CN111167500A - 一种Ag/g-C3N4复合薄膜及其制备方法和应用 - Google Patents
一种Ag/g-C3N4复合薄膜及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于光催化材料技术领域,具体涉及一种Ag/g‑C3N4复合薄膜的新的制备方法及其在光催化降解气态有机污染物中的应用。将三聚氰胺在管式炉中进行焙烧,研磨之后,在马弗炉进行二次焙烧,得到淡黄色的粉末;将适量g‑C3N4粉末放入丙酮溶液中,进行超声分散处理,加入固体单质碘,继续超声分散,在导电玻璃上镀膜;将薄膜置于马弗炉中焙烧,冷却至室温,在硝酸银溶液中进行沉积,得到目标产物。本发明,在使比表面积增大的同时,实现金属粒子的掺杂,增强Ag的表面等离子体共振效应,从而达到提高光催化活性的目的。本发明的制备方法简单,条件温和,所获得的“三明治”结构的薄膜在可见光下可以降解异丙醇。
Description
技术领域
本发明属于光催化材料技术领域,具体的涉及一种Ag/g-C3N4复合薄膜及其制备方法和应用。
背景技术
光催化技术是一种对环境来说很友好的技术,它可以利用太阳光来光催化降解有机污染物,在水的裂解实验中也有着很好的应用前景,是目前的实验研究中一种比较热门的技术。而g-C3N4(石墨相氮化碳)是一种N型二维非金属半导体结构,作为一种比较有前景的光催化材料,它不仅局限于紫外光,在可见光下就可以发生光催化反应,而且它的含量丰富,无毒无污染,无二次伤害。但是其自身的比表面积小,光生载流子易复合,导致了它的光催化活性小。
表面等离激元驱动化学反应比传统的化学反应在热效应的基础上有更多的优势。但是等离激元热电子的短暂的生命周期大约是一百飞秒,限制了等离激元的全面发展。解决等离子体或者激子驱动催化反应的这些问题,一个比较好的方法是把这些材料混合到一起。等离子体和激子耦合相互作用极大地促进了等离子体激子共同驱动的催化反应,提高光催化活性。
因此如何将两种材料混合,提高电子和空穴的分离效率,提高它的光催化活性,成为人们研究的一个重点的问题。
发明内容
为了解决以上问题,本发明提供一种新的方法用一种简单的方法设计Ag/g-C3N4复合光催化剂。合成的样品不仅具有银的表面等离子体共振效应,而且光催化活性强。
本发明采用的技术方案为:一种Ag/g-C3N4复合薄膜,制备方法包括如下步骤:
1)将三聚氰胺在管式炉中进行焙烧,研磨之后,在马弗炉进行二次焙烧,得到淡黄色的粉末g-C3N4;
2)将适量g-C3N4粉末放入丙酮溶液中,进行超声分散处理,加入固体单质碘,继续超声分散,在导电玻璃上镀膜;
3)将薄膜置于马弗炉中焙烧,冷却至室温,在硝酸银溶液中进行沉积,得到目标产物。
优选地,上述的一种Ag/g-C3N4复合薄膜,步骤1)中,一次焙烧的条件为N2保护,550℃,反应时间为4h。
优选地,上述的一种Ag/g-C3N4复合薄膜,步骤1)中,二次焙烧的条件为500℃,反应时间为2h。
优选地,上述的一种Ag/g-C3N4复合薄膜,步骤2)中,所述的镀膜方法为电沉积法。
优选地,上述的一种Ag/g-C3N4复合薄膜,步骤2)中,按质量比,g-C3N4:固体单质碘=0.6-1:1,电沉积的条件为25V-5min。
优选地,上述的一种Ag/g-C3N4复合薄膜,步骤3)中,所述的沉积方法为光沉积。
优选地,上述的一种Ag/g-C3N4复合薄膜,步骤3)中,在马弗炉中焙烧的条件为450℃,90min,光沉积的条件为300W的氙灯,照射10min。
上述的一种Ag/g-C3N4复合薄膜在光催化降解小分子有机物中的应用。
优选地,上述的应用,所述的小分子有机物是异丙醇。
优选地,上述的应用,方法如下:将Ag/g-C3N4复合薄膜放在含有小分子有机物的密闭空间中,在可见光照射下降解2-3h。
本发明具有以下有益效果:
1.本发明,电沉积和光沉积共同作用,操作简单,可有效加速电子移动。
2.本发明,得到的复合薄膜,粉末分布均匀,具有金属的表面等离子体共振效应。
3.本发明,通过采用电沉积的方法在导电玻璃上镀膜,最后将Ag纳米颗粒沉积在薄膜上,得到具有特殊形貌的光催化剂。使得合成的样品具有“三明治”状的特殊结构,不仅具有金属的表面等离子体共振效应,而且金属的加入有利于光生电子和空穴的分离,延长热电子的生命周期,因此可以增强光催化活性。
4.本发明,避免使用危险的化学药品,同时得到高活性的光催化剂。得到的银的沉积量为 0.01g Ag/g-C3N4复合薄膜,具有较大的光电流为5.5微安,这种结构的薄膜加快了电子的移动,使得在可见光下降解异丙醇至丙酮的速率达到32.349ppm/min,为纯的g-C3N4
薄膜的3倍多。
5.本发明,为了提高光催化活性,降低g-C3N4薄膜的载流子复合率,增强表面等离子体共振效应,选择在导电玻璃上沉积贵金属纳米颗粒来加速电子的快速移动,从而使电子空穴更容易分离。通过沉积Ag纳米粒子,在g-C3N4薄膜龟裂处形成较大的银纳米颗粒,当光照射在金属表面时,光子就会和金属表面的自由电子相结合,产生一种集体的相干震荡,从而形成一种量子化的电荷密度波,增强局域表面等离激元共振效应,加快光生电子和空穴的分离,从而提高光催化活性。同时通过二次焙烧,可以使g-C3N4具有孔结构,提供更多的表面活性位,从而提高催化效率。
附图说明
图1为整个镀膜过程的示意图。
图2在薄膜龟裂处Ag颗粒生长机制图。
图3为光催化过程的机理图。
图4为实施例1中步骤3得到的Ag/g-C3N4复合薄膜的PL全谱。
图5为实施例1中步骤3得到的Ag/g-C3N4复合薄膜的光电流图谱
图6为纯g-C3N4薄膜、0.006g Ag/g-C3N4复合薄膜、0.01g Ag/g-C3N4复合薄膜的光催化剂在可见光照射下降解异丙醇的活性对比示意图。
具体实施方式
纯g-C3N4薄膜的制备:
将2.52g三聚氰胺在管式炉中进行焙烧,条件为550℃,4h。将成品在马弗炉中进行二次焙烧,焙烧条件为500℃,2h,研磨后,得到g-C3N4粉末。
将0.06g g-C3N4粉末溶于20ml的丙酮溶液中,超声处理1小时,加入10mg的单质碘,继续超声1小时,25V条件下电沉积5min,即得纯g-C3N4薄膜。
将制备得到的纯片g-C3N4薄膜进行PL测试,结果如图4所示,由图可见,纯g-C3N4薄膜显示很高的荧光强度峰。
将制备得到的纯片g-C3N4薄膜进行光电流测试,结果如图5所示,由图可见,纯g-C3N4薄膜的光电流强度很低。
实施例1一种Ag/g-C3N4复合薄膜(0.006gAg)
(一)制备方法如下:
1)将2.52g三聚氰胺在管式炉中进行焙烧,条件为550℃,4h。将成品在马弗炉中进行二次焙烧,焙烧条件为500℃,2h,研磨后,得到g-C3N4粉末。
2)将0.006g g-C3N4粉末溶于20ml的丙酮溶液中,超声处理1小时,加入10mg的碘单质,
继续超声1小时,25V条件下电沉积5min镀在导电玻璃上,得到g-C3N4薄膜。
3)将得到的g-C3N4薄膜进一步在马弗炉中焙烧,条件为450℃,90min、冷却至室温。
4)将上述煅烧之后的薄膜置于含有0.006g Ag的硝酸银溶液中,在300W的氙灯光照下,照射时间为10min,得到0.006g Ag/g-C3N4复合薄膜,镀膜过程如图1所示。
(二)检测结果
将步骤3)制备的0.006g Ag/g-C3N4复合薄膜进行PL测试,测试结果如图4所示,由图可见,沉积Ag纳米颗粒的样品,荧光强度明显下降,说明光生电子和空穴很难复合。
将步骤3)制备的0.006g Ag/g-C3N4复合薄膜在电化学工作站中进行光电流测试,结果如图5所示,图中显示光电流的大小为4.5微安,由此可以看出沉积Ag之后的样品光电流强度明显高于纯样,说明抑制了光生载流子的复合,提高电子与空穴的分离,所以光电流有所增强。
(三)应用
将本实施例制备的0.006g Ag/g-C3N4复合薄膜进行光催化降解异丙醇实验。
测试过程为:以300W氙灯为光源,分别将上述制备的0.006g Ag/g-C3N4复合薄膜、制备的纯g-C3N4薄膜放入内含一个大气压空气的300ml反应器中,最后向反应器中注入5ul异丙醇液体,静置3小时使系统吸附-脱附平衡,然后在可见光照射120min下降解异丙醇。
当光照在金属表面上,光子与金属表面的自由电子相结合,形成一种集体相干振荡,对局域有极大的增强效应,从而加快电子的移动,使电子和空穴更容易分离,最终可以使更多的空穴与异丙醇发生反应,生成丙酮,最终生成无毒无害的产品。
结果如图6所示,图6中长方形的长度表示在可见光照射下丙酮产生的速率,由图可知, 0.006g Ag/g-C3N4复合薄膜的丙酮的产生速率为15.568ppm/min,而制备的纯g-C3N4薄膜只有 11.245ppm/min。
实施例2一种Ag/g-C3N4复合薄膜(0.01gAg)
(一)制备方法如下:
1)将2.52g三聚氰胺在管式炉中进行焙烧,条件为550℃,4h。将成品在马弗炉中进行二次焙烧条件为500℃,2h,研磨后,得到g-C3N4粉末。
2)将0.01g g-C3N4粉末溶于20ml的丙酮溶液中,超声处理1小时,加入10mg的碘单质,继续超声1小时,25V条件下电沉积5min镀在导电玻璃上,得到g-C3N4薄膜。
3)将得到的g-C3N4薄膜进一步在马弗炉中焙烧,条件为450℃,90min,冷却至室温。
4)将上述煅烧之后的薄膜置于含有0.01gAg的硝酸银溶液中,在300W的氙灯光照下,照射时间为10min,得到0.01g Ag/g-C3N4复合薄膜,镀膜过程如图1所示。
(二)检测结果
图2为在薄膜龟裂处Ag颗粒生长机制图,由图可见,当半导体光催化材料受到光照时会吸收光能,一旦能量超过其带隙能量时材料将受到激发,从而产生电子和空穴,由于导电玻璃的存在加快电子的移动,使得更多的电子向薄膜龟裂的地方移动,于是在薄膜龟裂的地方,银离子就会更容易被还原成单质银,沉积在材料的表面。
图3为光催化过程的机理图,由图可见,当光照在金属表面上,光子与金属表面的自由电子相结合,形成一种集体相干振荡,对局域有极大的增强效应,从而加快电子的移动,使电子和空穴更容易分离,最终可以使更多的空穴与异丙醇发生反应,生成丙酮,最终生成无毒无害的产品。
将步骤3)制备的0.01g Ag/g-C3N4复合薄膜进行PL测试,测试结果如图4所示,由图可见,沉积Ag纳米颗粒的样品,荧光强度明显下降,说明光生电子和空穴很难复合。
将步骤3)制备的0.01g Ag/g-C3N4复合薄膜在电化学工作站中进行光电流测试,结果如图5所示,图中显示光电流的大小为5.5微安,由此可以看出沉积Ag之后的样品光电流强度明显高于纯样,说明抑制了光生载流子的复合,提高电子与空穴的分离,所以光电流有所增强。
(三)应用
将本实施例制备的0.01g Ag/g-C3N4复合薄膜进行光催化降解异丙醇实验。
测试过程为:以300W氙灯为光源,分别将上述制备的0.01g Ag/g-C3N4复合薄膜、制备的纯g-C3N4薄膜放入内含一个大气压空气的300ml反应器中,最后向反应器中注入5ul异丙醇液体,静置3小时使系统吸附-脱附平衡,然后在可见光照射120min降解异丙醇。
结果如图6所示,图6中长方形的长度表示在可见光照射下丙酮产生的速率,由图可知,0.01g Ag/g-C3N4复合薄膜的丙酮的产生速率为32.349ppm/min,而制备的纯g-C3N4薄膜只有11.245ppm/min。
Claims (10)
1.一种Ag/g-C3N4复合薄膜,其特征在于,制备方法包括如下步骤:
1)将三聚氰胺在管式炉中进行焙烧,研磨之后,在马弗炉进行二次焙烧,得到淡黄色的粉末g-C3N4;
2)将适量g-C3N4粉末放入丙酮溶液中,进行超声分散处理,加入固体单质碘,继续超声分散,在导电玻璃上镀膜;
3)将薄膜置于马弗炉中焙烧,冷却至室温,在硝酸银溶液中进行沉积,得到目标产物。
2.根据权利要求1所述的一种Ag/g-C3N4复合薄膜,其特征在于,步骤1)中,一次焙烧的条件为N2保护,550℃,反应时间为4h。
3.根据权利要求1所述的一种Ag/g-C3N4复合薄膜,其特征在于,步骤1)中,二次焙烧的条件为Air,500℃,反应时间为2h。
4.根据权利要求1所述的一种Ag/g-C3N4复合薄膜,其特征在于,步骤2)中,所述的镀膜方法为电沉积。
5.根据权利要求1所述的一种Ag/g-C3N4复合薄膜,其特征在于,步骤2)中,按质量比,g-C3N4:固体单质碘=0.6-1:1,电沉积的条件为25V-5min。
6.根据权利要求1所述的一种Ag/g-C3N4复合薄膜,其特征在于,步骤3)中,所述的沉积方法为光沉积。
7.根据权利要求2所述的一种Ag/g-C3N4复合薄膜,其特征在于,步骤3)中,在马弗炉中焙烧的条件为450℃,90min,光沉积的条件为300W的氙灯,照射10min。
8.权利要求1所述的一种Ag/g-C3N4复合薄膜在光催化降解小分子有机物中的应用。
9.根据权利要求8所述的应用,其特征在于,所述的小分子有机物是异丙醇。
10.根据权利要求8所述的应用,其特征在于,方法如下:将Ag/g-C3N4复合薄膜放在含有小分子有机物的密闭空间中,在可见光照射下降解2-3h。
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