The control of crystal growth is important but challenging for multi-disciplinary research. Violet phosphorus, the most stable phosphorus allotrope, has recently been produced as a unique semiconducting layered structure. The crystal orientation and morphology bring extra performance due to its unique structure and anisotropy. Herein, the layered violet phosphorus has been controlled to grow along the c-axis to give tunable length up to centimeters with the assistance of tin, while the reported flat bulk ones with thickness are limited to micrometers. The as-produced needle-shaped violet phosphorus has also been demonstrated to significantly enhance the photocatalytic degradation of methyl orange pollutants due to its special crystallographic orientation. About 98.6% of methyl orange pollutants with a concentration of 50 ppm were degraded within 80 min under visible light conditions by needle-shaped violet phosphorus, which is much more effective than that of amorphous red phosphorus with only 14.1% degradation.

Recent preparation of black phosphorene and subsequent discovery of its excellent optical and electronic properties have attracted great attention, and renewed interest to phosphorus. Recent researches have indicated that phosphorus structures are promising anodes for lithium-ion and sodium-ion batteries. A high theoretical capacity of 2, 596 mAh·g^-1 was predicted for phosphorus according to the reaction of 3Li/Na + P → Li₃P/Na₃P. However, fast capacity degradation is accompanying with most phosphorus structures due to the low electronic conductivity and structural pulverization induced by large volume change in charging and discharging proceses. The electrochemical performances are significantly affected by the hierarchical structural design of phosphorus. A few reviews of phosphorus structures have been reported recently. However, no review about the electrochemical performances of phosphorus structures according to their hierarchical structures has been reported. First of all, phosphrus allotropes along with their structure and fundamental properties are briefly reviewed in this work. Secondly, the studies on lithiation/sodiation mechanism of red/black phosphorus are presented. Thirdly, a summary about the electrochemical performances of red/black phosphorus composites with different hierarchical structures is presented. Furthermore, the development challenges and future perspectives of phosphorus structures as anodes for LIBs and SIBs are discussed.