CN106925252A - 一种金属掺杂纳米TiO2/海泡石复合材料及制备方法 - Google Patents
一种金属掺杂纳米TiO2/海泡石复合材料及制备方法 Download PDFInfo
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Abstract
本发明涉及一种金属掺杂纳米TiO2/海泡石复合材料及制备方法，属于矿物材料加工与应用领域。本发明以海泡石为载体，利用溶剂蒸发‑煅烧晶化法将金属元素铈、铋、钒掺杂纳米TiO2负载于海泡石表面，得到具有可见光响应的纳米TiO2/海泡石复合材料。该方法实现了海泡石与金属掺杂纳米TiO2的复合，增强了纳米TiO2对可见光的利用率。这种负载型光催化材料在可见光下具有优良的光催化活性，在污染物处理领域具有很大的潜在应用价值。
Description
技术领域
本发明涉及一种用于降解污染物的金属掺杂纳米TiO2/海泡石复合光催化材料及制备方法，属于矿物材料加工与应用领域。
背景技术
光催化技术作为一种高级氧化技术，在污水处理、空气净化等领域有广阔的应用前景。光催化材料在光照情况下，受激发产生自由基，将吸附于其表面的污染物催化氧化，最终矿化降解为二氧化碳、水等产物。在众多光催化剂中，TiO2因具有良好的化学稳定性、强氧化性、无毒和低成本等特点，成为目前研究最广泛的光催化材料。但是，在实际制备及应用过程中，由于纳米TiO2颗粒比表面积大，表面自由能高，极易团聚成二次颗粒，使其光催化活性降低。为了克服以上缺点，人们提出将纳米TiO2固定于一定载体之上。
目前，以海泡石为载体负载纳米TiO2颗粒已有一些研究。在这些研究中最常用的方法是溶胶-凝胶法，见以下参考文献：(1)发明专利“海泡石/纳米TiO2复合材料的合成方法”，申请号CN201310459169.9，申请人四川嘉宝莉涂料有限公司；(2)谢治民,等.TiO2/海泡石催化剂的制备及其对印染废水的处理.环境科学与技术,2009,32(5):123-127。在溶胶凝胶法中使用的钛酸四丁酯等钛醇盐具有刺激性气味，且制备过程需要乙醇等大量有机溶剂，制备方法不易实现工业化。此外，四氯化钛水解法也是广泛使用的制备方法，见参考文献：(1)发明专利“纳米TiO2/海泡石复合材料的制备方法及其用途”，申请号CN201410063295.7，申请人张吉鹏；(2)贺洋,等.纳米TiO2/海泡石复合粉体的制备及光催化性能研究.非金属矿,2010,33(1):67-69。在这种方法中所用的四氯化钛水解过程不易控制，工业生产中对设备腐蚀严重，制备工艺流程复杂。
TiO2的禁带宽度决定了其只能吸收紫外光，在可见光区域没有明显的吸收。此外，TiO2光生电子-空穴复合率较高，量子效率较低。近年来，研究者们通过多种方法(贵金属沉积、元素掺杂、染料敏化等)对TiO2进行修饰改性，拓宽TiO2的可见光响应区域，使其光生电子-空穴对能够有效分离，从而提高其光量子效率。通过金属元素掺杂制备的TiO2既能有效扩展材料的光响应范围，又能促进二者空穴-电子对的有效分离。目前，已有诸多关于金属掺杂TiO2的制备研究，见以下参考文献：(1)发明专利“钒-氮共掺杂TiO2光催化剂的制备方法”，申请号CN201110146031.4，申请人甘肃省科学院自然能源研究所；(2)王淑勤,等.掺钒TiO2可见光催化氧化SO2的动力学和机理.太阳能学报,2015,36(11):2690-2697。这些文献都是关于纯TiO2的制备，未解决催化剂易团聚、回收难的问题。
本发明针对目前纳米TiO2催化剂存在的不足，提出了一种具有可见光响应的纳米TiO2/海泡石复合材料及制备方法。海泡石是一种纤维状富镁含水硅酸盐轻质黏土矿物，主要化学成分为SiO2和MgO。海泡石独特的晶体结构使其具有比表面积高、吸附能力强等特点，广泛应用于建材、化工、环保等领域。将具有可见光响应的纳米TiO2负载于海泡石上，既能有效提高催化剂分散性能与可回收性，降低使用成本，又可以利用载体对污染物良好的吸附捕捉性能，提高材料光催化效率。因此，这种复合光催化剂具有良好的应用前景。
发明内容
本发明的技术方案是，以海泡石为载体，采用溶剂蒸发-煅烧晶化法，制备出一种具有可见光响应的金属掺杂纳米TiO2/海泡石复合光催化材料。
本发明制备的纳米TiO2/海泡石复合光催化材料，海泡石表面负载了钒(V)、铈(Ce)或铋(Bi)掺杂锐钛型TiO2，催化剂禁带宽度为2.7～3.0eV，纳米TiO2质量为海泡石质量的10％～60％。
其制备方法及工艺步骤如下：
(1)配制浓度为0.1～0.5mol/L的硫酸氧钛(TiOSO4)溶液，在TiOSO4溶液中加入金属元素前驱体，金属元素前驱体与TiOSO4的摩尔比为0.005～0.05，在温度为30～100℃的水浴中搅拌，直至金属元素前驱体溶解。所述金属元素前驱体为六水合硝酸铈、硫酸铈、偏钒酸铵、偏钒酸钠、五水合硝酸铋。
(2)按固体质量(g)：液体体积(ml)为1:10～30将海泡石加入步骤(1)中的TiOSO4溶液中，在温度为30～100℃的水浴中搅拌，直至溶剂蒸发完全；
(3)将上述步骤中所得的产物研磨至97％通过200目筛后，在450～800℃下煅烧1～10h，煅烧过程中升温速率1～10℃/min，最终得到金属元素掺杂-纳米TiO2/海泡石复合光催化材料。
上述制备过程利用海泡石具有较大的比表面积，抑制了TiO2的团聚，实现了金属元素掺杂纳米TiO2在海泡石表面的负载，提高了TiO2光催化剂的可见光利用率，并降低了催化剂的应用成本。
附图说明
图1：金属元素掺杂-纳米TiO2/海泡石复合材料制备工艺流程图；
具体实施方式
下面结合具体实施例对本发明的产品制备方法作进一步的说明。
实施例1：
具体实施步骤如下：
(1)将0.195g六水合硝酸铈溶于100mL、0.3mol/L硫酸氧钛溶液中，在温度为60℃的水浴中搅拌，待六水硝酸铈完全溶解后，加入5g海泡石，搅拌均匀，直至溶剂蒸发完全。
(2)将上述步骤所得的蒸发完样品在750℃下煅烧2小时，升温速率2.5℃/min。最终得到金属元素掺杂纳米TiO2/海泡石复合光催化材料。
实施例2：
与实施例1中步骤相同，不同之处在于：步骤(1)中硫酸氧钛溶液的体积为80mL，水浴温度为80℃；步骤(2)中煅烧温度650℃，煅烧时间3h。
实施例3：
与实施例1中步骤相同，不同之处在于：步骤(1)中金属元素前驱体为五水合硝酸铋，五水合硝酸铋加入量为0.218g；步骤(2)中煅烧温度500℃，煅烧时间3h。
实施例4：
与实施例1中步骤相同，不同之处在于：步骤(1)中金属元素前驱体为偏钒酸铵，偏钒酸铵加入量为0.053g；步骤(3)中煅烧温度650℃，煅烧时间2h。
实施例5：
与实施例1中步骤相同，不同之处在于：步骤(1)中金属元素前驱体为偏钒酸铵，偏钒酸铵加入量为0.105g；步骤(3)中煅烧温度550℃，煅烧时间2h。
按照下面所述的方法，测试和计算实施例1到5中最终产品的性能指标，所得的结果列于表1中。
罗丹明B溶液降解率的测试：在光催化领域，罗丹明B溶液通常作为光催化降解对象，用来测试样品的光催化性能。本具体实施方式中，所用罗丹明B溶液的浓度为10mg/L，所用可见光源为500W氙灯，在北京普林塞斯科技有限公司生产的PL-02光化学反应仪上测试产品的光催化性能。每次取100ml罗丹明B溶液和0.1g制备样混合，先在无光照条件下搅拌1h，使溶液混合均匀。然后开灯光照，进行光催化反应。光照60min时用离心管取样，经高速离心后，取上清液在分光光度计上554nm波长处测吸光度值，则罗丹明B溶液的降解率计算公式为：降解率＝(A0－A60)/A0×100％，式中A0为初始罗丹明B溶液的吸光度值，A60为光照6h时罗丹明B溶液的吸光度值。
甲醛降解率的测试：甲醛是常见的室内污染物，《GB/T 16127-1995居室空气中甲醛的卫生标准》规定的室内甲醛最高容许浓度为0.08mg/m3。本具体实施方式中，所用可见光源为5支，每支功率为14W的T5直管荧光灯管，在湖南华思仪器有限公司生产的PFD-5060型光化学反应仪(250L)上测试产品的光催化性能。每次将2g制备样品涂在50cm×50cm的玻璃板上，待样品板自然干燥后，将其放入试验舱，调节升降台使得样品表面与灯的距离为20cm，密闭试验舱，然后用微量注射器取30μL浓度为0.016mg/μL的甲醛溶液，通过仪器自带的进样装置，将甲醛以气体形式进入试验舱中。打开灯管、风扇(20W)，进行光催化反应。光照24h后，用恒流大气采样器采样20L(流速1L/min，采气时间20min)。随后按照国家标准《GB/T 16129-1995居住区大气中甲醛卫生检验标准方法-分光光度法》测试甲醛浓度，甲醛的降解率计算公式为：降解率＝(C0－C)/C0×100％，式中C0为空白样(无样品)测试后的甲醛浓度值，C为样品测试后的甲醛浓度值。
表1实施例1到5中最终产品的性能指标
最后需要说明的是，上面虽然结合实施例对本发明做了详细的说明，但是，所属技术领域的技术人员能够理解，在不脱离本发明宗旨的前提下，在权利要求保护范围内，还可以对上述实施例进行变更和改变。
Claims (3)
1.一种金属掺杂纳米TiO2/海泡石复合材料，即在海泡石表面均匀负载金属元素掺杂纳米TiO2，其特征在于：
所述纳米TiO2为锐钛矿晶型，晶粒尺寸为5～30nm；
所述金属元素掺杂为钒(V)、铈(Ce)、铋(Bi)掺杂；
所述金属元素掺杂纳米TiO2负载于海泡石表面，质量为海泡石质量的10％～60％；
所述的光催化剂的禁带宽度为2.7～3.0eV。
2.根据权利要求1所述的一种金属掺杂纳米TiO2/海泡石复合材料的制备方法，包括以下工艺步骤：
(1)配制浓度为0.1～0.5mol/L的硫酸氧钛(TiOSO4)溶液，在TiOSO4溶液中加入金属元素前驱体，金属元素前驱体与TiOSO4的摩尔比为0.005～0.05，在温度为30～100℃的水浴中搅拌，直至金属元素前驱体溶解。
(2)按固体质量(g):液体体积(mL)为1:10～30将海泡石加入步骤(1)中的TiOSO4溶液中，在温度为30～100℃的水浴中搅拌，直至溶剂蒸发完全；
(3)将步骤(2)中所得的产物研磨至97％通过200目筛后，在450～800℃下煅烧1～10h，煅烧过程中升温速率1～10℃/min，最终得到金属元素掺杂纳米TiO2/海泡石复合光催化材料。
3.根据权利要求2所述的金属掺杂掺杂纳米TiO2/海泡石复合光催化材料的制备方法，所述金属元素前驱体为六水合硝酸铈、五水合硝酸铋、偏钒酸铵。
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