Preparation And Performance Of Functionalized Phosphorous Nanomaterials By Mechanochemical Method

Recently,with the depletion of fossil energy,exploting renewable energy have become urgent needs for modern society.Hydrogen evolution from water by semiconductor photocatalysis technology provides us a practical and effective way to produce clean energy.Phosphorus,with its excellent UV-vis-NIR light response performance,is widely used as an important inorganic non-metallic semiconductor photocatalyst.In this paper,phosphorous nanomaterials were prepared by mechanochemical method based on phosphorous allotrope,red phosphorus and black phosphorus.Their properties were characterized and tested,and their applications in photocatalytic hydrogen generation and photothermal properties were explored.The details are as follows:（1）The orthorhombic black phosphorus powder crystals were prepared by mechanical ball milling with cheap commercial red phosphorus as raw material.The structure and properties of the prepared black phosphorus crystal remained stable after 6months storage.Based on the analysis of Raman and X-ray diffraction,the key process parameters for the transformation of red phosphorus to black phosphorus are obtained,which are ball to powder weight ratio of 500:1,rotating speed of 400 rpm and argon atmosphere.The conversion was evaluated by TGA and UV-vis-NIR diffuse reflectance.It was found that the phase of red phosphorus could be completely transformed into black phosphorus powder crystal by prolonging the milling time to 8 h.（2）A new method of"mechanical milling"and"ultrasonic exfolidation"was proposed to prepare functionalized black phosphorene.In the process of ball milling,glucose was used as grinding aid to intercalate and nano-sized black phosphorus crystal,and then ultrasonic stripping was used to get functionalized black phosphorene.The highest yield of functionalized black phosphorene is 53%,and the highest efficiency of photothermal conversion is 34%.At the same time,it also showed good photocatalytic hydrogen production and thermal catalytic hydrogen production activities,350 and 3360μmol g^-1 h^-1,respectively.（3）A mechanochemical method for the preparation of functionalized red phosphorus nanomaterials was proposed.This method uses red phosphorus as raw material and glucose as grinding aid.The nano materials were obtained by ball milling and ultrasonic process.The photocatalytic hydrogen production efficiency of the functionalized red phosphorus nanomaterials in the whole spectrum and visible region is up to 154 and 511μmol g^-1 h^-1,respectively.