【摘要】：近年來,有關(guān)多酸基金屬有機(jī)配位網(wǎng)絡(luò)的研究已經(jīng)成為無機(jī)化學(xué)領(lǐng)域一個熱點問題。將具有獨特性能的多酸基元與結(jié)構(gòu)豐富的金屬有機(jī)配位網(wǎng)絡(luò)相結(jié)合,可以獲得一系列具有多重功能特性的雜化材料。迄今為止,這些雜化材料已經(jīng)在酸催化、氧化催化、光催化、電催化等方面展現(xiàn)出潛在的應(yīng)用前景。然而,與多酸基金屬有機(jī)配位網(wǎng)絡(luò)制備和合成的數(shù)量相比,對其功能特性的開發(fā)卻僅僅只占了一小部分。因此,制備具有新型功能特性的多酸基金屬-有機(jī)配位網(wǎng)絡(luò),拓展其新的應(yīng)用領(lǐng)域已成為當(dāng)前備受關(guān)注的課題�；诖�,本論文利用水熱合成方法設(shè)計合成了兩類新型多酸基金屬有機(jī)配位網(wǎng)絡(luò),并且開發(fā)其在電催化析氫和貴金屬附載兩個領(lǐng)域的功能特性。1、我們以α-Keggin型{PMo_(12)}多酸為模板,通過與過渡金屬Zn~(2+)以及兩種剛性咪唑橋連配體(bimbp/bimb)反應(yīng),成功獲得了兩例多酸嵌入型金屬有機(jī)配位網(wǎng)絡(luò)：[Zn(bimbp)_2]_3[PMo_(12)O_(40)]_2·2H_2O (1)[Bu_4N][Zn_3(bimb)_4Cl(MoO_4)][PMo~ⅤMo_(11)~(Ⅵ)O_(40)]·4H_2O (2)(bimbp= 4,4'-bis(imidazolyl)biphenyl, bimb=1,4-bis(1-imidazolyl)benzene)對化合物1-2進(jìn)行了紅外、熱重、元素分析、X-射線粉末衍射和X-射線單晶結(jié)構(gòu)解析,明確了晶體結(jié)構(gòu)。之后,將化合物1-2在管式爐中氮氣保護(hù)條件下進(jìn)行800℃高溫煅燒；并在冷卻后進(jìn)行酸蝕刻處理,獲得了能夠替代貴金屬鉑的新型析氫反應(yīng)(HER)電催化劑：MoC_x@C-1和MoC_x-2。Mo@C-1為氮摻雜類石墨化碳包覆的碳化鉬納米粒子,MoC_x-2為超細(xì)碳化鉬納米粒子；二者均在酸性介質(zhì)中展現(xiàn)出了卓越的HER性能。其中,MoC_x@C-1具有比較正起始電位,在電流密度10 mA·cm~(-2)條件下的過電位為79 mV,接近該條件下的商用催化劑Pt/C (20%); MoC_x@C-1還具有低的塔菲爾斜率(56mV-dec~(-1)),高的交換電流密度(0.27 mA·cm~(-2)),以及卓越的循環(huán)穩(wěn)定性。2、我們通過使用ε-Keggin型多酸建筑單元和四種剛性咪唑橋連配體(bimbp/bimb/bimbp/timb)在水熱條件下自組裝,成功構(gòu)筑了四例新穎的還原型多酸基金屬有機(jī)配位網(wǎng)絡(luò)：H[(Hbimb)_2(bimb) {Zn_4PMO_8~ⅤMo_4~(Ⅵ)O_(40)}]·6H_2O (3),[Zn(Hbimbp)(bimbp)_3{Zn_4PMo~ⅤgMo_4~(Ⅵ)O_(40)}]·DMF·3.5H_2O (4),H[Zn_2(timb)_2(bimba)_2Cl2]{Zn_4PMO_8~ⅤMo_4~(Ⅵ)O_(40)}]·7H_2O (5),imb)_2] [PMO_8~ⅤMo_4~(Ⅵ)O_(40)]·12H_2O(6)。(timb=1,3,5-tris(1-imidazolyl)benzene, bimba= 3,5-bis(1-imidazolyl)benzenamine)通過結(jié)構(gòu)表征證實,化合物3是由1D鋸齒鏈通過分子間的氫鍵作用拓展形成的3D超分子結(jié)構(gòu)�；衔�4是二維曲面,化合物5是手性配位網(wǎng)絡(luò),化合物6為四重互穿型金剛石網(wǎng)絡(luò)�；诰W(wǎng)絡(luò)結(jié)構(gòu)中多酸潛在的還原性能,將化合物3-5用于擔(dān)載貴金屬納米粒子)(NPs)的研究,得到了Ag NPs/化合物3-5復(fù)合材料。發(fā)現(xiàn)其在對硝基苯酚的還原上表現(xiàn)出極高的催化活性。
[Abstract]:In recent years, the study of polyacid-based organometallic coordination networks has become a hot issue in inorganic chemistry. A series of hybrid materials with multi-functional properties can be obtained by combining the unique polyacid units with the metal-organic coordination network with rich structure. So far, these hybrid materials have shown potential applications in acid catalysis, oxidation catalysis, photocatalysis, electrocatalysis and so on. However, compared with the preparation and synthesis of polyacid-based organometallic coordination networks, the development of their functional properties is only a small part. Therefore, the preparation of polyacid-base metal-organic coordination networks with new functional characteristics and the expansion of their new application fields have become a subject of great concern. Based on this, two kinds of novel polyacid-base organometallic coordination networks were designed and synthesized by hydrothermal synthesis method, and their functional characteristics in the fields of electrocatalytic hydrogen evolution and noble metal loading were developed. 偽-Keggin {PMo_ (12)} polyacid was used as a template to react with transition metal Zn~ (2) and two rigid imidazole bridged ligand (bimbp/bimb). Two polyacid-embedded organometallic coordination networks have been successfully obtained: [Zn (bimbp) _ 2] _ 3 [PMo_ (12) O _ (40)] _ 2 2H_2O (1) [Bu_4N] [Zn_3 (bimb) _ 4Cl (MoO_4)] [PMo~ 鈪，

本文編號：2371267