石墨烯基复合材料用于co2光催化还原的第一性原理分析-first principle analysis of graphene-based composites for photocatalytic reduction of co2.docxVIP

AbstractDuetothewidelyuseoffossilfuels,theconcentrationofCO2intheairhasincreasedrapidlyyearbyyear,whichhasbecameaseriousglobalproblem.Ontheotherhand,asthehugeconsumptionofcoal,oilandnaturalgasalsocausedworldwideenergyshortage.Therefore,theeffectiverecoveryandutilizationofCO2haveadualsignificancetoresolveenergyandenvironmentalissues.Sofar,convertingCO2intohighvalue-addedchemicalproductsororganicfuelbyphotocatalyticreactionisthemostpromisingandeffectiveoneinmanyconversionmethods.Therapiddevelopmentofquantumchemistrytheoreticalstudyandtherapidincreaseincomputerperformancemaketreatingcomplexcatalyticsystemmoreaccuratelyaspossible.Inthispaper,adsorptionandactivationofCO2andcatalyticreductionprocessformetal-graphenecompositesystemswerestudiedbyfirst-principlescalculations,andthenscreenthecatalystbytheoreticalcalculationandanalysis.TheadsorptionandactivationofCO2isacrucialstepinthereactionsystemoftheCO2photocatalysis.ThedifferentactivatedmodesandstatesofCO2determinetherouteofthereactionandthefinalproducts.Metal-graphenesystemwastakenastheresearchobjectinthisstudy.Densityfunctionaltheory(DFT),combinedwithlocaldensityapproximation(LDA)andPWCfunctional,wasemployedtostudythechangesinthegeometrystructure,energy,chargedistributionanddensityofstates(DOS)ofthesystemsbeforeandafterabsorptionofCO2onthem.TheresultsshowthattheelectronsaretransferredfromtheM-graphenesystemtoCO2,whichiseventuallyactivatedbynegativecharge.TheCu-GsystemismosteffectivetoactivateCO2inthesethreecomplexes.ThebondlengthofCO2increasedby6and14pm,respectively,andthebondangleofO-C-Odecreasedto122°.Furthermore,thefirstionizationenergyandelectronaffinityofmetalclustersandgrapheneplayadecisiveroleintheelectrontransfer.Comparedwiththefirstionizationenergyofgraphene,thelargerelectronaffinityofmetalclusters,themoreelectronstransferredfromgraphenetometalcluster.ThecatalyticreductionofCO2occurswhentheyadsorbedandactivatedontheCu-G.ThecatalyticreductionpathwaysofCu-GsystemandCuclustersystemascatalystsreducingCO2werestudied