【摘要】：利用脫合金法制備納米多孔金屬,是一種較簡單且能有效得到具有高內表面積、高孔隙率和較均勻孔徑的納米孔結構的方法。此外,納米多孔金屬不僅保留了金屬材料的高導熱率、高導電率等優(yōu)異性能,還因其納米級的特征尺寸而具備了塊體金屬所沒有的性質(如高催化能力)。因此,納米多孔金屬及脫合金方法近年來引起了越來越多的關注。目前可用脫合金化法來制備納米多孔金屬(如納米多孔金、鉑、鈀、銀、銅等)、納米多孔合金(如:納米多孔金鉑、鉑鈀等)等材料。雖然貴重金屬(合金)具有優(yōu)異的性能,但對性質活潑的銅的研究不僅具有科學研究價值還能為工業(yè)上合理利用銅資源提供指導。本文主要通過球磨-冷壓-燒結、冷壓-燒結的方法制備Al-Cu(NaCl)合金并通過水浴的方法除去NaCl模板從而得到多孔的Al-Cu合金前驅體,通過脫合金方法最終得到具有雙模式孔結構的銅/銅氧化物。一是選取Al_(67)Cu_(33)為研究對象,用球磨法均勻混合Al、Cu、NaCl粉末,常溫下壓制成粉坯后進行燒結(本文稱其為冷壓-燒結),研究NaCl的加入量、燒結溫度和燒結時間對納米多孔銅/銅氧化物結構及組成的影響,并將其脫合金產物應用于催化降解甲基橙和超級電容器性能的測試;二是采用轉速較低的研磨儀混合不同比例的Al、Cu、NaCl粉末,通過冷壓-燒結來制備NaCl比例不同的Al-Cu(NaCl)合金,再通過去鹽-脫合金法獲得雙模式納米多孔銅/銅氧化物。根據納米多孔銅/銅氧化物超聲催化降解甲基橙的效率確定Al-Cu合金的最優(yōu)加鹽量。然后使用化學鍍金的方法,以脫合金產物為載體在其表面鍍金,制備負載型金催化劑。最后根據其催化氧化CO的活性溫度探究工藝的可行性并確定最佳工藝參數(shù),初步探究了負載型納米金催化劑催化CO氧化的原理。用冷壓-燒結制備加鹽的Al-Cu合金,通過探究實驗發(fā)現(xiàn)Al-Cu合金中最佳加鹽量為5 wt.%。究其原因是脫合金產物中形成兩種不同尺寸范圍的孔道,兩種孔道作用不同:較大孔道(~1000nm)加快擴散,小孔道(~40nm)有利于提高比表面積進而提供更多化學反應活性位點,這種擁有雙模式結構的納米多孔材料比只有單一尺度范圍孔道的納米多孔材料具有更好的催化效率。脫合金一般產物為Cu/Cu2O,但產物為Cu/CuO/Cu2O時,催化效率最高。通過置換的方式在納米多孔銅/銅氧化物表面再沉積貴金屬Au顆粒,主要研究了負載型納米金對催化劑整體催化氧化CO反應中的效果,包括CO的轉化率達到百分之百時所處的溫度,以及在相同溫度下不同催化劑對CO的轉化率,并分析了負載型催化劑催化CO氧化的原理。研究發(fā)現(xiàn),負載Au納米顆粒的納米多孔銅/銅氧化物對CO氧化的催化效率比未負載的有大幅度的提高(可提升27%)。脫合金產物基體表面沉積微量的金,由于Au與載體之間的協(xié)同效應使催化劑對CO的催化氧化具有比未負載Au產物更高的催化活性。
[Abstract]:The preparation of nano-porous metal by dealloying method is a simple and effective method to obtain nano-pore structure with high internal surface area, high porosity and uniform pore size. In addition, nano-porous metals not only retain the excellent properties of metal materials such as high thermal conductivity and high conductivity, but also possess the properties (such as high catalytic ability) of bulk metals because of their characteristic size. Therefore, nano-porous metals and dealloying methods have attracted more and more attention in recent years. At present, nano-porous metals (such as nano-porous gold, platinum, palladium, silver, copper, etc.) and nano-porous alloys (such as nano-porous gold platinum, platinum-palladium, etc.) and nano-porous alloys (such as nano-porous gold platinum, platinum-palladium, etc.) can be prepared by dealloying method. Although precious metals (alloys) have excellent properties, the study of active copper has not only scientific research value, but also can provide guidance for the rational utilization of copper resources in industry. In this paper, Al-Cu (NaCl) alloy was prepared by ball milling, cold pressing sintering, and the porous Al-Cu alloy precursor was obtained by removing NaCl template by water bath. Finally, copper / copper oxide with double mode pore structure was obtained by dealloying method. One is to select Al _ (67) Cu _ (33) as the object of study, mix the Al _ (67) Cu _ (33) powder uniformly with the ball milling method, press it into powder billet at room temperature, and then sintered (this paper calls it "cold pressing sintering"), and study the adding amount of NaCl. The effects of sintering temperature and sintering time on the structure and composition of nano-porous copper / copper oxide were investigated. The dealloying products were used to test the catalytic degradation of methyl orange and supercapacitor. Secondly, Al-Cu (NaCl) alloys with different NaCl ratios were prepared by cold pressing and sintering with a low rotating speed grinder, and double mode porous copper / copper oxides were obtained by desalination and desalination. According to the ultrasonic degradation efficiency of nano-porous copper / copper oxide, the optimum salt addition of Al-Cu alloy was determined. Then the supported gold catalyst was prepared by electroless gold plating. Finally, according to the feasibility of the catalytic oxidation of CO and the optimum process parameters, the principle of the supported nanometer gold catalyst for CO oxidation was preliminarily explored. Al-Cu alloy was prepared by cold pressing and sintering. The optimum salt addition in Al-Cu alloy was found to be 5 wt. The reason is that two kinds of pores with different sizes are formed in the dealloyed products. The two channels act differently: the larger channels (1000 nm) accelerate the diffusion, and the small channels (40 nm) increase the specific surface area and provide more chemical reactive sites. This kind of nano-porous material with two-mode structure has better catalytic efficiency than the nano-porous material with only a single pore size range. The general product of dealloying is Cu / Cu _ 2O, but the catalytic efficiency is the highest when the product is Cu / Cu _ 2O / Cu _ 2O. The noble metal au particles were redeposited on the surface of nano-porous copper / copper oxide by displacement. The effect of supported nano-gold on the overall catalytic oxidation of CO on the catalyst was studied. It includes the temperature at which the conversion of CO reaches 100% and the conversion of CO by different catalysts at the same temperature. The principle of catalytic oxidation of CO with supported catalyst is analyzed. It was found that the catalytic efficiency of au nanoparticles supported on nano-porous copper / copper oxides for CO oxidation was much higher than that of unloaded copper nanoparticles (up to 27%). Due to the synergistic effect between au and the support, the catalyst has higher catalytic activity for CO oxidation than the unsupported au product, due to the trace amount of gold deposited on the substrate surface of the dealloyed product.
【學位授予單位】：濟南大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O643.36

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