CN106881137A - 一种光催化材料及其制备方法和用途 - Google Patents
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Abstract
本发明属于半导体材料领域,涉及一种光催化材料,由空心(GaN)1‑x(ZnO)x复合纳米纤维和Rh2‑yCryO3复合制成,所述的Rh2‑yCryO3占所述的光催化材料的质量百分比为1‑5wt%;本发明还提供了上述光催化材料的制备方法,先通过静电纺丝、煅烧及氨气中氨化获得具有中空结构的(GaN)1‑x(ZnO)x复合纳米纤维,再通过中空结构的(GaN)1‑x(ZnO)x复合纳米纤维与共催化剂Rh2‑ yCryO3混合得到粉体,即为光催化材料。本发明还提供了上述的光催化材料作为光催化剂用于可见光分解水制氢气的用途。本发明制得的光催化主体材料具有中空纤维结构,其对可见光吸收较强,比表面大,孔结构丰富,其在可见光下分解水制氢产量为1.83μmol/h。
Description
技术领域
本发明属于半导体材料领域,涉及一种光催化材料,具体来说是一种用于可见光分解水制氢气的光催化材料及其制备方法。
背景技术
纳米ZnO作为一种重要的催化剂,因其具有较高的光催化活性、无毒、较低的介电常数、强的紫外与红外吸收以及光电化学稳定性等优点,在光催化降解污染物方面受到广泛关注。但是ZnO的带隙能较宽,对于光的吸收仅局限于紫外区,并且电子-空穴对的复合几率高,大大限制了其推广应用。所以要提高ZnO的光催化性能需要对ZnO进行改性,一方面降低禁带宽度,使其在可见光区和紫外光区都表现出好的光电响应,另一方面需要抑制光生电子-空穴对的复合。其中一种有效途径是复合两种带隙相近的半导体形成固溶体,制备出带隙宽度连续变化可见光响应光催化剂。
GaN是一种宽禁带半导体,室温下禁带宽度为3.4eV。常温下有纤锌矿、闪锌矿和岩盐矿三种晶体结构,其中热力学最稳定的是纤锌矿结构,晶格参数为a=0.319,c=0.519。GaN具有优良的光学、电学性质和优异的机械性质、热稳定性,广泛应用于发光二极管和激光二极管,同时可用于光电极,而且已被证实在紫外光下具有光催化全分解水的能力。通过固溶体的制备,GaN基材料的禁带宽度可以从InN的1.89eV到AlN的6.2eV之间连续变化,对应于波长为210nm到660nm的发光区,这个波段覆盖了整个紫外区和大部分的可见光区。六方纤锌矿结构的ZnO和GaN具有相似的禁带宽度,非常接近的晶格参数,可以形成具有相同晶体结构的固溶体。Maeda K课题组对ZnO和GaN形成的固溶体进行了深入的研究,研究结果表明通过控制制备条件和产物中Zn的含量,可以将固溶体的禁带宽度降低至2.29eV。
Zou课题组将GaN:ZnO固溶体在可见光下光催化降解四种多环芳烃(分别是菲(PHE),蒽(ANT)、苊(ACE),和苯蒽(BaA)),实验结果表明GaN:ZnO固溶体在可见光区对多环芳烃的降解表现出优异的光催化性能,对四种多环芳烃的光催化活性关系是PHE>BaA>ANT>ACE。鉴于(GaN)1-x(ZnO)x固溶体具有较小的带隙能和可见光响应特性,将GaN和ZnO复合后用于光解水制氢具有重要的研究意义,但是现有的GaN和ZnO复合材料比表面较小,对可见光吸收较弱及纳米光催化材料不稳定的问题严重制约了该项技术的发展。
发明内容
针对现有技术中的上述技术问题,本发明提供了一种光催化材料及其制备方法和用途,所述的这种材料制备方法要解决现有技术中的材料比表面较小,对可见光吸收较弱及纳米光催化材料不稳定等技术问题。
本发明提供了一种光催化材料,由空心(GaN)1-x(ZnO)x复合纳米纤维和Rh2-yCryO3复合制成,其中,0<x<1,0<y<2,所述的Rh2-yCryO3占所述的光催化材料的质量百分比为1-5wt%。
进一步的,所述的空心(GaN)1-x(ZnO)x复合纳米纤维为固溶体结构,空心(GaN)1-x(ZnO)x复合纳米纤维的外径分布在100~300nm之间,管壁厚度为20~50nm。
进一步的,所述的空心(GaN)1-x(ZnO)x复合纳米纤维中,GaN和ZnO的摩尔比为1:4~1:2。
本发明的光催化材料主要技术指标如下:
1.晶体结构:(JCPDS 50-0792)和ZnO(JCPDS 36-1451)形成固溶体;
2.形貌:空心纤维结构,外径分布在100-300nm之间,管壁厚度为20-50nm;
3.比表面:31.52m2/g;
本发明还相应的提供了上述的光催化材料的制备方法,包括如下步骤:
(1)通过静电纺丝法制备空心(GaN)1-x(ZnO)x复合纳米纤维,其中,0<x<1;
(2)将空心(GaN)1-x(ZnO)x复合纳米纤维加入到去离子水中,同时加入RhCl3和Cr(NO3)3·9H2O,将此溶液放在烧杯中于70℃水浴蒸发,同时用玻璃棒不断搅拌至形成结晶,然后将结晶粉末在空气气氛下于350℃条件下煅烧1h获得最终的光催化材料。
进一步的,制备空心(GaN)1-x(ZnO)x复合纳米纤维的方法,即静电纺丝法包括以下步骤:
1)配置静电纺丝液
以镓盐和锌盐为溶质,加入到去离子水中,制备得到Ga-Zn混合溶液;优选的,所述的镓盐为硝酸镓或其水合物,所述的锌盐为醋酸锌或其水合物,当然还可以由其他锌盐替代,如硝酸锌、草酸锌或它们的水合物;
以聚乙烯类聚合物为溶质,加入到溶剂中,制备得到聚乙烯类聚合物溶液;优选的,所述的聚乙烯类聚合物为聚乙烯吡咯烷酮(PVP),当然还可以由其它的相似溶质代替,如聚乙烯醇(PVA),所述的溶剂为乙醇,当然还可以由DMF或四氢呋喃代替;所述的聚乙烯类聚合物溶液优选为聚乙烯吡咯烷酮的乙醇溶液。
将上述的Ga-Zn混合溶液和聚乙烯类聚合物溶液混合后搅拌8~14h,制得静电纺丝液;
更为优选的,一种具体的配制过程可以为:以去离子水为溶剂,Ga(NO3)3·zH2O和(Zn(CH3COO)2·2H2O)为溶质,Ga:Zn=1:2-1:4,配制成浓度为1~2mol/L的Ga-Zn混合溶液;以乙醇为溶剂,聚乙烯吡咯烷酮为溶质,配制成浓度为0.125~0.5g/mL的聚乙烯吡咯烷酮溶液;将Ga-Zn混合溶液和聚乙烯吡咯烷酮溶液混合后搅拌8~14h,其中的镓盐/锌盐和聚乙烯吡咯烷酮的质量比为7:2~4。
2)静电纺丝
将步骤1)制得的静电纺丝液加入到静电纺丝机中,进行静电纺丝,获得镓盐/锌盐/聚乙烯类聚合物复合材料;优选的,静电纺丝机的运行参数为:静电纺丝机内温度保持为40℃,相对湿度为20%,调节极板与针尖电压为18kV、极板与针尖距离20cm。
3)煅烧及氨化
将步骤2)得到的镓盐/锌盐/聚乙烯类聚合物复合材料进行煅烧,制得Ga-Zn-O复合氧化物纳米纤维,将其氨气气氛中氨化后,获得具有中空结构的(GaN)1-x(ZnO)x复合纳米纤维;优选的,煅烧条件为:按照升温速率为2℃/min升温至650℃,并保温煅烧2~5h;氨化条件为:将Ga-Zn-O复合氧化物纳米纤维在200sccm氨气气氛中,在750℃条件下氨化2h。
本发明还公开了上述的光催化材料以及通过上述的各种方法制备的光催化材料作为光催化剂用于可见光分解水制氢气的用途,具体的,将所述的光催化材料放入水中,经可见光照射将水分解为氢气和氧气。采用本发明的光催化材料,在可见光下分解水制氢产量为1.83μmol/h。
本发明和已有技术相比,其技术进步是显著的。本发明制得的光催化材料为空心多孔结构,比表面较大,具有孔隙率高、比表面积大等优点,用作光催化剂具有更高的稳定性,不存在粉体材料易团聚、不易回收等问题,能够进一步提高材料的光催化活性。
附图说明
图1为实施例1~4所得(GaN)1-x(ZnO)x复合纳米纤维的X射线衍射图。
图2为实施例1~4所得(GaN)1-x(ZnO)x复合纳米纤维和ZnO纳米纤维的SEM图以及实施例2所得(GaN)1-x(ZnO)x复合纳米纤维的TEM图,其中(a)为实施例2的SEM图,Ga:Zn=1:1;(b)为实施例1的SEM图,Ga:Zn=1:2;(c)为实施例3的SEM图,Ga:Zn=1:3;(d)为实施例4的SEM图,Ga:Zn=1:4;(e)为ZnO纳米纤维的SEM图;(f)为实施例2的TEM图,Ga:Zn=1:1。
图3为实施例1~4所得(GaN)1-x(ZnO)x复合纳米纤维和ZnO纳米纤维,即具有不同Ga/Zn比的(GaN)1-x(ZnO)x(X=1/2,2/3,3/4,4/5,1)复合纳米纤维的紫外-可见漫反射光谱图(a);Ga-Zn-O复合氧化物纳米纤维及(GaN)1-x(ZnO)x(X=2/3、X=1)复合纳米纤维的光致发光光谱图(b);Ga-Zn-O复合氧化物纳米纤维及(GaN)1-x(ZnO)x(X=2/3、X=1)复合纳米纤维的N2吸附等温线图(c);Ga-Zn-O复合氧化物纳米纤维及(GaN)1-x(ZnO)x(X=2/3、X=1)复合纳米纤维的孔径分布图(d)。
注:图a中横坐标为波长,单位为纳米(nm),在波长为650纳米时,吸光度由大到小的曲线所对应的(GaN)1-x(ZnO)x复合纳米纤维的X取值依次为:2/3、3/4、4/5、1/2、1;图b中在波长为500纳米时,发光强度有大到小的曲线多对应的物质分别为ZnO纳米纤维、Ga-Zn-O复合氧化物纳米纤维、(GaN)1-x(ZnO)x复合纳米纤维(X=2/3)。
图4为以本发明方法制备的光催化材料的产氢性能图。
具体实施方式
以下用实例对本发明作进一步说明,但不限于此。
实施例1:
光催化材料的制作步骤:
a.以去离子水为溶剂,Ga(NO3)3·zH2O和(Zn(CH3COO)2·2H2O)为溶质,镓元素与锌元素的摩尔比为1:2,即Ga:Zn=1:2。配制成浓度为1.2mol/L的Ga-Zn混合溶液;
b.以乙醇为溶剂,聚乙烯吡咯烷酮为溶质,配制成浓度为0.5g/mL的聚乙烯吡咯烷酮溶液;
c.将步骤a的Ga-Zn混合溶液和步骤b的聚乙烯吡咯烷酮溶液混合后搅拌12h,步骤a中的镓盐/锌盐和步骤b的聚乙烯吡咯烷酮的质量比为2:1,将其收集入注射装置中备用;
d.将步骤3)配置好的注射装置放入静电纺丝机中,参数设定为:纺丝机内温度保持为40℃,相对湿度为20%,调节极板与针尖电压为18kV、极板与针尖距离20cm,纺丝完成后,将收集的Ga(NO3)3/Zn(CH3COO)2/PVP复合材料进行煅烧,按照升温速率为2℃/min升温至650℃,并保温煅烧2~5h后制得Ga-Zn-O复合氧化物纳米纤维,将其在200sccm氨气气氛中750℃氨化2h后获得具有中空结构的(GaN)1-x(ZnO)x复合纳米纤维。
e.将(GaN)1-x(ZnO)x复合纳米纤维加入到1ml去离子水中,同时加入适量RhCl3和Cr(NO3)3·9H2O。将此溶液放在烧杯中于70℃水浴蒸发,同时用玻璃棒不断搅拌至形成结晶,然后将结晶粉末在空气气氛下于350℃条件下煅烧1h获得最终的光催化材料。
实施例2:本实施例与实施例1基本相同,所不同的是:a步骤中Ga:Zn的摩尔比为1:1。
实施例3:本实施例与实施例1基本相同,所不同的是:a步骤中Ga:Zn的摩尔比为1:3。
实施例4:本实施例与实施例1基本相同,所不同的是:a步骤中Ga:Zn的摩尔比为1:4。
试验例一:
将实施例1~4所得(GaN)1-x(ZnO)x复合纳米纤维物象通过X-射线衍射进行表征。得到图1所示的实施例1~4制备的具有不同Ga/Zn比的(GaN)1-x(ZnO)x复合纳米纤维的X射线衍射图。由图可知,(GaN)1-x(ZnO)x复合纳米纤维为固溶体结构且图1中的衍射峰主要为(JCPDS 50-0792)和ZnO(JCPDS 36-1451)形成固溶体。
试验例二:
通过扫描电子显微镜观察实施例1~4所得(GaN)1-x(ZnO)x复合纳米纤维和ZnO纳米纤维的微观表面形态,得到图2(a~e)的SEM图;
通过透射电子显微镜观察实施例2所得产物的超微结构,得到图2(f)的TEM图;
由图可知,(GaN)1-x(ZnO)x为空心纤维结构,其外径分布在100-300nm之间,管壁厚度为20-50nm。
试验例三:
测定实施例1~4所制得的(GaN)1-x(ZnO)x复合纳米纤维及ZnO纳米纤维的紫外-可见漫反射光谱图,得图3(a);
测定Ga-Zn-O复合氧化物纳米纤维及(GaN)1-x(ZnO)x复合纳米纤维的光致发光光谱图,参见图3(b),
测定Ga-Zn-O复合氧化物纳米纤维及(GaN)1-x(ZnO)x复合纳米纤维的N2吸附等温线图,参见图3(c)
测定Ga-Zn-O复合氧化物纳米纤维及(GaN)1-x(ZnO)x复合纳米纤维的孔径分布图,参见图3(d)。
由图看出,a、(GaN)1-x(ZnO)x复合纳米纤维对可见光区域光吸收能力增强;b、GaN和ZnO复合后抑制了光生电子-空穴对的复合;c、(GaN)1-x(ZnO)x复合纳米纤维具有较大的比表面积和双孔分布
试验例四:
分别以实施例一得到的没有负载Rh2-yCryO3的(GaN)1-x(ZnO)x(Ga:Zn=1:2)固溶体和负载Rh2-yCryO3后的(GaN)1-x(ZnO)x(Ga:Zn=1:2)为光催化剂,在可见光下进行光解水的试验,具体的,光催化反应在玻璃内照式反应器中进行,反应器连接有一个玻璃封闭式气体循环和疏散系统。采用300W的氙灯(带有截止滤波片滤去紫外光)持续照射反应溶液。通过气相色谱仪(Ar气作为载气)进行测定,获得催化剂在单位时间内产生氢气的量,试验结果参见图4。由图看出,未负载Rh2-yCryO3助催化剂的复合纳米纤维没有产生氢气,这证实了单一的(GaN)1-x(ZnO)x(Ga:Zn=1:2)固溶体在可见光区不具备光解水产氢能力或其产氢速率很慢。负载Rh2-yCryO3后的催化剂具有一定的光催化活性,光照5h后产氢总量为9.15ml,平均产氢速率约为1.83μmol/h。
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种光催化材料,其特征在于,由空心(GaN)1-x(ZnO)x复合纳米纤维和Rh2-yCryO3复合制成,其中,0<x<1,0<y<2,所述的Rh2-yCryO3占所述的光催化材料的质量百分比为1-5wt%。
2.根据权利要求1所述的光催化材料,其特征在于,所述的空心(GaN)1-x(ZnO)x复合纳米纤维为固溶体结构,空心(GaN)1-x(ZnO)x复合纳米纤维的外径分布在100~300nm之间,管壁厚度为20~50nm。
3.根据权利要求1或2所述的光催化材料,其特征在于,所述的空心(GaN)1-x(ZnO)x复合纳米纤维中,GaN和ZnO的摩尔比为1:4~1:2。
4.一种权利要求1~3任一项所述的光催化材料的制备方法,其特征在于,包括如下步骤:
(1)通过静电纺丝法制备空心(GaN)1-x(ZnO)x复合纳米纤维,其中,0<x<1;
(2)将空心(GaN)1-x(ZnO)x复合纳米纤维加入到去离子水中,同时加入RhCl3和Cr(NO3)3·9H2O,将此溶液放在烧杯中于70℃水浴蒸发,同时用玻璃棒不断搅拌至形成结晶,然后将结晶粉末在空气气氛下于350℃条件下煅烧1h获得最终的光催化材料。
5.根据权利要求4所述的光催化材料的制备方法,其特征在于,制备空心(GaN)1-x(ZnO)x复合纳米纤维的方法包括以下步骤:
1)配置静电纺丝液
以镓盐和锌盐为溶质,加入到去离子水中,制备得到Ga-Zn混合溶液;
以聚乙烯类聚合物为溶质,加入到溶剂中,制备得到聚乙烯类聚合物溶液;
将上述的Ga-Zn混合溶液和聚乙烯类聚合物溶液混合后搅拌8~14h,制得静电纺丝液;
2)静电纺丝
将步骤1)制得的静电纺丝液加入到静电纺丝机中,进行静电纺丝,获得镓盐/锌盐/聚乙烯类聚合物复合材料;
3)煅烧及氨化
将步骤2)得到的镓盐/锌盐/聚乙烯类聚合物复合材料进行煅烧,制得Ga-Zn-O复合氧化物纳米纤维,将其氨气气氛中氨化后,获得具有中空结构的(GaN)1-x(ZnO)x复合纳米纤维。
6.根据权利要求5所述的光催化材料的制备方法,其特征在于,在步骤1)中,所述的镓盐为硝酸镓或其水合物,所述的锌盐为醋酸锌或其水合物,所述的聚乙烯类聚合物为聚乙烯吡咯烷酮,所述的溶剂为乙醇,所述的聚乙烯类聚合物溶液为聚乙烯吡咯烷酮的乙醇溶液。
7.根据权利要求6所述的光催化材料的制备方法,其特征在于,步骤1)中,Ga与Zn的摩尔比为1:2~1:4,配制成浓度为1~2mol/L的Ga-Zn混合溶液;聚乙烯吡咯烷酮的乙醇溶液的浓度为0.125~0.5g/mL;静电纺丝液中镓盐/锌盐和聚乙烯吡咯烷酮的质量比为7:2~4。
8.根据权利要求5所述的光催化材料的制备方法,其特征在于,在步骤2)中,静电纺丝机的运行参数为:静电纺丝机内温度保持为40℃,相对湿度为20%,调节极板与针尖电压为18kV、极板与针尖距离20cm。
9.根据权利要求5所述的光催化材料的制备方法,其特征在于,在步骤3)中,煅烧条件为:按照升温速率为2℃/min升温至650℃,并保温煅烧2~5h;氨化条件为:将Ga-Zn-O复合氧化物纳米纤维在200sccm氨气气氛中,在750℃条件下氨化2h。
10.权利要求1~3任一项所述的光催化材料作为光催化剂用于可见光分解水制氢气的用途,其特征在于,将所述的光催化材料放入水中,经可见光照射将水分解为氢气和氧气。
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