CN110156073B - 蒸汽热溶液蒸发制备TiO2的方法 - Google Patents
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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Abstract
本发明公开了蒸汽热溶液蒸发制备TiO2的方法。将钛盐滴入到有机溶剂中,磁力搅拌并混合,转移到高脚石英杯中,随后在哈氏合金反应釜内加入有机溶剂,并将高脚石英杯放入反应釜中,在温度为240‑500℃下,蒸汽水热反应5小时,反应结束后,反应釜内的冷凝管开始通入冷却水,使釜内温度快速降低,待冷却至室温后,取出杯中产物,杯中产物为固体状态时经过磨细后得到TiO2光催化剂,杯中产物为液体状态时,经过固液分离,然后加入乙醇洗涤,放入真空烘箱内干燥得到TiO2光催化剂。本发明得到的TiO2光催化剂具备催化性能优秀,制备工艺简单安全,在光催化领域有很好的应用前景。
Description
技术领域
本发明涉及蒸汽热溶液蒸发制备TiO2的方法,属于光催化剂技术 领域。
背景技术
TiO2在光催化降解领域有着广阔的应用前景,常规方法制备出来 的TiO2晶体通常暴露出来的是(101)晶面,而(101)面的缺点是载流子 迁移率低、反应活性位置少等。
研究人员发现,TiO2的(001)面上有着高密度的活性的不饱和Ti 原子,具有比(101)面更高的光催化活性。因此(001)面暴露的TiO2在光催化领域有着很大的应用潜力。为了让(001)面在晶体生长过程 中暴露,通常需要在制备过程中加入F-离子比如强腐蚀的氢氟酸, 或者强氧化剂比如H2O2,加入这些物质会造成一定的安全隐患,不利 于安全生产。
目前最常用的TiO2制备方法是水热法或者溶剂热法。水热法合成 的样品具有缺陷少,产物的结晶度高,大小均匀等优点。但也存在一 些不足,首先常规水热反应制备TiO2过程中,用水作为溶剂,水解反 应速率快,因此水解过程难以控制,制备的样品颗粒大,比表面积小 ,对光催化降解性能不利,为了解决这一问题,通常是在反应溶液中 加入分散剂,又会面临难以清洗的问题。其次,常规水热法制备样品 时,受反应釜本身的限制,反应温度通常在220℃以下,因为反应釜 中聚四氟乙烯内衬在230℃时就会严重变形,导致密封不好,容易发 生***危险。但是较低的反应温度会导致样品的晶化程度不高,需要 后续热处理进一步晶化。
发明内容
有鉴于此,本发明提出了蒸汽热溶液蒸发制备TiO2的方法,在超 临界状态下反应,得到的TiO2光催化剂具备催化性能优越,制备工艺 简单安全,在光催化领域有很好的应用前景。
为实现上述发明目的,本发明的蒸汽热溶液蒸发制备TiO2的方法, 将钛盐滴入到有机溶剂中,磁力搅拌并混合,得到澄清液体,并转移 到高脚石英杯中,随后在哈氏合金反应釜内加入有机溶剂,并将高脚 石英杯放入反应釜中,在温度为240-500℃下,蒸汽水热反应5小时, 反应结束后,反应釜内的冷凝管开始通入冷却水,使釜内温度快速降 低,待冷却至室温后,取出杯中产物,杯中产物为固体状态时经过磨 细后得到TiO2光催化剂,杯中产物为液体状态时,经过固液分离,然 后加入乙醇洗涤4-5次后,倒掉上清液,放入真空烘箱内干燥得到 TiO2光催化剂。
所述钛盐为钛酸异丙酯、钛酸四丁酯、四氯化钛或四氟化钛中的 至少一种。
所述有机溶剂为超临界温度低于500℃的醇类化合物。
本发明在超临界条件下进行反应,溶剂在超临界状态时,蒸汽压 升高,密度、表面张力和粘度都变低,这些变化会加快重要离子间的 反应,能够实现通常状态下难以发生的反应。同时,由于反应温度较 高,所制备样品的晶化程度高,不需要后续处理。
本发明采用非水的液体如醇类做为溶剂,加热到超临界温度以上, 使乙醇成为蒸汽,在蒸汽中反应缓慢生成水,降低钛源的水解速度, 以制备较小的TiO2颗粒;由于反应温度高,样品的结晶性好,不需要 后续晶化处理。在反应一段时间后,冷凝管通水快速冷却蒸汽成为液 体,收集到反应釜中,使得石英杯中的液体减少或者消失,经过处理 得到TiO2粒子,TiO2粒子仅10~20nm大小,比常规水热合成的粒子小得 多;重要的是,通过快速冷却过程,促进了TiO2(001)面的暴露,并 且TiO2表面吸附了一定的有机基团,提高了光响应范围和光催化性能, 有利于对可见光的吸收。
本发明通过超临界状态下反应,随后通过快速冷却的方法,使蒸 发的溶液在石英杯外的冷凝管上快速凝结,促进TiO2的(001)面暴露生 长;同时,石英杯内产物成为干燥粉末并吸附了一定有机基团,二者 共同提高了光催化性能,制备的催化剂光催化性能已经远超过工业 P25的水平,该催化剂无须经过金、银、铂等价格昂贵的金属修饰;也 无须利用氢氟酸等有害物质调控晶面;通过醇类会在高温下脱水缩合 的原理,使得原材料缓慢水解,生成的颗粒较小且均匀。
本发明的有益效果为:在超临界状态下反应,得到的TiO2光催化 剂具备催化性能优秀,制备工艺简单安全,在光催化领域有很好的应 用前景。
附图说明
图1为反应装置示意图。
图2为TiO2纳米粒子的XRD图谱,根据TiO2的标准PDF卡片(No.21-1272),可以确定TiO2为四方锐钛矿结构。其中,横坐标为衍 射角,纵坐标为相对强度。
图3为TiO2纳米粒子的透射电子显微(TEM)图。
图4为TiO2纳米粒子的UV-vis图。其中横坐标为波长,纵坐标 为吸收强度。
图5为TiO2纳米粒子的红外图谱。其中,横坐标为波长,纵坐标 为吸收强度。
图6为TiO2纳米粒子的荧光图谱。其中,横坐标为发射波长,纵 坐标为发光相对强度。
图7为TiO2纳米粒子对亚甲基蓝的光催化降解效率图。其中,横 坐标为光照时间,纵坐标为降解效率。
具体实施方式
下面结合附图和实施例对本发明作进一步详细的说明。
蒸汽热溶液蒸发制备TiO2的方法,将钛盐滴入到有机溶剂中,磁 力搅拌并混合,得到澄清液体,并转移到高脚石英杯中,随后在哈氏 合金反应釜内加入有机溶剂,并将高脚石英杯放入反应釜中,在温度 为240-500℃下,蒸汽水热反应5小时,反应结束后,反应釜内的冷凝 管开始通入冷却水,使釜内温度快速降低,待冷却至室温后,取出杯 中产物,杯中产物为固体状态时经过磨细后得到TiO2光催化剂,杯中 产物为液体状态时,经过固液分离,然后加入乙醇洗涤4-5次后,倒 掉上清液,放入真空烘箱内干燥得到TiO2光催化剂。
所述钛盐为钛酸异丙酯、钛酸四丁酯、四氯化钛或四氟化钛中的 至少一种。
所述有机溶剂为超临界温度低于500℃的醇类化合物。
实施例1
(1)吸取4mL钛酸异丙酯(TIP),滴入到96mL乙醇中,并磁力搅 拌30min。
(2)将步骤(1)中溶液转移到120mL的石英高脚中。
(3)称量200mL乙醇到1000mL的高温高压反应釜中,并将(2)中 的石英杯放入高温高压反应釜。随后分别进行如下条件反应:
在240℃环境下反应5小时。待溶液冷却后,石英杯中为少量液体 的沉淀物,离心分离所得产物,利用无水乙醇清洗4-5次后,倒掉上 清液,将所得沉淀物放入真空干燥箱中,在60℃的情况下干燥12小时, 获得TiO2纳米粒子①;
在250℃环境下反应5小时。待溶液冷却后,杯内产物呈干燥的淡 黄色固体,研磨后即获得TiO2纳米粒子②。
得到的TiO2纳米粒子②,具有非常强的催化性能,它对亚甲基蓝 的降解速率是工业P25的近3倍。
实施例2
(1)用X-射线多晶体衍射仪(XRD;Smartlab9KW)测试TiO2纳米粒 子的X-射线衍射图谱,见图2。由图2中TiO2纳米粒子衍射峰的位置和 相对强度与标准PDF卡片No.21-1272对比可知我们所制备的TiO2纳米 粒子的晶体结构为四方锐钛矿相。
(2)用透射电子显微镜(JEOLJEM-2100)表征240℃环境制备的 TiO2纳米粒子(即粒子①)的透射电子显微镜(TEM)图,见图3(a);表 征250℃TiO2纳米粒子(即粒子②)的透射电子显微图(TEM),见图3(b) ;表征250℃TiO2纳米粒子的高分辨透射电子显微图(HRTEM),见图 3(c)和(d)
由图3(a)和图3(b)可知,所制备的TiO2纳米粒子是粒径为约 10-20nm的纳米颗粒。如图3(c)所示,间距为0.35的条纹对应于 TiO2的(101)晶格条纹。图3(d)显示了来自TiO2的晶格条纹,分别 为0.19nm和0.35nm。其中0.19nm的条纹对应TiO2的(200)面,而0.35nm的条纹对应了TiO2的(101)面。
(3)利用紫外可见近红外分光光度计(U-4100)表征TiO2纳米粒子 ①和TiO2纳米粒子②的紫外可见光吸收谱,见图4。TiO2纳米粒子① 的吸收边在380nm左右,说明了TiO2纳米粒子①的带隙在3.2ev左右 ,对可见光的吸收能力不足;而TiO2纳米粒子②的吸收边有显著的红 移现象,有明显的对可见光的吸收能力。
(4)利用傅里叶红外显微***(Vertex80)对TiO2纳米粒子①和 TiO2纳米粒子②的红外吸收进行表征,结果见图5。对比TiO2纳米粒 子①和TiO2纳米粒子②,发现TiO2纳米粒子②的红外光谱在1731cm-1 处出现了吸收峰,此处的吸收峰是由C=O双键的伸缩振动产生的,说 明了TiO2纳米粒子②吸附了一定的C=O有机基团。
(5)利用荧光分光光度计(F-4500)对TiO2纳米粒子①和TiO2纳米 粒子②进行荧光表征。通过扫描确定了样品二者受300nm紫外光激发 的发射光强度最大,并且在发射波长为425nm和475nm处出现最高峰 。通过比较发现,TiO2纳米粒子①发射光强度大于TiO2纳米粒子②的 发射光强度,说明了TiO2纳米粒子②的有着更低的电子-空穴复合率 ,即更高的载流子寿命。
(6)利用紫外可见分光光度计(UV-6100)分别测试了TiO2纳米粒 子①和TiO2纳米粒子②以及工业P25粉末对亚甲基蓝的光催化降解 性能,结果如图7显示。在光照90min后,三者对亚甲基蓝的降解效 率都达到了99%以上。其中TiO2纳米粒子②对亚甲基蓝有着优秀的降 解能力,在30min左右就降解了99%的亚甲基蓝,快于工业P25粉末。
最后说明的是,以上实施例仅用以说明本发明的技术方案而非限 制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技 术人员应当理解,可以对本发明的技术方案进行修改或者等同替换, 而不脱离本发明技术方案的宗旨和范围,其均应涵盖在本发明的权利 要求范围当中。
Claims (3)
1.蒸汽热溶液蒸发制备TiO2的方法,其特征在于,将钛盐滴入到有机溶剂中,磁力搅拌并混合,得到澄清液体,并转移到高脚石英杯中,随后在哈氏合金反应釜内加入有机溶剂,并将高脚石英杯放入反应釜中,在温度为240-500℃下,蒸汽水热反应5小时,反应结束后,反应釜内的冷凝管开始通入冷却水,使釜内温度快速降低,待冷却至室温后,取出杯中产物,杯中产物为固体状态时经过磨细后得到TiO2光催化剂,杯中产物为液体状态时,经过固液分离,然后加入乙醇洗涤4-5次后,倒掉上清液,放入真空烘箱内干燥得到TiO2光催化剂。
2.如权利要求1所述的蒸汽热溶液蒸发制备TiO2的方法,其特征在于,所述钛盐为钛酸异丙酯、钛酸四丁酯、四氯化钛或四氟化钛中的至少一种。
3.如权利要求1所述的蒸汽热溶液蒸发制备TiO2的方法,其特征在于,所述有机溶剂为超临界温度低于500℃的醇类化合物。
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