CN112221481A - 一种Z型结构转化水中Cr(VI)的催化剂及其制备方法和应用 - Google Patents
一种Z型结构转化水中Cr(VI)的催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于化工催化领域,公开了一种Z型结构转化水中Cr(VI)的催化剂及其制备方法和应用。该催化剂的化学式为Er3+:Y3Al5O12@(Pt/SrTiO3)‑Pt‑WO3。其制备方法依次包括:Er3+:Y3Al5O12@SrTiO3的制备、Er3+:Y3Al5O12@(Pt/SrTiO3)‑Pt的制备和Er3+:Y3Al5O12@(Pt/SrTiO3)‑Pt‑WO3的制备。该催化剂解决了宽带半导体只能利用占太阳光4%的紫外光的缺点,提高了宽带半导体对太阳光的利用率,同时又保证了宽带半导体的光催化性能;此外,Z型结构抑制了光生电子空穴对的产生,加快了光催化反应速率,提高了光催化还原性能。
Description
技术领域
本发明属于化工催化领域,特别涉及一种Z型结构转化水中Cr(VI)的催化剂及其制备方法和应用。
背景技术
随着采矿、电镀、金属表面处理、制革、印染以及铸造等行业的不断发展,工业废水及自然水体中的六价铬Cr(VI)已经成为自然环境和人类社会的重要污染物质。以铬酸盐(HCrO4 -/CrO4 2-)和重铬酸盐(Cr2O7 2-)等不同形式存在的Cr(VI)进入水体环境后,表现出相对于Cr(III)高出1000倍的致癌性。六价铬为吞入性毒物/吸入性极毒物,皮肤接触可能导致过敏;更可能造成遗传性基因缺陷,吸入可能致癌,对环境有持久危险性。短期大剂量的接触,在接触部位会产生不良后果,包括溃疡、鼻黏膜刺激和鼻中隔穿孔。摄入超大剂量的铬会导致肾脏和肝脏的损伤、恶心、胃肠道刺激、胃溃疡、痉挛甚至死亡。相反,适量的Cr(III)是人体所必须的元素,因此,将Cr(VI)还原成Cr(III)是十分必要的。
光催化技术因其能直接利用吸收的光去除水体中污染物,并且易分离回用,而受到广泛的关注,如TiO2因其催化活性相对较高,物理化学性质稳定,而被广泛应用。对于光催化还原Cr(VI),需要选择一个具有较强还原能力的半导体催化剂,将Cr(VI)转化为Cr(III)。钛酸锶(SrTiO3)因其较高的导带而具有较强的光催化还原性能,可以用于光催化转化六价铬,然而因为具有较宽的能带间隙,SrTiO3只能吸收紫外光进行光催化反应。紫外光只占太阳光谱的4%,这使太阳能的利用率变得极小。为了获得更高的太阳能利用率,必须开发出能够利用可见光的催化剂。
发明内容
为了克服现有技术的缺点与不足,本发明的首要目的在于提供一种Z型结构转化水中Cr(VI)的催化剂;该催化剂是纳米级的可见光催化剂,具有比表面积大,去除率高等优点,解决了宽带半导体只能利用占太阳光4%的紫外光的缺点,提高了宽带半导体对太阳光的利用率,同时又保证了宽带半导体的光催化性能;此外,Z型结构抑制了光生电子空穴对的产生,加快了光催化反应速率,提高了光催化还原性能。
本发明的又一目的在于提供一种上述Z型结构转化水中Cr(VI)的催化剂的制备方法。
本发明的再一目的在于提供一种上述Z型结构转化水中Cr(VI)的催化剂的应用;将其应用于Cr(VI)转化,方法简单,无污染,催化剂稳定且易于分离,解决了现有宽带半导体对太阳光利用率低、对污染物去除效果差等技术问题。
本发明的目的通过下述技术方案实现:
一种Z型结构转化水中Cr(VI)的催化剂,该催化剂的化学式为Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt-WO3。
上述的一种Z型结构转化水中Cr(VI)的催化剂的制备方法,包括以下操作步骤:
(1)将Ti(OBu)4(钛酸四丁酯)溶解在乙二醇中,加入Sr(NO3)2(硝酸锶)和NaOH溶液,磁力搅拌使溶液充分混合;随后加入上转光剂Er3+:Y3Al5O12并保持磁力搅拌,溶液混合均匀后转移至水热反应釜中,在180℃条件下反应24h;冷却,过滤,固体物洗涤,干燥,研磨后,得Er3+:Y3Al5O12@SrTiO3;
(2)将步骤(1)所得Er3+:Y3Al5O12@SrTiO3溶解在乙醇中,超声分散30-40分钟使溶液混合均匀,随后加入H2PtCl6·6H2O(氯铂酸)溶液并保持超声分散;溶液混合均匀后,在磁力加热搅拌下至沸点下加热30-40min;随后冷却,过滤,固体物洗涤,干燥后,在300-400℃下煅烧1-2h,研磨,得Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt;
(3)将步骤(2)所得Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt和WO3混合,加去离子水,超声分散30-40分钟,得混合液,将混合液加热到沸点,沸点下加热30-40分钟,离心,沉淀物洗涤,干燥后,在300-400℃下煅烧1-2h,研磨,得Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt-WO3。
步骤(1)所述Sr(NO3)2、Ti(OBu)4和NaOH的用量是按照摩尔比Sr:Ti:Na=1:1:5;所述Er3+:Y3Al5O12@SrTiO3中Er3+:Y3Al5O12和SrTiO3的质量比按照0.7:1。
步骤(2)所述H2PtCl6·6H2O的加入量为Er3+:Y3Al5O12@SrTiO3质量的1-2%。
步骤(3)所述Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt和WO3的质量比为1:1。
步骤(1)所述的Er3+:Y3Al5O12的制备方法按照以下步骤:将0.013g Er2O3和2.271gY2O3溶解在浓硝酸中,在加热条件下搅拌至无色透明,得均匀溶液;然后依次加入Al(NO3)3·9H2O和柠檬酸的水溶液,于50-60℃加热搅拌,当溶液呈粘稠状时停止,得发泡黏胶状溶液,将发泡黏胶状溶液于90-110℃下加热24h,得泡沫溶胶,将泡沫溶胶在500℃下加热50-60min后,在1100℃煅烧120-180min,冷却研磨后,得Er3+:Y3Al5O12。
步骤(3)所述的WO3的制备方法按照以下步骤:将质量比为5:2的Na2WO4·2H2O和柠檬酸加水搅拌均匀后,加入HCl,直至混合液pH=1.00,并搅拌30min,将混合液转移至反应釜中,在120℃下处理12h,冷却至室温,弃上清液,沉淀物洗涤,干燥后,于500℃马弗炉中煅烧2h,研磨,得WO3粉末。
上述的一种Z型结构转化水中Cr(VI)的催化剂在转化水中Cr(VI)中的应用。
所述应用按照以下步骤:于含有Cr(VI)的溶液中,加入所述的催化剂,在常温和太阳光照下照射。
本发明相对于现有技术具有如下的优点及效果:
(1)本发明为了提高SrTiO3的光催化效率,进而更有效的转化六价铬离子,将上转光剂Er3+:Y3Al5O12包覆在SrTiO3内部,在这个光催化剂组合中,外部的SrTiO3表面可以直接利用太阳光中的紫外光进行光催化反应,内部的Er3+:Y3Al5O12可以将吸收的可见光转化为能被SrTiO3直接利用的紫外光,从而使具有较宽能带间隙的SrTiO3能更有效的利用太阳光进行光催化反应。
(2)本发明为了达到抑制光生电子-空穴对来提高光催化效率的目的,添加了少量的贵金属Pt在半导体表面,以及窄带助催化剂WO3的复合;Pt沉积在Er3+:Y3Al5O12@SrTiO3表面作为倒带助催剂可以捕获游离电子进行还原反应,而沉积在Er3+:Y3Al5O12@SrTiO3及WO3之间的Pt则起到一个连接的作用,Er3+:Y3Al5O12@SrTiO3产生的光生空穴及WO3产生的光生电子在此处湮灭,抑制光生电子空穴对复合,提高光催化效率;此外,贵金属Pt在展示了对于六价铬的最佳光催化还原效率。
(3)本发明在多种光催化技术的基础上,针对Cr(VI)研究了以Er3+:Y3Al5O12包覆上转光发光材料并添加助催剂进行Cr(VI)转化的技术;通过本发明的方法,Cr(VI)的转化率达到99%以上,而不影响其它质量指标。与其它光催化技术相比,本发明过程简单,常温常压进行,条件温和,并且可利用太阳能。
附图说明
图1是Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt-WO3反应机理图。
图2是Er3+:Y3Al5O12的SEM表征。
图3是WO3的SEM表征。
图4是Er3+:Y3Al5O12@SrTiO3的SEM表征。
图5是Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt-WO3的SEM表征。
图6是Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt-WO3的TEM表征。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1:Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt-WO3的制备
Er3+:Y3Al5O12的制备:将0.013g Er2O3、2.271g Y2O3溶解在浓硝酸(100ml,质量百分比浓度65%)中,60℃条件下磁力加热搅拌直至无色透明,得稀土离子溶液;然后另取一烧杯,称取12.621g Al(NO3)3·9H2O溶解在蒸馏水中,在室温下用玻璃棒搅拌并慢慢加入到上述稀土离子溶液中;称取33.935g柠檬酸(按照摩尔比,柠檬酸:稀土离子=3:1)作为螯合剂和助溶剂并用蒸馏水溶解,然后加入到上述溶液中;随后在50-60℃加热搅拌,当溶液呈粘稠状时停止。在这个过程中没有沉淀生成,最终得到发泡黏胶状溶液。将发泡黏胶状溶液放入烘箱,90-110℃恒温加热24h。在干燥过程中直到蒸干溶剂没有沉淀物生成,最终得到泡沫溶胶。将得到的泡沫溶胶在500℃加热50-60min,然后在1100℃煅烧120-180min。最后,从高温炉中取出烧结的物质并且在空气中冷却至室温得到Er3+:Y3Al5O12粉末。
WO3的制备:将3.00g Na2WO4·2H2O和1.20g的柠檬酸溶解于100ml去离子水中,磁力搅拌至溶液混合均匀,得混合液。随后,将6.00mol/L的HCl在持续搅拌下逐滴加入到混合液中,直至混合液pH=1.00,此时溶液呈现淡黄色。持续搅拌30min,然后将混合液转移至50ml反应釜中,在120℃条件下反应12h。反应完成后,在室温下冷却,弃上清液,沉淀物用去离子水及酒精分别离心清洗3次,在60℃烘干一夜后,得到淡黄色粉末。研磨,将研磨过的淡黄色粉末放入500℃马弗炉中煅烧2h,得到WO3粉末。
Er3+:Y3Al5O12@SrTiO3的制备:将10mmol的钛酸四丁酯(Ti(OBu)4)溶于25ml乙二醇中,并磁力搅拌。随后,加入2.1163g硝酸锶(Sr(NO3)2)和10ml 5.00mol/L NaOH溶液;然后,按质量比,Er3+:Y3Al5O12:SrTiO3=0.7:1,加入Er3+:Y3Al5O12,持续搅拌。待搅拌1.0h至溶液混合均匀后,将混合液转移至50ml水热反应釜中,在180℃条件下反应24h。待反应完成,反应釜自然冷却后,将上清液倒掉,留下反应所得白色粉末。分别用去离子水及酒精离心清洗3次,倒掉上清液后将所得产物置于烘箱中,在60℃条件下干燥12h,得到Er3+:Y3Al5O12@SrTiO3粉末。
Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt的制备:将1.0g Er3+:Y3Al5O12@SrTiO3加入至25ml乙醇中,置于超声机中进行超声分散。在超声分散过程中,逐滴加入适量氯铂酸(H2PtCl6·6H2O)溶液(H2PtCl6·6H2O的质量为Er3+:Y3Al5O12@SrTiO3质量的1%),超声30分钟后,将混合液在磁力搅拌下加热至沸点,并保持30-40分钟。过滤,固体物用去离子水及酒精分别清洗3次,然后在60℃条件下烘干12h。将所得粉末研磨后,置于300-400℃马弗炉中煅烧1-2h,反应结束后,研磨收集,得到Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt粉末。
Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt-WO3的制备:将1g Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt3和1g WO3粉末,倒入50ml去离子水中,超声分散30-40分钟(80kHZ,超声波输出功率为50W),得到分散均匀的混合液。随后,将混合液在磁力搅拌条件下加热至液体沸腾,并保持沸腾30-40分钟。反应完成后,过滤,沉淀物用去离子水及酒精分别清洗3次,随后将所得粉末在60℃条件下干燥12h。最后,将所得粉末研磨并置于300-400℃马弗炉中煅烧1-2h,待反应结束后,得到Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt-WO3。
上述制备过程中每一步所得物质的表征数据如下:
制备的Er3+:Y3Al5O12的SEM如图1所示,由图1看出,所得晶体呈现球形或类球形,粒径为40-60nm,大小分布比较均匀,分散性也较好。说明样品制备成功。
制备的WO3的SEM如图2所示,由图2看出,纳米级WO3粒子呈现片状,平均粒径大小为300nm。
制备的Er3+:Y3Al5O12@SrTiO3的SEM如图3所示。包覆后的复合物表现为粒径大小在270nm的杆状物质。
制备的Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt-WO3的SEM如图4所示。由图4看出,在杆状的Er3+:Y3Al5O12@SrTiO3表面上附着了一些小的颗粒状物质,即为Pt粒子作为助催剂复合在了Er3+:Y3Al5O12@SrTiO3的表面。此外,在Er3+:Y3Al5O12@SrTiO3与WO3之间,发现了小颗粒物质,即是Pt粒子作为两个半导体连接的通路复合在了两者之间,使两个半导体在太阳光照射下产生的电子在通路Pt上进行复合、抵消,获得更高的光催化活性。可以看出,太阳光催化剂Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt-WO3复合物已被成功的制备合成。
制备的Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt-WO3的TEM如图5所示。由图5可以看出,在杆状半导体SrTiO3的内部有一些黑色不透光的物质,根据催化剂设置得意得出这是纳米粒子上转光剂Er3+:Y3Al5O12包覆在SrTiO3之中所造成的透射结果,表明Er3+:Y3Al5O12@SrTiO3已经成功的制备。从图中可以看到,在有Er3+:Y3Al5O12包覆的SrTiO3和片状WO3纳米粒子之间,有一些小颗粒夹在中间,根据SEM表征结果可以得知,贵金属Pt呈小颗粒状,因此可以得出在图5中观察到的小颗粒为贵金属Pt,此处即为充当电子通路的Pt粒子。此外,在SrTiO3表面,同样有一些小颗粒附着,此处即为充当导带助催剂的Pt粒子。由此可知,太阳光催化剂Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt-WO3已经被成功的合成。
实施例2:Cr(VI)转化方法
在光催化反应仪的试管中,加入50mL Cr(VI)溶液(5ppm)和50mg实施例1所制备得到的催化剂Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt-WO3,在常温模拟太阳光照下,开启磁力搅拌,反应6h,反应完毕,将催化剂和溶液进行分离。
以二苯碳酰二肼分光光度法测定Cr(VI)浓度,得到转化率达到95%以上
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (9)
1.一种Z型结构转化水中Cr(VI)的催化剂,其特征在于:该催化剂的化学式为Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt-WO3。
2.根据权利要求1所述的一种Z型结构转化水中Cr(VI)的催化剂的制备方法,其特征在于包括以下操作步骤:
(1)将Ti(OBu)4溶解在乙二醇中,加入Sr(NO3)2和NaOH溶液,磁力搅拌使溶液充分混合;随后加入上转光剂Er3+:Y3Al5O12并保持磁力搅拌,溶液混合均匀后转移至水热反应釜中,在180℃条件下反应24h;冷却,过滤,固体物洗涤,干燥,研磨后,得Er3+:Y3Al5O12@SrTiO3;
(2)将步骤(1)所得Er3+:Y3Al5O12@SrTiO3溶解在乙醇中,超声分散30-40分钟使溶液混合均匀,随后加入H2PtCl6·6H2O溶液并保持超声分散;溶液混合均匀后,在磁力加热搅拌下至沸点下加热30-40min;随后冷却,过滤,固体物洗涤,干燥后,在300-400℃下煅烧1-2h,研磨,得Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt;
(3)将步骤(2)所得Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt和WO3混合,加去离子水,超声分散30-40分钟,得混合液,将混合液加热到沸点,沸点下加热30-40分钟,离心,沉淀物洗涤,干燥后,在300-400℃下煅烧1-2h,研磨,得Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt-WO3。
3.根据权利要求2所述的制备方法,其特征在于:步骤(1)所述Sr(NO3)2、Ti(OBu)4和NaOH的用量是按照摩尔比Sr:Ti:Na=1:1:5;所述Er3+:Y3Al5O12@SrTiO3中Er3+:Y3Al5O12和SrTiO3的质量比按照0.7:1。
4.根据权利要求2所述的制备方法,其特征在于:步骤(2)所述H2PtCl6·6H2O的加入量为Er3+:Y3Al5O12@SrTiO3质量的1-2%。
5.根据权利要求2所述的制备方法,其特征在于:步骤(3)所述Er3+:Y3Al5O12@(Pt/SrTiO3)-Pt和WO3的质量比为1:1。
6.根据权利要求2所述的制备方法,其特征在于:步骤(1)所述的Er3+:Y3Al5O12的制备方法按照以下步骤:将0.013g Er2O3和2.271g Y2O3溶解在浓硝酸中,在加热条件下搅拌至无色透明,得均匀溶液;然后依次加入Al(NO3)3·9H2O和柠檬酸的水溶液,于50-60℃加热搅拌,当溶液呈粘稠状时停止,得发泡黏胶状溶液,将发泡黏胶状溶液于90-110℃下加热24h,得泡沫溶胶,将泡沫溶胶在500℃下加热50-60min后,在1100℃煅烧120-180min,冷却研磨后,得Er3+:Y3Al5O12。
7.根据权利要求2所述的制备方法,其特征在于:步骤(2)所述的WO3的制备方法按照以下步骤:将质量比为5:2的Na2WO4·2H2O和柠檬酸加水搅拌均匀后,加入HCl,直至混合液pH=1.00,并搅拌30min,将混合液转移至反应釜中,在120℃下处理12h,冷却至室温,弃上清液,沉淀物洗涤,干燥后,于500℃马弗炉中煅烧2h,研磨,得WO3粉末。
8.根据权利要求1所述的一种Z型结构转化水中Cr(VI)的催化剂在转化水中Cr(VI)中的应用。
9.根据权利要求8所述的应用,其特征在于:所述应用按照以下步骤:于含有Cr(VI)的溶液中,加入所述的催化剂,在常温和太阳光照下照射。
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