CN112588302B - 一种含ɑ-MnO2的光催化体系、其制备方法及应用 - Google Patents
一种含ɑ-MnO2的光催化体系、其制备方法及应用 Download PDFInfo
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Abstract
本发明提供一种含ɑ‑MnO2的光催化体系、其制备方法及应用,属于光催化剂技术领域。所述光催化体系包括ɑ‑MnO2以及NaHSO4,NaHSO4与ɑ‑MnO2的质量比为0.05‑1:1;ɑ‑MnO2通过以下方法制备:将KMnO4溶于去离子水中,在搅拌下滴入含MnSO4·H2O的水溶液中,得混合浆料,转移到聚四氟乙烯内衬的不锈钢高压釜中,于烘箱中130‑145℃下保温10‑13h;待混合浆料冷却后抽滤洗涤,将所得产品于烘箱中干燥,在马弗炉中280‑320℃的空气氛围下煅烧1.5‑2.5h,即得ɑ‑MnO2。本发明具有较高的光催化效率,对多种有机物有明显的降解效果,降解效率高,体系操作简单。
Description
技术领域
本发明涉及有机物废水的光催化降解处理技术,涉及光催化剂技术领域,具体涉及一种含ɑ-MnO2的光催化体系、其制备方法及应用。
背景技术
工业生产过程中会排放大量的有机废水,这些有机废水中的有机物以悬浮或溶解状态存在于水体系,很难降解。大多数有机物有毒有害,本身对水体当中的其他生物造成危害,中间也可能通过微生物等生物作用继续降解,但分解过程需要消耗氧气,水中溶解氧量减少,也会影响其他生物的生长。
现有技术中,对有机物废水的处理方法有生物降解、吸附、光催化等。光降解有机物的相关研究较多,光降解过程中有机物直接降解成CO2和H2O等,绿色环保,无需二次处理,具有广阔的研究前景。
光催化降解技术需要光催化材料的支撑,常见的光催化材料有TiO2,ZnO或相应掺杂的金属氧化物等。光催化的机理是紫外光或可见光照射光催化材料,相应产生空穴(h+)和电子(e-),并将OH-和O2等氧化还原生成OH·和O2 -·等相应自由基。这些自由基活性很高,很容易将有机物还原成CO2和H2O。光催化可以室温下进行,但存在光照时间长,光催化效率低的问题。MnO2也可用于光催化领域,但同样存在光催化效率低等问题。
常用的解决光催化剂催化效率低的方法要么是对基底催化剂进行金属、非金属负载或其他化合物复合负载改性,要么就是加一些助催化剂如H2O2、O3、过硫酸盐(Na2S2O8)等与光催化剂协同改性处理。MnO2本身具有一定的光催化性,但其同样存在光催化效率低等问题。因此,在光催化剂技术领域还有进一步研究发展的空间。
发明内容
针对上述存在的问题,本发明的发明目的之一在于提供一种含ɑ-MnO2的光催化体系,通过制备出纳米线状形貌的ɑ-MnO2,并与NaHSO4协同构成复合体系,具有较高的光催化效率,对多种有机物有明显的降解效果,降解效率高,体系操作简单。
本发明实现上述目的的技术方案为:
一种含ɑ-MnO2的光催化体系,包括ɑ-MnO2以及NaHSO4;本发明中,添加少量NaHSO4即可对ɑ-MnO2的光催化效率起协同增效作用,但优选所述NaHSO4与ɑ-MnO2的质量比为0.05-1:1,增效效果最明显。
本发明中,优选地,所述ɑ-MnO2为特定晶型,其是通过以下制备方法制备得到:将KMnO4溶于去离子水中,在磁力搅拌下滴入含MnSO4·H2O的水溶液中,得混合浆料,将混合浆料转移到聚四氟乙烯内衬的不锈钢高压釜中,于烘箱中130-145℃下保温10-13h;待混合浆料冷却后抽滤洗涤,将所得到的固体产品于烘箱中干燥,然后在马弗炉中280-320℃的空气氛围下煅烧1.5-2.5h,即得所述ɑ-MnO2,其为纳米线状。
本发明中,优选地,所述KMnO4与去离子水的固液比为1g:20-30ml;MnSO4·H2O与KMnO4的摩尔比为1:2-3.5。
本发明中,优选地,所述干燥的温度为75-90℃,干燥时间为10-14h。
本发明的目的之二是提供一种含ɑ-MnO2的光催化体系的制备方法,包括以下步骤:
(1)制备ɑ-MnO2:将KMnO4溶于去离子水中,在磁力搅拌下滴入含MnSO4·H2O的水溶液中,得混合浆料,将混合浆料转移到聚四氟乙烯内衬的不锈钢高压釜中,于烘箱中 130-145℃下保温10-13h;待混合浆料冷却后抽滤洗涤,将所得到的固体产品于烘箱中干燥,在马弗炉中280-320℃的空气氛围下煅烧1.5-2.5h,即得所述ɑ-MnO2;
(2)将ɑ-MnO2和NaHSO4分别分装。使用时再分别添加。
本发明的目的之三是提供一种含ɑ-MnO2的光催化体系的应用,具体是指将所述光催化体系用于有机污染废水的降解中。
具体的应用方法为:向有机污染废水中投加一定量的ɑ-MnO2,同时投加一定量NaHSO4,对有机物污染废水施以光照,光照0.5h以上,即可看到明显降解效果。
为了起到最佳的光催化效果,优选地,所述ɑ-MnO2在废水的浓度为0.5g/L-3g/L。
本发明的光催化体系对光源的依赖性较弱,但有200nm-800nm范围的波长光施加效果更好。
综上所述,由于采用了上述技术方案,本发明的有益效果是:本发明用特定晶型的ɑ-MnO2与NaHSO4构建一种强的氧化还原体系,对多种有机物有明显的降解效果。相对传统类芬顿光催化等技术,处理成本低,反应体系温和,无明显二次污染,循环利用率高。该发明对工业有机污染废水有非常广阔的商业应用价值。
附图说明
图1为实施例2(方案a)制备得到的ɑ-MnO2的x射线衍射图;
图2为实施例2(方案a)制备得到的ɑ-MnO2的扫描电镜图;
图3为实施例2(方案a)制备得到的光催化体系的光催化降解率随时间变化的曲线图;
图4为方案b制备得到的ɑ-MnO2的x射线衍射图;
图5为方案b制备得到的ɑ-MnO2的扫描电镜图;
图6为方案b制备得到的光催化体系的光催化降解率随时间变化的曲线图;
图7为方案c制备得到的ɑ-MnO2的x射线衍射图
图8为方案c制备得到的ɑ-MnO2的扫描电镜图
图9为方案c制备得到的ɑ-MnO2的光催化体系的光催化降解率随时间变化的曲线图;
图10为α-MnO2与不同无机盐协同的光催化降解能力比较图。
具体实施方式
为了更清楚地表达本发明,以下通过具体实施例对本发明作进一步说明。
一、制备实施例
实施例1
一种含ɑ-MnO2的光催化体系,包括ɑ-MnO2以及NaHSO4;且NaHSO4与ɑ-MnO2的质量比为0.05:1。
一种含ɑ-MnO2的光催化体系的制备:(1)将1gKMnO4溶于20ml去离子水中,在磁力搅拌下滴入含0.53gMnSO4·H2O的15ml水溶液,得混合浆料,将混合浆料转移到聚四氟乙烯内衬的不锈钢高压釜中,于烘箱中130℃下保温13h;待混合浆料冷却后抽滤洗涤,将所得到的固体产品于75℃烘箱中干燥14h,然后在马弗炉中280℃的空气氛围下煅烧2.5h,即得所述ɑ-MnO2,其为纳米线状。
(2)将ɑ-MnO2和NaHSO4分别分装,使用时再分别添加。
一种含ɑ-MnO2的光催化体系的应用,是指将所述光催化体系用于有机污染废水的降解中。具体的方法为:向机污染废水中投加一定量的ɑ-MnO2,使ɑ-MnO2在废水的浓度为0.5g/L,同时投加一定量NaHSO4,使得NaHSO4与ɑ-MnO2的质量比为0.05:1,对有机物污染废水施以200nm-800nm范围的波长光照,光照0.5h以上,即可看到明显降解效果。
实施例2
一种含ɑ-MnO2的光催化体系,包括ɑ-MnO2以及NaHSO4;且NaHSO4与ɑ-MnO2的质量比为0.8:1。
一种含ɑ-MnO2的光催化体系的制备:(1)将1.0gKMnO4溶于25ml去离子水中,在磁力搅拌下滴入含0.4gMnSO4·H2O的18ml水溶液,得混合浆料,将混合浆料转移到聚四氟乙烯内衬的不锈钢高压釜中,于烘箱中140℃下保温12h;待混合浆料冷却后抽滤洗涤,将所得到的固体产品于80℃烘箱中干燥12h,然后在马弗炉中300℃的空气氛围下煅烧2h,即得所述ɑ-MnO2,其为纳米线状。
(2)将ɑ-MnO2和NaHSO4分别分装,使用时再分别添加。
一种含ɑ-MnO2的光催化体系的应用,是指将所述光催化体系用于有机污染废水的降解中。具体的方法为:向机污染废水中投加一定量的ɑ-MnO2,使ɑ-MnO2在废水的浓度为1.25g/L,同时投加一定量NaHSO4,使得NaHSO4与ɑ-MnO2的质量比为0.8:1,对有机物污染废水施以200nm-800nm范围的波长光照,光照0.5h以上,即可看到明显降解效果。
实施例3
一种含ɑ-MnO2的光催化体系,包括ɑ-MnO2以及NaHSO4;且NaHSO4与ɑ-MnO2的质量比为1:1。
一种含ɑ-MnO2的光催化体系的制备:(1)将1.0gKMnO4溶于30ml去离子水中,在磁力搅拌下滴入含0.3gMnSO4·H2O的20ml水溶液,得混合浆料,将混合浆料转移到聚四氟乙烯内衬的不锈钢高压釜中,于烘箱中145℃下保温10h;待混合浆料冷却后抽滤洗涤,将所得到的固体产品于90℃烘箱中干燥10h,在马弗炉中320℃的空气氛围下煅烧1.5h,即得所述ɑ-MnO2,其为纳米线状。
(2)将ɑ-MnO2和NaHSO4分别分装,使用时再分别添加。
一种含ɑ-MnO2的光催化体系的应用,是指将所述光催化体系用于有机污染废水的降解中。具体的方法为:向机污染废水中投加一定量的ɑ-MnO2,使ɑ-MnO2在废水的浓度为0.5g/L-3g/L,同时投加一定量NaHSO4,使得NaHSO4与ɑ-MnO2的质量比为1:1,对有机物污染废水施以200nm-800nm范围的波长光照,光照0.5h以上,即可看到明显降解效果。
实施例1-3所得产物的x射线衍射图的分析结果表明其为ɑ型MnO2,其中实施例2的x 射线衍射图如图1所示;扫描电子显微镜微观形貌表明制备出的MnO2为纳米线状,其中实施例2的扫描电镜图如图2所示。
二、光催化降解试验:
本申请在研究过程中作了大量的试验,得到了本申请的最佳方案,为了更好地表达本申请的优势,现将一些光催化降解的研究试验记载如下。
1、光催化降解方法:
以甲基橙、罗丹明B和盐酸四环素有机物为例,采用本实例制备得到的产物催化降解有机物的应用实验做如下说明:将光催化剂分别加入40ml浓度皆为35mg/L甲基橙溶液、罗丹明B溶液和盐酸四环素溶液中,黑暗静止30min以达到吸附/脱附平衡,开启可见光照射,每隔20min,从上述溶液中移取2mL溶液,加入1mL甲醇溶液,用过滤头抽滤,把固体颗粒滤掉,再将滤液装入比色皿,分别于有机物的特征波长下(甲基橙:464nm;罗丹明B: 554nm;盐酸四环素:358nm)下测其溶液吸光度,并与初始溶液吸光度做对比。
光降解率(D)依照下式计算:D=(C0-Ct)/C0*100%=(A0-At)/A0*100%,其中,C0为溶液初始浓度,Ct为光照时间为t后溶液的浓度;C0为溶液初始吸光度,Ct为光照时间为t后溶液的吸光度。
2、不同晶型ɑ-MnO2光催化剂体系的催化效果试验
方案a:试验组a采用实施例2制备得到的光催化体系进行光催化试验,催化剂体系的加入量与实施例2相同;对比组a采用实施例2制备得到的ɑ-MnO2进行光催化试验,ɑ-MnO2的加入量与试验组a中的ɑ-MnO2的加入量相同;对三种有机物的光催化降解能力测试结果如图3。
方案b:试验组b采用以下方法制备ɑ-MnO2;采用NaHSO4与ɑ-MnO2按照质量比0.8:1进行投加,且加入量与实施例2中催化剂体系相同,作为光催化体系进行光催化试验;对比组b采用试验组b得到的ɑ-MnO2进行光催化试验,ɑ-MnO2的加入量与试验组b中的ɑ-MnO2的加入量相同;对三种有机物的光催化降解能力测试结果如图6;
试验组b中ɑ-MnO2的制备方法:将8mmolK2S2O8、8mmolMnSO4·H2O和8mmolK2SO4溶于60mL去离子水中,加入98wt%H2SO4溶液2mL。随后将上述溶液转移到聚四氟乙烯内衬的不锈钢高压釜中,于烘箱中140℃加热12小时。最后,离心收集a-MnO2纳米粒子的沉淀,105℃干燥即得。得到的产物的x射线衍射图的分析结果表明其为ɑ型MnO2,如图4 所示。扫描电子显微镜微观形貌表明制备出的MnO2为针状聚拢成蒲公英花状,如图5所示。
试验组c:试验组c采用以下方法制备ɑ-MnO2;采用NaHSO4与ɑ-MnO2按照质量比为0.8:1进行投加,且加入量与实施例2中催化剂体系相同,作为光催化体系进行光催化试验;对比组c采用试验组c得到的ɑ-MnO2进行光催化试验,ɑ-MnO2的加入量与试验组c中的ɑ-MnO2的加入量相同;对三种有机物的光催化降解能力测试结果如图9。
试验组c中ɑ-MnO2的制备方法:1.35g高锰酸钾和3.0ml盐酸(37%)加入到120ml去离子水中,将其溶解,磁力搅拌30min后,移至高压反应釜中,将反应釜放入干燥箱中加热至160℃,反应12h;自然降至室温,将所得悬浮液过滤,洗涤至pH不再变化,所得样品在干燥箱80℃干燥24h即得。所得产物的x射线衍射图的分析结果表明其为ɑ型MnO2,如图7所示。扫描电子显微镜微观形貌表明制备出的MnO2为针状聚拢成板栗外壳状,如图8所示。
从图3、6和9的光催化降解能力测试结果可以看出,三种方案所制备得到的ɑ型MnO2均有一定的催化降解能力,三种方案制备得到的ɑ型MnO2在协同NaHSO4后,光催化降解率均得到了明显的上升。说明NaHSO4的加入有利于光催化效率的提升。而方案a(即本发明最佳方案)所制备得到的ɑ型MnO2在协同NaHSO4后,对甲基橙溶液、罗丹明B溶液和盐酸四环素溶液的降解率均最高,方案b和c制备得到的ɑ型MnO2在协同NaHSO4后,对甲基橙溶液具有较高的降解率,但对罗丹明B溶液和盐酸四环素溶液的降解率的提升效果明显不如方案a;说明方案a制备得到的ɑ型MnO2在协同NaHSO4后,光催化效果是最佳的。
3、离子对光催化性能的影响试验
以实施例2制备得到的α-MnO2为催化剂主体,其加入量统一为0.05克,其他无机盐的加入量统一为0.04g,甲基橙用量为40mL浓度为35mg/L。探讨其他无机盐,包括Na2SO4、NaHSO3、NaHSO4、MnSO4、NaNO3、NaH2PO4与α-MnO2的协同作用对甲基橙的光催化降解效果,结果如图10所示。可以看出,本发明制备的α-MnO2与NaHSO4协同作用后,光催化降解率远远高于其他组,光催化效果最佳。
上述说明是针对本发明较佳可行实施例的详细说明,但实施例并非用以限定本发明的专利申请范围,凡本发明所提示的技术精神下所完成的同等变化或修饰变更,均应属于本发明所涵盖专利范围。
Claims (7)
1.一种含ɑ-MnO2的光催化体系,其特征在于:包括ɑ-MnO2以及NaHSO4,所述NaHSO4与ɑ-MnO2的质量比为0.05-1:1;所述ɑ-MnO2为特定晶型,其是通过以下制备方法制备得到:将KMnO4溶于去离子水中,在磁力搅拌下滴入含MnSO4·H2O的水溶液中,得混合浆料,将混合浆料转移到聚四氟乙烯内衬的不锈钢高压釜中,于烘箱中130-145℃下保温10-13h;待混合浆料冷却后抽滤洗涤,将所得到的固体产品于烘箱中干燥,然后在马弗炉中280-320℃的空气氛围下煅烧1.5-2.5h,即得所述ɑ-MnO2;所述光催化体系用于含甲基橙、四环素和罗丹明B的有机污染废水的降解。
2.根据权利要求1所述的一种含ɑ-MnO2的光催化体系,其特征在于:所述KMnO4与去离子水的固液比为1g:20-30ml;MnSO4·H2O与KMnO4的摩尔比为1:2-3.5。
3.根据权利要求1所述的一种含ɑ-MnO2的光催化体系,其特征在于:所述干燥的温度为75-90℃,干燥时间为10-14h。
4.根据权利要求1-3任一项所述的一种含ɑ-MnO2的光催化体系的制备方法,其特征在于,包括以下步骤:
(1)制备ɑ-MnO2:将KMnO4溶于去离子水中,在磁力搅拌下滴入MnSO4·H2O的水溶液,得混合浆料,将混合浆料转移到聚四氟乙烯内衬的不锈钢高压釜中,于烘箱中130-145℃下保温10-13h;待混合浆料冷却后抽滤洗涤,将所得到的固体产品于烘箱中干燥,然后在马弗炉中280-320℃的空气氛围下煅烧1.5-2.5h,即得所述ɑ-MnO2;
(2)将ɑ-MnO2和NaHSO4分别分装。
5.根据权利要求1所述的含ɑ-MnO2的光催化体系的应用,其特征在于:具体应用方法为,向有机污染废水中投加一定量的ɑ-MnO2,同时投加一定量NaHSO4,对有机物污染废水施以光照,光照0.5h以上,即可看到明显降解效果。
6.根据权利要求5所述的含ɑ-MnO2的光催化体系的应用,其特征在于:所述ɑ-MnO2在废水的浓度为0.5g/L-3g/L。
7.根据权利要求5所述的含ɑ-MnO2的光催化体系的应用,其特征在于:所述光照的光波长范围为200nm-800nm。
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