CN116037215A - 铜金属掺杂氮化碳光芬顿催化过滤膜及其制备方法与应用 - Google Patents
铜金属掺杂氮化碳光芬顿催化过滤膜及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种铜金属掺杂氮化碳光芬顿催化过滤膜及其制备方法与应用,涉及催化过滤膜技术领域。本发明在N2氛围下制备出铜金属掺杂的Cu‑g‑C3N4光催化剂,经检测可知,催化剂内不含有相应金属的氧化物,金属通过与g‑C3N4中的N元素形成配位键存在于光催化剂中。对g‑C3N4进行金属掺杂制备出的Cu‑g‑C3N4光催化剂,相比g‑C3N4具有更小的禁带宽度,金属掺杂增强了对可见光的吸收。经6.165 mmol Cu元素掺杂制备的CuCN4对高浓度SMT具有比较明显的光芬顿降解性能。同时本发明将粉体催化剂固定在PTFE支撑基底上,提高了粉体材料的利用效果。
Description
技术领域
本发明涉及催化过滤膜技术领域,尤其涉及一种铜金属掺杂氮化碳光芬顿催化过滤膜及其制备方法与应用。
背景技术
以药品及个人护理品(pharmaceutical and personal care products,PPCPs)为代表的有机微量污染物对生态系统和人类健康造成了潜在的威胁,例如破坏若干生物过程、抑制发育和繁殖过程以及引起抗性基因的传播等。现有水相污染物多采用吸附和催化两种方法处理,吸附法产生大量的固体废物,催化法目前的材料催化效率低,需要昂贵的牺牲试剂。
g-C3N4是一种主要含有C和N的非金属半导体材料,与其他氮化碳材料相比具有优异的稳定性,g-C3N4可通过氰胺、双氰胺、三聚氰胺、硫脲和尿素等在相应温度下经热缩合反应制备出来,g-C3N4在约600℃下稳定,禁带宽度大约为2.7eV,因此能在可见光激发下产生光生电子和空穴。
g-C3N4根据基本结构单元主要分为三嗪环(C3N3)和3-s-三嗪环(C6N7)两种结构,三嗪环(C3N3)结构主要是C和N元素构成单环,这些单环上的C原子与N原子通过共价键连接形成共轭π键结构;3-s-三嗪环主要是C和N元素连接组成由三个环连接而成的基本结构单元,然后这些基本结构单元再经N原子通过共价键和环上的C原子连接起来,形成共轭π键;上述两种结构单元再经层间堆积方式,通过层间作用力形成g-C3N4,其中3-s-三嗪环(C6N7)结构相比三嗪环(C3N3)具有更好的热稳定性。
发明内容
本发明提供了一种铜金属掺杂氮化碳光芬顿催化过滤膜及其制备方法与应用,通过金属掺杂策略将Cu元素掺杂到g-C3N4中制备出Cu-g-C3N4光催化剂以及水相过滤膜,从而克服目前催化剂效率低的问题。
为实现此技术目的,本发明采用如下方案:
铜金属掺杂氮化碳光芬顿催化过滤膜的制备方法,按如下步骤进行:
S1、制备粉体Cu-g-C3N4材料:
S1-1、称取双氰胺和CuCl2并置于容器中,并添加去离子水加热搅拌,之后将容器内材料烘干,烘干后材料进行煅烧;
S1-2、煅烧后的材料研磨成粉,得到Cu-g-C3N4光催化剂,简写为CuCNx光催化剂,x为≥1的正整数,x的数值取决于Cu元素的加入量,x=Cu元素实际添加量/1.541mmol;
S2、制备Cu-g-C3N4/PTFE膜材料:
S2-1、将制备好的Cu-g-C3N4光催化剂放入离心管中,然后加入无水乙醇、无离子水和全氟磺酸离子交换树脂分散液,摇晃离心管使Cu-g-C3N4光催化剂、溶液分散均匀;
S2-2、用无水乙醇冲洗后的PTFE膜放在砂芯漏斗上,将离心管内分散好的混合物倒在砂芯漏斗的PTFE膜上,进行真空抽滤,最后取下负载光催化剂的PTFE膜烘干,得到Cu-g-C3N4/PTFE过滤膜。
与现有技术相比,本发明的有益效果在于:本发明在N2氛围下制备出啊金属掺杂的CuCNx光催化剂,经检测可知,催化剂内不含有相应金属的氧化物,金属通过与g-C3N4中的N元素形成配位键存在于光催化剂中。对g-C3N4进行金属掺杂制备出的CuCNx光催化剂,相比g-C3N4具有更小的禁带宽度,金属掺杂增强了对可见光的吸收。经6.165 mmol Cu元素掺杂制备的CuCN4对高浓度SMT具有比较明显的光芬顿降解性能。同时本发明将粉体催化剂固定在PTFE支撑基底上,提高了粉体材料的利用效果。
本发明的优选方案为:
S1-1中双氰胺、CuCl2和去离子水的质量比为5:(0.2070~0.8280):100。
S1-1中加热搅拌时温度为80℃,搅拌时间为2.5h。
S1-1中煅烧在N2氛围下进行,由室温升至550℃,升温速率为2℃/min,并在550℃下保温4h。
S1-2中研磨先采用研钵研磨成粉末,再用球磨机进行3次球磨,球磨机设置转速为600rpm/min,每次球磨时间为14min。
S2-1中光催化剂、无水乙醇、去离子水和全氟磺酸离子交换树脂分散液的用量比为15mg:15mL:2mL:200μL。
S1-1和S2-2的烘干温度均为60℃。
上述方法制备得到铜金属掺杂氮化碳光芬顿催化过滤膜,并将其应用在药品及个人护理品,有机微量污染物水相中,尤其是磺胺二甲氧嘧啶,提高了催化效率。
附图说明
图1为本发明实施例1-4提供的光催化剂的PXRD图;
图2为本发明实施例1-4提供的光催化剂的红外图;
图3为本发明实施例1-4提供的光催化剂光芬顿降解SMT的去除效果图,为了清楚显示曲线含义,在此进行说明:横坐标X=60时,对应的纵坐标所在由上至下分别表示H2O2+light、g-C3N4+H2O2+light、CuCN1+H2O2+light、CuCN2+H2O2+light、CuCN3+H2O2+light、CuCN4+H2O2+light,时间t=30min时开启光照(light on),Ct为t时间浓度,C0为初始浓度;
图4为本发明实施例1-4提供的光催化剂光芬顿降解SMT的动力学拟合图,图4中正方形标记线代表CuCN4+H2O2+light实验条件,圆形标记线代表CuCN3+H2O2+light实验条件,上三角形标记线代表CuCN2+H2O2+light实验条件,下三角形标记代表CuCN1+H2O2+light实验条件,五边形标记线代表g-C3N4+H2O2+light实验条件,菱形标记线代表H2O2+light实验条件,Ct为t时间浓度,C0为初始浓度;
图5为本发明提供CuCN4/PTFE过滤膜对SMT的降解率。
具体实施方式
为充分了解本发明之目的、特征及功效,借由下述具体的实施方式,对本发明做详细说明,但本发明并不仅仅限于此。
实施例1
铜金属掺杂氮化碳光芬顿催化过滤膜的制备方法,按如下步骤进行:
S1、制备粉体CuCN1材料:
S1-1、称取5g双氰胺和0.2070g(1.541mmol)CuCl2并置于500mL烧杯中,并在烧杯中添加100mL去离子水,在80℃条件下加热搅拌2.5h,烧杯中溶液量明显减少,之后将烧杯放在60℃烘箱中烘干烧杯内产物。
将烘干后材料放入管式炉中进行煅烧:取5g烘干后材料放在陶瓷坩埚中,把陶瓷坩埚放到管式炉中,在N2氛围下设置升温速率为2℃/min,从室温升到550℃,并在550℃下保温4h,然后冷却至室温。
S1-2、将冷却后的烧断材料用研钵研磨成粉末,再用球磨机对粉末材料进行3次球磨,球磨机设置转速为600rpm/min,每次球磨时间为14min,球磨后收集该材料,记为CuCN1光催化剂。
S2、制备CuCN1/PTFE膜材料:
S2-1、将15mg制备好的CuCN1光催化剂放入50mL离心管中,然后加入15mL无水乙醇、2mL无离子水和200μL全氟磺酸离子交换树脂分散液(质量浓度为5%,Nafion溶液D520,),盖好离心管盖子并摇晃离心管使CuCN1光催化剂、溶液分散均匀。
S2-2、用无水乙醇冲洗数次后的PTFE膜放在砂芯漏斗上,砂芯漏斗安装好,接上真空泵,将离心管内分散好的混合物倒在砂芯漏斗的PTFE膜上,进行真空抽滤,抽滤一段时间待溶液几乎没有后关闭真空泵,最后取下负载光催化剂的PTFE膜放在60℃烘箱烘干,得到CuCN1/PTFE过滤膜。
实施例2中CuCl2用量为0.4140g(3.083mmol),其他参数和条件与实施例1相同,得到的光催化剂记为CuCN2,得到过滤膜记为CuCN2/PTFE过滤膜。
实施例3中CuCl2用量为0.6217g(4.624mmol),其他参数和条件与实施例1相同,得到的光催化剂记为CuCN3,得到过滤膜记为CuCN3/PTFE过滤膜。
实施例4中CuCl2用量为0.8280g(6.165mmol),其他参数和条件与实施例1相同,得到的光催化剂记为CuCN4,得到过滤膜记为CuCN4/PTFE过滤膜。
分别对实施例1-4的CuCN1、CuCN2、CuCN3、CuCN4光催化剂及标准g-C3N4药剂进行PXRD检测,结果如图1所示。分析可知,本项发明中g-C3N4在大约13.1°和27.4°分别有两个峰(图1),这两个峰分别是(100)和(002)的两个衍射峰,其中(100)衍射峰对应于三嗪单元的平面内结构堆积基序,(002)衍射峰对应CN芳基的层间堆积,与标准卡片(JCPDS 87-1526)一致,说明成功制备出g-C3N4,并且CuCN1、CuCN2、CuCN3、CuCN4的衍射峰与g-C3N4一致,说明成功制备出Cu元素掺杂的CuCN1、CuCN2、CuCN3和CuCN4,并且金属掺杂不改变g-C3N4的晶体结构。此外,据图1可得,CuCNx中不存在CuO和Cu2O的衍射峰,说明CuCNx中不含有CuO和Cu2O。与原始标准g-C3N4相比可看出随Cu元素的掺杂以及掺杂量的增多,CuCNx的(100)和(002)衍射峰强度减弱,这是因为金属掺杂影响了双氰胺的热缩合反应,导致晶面结晶度降低。
分别对实施例1-4的CuCN1、CuCN2、CuCN3、CuCN4光催化剂及标准g-C3N4药剂进行红外谱图检测,结果如图2所示。在g-C3N4的红外谱图中,808 cm-1对应三嗪结构的简正振动,1240 cm-1对应C-N键的伸缩振动,1640 cm-1对应C=N键的伸缩振动,3180 cm-1对应N-H键的伸缩振动。由红外谱图可得,Cu元素掺杂后制备的CuCN1、CuCN2、CuCN3和CuCN4与g-C3N4红外谱图一致,具有相同的红外基团,说明Cu元素掺杂并不改变g-C3N4的特征基团。
分别使用CuCN1、CuCN2、CuCN3、CuCN4光催化剂及标准g-C3N4药剂采用光芬顿法降解磺胺二甲氧嘧啶(SMT),去除效果如图3所示,降解动力学模型拟合如图4所示。
图3显示H2O2在光照下以及g-C3N4和CuCN1、CuCN2、CuCN3、CuCN4在模拟太阳光及H2O2作用下对SMT的光芬顿降解率分别是11%、23%、34%、41%、42%、61%,据结果可得,经Cu掺杂制备的CuCNx比g-C3N4具有更高的SMT去除率,并且随Cu掺杂量的增多,光芬顿降解性能也随之提升,其中CuCN4对SMT具有最高的去除率,这是由于Cu作为光芬顿反应的催化位点,掺杂量增多则催化位点也增多,产生更多的强氧化性自由基来降解SMT。由图4可知,Cu掺杂后的CuCNx对SMT具有更快的去除速率,而且随Cu掺杂量的增多,去除速率也随之提高,其中CuCN4的去除速率是g-C3N4的3倍。
使用CuCN4/PTFE过滤膜结合光芬顿法降解SMT,具体条件为:磺胺二甲氧嘧啶的初始浓度为C0=20mg/L,反应溶液体积VSMT=80mL,投加过氧化氢体积VH2O2=75μL,数据如图5所示,CuCN4/PTFE膜对SMT溶液进行光芬顿降解时,降解率随时间的增长而提高,在经2小时的光芬顿降解后,光芬顿体系对80mL浓度为20ppm的SMT达到84 %的去除率。
最后,需要注意的是:以上列举的仅是本发明的优选实施例,当然本领域的技术人员可以对本发明进行改动和变型,倘若这些修改和变型属于本发明权利要求及其等同技术的范围之内,均应认为是本发明的保护范围。
Claims (9)
1.一种铜金属掺杂氮化碳光芬顿催化过滤膜的制备方法,其特征在于,按如下步骤进行:
S1、制备粉体Cu-g-C3N4材料:
S1-1、称取双氰胺和CuCl2并置于容器中,并添加去离子水加热搅拌,之后将容器内材料烘干,烘干后材料进行煅烧;
S1-2、煅烧后的材料研磨成粉,得到Cu-g-C3N4光催化剂;
S2、制备Cu-g-C3N4/PTFE膜材料:
S2-1、将制备好的Cu-g-C3N4光催化剂放入离心管中,然后加入无水乙醇、无离子水和全氟磺酸离子交换树脂分散液,摇晃离心管使Cu-g-C3N4光催化剂、溶液分散均匀;
S2-2、用无水乙醇冲洗后的PTFE膜放在砂芯漏斗上,将离心管内分散好的混合物倒在砂芯漏斗的PTFE膜上,进行真空抽滤,最后取下负载光催化剂的PTFE膜烘干,得到Cu-g-C3N4/PTFE过滤膜。
2.根据权利要求1所述的铜金属掺杂氮化碳光芬顿催化过滤膜的制备方法,其特征在于,S1-1中双氰胺、CuCl2和去离子水的质量比为5:(0.2070~0.8280):100。
3.根据权利要求1所述的铜金属掺杂氮化碳光芬顿催化过滤膜的制备方法,其特征在于,S1-1中加热搅拌时温度为80℃,搅拌时间为2.5h。
4.根据权利要求1所述的铜金属掺杂氮化碳光芬顿催化过滤膜的制备方法,其特征在于,S1-1中煅烧在N2氛围下进行,由室温升至550℃,升温速率为2℃/min,并在550℃下保温4h。
5.根据权利要求1所述的铜金属掺杂氮化碳光芬顿催化过滤膜的制备方法,其特征在于,S1-2中研磨先采用研钵研磨成粉末,再用球磨机进行3次球磨,球磨机设置转速为600rpm/min,每次球磨时间为14min。
6.根据权利要求1所述的铜金属掺杂氮化碳光芬顿催化过滤膜的制备方法,其特征在于,S2-1中光催化剂、无水乙醇、去离子水和全氟磺酸离子交换树脂分散液的用量比为15mg:15mL:2mL:200μL。
7.根据权利要求1所述的铜金属掺杂氮化碳光芬顿催化过滤膜的制备方法,其特征在于,S1-1和S2-2的烘干温度均为60℃。
8.一种权利要求1-7任一项所述的铜金属掺杂氮化碳光芬顿催化过滤膜的制备方法得到的铜金属掺杂石墨相氮化碳光芬顿催化过滤膜。
9.一种权利要求8所述的铜金属掺杂氮化碳光芬顿催化过滤膜在药品及个人护理品有机微量污染物水相中的应用。
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