CN114984949A - 一种基于钯金属复合双面电催化膜及过滤活化过氧单硫酸盐用于处理微污染物废水的方法 - Google Patents
一种基于钯金属复合双面电催化膜及过滤活化过氧单硫酸盐用于处理微污染物废水的方法 Download PDFInfo
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Abstract
一种基于钯金属复合双面电催化膜及过滤活化过氧单硫酸盐用于处理微污染物废水的方法,它涉及微污染物废水处理的技术领域。本发明要解决目前电活化PMS氧化体系中PMS的反应速率和电能利用效率低的问题。本发明采用纯度大于或等于99.95%的钯(Pd)金属靶体作为金属纳米粒子供体,在超纯氩气氛围,溅射Pd纳米粒子于陶瓷膜基底的两面,陶瓷膜两面溅射Pd的厚度为10nm~50nm,获得Pd金属复合双面电催化膜(PdCM)。相比于其他的电过滤体系,PMS/PdCM电过滤体系对微污染物去除效率高,且电能耗极低。其扩展了电催化膜的水净化过滤策略,具有较大水处理应用前景。
Description
技术领域
本发明涉及微污染物废水处理的技术领域。具体地,涉及一种基于钯金属复合双面电催化膜及过滤活化过氧单硫酸盐用于处理微污染物废水的方法。
背景技术
近年来,人类生产生活产生的废物排放导致环境水体与饮用水源中重金属、染料、抗生素、农药、多环芳烃等微污染物不断增多,对生态环境安全和人类健康造成严重威胁。由于微污染物含量少,但有毒、有害、难降解的特点,通过传统水处理工艺往往难以去除。因此开发了多种先进的水处理技术,包括吸附、氧化、膜处理等。在这些处理工艺中,高级氧化工艺(AOPs)可以有效地将有毒有害有机物转化为可生物降解的无毒有机物。
过氧单硫酸盐(PMS)是强氧化剂,基于PMS活化的AOPs会产生一些活性物种,如自由基(羟基自由基和硫酸根自由基)和单线态氧,可有效去除废水中的微污染物。传统的过硫酸盐活化方法包括金属离子活化、紫外线辐射、碱活化和热活化,但这些方法存在能耗高、金属离子浸出造成二次污染等缺点。
针对这一问题,PMS的电化学活化已被开发出来,它是一种能耗低、环境友好、回收性能高的方法。在电解过程中,阴极和阳极都能激活PMS产生活性物种。相比于传统静态批式电催化反应体系,电催化膜可以实现“流通式”电催化模式(即对流传输垂直于电极表面)和膜孔空间限域效应,从而增强电荷转移和传质,提高电化学反应速率。进一步地,耦合正负极电反应能于膜内的方式,可以进一步提高电催化膜电活化PMS时对于电能的利用,从而进一步提高反应速率和电能利用效率。因此,PMS/双面复合电催化膜的电过滤体系,在微污染物去除这一水处理领域展现出很大应用潜力。
发明内容
本发明提供一种基于钯金属复合双面电催化膜及过滤活化过氧单硫酸盐用于处理微污染物废水的方法。以解决目前电活化PMS氧化体系中PMS的反应速率和电能利用效率低的问题。
本发明的一种钯金属复合双面电催化膜的制备方法,它是按照以下方式进行的:
采用纯度大于或等于99.95%的钯(Pd)金属靶体作为金属纳米粒子供体,在超纯氩气氛围,溅射Pd纳米粒子于陶瓷膜基底的两面,陶瓷膜两面溅射Pd的厚度为10nm~50nm,获得Pd金属复合双面电催化膜。
进一步地,溅射Pd纳米粒子于陶瓷膜基底的两面操作为:将陶瓷膜基底放置于硅支架上,陶瓷膜活性面面向Pd靶体,随后,将陶瓷膜倒置于硅支架上,陶瓷膜的基底面面向Pd靶体,以Pd溅射功率为25~35W,沉积速率为2~3nm min-1的条件进行溅射。
进一步地,所述的超纯氩气氛围为通入超纯氩气,使得溅射室的工作压力为0.2~0.4 Pa。
本发明的一种钯金属复合双面电催化膜的应用,它作为电过滤体系在去除水体微污染物中的应用,所述的电过滤体系含有0.5~2mmol·L-1的过氧单硫酸盐。
进一步地,所述的水体中微污染物的浓度为5~50μmol·L-1。
进一步地,所述的微污染物是指亚甲基蓝、磺胺甲恶唑、苯酚、4-氯苯酚或双酚-A。
进一步地,去除水体微污染物中的水力驱动压力为0.1~0.2bar。
进一步地,去除水体微污染物中,钯金属复合双面电催化膜的面向原料液侧和滤出液侧分别与直流电源相连作为阴极和阳极。
进一步地,去除水体微污染物中,钯金属复合双面电催化膜的两极电压为恒电压,电压为1.2V~2.5V。
进一步地,所述的电压为1.6V~2.0V。
优选地,陶瓷膜两面溅射Pd的厚度为20nm~40nm,更优选的陶瓷膜两面溅射Pd 的厚度为30nm。
优选地,采用共聚焦磁控溅射仪进行磁控溅射Pd纳米粒子。
优选地,Pd的沉积厚度通过位于溅射腔室中央的石英测厚仪调控。
优选地,所采用的微污染物是亚甲基蓝,浓度为10μmol L-1。
优选地,所采用的电催化膜滤以错流模式进行驱动。电过滤时采用齿轮泵提供0.1bar 的超低水力驱动压力。
本发明所述的一种PMS/双面复合电催化膜的电过滤体系,通过耦合正负极电反应能于膜内,可以进一步提高电催化膜电活化PMS时对于电能的利用,从而进一步提高反应速率和电能利用效率,并且,与基于自由基的氧化方式相比,本发明的非自由基介导的氧化途径(如单线态氧和直接电子转移),不受水体中自由基猝灭剂(如天然有机物和无机阴离子)的影响,因此在复杂的水质条件下能表现出高且稳定的微污染物去除性能。PMS/ 双面复合电催化膜的电过滤体系在处理含微污染物的各类废水中具有很大应用潜力。
本发明以陶瓷膜为基底,分别在膜两面喷涂高度分散的钯(Pd)金属纳米粒子,在膜孔内不同区域分别构建了两个具有一定深度的电催化活性功能区。在电过滤中,钯金属复合双面电催化膜(PdCM)通过增强电子转移和传质、放大空间限域效应,快速电活化 PMS,从而实现高效、超快速降解水中微污染物的效果。与现有的基于PMS活化的AOPs 相比,本发明基于电催化膜过滤活化PMS,在电过滤中,PdCM通过最大限度地利用非自由基介导的PMS氧化(包括单线态氧和直接电子转移),快速电活化PMS,从而实现高效、超快速降解水中微污染物的效果。水体净化效果稳定,并且复合膜易回收。此外,本发明的电过滤体系对微污染物去除效率高,且电能耗极低。
附图说明
图1为本发明实施例1中获得的Pd金属复合双面电催化膜(PdCM)的Pd活性面-1 侧(即:面向原料液侧)的膜截面的扫描电镜照片(左图)和对应Pd元素的X射线能谱分析(EDSmapping)图(右图);
图2为本发明实施例1中获得的PdCM的Pd活性面-2侧(即:面向滤出液侧)的膜截面的扫描电镜照片(左图)和对应Pd元素的EDS mapping图(右图);
图3为本发明实施例1中获得的PdCM的Pd活性面-1的X射线光电子能谱(XPS) 图;
图4为本发明实施例1中获得的PdCM的Pd活性面-2的XPS图;
图5为本发明实施例2中PMS/PdCM电过滤体系装置示意图;
图6为本发明实施例2中电过滤过程中PdCM的结构示意图;
图7为本发明实施例3中微污染物去除效果图。所采用的微污染物有亚甲基蓝、磺胺甲恶唑、苯酚、4-氯苯酚、双酚-A;
图8为本发明实施例3中微污染物亚甲基蓝经过8个电过滤周期后的去除率;
图9为本发明实施例3中将PMS/PdCM电过滤体系与现有的电过滤体系在微污染物去除和电能耗两方面的对比图;
图10为本发明实施例3中不同猝灭剂对PMS/PdCM电过滤体系中亚甲基蓝去除的影响。所采用的猝灭剂有叔丁醇、糠醇、乙醇;
图11为本发明实施例3中采用电化学工作站计时电流法,测量电过滤体系中PdCM活性面-1加入PMS、亚甲基蓝后的电流密度变化。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚明白,下面将详细叙述本发明所揭示内容的精神,任何所属技术领域技术人员在了解本发明内容的实施例后,当可由本发明内容所教示的技术,加以改变及修饰,其并不脱离本发明内容的精神与范围。
本发明的示意性实施例及其说明用于解释本发明,但并不作为对本发明的限定。
实施例1
本实施例的一种钯金属复合双面电催化膜(PdCM)的制备方案,包含以下内容:
采用共聚焦磁控溅射仪进行PdCM的制备。其中,采用纯度大于或等于99.95%的钯(Pd)靶体作为金属纳米粒子供体。采用陶瓷膜作为催化膜基底,其主要成分为二氧化钛和二氧化锆,截留分子量为300kDa。
溅射制备前,陶瓷膜基底的侧面采用封口膜缠绕覆盖,以避免溅射制备时Pd金属粒子溅射至膜侧面而造成两个电活性面的外侧导电连通。
溅射制备时,首先使用超纯氩气提供0.3Pa的工作压力,以消除溅射室中可能存在的污染。在超纯氩气氛围,依次溅射Pd纳米粒子于陶瓷膜基底的两面,即:陶瓷膜首先被放置于硅支架上,陶瓷膜活性面(即:过滤时面向原料液侧的表面)面向Pd靶体。随后,将陶瓷膜倒置于硅支架上,则陶瓷膜的基底面(即:过滤时面向透过液侧的表面)面向 Pd靶体。Pd溅射功率为30W,沉积速率为2.1nm min-1。Pd的沉积厚度通过位于溅射腔室中央的石英测厚仪调控。
当PdCM的溅射厚度(即:膜制备时磁控溅射Pd在陶瓷膜两面的厚度)在10nm,20nm,30nm,50nm,100nm时,将不同溅射厚度的PdCM放置于电过滤过程中,其对亚甲基蓝的去除率进行验证,去除率分别为55%,72%,94.5%,95.0%,95.2%。因此,优选的喷涂厚度为30nm。
图1为制备的Pd金属复合双面电催化膜的Pd活性面-1侧(即:面向原料液侧)的膜截面的扫描电镜(SEM)照片(左图)和对应Pd元素的X射线能谱分析(EDS mapping) 图(右图)。两图表明,Pd纳米颗粒成功溅射入膜孔中,并且在膜孔内所形成的活性层深度为60μm。
图2为制备的Pd金属复合双面电催化膜的Pd活性面-2侧(即:面向滤出液侧)的膜截面的SEM照片(左图)和对应Pd元素的EDS mapping图(右图)。两图表明,Pd 纳米颗粒成功溅射入膜孔中,并且在膜孔内所形成的活性层深度为90μm。
图1和图2说明,通过共聚焦磁控溅射仪可在多孔陶瓷膜内部不同区域分别构建催化活性功能层,并且催化活性功能层在膜内均具有较大深度,可确保催化反应效能。
图3和图4为制备的PdCM的Pd活性面-1和Pd活性面-2的X射线光电子能谱(XPS)图。XPS图进一步表明Pd纳米颗粒被成功负载到陶瓷膜基底的两面。
实施例2
如图5所示,PMS/电催化膜滤以错流过滤方式进行,采用实施例1所述的PdCM进行膜过滤。
电催化膜滤时,采用齿轮泵提供0.1bar的跨膜压差。其中,所述的Pd活性面-1和Pd活性面-2分别面向原料液侧和滤出液侧。
电催化膜滤时,所述的Pd活性面-1和Pd活性面-2分别与直流电源相连作为阴极和阳极;膜两极电压为恒电压:1.6V。
图6展示的是电过滤过程中PdCM的结构示意图。
实施例3
采用PdCM去除水体中微污染物。
所采用的微污染物包括亚甲基蓝、磺胺甲恶唑、苯酚、4-氯苯酚、双酚-A。均采用PMS/PdCM电过滤体系进行错流过滤,跨膜压差0.1bar;Pd活性面-1和Pd活性面-2分别与直流电源相连作为阴极和阳极,膜两极电压为1.6V;收集滤出液,采用高效液相色谱检测出水前后微污染物(亚甲基蓝、磺胺甲恶唑、苯酚、4-氯苯酚、双酚-A)浓度。此外,在猝灭实验中,还需将猝灭剂(叔丁醇或糠醇或乙醇)添加到进料溶液中。
图7分别展示了PMS/PdCM电过滤体系对五种微污染物(亚甲基蓝、磺胺甲恶唑、苯酚、4-氯苯酚、双酚-A)的去除效果,去除率均高于85%,甚至可以达到95%以上。
图8展示了PMS/PdCM电过滤体系在8个过滤周期中对于亚甲基蓝的去除率均高于85%,且去除率没有明显下降,显示了体系对于微污染物去除效果的稳定性。
图9展示了PMS/PdCM电过滤体系与现有文献报道的电过滤体系在微污染物去除和电能耗两方面的对比,该图显示出PMS/PdCM电过滤体系对微污染物(本研究亚甲基蓝) 去除效率较高,且电能耗极低。现有文献报道污染物的具体参考文献如下:
甲基橙:Li X,Liu G,Shi M,Li J,Li J,Guo C,Lee J K,Zheng J.Using TiO2mesoflower interlayer in tubular porous titanium membranes for enhancedelectrocatalytic filtration. Electrochimica Acta.2016,218,318-324.
氟曲甘醇:Liu S,Wang Y,Zhou X,Han W,Li J,Sun X,Shen J,Wang L.Improveddegradation of the aqueous flutriafol using a nanostructure macroporous PbO2as reactive electrochemical membrane.Electrochimica Acta.2017,253,357-367.
罗丹明B:Yang K,Lin H,Liang S,Xie R,Lv S,Niu J,Chen J,Hu Y.A reactiveelectrochemical filter system with an excellent penetration flux porous Ti/SnO2–Sb filter for efficient contaminant removal from water.RSCAdvances.2018,8(25),13933-13944.
布洛芬:Bakr A R,Rahaman M S.Crossflow electrochemical filtration forelimination of ibuprofen and bisphenol a from pure and competing electrolyticsolution conditions.Journal of Hazardous Materials.2019,365,615-621.
对氯苯胺:Zheng J,Xu S,Wu Z,Wang Z.Removal of p-chloroaniline frompolluted waters using a cathodic electrochemical ceramic membranereactor.Separation and Purification Technology.2019,211,753-763.
磺胺酸:Zheng J,Yan K,Wu Z,Liu M,Wang Z.Effective removal ofsulfanilic acid from water using a low-pressure electrochemical RuO2-TiO2@Ti/PVDF composite membrane. Frontiers in Chemistry.2018,395.
图10展示了不同猝灭剂对PMS/PdCM电过滤体系中亚甲基蓝去除的影响。所采用的猝灭剂有叔丁醇、糠醇、乙醇。该图显示出叔丁醇和乙醇的加入对亚甲基蓝去除率的影响极小,表明羟基自由基和硫酸根自由基对亚甲基蓝去除率的贡献微弱;而糠醇显著地抑制了亚甲基蓝的去除,表明单线态氧对亚甲基蓝去除率的贡献较大。
图11展示了采用电化学工作站计时电流法,测量电过滤体系中PdCM活性面-1加入PMS、亚甲基蓝后的电流密度变化。该图显示出在添加亚甲基蓝后,电流强度急剧增加,随后变得稳定,表明PMS/PdCM电过滤体系可通过直接电子转移的非自由基方式电活化 PMS,从而去除亚甲基蓝。
以上所述为本发明的较优实施方式。然而,本发明的实施方式不受以上实施方式的限制。基于本发明所述,任何不脱离本发明技术原理的修改、组合、简化,均应为等效的置换方式,都涵盖在本发明的保护范围内。
Claims (10)
1.一种钯金属复合双面电催化膜的制备方法,其特征在于它是按照以下方式进行的:
采用纯度大于或等于99.95%的Pd金属靶体作为金属纳米粒子供体,在超纯氩气氛围,溅射Pd纳米粒子于陶瓷膜基底的两面,陶瓷膜两面溅射Pd的厚度为10nm~50nm,获得Pd金属复合双面电催化膜。
2.根据权利要求1所述的一种钯金属复合双面电催化膜的制备方法,其特征在于溅射Pd纳米粒子于陶瓷膜基底的两面操作为:将陶瓷膜基底放置于硅支架上,陶瓷膜活性面面向Pd靶体,随后,将陶瓷膜倒置于硅支架上,陶瓷膜的基底面面向Pd靶体,以Pd溅射功率为25~35W,沉积速率为2~3nm min-1的条件进行溅射。
3.根据权利要求1所述的一种钯金属复合双面电催化膜的制备方法,其特征在于所述的超纯氩气氛围为通入超纯氩气,使得溅射室的工作压力为0.2~0.4Pa。
4.如权利要求1所制备的一种钯金属复合双面电催化膜的应用,其特征在于它作为电过滤体系在去除水体微污染物中的应用,所述的电过滤体系含有0.5~2mmol·L-1的过氧单硫酸盐。
5.根据权利要求4所述的一种钯金属复合双面电催化膜的应用,其特征在于所述的水体中微污染物的浓度为5~50μmol·L-1。
6.根据权利要求4或5所述的一种钯金属复合双面电催化膜的应用,其特征在于所述的微污染物是指亚甲基蓝、磺胺甲恶唑、苯酚、4-氯苯酚或双酚-A。
7.根据权利要求6所述的一种钯金属复合双面电催化膜的应用,其特征在于去除水体微污染物时膜过滤的水力驱动压力为0.1~0.2bar。
8.根据权利要求6所述的一种钯金属复合双面电催化膜的应用,其特征在于去除水体微污染物中,钯金属复合双面电催化膜的面向原料液侧和滤出液侧分别与直流电源相连作为阴极和阳极。
9.根据权利要求4或8所述的一种钯金属复合双面电催化膜的应用,其特征在于去除水体微污染物中,钯金属复合双面电催化膜的两极电压为恒电压,电压为1.2V~2.5V。
10.根据权利要求9所述的一种钯金属复合双面电催化膜的应用,其特征在于所述的电压为1.6V~2.0V。
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