CN105854908A - 用于醇类分解制备氢气和对应的醛、酮的光催化剂 - Google Patents
用于醇类分解制备氢气和对应的醛、酮的光催化剂 Download PDFInfo
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- B01J35/39—Photocatalytic properties
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Abstract
本发明公布了一种用于醇类分解制备氢气和对应的醛、酮的光催化剂，包括半导体光催化剂和负载在其表面的镍基纳米颗粒，其中所述镍基纳米颗粒是含有金属镍、氧化镍和氯化镍中的一种或多种成分的纳米颗粒。该光催化剂能够利用太阳光在室温常压下将醇类分解为氢气和对应的醛或酮，反应表观量子效率达40％。且该催化剂不含贵金属，成本低廉，易回收，反应能在无溶剂条件下进行，产生的氢气的纯度高，可以用于质子交换膜燃料电池。
Description
技术领域
本发明属于光催化剂制备技术领域，涉及到一种能在光照下将醇分解成氢气和对应的醛或酮的光催化剂及其制备方法。
背景技术
简单的醇类，比如甲醇、乙醇，在室温下是液体，可以来源于生物质和化工生产。醇类脱氢可以制取氢气和对应的醛或酮，因此醇类被认为是一种潜在的产氢和储氢材料。氢能是一种清洁的可再生能源，此外，醛和酮是有机合成中重要的原料，醇类脱氢制备对应的醛或酮的反应在化学工业上有着重要的应用价值。目前醇类制备对应的醛、酮主要通过氧化脱氢和直接脱氢两种技术路线来实现。氧化脱氢是指使用氧化剂将醇类氧化制得醛、酮等化合物，这类方法存在的问题是氧化产物醛更容易被氧化，造成过度氧化，反应选择性较低。而直接脱氢反应往往需要相对较高的温度。利用光催化剂在常温常压下实现醇类的脱氢反应能耗较低，反应过程符合原子经济性原则，是一种理想的醇类脱氢技术。目前公开的光催化醇类制氢方法(CN1068546A)往往是在水-醇混合体系中进行的，存在的主要的问题是产物的选择性较差，分离较困难。
发明内容
目前用于醇类脱氢的方法都是在回流温度或者更高的温度下进行，能耗高，而太阳能作为一种清洁能源，是驱动醇类分解最理想的方式。本发明的第一个目的是提供一种能够利用太阳光，在常温常压下将醇类高选择性地分解成氢气和对应的醛或酮的催化剂。
本发明所提供的光催化剂能在光照下将醇分解成氢气和对应的醛或酮，是负载镍基纳米颗粒的半导体光催化剂，其中所述镍基纳米颗粒是含有金属镍、氧化镍和氯化镍其中一种或多种成分混合物的纳米颗粒；镍基纳米颗粒中的镍元素与半导体光催化剂的质量比为(0.01～50)∶100；镍基纳米颗粒的粒径为1～10纳米，负载在半导体光催化剂的表面。
上述半导体光催化剂可以是金属氧化物或硫化物半导体材料，例如二氧化钛、硫化镉等；也可以是两种或更多种半导体材料复合的多元复合半导体光催化剂。
本发明的光催化剂中，镍基纳米颗粒中的Ni元素与半导体光催化剂的质量比优选为(0.1～20)∶100，最优选为2∶100。
本发明光催化剂中Ni元素的X射线光电子能谱信号如图1所示，852.1电子伏特的峰为金属Ni的信号峰，853.3电子伏特为氧化镍(NiO)，856.0电子伏特为氯化镍(NiCl2)。图2是本发明光催化剂的透射电子显微镜图，可以看出镍基纳米颗粒的尺寸为5纳米左右，并负载在半导体光催化剂的表面。
本发明的光催化剂可以通过以下方法制备得到：
1)将半导体光催化剂与氯化镍按照Ni和半导体光催化剂的质量百分比为0.01％～50％在含有醇的液态体系中混合；
2)将体系除氧，然后在搅拌下用波长为200～800纳米的光照射0.5～1.5小时，得到本发明所述的光催化剂。
步骤1)中所述半导体光催化剂优选为硫化镉或二氧化钛；所述含有醇的液态体系是指只含有醇的体系或者是醇和极性有机溶剂的混合体系，所述醇例如甲醇、乙醇等，所述极性有机溶剂例如乙腈、四氢呋喃等；Ni和半导体光催化剂的质量百分比优选为0.1％～20％，最优选为2％。
步骤2)光照之后可以进一步将所得光催化剂进行洗涤、真空干燥，备用。
本发明的光催化剂能够利用太阳光，在常温常压下将醇类高选择性地分解成氢气和对应的醛或酮，具体的方法是将所述光催化剂与醇类混合，在太阳光或模拟太阳光下光照，产生氢气和对应的醛或酮。
其中，光催化剂的用量优选为0.1～10毫克光催化剂/毫升醇类。
本发明的有益效果：
本发明制备了一种能够利用太阳光在室温下、常压下将醇类分解为氢气和对应的醛或酮的光催化剂，反应表观量子效率达40％。该催化剂不含贵金属，成本低廉，易回收。反应能在无溶剂条件下进行，产生的氢气的纯度高(CO浓度低于10ppm)，可以用于质子交换膜燃料电池。
附图说明
图1是本发明光催化剂中Ni元素的X射线光电子能谱图；
图2是本发明光催化剂的透射电子显微镜图；
图3是实施例1至3光催化产氢体积随光照时间变化的关系图；
图4是实施例3在长时间连续照射时的产氢体积随光照时间变化的关系图。
具体实施方式
下面通过实施例，进一步阐述本发明，但不以任何方式限制本发明的范围。
实施例1：
1)将7毫克硫化镉与5毫克六水合氯化镍在甲醇中混合；
2)将体系除氧，然后在搅拌下氩气气氛中用可见光(波长为420～800纳米)照射1小时，得到催化剂；
3)将上清液移走，将催化剂用甲醇洗涤，室温真空干燥；
4)加入5毫升的甲醇作为原料，用300瓦氙灯光照24小时，产生氢气27毫升。
CH3OH＝HCHO+H2
产氢体积随光照时间的变化如图3所示，可以看出产生的氢气量随着光照时间的增加而增加。通过气相色谱分析反应后溶液中甲醛的量，得到的氢气的量与甲醛的量的摩尔比为1.0，说明反应是按照化学计量比进行的。
实施例2：
按实施例1的条件，将原料改成5毫升乙醇，催化剂的量同实施例1，光照24小时，产生氢气38毫升，得到的氢气的量与乙醛的量的摩尔比为1.0。
实施例3：
按实施例1的条件，将原料改成5毫升异丙醇，催化剂的量同实施例1，光照24小时，产生氢气165毫升，得到的氢气的量与丙酮的量的摩尔比为1.0。图4是该实施例在长时间连续照射时产氢体积随光照时间变化的关系图，从图中可以看出光催化剂可以在121小时内连续产氢，说明催化剂稳定性很好。
实施例4：
按实施例1的条件，步骤1)将六水合氯化镍的质量改为15毫克；步骤4)5毫升甲醇作为原料，光照24小时，产生氢气25毫升，得到的氢气的量与甲醛的量的摩尔比为1.0。
实施例5：
6毫克硫化镉，1.2毫克氯化镍，3毫升乙腈，0.2毫摩尔苯乙醇混合。除氧，在7W的蓝色LED下照射20小时，期间不断搅拌。反应结束后用气相色谱分析。苯乙醇转化率为99％，苯乙酮的选择性为96％。
实施例6：
按照实施例5的条件，将0.2毫摩尔苯乙醇改为0.1毫摩尔环辛醇，光照20小时，环辛醇转化率为93％，环辛酮的选择性为99％。
Claims (10)
1.一种光催化剂，能在光照下将醇分解成氢气和对应的醛或酮，包括半导体光催化剂和负载在半导体光催剂表面的镍基纳米颗粒，其中所述镍基纳米颗粒是含有金属镍、氧化镍和氯化镍中的一种或多种成分的纳米颗粒；镍基纳米颗粒中的镍元素与半导体光催化剂的质量比为(0.01～50)∶100；镍基纳米颗粒的粒径为1～10纳米。
2.如权利要求1所述的光催化剂，其特征在于，所述半导体光催化剂是金属氧化物或硫化物半导体材料。
3.如权利要求2所述的光催化剂，其特征在于，所述半导体光催化剂是二氧化钛或硫化镉。
4.如权利要求1所述的光催化剂，其特征在于，所述镍基纳米颗粒中的Ni元素与半导体光催化剂的质量比为(0.1～20)∶100。
5.如权利要求4所述的光催化剂，其特征在于，所述镍基纳米颗粒中的Ni元素与半导体光催化剂的质量比为2∶100。
6.权利要求1～5任一所述光催化剂的制备方法，包括以下步骤：
1)将半导体光催化剂与氯化镍按照Ni和半导体光催化剂的质量百分比为0.01％～50％在含有醇的液态体系中混合；
2)将体系除氧，然后在搅拌下用波长为200～800纳米的光照射0.5～1.5小时，得到所述光催化剂。
7.如权利要求6所述的制备方法，其特征在于，步骤1)中所述半导体光催化剂为硫化镉或二氧化钛。
8.如权利要求6所述的制备方法，其特征在于，步骤1)所述含有醇的液态体系是指只含有醇的体系或者是醇和极性有机溶剂的混合体系。
9.一种将醇类分解成氢气和对应的醛或酮的方法，将权利要求1～5任一所述光催化剂和醇类混合，在常温常压下用太阳光或模拟太阳光进行光照，产生氢气和对应的醛或酮。
10.如权利要求9所述的方法，其特征在于，所述光催化剂的用量为0.1～10毫克光催化剂/毫升醇类。
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