth process of the prismatic-like biomimetic film:the graphene oxide layer covered on polymer substrates has the dual ability of controlling the selective transport of calcium ions and acting as a template to induce the orientation crystallization of calcium carbonate.The prismatic-like calcium carbonate film is formed in the compartment between the graphene oxide layer and the polymer substrates,which is similar to the formation mechanism of prismatic layer in mollusk shells.It is found that the method of biomimetic prismatic CaCO3 thin film is applicable to a variety of polymer substrates,which can improve the friction resistance of polymer substrates.In short,the controllable adsorption behavior of GO on a variety of polymer substrates can be used to construct a compartment,and become a universal new method for the synthesis of prismatic-like calcium carbonate films,effectively improving the friction resistance of polymer surfaces.