【光催化合成氨的基本原理概述2400字】

光催化合成氨的基本原理概述目录TOC\o"1-3"\h\u1429光催化合成氨的基本原理概述 185941.1氨的基本性质 1226871.2合成氨的发展 1101421.3光催化合成氨的基本原理 3242241.4光催化合成氨的目的和意义 91.1氨的基本性质氨气（Ammonia），一种无机物，化学式为NH3，分子量为17.031，无色、有强烈的刺激气味。密度小，氨气在标况下，密度为0.771g/L，但沸点较高。氨易溶于水。氨的气味比较浓，在家具中主要存在于色料中，挥发的也比较快，危害不大。ADDINCSL_CITATION{"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1002/anie.201504135","ISSN":"15213773","abstract":"Spatiallyresolvedsurfacephotovoltagespectroscopy(SRSPS)wasemployedtoobtaindirectevidenceforhighlyanisotropicphotogeneratedchargeseparationondifferentfacetsofasingleBiVO4photocatalyst.Throughthecontrolledsynthesisofasinglecrystalwithpreferentiallyexposed{010}facets,highlyanisotropicphotogeneratedholetransfertothe{011}facetofsingleBiVO4crystalswasobserved.Thesurfacephotovoltagesignalintensityonthe{011}facetwas70timesstrongerthanthatonthe{010}facets.Theinfluenceofthebuilt-inelectricfieldinthespacechargeregionofdifferentfacetsontheanisotropicphotoinducedchargetransferinasinglesemiconductorcrystalisrevealed.","author":[{"dropping-particle":"","family":"Zhu","given":"Jian","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Fan","given":"Fengtao","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Chen","given":"Ruotian","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"An","given":"Hongyu","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Feng","given":"Zhaochi","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Li","given":"Can","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"AngewandteChemie-InternationalEdition","id":"ITEM-1","issue":"31","issued":{"date-parts":[["2015"]]},"page":"9111-9114","title":"DirectImagingofHighlyAnisotropicPhotogeneratedChargeSeparationsonDifferentFacetsofaSingleBiVO4Photocatalyst","type":"article-journal","volume":"54"},"uris":["/documents/?uuid=4c8cf73a-545f-47b3-aff6-1311c3459975"]}],"mendeley":{"formattedCitation":"[3]","plainTextFormattedCitation":"[3]","previouslyFormattedCitation":"³"},"properties":{"noteIndex":0},"schema":"/citation-style-language/schema/raw/master/csl-citation.json"}[3]氮气是极性分子，其中氮≡氮三键以sp3杂化轨道成键。图1.1氨的电子式和三维模型。从图1.1可知，氨分子是一种三角锥型的极性分子，其中N原子以sp3杂化轨道成键。1.2合成氨的发展空气中的氮固定最开始存在于自然界中，其通过一种称为生物固氮的过程而实现的。在这个过程中，氮气在环境温度和压力条件下，在植物的光合作用产生的能量驱动下还原吸附的氮分子而实现氮固定。一开始人们认为氨是不能人工合成的，直到第一次发现人工大规模合成氨是在20世纪Haber-Bosch法的发明。在工业领域，化学催化固氮是一项重要的人工合成NH3途径。目前，该过程主要通过哈伯-博施（Haber-Bosch）流程来实现，但是其存在一些弊端，例如其需要高温（400-500℃）和高压（15-25MPa）条件，且合成过程中所需的氢气主要来源于含碳有机物的重整，导致其是一个高耗能高污染的过程。相关研究显示，其耗能约占全球总能耗的2%，并且碳排放量约占全球总排放量的1.6%。ADDINCSL_CITATION{"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1126/science.1186120","ISSN":"00368075","PMID":"20929768","abstract":"AtmosphericreactionsandslowgeologicalprocessescontrolledEarth'searliestnitrogencycle,andby∼2.7billionyearsago,alinkedsuiteofmicrobialprocessesevolvedtoformthemodernnitrogencyclewithrobustnaturalfeedbacksandcontrols.Overthepastcentury,however,thedevelopmentofnewagriculturalpracticestosatisfyagrowingglobaldemandforfoodhasdrasticallydisruptedthenitrogencycle.Thishasledtoextensiveeutrophicationoffreshwatersandcoastalzonesaswellasincreasedinventoriesofthepotentgreenhousegasnitrousoxide(N2O).Microbialprocesseswillultimatelyrestorebalancetothenitrogencycle,butthedamagedonebyhumanstothenitrogeneconomyoftheplanetwillpersistfordecades,possiblycenturies,ifactiveinterventionandcarefulmanagementstrategiesarenotinitiated.","author":[{"dropping-particle":"","family":"Canfield","given":"DonaldE.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Glazer","given":"AlexanderN.","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Falkowski","given":"PaulG.","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"Science","id":"ITEM-1","issue":"6001","issued":{"date-parts":[["2010"]]},"page":"192-196","title":"Theevolutionandfutureofearth'snitrogencycle","type":"article-journal","volume":"330"},"uris":["/documents/?uuid=a03d56fa-d2f7-4e26-9bc2-6253f8609b87"]}],"mendeley":{"formattedCitation":"[2]","plainTextFormattedCitation":"[2]","previouslyFormattedCitation":"²"},"properties":{"noteIndex":0},"schema":"/citation-style-language/schema/raw/master/csl-citation.json"}[2]随着着能源领域所面临的压力日益严峻，以及相关领域环保意识的不断增强，该行业急需一种能够以更为绿色的方式来合成NH3的途径，这时利用太阳光、氮气和水为出发点实现氨制备的光催化固氮契合了时代发展要求。但是，对于光催化固氮而言，普遍存在半导体光生载流子分类效率不高的问题。除此之外，由于N2的三键具有941kJ/mol的较高键能，难于活化，因此光催化固氮性能较低。如何提高光催化固氮性能成为该领域的研究热点。图1.2展示了光催化剂氮气还原类别和方式。图1.2光催化剂氮气还原类别和方式示意图。ADDINCSL_CITATION{"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1038/s41929-020-0476-3","ISSN":"25201158","abstract":"Unravelinghowreactivefacetspromotephotocatalysisatthemolecularlevelremainsagrandchallenge,whileidentificationofthereactivefacetscanprovideguidelinesfordesigninghighlyefficientphotocatalystsandunravellingthemicroscopicmechanismsbehindthem.Recently,aseriesofpolytriazineimides(PTIs)wasreportedwithhighlycrystallinestructures;allhadarelativelylowphotocatalyticactivityforoverallwatersplitting.Here,high-angleannulardark-fieldscanningtransmissionelectronmicroscopy,energydispersivespectroscopymapping,andaberration-correctedintegrateddifferentialphasecontrastimagingwereusedtostudyPTI/Li+Cl−singlecrystalsbeforeandafterinsituphotodepositionofco-catalysts,showingthattheprismatic{101¯0}planesaremorephotocatalyticallyreactivethanthebasal{0001}planes.Theoreticalcalculationsconfirmedthattheelectronsareenergeticallyfavourabletotransfertowardthe{101¯0}planes.Uponthisdiscovery,PTI/Li+Cl−crystalswithdifferentaspectratioswereprepared,andtheoverallwatersplittingperformancefollowedalinearcorrelationwiththerelativesurfaceareasofthe{101¯0}and{0001}planes.Ourcontrollingofthereactivefacetsdirectlyinstructsthedevelopmentofhighlyefficientpolymerphotocatalystsforoverallwatersplitting.[Figurenotavailable:seefulltext.]","author":[{"dropping-particle":"","family":"Lin","given":"Lihua","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lin","given":"Zhiyou","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Jian","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Cai","given":"Xu","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lin","given":"Wei","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yu","given":"Zhiyang","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Xinchen","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"NatureCatalysis","id":"ITEM-1","issue":"8","issued":{"date-parts":[["2020"]]},"page":"649-655","publisher":"SpringerUS","title":"Molecular-levelinsightsonthereactivefacetofcarbonnitridesinglecrystalsphotocatalysingoverallwatersplitting","type":"article-journal","volume":"3"},"uris":["/documents/?uuid=ed58ee1a-4df4-4841-b9df-f054725a63bb"]}],"mendeley":{"formattedCitation":"[4]","plainTextFormattedCitation":"[4]","previouslyFormattedCitation":"⁴"},"properties":{"noteIndex":0},"schema":"/citation-style-language/schema/raw/master/csl-citation.json"}[3]图1.31940年-2020年关于合成氨的文章数量图（以催化剂种类分类）。ADDINCSL_CITATION{"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1038/s41929-020-0476-3","ISSN":"25201158","abstract":"Unravelinghowreactivefacetspromotephotocatalysisatthemolecularlevelremainsagrandchallenge,whileidentificationofthereactivefacetscanprovideguidelinesfordesigninghighlyefficientphotocatalystsandunravellingthemicroscopicmechanismsbehindthem.Recently,aseriesofpolytriazineimides(PTIs)wasreportedwithhighlycrystallinestructures;allhadarelativelylowphotocatalyticactivityforoverallwatersplitting.Here,high-angleannulardark-fieldscanningtransmissionelectronmicroscopy,energydispersivespectroscopymapping,andaberration-correctedintegrateddifferentialphasecontrastimagingwereusedtostudyPTI/Li+Cl−singlecrystalsbeforeandafterinsituphotodepositionofco-catalysts,showingthattheprismatic{101¯0}planesaremorephotocatalyticallyreactivethanthebasal{0001}planes.Theoreticalcalculationsconfirmedthattheelectronsareenergeticallyfavourabletotransfertowardthe{101¯0}planes.Uponthisdiscovery,PTI/Li+Cl−crystalswithdifferentaspectratioswereprepared,andtheoverallwatersplittingperformancefollowedalinearcorrelationwiththerelativesurfaceareasofthe{101¯0}and{0001}planes.Ourcontrollingofthereactivefacetsdirectlyinstructsthedevelopmentofhighlyefficientpolymerphotocatalystsforoverallwatersplitting.[Figurenotavailable:seefulltext.]","author":[{"dropping-particle":"","family":"Lin","given":"Lihua","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lin","given":"Zhiyou","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Jian","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Cai","given":"Xu","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Lin","given":"Wei","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Yu","given":"Zhiyang","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Wang","given":"Xinchen","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"NatureCatalysis","id":"ITEM-1","issue":"8","issued":{"date-parts":[["2020"]]},"page":"649-655","publisher":"SpringerUS","title":"Molecular-levelinsightsonthereactivefacetofcarbonnitridesinglecrystalsphotocatalysingoverallwatersplitting","type":"article-journal","volume":"3"},"uris":["/documents/?uuid=ed58ee1a-4df4-4841-b9df-f054725a63bb"]}],"mendeley":{"formattedCitation":"[4]","plainTextFormattedCitation":"[4]","previouslyFormattedCitation":"⁴"},"properties":{"noteIndex":0},"schema":"/citation-style-language/schema/raw/master/csl-citation.json"}[4]1.3光催化合成氨的基本原理相比Haber-Bosch法，光催化氮还原固氮以清洁和储能丰富的太阳能为驱动力，以来源广泛的水和氮气为原料，可促使氮的还原在常温常压下进行，这为氨的合成提供了潜在可替代的新方法。Schrauzer和Guth在1977年的研究结果表明半导体TiO2光催化剂在水和氮气下表现出了氮还原催化活性。于是，光催化合成氨等课题开始逐渐被探索。近年来，除了二氧化钛的改性工作，其他材料，尤其是金属氧化物光催化剂如Fe2O3,ZnO,Ga2O3和ZrOx复合物，也开始被用在光催化合成氨课题中。ADDINCSL_CITATION{"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/acs.jpclett.0c02833","ISSN":"19487185","PMID":"33119324","abstract":"ItisstillagrandchallengetoexploitefficientcatalyststoachievesustainablephotocatalyticN2reductionunderambientconditions.Here,wedevelopedaruthenium-basedsingle-Atomcatalystanchoredondefect-richTiO2nanotubes(denotedRu-SAs/Def-TNs)asamodelsystemforN2fixation.TheconstructedRu-SAs/Def-TNsexhibitedacatalyticefficiencyof125.2μmolg-1h-1,roughly6and13timeshigherthanthoseofthesupportedRunanoparticlesandDef-TNs,respectively.Throughultrafasttransientabsorptionandphotoluminescencespectroscopy,werevealedtherelationshipbetweencatalyticactivityandphotoexcitedelectrondynamicsinsuchamodelSAcatalyticsystem.Theuniqueligand-To-metalcharge-TransferstateformedinRu-SAs/Def-TNswasfoundtoberesponsibleforitshighcatalyticactivitybecauseitcangreatlypromotethetransferofphotoelectronsfromDef-TNstotheRu-SAscenterandthesubsequentcapturebyRu-SAs.ThisworkshedslightontheoriginofthehighperformanceofSAcatalystsfromtheperspectiveofphotoexcitedelectrondynamicsandhenceenrichesthemechanisticunderstandingofSAcatalysis.","author":[{"dropping-particle":"","family":"Niu","given":"Xiaoyou","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhu","given":"Qing","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Jiang","given":"Shenlong","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Zhang","given":"Qun","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"JournalofPhysicalChemistryLetters","id":"ITEM-1","issued":{"date-parts":[["2020"]]},"page":"9579-9586","title":"PhotoexcitedElectronDynamicsofNitrogenFixationCatalyzedbyRutheniumSingle-AtomCatalysts","type":"article-journal"},"uris":["/documents/?uuid=a45b5631-4b84-4352-97c7-5d265ce2c38a"]}],"mendeley":{"formattedCitation":"[5]","plainTextFormattedCitation":"[5]","previouslyFormattedCitation":"⁵"},"properties":{"noteIndex":0},"schema":"/citation-style-language/schema/raw/master/csl-citation.json"}[5]图1.4半导体催化剂在光照下将N2转化为NH3原理示意图。ADDINCSL_CITATION{"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/acsanm.9b02380","ISSN":"25740970","abstract":"PhotocatalyticsplittingofaqueousNH3intoH2andN2onsemiconductorpowdersisanimportantreactiontowardon-siteproductionofH2fromNH3,apromisinghydrogencarrierforsustainableenergysociety.EarlierreportsrevealedthatTiO2loadedwithPtnanoparticles(Pt/TiO2)isthemosteffectivecatalystforthisreaction.Herein,wereportthatTiO2loadedwithhomogeneouslymixedbimetallicalloynanoparticlescontaining90mol%Ptand10mol%Au(Pt0.9Au0.1/TiO2)promotesphotocatalyticNH3splittingveryefficiently.ElectrochemicalanalysisindicatesthatAualloyingtoPtlowerstheheightofSchottkybarriercreatedatthemetal/TiO2interface.ThispromotesefficienttransferofconductionbandelectronsonTiO2tometalparticles.Thisresultsinenhancedseparationofthephotogeneratedcharges,thuspromotingefficientNH3splitting.","author":[{"dropping-particle":"","family":"Shiraishi","given":"Yasuhiro","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Toi","given":"Shota","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Ichikawa","given":"Satoshi","non-dropping-particle":"","parse-names":false,"suffix":""},{"dropping-particle":"","family":"Hirai","given":"Takayuki","non-dropping-particle":"","parse-names":false,"suffix":""}],"container-title":"ACSAppliedNanoMaterials","id":"ITEM-1","issue":"2","issued":{"date-parts":[["2020"]]},"page":"1612-1620","title":"PhotocatalyticNH3SplittingonTiO2ParticlesDecoratedwithPt-AuBimetallicAlloyNanoparticles","type":"article-journal","volume":"3"},"uris":["/documents/?uuid=8ce5c50f-7460-4df7-b486-524721c0aa40"]}],"mendeley":{"formattedCitation":"[6]","plainTextFormattedCitation":"[6]","previouslyFormattedCitation":"⁶"},"properties":{"noteIndex":0},"schema":"/citation-style-language/schema/raw/master/csl-citation.json"}[6]如图1.4所示，半导体光催化固氮合成氨反应主要包括以下几个过程：（1）半导体光催化材料吸收光产生光生电子-空穴；（2）光生电子-空穴的复合与传输；（3）未复合的光生电子在催化剂表面还原N2分子并与水中的质子结合生成氨气，同时未复合的光生空穴在催化剂表面氧化氢氧根生成氧气。过程（1）主要由半导体的禁带宽度决定，过程（2）由半导体材料种类、尺寸和结晶性等因素决定，过程（3）需要N2分子活化中心来促进光催化固氮反应的发生。光催化固氮节约了建设高温高压反应的设备成本，同时避免了燃烧和重整化石原料而产生的温室气体排放。然而，受制于半导体材料低的光吸收能力（较宽的禁带宽度）和光转化利用率（严重的光生载流子复合），使光催化固氮效率远未达到工业生产的要求。因此，如何提高光催化材料固氮效率成为该领域的前沿热点与难点。ADDINCSL_CITATION{"citationItems":[{"id":"ITEM-1","itemData":{"DOI":"10.1021/acsnano.7b04617","ISSN":"1936086X","abstract":"©2017AmericanChemicalSociety.ByscrutinizingtheenergystorageprocessinLi-ionbatteries,tuningLi-ionmigrationbehaviorbyatomicleveltailoringwillunlockgreatpotentialforpursuinghigherelectroche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potentialasanewartific