CN114192102A - 一种一步制备多酸改性的石墨相氮化碳材料及其应用 - Google Patents
一种一步制备多酸改性的石墨相氮化碳材料及其应用 Download PDFInfo
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Abstract
本发明公开了一种一步制备多酸改性的石墨相氮化碳材料及其应用,它涉及石墨相氮化碳改性技术领域。本发明将双氰胺和Anderson型钴钼酸均匀混合,在马弗炉中500℃温度下煅烧4小时,即得到钴钼双金属掺杂的多孔层状石墨相氮化碳材料。相比于体相块状石墨相氮化碳,本发明提供的多酸改性的石墨相氮化碳材料制备方法简单,成本很低,多酸改性的石墨相氮化碳材料具有较大的比表面积,以及更宽的可见光响应范围,并且染料吸附能力和光催化还原六价铬的能力有较大的提升。
Description
技术领域
本发明涉及的是石墨相氮化碳改性技术领域,具体涉及一种一步制备多酸改性的石墨相氮化碳材料及其应用。
背景技术
石墨相氮化碳(g-C3N4),是一种新型的聚合物半导体光催化材料,因其具有特殊的二维层状结构,具有一定的可见光响应等优点,使其成为光催化研究领域内的热门材料之一。但是对于纯g-C3N4而言,还存在着以下问题:
1、对可见光吸收范围有限,仅为460nm左右,极大限制了其可见光催化效率。
2、目前纯g-C3N4通常将一系列含C-C键的富含氮元素的前驱体(如三聚氰胺、双氰胺、尿素等)通过高温热聚合反应制备,然而,这种g-C3N4具有很小的比表面积(通常在10m2·g-1以下),严重限制了其对污染物的吸附能力。
3、在g-C3N4半导体材料中,光生电子和空穴容易复合,从而影响载流子的传输,导致光催化性能减弱。此外,其元素组成仅为碳和氮,相对于金属元素其催化能力略显不足,也在一定程度上限制了其光催化性能。
多金属氧酸盐(即多酸,Polyoxometalates,POMs)是一类多核金属团簇,至今有近二百年的发展历史,已成为无机化学中的重要研究领域。多酸具有明确的分子结构、可调的组成、纳米级尺寸、较强的酸性和优异的氧化还原能力。
基于此,研究一种简单绿色的制备方法,同时提高g-C3N4的吸附性能和光催化活性,是本技术领域目前亟待解决的关键技术问题。
发明内容
针对现有技术上存在的不足,本发明目的是在于提供一种一步制备多酸改性的石墨相氮化碳材料及其应用,工艺简单,将多酸引入到g-C3N4体系,多酸可以提供丰富的金属源,调节g-C3N4电子结构和带隙,进而拓宽光响应范围并增强载流子分离,且可以氧化剪切制造多孔结构,增大比表面积,从而明显提高g-C3N4的吸附性能和光催化活性。
为了实现上述目的,本发明是通过如下的技术方案来实现:一种一步制备多酸改性的石墨相氮化碳材料,钴钼酸与双氰胺质量比为:0.015-0.04:1、优选为0.03:1
一种一步制备多酸改性的石墨相氮化碳材料的制备方法,包括以下步骤:
1、将双氰胺、多酸混合均匀;
2、在马弗炉中煅烧于500℃保温4小时;
3、最终得到多酸改性的钴钼双金属掺杂的石墨相氮化碳。
所述的多酸为一种Anderson型钴钼酸,其化学式为:(NH4)4[Co(II)Mo6O24H6];所述的多酸与双氰胺的质量比0.015-0.04:1、优选为0.03:1。
所述的步骤1具体包括如下:通过溶液搅拌混合均匀,将双氰胺溶解在水中,在60-80℃温度下持续搅拌形成透明溶液,然后加入钴钼酸,搅拌混合均匀,在60-80℃温度下继续搅拌直至所有水分蒸发完全得到固体,研磨成粉。所述温度优选为70℃。
所述的步骤2中的马弗炉以5-10℃/min、优选10℃/min的升温速率,升温至500℃。
所述的步骤3中的多酸改性的钴钼双金属掺杂的石墨相氮化碳为孔层状石墨相氮化碳材料。由片层状堆积而成,其片层表面分布大量10-40nm尺寸的孔。其比表面积为93.6m2/g,是未进行多酸改性的产品的12倍。
一种一步制备的多酸改性石墨相氮化碳材料的应用,包括污水处理,用作吸附剂和光催化剂。
本发明的有益效果:本发明通过多酸提供双金属源,拓宽光吸收范围,并强化光生载流子的分离,同时氧化剪切制备多孔,增大比表面积,从而提升吸附性能和光催化活性。本发明提供的制备工艺简单,成本较低,其方法可用于制备其他多金属的掺杂改性,具有较好的应用前景。
附图说明
下面结合附图和具体实施方式来详细说明本发明;
图1是本发明中Anderson型钴钼酸的晶体结构;
图2是本发明中制得的多酸改性的石墨相氮化碳材料的扫描电镜图;
图3是本发明中制得的多酸改性的石墨相氮化碳材料的X射线粉末衍射图;
图4是本发明中制得的多酸改性的石墨相氮化碳材料的红外光谱图;
图5是本发明中制得的多酸改性的石墨相氮化碳材料的紫外可见漫反射光谱图;
图6是本发明中制得的多酸改性的石墨相氮化碳材料的荧光光谱图;
图7是本发明实施案例中的多酸改性的石墨相氮化碳材料对罗丹明B吸附的紫外可见吸收光谱;
图8是本发明实施案例中的多酸改性的石墨相氮化碳材料光催化还原重铬酸钾的曲线。
具体实施方式
为使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体实施方式,进一步阐述本发明。
参照图1-8,本具体实施方式采用以下技术方案:一种一步制备多酸改性的石墨相氮化碳材料,钴钼酸与双氰胺质量比为:0.015-0.04:1、优选为0.03:1
一种一步制备多酸改性的石墨相氮化碳材料的制备方法,包括以下步骤:
1、将双氰胺、多酸混合均匀;
2、在马弗炉中煅烧于500℃保温4小时;
3、最终得到多酸改性的钴钼双金属掺杂的石墨相氮化碳。
所述的多酸为一种Anderson型钴钼酸,其化学式为:(NH4)4[Co(II)Mo6O24H6];所述的多酸与双氰胺的质量比0.015-0.04:1、优选为0.03:1。
所述的步骤1具体包括如下:通过溶液搅拌混合均匀,将双氰胺溶解在水中,在60-80℃温度下持续搅拌形成透明溶液,然后加入钴钼酸,搅拌混合均匀,在60-80℃温度下继续搅拌直至所有水分蒸发完全得到固体,研磨成粉。所述温度优选为70℃。
所述的步骤2中的马弗炉以5-10℃/min、优选10℃/min的升温速率,升温至500℃。
所述的步骤3中的多酸改性的钴钼双金属掺杂的石墨相氮化碳为孔层状石墨相氮化碳材料。由片层状堆积而成,其片层表面分布大量10-40nm尺寸的孔。其比表面积为93.6m2/g,是未进行多酸改性的产品的12倍。
上述方法制得的改性石墨相氮化碳的结构通过X射线粉末衍射(PXRD,见附图3)、傅里叶变换红外光谱(FTIR,见附图4)、紫外可见漫反射光谱(见附图5)、荧光光谱(见附图6)进行表征。可以发现,在XRD谱图中,观察到较弱的13.1°衍射峰和较强的27.5°衍射峰,分别对应g-C3N4的(100)晶面和(002)晶面,这证明了用上述方法合成的材料确实为g-C3N4,钴钼的引入并没有改变氮化碳的原始晶相结构。但峰强度降低,表面氮化碳面内有序结构在一定程度上被破坏,这是由于多酸在热聚合过程中的作用不仅引入双金属,还有“氧化刻蚀”作用,进一步降低了氮化碳的聚合有序度。在XRD谱图中并没有观察到钴物质和钼物质的存在,说明钴和钼嵌入氮化碳骨架内。在FTIR谱图中,所合成的材料的典型振动峰与g-C3N4一致,说明钴钼的引入并没有改变氮化碳的典型结构。由图5可见,所制备的酸改性石墨相氮化碳出现了可见光的延伸吸收,将可见光响应范围延伸到800nm。从图6可见,所制备的酸改性石墨相氮化碳的荧光强度明显降低,光生载流子分离效率提高。
一种一步制备的多酸改性石墨相氮化碳材料的应用,包括污水处理,用作吸附剂和光催化剂。
实施例1:在敞开反应器中加入25mg所制备吸附剂多酸改性石墨相氮化碳和50mL浓度为10mg/L的罗丹明B溶液,在黑暗条件下超声1min,从吸附体系中取5mL溶液,经过高速离心后去除吸附剂,取上层清液对其进行紫外可见分光光度计测试来评估吸附性能。实验结果表明,所制备的吸附剂多酸改性石墨相氮化碳材料可在1min,对罗丹明B的吸附率达到87%以上(见附图7)。
实施例2:在敞开反应器中加入50mg所制备催化剂多酸改性石墨相氮化碳和100mL浓度为20mg/L的重铬酸钾溶液(用1mol/L柠檬酸调节重铬酸钾溶液pH=3),在黑暗条件下搅拌30min达到吸附平衡后,以300W氙灯作为光源对混合溶液进行照射,并用420nm的滤光片滤掉波长为420nm以下的紫外光,然后每隔5min从反应体系中取5mL溶液,经过高速离心后去除催化剂,取上层清液对其进行紫外可见分光光度计测试来评估催化性能。实验结果表明,所制备的催化剂多酸改性石墨相氮化碳材料可在可见光照射20min后,重铬酸钾的降解率大于88%(见附图8)。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (10)
1.一种一步制备多酸改性的石墨相氮化碳材料的制备方法,其特征在于,包括以下步骤:
(1)、将双氰胺、多酸混合均匀;
(2)、在马弗炉中煅烧于500℃保温4小时;
(3)、最终得到多酸改性的钴钼双金属掺杂的石墨相氮化碳。
2.根据权利要求1所述的一种一步制备多酸改性的石墨相氮化碳材料的制备方法,其特征在于,所述的多酸为一种Anderson型钴钼酸,其化学式为:(NH4)4[Co(II)Mo6O24H6];所述的多酸与双氰胺的质量比为0.03:1。
3.根据权利要求1所述的一种一步制备多酸改性的石墨相氮化碳材料的制备方法,其特征在于,所述的步骤(1)具体包括如下:通过溶液搅拌混合均匀,将双氰胺溶解在水中,在60-80℃温度下持续搅拌形成透明溶液,然后加入钴钼酸,搅拌混合均匀,在60-80℃温度下继续搅拌直至所有水分蒸发完全得到固体,研磨成粉。
4.根据权利要求3所述的一种一步制备多酸改性的石墨相氮化碳材料的制备方法,其特征在于,所述温度为70℃。
5.根据权利要求1所述的一种一步制备多酸改性的石墨相氮化碳材料的制备方法,其特征在于,所述的步骤(2)中的马弗炉以10℃/min的升温速率,升温至500℃。
6.根据权利要求1所述的一种一步制备多酸改性的石墨相氮化碳材料的制备方法,其特征在于,所述的步骤(3)中的多酸改性的钴钼双金属掺杂的石墨相氮化碳为孔层状石墨相氮化碳材料,由片层状堆积而成,其片层表面分布大量10-40nm尺寸的孔,其比表面积为93.6m2/g。
7.一种一步制备的多酸改性石墨相氮化碳材料的应用,其特征在于,包括用作吸附剂和催化剂。
8.根据权利要求7所述的一种一步制备的多酸改性石墨相氮化碳材料的应用,其特征在于,包括染料吸附剂和重金属还原光催化剂。
9.根据权利要求7所述的一种一步制备的多酸改性石墨相氮化碳材料的应用,其特征在于,所述作为染料吸附剂的使用方法为:多酸改性的石墨相氮化碳材料分散于罗丹明B溶液中。
10.根据权利要求7所述的一种一步制备的多酸改性石墨相氮化碳材料的应用,其特征在于,所述作为重金属还原光催化剂的使用方法为多酸改性的石墨相氮化碳材料分散于重铬酸钾溶液中,可见光照射20min。
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