Electrochemically Assisted Preparation And Stability Study Of Novel Nano Black Phosphorus

Nano black phosphorus shows good application prospects in the fields of catalysis,energy storage,field effect transistor and other fields due to its excellent photoelectronic effect,high carrier mobility,adjustable direct band gap and other properties etc..However,the application of nano-black phosphorus is limited by its preparation method.In addition,the properties and application fields of nano-black phosphorus are closely related to its structure and morphology.Furthermore,due to the poor stability of nanoblack phosphorus in air and water,its application performance is restricted to some extent.Therefore,to develop preparation methods of novel nano-black phosphorus and improve their stability can not only broaden the application field of nano black phosphorus,but also improve its application performance.In this paper,the electrochemical-assisted preparation and stability of novel nanoblack phosphorus were studied.Two new preparation methods of black phosphorus nanoribbons and holey phosphorene have been developed.Besides,the stability of the holey phosphorene was improved by doping Zn.Detailed research work are as follows:(1)An electrochemical-assisted method for preparing black phosphorus nanoribbons was developed,and the influence of different discharge specific capacities on the morphology of nano-black phosphorus was studied.TEM,XPS,Raman and UVVis were used to characterize namo-black phosphorus.The results show that the black phosphorus nanoribbons with length of 202 ? 737 nm and width of 7.9 ? 13.2 nm can be prepared at the discharge specific capacity of 350 m Ah/g,and the optical absorption properties of black phosphorus nanoribbons are different from ordinary phosphorene.(2)A low temperature electrochemically assisted method for the preparation of holey phosphorene was developed.Besides,the effects of temperature and voltage on the electrochemical exfoliation were studied.The results show that at the same voltage,black phosphorus nanosheets can be obtained at 0 ?,and holey phosphorene can be obtained at-5 ?.The holey phosphorene was characterized by AFM,TEM,XPS,Raman and UV-Vis.The results show that the horizontal size of holey phosphorene is about 0.3 ? 1.4 ?m,the thickness is less than 2 nm,and the pore size is 20 ? 170 nm.Moreover,with the increase of voltage,the pore size of holey phosphorene become larger,the horizontal size and thickness become smaller.In addition,the optical absorption properties of holey phosphorene are different with different pore sizes.(3)Holey phosphorene,one of the novel nano-black phosphorus,in order to solve the problem of the instability of it in air and water,a comparative experiment was designed to explore the structure,morphology and stability of the Zn-doped nano-black phosphorus prepared at multi-stage potentials and different square wave potentials.The results show that the lower limit of square wave potential is-0.3 V,the upper limit of square wave potential is 3 V,the application time of each voltage is 5 min,and the cycle time is 12.Zn-doped holey phosphorene can be prepared.The results of TEM,AFM,XRF,XPS,Raman and UV-Vis spectra show that the the horizontal size of holey phosphorene is about 2 ?m,the thickness is less than 1.6 nm,and the pore size is several to tens of nanometers.Moreover,the distribution of Zn element is uniform,and the Zndoped holey phosphorene has good stability in air and water.