CN110075895A - 一种碳氮烯-硫化锌复合纳米材料及其制备方法和应用 - Google Patents
一种碳氮烯-硫化锌复合纳米材料及其制备方法和应用 Download PDFInfo
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- YYNIVGIURMZWQU-UHFFFAOYSA-N diethyl(hexadecyl)azanium;bromide Chemical group Br.CCCCCCCCCCCCCCCCN(CC)CC YYNIVGIURMZWQU-UHFFFAOYSA-N 0.000 claims description 2
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 2
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Abstract
本发明公开了一种碳氮烯‑硫化锌复合纳米材料及其制备方法和应用,所述材料的粒度为30‑100nm,碳氮烯的含量为5‑25wt%,余量为硫化锌。所述方法是先后向乙醇水溶液中加入锌源、g‑C3N4纳米片、表面活性剂和硫源,超声分散,水热反应后分离、洗涤、干燥,即可得所述复合纳米材料。将该复合纳米材料与固化剂和填料球磨,加入无机粘合剂,搅拌均匀,得到喷涂浆料,将其以0.4~0.6m/s、0.45~0.55MPa喷涂到基材表面,经过多级热处理后,清洗、晾干,得到所述碳氮烯/硫化锌复合光催化涂层。本发明制备工艺简单,用其制备的复合光催化涂层具备较强的甲醛降解能力,可在空气净化、污水处理等领域中具有重要的应用。
Description
技术领域
本发明涉及纳米材料及环保材料领域,涉及一种碳氮烯-硫化锌复合纳米材料及其制备方法和应用。
背景技术
以二氧化钛为代表的传统光催化材料因其优异的物理化学性能而被广泛应用于光催化净化环境,是解决当前日趋严重的环境污染问题的重要途径之一。目前基于二氧化钛的光催化技术应用的核心主要是提高自身的光催化性能及镀膜结合强度。然而二氧化钛仅能吸收太阳光谱中4%~5%的紫外光,可见光利用率低,因此发展新颖的高效复合光催化材料是当前光催化领域研究的重点。
众所周知,碳氮烯(g-C3N4)是一种非金属半导体光催化剂,它可以应用于分解水和有机污染物。近期大量的g-C3N4半导体光催化剂与银基的复合材料被报道,国家发明专利201811187940.0,201610332673.6,201510615287.3报道了g-C3N4半导体光催化剂的制备方法及在光催化领域的应用。
g-C3N4的低毒、稳定性高及合适的禁带宽度,能有效利用可见光,而被g-C3N4作为其他光催化材料的改性的增强相。但是单一的g-C3N4光催化剂可见光条件下的光降解性能不高,由于其光生电子空穴对符合率高及量子效率低的原因,限制了其在光催化领域的应用。
发明内容
针对现有技术的不足,本发明的目的之一在于提供一种碳氮烯-硫化锌(g-C3N4/ZnS)复合纳米材料,具体技术方案如下:
一种碳氮烯-硫化锌复合纳米材料,所述复合纳米材料的粒度为30-100nm,碳氮烯的质量含量为5-25%,余量为硫化锌。
本发明的目的之二是提供上述碳氮烯-硫化锌复合纳米材料的制备方法,具体技术方案如下:
一种所述碳氮烯-硫化锌复合纳米材料的制备方法,包括以下步骤:将锌源溶于乙醇水溶液,再将g-C3N4纳米片和表面活性剂加入上述溶液,超声分散1~2h,逐滴加入硫源至沉淀完全,将混合液转移至不锈钢反应釜中,置于真空干燥箱中于160~180℃保温16~24h,冷却至室温;将反应产物离心分离后,分别用去离子水和无水乙醇洗涤1~3次,最后在70-90℃真空干燥8~12h,得到所述碳氮烯/硫化锌复合纳米材料。
优选地,所述乙醇水溶液是按体积比V乙醇:V去离子水=1:0.5~2配制而成;所述锌源为Zn(AC)2、Zn(NO3)2或Zn(SO4)2,与所述乙醇水溶液中的质量体积比为24.8~55.0g/L;所述g-C3N4纳米片与所述乙醇水溶液中的质量体积比为1~5g/L;所述表面活性剂为十六烷基二乙基溴化铵、聚乙二醇或十二烷基硫酸钠,与所述乙醇水溶液中的质量体积比为0.4~1.2g/L;所述硫源为硫化钠溶液、硫化铵溶或硫脲水溶液,与所述乙醇水溶液的物质的量体积比为50~100mmol/L。
本发明的目的之三是提供一种上述碳氮烯-硫化锌复合纳米材料的应用,具体技术方案如下:
所述碳氮烯-硫化锌复合纳米材料应用于碳氮烯-硫化锌复合光催化涂层,所述涂层的制备方法包括以下步骤:将碳氮烯-硫化锌复合纳米材料、固化剂、填料球磨1~3h,逐滴加入无机粘合剂,搅拌均匀,得到喷涂浆料;将所述喷涂浆料以喷涂速度0.4~0.6m/s、气压压力0.45~0.55MPa喷涂到基材表面,经过多级热处理后,用水清洗、晾干,得到所述碳氮烯-硫化锌复合光催化涂层。
优选地,所述多级热处理工艺如下:真空或惰性气体条件下,在80~120℃热处理5~10min,再在220~300℃热处理10~15min,接着在400~450℃热处理30~40min,然后随炉冷却至室温。
优选地,所述固化剂为50~100nm粒径的MgO、CuO或ZnO纳米颗粒;所述填料为SiO2、铝粉或Al2O3,粒度为100-200nm;所述无机粘合剂为1.25~15g/L的磷酸二氢铝溶液、水溶性硅酸钠或硼酸钠溶液;所述基材为陶瓷、玻璃或金属材料。
优选地,所述碳氮烯-硫化锌复合纳米材料、固化剂、填料、无机粘合剂溶质的质量比为1:0.4~1.6:0.1~5:0.25~3,所述无机粘合剂溶质为上述磷酸二氢铝、水溶性硅酸钠或硼酸钠。
优选地,所述碳氮烯-硫化锌复合光催化涂层应用于可见光条件下光催化降解空气中的气态或液态有机污染物。
更优选地,将所述碳氮烯-硫化锌复合光催化涂层置于含有气态污染物的容器内,可见光条件下光照1-3h。
本发明的有益效果
本发明提供一种简易合成的碳氮烯-硫化锌复合光催化剂,该催化剂有效提升了光催化降解能力及其稳定性;将该催化剂应用于碳氮烯-硫化锌复合光催化涂层,该涂层具备较强的甲醛降解能力(3小时甲醛降解率最高可达49.5%),可在空气净化、污水处理等领域中具有重要的应用,有望用于大规模的工业生产。
附图说明
图1为本发明制得的碳氮烯-硫化锌复合光催化涂层的EDS谱图。
图2为本发明制得的碳氮烯-硫化锌复合光催化涂层的微观扫描电镜图(SEM)。
图3为本发明制得的碳氮烯-硫化锌复合光催化涂层的微观透射电镜图(TEM)。
具体实施方式
以下通过具体实施方式进一步描述本发明,由技术常识可知,本发明也可通过其它的不脱离本发明技术特征的方案来描述,因此所有在本发明范围内或等同本发明范围内的改变均被本发明包含。
实施例1
1、碳氮烯-硫化锌复合纳米材料的制备
将1.78g Zn(AC)2溶于50mL乙醇水溶液(按体积比V乙醇:V去离子水=1:0.5~2配制而成),再将0.05g固相法制备所得g-C3N4纳米片和0.02g的十六烷基二乙基溴化铵加入上述溶液,超声分散2h后,逐滴加入硫化钠溶液(25mL,0.1mol/L)至沉淀完全,将混合液转移至100ml的不锈钢反应釜中,置于真空干燥箱中于160℃保温24h,冷却至室温。反应产物经离心分离后,分别用去离子水和无水乙醇反复洗涤3次,最后在真空条件下80℃干燥10h得g-C3N4/ZnS复合纳米材料。
2、碳氮烯-硫化锌复合光催化涂层的制备
将0.1g的g-C3N4/ZnS复合纳米材料,0.04g MgO纳米颗粒(固化剂),0.01g SiO2(填料,粒度为100nm)球磨1h后,再用移液管量取20ml磷酸二氢铝溶液(1.25g/L)逐滴加入上述混合物中,将研钵内的混合物均匀搅拌制成喷涂浆料;将喷涂浆料以喷涂速度0.5m/s、气压压力0.5MPa的工艺条件喷涂到预处理好的玻璃基材表面,然后进行多级热处理工艺处理,先在80℃下热处理10min,然后在220℃下热处理10min,最后在400℃下热处理30min,随炉冷却至室温,然后将含有碳氮烯-硫化锌复合光催化涂层的基材在净水中冲洗5分钟,晾干,得到涂覆在玻璃表面的碳氮烯/硫化锌复合光催化涂层。
实施例2
1、碳氮烯-硫化锌复合纳米材料的制备
将2.75g Zn(NO3)2溶于50mL乙醇水溶液(按体积比V乙醇:V去离子水=1:0.5~2配制而成),再将0.1g固相法制备所得g-C3N4纳米片和0.04g的聚乙二醇加入上述溶液,超声分散1h后,逐滴加入硫化铵溶液(25mL,0.1mol/L)至沉淀完全,将混合液转移至100ml的不锈钢反应釜中,置于真空干燥箱中于160℃保温24h,冷却至室温。反应产物经离心分离后,分别用去离子水和无水乙醇反复洗涤3次,最后在真空条件下80℃干燥10h得g-C3N4/ZnS复合纳米材料。
2、碳氮烯-硫化锌复合光催化涂层的制备
将0.1g的g-C3N4/ZnS复合纳米材料,0.1g CuO纳米颗粒(固化剂),0.03g铝粉(填料,粒度为200nm),球磨1h后,再用移液管量取20ml水溶性硅酸钠(5g/L)逐滴加入上述混合物中,将研钵内的混合物均匀搅拌制成喷涂浆料;将喷涂浆料以喷涂速度0.5m/s、气压压力0.5MPa的工艺条件喷涂到预处理好的玻璃基材表面,然后进行多级热处理工艺处理,先在120℃下热处理5min,然后在300℃下热处理15min,最后在450℃下热处理40min,随炉冷却至室温,然后将含有碳氮烯-硫化锌复合光催化涂层的基材在净水中冲洗5分钟,晾干,得到涂覆在玻璃表面的碳氮烯/硫化锌复合光催化涂层。
实施例3
1、碳氮烯-硫化锌复合纳米材料的制备
将1.24g Zn(SO4)2溶于50mL乙醇水溶液(按体积比V乙醇:V去离子水=1:0.5~2配制而成),再将0.25g固相法制备所得g-C3N4纳米片和0.06g的十二烷基硫酸钠加入上述溶液,超声分散2h后,逐滴加入硫脲水溶液[CS(NH2)2](10mL,0.5mol/L)至沉淀完全,将混合液转移至100ml的不锈钢反应釜中,置于真空干燥箱中于180℃保温16h,冷却至室温。反应产物经离心分离后,分别用去离子水和无水乙醇反复洗涤3次,最后在真空条件下80℃干燥10h得g-C3N4/ZnS复合纳米材料。
2、碳氮烯-硫化锌复合光催化涂层的制备
将0.1g的g-C3N4/ZnS复合纳米材料,0.16g ZnO纳米颗粒(固化剂),0.5g Al2O3(填料,粒度为100nm)球磨1h后,再用移液管量取20ml硼酸钠溶液(15g/L)逐滴加入上述混合物中,将研钵内的混合物均匀搅拌制成喷涂浆料;将喷涂浆料以喷涂速度0.5m/s、气压压力0.5MPa的工艺条件喷涂到预处理好的玻璃基材表面,然后进行多级热处理工艺处理,先在80℃下热处理10min,然后在220℃下热处理10min,最后在400℃下热处理30min,随炉冷却至室温,然后将含有碳氮烯-硫化锌复合光催化涂层的基材在净水中冲洗5分钟,晾干,得到涂覆在玻璃表面的碳氮烯/硫化锌复合光催化涂层。
图1为碳氮烯-硫化锌复合光催化涂层的EDS图谱,表明产物由C、N、Zn、S元素组成,无其它杂质,其C:N为1:1.32,Zn:S为1:2.05,与化学式相一致,证明了碳氮烯/硫化锌的成功制备。图2和图3分别为合成产物碳氮烯-硫化锌的SEM和TEM图,由图可知直径大约40nm的硫化锌纳米颗粒生长在片状g-C3N4之上,其平均尺度约为100nm。
为了考察光催化涂料降解甲醛的实际效果,本发明利用欧盟普遍采用的HJC-1型环境测试舱模拟可见光源下室内环境。采用乙酰丙酮分光光度法(GB/T 15516-1995),选择每隔2h采样5L舱内的气体,检测环境测试舱中甲醛气体的浓度变化,从而可以计算出碳氮烯-硫化锌复合光催化涂层光催化降解甲醛气体的效率,具体见表1。
表1.碳氮烯-硫化锌复合光催化涂层光催化降解甲醛气体的效率(%)
从表1中可以看出,本发明的实施例3所得的碳氮烯/硫化锌复合光催化涂层对甲醛的降解效果最好,3h降解效率达到了49.5%。
Claims (9)
1.一种碳氮烯-硫化锌复合纳米材料,其特征在于,所述复合纳米材料的粒度为30-100nm,碳氮烯的质量含量为5-25%,余量为硫化锌。
2.一种根据权利要求1所述的碳氮烯-硫化锌复合纳米材料的制备方法,其特征在于,包括以下步骤:将锌源溶于乙醇水溶液,再将g-C3N4纳米片和表面活性剂加入上述溶液,超声分散1~2h,逐滴加入硫源至沉淀完全,将混合液转移至不锈钢反应釜中,置于真空干燥箱中于160~180℃保温16~24h,冷却至室温;将反应产物离心分离后,分别用去离子水和无水乙醇洗涤1~3次,最后在70-90℃真空干燥8~12h,得到所述碳氮烯/硫化锌复合纳米材料。
3.根据权利要求2所述的碳氮烯-硫化锌复合纳米材料的制备方法,其特征在于,所述乙醇水溶液是按体积比V乙醇:V去离子水=1:0.5~2配制而成;所述锌源为Zn(AC)2、Zn(NO3)2或Zn(SO4)2,与所述乙醇水溶液中的质量体积比为24.8~55.0g/L;所述g-C3N4纳米片与所述乙醇水溶液中的质量体积比为1~5g/L;所述表面活性剂为十六烷基二乙基溴化铵、聚乙二醇或十二烷基硫酸钠,与所述乙醇水溶液中的质量体积比为0.4~1.2g/L;所述硫源为硫化钠溶液、硫化铵溶或硫脲水溶液,与所述乙醇水溶液的物质的量体积比为50~100mmol/L。
4.权利要求1所述的碳氮烯-硫化锌复合纳米材料应用于碳氮烯-硫化锌复合光催化涂层,其特征在于,所述涂层的制备方法包括以下步骤:将碳氮烯-硫化锌复合纳米材料、固化剂、填料球磨1~3h,逐滴加入无机粘合剂,搅拌均匀,得到喷涂浆料;将所述喷涂浆料以喷涂速度0.4~0.6m/s、气压压力0.45~0.55MPa喷涂到基材表面,经过多级热处理后,用水清洗、晾干,得到所述碳氮烯/硫化锌复合光催化涂层。
5.根据权利要求4所述的应用的方法,其特征在于,所述多级热处理工艺如下:真空或惰性气体条件下,在80~120℃热处理5~10min,再在220~300℃热处理10~15min,接着在400~450℃热处理30~40min,然后随炉冷却至室温。
6.根据权利要求5所述的应用的方法,其特征在于,所述固化剂为50~100nm粒径的MgO、CuO或ZnO纳米颗粒;所述填料为SiO2、铝粉或Al2O3,粒度为100-200nm;所述无机粘合剂为1.25~15g/L的磷酸二氢铝溶液、水溶性硅酸钠或硼酸钠溶液;所述基材为陶瓷、玻璃或金属材料。
7.根据权利要求5所述的应用的方法,其特征在于,所述碳氮烯-硫化锌复合纳米材料、固化剂、填料、无机粘合剂溶质的质量比为1:0.4~1.6:0.1~5:0.25~3,所述无机粘合剂溶质为上述磷酸二氢铝、水溶性硅酸钠或硼酸钠。
8.一种如权利要求4所述的碳氮烯-硫化锌复合光催化涂层应用于可见光条件下光催化降解空气中的气态或液态有机污染物。
9.根据权利要求8所述的应用的方法,其特征在于,将所述碳氮烯-硫化锌复合光催化涂层置于含有气态污染物的容器内,可见光条件下光照1-3h。
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110918108A (zh) * | 2019-12-02 | 2020-03-27 | 镇江市高等专科学校 | 一种MXene复合纳米材料及其制备方法和应用 |
CN112295583A (zh) * | 2020-10-23 | 2021-02-02 | 南昌航空大学 | 一种硫化锌/硼化石墨相氮化碳可见光催化剂的制备方法及其应用 |
CN112751140A (zh) * | 2019-10-16 | 2021-05-04 | 珠海冠宇电池股份有限公司 | 一种提高锂离子电池电解液保液量和安全性能的隔膜功能涂层材料 |
CN112774693A (zh) * | 2019-11-04 | 2021-05-11 | 北京氦舶科技有限责任公司 | 一种单原子Ag/ZnS催化剂及其制备方法和应用 |
CN113441001A (zh) * | 2021-06-10 | 2021-09-28 | 香港理工大学深圳研究院 | 一种复合光催化材料在光催化降解甲醛中的应用 |
CN114314735A (zh) * | 2021-12-13 | 2022-04-12 | 湖南农业大学 | 利用氮化碳/三氧化钨/硫化锌双z型复合光催化剂处理抗生素废水的方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106241877A (zh) * | 2016-07-15 | 2016-12-21 | 江苏大学 | 一种g‑C3N4/MoS2/ZnS纳米复合材料的制备方法 |
CN106311304A (zh) * | 2016-07-26 | 2017-01-11 | 东华大学 | 一种紫外光及可见光催化复合纳米材料及其制备和应用 |
CN106430288A (zh) * | 2016-11-30 | 2017-02-22 | 江苏大学 | 一种g‑C3N4/ZnS纳米复合材料的制备方法 |
CN108246331A (zh) * | 2018-01-16 | 2018-07-06 | 东北师范大学 | 石墨烯碳化氮量子点修饰的ZnS微米复合材料及其制备方法和应用 |
CN109174160A (zh) * | 2018-10-12 | 2019-01-11 | 辽宁大学 | 一种g-C3N4光催化剂涂层及其制备方法和应用 |
-
2019
- 2019-04-08 CN CN201910274863.0A patent/CN110075895A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106241877A (zh) * | 2016-07-15 | 2016-12-21 | 江苏大学 | 一种g‑C3N4/MoS2/ZnS纳米复合材料的制备方法 |
CN106311304A (zh) * | 2016-07-26 | 2017-01-11 | 东华大学 | 一种紫外光及可见光催化复合纳米材料及其制备和应用 |
CN106430288A (zh) * | 2016-11-30 | 2017-02-22 | 江苏大学 | 一种g‑C3N4/ZnS纳米复合材料的制备方法 |
CN108246331A (zh) * | 2018-01-16 | 2018-07-06 | 东北师范大学 | 石墨烯碳化氮量子点修饰的ZnS微米复合材料及其制备方法和应用 |
CN109174160A (zh) * | 2018-10-12 | 2019-01-11 | 辽宁大学 | 一种g-C3N4光催化剂涂层及其制备方法和应用 |
Non-Patent Citations (2)
Title |
---|
SHOUHENG LIU ET AL.: "A simple method to prepare g-C3N4-TiO2/waste zeolites as visible - lightresponsive photocatalytic coatings for degradation of indoor formaldehyde", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
YONGQIAN SHI ET AL.: "Facile preparation of ZnS/g-C3N4 nanohybrids for enhanced optical properties", 《RSC ADVANCES》 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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