CN108404960B - 一种硫铟锌金氮化碳二维层状复合光催化剂的制备方法 - Google Patents
一种硫铟锌金氮化碳二维层状复合光催化剂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种硫铟锌金氮化碳二维层状复合光催化剂的制备方法,C6H5Na3O7·2H2O溶解于去离子水中,HAuCl4稀释加热至沸腾后加上述柠檬酸钠溶液,沸腾,冷却至室温,得金胶体混合溶液;g‑C3N4溶解乙醇中超声处理,Zn(NO3)2·6H20,In(NO3)3·4.5H2O,L‑Cysteine溶于丙三醇和金胶体混合液中,和g‑C3N4溶液混合进行吸附,得ZnIn2S4/Au/g‑C3N4前驱体溶液;于水热反应釜加热反应,真空冷冻干燥得粉末状的硫铟锌/金/氮化碳二维层状复合光催化剂。本发明原材料易得,一釜合成,可靠性强,操作简便,催化剂在可见光区具有较强的光催化活性,有广泛的应用前景。
Description
技术领域
本发明涉及一种硫铟锌金氮化碳二维层状复合光催化剂的制备方法。
背景技术
1972年,日本东京大学的Fujishima和Honda在实验中发现,在TiO2光电极上可以直接分解水来制取氢气,在这之后,利用TiO2在紫外光的照射下进行光催化降解有机污染物也取得了非常大的进展。半导体光催化技术表现出巨大的应用前景。为进一步拓宽光催化材料的利用范围,并在可见光的照射下对有机物进行降解,金属硫化物被广泛运用于可见光的光催化反应中,这是因为其禁带较窄,可在较大范围内吸收太阳光中的可见光部分,但硫化物也普遍存在光腐蚀现象,导致其使用寿命被大大缩短。
为了解决这一问题,通过三元硫化物ZnIn2S4与g-C3N4复合形成的异质结可有效分离光生电子与空穴,增强材料的抗光腐蚀能力。中国专利申请201510010704.1公开了一种氮化碳/硫铟锌(ZnIn2S4/g-C3N4)复合纳米材料及其制备方法。其中,ZnIn2S4/g-C3N4中六方相的ZnIn2S4以大的球状存在,层片状的g-C3N4复合在其表面,其实际接触面积有限,提供的电子转移位点较少。
CN107159288A公开了一种氮化碳基复合纳米材料的制备方法,所述氮化碳基复合纳米材料为硫铟锌/氮化碳/氧化石墨烯复合纳米材料,CdIn2S4纳米立方体与g-C3N4纳米片、石墨烯薄片结合在一起,它采用一步水热法制备氮化碳基复合纳米材料,称取g-C3N4粉体与氧化石墨烯片溶于去离子水中并超声分散,在搅拌的情况下依次加入Cd(NO3)2·4H2O,In(NO3)3·4.5H2O,搅拌均匀后依次加入巯基乙酸溶液(C2H5NS)与Na2S溶液,再次搅拌后将反应液转移到内衬为聚四氟乙烯的反应釜中,水热反应,得到的产物洗净、离心、烘干得到硫铟锌/氮化碳/氧化石墨烯复合纳米材料。
迄今为止,尚无ZnIn2S4/Au/g-C3N4二维层状复合材料的报道。
发明内容
本发明目的在于提供一种原材料易得,一釜合成,可靠性强,操作简便,所制备的催化剂在可见光区具有较强的光催化活性,应用广泛的硫铟锌金氮化碳二维层状复合光催化剂的制备方法。
本发明目的的实现方式为,一种硫铟锌金氮化碳二维层状复合光催化剂的制备方法,具体步骤如下:
1)取7.3525g的C6H5Na3O7·2H2O溶解于50mL去离子水中,搅拌30min;
2)取2.5mL 0.01M/L的HAuCl4,稀释至100mL,加热至沸腾后加入步骤1)配制的柠檬酸钠溶液200uL,保持沸腾15min,恢复体积至100mL,冷却至室温,得到稳定的金胶体混合溶液;
3)将0.5g g-C3N4溶解到52.5mL乙醇中超声30min;
超声条件:超生频率为40kHz,超声功率为150W;
4)将0.0176-0.1232g Zn(NO3)2·6H20,0.0045-0.0315g In(NO3)3·4.5H2O,0.0572-0.4004g L-Cysteine溶于17.5mL丙三醇和10mL步骤2)所得的金胶体混合溶液中,然后搅拌15min;
5)将步骤3),4)所得的两个溶液混合后搅拌30min,使g-C3N4吸附游离的离子和L-Cysteine分子,得到ZnIn2S4/Au/g-C3N4的前驱体溶液;
6)将步骤5)所得前驱体溶液转入100mL含聚四氟乙烯内衬的不锈钢水热反应釜中,在160-200℃下反应20-26h,获得粉末状样品;
7)将步骤6)获得的粉末状样品取出,分别用酒精和去离子水清洗数次,真空冷冻干燥获得粉末状ZnIn2S4/Au/g-C3N4二维层状复合光催化剂;
真空冷冻干燥条件:-40℃预冻4h,真空度5Pa,真空干燥6h;
所得ZnIn2S4/Au/g-C3N4二维层状复合催化剂中g-C3N4与ZnIn2S4的质量比为1:0.05-0.35。
本发明以L型半胱氨酸作为硫源,通过生物分子半胱氨酸表面丰富的官能团与金属离子、Au胶体以及g-C3N4的交互作用,使得ZnIn2S4以层片状生长在层片状g-C3N4表面,形成一种二维复合结构,大大增加了接触面积,为反应提供了更多电子转移位点,并且金粒子作为一种良好的电子传导体可以进一步增加光催化效率。
本发明原材料易得,一釜合成,可靠性强,操作简便;本发明所制备的ZnIn2S4/Au/g-C3N4二维层状复合催化剂在可见光区具有较强的光催化活性;可在环境污染治理,太阳能的利用,水解制氢等方面应用,有广泛的应用前景。
附图说明
图1为实施例1中复合光催化剂的扫描电子显微镜照片;
图2为实施例3中复合光催化剂的扫描电子显微镜照片;
图3为实施例3中复合光催化剂的透射电子显微镜照片;
图4为实施例1-4中复合光催化剂对甲基橙降解性能测试图。
具体实施方式
下面用具体实施例详述本发明。
实施例1
1)取7.3525g的C6H5Na3O7·2H2O溶解于50mL去离子水中,搅拌30min;
2)取2.5mL 0.01M/L的HAuCl4,稀释至100mL,加热至沸腾后加入步骤1)配制的柠檬酸钠溶液200uL,保持沸腾15min,恢复体积至100mL,冷却至室温,得到稳定的金胶体混合溶液;
3)将0.5g g-C3N4溶解到52.5mL乙醇中超声30min;
超声条件:超生频率为40kHz,超声功率为150W;
4)将0.0176g Zn(NO3)2·6H20,0.0045g In(NO3)3·4.5H2O,0.0572g L-Cysteine溶于17.5mL丙三醇和10mL步骤2)所得的金胶体混合溶液中,然后搅拌15min;
5)将步骤3),4)所得的两个溶液混合后搅拌30min,使g-C3N4吸附游离的离子和L-Cysteine分子,得到ZnIn2S4/Au/g-C3N4的前驱体溶液;
6)将步骤5)所得前驱体溶液转入100ml含聚四氟乙烯内衬的不锈钢水热反应釜中,在180℃下反应24h,获得粉末状样品。
7)将步骤6)获得的粉末状样品取出,分别用酒精和去离子水清洗数次,真空冷冻干燥获得粉末状ZnIn2S4/Au/g-C3N4二维层状复合催化剂。
真空冷冻干燥条件:-40℃预冻4h,真空度5Pa,真空干燥6h。
本实施例所制备的ZnIn2S4/Au/g-C3N4二维层状复合催化剂中g-C3N4与ZnIn2S4的质量比为1:0.05。ZnIn2S4/Au/g-C3N4二维层状复合催化剂的扫描电镜照片见图1。
实施例2,同实施例1,不同的是,
4)将0.0528g Zn(NO3)2·6H20,0.0135g In(NO3)3·4.5H2O,0.1716g L-Cysteine溶于17.5mL丙三醇和10mL步骤2)所得的金胶体混合溶液中,然后搅拌15min;
5)将步骤3),4)所得的两个溶液混合后搅拌30min,使g-C3N4吸附游离的离子和L-Cysteine分子,得到ZnIn2S4/Au/g-C3N4的前驱体溶液;
6)将步骤5)所得前驱体溶液转入100mL含聚四氟乙烯内衬的不锈钢水热反应釜中,在180℃下反应24h,获得粉末状样品。
夲实施例所制备的ZnIn2S4/Au/g-C3N4二维层状复合催化剂中g-C3N4与ZnIn2S4的质量比为1:0.15。
实施例3,同实施例1,不同的是,
4)将0.088g Zn(NO3)2·6H20,0.0225g In(NO3)3·4.5H2O,0.286g L-Cysteine溶于17.5mL丙三醇和10mL步骤2)所得的金胶体混合溶液中,然后搅拌15min;
5)将步骤3),4)所得的两个溶液混合后搅拌30min,使g-C3N4吸附游离的离子和L-Cysteine分子,得到ZnIn2S4/Au/g-C3N4的前驱体溶液;
6)将步骤5)所得前驱体溶液转入100mL含聚四氟乙烯内衬的不锈钢水热反应釜中,在160℃下反应26h,获得粉末状样品。
本实施例所制备的ZnIn2S4/Au/g-C3N4二维层状复合催化剂中g-C3N4与ZnIn2S4的质量比为1:0.25。粉末状ZnIn2S4/Au/g-C3N4二维层状复合催化剂的扫描电镜照片见图2,透射电镜照片见图3。
实施例4,同实施例1,不同的是,
4)将0.1232g Zn(NO3)2·6H20,0.0315g In(NO3)3·4.5H2O,0.4004g L-Cysteine溶于17.5mL丙三醇和10mL步骤2)所得的金胶体混合溶液中,然后搅拌15min;
5)将步骤3),4)所得的两个溶液混合后搅拌30min,使g-C3N4吸附游离的离子和L-Cysteine分子,得到ZnIn2S4/Au/g-C3N4的前驱体溶液;
6)将步骤5)所得前驱体溶液转入100mL含聚四氟乙烯内衬的不锈钢水热反应釜中,在200℃下反应20h,获得粉末状样品。
本实施例所制备的ZnIn2S4/Au/g-C3N4二维层状复合催化剂中g-C3N4与ZnIn2S4的质量比为1:0.35。
从图1的扫描电镜照片中观察到了层片状的g-C3N4,图2的ZnIn2S4/Au/g-C3N4的扫描电镜照片相比于图1,明显发现了g-C3N4表面形成了层片状的ZnIn2S4,而在图3的ZnIn2S4/Au/g-C3N4的透射电镜照片中还观察到了层状结构中金粒子的存在,因此说明了本发明层状二维结构的成功构成。
本申请人以300W氙灯作为光源,400nm波长的截止片将光辐照控制在可见光区域,对甲基橙(MO)进行降解。催化剂选用实施例1、2、3、4所制备的粉末ZnIn2S4/Au/g-C3N4复合催化剂样品。
方法如下:分别称取100mg实施例1、2、3、4所制备的ZnIn2S4/Au/g-C3N4复合催化剂,置于100ml浓度为10mg/L的甲基橙水溶液中,在光催化反应器中进行实验。在光照之前,将体系置于暗箱中搅拌30min,达到吸附平衡,取2mL溶液,采用紫外-可见光分光光度计测试其浓度,并作为光反应初始浓度。然后打开光源并每隔5min取样,用紫外-可见分光光度计进行检测。检测结果如图4所示。
从图4可见,在波长大于400nm的可见光照射20min之后,实施例1所制备的ZnIn2S4/Au/g-C3N4二维层状复合催化剂对甲基橙溶液的降解率只有了43.3%,实施例2所制备的ZnIn2S4/Au/g-C3N4二维层状复合催化剂的降解率为82.5%,实施例3所制备的ZnIn2S4/Au/g-C3N4二维层状复合催化剂对甲基橙溶液的降解率达到了99.4%,实施例4所制备的ZnIn2S4/Au/g-C3N4二维层状复合催化剂对甲基橙溶液的降解率为96.5%,说明用本发明制备的ZnIn2S4/Au/g-C3N4复合催化剂对甲基橙具有显著的降解效果,二维层状结构的构建确实对光催化性能带来了很大的提升,而其中以实施例2所制备的ZnIn2S4/Au/g-C3N4样品,即g-C3N4与ZnIn2S4的质量比为1:0.25的ZnIn2S4/Au/g-C3N4二维层状复合催化剂效果最佳。
Claims (2)
1.一种硫铟锌金氮化碳二维层状复合光催化剂的制备方法,其特征在于:具体步骤如下:
1)取7.3525g的C6H5Na3O7·2H2O溶解于50mL去离子水中,搅拌30min;
2)取2.5mL 0.01M/L的HAuCl4,稀释至100mL,加热至沸腾后加入步骤1)配制的柠檬酸钠溶液200uL,保持沸腾15min,恢复体积至100mL,冷却至室温,得到稳定的金胶体混合溶液;
3)将0.5g g-C3N4溶解到52.5mL乙醇中超声30min;
超声条件:超生频率为40kHz,超声功率为150W;
4)将0.0176-0.1232g Zn(NO3)2·6H2O ,0.0045-0.0315g In(NO3)3·4.5H2O,0.0572-0.4004g L-Cysteine溶于17.5mL丙三醇和10mL步骤2)所得的金胶体混合溶液中,然后搅拌15min;
5)将步骤3),4)所得的两个溶液混合后搅拌30min,使g-C3N4吸附游离的离子和L-Cysteine分子,得到ZnIn2S4/Au/g-C3N4的前驱体溶液;
6)将步骤5)所得前驱体溶液转入100mL含聚四氟乙烯内衬的不锈钢水热反应釜中,在160-200℃下反应20-26h,获得粉末状样品;
7)将步骤6)获得的粉末状样品取出,分别用酒精和去离子水清洗数次,真空冷冻干燥获得粉末状ZnIn2S4/Au/g-C3N4二维层状复合光催化剂;
真空冷冻干燥条件:-40℃预冻4h,真空度5Pa,真空干燥6h;
所得ZnIn2S4/Au/g-C3N4二维层状复合催化剂中g-C3N4与ZnIn2S4的质量比为1:0.05-0.35。
2.根据权利要求1所述的一种硫铟锌金氮化碳二维层状复合光催化剂的制备方法,其特征在于:ZnIn2S4/Au/g-C3N4二维层状复合催化剂中g-C3N4与ZnIn2S4的质量比为1:0.25。
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