CN111229205B - WO3/Zn2GeO4非贵金属双金属氧化物光催化剂及其制备方法和应用 - Google Patents
WO3/Zn2GeO4非贵金属双金属氧化物光催化剂及其制备方法和应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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Abstract
本发明涉及一种氧化钨/锗酸锌非贵金属双金属氧化物光催化剂的制备方法及其在光催化分解水析氢方面的应用。该催化剂首先通过水热法以氢氧化钠做溶剂合成金属锗基纳米棒光催化剂，再在水热条件下以盐酸水溶液做溶剂合成方块状氧化钨纳米材料，最后采用高温固相法将两种材料复合得到本发明所述锗酸锌/氧化物非贵金属双金属氧化物异质结纳米光催化剂。该方法制备的复合型纳米光催化剂显著拓宽了光响应范围广，异质结的形成加快了电荷的传输，有效抑制光生电子和空穴的复合，用于光催化分解水析氢具有很好的催化活性。并且该制备方法操作简单，易于调控，成本低，绿色环保。
Description
技术领域
本发明涉及光催化分解水制氢催化技术领域，具体涉及一种采用高温固相法合成的氧化钨/锗酸锌非贵金属双金属氧化物光催化剂；还涉及所述催化剂的制备方法及其在光催化析分解水析氢方面的应用。
背景技术
随着社会经济的发展，环境污染问题日益严重。利用可再生、环境友好型的化学燃料替代化石燃料是科学家们广泛关注的话题。需要开发清洁、环保的新能源以应对当前的能源危机。而利用模拟太阳光光催化分解水制取氢气是一种经济环保又有发展前景的技术。迄今为止，已经研究开发了大量的半导体光催化剂用于光解水析氢，但是研究工作者依然致力于设计并合成成本低且更高效的光催化剂。因此，开发活性高、稳定性好、成本低的非贵金属光催化剂是实现光催化分解水制氢的关键。
三氧化钨(WO3)是一种典型的n型半导体催化剂，具有成本低，无污染以及光稳定等优点。在光降解污染物、光电化学光电极、光氢传感器、二氧化碳光还原和光催化分解水制氢等方面有广泛的应用。但由于其导带位置较低，使得其具有较高氧化能力的价带所产生的光生空穴在光氧化过程中受到了抑制作用，此外对光的响应性较低，因此WO3光催化活性较低，一定程度上限制了其实际的应用。为了解决这些问题，需要设计将其与它材料复合，制备异质结复合材料可加快电荷传输，有效抑制光生电子和空穴对复合，拓宽光响应范围从而提高光催化性。
锗酸锌(Zn2GeO4)是一种极具研究价值的三元金属氧化物光催化剂，具有比 TiO2及ZnO更负的导带，表现出更高的还原能力，特别是，Zn2GeO4中Zn-Ge-O和 Ge-Ge键的存在可以增强光吸收，诱导内部结构抑制电子和空穴的复合，从而有良好的化学稳定性以及优异的光学性能。在发光，光催化，染料降解和锂离子电池领域都有广泛的应用。但由于其较宽的带隙值，光吸收只限于紫外光，因此降低带隙宽度，拓展光吸收至可见光范围对于Zn2GeO4在光催化方面的发展至关重要。
为了设计制备新型稳定具有较宽光吸收响应的光催化剂，本发明首先通过水热法分别以氢氧化钠做溶剂合成金属锗基纳米棒光催化剂，再以盐酸水溶液做溶剂合成新型方块状氧化钨纳米材料，最后采用高温固相法将两种材料复合构建了具有异质结的双金属氧化物纳米复合材料显著提高了复合催化剂的电荷转移速度和光响应范围。目前采用此方法制备WO3/Zn2GeO4非贵金属双金属氧化物光催化剂及该催化剂用于光催化分解水产氢的研究还未见报道。该制备过程简单可控，产量高，成本低，缩短了制备周期，而且非贵金属光催化剂具有高效的光催化产氢性能。对解决水污染和能源危机的问题具有很重要的理论指导和实际意义。
发明内容
本发明的目的之一是提供一种氧化钨/锗酸锌非贵金属双金属氧化物光催化剂；即通过水热法分别以氢氧化钠做溶剂合成金属锗基纳米棒光催化剂，再以盐酸水溶液做溶剂合成方块状氧化钨纳米材料，最后采用高温固相法将两种材料复合得到氧化钨/锗酸锌非贵金属双金属氧化物光催化剂。
本发明的目的之二就是提供一种氧化钨/锗酸锌非贵金属双金属氧化物光催化剂的制备方法，具体包括以下步骤：
1.锗酸锌(Zn2GeO4)的制备
(1)称取1～6mmol乙酸锌分散到20mL 0.5M氢氧化钠溶液中，磁力搅拌至充分溶解，得到无色透明溶液；
(2)称取1～6mmol氧化锗分散溶液到(1)中，磁力搅拌至完全溶解后继续磁力搅拌1～60min得乳白色溶液；
(3)将(2)中搅拌好的溶液转入50mL高压反应釜中200℃下反应12h，产物用无水乙醇离心洗涤数次，50℃干燥8h，得到白色粉末，备用；
2.氧化钨(WO3)纳米光催化剂的制备
(1)取0～1.650g钨酸钠分散到25mL去离子水和10mL盐酸中,磁力加热搅拌至充分溶解,得到无色透明溶液；
(2)称取0～0.584g氯化钠分散到上述溶液(1)中,磁力加热搅拌至完全溶解；
(3)将(2)中搅拌好的溶液转入50mL高压反应釜中180℃下反应24h,产物用无水乙醇离心洗涤数次，80℃干燥12h，得到淡黄色粉末，备用；
3.WO3/Zn2GeO4异质结纳米光催化剂的制备
(1)分别称量0～0.66g纳米棒锗酸锌与0～0.825g纳米方块状氧化钨放入石英研钵研磨1～10min,研磨均匀；
(2)将上述研磨好的粉末转移至氧化铝瓷舟中,最后转移至马弗炉中100～200℃一定的升温速率下煅烧2～4h，将所得粉末收集备用。
本发明目的之三是提供一种一种氧化钨/锗酸锌非贵金属双金属氧化物光催化剂在光催化分解水析氢方面的应用。
本发明首先通过水热法分别以氢氧化钠做溶剂合成金属锗基纳米棒光催化剂，再以盐酸水溶液做溶剂合成方块状氧化钨纳米材料，最后采用高温固相法将两种材料复合形成异质结型非贵金属双金属氧化物光催化剂。该方法制备的复合型纳米复合材料显著拓宽了光响应范围广，异质结的形成加快了电荷的传输，有效抑制光生电子和空穴的复合，对其用于光催化制氢的研究具有很好的催化析氢效果。
本发明采用的高温固相法合成异质结纳米光催化剂的方法，对反应产物有可控性，可得到双金属氧化物的复合纳米材料，同时具有较高的产率和光催化产氢活性。本发明所述方法可用于制备多种双金属氧化物异质结型纳米复合材料。
附图说明
图1为实施例1所得Zn2GeO4的扫描电镜图(a)；WO3的扫描电镜图(b)； WO3/Zn2GeO4复合材料的扫描电镜图(c)和透射电镜图(d)。
图2为实施例2所得WO3/Zn2GeO4复合材料在氙灯光源下光催化氢气析出量(a)和氢气析出循环稳定图(b)。
具体实施方式：
为进一步理解本发明，下面结合附图和实施例对本发明作进一步说明，但并不以任何方式限制本发明。
实施例1
(a).锗酸锌(Zn2GeO4)的制备
(1)称取3mmol乙酸锌分散到20mL 0.5M氢氧化钠溶液中，磁力搅拌至充分溶解,得到无色透明溶液；
(2)称取1mmol氧化锗分散溶液到(1)中，磁力搅拌至完全溶解后继续磁力搅拌60min得乳白色溶液；
(3)将(2)中搅拌好的溶液转入50mL高压反应釜中200℃下反应12h，产物用无水乙醇离心洗涤数次，50℃干燥8h，得到白色粉末，如图1(a)所示。
(b)氧化钨(WO3)纳米光催化剂的制备
(1)取1.650g钨酸钠分散到25mL去离子水和10mL盐酸中，磁力加热搅拌至充分溶解，得到无色透明溶液；
(2)称取0.584g氯化钠分散到上述溶液(1)中，磁力加热搅拌至完全溶解；
(3)将(2)中搅拌好的溶液转入50mL高压反应釜中180℃下反应24h，产物用无水乙醇离心洗涤数次，80℃干燥12h，得到淡黄色粉末，如图1(b)所示。
(c)WO3/Zn2GeO4异质结纳米光催化剂的制备
(1)分别称量0.66g纳米棒锗酸锌与0.825g纳米方块状氧化钨放入石英研钵研磨10min，研磨均匀；
(2)将上述研磨好的粉末转移至氧化铝瓷舟中,最后转移至马弗炉中200℃以 5℃/min的升温速率下煅烧4h，自然降温得淡黄色氧化钨/锗酸锌粉末，记为WG-5，如图1(c)和1(d)所示。
实施例2
(a).锗酸锌(Zn2GeO4)的制备
按照实施例1中步骤(a)的方法和条件制备；
(b)氧化钨(WO3)纳米光催化剂的制备
按照实施例1中步骤(b)的方法和条件制备；
(c)WO3/Zn2GeO4异质结纳米光催化剂的制备
按照实施例1中步骤(c)的方法和条件制备；
(d)光催化制氢应用评价
光催化剂制氢性能测试用光催化活性评价系统测试，具体实验步骤如下所述：
25mg WO3/Zn2GeO4异质结纳米光催化剂分散于100mL 0.25M Na2SO3和0.35 M Na2S水溶液，超声搅拌10min，加入石英反应器皿，反应器皿接入系统继续抽真空至溶液没有气泡冒出关闭真空泵后开灯(灯源为300W氙灯)→反应产生的氢气接入气相色谱开始分析并记录峰面积(保留时间大约在1min左右)。仪器下方连接有循环冷却水(6℃)，以保证反应过程中恒定的温度，最后根据峰面积和产氢时间计算氢气析出量和氢气析出速率并作图，在氙灯照射下催化反应6小时，每隔1h取样检测。实验结果如图2(a)所示，结果显示光催化剂最大产氢量为6656.859μmolg-1。如图2(a)所示。
(e)光催化剂稳定性和循环稳定性测试
以实施例1得到的WO3/Zn2GeO4异质结纳米光催化剂测试其稳定性和循环稳定性。测试条件为在氙灯照射下，进行了四个循环测试，每次循环4h，其测试结果如图 2(b)所示，结果表明在4个循环(16h)后，产氢速率并没有出现显著下降趋势。说明 WO3/Zn2GeO4异质结纳米光催化剂具有很好的稳定性和可循环性能。
Claims (5)
1.一种氧化钨/锗酸锌非贵金属双金属氧化物异质结纳米光催化剂的合成方法，其特征在于该催化剂首先通过水热法以氢氧化钠做溶剂合成金属锗基纳米棒光催化剂，再以盐酸水溶液做溶剂合成方块状氧化钨纳米材料，最后采用高温固相法将两种材料复合形成异质结纳米光催化剂；
所述的双金属氧化物异质结纳米光催化剂的制备方法，其特征在于：步骤如下：
(a)锗酸锌(Zn2GeO4)的制备
(1)称取1～6mmol乙酸锌分散到20mL 0.5M氢氧化钠溶液中，磁力搅拌至充分溶解，得到无色透明溶液；
(2)称取1～6mmol氧化锗分散溶液到(1)中，磁力搅拌至完全溶解后继续磁力搅拌1～60min得乳白色溶液；
(3)将(2)中搅拌好的溶液转入50mL高压反应釜中100～200℃下反应12h,产物用无水乙醇离心洗涤数次，50℃干燥8h，得到白色粉末，备用；
(b)氧化钨(WO3)纳米光催化剂的制备
(1)取0～1.650g钨酸钠分散到25mL去离子水和10mL盐酸中，磁力加热搅拌至充分溶解，得到无色透明溶液；
(2)称取0～0.584g氯化钠分散到上述溶液(1)中，磁力加热搅拌至完全溶解；
(3)将(2)中搅拌好的溶液转入50mL高压反应釜中100～180℃下反应24h,产物用无水乙醇离心洗涤数次，80℃干燥12h，得到淡黄色粉末，备用；
(c)WO3/Zn2GeO4异质结纳米光催化剂的制备
(1)分别称量0～0.66g纳米棒锗酸锌与0～0.825g纳米方块状氧化钨放入石英研钵研磨1～10min，研磨均匀；
(2)将上述研磨好的粉末转移至氧化铝瓷舟中，最后转移至马弗炉中以一定的升温速率升温至100～200℃煅烧2～4h，将所得粉末收集备用。
2.根据权利要求1所述的方法，其特征在于采用高温固相法在空气下煅烧合成氧化钨/锗酸锌异质结纳米光催化剂。
3.根据权利要求1中所述的合成方法，其特征在于步骤(a)中乙酸锌的用量为3mmol；氧化锗为1mmol。
4.根据权利要求1中所述的合成方法，其特征在于步骤(b)中钨酸钠的用量为1.650g；氯化钠的用量为0.584g。
5.根据权利要求1所述的合成方法合成的氧化钨/锗酸锌异质结纳米光催化剂，其特征在于所述催化剂用于光催化产氢，表现出显著提高的光催化产氢活性。
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