CN111135843A - 一种铝酸锌-磷酸铋异质结光催化剂及其制备方法和应用 - Google Patents
一种铝酸锌-磷酸铋异质结光催化剂及其制备方法和应用 Download PDFInfo
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- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
本发明公开了一种铝酸锌‑磷酸铋异质结光催化剂，所述的催化剂是由ZnAl2O4和BiPO4形成的异质结催化剂，先采用共沉淀法制备出ZnAl2O4，然后将ZnAl2O4置于Na3PO4和Bi(NO3)3•5H2O的水溶液中，采用水热法合成ZnAl2O4/BiPO4异质结光催化剂。该发明制备的复合粉末结晶性高，方法简单环保，重复使用性能良好，催化活性高。在紫外光下可用于亚甲基蓝印染废水（降解率高达92.55%）和桉木化机浆废水（COD去除率高达62.73%）的处理，在印染和制浆造纸等工业废水领域具有广泛的应用前景。
Description
技术领域
本发明涉及到环境材料领域，特别针对印染和制浆造纸等工业废水，具体涉及到一种铝酸锌-磷酸铋异质结光催化剂的制备方法及其应用。
背景技术
制浆造纸业和纺织业废水排放量已位居我国行业废水排放量的前列，其生产过程中生产废水具有水量大、有机污染物含量高、碱性大、水质变化大等特点，属难处理的工业废水。如何高效低成本处理造纸和印染废水，已成为全世界各国科学家们积极探索的方向。半导体光催化技术具有节能高效、无毒无污染、寿命长、维护简单等优势，已被广泛应用于环境净化领域。
磷酸铋(BiPO4)的禁带宽度3.8-4.2eV，是一种宽禁带半导体，具有良好的紫外光响应，光生电子-空穴分离效率高。朱永法教授课题组在2010年首次发现BiPO4纳米催化剂具有较高的紫外光催化活性，合成了一系列高催化活性的BiPO4光催化剂，并将其用于亚甲基蓝染料废水的降解，结果表明其催化活性是商用TiO2(P25)的两倍(Environ.Sci.Technol.2010,44,5570–5574)。但是由于BiPO4存在吸附效果差、只能吸收紫外光、可见光吸收能力低和纳米颗粒尺寸大等问题，这直接影响其催化性能，因此，设计和制备具备高催化性能的BiPO4光催化剂也是现代科学研究的热点。掺杂过渡金属半导体，制备高催化活性异质结光催化被认为是解决能源和环境危机的一个最有前景的方法。铝酸锌(ZnAl2O4)具有宽的禁带宽度(约3.8eV)，是一种优良的紫外光电半导体材料，其在紫外光的照射下对甲苯的去除率高达73.4％(Catal.Sci.Technol.,2013,3,788-796)。根据文献查阅，目前还没有将ZnAl2O4和BiPO4结合起来制备ZnAl2O4/BiPO4异质结光催化剂的相关报道。
发明内容
发明目的：本发明的目的是为了解决废水处理难度大、成本高等难题,以及紫外光催化效率差等难题，提供了一种铝酸锌-磷酸铋异质结光催化剂的制备方法及其应用。
技术方案：为实现上述技术目的，本发明提供了一种高效ZnAl2O4/BiPO4异质结紫外光催化剂，所述的光催化剂是由ZnAl2O4和BiPO4组合形成的异质结催化剂，其中ZnAl2O4与Bi2MoO6质量比1:10～500。
本发明进一步提出了上述高效紫外ZnAl2O4/BiPO4光催化剂的制备方法，包括如下步骤：
(1)制备ZnAl2O4粉末；
(2)制备ZnAl2O4/BiPO4光催化剂：将ZnAl2O4、铋盐和磷酸盐溶于蒸馏水中，调节HNO3溶液pH值，超声搅拌后放入水热釜中，反应完成后，冷却至室温，产物经离心洗涤多次后，真空干燥，优选地，在50-60℃下真空干燥，得到ZnAl2O4/BiPO4异质结催化剂。
具体地，步骤(2)中铋盐和磷酸盐的摩尔比为2:1～3:4。
具体地，步骤(2)中用HNO3溶液调节溶液pH至1～5，在水热釜中的反应条件为140～200℃下反应24～60h。
具体地，步骤(2)中所述的铋盐为硝酸铋、硫酸铋、氯化铋或醋酸铋中的任意一种；所述的含磷酸盐为磷酸钠、磷酸钾、磷酸铵或磷酸氢二钠的任意一种或两种。
具体地，所述的铝酸锌-磷酸铋异质结光催化剂在紫外光下处理废水中的应用。
优选地，所述废水为印染和制浆造纸废水中的任意一种。
有益效果：本发明与现有技术相比，具有以下优点：
(1)本发明方法制备的ZnAl2O4/BiPO4光催化剂催化效率高效、性质稳定、使用寿命长、循环使用效率高，对印染和制浆造纸等工业废水的处理具有良好的效果。
(2)本发明制备的ZnAl2O4/Bi2MoO6光催化剂属于异质结领域，可加快光生电子和空穴的分离，提高光催化反应性能。
附图说明
图1为ZnAl2O4、BiPO4和ZnAl2O4/BiPO4光催化剂的XRD图；
图2为BiPO4(a)、ZnAl2O4(b)和1wt％ZnAl2O4/BiPO4(c-d)的扫描电子显微镜图，1wt％ZnAl2O4/BiPO4的X射线能谱图(EDS)；
图3为BiPO4和1wt％ZnAl2O4/BiPO4的XPS图谱(a)，Bi、P、O、Zn和Al元素的高分辨的XPS图谱(b-f)。
具体实施方式
本发明提供了一种高效ZnAl2O4/BiPO4异质结光催化剂，通过如下方法制备得到：
(1)制备ZnAl2O4粉末：可利用现有技术制备ZnAl2O4粉末，如参照文献(Microporous and Mesoporous Materials 163(2012)29-33)
(2)制备ZnAl2O4/BiPO4光催化剂：将ZnAl2O4、铋盐和磷酸盐溶于蒸馏水中，调节HNO3溶液pH值，超声搅拌后放入水热釜中，反应完成后，冷却至室温，产物经离心洗涤多次后，真空干燥，得到ZnAl2O4/BiPO4异质结催化剂。
下面通过实施例对本发明技术方案作进一步详细说明。
实施例1：
将5.75g ZnSO4·7H2O和15g Al(NO3)3·9H2O分别溶于10mL的蒸馏水中，然后ZnSO4·7H2O溶液逐滴滴加到Al(NO3)3·9H2O的水溶液中，用28wt％氨水调节上述混合液至9。制备的样品经过滤洗涤干燥，并在700℃马弗炉中煅烧4h，即可得到白色的ZnAl2O4粉末。将3mmol Bi(NO3)3·6H2O和3mmol Na3PO4的加入到40ml蒸馏水中中，搅拌均匀，然后0.0092粉末添加到40mL溶液中，超声30min，剧烈搅拌30min。溶液的pH用稀硝酸调节至1。将上述混合物放入100mL的聚四氟乙烯的不锈钢水热釜中，置于烘箱中180℃加热48h。冷却结束后，将样品离心分离，洗涤干燥。即可得到1wt％-ZnAl2O4/BiPO4光催化剂(1wt％表示ZnAl2O4占整个催化剂的百分比含量)。
将0.2g的ZnAl2O4、BiPO4和1wt％ZnAl2O4/BiPO4催化剂分别加入到250mL的30mg/L的亚甲基蓝溶液中，100w的Hg灯照射，3h后亚甲基蓝的降解率分别为14.33％、65.58％和92.55％。
实施例2：
ZnAl2O4粉末的制备方法同实施例1。将3mmol Bi(NO3)3·6H2O和3mmol Na3PO4的加入到40ml蒸馏水中中，搅拌均匀，然后将0.0018g、0.046g、0.0183g、0.0456g和0.09118gZnAl2O4添加到40mL溶液中，超声30min，剧烈搅拌30min。溶液的pH用稀硝酸调节至1。将上述混合物放入100mL的聚四氟乙烯的不锈钢水热釜中，置于烘箱中180℃加热48h。冷却结束后，将样品离心分离，洗涤干燥。即可得到0.2wt％ZnAl2O4/BiPO4、0.5wt％ZnAl2O4/BiPO4、2wt％ZnAl2O4/BiPO4、5wt％ZnAl2O4/BiPO4和10wt％ZnAl2O4/BiPO4光催化剂。将0.2gZnAl2O4/BiPO4催化剂分别加入到250mL的30mg/L的亚甲基蓝溶液中，100w的Hg灯照射，3h后亚甲基蓝的降解率如下表所示：
使用后的1wt％ZnAl2O4/BiPO4经过离心洗涤干燥后，重复四次用于亚处理250mL的30mg/L的亚甲基蓝溶液，100w的Hg灯照射，3h后亚甲基蓝的降解率如下表所示：
实施例3：
ZnAl2O4粉末的制备方法同实施例1。将3mmol Bi(NO3)3·6H2O和4mmol Na2HPO4的加入到40ml蒸馏水中中，搅拌均匀，然后将0.09118g ZnAl2O4添加到40mL溶液中，超声30min，剧烈搅拌30min。溶液的pH用稀硝酸调节至3。将上述混合物放入100mL的聚四氟乙烯的不锈钢水热釜中，置于烘箱中200℃加热36h。冷却结束后，将样品离心分离，洗涤干燥。即可得到10wt％ZnAl2O4/BiPO4光催化剂。将0.2g10wt％ZnAl2O4/BiPO4催化剂分别加入到250mL的30mg/L的亚甲基蓝溶液中，100w的Hg灯照射，3h后亚甲基蓝的降解率为73.23％。
实施例4：
ZnAl2O4粉末的制备方法同实施例1。将3mmol BiCl3和4mmol Na3PO4的加入到40ml蒸馏水中中，搅拌均匀，然后将0.0018g ZnAl2O4添加到40mL溶液中，超声30min，剧烈搅拌30min。溶液的pH用稀硝酸调节至5。将上述混合物放入100mL的聚四氟乙烯的不锈钢水热釜中，置于烘箱中140℃加热60h。冷却结束后，将样品离心分离，洗涤干燥。即可得到0.2wt％ZnAl2O4/BiPO4光催化剂。将0.2g0.2wt％ZnAl2O4/BiPO4催化剂分别加入到250mL的30mg/L的亚甲基蓝溶液中，100w的Hg灯照射，3h后亚甲基蓝的降解率为79.85％。
实施例5：
ZnAl2O4粉末的制备方法同实施例1。将3mmol Bi(CH3COO)3和2mmol Na3PO4的加入到40ml蒸馏水中中，搅拌均匀，然后将0.0061g ZnAl2O4添加到40mL溶液中，超声30min，剧烈搅拌30min。溶液的pH用稀硝酸调节至2。将上述混合物放入100mL的聚四氟乙烯的不锈钢水热釜中，置于烘箱中160℃加热48h。冷却结束后，将样品离心分离，洗涤干燥。即可得到1wt％ZnAl2O4/BiPO4光催化剂。将将0.2g 15wt％ZnAl2O4/BiPO4催化剂分别加入到250mL的COD分别为273mg/L的桉木化机浆生化出水中，100w的Hg灯照射，3h后COD的去除率分别为62.73％。
实施例6：材料表征。
对制备ZnAl2O4/BiPO4纳米异质结催化剂进行了XRD图表征，从而确定制备的光催化剂的结构和晶型，其结果如图1所示。由图1可知，采用水热方法成功合成了ZnAl2O4和BiPO4纳米粒子。所制备ZnAl2O4为立方晶系，所有峰均与JCPDS No.05-0669相匹配，且无杂峰。对于制备的纯BiPO4，所有的峰均为独居石型钙钛矿型的BiPO4(JCPDS No.80-0209，空间群：P21/n)。ZB3、ZB5和ZB6的衍射峰与纯BiPO4峰基本一致，并没有观察到ZnAl2O4峰的存在，这可能是由于样品中的ZnAl2O4的负载量较低、分布均匀和结晶性不好等原因。
图2为制备的催化剂的SEM和EDS图。图2(a-b)分别为纯BiPO4和ZnAl2O4的SEM图，可知BiPO4为不规则的纳米棒，且尺寸分布在100nm到600nm之间；纯ZnAl2O4形貌为不规则形状。由图2(c-d)可以看出ZnAl2O4覆盖在BiPO4纳米棒上，且BiPO4和ZnAl2O4均未改变其各自的形貌。同时本研究对ZnAl2O4/BiPO4做了EDS能谱分析，由图2e可以看出，ZnAl2O4/BiPO4催化剂中含有Zn、Al、Bi、P和O元素，进一步证明了ZnAl2O4成功的掺杂在BiPO4纳米棒中。
为了分析ZnAl2O4/BiPO4中的元素组成及各元素化合价态，采用X射线光电能谱对其进行表征，图3为BiPO4和1wt％ZnAl2O4/BiPO8及各元素的XPS谱图。XPS分析中的电子结合能用位于284.6eV的C1s波峰来进行校正。由图3(b-d)对比纯BiPO4和1wt％ZnAl2O4/BiPO4的元素Bi 4f、P 2p和O1s，可以发现由于ZnAl2O4的复合导致Bi 4f、P 2p和O1s的电子结合能变大，这是由于电子和空穴的转移，但是纯BiPO4的谱图和复合了ZnAl2O4之后的ZnAl2O4/BiPO4的XPS谱图走势基本一致，没有什么突出变化。从图3f中观察到，XPS高分辨率谱图中在73.91eV处出现峰，对应Al 2p。图3e中为Zn元素的XPS图，价带能量为1044.18eV和1021.41eV分别为Zn 2p1/2和Zn 2p3/2的吸收峰。由于了ZnAl2O4的掺杂量非常低，从而使得Zn 2p和Al 2p的XPS峰非常不平滑。
综上所述，本发明方法制备的ZnAl2O4/BiPO4光催化剂催化效率高效、性质稳定、使用寿命长、循环使用效率高，对印染和制浆造纸等工业废水的处理具有良好的效果。本发明制备的ZnAl2O4/Bi2MoO6光催化剂属于异质结领域，可加快光生电子和空穴的分离，提高光催化反应性能。
Claims (8)
1.一种铝酸锌-磷酸铋异质结光催化剂，其特征在于，所述的光催化剂是由ZnAl2O4和BiPO4组合形成的异质结催化剂，其中ZnAl2O4与BiPO4质量比1:10~500。
2.权利要求1所述的高效异质结紫外光催化剂的制备方法，其特征在于，包括如下步骤：
（1）制备ZnAl2O4粉末；
（2）制备ZnAl2O4/BiPO4光催化剂：将ZnAl2O4、铋盐和磷酸盐溶于蒸馏水中，调节HNO3溶液pH值，超声搅拌后放入水热釜中，反应完成后，冷却至室温，产物经离心洗涤多次后，真空干燥，得到ZnAl2O4/BiPO4异质结催化剂。
3.根据权利要求2所述的制备方法，其特征在于，铋盐和磷酸盐的摩尔比为2:1~3:4。
4.根据权利要求2所述的制备方法，其特征在于，用HNO3溶液调节溶液pH至1~5。
5.根据权利要求2所述的制备方法，其特征在于，在水热釜中的反应条件为140~200℃下反应24~60 h。
6.根据权利要求2所述的制备方法，其特征在于，步骤（2）中，所述的铋盐为硝酸铋、硫酸铋、氯化铋或醋酸铋中的任意一种；所述的含磷酸盐为磷酸钠、磷酸钾、磷酸铵或磷酸氢二钠的任意一种或两种。
7.权利要求1所述的铝酸锌-磷酸铋异质结光催化剂在紫外光下处理废水中的应用。
8.根据权利要求7所述的应用，其中，所述废水为印染和制浆造纸废水中的任意一种。
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