本文主要研究内容
作者卢姝（2019）在《三元非贵金属硫化物的可控合成及其氧电极催化性能研究》一文中研究指出：新型清洁可再生能源的转化和储存技术,包括电解水、燃料电池和金属空气电池等为解决日益严重的能源短缺和环境污染问题带来了新的希望。在这些电化学驱动的技术中存在重要的电极反应:氧还原反应（ORR）,氢氧化反应（HOR）,析氢反应（HER）和产氧反应（OER）,其中ORR和OER涉及复杂的四电子转移和中间态转化过程,动力学速率缓慢,是这些电极反应中的“速控步骤”。在目前的商业应用中,这两个电极反应仍需通过以Pt、Ir和Ru为基础的贵金属材料来进行催化,但贵金属高昂的价格和稀少的储量限制了其大规模商业化应用。因此,研究者们一直致力于研发具有高活性和高稳定性的非贵金属类化合物作为催化剂以代替贵金属。根据电极表面的吸附模型和理论计算推测,与二元金属化合物相比,多元金属化合物因其可以产生不同金属之间的合金效应,使金属与金属之间的自由电子发生相互作用,重新进行电荷分布,达到调控彼此电子结构的目的,产生反应活性更高的位点,从而优化其本征催化性能。因此,多元金属化合物具有成为高效OER和ORR催化剂的潜力。本论文利用油相合成反应精确控制反应条件,调控前驱体投入量、溶剂比例、表面活性剂种类及加入量、反应温度和反应时间等一系列影响因素,实现一步法对高纯度三元非贵金属硫化物的制备、物相和形貌的优化及其与氧化石墨烯的原位复合;利用实验结果和理论计算分析过渡金属硫化物组成成分、形貌特征和复合结构与其催化性能之间的关系;采用锌空气电池器件评估催化剂在实际应用中的价值,以期为研究和开发非贵金属硫化物双功能电催化剂提供新的思路。本论文主要包括以下几方面内容:1.基于合金效应对非贵金属化合物本征催化性能的提升作用和金属硫化物相对良好的导电性,通过一步油相法合成出三元金属硫化物FeNiS2纳米片,实现了非贵金属硫化物本征OER活性的优化。首先通过不同反应时间的控制,结合物相与相貌表征分析,对FeNiS2纳米片在合成过程中的生长机制进行了解析;在退火处理之后将其作为电化学OER催化剂进行性能测试,结果表明FeNiS2纳米片与其二元硫化物FeS纳米片和Ni9S8纳米棒相比,OER催化性能得到大幅提升,甚至超越商业Ru02;这种功能提升归因于FeNiS2纳米片独特的二维片状纳米结构对其催化活性面积的提升,以及Fe、Ni合金效应对彼此电子结构的调控,使价态电子发生了变化。本工作通过金属间的合金效应和材料二维结构的构建增强了非贵金属硫化物的本征OER催化活性,可为相关研究提供有效可行的材料优化思路。2.针对FeNiS2在碱性条件下催化OER过程中发生的表面不可逆自氧化现象,通过全面、细致的表征,揭示了自氧化过程对其催化性能和形貌结构的影响,并通过一步油相法和后续退火实现了FeNiS2二维纳米片与还原氧化石墨烯（rGO）的原位均匀复合,削弱了自氧化过程对材料的负面作用,实现其OER催化性能的进一步提升;发现在OER过程中FeNiS2处于较高的电位区间,表面发生自氧化生成真正的反应活性位点,有益于提升其催化活性;但长时间的过度氧化会导致材料的无定形化和表面Ni、S的大量溶出,不利于FeNiS2在反应中保持稳定性;形貌表征和电化学测试结果表明,FeNiS2二维纳米片在与rGO进行原位复合后可形成相互关联的三维结构,而rGO良好的导电性加快了电子在两者之间的传递速率,并抑制了活性成分的溶解,使FeNiS2/rGO在连续5000圈CV循环后保持活性。因此,本工作中所提出的与rGO原位复合的方法提升了材料的导电性和稳定性,增加了该类材料在实际应用中的可能性。3.在OER性能提升的基础上,锌空气电池的发展和应用迫切需要具有OER/ORR双催化功能的非贵金属类催化剂。二维片状Co9S8在电化学催化中具有优异的ORR性能,但是其本征OER性能却有所欠缺。以Co9S8纳米片为优化对象,通过一步油相合成法在其晶格中引入适量Fe取代Co的位置生成FeCo8S8纳米片,以此增强其本征OER活性;同时在反应过程中也采用了上面所述的同样方法实现了与rGO的原位复合（一步油相法和后续退火）,制得了FeCo8S8/rGO;实验和理论计算结果均表明,Fe的引入优化了Co9S8表面的活性原子位点,显著提升了材料的本征OER催化活性,而少量Fe并未对Co9S8的晶格结构造成影响,因此材料仍保持良好的ORR催化活性,且FeCo8S8与rGO的原位复合结构增强了材料整体的导电能力和长时间循环稳定性;将该材料作为锌空气电池的空气电极,可以在常温下稳定充放电运行800圈（44小时）。该复合物优异的双功能电催化性能使得它有望成为贵金属催化剂潜在的替代品,对双功能电催化剂的设计与优化提供了新的途径。
Abstract
xin xing qing jie ke zai sheng neng yuan de zhuai hua he chu cun ji shu ,bao gua dian jie shui 、ran liao dian chi he jin shu kong qi dian chi deng wei jie jue ri yi yan chong de neng yuan duan que he huan jing wu ran wen ti dai lai le xin de xi wang 。zai zhe xie dian hua xue qu dong de ji shu zhong cun zai chong yao de dian ji fan ying :yang hai yuan fan ying （ORR）,qing yang hua fan ying （HOR）,xi qing fan ying （HER）he chan yang fan ying （OER）,ji zhong ORRhe OERshe ji fu za de si dian zi zhuai yi he zhong jian tai zhuai hua guo cheng ,dong li xue su lv huan man ,shi zhe xie dian ji fan ying zhong de “su kong bu zhou ”。zai mu qian de shang ye ying yong zhong ,zhe liang ge dian ji fan ying reng xu tong guo yi Pt、Irhe Ruwei ji chu de gui jin shu cai liao lai jin hang cui hua ,dan gui jin shu gao ang de jia ge he xi shao de chu liang xian zhi le ji da gui mo shang ye hua ying yong 。yin ci ,yan jiu zhe men yi zhi zhi li yu yan fa ju you gao huo xing he gao wen ding xing de fei gui jin shu lei hua ge wu zuo wei cui hua ji yi dai ti gui jin shu 。gen ju dian ji biao mian de xi fu mo xing he li lun ji suan tui ce ,yu er yuan jin shu hua ge wu xiang bi ,duo yuan jin shu hua ge wu yin ji ke yi chan sheng bu tong jin shu zhi jian de ge jin xiao ying ,shi jin shu yu jin shu zhi jian de zi you dian zi fa sheng xiang hu zuo yong ,chong xin jin hang dian he fen bu ,da dao diao kong bi ci dian zi jie gou de mu de ,chan sheng fan ying huo xing geng gao de wei dian ,cong er you hua ji ben zheng cui hua xing neng 。yin ci ,duo yuan jin shu hua ge wu ju you cheng wei gao xiao OERhe ORRcui hua ji de qian li 。ben lun wen li yong you xiang ge cheng fan ying jing que kong zhi fan ying tiao jian ,diao kong qian qu ti tou ru liang 、rong ji bi li 、biao mian huo xing ji chong lei ji jia ru liang 、fan ying wen du he fan ying shi jian deng yi ji lie ying xiang yin su ,shi xian yi bu fa dui gao chun du san yuan fei gui jin shu liu hua wu de zhi bei 、wu xiang he xing mao de you hua ji ji yu yang hua dan mo xi de yuan wei fu ge ;li yong shi yan jie guo he li lun ji suan fen xi guo du jin shu liu hua wu zu cheng cheng fen 、xing mao te zheng he fu ge jie gou yu ji cui hua xing neng zhi jian de guan ji ;cai yong xin kong qi dian chi qi jian ping gu cui hua ji zai shi ji ying yong zhong de jia zhi ,yi ji wei yan jiu he kai fa fei gui jin shu liu hua wu shuang gong neng dian cui hua ji di gong xin de sai lu 。ben lun wen zhu yao bao gua yi xia ji fang mian nei rong :1.ji yu ge jin xiao ying dui fei gui jin shu hua ge wu ben zheng cui hua xing neng de di sheng zuo yong he jin shu liu hua wu xiang dui liang hao de dao dian xing ,tong guo yi bu you xiang fa ge cheng chu san yuan jin shu liu hua wu FeNiS2na mi pian ,shi xian le fei gui jin shu liu hua wu ben zheng OERhuo xing de you hua 。shou xian tong guo bu tong fan ying shi jian de kong zhi ,jie ge wu xiang yu xiang mao biao zheng fen xi ,dui FeNiS2na mi pian zai ge cheng guo cheng zhong de sheng chang ji zhi jin hang le jie xi ;zai tui huo chu li zhi hou jiang ji zuo wei dian hua xue OERcui hua ji jin hang xing neng ce shi ,jie guo biao ming FeNiS2na mi pian yu ji er yuan liu hua wu FeSna mi pian he Ni9S8na mi bang xiang bi ,OERcui hua xing neng de dao da fu di sheng ,shen zhi chao yue shang ye Ru02;zhe chong gong neng di sheng gui yin yu FeNiS2na mi pian du te de er wei pian zhuang na mi jie gou dui ji cui hua huo xing mian ji de di sheng ,yi ji Fe、Nige jin xiao ying dui bi ci dian zi jie gou de diao kong ,shi jia tai dian zi fa sheng le bian hua 。ben gong zuo tong guo jin shu jian de ge jin xiao ying he cai liao er wei jie gou de gou jian zeng jiang le fei gui jin shu liu hua wu de ben zheng OERcui hua huo xing ,ke wei xiang guan yan jiu di gong you xiao ke hang de cai liao you hua sai lu 。2.zhen dui FeNiS2zai jian xing tiao jian xia cui hua OERguo cheng zhong fa sheng de biao mian bu ke ni zi yang hua xian xiang ,tong guo quan mian 、xi zhi de biao zheng ,jie shi le zi yang hua guo cheng dui ji cui hua xing neng he xing mao jie gou de ying xiang ,bing tong guo yi bu you xiang fa he hou xu tui huo shi xian le FeNiS2er wei na mi pian yu hai yuan yang hua dan mo xi （rGO）de yuan wei jun yun fu ge ,xiao ruo le zi yang hua guo cheng dui cai liao de fu mian zuo yong ,shi xian ji OERcui hua xing neng de jin yi bu di sheng ;fa xian zai OERguo cheng zhong FeNiS2chu yu jiao gao de dian wei ou jian ,biao mian fa sheng zi yang hua sheng cheng zhen zheng de fan ying huo xing wei dian ,you yi yu di sheng ji cui hua huo xing ;dan chang shi jian de guo du yang hua hui dao zhi cai liao de mo ding xing hua he biao mian Ni、Sde da liang rong chu ,bu li yu FeNiS2zai fan ying zhong bao chi wen ding xing ;xing mao biao zheng he dian hua xue ce shi jie guo biao ming ,FeNiS2er wei na mi pian zai yu rGOjin hang yuan wei fu ge hou ke xing cheng xiang hu guan lian de san wei jie gou ,er rGOliang hao de dao dian xing jia kuai le dian zi zai liang zhe zhi jian de chuan di su lv ,bing yi zhi le huo xing cheng fen de rong jie ,shi FeNiS2/rGOzai lian xu 5000juan CVxun huan hou bao chi huo xing 。yin ci ,ben gong zuo zhong suo di chu de yu rGOyuan wei fu ge de fang fa di sheng le cai liao de dao dian xing he wen ding xing ,zeng jia le gai lei cai liao zai shi ji ying yong zhong de ke neng xing 。3.zai OERxing neng di sheng de ji chu shang ,xin kong qi dian chi de fa zhan he ying yong pai qie xu yao ju you OER/ORRshuang cui hua gong neng de fei gui jin shu lei cui hua ji 。er wei pian zhuang Co9S8zai dian hua xue cui hua zhong ju you you yi de ORRxing neng ,dan shi ji ben zheng OERxing neng que you suo qian que 。yi Co9S8na mi pian wei you hua dui xiang ,tong guo yi bu you xiang ge cheng fa zai ji jing ge zhong yin ru kuo liang Fequ dai Code wei zhi sheng cheng FeCo8S8na mi pian ,yi ci zeng jiang ji ben zheng OERhuo xing ;tong shi zai fan ying guo cheng zhong ye cai yong le shang mian suo shu de tong yang fang fa shi xian le yu rGOde yuan wei fu ge （yi bu you xiang fa he hou xu tui huo ）,zhi de le FeCo8S8/rGO;shi yan he li lun ji suan jie guo jun biao ming ,Fede yin ru you hua le Co9S8biao mian de huo xing yuan zi wei dian ,xian zhe di sheng le cai liao de ben zheng OERcui hua huo xing ,er shao liang Febing wei dui Co9S8de jing ge jie gou zao cheng ying xiang ,yin ci cai liao reng bao chi liang hao de ORRcui hua huo xing ,ju FeCo8S8yu rGOde yuan wei fu ge jie gou zeng jiang le cai liao zheng ti de dao dian neng li he chang shi jian xun huan wen ding xing ;jiang gai cai liao zuo wei xin kong qi dian chi de kong qi dian ji ,ke yi zai chang wen xia wen ding chong fang dian yun hang 800juan （44xiao shi ）。gai fu ge wu you yi de shuang gong neng dian cui hua xing neng shi de ta you wang cheng wei gui jin shu cui hua ji qian zai de ti dai pin ,dui shuang gong neng dian cui hua ji de she ji yu you hua di gong le xin de tu jing 。
论文参考文献
论文详细介绍
论文作者分别是来自中国科学技术大学的卢姝，发表于刊物中国科学技术大学2019-07-12论文，是一篇关于非贵金属硫化物论文,油相合成反应论文,氧还原反应论文,产氧反应论文,双功能电催化剂论文,锌空气电池论文,中国科学技术大学2019-07-12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，资料来自中国科学技术大学2019-07-12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：非贵金属硫化物论文; 油相合成反应论文; 氧还原反应论文; 产氧反应论文; 双功能电催化剂论文; 锌空气电池论文; 中国科学技术大学2019-07-12论文;