Preparation And Electrochemical Sensing Performance Of Metal Doped Black Phosphorene With Water-oxygen Stability

Black phosphorene(BP)is a new graphene-like material at the forefront of new two-dimensional semiconductor research.It has a unique wrinkled structure,high electron mobility,excellent mechanical properties,tunable band structure,and the anisotropy of thermal,electrical and optical properties.However,BP is easily degraded rapidly in water and oxygen environment,which limits its excellent properties and its application in electronic devices,energy storage and other fields.Therefore,this paper aims to use several metal doping strategies to stabilize BP and form hybrids with different materials to further improve the stability and catalytic properties of BP.Electrochemical sensors are prepared,combined with machine learning,and applied to different molecules.Details are as follows:(1)Preliminary research on black phosphorene:The liquid phase ultrasonic-assisted method was used to prepare BP,and the morphology of black phosphorus crystals and unmodified BP was characterized.It can be seen that BP has a wrinkled structure and the sign of degradation"bubbles",verifying the necessity of subsequent doping strategies.The efficiency of several common organic solvents in stripping BP was explored,and N-methylpyrrolidone was selected as an efficient solvent for stripping BP in subsequent experiments.For the preliminary screening of metals for doping engineering,the Ag NO₃and Cu Cl with satisfactory results were selected for subsequent experiments to be combined with different materials to further stabilize BP and improve the catalytic performance for electrochemical sensing.(2)A highly water-oxygen stable nano-silver decorated phosphorene nanohybrid with phosphorus-doped porous carbon microsphere and its nanozyme sensor for intelligent analysis of oxidative DNA damage biomarker:We prepared silver nanoparticles(Ag NPs)decorated highly water-oxygen stable phosphorene(BP)nanohybrid with phosphorus-doped porous carbon microspheres(P-PCMs)as nanozyme sensing platform for intelligent analysis of 8-hydroxy-2'-deoxyguanosine(8-OHd G)as a biomarker of oxidative DNA damage.Ag⁺in-situ reduced as Ag NPs and grown on the BP surface for controllable preparation of BP-Ag NPs with effective surface passivation among metal ions decorated BP.P-PCMs with4.9-fold enhancement for 1636.73 m² g^-1 of specific surface area were prepared by hydrothermal carbonization of?-cyclodextrin as carbon sources,then calcination in the presence of phosphoric acid as an activator and dopant.P-PCMs-BP-Ag NPs were prepared by ultrasound-assisted liquid-phase exfoliation with the addition of Ag⁺,P-PCMs and black phosphorus crystals that were sufficiently grinded.P-PCMs-BP-Ag NPs displayed good long-term water-oxygen stability,extraordinary specific surface area,superior electrocatalytic capacity with 303-fold enhancement,enzyme-like characteristics.Machine learning(ML)model with artificial neural network(ANN)algorithm was employed for intelligent operation and digital output of 8-OHd G in real sample with acceptable recovery in work range from 0.2 to 125?M.(3)Detection of naphthalene acetic acid by a portable sensor based on laser-induced porous graphene self-assembly BN/Ti₃C₂-Mxene:Using Cu Cl modified BP(BN)and hydrofluoric acid etched Ti₃C₂-MXene,the composite BN/Ti₃C₂-MXene was prepared by the method of liquid phase ultrasonic co-exfoliation.Laser writing graphene(LIPG)on a commercial polyimide film,and patterning design through a computer-aided design system.The composite material was drip-coated on the LIPG to prepare the nanozyme flexible electrode,and the intelligent ultra-trace analysis of the plant regulator?-naphthaleneacetic acid(NAA)residues in the farmland environment and agricultural products was performed through machine learning(ML).We discussed the artificial neural network model ML algorithm NAA intelligent output and using a portable wireless smart sensor detecting NAA electrochemical detection range of 0.02?40?M with acceptable recovery.The nanozyme flexible electrode has a large and rough surface,good electrochemical response and satisfactory practicability,which proves the feasibility and detection ability of this method.This will provide a portable wireless smart nanozyme flexible sensing platform for low-cost,simple,fast and ultra-trace detection of hazardous substances in environment,product and food safety.