The Constructions And Characteristics Of Nonenzymatic Electrochemical Sensors Based On The Porphyrinato And Phthalocayninato Metal Complexes

As a novel functional materials with outstanding electrical,optical,and magnetic properties,associated with the macrocyclic conjugation system,porphyrinato and phthalocyaninato based metal coordination,have been studied to be widely potential applications in the fieled of materials science.In recent years,many efforts have been centered on the research of new electrocatalytic materials based on the rare earth metal coordination of porphyrins and phthalocyanines in sensor researches.This paper mainly includes the following several parts:1.Construction of porphyrinato and phthalocyaninato triple-decker coordination of rare earth metal hybrid film with grapheme oxide and its application in electrochemical H₂O₂ sensor.A mixed?phthalocyaninato??porphyrinato?europium?III?triple-decker compound?Pc?Eu?Pc?Eu[trans-T?COOCH3?2PP] with novel structure was designed and synthesized.And a facile approach was developed for preparing the multilayer hybrid films of novel mixed?phthalocyaninato??porphyrinato?europium?III?triple-decker compound?Pc?Eu?Pc?Eu[trans-T?COOCH3?2PP] and graphene oxide?GO?using the solution-processing QLS method.The combination of the nature of relatively high conductivity and great surface area for GO with the electroactive and semiconductive triple-decker compound in ITO electrode renders the hybrid film excellent sensing property for H₂O₂,due to the optimized triple-decker molecular packing in the uniformsized nanoparticles?ca.70 nm?formed on the GO surface.The amperometric responses are linearly proportional to the concentration of H₂O₂ in the range of 0.05-1800 ?M with a fast response time of 0.03 s·?M-1,a low detection limit of 0.017 ?M,and good sensitivity of 7.4 ?A·m M-1.The present work represents the best result of tetrapyrrolebased nonenzymatic electrochemical sensor for H₂O₂.Nevertheless,the triple-decker/GO/ITO also shows excellent stability,reproducibility,and selectivity,indicating the great potential of electroactive tetrapyrrole rare earth sandwich compounds in combination with GO in the field of nonenzymatic electrochemical sensors.2.The construction of hybrid films,associated with characteristic of electrochemical supramolecular recognition,based on the porphyrinato/phthalocyaninato triple-decker coordination of rare earth metal and calixarenes and its application in electrochemical sensors.The mixed solutions of?porphyrinato??phthalocyaninato?europium?III?triple-decker compound?Pc?Eu?Pc?Eu[T?OH?PP] with excellent electroactivity and the calix[4 or 8]arenes with the activity of supramolecular recognition were employed to make the electrodes modified by hybrid films using a facile QLS method.And the characteristics of nonenzymatic electrochemical sensors based on the property of electrochemical supramoleclar recognition were studied.The?Pc?Eu?Pc?Eu[T?OH?PP] molecules were all take J-type aggeragation in both pure triple-decker film and hybid films,and the angle of orientation was not changed before and after the addition of calixarenes.Besides,the calixarenes and?Pc?Eu?Pc?Eu[T?OH?PP] almost take a mixed way of molecular level.The sensing performance of modifing electrodes with the properties of supramolecular recognition was determined by a series of electrochemical methods.And as a result,indeed,the sensing performance for the different analytes was improved by the addition of calixarenes,and improvement was derived from the combination of the prominent electroactive of triple-decker and the enrichment of calixarenes to the analytes by supramolecular interactions.This work should to be helpful for the applications of porphyrinato phthalocyanito triple-decker compounds in the field of the electrochemical sensors and should to be helpful in opening the new methods to the improvement of electrochemical sensing performance,and this work provide another way to design the imitation of enzyme systems.