CN110801853A - 一种复合光催化剂及其制备方法和应用 - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910001195 gallium oxide Inorganic materials 0.000 claims abstract description 28
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 28
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- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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Abstract
本发明公开了一种复合光催化剂及其制备方法和应用,属于材料制备和环境治理技术领域。将钼源、磷源和镓源的水溶液通过水热反应后生成氧化镓前驱体、钼源、磷源的混合物,通过水热搅拌将其均匀混合,最后在惰性气氛中高温煅烧得到了氧化镓、磷酸镓以及氧化钼的复合光催化剂。用钼元素、磷元素对氧化镓改性以后不仅可以提高对紫外光的响应,而且可以提高一氧化碳的产量,可代替贵金属来达到提高一氧化碳产量的目的,显著降低了成本。本方法的制备过程简单、成本低廉、原料易得。
Description
技术领域
本发明属于材料制备和环境治理技术领域,具体涉及一种复合光催化剂及其制备方法和应用。
背景技术
化石燃料燃烧排放的大量二氧化碳是导致全球变暖的根本原因,由此产生了很多的环境问题。二氧化碳作为一个重要的碳源,将其转化成燃料或者其它化学品,既有利于减少CO2的排放,又有利于能源利用。光催化二氧化碳转化技术由于常温常压下进行,无需消耗辅助能源而吸引了众多研究者的目光。TiO2是目前比较常见的一种光催化剂,但是其导带电位几乎与二氧化碳还原电位几乎一致,导致TiO2对于二氧化碳的还原效果不太理想。通常认为,当半导体导带位置越高光生电子还原能力越强。氧化镓的导带电位为-2.95ev,高于TiO2和绝大多数的光催化材料。由此可见,氧化镓这种半导体材料在光催化还原二氧化碳方面有很大的潜力。
Teramura等人以硝酸镓为前驱体,采用水热再煅烧的方法制备了纯相的氧化镓材料,将其应用于光催化氧化降解甲醛研究(Current Opinion in Chemical Engineering,2018,20:114–121)。Yidong Hou等人利用硝酸镓为前驱体,乙醇为溶剂,制备了纯相的氧化镓材料,并将其应用于光催化甲醛降解和二氧化碳还原研究。(Environ.Sci.Technol,2006,40,5799-5803)。但是氧化镓自身带隙较大光吸收较弱,导致纯相的氧化镓光催化效果不太理想。
发明内容
为了克服上述现有技术存在的缺陷,本发明公开了一种复合光催化剂及其制备方法和应用,具有操作简便、原料易得、成本低、能源消耗少等优点;稳定性良好,活性高,光催化还原二氧化碳的效率高。
本发明是通过以下技术方案来实现:
本发明公开的一种复合光催化剂的制备方法,包括以下步骤:
步骤1:配制含有钼源、磷源和镓源的混合水溶液;
步骤2:将步骤1制得水溶液在120~160℃下反应16~20h,得到悬浊液;取出悬浊液下层沉淀搅拌蒸干,得到沉淀物;
步骤3:将步骤2制得的沉淀物烘干,置于惰性气氛下高温煅烧后冷却至室温,得到复合光催化剂。
优选地,钼源、磷源和镓源中钼元素、磷元素和镓元素的摩尔比为(3~9):(3~9):100。
优选地,钼源四水仲钼酸铵。
优选地,磷源为磷酸氢二铵或磷酸二氢铵。
优选地,镓源为硝酸镓或氯化镓。
优选地,烘干的温度为50~80℃,烘干的时间为6~8h。
优选地,惰性气氛为氮气气氛。
优选地,煅烧温度为500~750℃,煅烧时间为2~6h。
本发明公开了采用上述制备方法制得的复合光催化剂,复合光催化剂中氧化镓为单斜相晶体β-Ga2O3。
本发明公开了上述复合光催化剂在光催化还原二氧化碳中的应用。
与现有技术相比,本发明具有以下有益的技术效果:
本发明公开的复合光催化剂的制备方法,将钼源、磷源和镓源的水溶液通过水热反应后生成氧化镓前驱体、钼源、磷源的混合物,通过水热搅拌将其均匀混合,最后在惰性气氛中高温煅烧得到了氧化镓、磷酸镓以及氧化钼的复合光催化剂。用钼元素、磷元素对氧化镓改性以后不仅可以提高对紫外光的响应,而且可以提高一氧化碳的产量,可代替贵金属来达到提高一氧化碳产量的目的,显著降低了成本。本方法的制备过程简单、成本低廉、原料易得。
进一步地,钼、磷的含量过低,复合光催化剂对紫外光的响应不足,催化效率低;钼、磷的含量过高,会覆盖氧化镓的活性位点,也会影响催化效率。
进一步地,钼源、镓源和磷源的来源多样化,易于购买、成本低廉。
进一步地,烘干温度过低,会导致烘干时间过长;烘干温度过高,则暴露在热空气中的钼元素化学价态会发生改变。
进一步地,煅烧温度为500~750℃,煅烧时间为2~6h,煅烧温度以及煅烧时间会影响氧化镓的晶型。
本发明还公开了采用上述制备方法制得的复合光催化剂,其中氧化镓为单斜相晶体β-Ga2O3,具有无毒,耐高温、耐酸碱腐蚀的特点,是一种稳定性良好的光催化材料。
本发明还公开了上述复合光催化剂在光催化还原二氧化碳中的应用,相比未改性的氧化镓材料,本发明的氧化镓、磷酸镓以及氧化钼形成的复合光催化剂活性明显提高,其中一氧化碳产量最高提高6倍。
附图说明
图1为本发明制得的复合光催化剂的XRD图,图中黑色垂直细线是对应β-Ga2O3的PDF卡片;
图2为本发明实施例1~4制得的复合光催化剂与氧化镓的催化活性对比图;
图3为本发明实施例1制得的复合光催化剂的紫外可见漫反射吸收谱图。
具体实施方式
下面结合附图和实施例对本发明做进一步的详细说明,所述是对本发明的解释而不是限定。
实施例1
称取100mg四水仲钼酸铵溶解在100mL去离子水中,摇匀得到浓度为1mg/mL的四水仲钼酸铵溶液。称取100mg磷酸氢二铵溶解在100mL去离子水中,摇匀得到浓度为1mg/mL的磷酸氢二铵溶液。在50mL聚四氟乙烯内衬中加入0.544g硝酸镓,再加入11mL四水仲钼酸铵溶液和8mL磷酸氢二铵溶液,搅拌30分钟,待固体充分溶解,混合均匀后将内衬装入反应釜中,在140℃条件下反应16小时。待反应结束,自然冷却后,留下悬浊液下层的沉淀物,搅拌蒸干后在50℃烘箱中烘6小时。将烘干样品放入管式炉中,在氮气气氛中750℃煅烧2h,即可得到氧化镓、磷酸稼以及氧化钼摩尔比为6:6:100的复合材料(6:6:100为钼元素、磷元素和镓元素的摩尔比)。
实施例2
称取100mg四水仲钼酸铵溶解在100mL去离子水中,摇匀得到浓度为1mg/mL的四水仲钼酸铵溶液。称取100mg磷酸氢二铵溶解在100mL去离子水中,摇匀得到浓度为1mg/mL的磷酸氢二铵溶液。在50mL聚四氟乙烯内衬中加入0.544g硝酸镓,再加入5.5mL四水仲钼酸铵溶液和4mL磷酸氢二铵溶液,搅拌30分钟,待固体充分溶解,混合均匀后将内衬装入反应釜中,在140℃条件下反应20小时。待反应结束,自然冷却后,留下悬浊液下层的沉淀物,搅拌蒸干后在80℃烘箱中烘6小时。将烘干样品放入管式炉中,在氮气气氛中750℃煅烧2h,即可得到氧化镓、磷酸稼以及氧化钼摩尔比为3:3:100的复合材料(3:3:100为钼元素、磷元素和镓元素的摩尔比)。
实施例3
称取100mg四水仲钼酸铵溶解在100mL去离子水中,摇匀得到浓度为1mg/mL的四水仲钼酸铵溶液。称取100mg磷酸氢二铵溶解在100mL去离子水中,摇匀得到浓度为1mg/mL的磷酸氢二铵溶液。在50mL聚四氟乙烯内衬中加入0.544g硝酸镓,再加入16.5mL四水仲钼酸铵溶液和12mL磷酸氢二铵溶液,搅拌30分钟,待固体充分溶解,混合均匀后将内衬装入反应釜中,在150℃条件下反应20小时。待反应结束,自然冷却后,留下悬浊液下层的沉淀物,搅拌蒸干后在60℃烘箱中烘8小时。将烘干样品放入管式炉中,在氮气气氛中750℃煅烧6h,即可得到氧化镓、磷酸稼以及氧化钼摩尔比为9:9:100的复合材料(9:9:100为钼元素、磷元素和镓元素的摩尔比)。
实施例4
称取100mg四水仲钼酸铵溶解在100mL去离子水中,摇匀得到浓度为1mg/mL的四水仲钼酸铵溶液。称取100mg磷酸二氢铵解在100mL去离子水中,摇匀得到浓度为1mg/mL的磷酸二氢铵。在50mL聚四氟乙烯内衬中加入0.476g氯化镓,再加入16.5mL四水仲钼酸铵溶液和12mL磷酸二氢铵溶液,搅拌30分钟,待固体充分溶解,混合均匀后将内衬装入反应釜中,在160℃条件下反应20小时。待反应结束,自然冷却后,留下悬浊液下层的沉淀物,搅拌蒸干后在60℃烘箱中烘8小时。将烘干样品放入管式炉中,在氮气气氛中750℃煅烧5h,即可得到氧化镓、磷酸稼以及氧化钼摩尔比为9:9:100的复合材料(9:9:100为钼元素、磷元素和镓元素的摩尔比)。
镓源、磷源和钼源添加量按照如下方法确定:
其中,镓源质量自主规定,如200mg,进一步推算其他结果。
取实施例1~4制得的样品150mg,经X射线衍射,得到如图1所示的XRD衍射图。图1中峰型尖锐,是典型的三氧化二镓晶体,图1中峰位置和标准卡片(PDF#41-1103)对比可以看出,只存在一种物质的相,即β-Ga2O3。
活性测试过程:分别称取实施例1~4的样品20mg及氧化镓20mg,设置四个实验,将四个样品分别分散在直径55mm的培养皿中,并放入真空反应装置中,用注射器向真空反应装置中加入20mL二氧化碳气体,再注入20μL去离子水,然后对样品光照5小时,每一小时用气相色谱检测产物浓度,得到如图2所示的曲线。从图2可知,实施例1~4的样品与未改性的氧化镓相比,对于二氧化碳的还原明显提高,一氧化碳的产量明显提高,实施例1最优,最高可提高6倍。
取本实施例1制得的样品100mg与等量的氧化镓,经过紫外可见漫反射测试对比,得到图3所示,从图3中看出,复合后的材料对紫外光的吸收强度明显提高。半导体光催化材料具有带隙,在光照下价带电子会跃迁到导带,电子具有还原性,跃迁后的电子会和吸附在材料表面的CO2发生还原反应,产生CO。因此,提高对紫外光的响应,可以提高CO的量。但是太多的钼、磷复合量却不利于产量提高,这是由于氧化镓活性位点被覆盖。当钼、磷复合量6:6:100时,活性最好。
用钼元素、磷元素对氧化镓改性以后不仅可以提高对紫外光的响应,而且可以提高一氧化碳的产量,因此钼元素与磷元素的共同复合可代替贵金属来达到提高一氧化碳产量的目的。
Claims (10)
1.一种复合光催化剂的制备方法,其特征在于,包括以下步骤:
步骤1:配制含有钼源、磷源和镓源的混合水溶液;
步骤2:将步骤1制得水溶液在120~160℃下反应16~20h,得到悬浊液;取出悬浊液下层沉淀搅拌蒸干,得到沉淀物;
步骤3:将步骤2制得的沉淀物烘干,置于惰性气氛下高温煅烧后冷却至室温,得到复合光催化剂。
2.如权利要求1所述的复合光催化剂的制备方法,其特征在于,步骤1中,钼源、磷源和镓源中钼元素、磷元素和镓元素的摩尔比为(3~9):(3~9):100。
3.如权利要求1所述的复合光催化剂的制备方法,其特征在于,步骤1中,钼源四水仲钼酸铵。
4.如权利要求1所述的复合光催化剂的制备方法,其特征在于,步骤1中,磷源为磷酸氢二铵或磷酸二氢铵。
5.如权利要求1所述的复合光催化剂的制备方法,其特征在于,步骤1中,镓源为硝酸镓或氯化镓。
6.如权利要求1所述的复合光催化剂的制备方法,其特征在于,步骤3中,烘干的温度为50~80℃,烘干的时间为6~8h。
7.如权利要求1所述的复合光催化剂的制备方法,其特征在于,步骤3中,惰性气氛为氮气气氛。
8.如权利要求1所述的复合光催化剂的制备方法,其特征在于,步骤3中,煅烧温度为500~750℃,煅烧时间为2~6h。
9.采用权利要求1~8中任意一项所述制备方法制得的复合光催化剂,其特征在于,复合光催化剂中氧化镓为单斜相晶体β-Ga2O3。
10.权利要求9所述的复合光催化剂在光催化还原二氧化碳中的应用。
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