發(fā)布時間：2018-03-15 19:38

  本文選題：SBA-15　切入點(diǎn)：硬模板　出處：《太原理工大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：在能源枯竭、環(huán)境惡化的時代背景下,尋求新型綠色能源迫在眉睫。綠色氫能能夠在很大程度上解決能源危機(jī)等問題。眾多制氫方式中,微生物電解池(MEC)由于自身的諸多優(yōu)勢脫穎而出,贏得科研學(xué)者的重視。本論文以MEC陰極鎳鈷氧化物催化材料為研究重心,以介孔硅為硬模板,進(jìn)行了一系列實(shí)驗(yàn),探討了不同浸漬方法,不同鎳、鈷硝酸鹽前驅(qū)體比例,不同焙燒溫度以及焙燒環(huán)境對介孔鎳鈷氧化物的影響,并對比了所制備樣品的電化學(xué)及MEC陰極析氫性能,主要實(shí)驗(yàn)與結(jié)論如下:(1)考查浸漬方法對微-介孔Ni O催化劑以及MEC陰極析氫量的影響。以SBA-15為硬模板,硝酸鎳為浸漬前體制得短程有序的介孔Ni O,其中雙溶劑法制備的介孔Ni O在疏水性溶劑正己烷作用下,對孔道的填充較為完全,較好的復(fù)制了SBA-15的有序介孔結(jié)構(gòu),所得介孔Ni O比表面積(123m2/g),以及微孔面積(169 m2/g)均遠(yuǎn)遠(yuǎn)高于其他幾種浸漬方法(介孔80m2/g,微孔107 m2/g)。雙溶劑合成法相對于其他方法更有利于金屬前體進(jìn)入SBA-15的微孔孔道,因此雙溶劑法電極材料具有豐富的微孔,進(jìn)而導(dǎo)致活性位點(diǎn)增多,與此同時,該電極材料豐富的介孔孔道還便于電解液離子的傳輸,促進(jìn)了材料倍率性能的改善。相對比其他幾種方法,由雙溶劑法制得的富含微孔的介孔結(jié)構(gòu)Ni O在MEC析氫實(shí)驗(yàn)中的氫氣選擇性最好。(2)采用硬模板法,利用雙溶劑法浸漬,以不同摩爾比的鎳鈷硝酸鹽為前體,制備得到微-介孔鎳鈷氧化物。通過XRD和N_2吸附等分析手段可知:隨著鎳摻雜比例的增加,晶胞參數(shù)a0值逐漸增大,Ni O的峰出現(xiàn)并逐漸增強(qiáng),Co3O4的峰減弱消失,當(dāng)鎳鈷摩爾比為1:2時,鎳離子進(jìn)入鈷尖晶石的晶格,生成了鎳鈷尖晶石結(jié)構(gòu)。介孔Ni Co_2O_4的介孔比表面積為100m2/g,微孔比表面積78 m2/g。高的微介孔比表面積和有序介孔孔道結(jié)構(gòu)導(dǎo)致Ni Co_2O_4電極較優(yōu)的電化學(xué)性能。究其原因,可能是由于尖晶石的特殊結(jié)構(gòu),導(dǎo)致Ni Co_2O_4析氫催化效果優(yōu)于其他比例樣品,氫氣含量達(dá)到68.96%,析氫總量達(dá)到8.5 ml。(3)采用不同焙燒溫度制備微-介孔鎳鈷氧化物。低溫焙燒(300℃)時,可得到較為純凈的Ni Co_2O_4單相,而溫度升高至400℃以上時,Ni Co_2O_4尖晶石開始分解形成Ni O,形成有缺陷的尖晶石結(jié)構(gòu)。當(dāng)溫度達(dá)到800℃,出現(xiàn)Co O結(jié)構(gòu)衍射峰。500℃焙燒溫度時,介孔表面積(129 m2/g),微孔面積(166 m2/g)最為豐富,此時帶有Ni O缺陷的鎳鈷尖晶石的CV曲線面積明顯高于單純的鎳氧化物或者鈷氧化物。由于受到比表面積與結(jié)晶度的雙重影響,在焙燒溫度為500℃,鎳鈷摩爾比為1:2時,得到的微-介孔鎳鈷氧化物具有最高的比表面積和較好的孔徑分布,在自組裝的單室MEC裝置中得到較好的析氫效果。(4)探究帶蓋坩堝與開放坩堝在煅燒過程中對材料的晶體生長行為的影響。帶蓋坩堝中的Ni Co(C)樣品的BET比表面積(118 m2/g),微孔面積(58 m2/g),均高于無蓋坩堝中樣品Ni Co(O),獲得了較高有序度的介孔金屬氧化物。將最優(yōu)實(shí)驗(yàn)方案:雙溶劑浸漬法、鎳鈷前體摩爾比1:2、500℃帶蓋坩堝焙燒,推廣至硬模板KIT-6,同樣得到了有序度較好的鎳鈷Ni Co_2O_4,樣品比表面積的達(dá)到101 m2/g。
[Abstract]:In the energy depletion, deterioration of the environment under the background of the times, seeking new green energy imminent. Green hydrogen can solve the problem of energy crisis in a large extent. Many hydrogen production methods, microbial electrolysis cell (MEC) because of its many advantages in science research scholars talent shows itself, to win attention. This thesis MEC cathode nickel cobalt oxide catalyst materials for research, using mesoporous silica as a hard template, conducted a series of experiments on different impregnation methods, different nickel, cobalt nitrate precursor ratio, the influence of different calcination temperature and calcination conditions on Mesoporous Nickel Cobalt oxide, and compared the electrochemical cathodic hydrogen and MEC prepared the main results and conclusions are as follows: (1) to examine the impregnation method of micro - mesoporous Ni O MEC catalyst and the amount of cathodic hydrogen. The effect of using SBA-15 as hard template for impregnating nickel nitrate precursor to short-range order The mesoporous Ni O, the double solvent method for preparing mesoporous Ni O in hydrophobic solvent hexane under the action of pore filling is complete, the mesoporous structure of a good copy of SBA-15, the specific surface area of mesoporous Ni O (123m2/g), and the surface area (169 m2/g) were far much higher than other types of impregnation method (mesoporous 80m2/g, microporous m2/g 107). The double solvent method compared to other methods is more conducive to the pore pore into the metal body before SBA-15, so the double solvent extraction electrode material has rich pores, resulting in increased active sites, and at the same time, the transmission of mesopores rich the electrode material also for electrolyte ions, promoted the rate performance of the material improved. Compared to other methods, the double solvent prepared rich microporous mesoporous structure of Ni O MEC in the best hydrogen selectivity of hydrogen evolution experiment. (2) by hard template method, and Impregnated with double solvent method using nickel cobalt nitrate with different molar ratios were prepared by micro - mesoporous nickel cobalt oxide. By XRD and N_2 adsorption analysis method shows that with increasing Ni doping ratio, the lattice parameter A0 increases, the peak of Ni O and Co3O4 gradually increased. The peak weakened and disappeared, when the Ni / co molar ratio is 1:2, nickel ions into the cobalt spinel lattice generated nickel cobalt spinel structure. The mesoporous Ni Co_2O_4 mediated 100m2/g specific surface area, micropore surface area of 78 m2/g. high dielectric micro pore surface area and ordered mesoporous channel structure leads to the electrochemical properties of Ni Co_2O_4 the electrode is better. The reason may be due to the special structure of Ni Co_2O_4 spinel, leading to hydrogen evolution is better than other proportion of samples, the hydrogen content reached 68.96%, the hydrogen evolution volume reached 8.5 ml. (3) with different calcination temperature for preparing micro - and Mesoporous Nickel Cobalt Oxide. Roasting at low temperature (300 DEG C), can obtain more pure single-phase Ni Co_2O_4, while the temperature rises to 400 degrees above, Ni Co_2O_4 Ni O began to form spinel decomposition, the formation of spinel structure defects. When the temperature reaches 800 DEG C, Co O diffraction peak of.500 DEG C calcination temperature, mesoporous the surface area (129 m2/g), surface area (166 m2/g) is the most abundant, the area of CV curve at Ni O with nickel cobalt spinel defect was obviously higher than that of pure nickel oxide or cobalt oxide. Due to the double influence than the surface area and the crystallinity of the calcination temperature at 500 DEG C, Ni / CO molar ratio is 1:2 when the micro - and mesoporous nickel cobalt oxide has the highest specific surface area and good pore size distribution, obtained good effect in a single hydrogen chamber MEC self-assembly device. (4) explore with crucible cover and open crucible in the calcination process of materials for crystal growth Effect of long behavior. With a cover in the crucible of Ni Co (C) BET of the sample surface area (118 m2/g), surface area (58 m2/g), were higher than those without cover in the crucible samples of Ni Co (O), obtained mesoporous metal oxides have high degree of order. The optimal experimental scheme: double solvent the impregnation method, nickel cobalt precursor 1:2500 molar ratio of C with crucible cover roasting, extended to the hard template KIT-6, are also well ordered nickel cobalt Ni Co_2O_4 sample surface area up to 101 m2/g.

【學(xué)位授予單位】：太原理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O643.36;O646.5

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 鄭津洋;張俊峰;陳霖新;王賡;顧超華;趙永志;劉鵬飛;張鑫;蒙波;;氫安全研究現(xiàn)狀[J];安全與環(huán)境學(xué)報;2016年06期

2 周俊琛;周權(quán);李建保;林仕偉;;復(fù)合半導(dǎo)體光電解水制氫研究進(jìn)展[J];硅酸鹽學(xué)報;2017年01期

3 靳捷;劉奕梅;邵俊捷;徐向陽;朱亮;;基于陰極材料優(yōu)化的微生物電解池研究進(jìn)展[J];化工進(jìn)展;2016年02期

4 趙永志;蒙波;陳霖新;王賡;鄭津洋;顧超華;張鑫;張俊峰;;氫能源的利用現(xiàn)狀分析[J];化工進(jìn)展;2015年09期

5 張凌峰;胡忠攀;高澤敏;劉亞錄;袁忠勇;;有序介孔碳基金屬復(fù)合材料的制備及催化應(yīng)用[J];化學(xué)進(jìn)展;2015年08期

6 蘭海;周桂林;楊興會;任圓圓;謝紅梅;;硬模板法制備鈰基復(fù)合氧化物及其對甲苯燃燒的催化性能[J];燃料化學(xué)學(xué)報;2015年04期

7 夏云生;劉靖婷;魯奇林;包德才;;高比表面積介孔氧化鎳制備及表征[J];化學(xué)研究與應(yīng)用;2015年02期

8 樊東黎;;世界能源現(xiàn)狀和未來[J];金屬熱處理;2011年10期

9 張文莉;吳小黎;王釗;蔣銀花;倪良;;Co_3O_4納米線的模板合成及其電化學(xué)性能[J];功能材料與器件學(xué)報;2011年02期

10 李金來;李偉;萬新華;張國濤;馮亞青;;添加Sn的Ni-Al合金生物電化學(xué)制氫陰極催化劑[J];化工學(xué)報;2010年10期

相關(guān)博士學(xué)位論文 前2條

1 鄭春蕊;金屬氧族化合物納米材料的制備及其光催化和電化學(xué)性能研究[D];北京理工大學(xué);2015年

2 劉文宗;有機(jī)廢水微生物電解產(chǎn)氫研究及電極微生物功能解析[D];哈爾濱工業(yè)大學(xué);2011年

相關(guān)碩士學(xué)位論文 前2條

1 褚瑞霞;鎳鈷氧化物納米材料制備及其在超級電容器中的應(yīng)用[D];濟(jì)南大學(xué);2015年

2 程超;基于Co_3O_4納米材料的制備及電化學(xué)性能研究[D];湖南大學(xué);2014年

，

本文編號：1616514