CN105688884B - 一种复合光催化剂GO@CexYbyO2、其制备方法及应用 - Google Patents
一种复合光催化剂GO@CexYbyO2、其制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种复合光催化剂GO@CexYbyO2、其制备方法及应用。所述复合光催化剂包括层状的氧化石墨烯和分布于所述氧化石墨烯上的CexYbyO2颗粒,其中所述CexYbyO2中x的取值范围为0<x<1,y的取值范围为0.01<y<1,且所述复合光催化剂的禁带宽度为3.16‑2.85eV。所述复合光催化剂制备方法包括:将可溶性铈盐、可溶性镱盐溶解和碱性溶液混合搅拌至沉淀为亮黄色,得到混合液与氧化石墨烯悬浊液混合后水热反应。本发明的复合光催化剂采用氧化石墨烯修饰氧化铈制得复合光催化剂,能够使吸收光谱红移,增大了对太阳能的利用率,且制备过程简单,制得还原产物甲醇的产率较高。
Description
技术领域
本发明涉及一种光催化剂,特别涉及一种复合光催化剂GO@CexYbyO2、其制备方法及应用,属于光催化技术领域。
背景技术
近年来,利用太阳能光催化还原二氧化碳为有机燃料小分子已经成为研究的热点。TiO2是一种常见的光催化剂,可以将CO2光催化还原为有机燃料分子。但是TiO2只能吸收紫外光,因此对太阳能的利用率较低。CeO2是一种稀土金属元素氧化物半导体材料,其晶格氧离子容易缺失,导致CeO2晶体中的电子浓度较高,容易形成Ce3+。这种独特的性质使得氧化铈的能带结构更易调控,因此该半导体材料与TiO2相比具有更高的太阳能利用率,更快的电子转移速率,更低的空穴/电子复合率,更高的光催化活性。然而,纯CeO2的带隙比较大,对太阳能中的可见光利用率十分有限,因此有必要对其进行改性。
发明内容
针对现有技术的不足,本发明的主要目的在于提供一种复合光催化剂GO@CexYbyO2、其制备方法及应用。
为实现前述发明目的,本发明采用的技术方案包括:
在一些实施例中提供了一种复合光催化剂,所述复合光催化剂包括层状的氧化石墨烯和分布于所述氧化石墨烯表面的CexYbyO2颗粒,其中所述CexYbyO2中x的取值范围为0<x<1,y的取值范围为0.01<y<1,且所述复合光催化剂的禁带宽度为3.16-2.85eV。
在一些实施例中提供了一种上述的复合光催化剂的制备方法包括:将可溶性铈盐、可溶性镱盐溶解和碱性溶液混合搅拌至沉淀为亮黄色,得到混合液与氧化石墨烯悬浊液混合后于160- 180℃下水热反应8-6h,制得所述复合光催化剂。
在一些实施例中提供了上述的复合光催化材料于光催化二氧化碳为甲醇中的应用。
与现有技术相比,本发明的优点包括:
(1)本发明的复合光催化剂,包括层状的氧化石墨烯和分布于所述氧化石墨烯表面的 CexYbyO2颗粒,所述CexYbyO2颗粒的禁带宽度为3.16-2.97eV,复合氧化石墨烯之后,所述复合光催化剂的禁带宽度进一步减小为2.85eV,导致吸收光谱红移,增大了对太阳能的利用率,且氧化石墨烯的加入进一步加速了光催化反应过程中光生电子和光生空穴对的分离,提高光催化还原二氧化碳为甲醇的产率。
(2)本发明的复合光催化剂的制备方法,采用氧化石墨烯悬浊液代替传统的贵金属,节约了成本,且光催化剂制备过程简单,制得光催化剂对光催化还原二氧化碳为甲醇的选择性较高。
附图说明
图1是本发明一较为具体的实施例中的反应机理图;
图2a是本发明实施例1中氧化石墨烯的透射电镜图,图2b-图2d是本发明实施例1中不同尺度下氧化石墨烯复合镱掺杂氧化铈材料(GO@CexYbyO2)的透射电镜图;
图3是本发明实施例1中氧化铈(CeO2)、镱掺杂氧化铈材料(CexYbyO2)和氧化石墨烯复合镱掺杂氧化铈材料(GO@CexYbyO2)的拉曼图谱;
图4是本发明实施例1中氧化铈(CeO2)、镱掺杂氧化铈材料(CexYbyO2)和氧化石墨烯复合镱掺杂氧化铈材料(GO@CexYbyO2)的漫反射光谱图;
图5是本发明实施例2中氧化石墨烯复合镱掺杂氧化铈材料(GO@CexYbyO2)的XPS宽扫描谱图;
图6是本发明实施例2中氧化铈(CeO2)、镱掺杂氧化铈材料(CexYbyO2)和氧化石墨烯复合镱掺杂氧化铈材料(GO@CexYbyO2)的X射线衍射谱图。
具体实施方式
鉴于现有技术中的不足,本案发明人经长期研究和大量实践,得以提出本发明的技术方案。如下将对该技术方案、其实施过程及原理等作进一步的解释说明。
本发明的原理如图1所示,当CexYbyO2吸收光能量后激发光生电子,光生电子将碳酸氢钠溶液中释放的二氧化碳还原为甲醇,CexYbyO2吸收光能量后留下的光生空穴被溶液中的亚硫酸根离子吸收,转化为硫酸根离子。
在一些实施例中提供了一种复合光催化剂,所述复合光催化剂包括层状的氧化石墨烯和分布于所述氧化石墨烯表面的CexYbyO2颗粒,其中所述CexYbyO2中x的取值范围为0<x<1,y的取值范围为0.01<y<1,且所述复合光催化剂的禁带宽度为3.16-2.85eV。
较为优选的,所述氧化石墨烯于所述复合光催化剂中的含量为0.0-5.0wt%。
较为优选的,所述CexYbyO2的禁带宽度为3.16-2.85eV。
较为优选的,所述CexYbyO2的粒子直径为3.4-5.2nm。
和/或,所述复合光催化材料的粒子直径为5-8nm。
在一些实施例中提供了一种上述的复合光催化剂的制备方法包括:将可溶性铈盐、可溶性镱盐溶解和碱性溶液混合搅拌至沉淀为亮黄色,得到混合液与氧化石墨烯悬浊液混合后于160- 180℃下水热反应8-6h,制得所述复合光催化剂。
较为优选的,所述可溶性铈盐、可溶性镱盐和氧化石墨烯的质量比为1:0.012:0.022。
较为优选的,所述可溶性铈盐包括硝酸铈、氯化铈或硫酸铈中的任意一种或两种以上组合。
较为优选的,所述可溶性镱盐包括硝酸镱、氯化镱中的任意一种或两种以上组合。
较为优选的,所述碱性溶液包括氢氧化钠溶液、氢氧化钾中的任意一种或两种以上组合。
较为优选的,所述氧化石墨烯悬浊液的pH值大于10。
较为优选的,所述混合溶液的pH值大于10。
在一些实施例中提供了上述的复合光催化材料于光催化二氧化碳为甲醇中的应用。
以下结合附图和实施例对本发明的技术作进一步的解释说明。
实施例1
(1)氧化石墨烯制备:采用改进的Hummers法制备氧化石墨烯(GO)。将2.0g石墨(99.85%,中国上海试剂总厂)与1.0g硝酸钠放入500ml烧杯中,加入50ml浓硫酸,在冰浴条件下缓慢加入6.0g高锰酸钾,搅拌反应2h,然后升温至35℃后继续搅拌2h,接着缓慢加入200ml的去离子水,持续搅拌20min,再加入20ml 5%的双氧水,中和未反应的高锰酸钾,至溶液变成亮黄色后,继续在室温下搅拌2h。将反应体系静置沉淀,倒出上清液,将下层沉淀进行过滤,用5%HCl洗涤至少3次,再用2000ml蒸馏水分多次洗涤。将产物在60℃真空干燥箱中干燥6h即得GO。如图2a所示,从图中可以清晰的观察到氧化石墨烯的二维片状结构。
(2)GO@CexYbyO2的制备:称取质量为0.020g的GO于20ml去离子水中,搅拌2h,超声震荡3h,得到均一稳定的GO悬浊液。依次准确称取CeCl3·7H2O(0.8660g,2.3mmol)和 Yb(NO3)3·5H2O(0.0110g,0.024mmol)溶解于20mL超纯水中搅拌至完全溶解,向溶液中缓慢滴加NaOH(1.0mol/L,30mL)至pH>10,继续搅拌直至混合液沉淀为亮黄色,得到溶液A.
在磁力搅拌下将GO悬浊液缓慢滴加到溶液A中,搅拌1h使其混合均匀,再超声3h。最后将此混合液转入到100mL的水热反应釜中,置于恒温箱中在180℃下水热反应8h后,将所得产物离心、洗涤三次,之后放入真空干燥箱中干燥(60℃,6h),即得镱掺杂及石墨烯负载的氧化铈杂化材料。如图2a-2d所示,从图中可以看出CexYbyO2分布在氧化石墨烯表面,样品粒径约在5nm左右,如图3所示,在595cm-1处有一小峰,该峰是由于三价铈离子引起的O2-缺陷的二次Raman振动峰,表明所制得的样品中含Ce3+杂质。19氧缺位的形成有助于提高材料的催化活性,如图4所示,掺杂镱以及负载GO均使CeO2的吸收带边发生红移,说明掺杂镱和负 GO扩展了CeO2对光谱的响应范围,可望提高对可见光的利用率。
(3)光催化还原CO2及产物的分析:光催化还原CO2反应在光反应器中进行,利用250W Xe灯作为光源,仪器配有冷冻循环水系统保证反应体系温度为恒定值(25±2℃);在浓度均为 0.1mol/L的Na2SO3和NaHCO3混合液250ml中加入0.1g的催化剂,再向悬浮液中通CO2鼓泡20min,以除去溶解在溶液里的氧气。光照3h,每隔1h抽取反应体系里的溶液,离心取上层清液,测定甲醇产率。
表1镱掺杂量对甲醇产率的影响
表1的数据表明,当镱含量为CeO2质量的2.0%时,光催化还原二氧化碳为甲醇的产率最高。
表2氧化石墨烯负载量对甲醇产率的影响
由表2可知,当GO的负载量为CexYbyO2催化剂质量的5.0%时,甲醇的产率达到最大,等于90.3μmol·g-1cat.·h-1。
实施例2
(1)氧化石墨烯制备:采用改进的Hummers法制备氧化石墨烯(GO)。将2.0g石墨(99.85%,中国上海试剂总厂)与1.0g硝酸钠放入500ml烧杯中,加入50ml浓硫酸,在冰浴条件下缓慢加入6.0g高锰酸钾,搅拌反应2h,然后升温至35℃后继续搅拌2h,接着缓慢加入200ml的去离子水,持续搅拌20min,再加入20ml 5%的双氧水,中和未反应的高锰酸钾,至溶液变成亮黄色后,继续在室温下搅拌2h。将反应体系静置沉淀,倒出上清液,将下层沉淀进行过滤,用5%HCl洗涤至少3次,再用2000ml蒸馏水分多次洗涤。将产物在60℃真空干燥箱中干燥6h即得GO。
(2)GO@CexYbyO2的制备:称取质量为0.010g的GO于20ml去离子水中,搅拌2h,超声震荡3h,得到均一稳定的GO悬浊液。依次准确称取CeCl3·7H2O(1.1170g,3.0mmol)和 Yb(NO3)3·5H2O(0.0220g,0.048mmol)溶解于20mL超纯水中搅拌至完全溶解,向溶液中缓慢滴加NaOH(1.0mol/L,15mL)至pH>10,继续搅拌直至混合液沉淀为亮黄色,得到溶液A.
在磁力搅拌下将GO悬浊液缓慢滴加到溶液A中,搅拌1h使其混合均匀,再超声3h。最后将此混合液转入到100mL的水热反应釜中,置于恒温箱中在180℃下水热反应10h后,将所得产物离心、洗涤三次,之后放入真空干燥箱中干燥(60℃,6h),即得镱掺杂及石墨烯负载的氧化铈杂化材料。如图5所示,图中分别观测到C 1s,O 1s和Ce 3d的电子亲和能。如图6所示,按照Debye-Scherrer公式:D=kλ/(Wcosθ)可以计算出杂化材料的晶粒大小CeO2的平均粒径为3.4nm,镱掺杂的CeO2的粒径为5.2nm以及负载氧化石墨烯之后的镱掺杂CeO2杂化材料的粒径为7.8nm,这表明GO的加入和镱的掺杂,促进了CeO2晶体的生长。
(3)光催化还原CO2及产物的分析:光催化还原CO2反应在光反应器中进行,利用250W Xe灯作为光源,仪器配有冷冻循环水系统保证反应体系温度为恒定值(25±2℃);在浓度均为 0.1mol/L的Na2SO3和NaHCO3混合液250ml中加入0.1g的催化剂,再向悬浮液中通CO2鼓泡20min,以除去溶解在溶液里的氧气。光照3h,每隔1h抽取反应体系里的溶液,离心取上层清液,测定甲醇产率。
以上检测手段采用岛津2450型紫外可见分光光度计用于测量漫反射光谱;美国FEI公司 Tecnai G22p型高分辨率透射电镜用于观测催化剂的形貌和尺寸;X-射线衍射仪(Bruker D8)用于表征催化剂的晶体结构;美国安捷伦公司7890B型气相色谱仪用于检测光催化还原产物;法国 JY公司LabRam HR800型显微共焦拉曼光谱仪用于表征催化剂的Raman位移;上海比朗仪器有限公司BL-GHX-V型光化学反应器用于光催化反应。
醇的测量方法:先用气相色谱建立一个标准工作曲线,分别配制甲醇的标准溶液,质量溶度分别为千分之一、万分之一、十万分之一和百万分之一,采用气相色谱仪分别测量标准溶液中甲醇的峰面积,作出标准曲线。甲醇的出峰时间为1.698,光催化后溶液的甲醇含量接近十万分之一,采用类比的方法测定溶液中甲醇的含量。
应当理解,上述实施例仅为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种复合光催化剂,其特征在于:所述复合光催化剂包括层状的氧化石墨烯和分布于所述氧化石墨烯表面的CexYbyO2颗粒,其中所述CexYbyO2中x的取值范围为0<x<1,y的取值范围为0.01<y<1,且所述复合光催化剂的禁带宽度为3.16-2.85eV。
2.根据权利要求1所述的复合光催化剂,其特征在于:所述氧化石墨烯于所述复合光催化剂中的含量为0.0-5.0wt%。
3.根据权利要求1所述的复合光催化剂,其特征在于:所述CexYbyO2的禁带宽度为3.16-2.97eV。
4.根据权利要求1所述的复合光催化剂,其特征在于:所述CexYbyO2的粒子直径为3.4-5.2nm,
和/或,所述复合光催化剂的粒子直径为5-8nm。
5.一种由权利要求1-4任一项所述的复合光催化剂的制备方法,其特征在于包括:将可溶性铈盐、可溶性镱盐溶解和碱性溶液混合搅拌至沉淀为亮黄色,得到混合液,将所述混合液与氧化石墨烯悬浊液混合后于160-180℃下水热反应8-6h,制得所述复合光催化剂。
6.根据权利要求5所述的复合光催化剂的制备方法,其特征在于:所述可溶性铈盐、可溶性镱盐和氧化石墨烯的质量比为1:0.012:0.022。
7.根据权利要求5所述的复合光催化剂的制备方法,其特征在于:所述可溶性铈盐包括硝酸铈、氯化铈或硫酸铈中的任意一种或两种以上组合,
和/或,所述可溶性镱盐包括硝酸镱和/或氯化镱,
和/或,所述碱性溶液包括氢氧化钠溶液和/或氢氧化钾溶液。
8.根据权利要求5所述的复合光催化剂的制备方法,其特征在于:所述氧化石墨烯悬浊液的pH值大于10。
9.根据权利要求5所述的复合光催化剂的制备方法,其特征在于:所述混合液的pH值大于10。
10.权利要求1-9所述的复合光催化剂于光催化二氧化碳为甲醇中的应用。
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