张奇：二维[4+3]型席夫碱共价有机骨架材料的设计与制备及性能研究论文

本文主要研究内容

作者张奇（2019）在《二维[4+3]型席夫碱共价有机骨架材料的设计与制备及性能研究》一文中研究指出：共价有机骨架(Covalent Organic Frameworks;COFs)是有机小分子通过动态化学键连接形成的结晶有机多孔材料,通常由C,H,O,N,B,Si等轻质原子组成,具有低密度,高比表面积和化学性质稳定等特点。COFs的孔道环境,对称性和构筑单元的连接都具有可设计性,可实现对COFs的物理化学性质进行精确的调控。COFs的纳米孔道使之成为了应用于气体存储与分离的理想材料,而其高的比表面积和确定的界面环境使之具有应用于催化和传感的等方面的潜力。同时,规律的结构和有机构筑单元的调控性使得COFs还可应用于光电和电池等领域。优异的物理化学性质和广泛地应用前景已经使得COFs成为当前研究的热点。与MOFs(Metal Organic Frameworks)相比,COFs具有与之相似的结构和网络化学设计的原则,但COFs拓扑结构的多样性与MOFs还存在着较大的差距,有限的拓扑结构类型仍然是限制COFs多样性发展的瓶颈。此外,COFs的功能化应用也是该领域重要的研究方向之一,而COFs的功能化修饰仍是COFs多领域应用的前提。目前,COFs修饰的连接反应和可修饰的COFs构筑单元的选择范围还较为有限,提出一种利用普通构筑单元实现制备具有修饰位点COFs的构筑方法就显得越发的重要。本文提出了一种全新的[4+3]2D COFs构筑策略,并提出了tth和bex两种全新的COFs拓扑类型,采取非饱和连接的构筑策略,利用构筑单元间的位阻一步制备了骨架中富含醛基的tth型ETTA-TFPT COF,比表面积达750 m2 g-1。通过软件对ETTA-TFPT COF进行结构模拟和精修,结合等温氮气吸附非定域密度泛函理论(NLDFT)孔径计算结果,证明了ETTA-TFPT COF的tth拓扑构型;同时结合透射电子显微镜(TEM)图中COFs的片层结构,有力的证明该COFs的2D属性,并且通过红外和固体核磁共振验证了连接基团醛基的存在。在4A-tth拓扑构型ETTA-TFPT COF成功合成的基础上,本文继续研究了[4+3]构筑策略的拓展性,并采用相同的策略合成了具有高比表面积的ETTB-TAPT COF(比表面积995 m2 g-1)和ETBC-TAPT COF(比表面积1987 m22-1)。研究了构筑单元连接基团和改变构筑单元尺寸对COFs拓扑结构和官能团保留的影响。研究发现,醛基在[4+3]策略构筑COFs的过程中具有更好的稳定。因此在[4+3]构筑策略中,当醛基构筑单元反应官能度为3时,COFs较大可能采取tth拓扑构型,而当醛基构筑单元反应官能度为4时,COFs更倾向于bex的拓扑构型。本文发现ETBC-TAPT COF具有介孔和微孔两种孔道类型,比表面积高达1987 m2 g-1,具有热稳定性优良的等特点,并首次研究了COFs材料在六氟化硫气体吸附方面的应用。考察了ETTB-TAPT COF(分子动力学孔径1.34 nm)和ETBC-TAPT COF(具有分子动力学1.1 nm的孔道)的六氟化硫吸附性能,其中具有更高比表面积和最适吸附孔径(六氟化硫最佳吸附孔径1.1 nm)的ETBC-TAPT COF对六氟化硫气体的吸附量达到了4.4 mmol g-1,具有较高的六氟化硫选择吸附性、良好的循环吸附性和中等的吸附热,意味着ETBC-TAPT COF在六氟化硫吸附领域具有较大的应用前景。综上,本文提出全新的[4+3]COFs构筑策略,实现了利用一般构筑单元一步制得保留反应基团的COFs的材料,并提出tth和bex两种全新的COFs拓扑结构,丰富了COFs拓扑结构多样性的发展,为制备骨架富含基团的COFs提供了思路。

Abstract

gong jia you ji gu jia (Covalent Organic Frameworks;COFs)shi you ji xiao fen zi tong guo dong tai hua xue jian lian jie xing cheng de jie jing you ji duo kong cai liao ,tong chang you C,H,O,N,B,Sideng qing zhi yuan zi zu cheng ,ju you di mi du ,gao bi biao mian ji he hua xue xing zhi wen ding deng te dian 。COFsde kong dao huan jing ,dui chen xing he gou zhu chan yuan de lian jie dou ju you ke she ji xing ,ke shi xian dui COFsde wu li hua xue xing zhi jin hang jing que de diao kong 。COFsde na mi kong dao shi zhi cheng wei le ying yong yu qi ti cun chu yu fen li de li xiang cai liao ,er ji gao de bi biao mian ji he que ding de jie mian huan jing shi zhi ju you ying yong yu cui hua he chuan gan de deng fang mian de qian li 。tong shi ,gui lv de jie gou he you ji gou zhu chan yuan de diao kong xing shi de COFshai ke ying yong yu guang dian he dian chi deng ling yu 。you yi de wu li hua xue xing zhi he an fan de ying yong qian jing yi jing shi de COFscheng wei dang qian yan jiu de re dian 。yu MOFs(Metal Organic Frameworks)xiang bi ,COFsju you yu zhi xiang shi de jie gou he wang lao hua xue she ji de yuan ze ,dan COFsta pu jie gou de duo yang xing yu MOFshai cun zai zhao jiao da de cha ju ,you xian de ta pu jie gou lei xing reng ran shi xian zhi COFsduo yang xing fa zhan de ping geng 。ci wai ,COFsde gong neng hua ying yong ye shi gai ling yu chong yao de yan jiu fang xiang zhi yi ,er COFsde gong neng hua xiu shi reng shi COFsduo ling yu ying yong de qian di 。mu qian ,COFsxiu shi de lian jie fan ying he ke xiu shi de COFsgou zhu chan yuan de shua ze fan wei hai jiao wei you xian ,di chu yi chong li yong pu tong gou zhu chan yuan shi xian zhi bei ju you xiu shi wei dian COFsde gou zhu fang fa jiu xian de yue fa de chong yao 。ben wen di chu le yi chong quan xin de [4+3]2D COFsgou zhu ce lve ,bing di chu le tthhe bexliang chong quan xin de COFsta pu lei xing ,cai qu fei bao he lian jie de gou zhu ce lve ,li yong gou zhu chan yuan jian de wei zu yi bu zhi bei le gu jia zhong fu han quan ji de tthxing ETTA-TFPT COF,bi biao mian ji da 750 m2 g-1。tong guo ruan jian dui ETTA-TFPT COFjin hang jie gou mo ni he jing xiu ,jie ge deng wen dan qi xi fu fei ding yu mi du fan han li lun (NLDFT)kong jing ji suan jie guo ,zheng ming le ETTA-TFPT COFde tthta pu gou xing ;tong shi jie ge tou she dian zi xian wei jing (TEM)tu zhong COFsde pian ceng jie gou ,you li de zheng ming gai COFsde 2Dshu xing ,bing ju tong guo gong wai he gu ti he ci gong zhen yan zheng le lian jie ji tuan quan ji de cun zai 。zai 4A-tthta pu gou xing ETTA-TFPT COFcheng gong ge cheng de ji chu shang ,ben wen ji xu yan jiu le [4+3]gou zhu ce lve de ta zhan xing ,bing cai yong xiang tong de ce lve ge cheng le ju you gao bi biao mian ji de ETTB-TAPT COF(bi biao mian ji 995 m2 g-1)he ETBC-TAPT COF(bi biao mian ji 1987 m22-1)。yan jiu le gou zhu chan yuan lian jie ji tuan he gai bian gou zhu chan yuan che cun dui COFsta pu jie gou he guan neng tuan bao liu de ying xiang 。yan jiu fa xian ,quan ji zai [4+3]ce lve gou zhu COFsde guo cheng zhong ju you geng hao de wen ding 。yin ci zai [4+3]gou zhu ce lve zhong ,dang quan ji gou zhu chan yuan fan ying guan neng du wei 3shi ,COFsjiao da ke neng cai qu tthta pu gou xing ,er dang quan ji gou zhu chan yuan fan ying guan neng du wei 4shi ,COFsgeng qing xiang yu bexde ta pu gou xing 。ben wen fa xian ETBC-TAPT COFju you jie kong he wei kong liang chong kong dao lei xing ,bi biao mian ji gao da 1987 m2 g-1,ju you re wen ding xing you liang de deng te dian ,bing shou ci yan jiu le COFscai liao zai liu fu hua liu qi ti xi fu fang mian de ying yong 。kao cha le ETTB-TAPT COF(fen zi dong li xue kong jing 1.34 nm)he ETBC-TAPT COF(ju you fen zi dong li xue 1.1 nmde kong dao )de liu fu hua liu xi fu xing neng ,ji zhong ju you geng gao bi biao mian ji he zui kuo xi fu kong jing (liu fu hua liu zui jia xi fu kong jing 1.1 nm)de ETBC-TAPT COFdui liu fu hua liu qi ti de xi fu liang da dao le 4.4 mmol g-1,ju you jiao gao de liu fu hua liu shua ze xi fu xing 、liang hao de xun huan xi fu xing he zhong deng de xi fu re ,yi wei zhao ETBC-TAPT COFzai liu fu hua liu xi fu ling yu ju you jiao da de ying yong qian jing 。zeng shang ,ben wen di chu quan xin de [4+3]COFsgou zhu ce lve ,shi xian le li yong yi ban gou zhu chan yuan yi bu zhi de bao liu fan ying ji tuan de COFsde cai liao ,bing di chu tthhe bexliang chong quan xin de COFsta pu jie gou ,feng fu le COFsta pu jie gou duo yang xing de fa zhan ,wei zhi bei gu jia fu han ji tuan de COFsdi gong le sai lu 。

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论文详细介绍

论文作者分别是来自南京大学的张奇，发表于刊物南京大学2019-07-02论文，是一篇关于共价有机骨架论文,拓扑结构论文,构筑策略论文,官能化论文,六氟化硫论文,南京大学2019-07-02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，资料来自南京大学2019-07-02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：共价有机骨架论文;  拓扑结构论文;  构筑策略论文;  官能化论文;  六氟化硫论文;  南京大学2019-07-02论文;