本文選題：Zr-MOF　切入點(diǎn)：Pd納米顆粒　出處：《浙江工業(yè)大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

【摘要】：最近十年,金屬-有機(jī)框架(Metal-Organic Frameworks,MOFs)作為一種新興的多孔材料,引起了材料學(xué)家的廣泛關(guān)注。一方面,MOFs的規(guī)整有序納米尺寸的孔道能提供獨(dú)特的微反應(yīng)器,另一方面,MOFs納微晶格表面常懸掛著有機(jī)配體,對(duì)金屬具有很強(qiáng)的吸附作用。因此,MOFs是一種非常好的固載金屬納米催化劑的載體。Zr基MOFs是由Zr4+金屬離子簇合物次級(jí)構(gòu)筑單元與有機(jī)剛性配體配位組裝形成的多孔材料。相對(duì)其他MOFs,其具有高的化學(xué)穩(wěn)定性。貴金屬納米顆粒因其量子尺寸效應(yīng),常表現(xiàn)出良好的催化活性。Pd納米顆粒是一種高效催化劑,但其價(jià)格昂貴,參與均相反應(yīng)不易回收,故選擇MOF負(fù)載得到高度分散的Pd納米顆粒,既能降低成本,又能回收。本文中,采用浸漬法選擇Zr-MOF材料(DUT-67、UiO-66-NH2)以及衍生的ZrO2作為載體材料制備三種不同的負(fù)載型Pd納米催化劑。采用一系列表征手段對(duì)其進(jìn)行表征,其結(jié)構(gòu)表征可知,Pd納米顆粒能高度分散在Zr-MOF框架中,且尺寸分布均勻,展示出很好的限域效應(yīng)。催化性質(zhì)測(cè)試表明:1)Pd/DUT-67在硝基苯加氫反應(yīng)和Suzuki耦合反應(yīng)中均有很好催化性能。在硝基苯加氫反應(yīng)中,當(dāng)溫度達(dá)到60oC時(shí),在2MPa H2的條件下反應(yīng)3h,轉(zhuǎn)化率達(dá)到99%。在Suzuki耦合反應(yīng)中,反應(yīng)條件以乙醇和水為混合溶劑,K2CO3為堿,溫度為60oC,反應(yīng)1h,能實(shí)現(xiàn)反應(yīng)物的完全轉(zhuǎn)換。2)Pd/UiO-66-NH2在CO催化氧化反應(yīng)中的催化劑性能研究表明,當(dāng)Pd的負(fù)載量分別為0.3%、0.5%以及1.0%時(shí),CO氧化反應(yīng)的T50分別為160 oC、165 oC和170 oC,T100均為180 oC。3)Pd/ZrO2-NH2在CO催化氧化中隨溫度升高均能實(shí)現(xiàn)CO的完全轉(zhuǎn)換。在600 oC、700 oC以及800 oC下焙燒得到的ZrO2負(fù)載Pd的T100分別170 oC、160 oC和180 oC,而1.0%Pd/ZrO2-A和1.0%Pd/ZrO2-P分別為220 oC和200 oC。
[Abstract]:In the last decade, Metal-Organic frameworks (MOFs), as a new porous material, have attracted extensive attention of materials scientists. On the one hand, the well-ordered nanometer-sized pores of MOFs can provide unique microreactors. On the other hand, organic ligands are often suspended on the surface of MOFs nanocrystalline lattice. Therefore, MOFs is a very good carrier for supported metal nanocatalysts. Zr-based MOFs is composed of Zr4 metal ion cluster secondary building units and organic rigid ligands. Materials. Higher chemical stability than other MOFs. Noble metal nanoparticles due to their quantum size effects, Pd nanoparticles often show good catalytic activity, but they are expensive and difficult to recover in homogeneous reactions. Therefore, choosing MOF loaded to obtain highly dispersed PD nanoparticles can reduce the cost. In this paper, three different kinds of supported PD nanocatalysts were prepared by dipping method, Zr-MOF material (DUT-67UiO-66-NH2) and derivative ZrO2 were used as carrier materials, and were characterized by a series of characterization methods. The structure characterization shows that the Pd nanoparticles can be highly dispersed in the Zr-MOF framework, and the size distribution is uniform. The catalytic properties test showed that the catalytic properties of 1% Pd / DUT-67 were very good in the hydrogenation of nitrobenzene and the coupling reaction of Suzuki. In the hydrogenation of nitrobenzene, when the temperature reached 60oC, Under the condition of 2 MPA H2 for 3 h, the conversion reached 99%. In the Suzuki coupling reaction, the reaction conditions were ethanol and water as the mixed solvent K _ 2CO _ 3 as the base. When the reaction temperature is 60oC and the reaction time is 1h, the catalyst performance of PD / UiO-66-NH2 can be realized in CO catalytic oxidation reaction. The T50 of CO oxidation reaction was 160oC 165oC and 170oC T100 180 oC.3)Pd/ZrO2-NH2 respectively when PD loading was 0.3wt% and 1.0% respectively. The complete conversion of CO was achieved by calcination at 600oC 700oC and 800oC respectively during CO catalytic oxidation. The T100 of PD loaded on PD is 170oC and 180oC, respectively, while the 1.0 Pd-ZrO2-A and 1.0Pd-ZrO2-P are 220oC and 200oC, respectively.
【學(xué)位授予單位】：浙江工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TB383.1;O643.36

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本文編號(hào)：1622347