本文主要研究内容
作者朱轩伯（2019）在《聚芳醚多孔异质膜的跨膜离子传输行为及在盐差发电器件中的应用研究》一文中研究指出：“物竞天择,适者生存”,经过长期的进化与选择,自然界中的生命体已经拥有了无与伦比的多级功能结构,以最为高效、灵活的方式完成了物质交换、信息传递和能量转换等复杂多样的生命活动过程,实现了不同的机能。我们在感叹其精妙的同时也在不断学习自然的智慧,从中寻找能够为己所用的灵感。例如,科研人员受荷叶的启发,开发了同样能够“出淤泥而不染”的自清洁表面;受大熊猫牙釉质的启发,构筑了能够自修复的纳米复合材料;受蜻蜓翅痣的启发,优化了能够抗震的飞机机翼平衡重锤结构。“师法自然”已经成为了我们构筑先进高性能材料和器件的最有效途径之一。有鉴于此,近些年来,科研人员受到生命体细胞膜上蛋白质离子通道精确控制离子跨膜传输实现多样功能的启发,开展了关于仿生人工纳米孔道的系列研究,取得了初步的成果,实现了对限域空间内离子运动的智能调控。但是,随着研究的深入,科研人员发现均质纳米孔道体系单一的结构组成限制了其对离子输运的调控效果,若要在均质膜内构筑多级孔道结构则需要高昂的加工成本和繁琐的制备工艺,限制了其实际应用,因此开发新型制备工艺简单、高稳定性的多功能复合异质离子传输膜体系势在必行。综合考虑上述的研究背景,本论文致力于制备高性能纳米多孔异质膜,并研究其独特的离子传输性质,开发其在能量转换领域的应用。主要内容如下:从分子设计的角度出发,基于对聚合物分子结构-性能关系的理解,受到生命体离子通道和前人工作的启发,我们以化学稳定性较高的聚芳醚体系为疏水主链骨架,采取化学修饰的方法引入了一定量的亲水侧链,利用主链和侧链的亲疏水差异,使聚合物通过亲疏水作用自组装发生相分离,形成能够大规模制备的高强度三维纳米孔道薄膜。并以此为基础构建了一系列多孔异质膜,研究了其跨膜离子输运性质,并将其应用于盐差能发电器件中,取得了理想的效果。首先,我们通过Suzuki交叉偶联,利用4-吡啶基硼酸制备了含有吡啶基团的对苯二酚单体Py-OH。通过其与联苯二酚和二氟二苯砜等单体进行共聚,成功将吡啶这一具有pH响应特性的功能基团引入了联苯聚芳醚砜(PPSU)中,通过控制聚合时的单体投料比例,制备了不同吡啶基团含量的系列共聚物PPSU-Pyx。并利用该系列聚合物和氧化石墨烯(GO)通过简单的抽滤、旋涂的方法,构建了2D/3D-GO/Py纳米多孔异质膜。GO形成了带有负电荷的孔径约0.8 nm的二维纳米孔道;Py层基于亲疏水作用自组装形成了带有正电荷的孔径约8 nm的三维互穿纳米孔道。两种孔道表面电荷与孔道限域结构的双重不对称性使这类多孔异质膜展现出了优异的离子整流效果。孔道表面的吡啶基团对环境的pH比较敏感,在酸性环境中,孔道内壁带正电荷并更加亲水;而在碱性环境中则不带电且疏水。这种电荷和浸润性的协同作用使该纳米孔道拥有了优异的pH响应离子门控效果。我们通过对电荷密度、孔道长度等关键因素的控制可以调控异质膜的跨膜离子传输效果,此外,我们还基于该系列膜构建了纳米盐差发电能量转换器件,得到了约0.76 W/m~2的输出功率。在以上工作的基础上,为了得到更高输出功率的盐差发电器件,我们优化了异质膜结构和孔道内壁的电荷密度,制备了更大孔径和孔隙率的多孔异质膜,在保证离子输运性质的同时提高了离子通量,最终得到了较高的输出功率。首先,我们通过威廉姆森成醚反应成功制备了具有高密度磺化位点的六苯基苯基团的DF-HS单体,然后用此单体与二氟二苯甲酮和六氟双酚A进行三元共聚反应,通过控制单体比例,制得了一系列带有不同比例磺化侧链的聚芳醚酮共聚物(PAEK-HS10,PAEK-HS15和PAEK-HS20)。并利用该系列聚合物与上述制得的吡啶聚醚砜(PPSU-Pyx)复合,通过聚芳醚亲疏水自组装的方法成功制备了一系列Janus多孔膜。基于该系列Janus多孔膜,构建了高性能的盐差发电系统,并在我们的工作中提出了一种新的观点:为了避免单层膜中的离子极化现象,我们将离子整流性质集成到能量转换系统中。具有整流效应的Janus膜可以作为从海水到河流的“离子高速公路”,显著提高盐差发电效率。由于海水浓度较高,为了保证系统能有较高的能量转换效率,需要使Janus多孔膜器件在高盐浓度环境中依然保持较好的离子整流和选择效果。本文通过提高表面电荷和孔隙率,有效工作浓度区域(最大整流比出现在1 M KCl)较以往文献报道的结果提高了至少一个数量级,打破了以往器件只能在低浓度工作的局限。该系列Janus多孔复合膜在高盐浓度溶液中的高效离子选择性和离子整流特性确保了盐差发电器件的能量转换效率和高功率密度。器件的输出功率高达2.66 W/m~2(通过混合海水和河水,效率为35.7%)和5.10 W/m~2(盐度梯度为500倍)。此外,本文所制备的Janus多孔异质膜主要是基于聚芳醚类高性能聚合物骨架功能化改性的薄膜材料,通过化学分子设计,在实现所预期的离子传输功能的同时也保持了较高的机械性能,为以后的实际应用奠定了基础。我们大胆的推测,带有离子整流效应的纳米孔道膜在收集盐差能方面具有巨大潜力。综上所述,通过合理的分子设计,我们实现了对孔道的尺寸、孔隙率、表面电荷密度以及浸润性等关键因素的控制。并通过孔道限域结构、电荷密度和浸润性的协同作用,实现了孔道离子选择性、离子门控性和离子整流性的有效调控,从而得到了较为理想的离子传输效果。还以此为基础,首次成功制备了聚芳醚体系的高效盐差发电器件。希望我们的工作可以拓宽功能化特种高分子的应用前景,能为今后设计和制备新型、高效的可持续清洁能源器件奠定基础。
Abstract
“wu jing tian ze ,kuo zhe sheng cun ”,jing guo chang ji de jin hua yu shua ze ,zi ran jie zhong de sheng ming ti yi jing yong you le mo yu lun bi de duo ji gong neng jie gou ,yi zui wei gao xiao 、ling huo de fang shi wan cheng le wu zhi jiao huan 、xin xi chuan di he neng liang zhuai huan deng fu za duo yang de sheng ming huo dong guo cheng ,shi xian le bu tong de ji neng 。wo men zai gan tan ji jing miao de tong shi ye zai bu duan xue xi zi ran de zhi hui ,cong zhong xun zhao neng gou wei ji suo yong de ling gan 。li ru ,ke yan ren yuan shou he xie de qi fa ,kai fa le tong yang neng gou “chu yu ni er bu ran ”de zi qing jie biao mian ;shou da xiong mao ya you zhi de qi fa ,gou zhu le neng gou zi xiu fu de na mi fu ge cai liao ;shou qing ting chi zhi de qi fa ,you hua le neng gou kang zhen de fei ji ji yi ping heng chong chui jie gou 。“shi fa zi ran ”yi jing cheng wei le wo men gou zhu xian jin gao xing neng cai liao he qi jian de zui you xiao tu jing zhi yi 。you jian yu ci ,jin xie nian lai ,ke yan ren yuan shou dao sheng ming ti xi bao mo shang dan bai zhi li zi tong dao jing que kong zhi li zi kua mo chuan shu shi xian duo yang gong neng de qi fa ,kai zhan le guan yu fang sheng ren gong na mi kong dao de ji lie yan jiu ,qu de le chu bu de cheng guo ,shi xian le dui xian yu kong jian nei li zi yun dong de zhi neng diao kong 。dan shi ,sui zhao yan jiu de shen ru ,ke yan ren yuan fa xian jun zhi na mi kong dao ti ji chan yi de jie gou zu cheng xian zhi le ji dui li zi shu yun de diao kong xiao guo ,re yao zai jun zhi mo nei gou zhu duo ji kong dao jie gou ze xu yao gao ang de jia gong cheng ben he fan suo de zhi bei gong yi ,xian zhi le ji shi ji ying yong ,yin ci kai fa xin xing zhi bei gong yi jian chan 、gao wen ding xing de duo gong neng fu ge yi zhi li zi chuan shu mo ti ji shi zai bi hang 。zeng ge kao lv shang shu de yan jiu bei jing ,ben lun wen zhi li yu zhi bei gao xing neng na mi duo kong yi zhi mo ,bing yan jiu ji du te de li zi chuan shu xing zhi ,kai fa ji zai neng liang zhuai huan ling yu de ying yong 。zhu yao nei rong ru xia :cong fen zi she ji de jiao du chu fa ,ji yu dui ju ge wu fen zi jie gou -xing neng guan ji de li jie ,shou dao sheng ming ti li zi tong dao he qian ren gong zuo de qi fa ,wo men yi hua xue wen ding xing jiao gao de ju fang mi ti ji wei shu shui zhu lian gu jia ,cai qu hua xue xiu shi de fang fa yin ru le yi ding liang de qin shui ce lian ,li yong zhu lian he ce lian de qin shu shui cha yi ,shi ju ge wu tong guo qin shu shui zuo yong zi zu zhuang fa sheng xiang fen li ,xing cheng neng gou da gui mo zhi bei de gao jiang du san wei na mi kong dao bao mo 。bing yi ci wei ji chu gou jian le yi ji lie duo kong yi zhi mo ,yan jiu le ji kua mo li zi shu yun xing zhi ,bing jiang ji ying yong yu yan cha neng fa dian qi jian zhong ,qu de le li xiang de xiao guo 。shou xian ,wo men tong guo Suzukijiao cha ou lian ,li yong 4-bi ding ji peng suan zhi bei le han you bi ding ji tuan de dui ben er fen chan ti Py-OH。tong guo ji yu lian ben er fen he er fu er ben feng deng chan ti jin hang gong ju ,cheng gong jiang bi ding zhe yi ju you pHxiang ying te xing de gong neng ji tuan yin ru le lian ben ju fang mi feng (PPSU)zhong ,tong guo kong zhi ju ge shi de chan ti tou liao bi li ,zhi bei le bu tong bi ding ji tuan han liang de ji lie gong ju wu PPSU-Pyx。bing li yong gai ji lie ju ge wu he yang hua dan mo xi (GO)tong guo jian chan de chou lv 、xuan tu de fang fa ,gou jian le 2D/3D-GO/Pyna mi duo kong yi zhi mo 。GOxing cheng le dai you fu dian he de kong jing yao 0.8 nmde er wei na mi kong dao ;Pyceng ji yu qin shu shui zuo yong zi zu zhuang xing cheng le dai you zheng dian he de kong jing yao 8 nmde san wei hu chuan na mi kong dao 。liang chong kong dao biao mian dian he yu kong dao xian yu jie gou de shuang chong bu dui chen xing shi zhe lei duo kong yi zhi mo zhan xian chu le you yi de li zi zheng liu xiao guo 。kong dao biao mian de bi ding ji tuan dui huan jing de pHbi jiao min gan ,zai suan xing huan jing zhong ,kong dao nei bi dai zheng dian he bing geng jia qin shui ;er zai jian xing huan jing zhong ze bu dai dian ju shu shui 。zhe chong dian he he jin run xing de xie tong zuo yong shi gai na mi kong dao yong you le you yi de pHxiang ying li zi men kong xiao guo 。wo men tong guo dui dian he mi du 、kong dao chang du deng guan jian yin su de kong zhi ke yi diao kong yi zhi mo de kua mo li zi chuan shu xiao guo ,ci wai ,wo men hai ji yu gai ji lie mo gou jian le na mi yan cha fa dian neng liang zhuai huan qi jian ,de dao le yao 0.76 W/m~2de shu chu gong lv 。zai yi shang gong zuo de ji chu shang ,wei le de dao geng gao shu chu gong lv de yan cha fa dian qi jian ,wo men you hua le yi zhi mo jie gou he kong dao nei bi de dian he mi du ,zhi bei le geng da kong jing he kong xi lv de duo kong yi zhi mo ,zai bao zheng li zi shu yun xing zhi de tong shi di gao le li zi tong liang ,zui zhong de dao le jiao gao de shu chu gong lv 。shou xian ,wo men tong guo wei lian mu sen cheng mi fan ying cheng gong zhi bei le ju you gao mi du huang hua wei dian de liu ben ji ben ji tuan de DF-HSchan ti ,ran hou yong ci chan ti yu er fu er ben jia tong he liu fu shuang fen Ajin hang san yuan gong ju fan ying ,tong guo kong zhi chan ti bi li ,zhi de le yi ji lie dai you bu tong bi li huang hua ce lian de ju fang mi tong gong ju wu (PAEK-HS10,PAEK-HS15he PAEK-HS20)。bing li yong gai ji lie ju ge wu yu shang shu zhi de de bi ding ju mi feng (PPSU-Pyx)fu ge ,tong guo ju fang mi qin shu shui zi zu zhuang de fang fa cheng gong zhi bei le yi ji lie Janusduo kong mo 。ji yu gai ji lie Janusduo kong mo ,gou jian le gao xing neng de yan cha fa dian ji tong ,bing zai wo men de gong zuo zhong di chu le yi chong xin de guan dian :wei le bi mian chan ceng mo zhong de li zi ji hua xian xiang ,wo men jiang li zi zheng liu xing zhi ji cheng dao neng liang zhuai huan ji tong zhong 。ju you zheng liu xiao ying de Janusmo ke yi zuo wei cong hai shui dao he liu de “li zi gao su gong lu ”,xian zhe di gao yan cha fa dian xiao lv 。you yu hai shui nong du jiao gao ,wei le bao zheng ji tong neng you jiao gao de neng liang zhuai huan xiao lv ,xu yao shi Janusduo kong mo qi jian zai gao yan nong du huan jing zhong yi ran bao chi jiao hao de li zi zheng liu he shua ze xiao guo 。ben wen tong guo di gao biao mian dian he he kong xi lv ,you xiao gong zuo nong du ou yu (zui da zheng liu bi chu xian zai 1 M KCl)jiao yi wang wen suo bao dao de jie guo di gao le zhi shao yi ge shu liang ji ,da po le yi wang qi jian zhi neng zai di nong du gong zuo de ju xian 。gai ji lie Janusduo kong fu ge mo zai gao yan nong du rong ye zhong de gao xiao li zi shua ze xing he li zi zheng liu te xing que bao le yan cha fa dian qi jian de neng liang zhuai huan xiao lv he gao gong lv mi du 。qi jian de shu chu gong lv gao da 2.66 W/m~2(tong guo hun ge hai shui he he shui ,xiao lv wei 35.7%)he 5.10 W/m~2(yan du ti du wei 500bei )。ci wai ,ben wen suo zhi bei de Janusduo kong yi zhi mo zhu yao shi ji yu ju fang mi lei gao xing neng ju ge wu gu jia gong neng hua gai xing de bao mo cai liao ,tong guo hua xue fen zi she ji ,zai shi xian suo yu ji de li zi chuan shu gong neng de tong shi ye bao chi le jiao gao de ji xie xing neng ,wei yi hou de shi ji ying yong dian ding le ji chu 。wo men da dan de tui ce ,dai you li zi zheng liu xiao ying de na mi kong dao mo zai shou ji yan cha neng fang mian ju you ju da qian li 。zeng shang suo shu ,tong guo ge li de fen zi she ji ,wo men shi xian le dui kong dao de che cun 、kong xi lv 、biao mian dian he mi du yi ji jin run xing deng guan jian yin su de kong zhi 。bing tong guo kong dao xian yu jie gou 、dian he mi du he jin run xing de xie tong zuo yong ,shi xian le kong dao li zi shua ze xing 、li zi men kong xing he li zi zheng liu xing de you xiao diao kong ,cong er de dao le jiao wei li xiang de li zi chuan shu xiao guo 。hai yi ci wei ji chu ,shou ci cheng gong zhi bei le ju fang mi ti ji de gao xiao yan cha fa dian qi jian 。xi wang wo men de gong zuo ke yi ta kuan gong neng hua te chong gao fen zi de ying yong qian jing ,neng wei jin hou she ji he zhi bei xin xing 、gao xiao de ke chi xu qing jie neng yuan qi jian dian ding ji chu 。
论文参考文献
论文详细介绍
论文作者分别是来自吉林大学的朱轩伯，发表于刊物吉林大学2019-06-25论文，是一篇关于离子整流性论文,纳米孔道论文,聚芳醚论文,盐差发电论文,吉林大学2019-06-25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，资料来自吉林大学2019-06-25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：离子整流性论文; 纳米孔道论文; 聚芳醚论文; 盐差发电论文; 吉林大学2019-06-25论文;