Excellent flame retardancy and air stability through surface coordination of few‐layer black phosphorus with <scp> TiL ₄ </scp> in epoxy resin

Black phosphorus (BP) has been attractive for many research groups as its promising properties. However, the poor air stability of BP has limited its practical applications. To simultaneously address this problem and improve the flame retardancy of BP in epoxy resin (EP), a surface coordination strategy was proposed. Herein, a titanium ligand (denoted as TiL4) was designed to coordinate BP nanosheets, which can occupy the lone pair electrons of BP. The Ti–P coordination contributed to the improvement of ambient stability of BP. The serious degradation was observed from pure BP owing to the oxidation. Whereas, the surface coordination can impede the ambient degradation rate of BP by 74.07%. With the addition of 1.5 wt% TiL4@BP, the char yield of EP nanocomposites was increased by 20.55% due to the catalytic charring effect of TiL4@BP. The incorporation of 1.5 wt% TiL4@BP can reduce the peak of heat release rate and total heat release values of EP by 29.41% and 23.32%. The EP/TiL4@BP 1.5 also can pass the UL-94 V-0 rating, and its value of limiting oxygen index was enhanced by 13.60%. The improvement in the flame retardancy of BP in EP can be largely ascribed to synergistic catalytic charring effects between BP and TiL4. The condense and compact char layer can act as a physical barrier to restrict the exchange of pyrolytic products and the transfer of heat. In addition, the free radical quenching effect of BP nanosheets also accounted for the excellent flame retardant performance of EP. This work proposed a reference for synchronically obtaining the improvement for the air stability and flame retardant performance of BP.