CN115121264A - 一种水溶性银锡硫纳米晶光催化剂的室温制备方法 - Google Patents
一种水溶性银锡硫纳米晶光催化剂的室温制备方法 Download PDFInfo
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Abstract
本发明涉及一种水溶性银锡硫纳米晶光催化剂的室温制备方法,属于水溶性纳米晶光催化剂领域。制备操作如下;(1)将锡源、盐酸、巯基化合物、银阳离子前体与水混合均匀,加入氢氧化钠或氢氧化钾至溶液澄清形成前体溶液;(2)再加入九水硫化钠,用酸溶液调节pH值,搅拌,离心,烘干沉淀物,得到深灰色粉末状的水溶性银锡硫纳米晶光催化剂。水溶性银锡硫纳米晶光催化剂的粉末状微颗粒的尺寸为1~5纳米;在可见光照射条件下,使用0.8~1.6毫克水溶性银锡硫纳米晶光催化剂催化10~20毫升浓度0.1毫克/毫升的甲基橙溶液,2~5分钟,实现降解甲基橙溶液中93%~99%甲基橙。本发明的催化剂毒性更低,绿色环保;制备成本更低,无稀有金属,原材料丰富。
Description
技术领域
本发明属于水溶性纳米晶光催化剂的技术领域,具体涉及一种水溶性银锡硫纳米晶光催化剂及室温制备方法。
背景技术
环境污染问题已经成为了当今社会亟待解决的重大问题,其中甲基橙、罗丹明B、亚甲基蓝等有机染料的会造成严重的水污染,它们在水中的自然降解速度十分缓慢,且具有生物累积性,严重威胁着人类及后代的健康,水污染治理迫在眉捷。光催化降解利用太阳光激发半导体产生电子、空穴,在半导体表面将有机污染物氧化成H2O和CO2等无机物,与生物和物理去除技术相比,能更有效的降解工业废水中的有机染料。受传输路径距离影响,粒径范围在纳米尺寸的纳米晶光催化剂活性明显强于体相材料,因此制备纳米晶光催化材料可以有效提高光催化活性。含镉的水溶性纳米晶(如硫化镉、锌镉硫等)已经作为光催化被人报道,但是由于含有剧毒元素镉,导致其在未来的应用收到严重的限制。银铟硫纳米晶也可以光催化剂降解有机污染物,但是铟本身作为一种稀有元素,价格昂贵,因此寻找替代银铟硫纳米晶的候选材料成为了研究热点。银锡硫纳米晶是一类I-IV-VI族过渡金属硫化物,兼具了硫化银和硫化锡的优点,其带隙可以在1.1 eV-2.35 eV之间任意调节,且具备较强的抗腐蚀能力,不仅如此,锡的价格成本要远远小于铟,因此其在光降解领域具备很大的应用前景。与油溶性纳米晶光催化剂相比,水溶性纳米晶光催化剂无需配体交换即可进行光催化降解反应,步骤简单,反应条件温和,更不需要用到昂贵及有毒的有机试剂,在光催化降解领域发展前景十分广阔。
目前绝大多数银锡硫纳米晶的制备过程均需在反应釜、三口瓶等容器内加热进行,受到诸多制约,如反应容器容量小(数毫升至数十毫升),反应温度高(通常100℃以上),反应时间较长(数小时至数十个小时)。虽然理论上降解有机染料的过程中光催化剂不会发生消耗,但是工业废水处理量巨大、浓度较高,目前的制备方法规模较小,无法宏量制备,难以实现光催化降解有机污染物的实际应用。鉴于此,发展一种可室温快速宏量制备、光催化降解效率高的水溶性银锡硫纳米晶光催化剂是非常必要的。
发明内容
为了解决镉基催化剂毒性较高、银铟硫纳米晶光催化剂成本过高以及现有纳米晶光催化剂制备过程反应容器容量小、反应温度高、反应时间较长等问题,本发明提供一种水溶性银锡硫纳米晶光催化剂的室温制备方法。
一种水溶性银锡硫纳米晶光催化剂的室温制备操作步骤如下:
(1)将锡源和盐酸按比例加入水中,所述锡源和盐酸加入的摩尔比为1:0.4~1:1.5;加入配体,加入银阳离子前体,配体的加入量为银阳离子前体和锡源总摩尔量的1-8倍,加入氢氧化钠或氢氧化钾直至溶液澄清形成前体溶液;前体溶液中银阳离子前体和锡源的摩尔比为1:9~4:1;
所述锡源为氯化亚锡或硫酸亚锡中的一种;
所述配体为3-巯基丙酸或硫代乙醇酸或柠檬酸或硫代苹果酸中的一种;
所述银阳离子前体为乙酸银或硝酸银或硫酸银中的一种;
(2)在前体溶液中加入九水硫化钠,九水硫化钠的加入量为前体溶液中银阳离子和锡阳离子前体总摩尔量的1-10倍;用酸溶液调节pH值为3~6,在室温下搅拌5分钟~30分钟,得到水溶性银锡硫纳米晶光催化剂溶液,离心,烘干沉淀物,得到粉末状的水溶性银锡硫纳米晶光催化剂;
所述水溶性银锡硫纳米晶光催化剂为深灰色粉末状微颗粒,微颗粒的尺寸为1~5纳米;
在可见光照射条件下,使用0.8~1.6 毫克水溶性银锡硫纳米晶光催化剂催化10~20毫升浓度0.1毫克/毫升的甲基橙溶液,2~5分钟,实现降解甲基橙溶液中93%~99%甲基橙。
进一步地技术方案如下:
步骤(2)中,所述酸溶液为3-巯基丙酸或硫代乙醇酸或硫代乙醇酸胺或柠檬酸或硫代苹果酸或稀盐酸或稀硝酸中的一种。
所述可见光为波长大于420纳米的可见光。
本发明的有益技术效果体现在以下方面:
1. 本发明的制备过程无需反应釜、三口烧瓶等反应容器,不受实验场地及实验容器限制;可在室温空气氛围下快速合成,不会出现因奥氏熟化而产生的团聚现象,实验重现性高,适合大规模生产的同时大大降低制备成本。
2. 本发明选取的银锡硫光催化剂可直接吸收可见光,能源利用率高;无需负载在其他材料上,可直接进行光催化降解,制备工艺简单。
3. 本发明制备的水溶性纳米晶光催化剂没有长链的有机配体,无需复杂的配体交换即可直接用于光催化制氢及降解有机染料,操作简单,易于实现产业化。
4. 相比于镉基光催化剂,本发明制备的水溶性银锡硫纳米晶光催化剂毒性更低,绿色环保;与银铟硫纳米晶光催化剂相比,本发明制备的水溶性银锡硫纳米晶光催化剂成本更低,无稀有金属,原材料产量丰富。
5. 本发明制备的银锡硫纳米晶光催化剂,属于纳米颗粒尺度,其光吸收系数大,激子扩散距离短,相比体相材料更利于载流子的分离,实现高效的光催化降解反应。
6. 图1为使用本发明制备的银锡硫光催化剂降解甲基橙的降解图,图2为使用本发明制备的银锡硫光催化剂降解甲基橙的紫外可见吸收光谱。从图中可以,使用1.6毫克本发明光催化剂在可见光下光催化降解含有2毫克甲基橙的水溶液,5分钟内最高降解效率可达99%,远超大部分光催化剂的降解速度。
附图说明
图1为实施例1中阳离子与硫源的摩尔比分别为1:2、1:3、1:4、1:5、1:6、时制备的水溶性纳米晶光催化剂降解甲基橙的降解图。
图2为实施例2中纳米晶光催化剂的透射电子显微镜图片。
图3为实施例2中纳米晶光催化剂降解甲基橙的紫外可见吸收光谱。
图4为实施例3中不同pH值的反应前体溶液制备的纳米晶光催化甲基橙的降解图。
图5为实施例中不同银锡比例制备的纳米晶光催化甲基橙的降解图。
具体实施方式
为了进一步理解本发明,下面结合实施例对本发明优选实施方案进行描述,但是应当理解,这些描述只是为进一步说明本发明的特征和优点,而不是对本发明权利要求的限制。
实施例1
一种水溶性银锡硫纳米晶光催化剂的制备操作步骤如下:
(1)取5个烧杯,每个烧杯中按配方加入物料混合,每个烧杯中的物料为15毫升去离子水、1.9 毫克氯化亚锡、0.18毫克盐酸、26毫克3-巯基丙酸和3.4毫克硝酸银,其中氯化亚锡和盐酸的摩尔比2:1;3-巯基丙酸的加入量为硝酸银和氯化亚锡总摩尔量的8倍;加入氢氧化钠直至溶液澄清,得到五份相同的前体溶液。
所述前体溶液中硝酸银和氯化亚锡的摩尔比为2:1。
(2)在五份前体溶液中分别加入7.2 毫克、14.4 毫克、21.6 毫克、28.8 毫克、36毫克九水硫化钠,五份九水硫化钠的加入量分别为前体溶液中硝酸银和氯化亚锡所需硫化钠摩尔总量的1倍、2倍、3倍、4倍和5倍;之后用3-巯基丙酸调节五份反应前体溶液的pH值至4.0,在搅拌条件下反应15分钟,得到五份银锡硫水溶性纳米晶光催化剂溶液,将溶液离心,烘干沉淀物,得到五份粉末状的水溶性银锡硫纳米晶光催化剂,水溶性银锡硫纳米晶光催化剂为深灰色粉末状微颗粒,微颗粒的尺寸为1~5 纳米。
甲基橙在自然环境中无法降解,加入本实施例1制备的水溶性银锡硫纳米晶光催化剂后在可见光光照条件下可快速降解。图1是本实施例1中使用不同阳离子/硫源摩尔比例制备得到的五份水溶性银锡硫纳米晶光催化剂降解甲基橙的降解图,分别使用1.6 毫克水溶性银锡硫纳米晶光催化剂降解20毫升浓度为0.1毫克/毫升的甲基橙溶液,从图1中可以看到,最初随着阳离子/硫源的比例的增大,光催化降解速率逐渐增加,在阳离子/硫源=1/4时达到最大,5分钟可降解溶液中99%甲基橙,之后继续增大阳离子/硫源的比例,光催化降解的速率不再发生明显提高。
实施例2
一种水溶性银锡硫纳米晶光催化剂的制备操作步骤如下:
(1)取1个50毫升烧杯,烧杯中按配方加入物料混合,每个烧杯中的物料为15毫升去离子水、1.9毫克氯化亚锡、0.18毫克盐酸、26毫克 3-巯基丙酸和3.4毫克硝酸银,按顺序加入烧杯中混合,加入氢氧化钠直至溶液澄清,得到纳米晶反应前体溶液。
(2)在反应前体溶液中分别加入28.8毫克九水硫化钠,之后用3-巯基丙酸调节反应前体溶液的pH值至4.0,在搅拌条件下反应15分钟,得到水溶性银锡硫纳米晶光催化剂溶液,将溶液离心,烘干,得到水溶性银锡硫纳米晶光催化剂粉末。
甲基橙在自然环境中无法降解,加入本实施例2制备的水溶性银锡硫纳米晶光催化剂后在可见光光照条件下可快速降解。图2是本实施例2中水溶性银锡硫纳米晶光催化剂的透射电子显微镜的图片,从图2中可以看出水溶性银锡硫纳米晶光催化剂的粉末尺寸分布窄,没有团聚现象,粉末颗粒的平均直径在3纳米左右。图3是本实施例2中水溶性银锡硫纳米晶光催化剂降解甲基橙的紫外可见吸收光谱,使用0.8 毫克水溶性银锡硫纳米晶催化剂降解10 毫升浓度为0.1毫克/毫升的甲基橙,从图3中可以看出,水溶性银锡硫纳米晶光催化降解甲基橙的速度很快,4分钟可降解95%的甲基橙。这说明纳米晶没有因为放大反应而出现催化降解速率的下降。
实施例3
一种水溶性银锡硫纳米晶光催化剂的制备操作步骤如下:
(1)取5个烧杯,烧杯中按配方加入物料混合,每个烧杯中的物料为15毫升去离子水、1.9 毫克氯化亚锡、0.18毫克盐酸、26 毫克3-巯基丙酸和3.4 毫克硝酸银,按顺序分别加入5个烧杯中混合,加入氢氧化钠直至溶液澄清,得到五份相同的纳米晶反应前体溶液。
(2)在五份反应前体溶液中分别加入28.8 毫克九水硫化钠,之后用3-巯基丙酸将五份纳米晶反应前体溶液的pH值分别调节至4.0、5.0、6.0、7.0、8.0,在搅拌条件下反应15分钟,得到五份银锡硫水溶性纳米晶光催化剂溶液,将溶液离心,烘干,得到银五份不同pH值的水溶性锡硫纳米晶光催化剂,五份水溶性锡硫纳米晶光催化剂均为粉末状。
甲基橙在自然环境中无法降解,加入本实施例3制备的水溶性银锡硫纳米晶光催化剂后在可见光光照条件下可快速降解。图4为本实施例3中不同pH值的水溶性锡硫纳米晶光催化剂降解甲基橙的降解图,使用1.6 毫克水溶性锡硫纳米晶光催化剂降解10 毫升浓度为0.1毫克/毫升的甲基橙,从图4中可以看到,随着pH值的不断降低,纳米晶光催化降解的速率呈增加的趋势,当前体溶液的pH=4时,水溶性锡硫纳米晶光催化剂的催化降解速率达到最大,2分钟可降解溶液中99%的甲基橙。
实施例4
一种水溶性银锡硫纳米晶光催化剂的制备操作步骤如下:
(1)取5个烧杯分别标记为一号烧杯至五号烧杯,在每只烧杯中按配方加入物料混合;在每个烧杯中加入15毫升去离子水,在一号烧杯中加2.84毫克氯化亚锡、0.2732毫克盐酸、26 毫克3-巯基丙酸和2.55毫克硝酸银;其中硝酸银和氯化亚锡的摩尔比为1:1。
在二号烧杯中加入3.79毫克氯化亚锡、0.3646毫克盐酸、26毫克 3-巯基丙酸和1.69毫克硝酸银;其中硝酸银和氯化亚锡的摩尔比为2:1。
在三号烧杯中加入4.26毫克氯化亚锡、0.4106毫克盐酸、26毫克 3-巯基丙酸和1.27毫克硝酸银;其中硝酸银和氯化亚锡的摩尔比为3:1。
在四号烧杯中加入4.55毫克氯化亚锡、0.438毫克盐酸、26毫克 3-巯基丙酸和1.02毫克硝酸银;其中硝酸银和氯化亚锡的摩尔比为4:1。
在五号烧杯中加入4.74毫克氯化亚锡、0.4563毫克盐酸、26毫克 3-巯基丙酸和0.85毫克硝酸银;其中硝酸银和氯化亚锡的摩尔比为5:1。
在五个烧杯内分别加入氢氧化钠直至溶液澄清,得到五份纳米晶反应前体溶液。
(2)在五份纳米晶反应前体溶液中分别加入9毫克 、6.78毫克 、12.25毫克、12.6毫克、13.33毫克九水硫化钠,之后用3-巯基丙酸调节pH值至4.0,在搅拌条件下反应15分钟,得到五份水溶性银锡硫纳米晶光催化剂溶液。
甲基橙在自然环境中无法降解,加入本实施例4制备的水溶性银锡硫纳米晶光催化剂后在可见光光照条件下可快速降解。图5是本实施例4中不同银锡比例制备得到的水溶性银锡硫纳米晶光催化剂降解甲基橙的降解图,从图中可以看到,当银/锡比例为1/2时,光催化降解速率达到最大,2分钟可降解溶液中93.1%的甲基橙。
实施例5
一种水溶性银锡硫纳米晶光催化剂的制备操作步骤如下:
(1)取一个50毫升烧杯中按配方加入物料混合,烧杯中的物料为15毫升去离子水、2.26毫克硫化亚锡、0.2174毫克盐酸、26毫克3-巯基丙酸和2.55毫克硝酸银,混合均匀,加入氢氧化钠直至溶液澄清,得到纳米晶反应前体溶液。
(2)在纳米晶反应前体溶液中加入36毫克九水硫化钠,之后用3-巯基丙酸调节pH值至4.0,在搅拌条件下反应15分钟,得到水溶性银锡硫水溶性纳米晶光催化剂溶液。
Claims (3)
1.一种水溶性银锡硫纳米晶光催化剂的室温制备方法,其特征在于,操作步骤如下:
(1)将锡源和盐酸按比例加入水中,所述锡源和盐酸加入的摩尔比为1:0.4~1:1.5;加入配体,加入银阳离子前体,配体的加入量为银阳离子前体和锡源总摩尔量的1-8倍,加入氢氧化钠或氢氧化钾直至溶液澄清形成前体溶液;前体溶液中银阳离子前体和锡源的摩尔比为1:9~4:1;
所述锡源为氯化亚锡或硫酸亚锡中的一种;
所述配体为3-巯基丙酸或硫代乙醇酸或柠檬酸或硫代苹果酸中的一种;
所述银阳离子前体为乙酸银或硝酸银或硫酸银中的一种;
(2)在前体溶液中加入九水硫化钠,九水硫化钠的加入量为前体溶液中银阳离子和锡阳离子总摩尔量的1-10倍;用酸溶液调节pH值为3~6,在室温下搅拌5分钟~30分钟,得到水溶性银锡硫纳米晶光催化剂溶液,离心,烘干沉淀物,得到粉末状的水溶性银锡硫纳米晶光催化剂;
所述水溶性银锡硫纳米晶光催化剂为深灰色粉末状微颗粒,微颗粒的尺寸为1~5 纳米;
在可见光照射条件下,使用0.8~1.6 毫克水溶性银锡硫纳米晶光催化剂催化10~20毫升浓度0.1毫克/毫升的甲基橙溶液,2~5分钟,实现降解甲基橙溶液中93%~99%甲基橙。
2.根据权利要求1所述一种水溶性银锡硫纳米晶光催化剂的室温制备方法,其特征在于:步骤(2)中,所述酸溶液为3-巯基丙酸或硫代乙醇酸或硫代乙醇酸胺或柠檬酸或硫代苹果酸或稀盐酸或稀硝酸中的一种。
3.根据权利要求2所述一种水溶性银锡硫纳米晶光催化剂的室温制备方法,其特征在于:所述可见光为波长大于420纳米的可见光。
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