| Shandong Nanshu graphite ore is one of the important graphite ores in China.In the recent years,Being influencedby the general recession of the graphite industry in the world,Shandong Nanshu graphite ore was closed in December of 2015.In order to revitalize the graphite industry of the study area,it is in urgent need of a new kind of resources development and utilization mode which can improve the economic value of the mining.Graphene is a new kind of expensive and high quality carbon nanomaterials,and graphite is the starting material for graphene preparation.If the graphite can be transferred into the graphene,it will greatly increase the potential economic value of graphite ore in the research area,and probably the closed mining enterprises could be remedied.The area is located in the western of Jiaodong peninsula,the emergence stratum mainly is Paleoproterozoic Erathem Jingshan group and quaternary strata;the structures developed very well in the region,which are mainly divided into the fold structures,fault structures and joint structures;the metamorphisms are dominated by regional metamorphism in the region,migmatitization and granitization are strong.The graphite ore formed in the Xucun section of Douya formation in Jingshan group of Paleoproterozoic Erathem in the region;The distribution of ore deposits is influenced by strata,metamorphic rocks,regional metamorphism and tectonics,the clay-semi clay stratums of construction of rich carbonate are the major signs of prospecting;The graphite deposit is mainly from the clastic sediments rich in organic matter in the stable sedimentary environment in the shallow sea,by the superposition role of the regional metamorphism and migmatization in the region,the ore deposit types are sedimentarymetamorphic.There are Liujiazhuang graphite mining and Yueshi graphite mining in the region.Passing through the resource and reserve checking,the region's total graphite ore reserves are 75270 kt,under the traditional management model,the potential economic value is 8billion 140 million yuan,if we transform the graphite into graphene using ball milling method and electrochemical method,the potential economic value will be 118404.4billion yuan,it's economic value will increase by14546 times.In order to verify the feasibility of graphene preparation using graphite in the region,the crystalline graphite mines of Liujiazhuang and Yueshi mining were selected as samples to experiment on the preparation of graphene by ball milling and electrochemical methods,The prepared graphene materials were characterized by the Raman spectra,transmission electron microscopy,X-ray diffraction and Fourier-transform infrared spectra.The experimental results indicated that high-quality graphene materials with uniform particle size and large specific surface area were prepared using these two approaches;Characterization results for the graphene prepared from two different graphite mining samples by the same method are similar,showing that both of the good crystalline of the graphite in the two areas and can be used high-quality graphene production.In order to verify the application potential of the as-prepared graphene,in this paper,the application of graphene electrochemiluminescence(ECL)sensor fabrication,and the application of graphene quantum dots in the detection of metal ions,sewage treatment and cell imaging were studied.The experimental results indicated preparation of graphene by ball milling could provide a green and environmental friendly carbon source for further preparation of graphene quantum dots,which could be applied in iron ion detection in tap water,sewage treatment and cell imaging.Graphene prepared by electrochemical method using for preparation of ECL sensor can be successfully detected in tripropylamine and tetracycline drugs,the method is simple,economical and practical,it is proved that graphene prepared in this region has great potential and economic value.In a word,based on the study of the geological characteristics of the study area,the resource reserves of graphite resources in the study area are estimated,we get the potential economic value of the mine.The potential economic value of graphite was improved by the preparation of graphene,finally the feasibility of the preparation andapplication of graphene was verified by different experimental methods.The experimental results indicated the crystalline graphite in this area could be prepared into graphene with superior properties,and great application potentials.The feasibility to improve the potential economic value of graphite resources in the study area have been confirmed by the preparation of graphene.The results of this study could provide theoretical basis for the geological exploration and development,and for the development of mining enterprises and the strategic decision of regional economy.The application of this research will play an important role in the revitalization of the region's mining enterprises and regional economy.The innovation points of this paper are as follows:Firstly,based on the study of the geological characteristics and ore deposit and ore characteristics,we estimate the resources and potential economic value based on the possible transformation of the graphite into graphene.As a result,a new model of resource development was established that can greatly enhance the potential economic value of graphite resources in the study area.In addition,the application feasibility of the as-obtained graphene was verified by practical experiments,which created a new model for the integration of production,learning and research in graphite resources.Secondly: graphite in the studied area was selected as the raw material and was used for preparation of high quality graphene by ball milling technology and electrochemical methods.Ball milling technology has prepared high quality graphene with uniform particle size and large specific surface using low cost,non-toxic dry ice as the wet medium.The technology overcomes the disadvantages of large energy consumption,low efficiency,high cost,environmental pollution,etc.The required equipment is easy and the preparation process is green and environmental friendl.The electrochemical method using pyrene functionalized polyacrylic acid(PAA)as auxiliary stripping medium,is simple,easy to operate and mild,realizing one-step synthesis of PAA functionalized graphene with good dispersion and good graphite lattice structure.The addition of PAA can improve the dispersion and the functionalization of of graphene,which greatly expands the application potential and values.The Raman spectra,transmission electron microscopy,X-ray diffraction and infrared spectra were used to characterize the materials,the results confirm that the method can provide a green,simple and efficient preparationtechnique for the preparation of high quality graphene in the research area.These methods provide a new idea for transforming the graphite into high economic value products stably and reliably.Thirdly: In this study,PAA functionalized graphene(PAAG)prepared by electrochemical method was used to form ion exchange composite film with Nafion,to prepare an ECL sensor.The use of PAAG can greatly improve the sensor conductivity.The electrostatic interaction between the positively charged ECL probes and negatively charged PAAcan greatly improve the adsorption capacity of the sensor probe,making the fabricated sensor efficient and stable,which can realize the sensitive detection of tripropylamine and tetracycline.In addition,the as-fabricated sensor has good long-term stability,simple operation,low energy consumption economy and so on.It has been proved that the functional graphene prepared by one-step electrochemical method has great application value.Forthly: In this study,the graphene prepared by ball milling method was used as the carbon source precursor for preparing quantum dots with good dispersion and average size of 4.8 nm via the one-step hydrothermal method.The method has the advantages of environmental protection,simple process,low cost and so on.The prepared graphene quantum dots can be used for the sensitive detection and decontamination of iron ions in tap water;Based on its low toxicity and good biocompatibility,the prepared graphene quantum dots have been successfully applied to cell imaging.This study provides a new way for the preparation of carbon nanomaterials,Furthermore,it deepened the research of graphene quantum dots in biochemical analysis,decontamination,bioimaging,etc. |
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