CN115382557A - ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂及其制备方法和应用 - Google Patents
ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂的制备方法及其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乙酸锌、氧化锗和氢氧化钠为原料合成Zn2GeO4纳米棒,再利用溶剂热以锗酸锌、乙酸锌、硝酸铟和硫代乙酰胺为原料制备ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂。该制备方法操作简单,易于调控,成本低,绿色环保。制备的ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂具更优异的光吸收性能和光生载流子的分离效率,表现出高效的光催化产氢活性。
Description
技术领域
本发明属于光催化分解水产氢催化技术领域,具体涉及一种采用溶剂热法合成的ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂;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
环境污染与能源短缺已成为人类社会发展过程中亟需解决的主要问题。因此,开发利用可再生、环境友好型的化学燃料替代化石燃料受到越来越多的关注。氢能是一种清洁环保高效的可再生能源,是化石燃料最理想的替代品。由太阳能驱动的光催化分解水制取氢气是最有前途和最具实际应用前景的重要途径之一,而设计具有强的可见光吸收,低的光生载流子的重组率和化学稳定性的优良光催化剂来提高光催化产氢效率是获得大量氢能的关键。
硫铟锌(ZnIn2S4)是一种双金属硫化物光催化剂,其禁带宽度约为2.0-2.4eV,由于其独特的光电性能和低毒性等优点,已在光催化分解水制取氢气和光催化降解有机污染物的应用中得到了广泛研究。但由于其光生电子空穴复合率高、载流子寿命较短和光吸收能力有限等问题导致ZnIn2S4的光催化性能不能满足实际应用的要求。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)是一种双金属氧化物光催化剂,它由锌氧四面体(ZnO4)和锗氧四面体(GeO4)以共角连接而成,产生内部偶极矩,在一定程度上能从内部抑制光生电子和空穴对的复合,是一种有应用潜力的光催化剂。但是由于其较宽的禁带宽度(约4.5eV)只能吸收利用紫外光,对太阳光的利用效率低,因而进一步的实际应用受到了阻碍。将Zn2GeO4与其他半导体的复合是提高光催化性能的有效途径,可以有效调节并缩小禁带宽度,拓宽光吸收范围,从而促进光生载流子的转移,抑制光生电子和空穴对的复合,提高光催化产氢性能。
为了设计制备新型稳定具有高可见光响应的光催化剂,本发明首先以乙酸锌、氧化锗和氢氧化钠为原料利用水热法制备锗酸锌纳米棒光催化剂,再以乙酸锌、硝酸铟和硫代乙酰胺为原料利用溶剂热法制备硫铟锌光催化剂,最后在制备硫铟锌的过程中加入一定量的制备好的锗酸锌纳米棒来获得ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂。目前采用此方法制备ZnIn2S4/Zn2GeO4双金属硫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。该方法制备的所述光催化剂不仅拓宽了光吸收范围,而且有效抑制了光生电子和空穴的复合,在光催化过程中表现出显著提高的光催化分解水产氢活性。对解决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ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂。本发明首先以乙酸锌、氧化锗和氢氧化钠为原料利用水热法制备锗酸锌纳米棒光催化剂,再以乙酸锌、硝酸铟和硫代乙酰胺为原料利用溶剂热法制备硫铟锌光催化剂,最后在制备硫铟锌的过程中加入一定量的制备好的锗酸锌纳米棒来获得 ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂。
本发明的目的之二就是提供一种ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂的制备方法,具体包括以下步骤:
1.Zn2GeO4的制备
(1)称取2mmol乙酸锌分散到20mL0.5M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Zn2GeO4纳米棒,备用;
2.ZnIn2S4的制备
(1)称取0.8mmol Zn(ac)2·2H2O、1.6mmol In(NO3)3·6H2O和3.5mmol CH3CSNH2在磁力搅拌下溶解在60mL去离子水和无水乙醇的混合溶剂中(v水:v乙醇=1:1),得到无色透明溶液;
(2)将(1)中搅拌好的溶液转入高压反应釜中180℃下反应24h,产物用无水乙醇离心洗涤数次,60℃干燥12h,得到产物,备用;
3.ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂的制备
(1)称量100mg Zn2GeO4纳米棒超声分散在60mL混合溶剂中(v水:v乙醇=1:1),磁力搅拌30min;
(2)分别将0.26~0.5mmol乙酸锌、0.52~1.0mmol硝酸铟和1.14~2.18mmol 硫代乙酰胺加入到上述溶液中,磁力搅拌30min;
(3)将(2)中获得的混合溶液转移至50mL不锈钢高压釜,180℃保持24h。产物用乙醇洗涤三次,并在60℃下干燥,获得ZnIn2S4/Zn2GeO4光催化剂,记作InGe-x 其中x表示ZnIn2S4纳米片占Zn2GeO4纳米棒的重量比
本发明目的之三是提供一种ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂在光催化分解水析氢方面的应用。
附图说明
图1为实施例1所得Zn2GeO4的扫描电镜图(a);ZnIn2S4的扫描电镜图(b); ZnIn2S4/Zn2GeO4的扫描电镜图(c)和高分辨透射电镜图(d)。
图2为实施例2所得ZnIn2S4/Zn2GeO4在氙灯光源下光催化氢气析出速率(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).Zn2GeO4的制备
(1)称取2mmol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Zn2GeO4纳米棒,如图1(a)所示。
(b)ZnIn2S4的制备
(1)称取0.8mmol Zn(ac)2·2H2O、1.6mmol In(NO3)3·6H2O和3.5mmol CH3CSNH2在磁力搅拌下溶解在60mL去离子水和无水乙醇的混合溶剂中(v水:v乙醇=1:1),得到无色透明溶液;
(2)将(1)中搅拌好的溶液转入高压反应釜中180℃下反应24h,产物用无水乙醇离心洗涤数次,60℃干燥12h,得到产物,如图1(b)所示。
(c)ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂的制备
(1)称量100mg锗酸锌纳米棒超声分散在60mL混合溶剂中(v水:v乙醇=1:1),磁力搅拌30min;
(2)分别将0.45mmol乙酸锌、0.90mmol硝酸铟和1.97mmol硫代乙酰胺加入到上述溶液中,磁力搅拌30min;
(3)将(2)中获得的混合溶液转移至50mL不锈钢高压釜,180℃保持24h。产物用乙醇洗涤三次,并在60℃下干燥,获得ZnIn2S4/Zn2GeO4光催化剂,记作 InGe-1.9,如图1(c)和1(d)所示
实施例2
(a).Zn2GeO4的制备
按照实施例1中步骤(a)的方法和条件制备;
(b)ZnIn2S4的制备
按照实施例1中步骤(b)的方法和条件制备;
(c)ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂的制备
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***测试,具体实验步骤如下所述:
在石英反应器皿加入10%的甲醇水溶液100mL,将50mg ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂分散于其中,超声搅拌均匀后,将反应器置于超声机中超声 2秒,重复2-3次,直到反应器底部的催化剂完全分散均匀。石英反应器皿接入***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,如图2(a)所示。
(e)光催化剂的循环稳定性测试
测试实施例1得到的ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂的循环稳定性。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5个循环(20h)后,产氢速率基本没有下降趋势。说明 ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂具有很好的可循环性能。
Claims (5)
1.一种ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂的制备方法,其特征在于该催化剂首先通过水热法以乙酸锌、氧化锗和氢氧化钠为原料合成Zn2GeO4纳米棒,再利用溶剂热法以乙酸锌、硝酸铟和硫代乙酰胺为原料法制备ZnIn2S4光催化剂,最后在制备ZnIn2S4的过程中加入一定量的制备好的Zn2GeO4纳米棒来获得ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂。
所述的双金属硫氧化物光催化剂的制备方法,其特征在于,步骤如下:
(a)Zn2GeO4的制备
(1)将2mmol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)将1mmol氧化锗分散溶液到(1)中,磁力搅拌至完全溶解得乳白色溶液;
(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Zn2GeO4纳米棒,备用;
(b)ZnIn2S4的制备
(1)称取0.8mmol Zn(ac)2·2H2O、1.6mmol In(NO3)3·6H2O和3.5mmol CH3CSNH2在磁力搅拌下溶解在60mL去离子水和无水乙醇的混合溶剂中(v水:v 乙醇=1:1),得到无色透明溶液;
(2)将(1)中搅拌好的溶液转入高压反应釜中180℃下反应24h,产物用无水乙醇离心洗涤数次,60℃干燥12h,得到产物;
(c)ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂的制备
(1)称量100mg Zn2GeO4纳米棒超声分散在60mL混合溶剂中(v水:v乙醇=1:1),磁力搅拌30min;
(2)分别将0.26~0.5mmol乙酸锌、0.52~1.0mmol硝酸铟和1.14~2.18mmol加入到上述溶液中,磁力搅拌30min;
(3)将(2)中获得的混合溶液转移至50mL不锈钢高压釜,180℃保持24h。产物用乙醇洗涤三次,并在60℃下干燥,获得ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂。
2.根据权利要求1所述的方法,其特征在于采用溶剂热法制备ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂。
3.根据权利要求1所述的方法,其特征在于步骤(b)中所述乙酸锌、硝酸铟、硫代乙酰胺的物质的量之比为1:2:4.375 。
4.根据权利要求1所述的方法,其特征在于步骤(c)中乙酸锌的用量为0.45mmol;硝酸铟为0.90mmol;硫代乙酰胺为1.97mmol。
5.根据权利要求1所述的方法合成的ZnIn2S4/Zn2GeO4双金属硫氧化物光催化剂,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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