CN107162097B - 共存体系中低浓度17β-雌二醇的选择性光电催化去除方法 - Google Patents
共存体系中低浓度17β-雌二醇的选择性光电催化去除方法 Download PDFInfo
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Abstract
本发明涉及一种共存体系中低浓度17β‑雌二醇的选择性光电催化去除方法,首先制备出具有择形催化选择性氧化废水中内分泌干扰物17β‑雌二醇的光电阳极,然后在光照射并施加一定电位的偏压条件下,对于化学需氧量COD为10~100mg/L的污水中含有低浓度17β‑雌二醇进行处理,该方法能实现选择性光电化学氧化功能,优先去除17β‑雌二醇污染物,处理后水中17β‑雌二醇浓度可低于15μg/L以下。与现有技术相比,本发明能有效去除实际复杂水体系中的低浓度17β‑雌二醇,无需进行预处理和分离,直接通过光电氧化技术达到优先氧化目标污染物、深度净化的目的,方法简单,选择性和催化效率高,抗干扰能力强等。
Description
技术领域
本发明涉及环境雌激素降解技术领域,尤其是涉及一种共存体系中低浓度17β-雌二醇的选择性光电催化去除方法。
背景技术
环境雌激素种类繁多,广泛存在于自然界中。其性质稳定不易被降解破坏,半衰期长,在生态环境中通过食物链被富集。影响生物体的主要方式是通过污染的食品、空气和水体,在ng/L-μg/L的痕量范围内依然可以干扰人类和动植物的正常的调控网络。内源性雌激素又称天然激素一般指雌二醇、雌酮和雌三醇,后两者是前者的代谢产物,它们的活性比例是100:3:1。因此,17β-雌二醇(简称为E2)是作用最强,最具生物效应的一种内分泌干扰物。
实际水体中污染物复杂多样,其中容易被降解的污染物占99%,难降解污染物占1%。然而,正是由于这1%的难降解的污染物存在,传统处理方法首先降解大量易降解的污染物,而那些难降解的污染物依然存在,降解后出水往往不尽如人意。传统水处理方法因为缺乏特异性而大大降低了在微量浓度的处理效率,因为大多数的吸附和氧化能力都浪费在去除其他通常无害的污染物上。而若雌激素在水体中与已有的化学品混合,并在人体内交互作用,产生化学反应,最后可能会合成出未知的副产物,使得毒性增加。因此,在共存体系中优先去除E2是非常重要的。
光电化学方法由于具有简单,快速,高效,易于实时在线检测等特点,在分析检测和降解中一直备受关注。而且采用TiO2等氧化物半导体作为催化剂的光催化和光电催化氧化方法,近年来在能量转化、环境污染物的降解处理中得到广泛的研究。光、电催化氧化方法主要是通过在催化剂表面产生具有强氧化能力的羟基自由基将底物进行氧化降解,尽管该方法具有快速高效、氧化降解彻底等优点,但是光、电本身并没有选择性,很难实现混合体系中不同底物的选择性光电催化氧化。因此,如何实现污染物的选择性催化氧化是目前光电催化研究领域中的研究热点同时也是难点。近年来众多科学家们尝试通过对催化剂表面进行修饰或改性以攻克光电催化氧化技术缺乏选择性这一难题,但是这些方法存在不够稳定,催化剂制备复杂,选择性单一等问题,很难对复杂体系中的一个低浓度物质进行识别,更无法实现选择性催化降解。
在共存体系中对选择性识别以及污染物氧化降解的还较少。Hg+、Ag+、Cu2+等金属离子会抑制E2的生物降解。在天然有机物共存的情况下,生物活性炭和粒状活性炭去除E2的效果,多组分共存情况下会产生竞争吸附和小孔堵塞,影响活性炭对E2的吸附,对生物活性炭而言,天然有机物的存在还会影响微生物对E2的降解。UV/H2O2体系中阴离子的存在对E2降解的影响,CO3 2-和HCO3 -会消除·OH,而NO3 -会阻碍紫外光同H2O2的反应,从而影响对E2的降解去除。随着腐殖酸的浓度升高,E2的光降解也会被愈加抑制。因此,如何有效的去除E2一直是水体污染体系中的重点和难点。中国专利201611147788.4公开了一种表面有机化蒙脱石/纳米二氧化锰复合材料,该吸附剂材料是将生物质和蒙脱石组装在一起水热碳化,再将纳米二氧化锰负载到其表面。该专利的吸附剂材料制备过程比较简单,对水体中的有机物17β-雌二醇也有一定的去除能力,但是,在选择性去除能力方面还有较大的提升空间。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种共存体系中低浓度17β-雌二醇的选择性光电催化去除方法。
本发明的目的可以通过以下技术方案来实现:
一种共存体系中低浓度17β-雌二醇的选择性光电催化去除方法,包括以下步骤:
(A)通过水热合成方法制备出具有择形催化选择性氧化废水中内分泌干扰物17β-雌二醇的光电阳极材料;
(B)利用步骤(A)所制得的光电阳极材料,在光照射并施加偏压的条件下,对共存废水体系中含有的低浓度17β-雌二醇进行实现选择性光电化学氧化处理。
优选的,步骤(A)中的光电阳极材料通过以下步骤制成:
(1)称取浓盐酸与水混合,再滴加钛酸四丁酯,搅拌,继续加入模板分子17β-雌二醇,得到前驱体溶液,其中,浓盐酸的浓度为37wt%,浓盐酸、水、钛酸四丁酯和17β-雌二醇的添加量的体积比为7.5:(5~15):(0.1~0.4):(0.01~0.1);
(2)将前驱体溶液转移至密封反应釜中,将预处理后的FTO的导电面朝下浸入前驱体溶液中,水热反应,其中,水热反应温度为100~200℃,水热时间为4~8h;
(3)反应完成后,取出产物,清洗,在400~600℃下煅烧15~45min,即得到目的产物17β-雌二醇选择性光电阳极材料。
优选的,步骤(B)中的选择性光电化学氧化处理具体为:
以光电阳极材料作为工作电极,工作电极面积为5cm2以上,Pt片作为对电极,饱和甘汞电极作为参比电极,在紫外光照并施加0.2V~1.2V电极电位的偏压条件下,对共存废水体系中的低浓度17β-雌二醇进行选择性光电催化氧化降解处理,处理过程中投加硫酸钠电解质,使其浓度为0.1mol/L,所述共存废水体系中化学需氧量COD为10~100mg/L,其中内分泌干扰物17β-雌二醇的含量为15μg/L~10mg/L,处理后,共存废水体系中17β-雌二醇的含量低于15μg/L。
本发明将择形吸附与光电催化技术相结合,利用择形吸附的选择识别能力对低浓度17β-雌二醇进行选择性吸附,再利用催化材料的光电催化氧化能力将吸附的17β-雌二醇氧化降解,从而实现17β-雌二醇在无机光电催化剂表面的选择性识别和催化氧化降解。
与现有技术相比,本发明具有以下优点:
(1)本发明选择将17β-雌二醇作为目标污染物,利用该目标制备具有择形催化效果的一维单晶TiO2光电催化剂,并在其表面实现对17β-雌二醇的选择性识别,在高效光电催化和一维单晶TiO2表面择形吸附这二者相结合的情况下,近而优先降解达到深度净化的目的。
(2)首次通过在一维单晶TiO2表面构筑17β-雌二醇择形催化位点实现了17β-雌二醇的选择性光电催化去除,能够在共存体系中对低浓度17β-雌二醇进行选择性光电催化去除。同时本发明中的光电阳极的构筑具有制备简单,稳定性好,抗干扰能力强,选择性高等优点。
(3)本发明中使用的17β-雌二醇选择性光电阳极有很强的抗干扰能力,能在有干扰污染物存在的情况下对目标污染物进行选择性光电化学氧化降解。
附图说明
图1本发明中制备的光电阳极对1mg/L 17β-雌二醇的降解曲线图。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1
一种17β-雌二醇选择性光电阳极,包括一维单晶TiO2纳米棒电极,以及印迹在一维单晶TiO2纳米棒电极表面的17β-雌二醇择形催化位点,通过以下步骤制成:
(1)称取浓盐酸与水混合,再滴加钛酸四丁酯,在450rpm下搅拌1h,加入模板分子17β-雌二醇,浓盐酸、水、钛酸四丁酯和17β-雌二醇的添加量的体积比为7.5:7.5:0.35:0.05,浓盐酸的浓度为37wt%,得到前驱体溶液;
(2)将前驱体溶液转移到密封反应釜中,将预处理后的FTO的导电面朝下浸入溶液中,在150℃下反应4h;
(3)反应完成后,取出产物,用去离子水冲洗,取出表面残留物,在500℃下煅烧30min,即得到目的产品带有17β-雌二醇择形位点的一维单晶TiO2纳米棒电极。
实施例2
用实施例1制得的带有17β-雌二醇择形位点的一维单晶TiO2纳米棒电极作为工作电极,电极面积为9cm2,饱和甘汞电极为参比电极,铂电极为对电极。用纯水配置浓度为1mg/L 17β-雌二醇溶液,同时溶液中分别含有1mg/L腐植酸、1mg/L阿特拉津、1mg/L双酚A等共存污染物。采用紫外光照射并外加0.6V偏压下进行光电化学氧化降解。处理过程中投加硫酸钠电解质,使其浓度为0.1mol/L。降解10小时后,17β-雌二醇的去除率为99.1%,测得处理后水中E2的浓度为9μg/L。这表明,对于水体系中的低浓度17β-雌二醇,该光电氧化技术能够得到深度氧化净化去除E2,且抗干扰能力强。
实施例3
用实施例1所制备的具有17β-雌二醇选择性氧化功能的光电阳极为工作电极,电极面积为9cm2,饱和甘汞电极为参比电极,铂电极为对电极,在紫外光照射并外加0.6V偏压下,对COD=30mg/L污水中含有的1mg/L 17β-雌二醇溶液进行光电化学氧化降解。处理过程中投加硫酸钠电解质,使其浓度为0.1mol/L。降解10小时后,17β-雌二醇的去除率为98.7%,测得处理后水中E2的浓度为13.7μg/L,如图1所示。该实施例子表明,对于COD为30mg/L实际复杂水体系中的低浓度17β-雌二醇,无需进行预处理和分离,可以直接通过该光电氧化技术达到优先氧化、深度净化E2的目的,方法简单,选择性和催化效率高,抗干扰能力强。
实施例4
采用不具有17β-雌二醇选择性氧化功能的TiO2光电阳极为工作电极,无需在前驱体溶液中添加模板分子17β-雌二醇,制备方法的其他步骤同实施例1。饱和甘汞电极为参比电极,铂电极为对电极,在紫外光照射并外加0.6V偏压下,对COD=30mg/L污水中含有的1mg/L 17β-雌二醇溶液进行光电化学氧化降解。处理过程中投加硫酸钠电解质,使其浓度为0.1mol/L。降解10小时后,17β-雌二醇的去除率为45.1%,最终溶液中含有的E2浓度为54.9μg/L。该实施例子表明,如果采用传统的光电催化阳极,由于不具有选择性氧化E2的功能,则对于复杂共存水体系中的低浓度17β-雌二醇,不能达到优先氧化、深度净化E2的目的。
由上述实施例可以看出,当与17β-雌二醇共存的污水,其COD浓度小于100mg/L时,本发明利用带有17β-雌二醇择形催化位点的光电阳极对17β-雌二醇的光电识别和选择氧化去除效果非常突出。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (1)
1.一种共存体系中低浓度17β-雌二醇的选择性光电催化去除方法,其特征在于,包括以下步骤:
(A)通过水热合成方法制备出具有择形催化选择性氧化废水中内分泌干扰物17β-雌二醇的光电阳极材料;
(B)利用步骤(A)所制得的光电阳极材料,在光照射并施加偏压的条件下,对共存废水体系中含有的低浓度17β-雌二醇进行实现选择性光电化学氧化处理;
步骤(A)中的光电阳极材料通过以下步骤制成:
(1)称取浓盐酸与水混合,再滴加钛酸四丁酯,搅拌,继续加入模板分子17β-雌二醇,得到前驱体溶液,其中,浓盐酸的浓度为37wt%,浓盐酸、水、钛酸四丁酯和17β-雌二醇的添加量的体积比为7.5:(5~15):(0.1~0.4):(0.01~0.1);
(2)将前驱体溶液转移至密封反应釜中,将预处理后的FTO的导电面朝下浸入前驱体溶液中,水热反应,其中,水热反应温度为100~200℃,水热时间为4~8h;
(3)反应完成后,取出产物,清洗,在400~600℃下煅烧15~45min,即得到目的产物17β-雌二醇选择性光电阳极材料;
步骤(B)中的选择性光电化学氧化处理具体为:
以光电阳极材料作为工作电极,工作电极面积为5cm2以上,Pt片作为对电极,饱和甘汞电极作为参比电极,在紫外光照并施加0.2V~1.2V电极电位的偏压条件下,对共存废水体系中的低浓度17β-雌二醇进行选择性光电催化氧化降解处理,处理过程中投加硫酸钠电解质,使其浓度为0.1mol/L,所述共存废水体系中化学需氧量COD为10~100mg/L,其中内分泌干扰物17β-雌二醇的含量为15μg/L~10mg/L,处理后,共存废水体系中17β-雌二醇的含量低于15μg/L。
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