本文主要研究内容
作者黄慧宁（2019）在《稀土掺杂氧化物半导体的上转换、光催化及协同性能研究》一文中研究指出：随着我国经济的不断增长和能源消耗的日益增多,能源短缺和环境污染已经成为制约我国经济进一步发展的两大难题。开发新型清洁能源和治理环境污染成为科学研究的重点和热点。在众多新型清洁能源中,太阳能是一种具有应用潜力的清洁可再生能源。而光催化技术能够有效利用太阳能,并将太阳能转化为化学能,是解决未来能源和环境问题最具潜力的解决方案之一。然而,目前光催化效率依然较低,成为制约其发展及实际应用的最主要问题。光催化效率主要由光催化材料的光吸收范围和载流子分离效率这两个因素决定。因此,进一步拓展光催化材料的光吸收范围和提高载流子分离效率,是提高光催化效率、推动光催化技术发展及其应用的关键。目前,光催化材料通常仅能吸收紫外光和部分可见光,而占太阳光谱能量50%以上的红外光却得不到有效的利用。上转换材料可以将红外光转换成能量更高的紫外光和可见光,进而可以被半导体吸收,是拓展利用红外光进行光催化的一种重要的手段。然而,目前上转换光催化材料的红外光催化效率普遍较低,极大地限制了红外光催化材料的发展。因此,为进一步提高上转换光催化材料的红外光催化活性,设计制备新型高效的上转换光催化材料具有重要的意义。在本论文中,从上转换发光材料入手,通过研究上转换发光过程与机理,进一步提高上转换发光效率,并结合半导体光催化材料的设计理论和微结构调控方法,探索制备了几种高效铋基上转换光催化功能复合材料,在同一种材料中同时实现了上转换和光催化的功能复合,不仅进一步提高了其红外光催化活性,同时为进一步拓展上转换光催化在生物标记和光动力学方面的应用提供了新的制备方法和材料体系。本论文在第一章中介绍并分析了半导体的基本原理和研究目标、稀土上转换发光的基本原理和研究进展、上转换光催化的设计和当前存在的问题,并在早期研究的基础上,提出了自己的思路。本论文工作共分为如下五个部分:在第二章中,采用宽禁带半导体LaNbO4作为基质掺杂敏化剂Yb3+离子和激活剂Er3+/Ho3+/Tm3+离子,对不同激活剂离子的上转换发光性质进行了详尽的探索。在980 nm激发下,LaNbO4:Yb3+,Er3+的主要发光峰分别位于525,550,650 nm的位置,分别对应着两个绿色发光峰和一个红色发光峰,对应的激发能量约为2.3,2.2,1.9 eV;LaNbO4:Yb3+,Ho3+的主要发光峰分别位于550,650,750 nm的位置,分别对应着一个绿色发光峰和两个红色发光峰,对应的激发能量约为2.2,1.9,1.6 eV;LaNbO4:Yb3+,Tm3+的主要发光峰分别位于475,650 nm的位置,分别对应着一个蓝色发光峰和一个红色发光峰,对应的激发能量约为2.6,1.9 eV。这为下一步选择合适的窄带隙半导体和掺杂的稀土元素奠定了基础。在第三章中,NaYF4:Yb3+,Tm3+@NaYF4:Yb3+,Nd3+@TiO2纳米颗粒通过溶剂热法制备并详细研究了其红外光催化活性。构筑了核@壳结构和Nd3+→Yb3+→Tm3+能量传输通道,提高了上转换发光效率。同时,Nd3+离子极大地拓展了材料可见光和红外光的吸收范围,最终实现了紫外-可见-近红外光响应的高效的上转换光催化活性,并能促进在其他领域的实际应用。在第四章中,通过使用窄带隙氧化物BiV04作为基质进行敏化剂Yb3+离子和激活剂Tm3+离子掺杂,在近红外光照射下产生强烈的单红光发射和红外光催化效应。这种设计是基于BiVO4半导体带隙宽度和激活剂Tm3+离子上转换发光位置的匹配。另外,Bi3+(1.08A)离子半径与Tm3+(0.869 A)和Yb3+(0.858 A)的离子半径相近,使得稀土可以对BiVO4材料进行有效的掺杂。在样品BiVO4:Yb3+,Tm3+中,虽然BiVO4本身不能响应红外光,但在BiVO4:Yb3+,Tm3+中,由激活剂Tm3+发出的蓝色和其他更高能量的发射光被基质BiVO4吸收并产生电子空穴对,使BiVO4:Yb3+,Tm3+在近红外光照下具有光催化的作用,其未被吸收的部分以红光的形式被发射出来。因此,利用半导体氧化物作为稀土离子的基质,在近红外光照下,可以实现单红色上转换发光和光催化活性,这一结论对开发出新型的单红色上转换发光和红外光催化材料具有重要的指导意义。在第五章中,采用窄带隙氧化物半导体Bi20TiO32作为基质掺杂Yb3+和Er3+离子,在近红外光照射下产生强烈的单红光发射和高效的光催化活性。因为Er3+离子主要的上转换发光峰位于550和660 nm,而位于550 nm的上转换强绿色发光恰好可以被Bi20TiO32有效吸收,从而产生电子-空穴对,使其在近红外光照射下表现出良好的光催化活性并产生强烈的单红光发射。同时,Yb3+和Er3+离子的掺杂可以使比表面积增大一倍,提供更多的活性位点来提高光催化效率。研究表明,经过Yb3+和Er3+掺杂的窄带隙半导体氧化物可以作为有效的紫外-可见-近红外响应光催化材料。在第六章中,将Yb3+、Er3+或者Tm3+离子掺杂到Bi2O3晶格中,可以通过增加掺杂浓度来诱导Bi2O3从α相到β相再到δ相的连续相变。基于此,合成了α-,β-和δ-Bi2O3三个纯相和α-/β-Bi2O3和β-/δ-Bi2O3两个异相结。同时,在红外光的激发下,敏化剂Yb3+可以吸收近红外光并将能量传递给激活剂Er3+或者Tm3+生成紫外-可见上转换发光,被窄带隙Bi2O3吸收。因此,制备的Yb3+,Er3+和Tm3+共掺杂的α-/β-Bi2O3和β-/δ-Bi2O3异相结,可以同时实现强烈的单红光发射、高效的载流子分离、红外光催化,并最终得到了具有紫外-可见-近红外光响应的高效的催化材料。在第七章中,对本论文的研究内容进行了全面的总结,提出并分析了当前工作中存在的不足,同时对未来的研究工作进行了展望。总之,探索具有红外光响应的高效上转换光催化材料对进一步提高太阳能利用效率,推动光催化技术的发展及其应用具有重要意义。在本论文中,通过研究上转换发光机理和基质材料,进一步提高了上转换光催化效率,同时探索了几种能够作为上转换发光机制的铋基光催化材料,在进一步提高上转换光催化活性的同时,实现了上转换和光催化的功能复合,这对推动具有上转换光催化材料的发展具有重要意义,并在上转换生物标记和光动力学治疗方面的实际应用具有重要的价值。
Abstract
sui zhao wo guo jing ji de bu duan zeng chang he neng yuan xiao hao de ri yi zeng duo ,neng yuan duan que he huan jing wu ran yi jing cheng wei zhi yao wo guo jing ji jin yi bu fa zhan de liang da nan ti 。kai fa xin xing qing jie neng yuan he zhi li huan jing wu ran cheng wei ke xue yan jiu de chong dian he re dian 。zai zhong duo xin xing qing jie neng yuan zhong ,tai yang neng shi yi chong ju you ying yong qian li de qing jie ke zai sheng neng yuan 。er guang cui hua ji shu neng gou you xiao li yong tai yang neng ,bing jiang tai yang neng zhuai hua wei hua xue neng ,shi jie jue wei lai neng yuan he huan jing wen ti zui ju qian li de jie jue fang an zhi yi 。ran er ,mu qian guang cui hua xiao lv yi ran jiao di ,cheng wei zhi yao ji fa zhan ji shi ji ying yong de zui zhu yao wen ti 。guang cui hua xiao lv zhu yao you guang cui hua cai liao de guang xi shou fan wei he zai liu zi fen li xiao lv zhe liang ge yin su jue ding 。yin ci ,jin yi bu ta zhan guang cui hua cai liao de guang xi shou fan wei he di gao zai liu zi fen li xiao lv ,shi di gao guang cui hua xiao lv 、tui dong guang cui hua ji shu fa zhan ji ji ying yong de guan jian 。mu qian ,guang cui hua cai liao tong chang jin neng xi shou zi wai guang he bu fen ke jian guang ,er zhan tai yang guang pu neng liang 50%yi shang de gong wai guang que de bu dao you xiao de li yong 。shang zhuai huan cai liao ke yi jiang gong wai guang zhuai huan cheng neng liang geng gao de zi wai guang he ke jian guang ,jin er ke yi bei ban dao ti xi shou ,shi ta zhan li yong gong wai guang jin hang guang cui hua de yi chong chong yao de shou duan 。ran er ,mu qian shang zhuai huan guang cui hua cai liao de gong wai guang cui hua xiao lv pu bian jiao di ,ji da de xian zhi le gong wai guang cui hua cai liao de fa zhan 。yin ci ,wei jin yi bu di gao shang zhuai huan guang cui hua cai liao de gong wai guang cui hua huo xing ,she ji zhi bei xin xing gao xiao de shang zhuai huan guang cui hua cai liao ju you chong yao de yi yi 。zai ben lun wen zhong ,cong shang zhuai huan fa guang cai liao ru shou ,tong guo yan jiu shang zhuai huan fa guang guo cheng yu ji li ,jin yi bu di gao shang zhuai huan fa guang xiao lv ,bing jie ge ban dao ti guang cui hua cai liao de she ji li lun he wei jie gou diao kong fang fa ,tan suo zhi bei le ji chong gao xiao bi ji shang zhuai huan guang cui hua gong neng fu ge cai liao ,zai tong yi chong cai liao zhong tong shi shi xian le shang zhuai huan he guang cui hua de gong neng fu ge ,bu jin jin yi bu di gao le ji gong wai guang cui hua huo xing ,tong shi wei jin yi bu ta zhan shang zhuai huan guang cui hua zai sheng wu biao ji he guang dong li xue fang mian de ying yong di gong le xin de zhi bei fang fa he cai liao ti ji 。ben lun wen zai di yi zhang zhong jie shao bing fen xi le ban dao ti de ji ben yuan li he yan jiu mu biao 、xi tu shang zhuai huan fa guang de ji ben yuan li he yan jiu jin zhan 、shang zhuai huan guang cui hua de she ji he dang qian cun zai de wen ti ,bing zai zao ji yan jiu de ji chu shang ,di chu le zi ji de sai lu 。ben lun wen gong zuo gong fen wei ru xia wu ge bu fen :zai di er zhang zhong ,cai yong kuan jin dai ban dao ti LaNbO4zuo wei ji zhi can za min hua ji Yb3+li zi he ji huo ji Er3+/Ho3+/Tm3+li zi ,dui bu tong ji huo ji li zi de shang zhuai huan fa guang xing zhi jin hang le xiang jin de tan suo 。zai 980 nmji fa xia ,LaNbO4:Yb3+,Er3+de zhu yao fa guang feng fen bie wei yu 525,550,650 nmde wei zhi ,fen bie dui ying zhao liang ge lu se fa guang feng he yi ge gong se fa guang feng ,dui ying de ji fa neng liang yao wei 2.3,2.2,1.9 eV;LaNbO4:Yb3+,Ho3+de zhu yao fa guang feng fen bie wei yu 550,650,750 nmde wei zhi ,fen bie dui ying zhao yi ge lu se fa guang feng he liang ge gong se fa guang feng ,dui ying de ji fa neng liang yao wei 2.2,1.9,1.6 eV;LaNbO4:Yb3+,Tm3+de zhu yao fa guang feng fen bie wei yu 475,650 nmde wei zhi ,fen bie dui ying zhao yi ge lan se fa guang feng he yi ge gong se fa guang feng ,dui ying de ji fa neng liang yao wei 2.6,1.9 eV。zhe wei xia yi bu shua ze ge kuo de zhai dai xi ban dao ti he can za de xi tu yuan su dian ding le ji chu 。zai di san zhang zhong ,NaYF4:Yb3+,Tm3+@NaYF4:Yb3+,Nd3+@TiO2na mi ke li tong guo rong ji re fa zhi bei bing xiang xi yan jiu le ji gong wai guang cui hua huo xing 。gou zhu le he @ke jie gou he Nd3+→Yb3+→Tm3+neng liang chuan shu tong dao ,di gao le shang zhuai huan fa guang xiao lv 。tong shi ,Nd3+li zi ji da de ta zhan le cai liao ke jian guang he gong wai guang de xi shou fan wei ,zui zhong shi xian le zi wai -ke jian -jin gong wai guang xiang ying de gao xiao de shang zhuai huan guang cui hua huo xing ,bing neng cu jin zai ji ta ling yu de shi ji ying yong 。zai di si zhang zhong ,tong guo shi yong zhai dai xi yang hua wu BiV04zuo wei ji zhi jin hang min hua ji Yb3+li zi he ji huo ji Tm3+li zi can za ,zai jin gong wai guang zhao she xia chan sheng jiang lie de chan gong guang fa she he gong wai guang cui hua xiao ying 。zhe chong she ji shi ji yu BiVO4ban dao ti dai xi kuan du he ji huo ji Tm3+li zi shang zhuai huan fa guang wei zhi de pi pei 。ling wai ,Bi3+(1.08A)li zi ban jing yu Tm3+(0.869 A)he Yb3+(0.858 A)de li zi ban jing xiang jin ,shi de xi tu ke yi dui BiVO4cai liao jin hang you xiao de can za 。zai yang pin BiVO4:Yb3+,Tm3+zhong ,sui ran BiVO4ben shen bu neng xiang ying gong wai guang ,dan zai BiVO4:Yb3+,Tm3+zhong ,you ji huo ji Tm3+fa chu de lan se he ji ta geng gao neng liang de fa she guang bei ji zhi BiVO4xi shou bing chan sheng dian zi kong xue dui ,shi BiVO4:Yb3+,Tm3+zai jin gong wai guang zhao xia ju you guang cui hua de zuo yong ,ji wei bei xi shou de bu fen yi gong guang de xing shi bei fa she chu lai 。yin ci ,li yong ban dao ti yang hua wu zuo wei xi tu li zi de ji zhi ,zai jin gong wai guang zhao xia ,ke yi shi xian chan gong se shang zhuai huan fa guang he guang cui hua huo xing ,zhe yi jie lun dui kai fa chu xin xing de chan gong se shang zhuai huan fa guang he gong wai guang cui hua cai liao ju you chong yao de zhi dao yi yi 。zai di wu zhang zhong ,cai yong zhai dai xi yang hua wu ban dao ti Bi20TiO32zuo wei ji zhi can za Yb3+he Er3+li zi ,zai jin gong wai guang zhao she xia chan sheng jiang lie de chan gong guang fa she he gao xiao de guang cui hua huo xing 。yin wei Er3+li zi zhu yao de shang zhuai huan fa guang feng wei yu 550he 660 nm,er wei yu 550 nmde shang zhuai huan jiang lu se fa guang qia hao ke yi bei Bi20TiO32you xiao xi shou ,cong er chan sheng dian zi -kong xue dui ,shi ji zai jin gong wai guang zhao she xia biao xian chu liang hao de guang cui hua huo xing bing chan sheng jiang lie de chan gong guang fa she 。tong shi ,Yb3+he Er3+li zi de can za ke yi shi bi biao mian ji zeng da yi bei ,di gong geng duo de huo xing wei dian lai di gao guang cui hua xiao lv 。yan jiu biao ming ,jing guo Yb3+he Er3+can za de zhai dai xi ban dao ti yang hua wu ke yi zuo wei you xiao de zi wai -ke jian -jin gong wai xiang ying guang cui hua cai liao 。zai di liu zhang zhong ,jiang Yb3+、Er3+huo zhe Tm3+li zi can za dao Bi2O3jing ge zhong ,ke yi tong guo zeng jia can za nong du lai you dao Bi2O3cong αxiang dao βxiang zai dao δxiang de lian xu xiang bian 。ji yu ci ,ge cheng le α-,β-he δ-Bi2O3san ge chun xiang he α-/β-Bi2O3he β-/δ-Bi2O3liang ge yi xiang jie 。tong shi ,zai gong wai guang de ji fa xia ,min hua ji Yb3+ke yi xi shou jin gong wai guang bing jiang neng liang chuan di gei ji huo ji Er3+huo zhe Tm3+sheng cheng zi wai -ke jian shang zhuai huan fa guang ,bei zhai dai xi Bi2O3xi shou 。yin ci ,zhi bei de Yb3+,Er3+he Tm3+gong can za de α-/β-Bi2O3he β-/δ-Bi2O3yi xiang jie ,ke yi tong shi shi xian jiang lie de chan gong guang fa she 、gao xiao de zai liu zi fen li 、gong wai guang cui hua ,bing zui zhong de dao le ju you zi wai -ke jian -jin gong wai guang xiang ying de gao xiao de cui hua cai liao 。zai di qi zhang zhong ,dui ben lun wen de yan jiu nei rong jin hang le quan mian de zong jie ,di chu bing fen xi le dang qian gong zuo zhong cun zai de bu zu ,tong shi dui wei lai de yan jiu gong zuo jin hang le zhan wang 。zong zhi ,tan suo ju you gong wai guang xiang ying de gao xiao shang zhuai huan guang cui hua cai liao dui jin yi bu di gao tai yang neng li yong xiao lv ,tui dong guang cui hua ji shu de fa zhan ji ji ying yong ju you chong yao yi yi 。zai ben lun wen zhong ,tong guo yan jiu shang zhuai huan fa guang ji li he ji zhi cai liao ,jin yi bu di gao le shang zhuai huan guang cui hua xiao lv ,tong shi tan suo le ji chong neng gou zuo wei shang zhuai huan fa guang ji zhi de bi ji guang cui hua cai liao ,zai jin yi bu di gao shang zhuai huan guang cui hua huo xing de tong shi ,shi xian le shang zhuai huan he guang cui hua de gong neng fu ge ,zhe dui tui dong ju you shang zhuai huan guang cui hua cai liao de fa zhan ju you chong yao yi yi ,bing zai shang zhuai huan sheng wu biao ji he guang dong li xue zhi liao fang mian de shi ji ying yong ju you chong yao de jia zhi 。
论文参考文献
论文详细介绍
论文作者分别是来自山东大学的黄慧宁，发表于刊物山东大学2019-07-16论文，是一篇关于上转换论文,光催化论文,稀土掺杂论文,铋基氧化物半导体论文,异相结论文,山东大学2019-07-16论文的文章。本文可供学术参考使用，各位学者可以免费参考阅读下载，文章观点不代表本站观点，资料来自山东大学2019-07-16论文网站，若本站收录的文献无意侵犯了您的著作版权，请联系我们删除。
标签：上转换论文; 光催化论文; 稀土掺杂论文; 铋基氧化物半导体论文; 异相结论文; 山东大学2019-07-16论文;