CN108543539B - 一种BiVO4/AgIO3异质结纳米光催化材料及其制备方法和应用 - Google Patents
一种BiVO4/AgIO3异质结纳米光催化材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于光催化材料技术领域,具体涉及一种BiVO4/AgIO3异质结纳米光催化材料及其制备方法和应用。所述光催化材料是由BiVO4与AgIO3复合而成。本发明是以硝酸银、碘酸钾、钒酸铵、硝酸铋为原料,利用水热法和沉淀法,得到具有较好的可见光响应的AgIO3/BiVO4异质结光催化材料,可用于在可见光下光催化降解废水中的有机染料和抗生素。本发明涉及的制备方法工艺简单、易于控制、成本低廉;制备的AgIO3/BiVO4异质结光催化材料,其可见光催化活性比AgIO3和BiVO4均有显著提高,光电流更大,较好的提高了其可见光催化活性和稳定性,对水体中的抗生素如四环素和染料如罗丹明B具有较好的降解效果,可进一步拓展其在挥发性有机废气光催化降解中的应用。
Description
技术领域
本发明属于光催化材料技术领域,具体涉及一种BiVO4/AgIO3异质结纳米光催化材料及其制备方法和应用。
背景技术
光催化技术是一种清洁的光能利用物质转化技术,它的应用领域包括光解水制氢、降解水体中的有机污染物、降解空气中的挥发性有机物(VOCs) 以及模拟植物光合作用过程等。借助半导体材料实现光催化反应的技术得到越来越广泛的关注,半导体材料在光照下能产生电子-空穴对,一部分电子和空穴在体相内或表面相遇而复合,另一部分电子迁移到半导体表面具有较强的还原能力,可以与吸附的氧结合,生成具有强氧化性的自由基;而迁移到半导体表面的空穴则具有较强的氧化能力,可以与吸附在半导体表面的O2和 H2O结合,形成诸如·OH、·HO2、H2O2和·O2-的强氧化性的自由基,这些自由基可以直接与反应物发生作用并将其氧化分解,不产生二次污染。而在半导体光催化技术中,缩小禁带宽度提高光量子的利用率使半导体的可见光响应性能改善,以及避免光生电子空穴的复合是提高光催化效率的关键。
众所周知,Bi系半导体催化剂是一类重要的具有可见光响应性能的光催化剂。其中,n-型BiVO4半导体因具有约2.3eV的禁带宽度而使其具有较好的可见光光催化效果,但单独的BiVO4光催化剂的光生电子空穴的分离效率较差而限制了其最终的光催化效率。另外据报道,正交晶系的碘酸银由于其较宽的禁带宽度而在紫外区有较好的光催化效果和光生电子-空穴分离效率。目前尚未有AgIO3/BiVO4异质结光催化剂的报道。
发明内容
本发明要解决的技术问题,在于提供一种BiVO4/AgIO3异质结纳米光催化材料及其制备方法和应用,将BiVO4与AgIO3进行杂化,形成复合光催化剂,拓展了其在光催化领域的应用。
本发明是这样实现的:
本发明首先提供了一种BiVO4/AgIO3异质结纳米光催化材料,是由 BiVO4与AgIO3复合而成。
其中,AgIO3与BiVO4的复合比例为20%-80%,该复合比例为摩尔比,其表示的含义为AgIO3占BiVO4的摩尔量比。
更优选地,AgIO3与BiVO4的复合比例为40%。
进一步地,所述BiVO4是以钒酸铵、硝酸铋为原料,利用水热法合成。
进一步地,所述AgIO3是以硝酸银、碘酸钾为原料,利用沉淀法合成。
本发明还提供了上述光催化材料的制备方法,包括以下步骤:
(1)将钒酸铵溶解于氢氧化钠溶液中,得到溶液A;另取五水硝酸铋溶解于浓硝酸,得到溶液B;将溶液B逐滴加入溶液A中,超声波处理使其混合均匀,后调节混合液的pH值为7,继续搅拌均匀,将其移入聚四氟乙烯高压反应釜中,180℃反应24h后,将产物经蒸馏水和乙醇洗涤过滤后干燥得到 BiVO4;
(2)将硝酸银溶解于蒸馏水,加入步骤(1)合成的BiVO4,搅拌均匀,将碘酸钾溶液在持续搅拌的条件下加入其中,继续搅拌2h,将产物经蒸馏水和乙醇洗涤过滤干燥后得到BiVO4/AgIO3异质结纳米光催化材料。
最后本发明提供了所述光催化材料的应用,用于在可见光下光催化降解废水中的有机染料、抗生素。
所述有机染料包括罗丹明B。
所述抗生素包括四环素。
本发明涉及的AgIO3和BiVO4在独自参与可见光光催化降解反应时均不能取得较好的效果,其在40分钟内的对废水中染料的降解率均不足10%,但将AgIO3和BiVO4进行复合后,在AgIO3与BiVO4的复合比为20%-100%较宽的范围内均能获得较好的光催化效果,当AgIO3:BiVO4=40%时,在 25min内对有机染料的降解率达到100%。因此将该异质结产品应用于光催化领域具有重大的意义,具体表现在:
(1)本发明涉及的制备方法工艺简单、易于控制、成本低廉;
(2)本发明制备的AgIO3/BiVO4异质结光催化材料经过紫外可见漫反射的测试,其光响应向可见光区移动,其可见光催化活性比AgIO3和BiVO4均有显著提高。
(3)本发明制备的AgIO3/BiVO4异质结光催化剂在光电流测试中与 AgIO3和BiVO4相比,光电流更大,其特殊的异质结结构加快了光生载流子的分离,减小了光生电子-空穴的复合几率,较好的提高了其可见光催化活性和稳定性,可进一步拓展其在挥发性有机废气光催化降解中的应用。
(4)本发明制备的AgIO3/BiVO4异质结光催化剂对水体中的抗生素如四环素也具有一定的降解效果。
附图说明
下面参照附图结合实施例对本发明作进一步的说明。
图1为本发明所制备样品的X-射线衍射(XRD)图谱,图中横坐标为2θ (角度),单位为度(°);纵坐标为Intensity(强度),单位为a.u.(绝对单位);
图2为本发明所制备样品的扫描电子显微镜(FESEM)图;
图3为本发明所制备的样品的紫外可见漫反射光谱(UV-DRS)图,其中横坐标为Wavelength(波长),单位为nm(纳米),纵坐标为Absorbance(吸光度),单位为a.u.(绝对单位);
图4为本发明所制备的样品的(αhν)1/2vs.hν谱图,其中横坐标为hν,单位是eV(电子伏特),纵坐标是(αhν)0.5,单位为无量纲;
图5为本发明所制备的样品光催化降解罗丹明B(RhB)随时间变化的曲线,取样间隔为5min不同比例的异质结的光催化图,横坐标为Time(时间),单位是min(分钟),纵坐标为C/C0,C0为反应开始前罗丹明的初始浓度,C 为取样时间下罗丹明的浓度;
图6为本发明所制备的AgIO3:BiVO4=40%的样品对罗丹明B的光催化降解谱图,横坐标为Wavelength(波长),单位是nm(纳米),纵坐标是Absorbtanc (吸光度),单位是a.u.(绝对单位)。
图7为本发明所制备的AgIO3:BiVO4=40%的样品的对四环素的光催化降解谱图。
具体实施方式
实施例1
本发明的制备方案:
将2.3g钒酸铵溶解于20ml的氢氧化钠溶液中,得到溶液A;另量取9.7g五水硝酸铋溶解于20ml浓硝酸,得到溶液B;将溶液B逐滴加入溶液A中,超声波处理25min后调混合液的pH值为7,磁力搅拌30min,将其移入100ml的聚四氟乙烯高压反应釜中,180℃反应24h后,将产物经蒸馏水和乙醇洗涤过滤后于80℃干燥12h得到BiVO4的光催化剂。
以合成的BiVO4光催化剂为基准,按物质的量比为0.4:1称取合成AgIO3时所需的硝酸银和碘酸钾。将称量好的硝酸银溶解于20ml的蒸馏水,加入 BiVO4,磁力搅拌30min,将溶解于20ml蒸馏水的碘酸钾在持续搅拌的条件下持续加入其中,继续搅拌2h,将产物经蒸馏水和乙醇洗涤过滤后于80℃干燥 12h得到AgIO3/BiVO4异质结光催化剂。
图1为AgIO3、BiVO4以及合成的AgIO3/BiVO4异质结光催化剂样品的XRD 谱图。A曲线为BiVO4单体样品的XRD谱图,其衍射峰的位置分别与标准卡 (JCPDS NO.14-0688)完全吻合,未出现任何杂质相,可以确定制备的样品为纯的BiVO4。B曲线为AgIO3单体样品的XRD谱图,其衍射峰与标准的 (JCPDS NO.71-1928)正交晶系AgIO3相对应且没有杂相衍射峰出现,表明所制备的样品为纯的AgIO3。图中C、D、E曲线为制备的AgIO3/BiVO4异质结光催化剂,图谱中包含了单体AgIO3和BiVO4的所有特征峰,说明这两者结合在一起形成复合材料,并且随着AgIO3用量的增大,其代表AgIO3的(041)、 (221)、(061)、(271)的峰逐渐增大。
图2为AgIO3、BiVO4以及合成的AgIO3/BiVO4异质结光催化剂样品的FESEM图。(A)为AgIO3单体光催化剂,其外观呈扁平型长方体,其长度约为 1.5-2μm,厚度约为250nm,棱边圆润。(B)为BiVO4单体光催化剂,其外观呈立方体,边长约为1-2μm,其棱边锐利。(C、D、E)为AgIO3:BiVO4=20%、 40%和80%的AgIO3/BiVO4异质结光催化剂样品,在视野中可见随着AgIO3的用量增加,扁平的长方体AgIO3越多,其与BiVO4形成的异质结界面越多。
图3为AgIO3、BiVO4以及合成的AgIO3/BiVO4异质结光催化剂样品的紫外可见漫反射谱图。图中AgIO3单体的吸收峰的边缘在360nm左右,而BiVO4的吸收峰涵盖了紫外到可见的区域(λ≤540),这表明AgIO3仅对紫外光有响应,而BiVO4的光响应区域从紫外光延伸到可见光区域。对AgIO3/BiVO4异质结光催化剂样品的谱图分析表明,它们三者的光响应情况大致相同,分别结合了AgIO3和BiVO4单体的紫外可见漫反射谱图,AgIO3加入量为80%的样品,其谱图中出现了AgIO3明显的吸收峰,且其吸收峰边缘与其他较少的添加量相比向紫外区靠近。这个结果杂化的异质结光催化剂的光响应性能优于单体的 AgIO3和BiVO4,并且将因为杂化比例的不同而出现光催化效果的差异。由于吸收峰边沿与光催化剂的禁带宽度息息相关,可用于预测样品的光吸收区,基于半导体光吸收理论和DRS的结果,可以用于估算样品的禁带宽度。通过 Tauc plot法(图4)对样品的禁带宽度进行计算,AgIO3和BiVO4的禁带宽度分别为2.15eV和3.12eV,与其他文献报道的这两者的禁带宽度相符合。
光催化活性测试方法:
采用PLS-SXE300型氙灯光源,称取50mg光催化剂加入200ml的20mg/L的罗丹明溶液中,暗反应30min达到吸附平衡后开启光源。通过紫外可见分光光度计测定罗丹明溶液浓度,计算其降解效率。
图5为AgIO3、BiVO4以及合成的AgIO3/BiVO4异质结光催化剂样品的对 200ml浓度为20mg/l的罗丹明B样品进行光降解的降解效率图。从图中可以看出,单体AgIO3和BiVO4对罗丹明B几乎没有降解效果,在经过40min的光降解时,其降解率仅为5%;而AgIO3/BiVO4异质结光催化剂则显示了较好的光催化效果,尤其是AgIO3:BiVO4=40%的样品,其在25min内对罗丹明B的光降解效率达到100%,且其降解速率优于具有同样降解效果的AgIO3:BiVO4=60%的样品。
图6是对200ml浓度为20mg/l的罗丹明B进行光催化时,在不同取样时间下 AgIO3:BiVO4=40%样品的紫外可见吸收谱图。从图中可以明确看出,随着时间推移,罗丹明B发生了显著降解,并在25min时降解完全。
本发明制备的AgIO3/BiVO4异质结光催化剂对水体中的四环素也有一定的降解效果,如图7所示,在30分钟内可看到四环素在360nm处的吸收峰逐渐降解,代表四环素得到一定程度的降解,但其229nm处的吸收峰呈现先增长后降低的趋势,说明在降解过程中AgIO3/BiVO4异质结光催化剂先是对四环素结构中的某一部分进行降解,但其环状结构没有得到根本性破坏,后在较长时间的持续降解过程中才逐步分解,但在经过2h的光催化降解后,其降解率约为78%,四环素结构不能得到完全的破坏,水体中仍有降解残片剩余。
综上,本发明具有如下优点:
1、首次合成了AgIO3/BiVO4异质结光催化剂。
2、该异质结结构加快了光生载流子的分离,减小了光生电子-空穴的复合几率,在可见光下具有较好的可见光吸收性能,大大优于半导体单体的光催化效果。
3、在较短的25时间内实现对水体中有机染料罗丹明B的完全降解,具有较好的实用价值。且在较宽的复合比例下(20%-80%)均具有较好的降解效果。
4、该复合光催化剂的制备方法简单可行、价格低廉。
虽然以上描述了本发明的具体实施方式,但是熟悉本技术领域的技术人员应当理解,我们所描述的具体的实施例只是说明性的,而不是用于对本发明的范围的限定,熟悉本领域的技术人员在依照本发明的精神所作的等效的修饰以及变化,都应当涵盖在本发明的权利要求所保护的范围内。
Claims (6)
1.一种BiVO4/AgIO3异质结纳米光催化材料,其特征在于:所述光催化材料是由BiVO4与AgIO3复合而成,制备方法包括以下步骤:
(1)将钒酸铵溶解于氢氧化钠溶液中,得到溶液A;另取五水硝酸铋溶解于浓硝酸,得到溶液B;将溶液B逐滴加入溶液A中,超声波处理使其混合均匀,后调节混合液的pH值为7,继续搅拌均匀,将其移入聚四氟乙烯高压反应釜中,180℃反应24h后,将产物经蒸馏水和乙醇洗涤过滤后干燥得到BiVO4;
(2)将硝酸银溶解于蒸馏水,加入步骤(1)合成的BiVO4,搅拌均匀,将碘酸钾溶液在持续搅拌的条件下加入其中,继续搅拌2h,将产物经蒸馏水和乙醇洗涤过滤干燥后,得到BiVO4/AgIO3异质结纳米光催化材料。
2.根据权利要求1所述的BiVO4/AgIO3异质结纳米光催化材料,其特征在于:AgIO3与BiVO4的复合比例为20%-80%。
3.根据权利要求2所述的BiVO4/AgIO3异质结纳米光催化材料,其特征在于:AgIO3与BiVO4的复合比例为40%。
4.如权利要求1-3中任一项所述的BiVO4/AgIO3异质结纳米光催化材料的应用,其特征在于:所述光催化材料用于在可见光下光催化降解废水中的有机染料、抗生素。
5.根据权利要求4所述的应用,其特征在于:所述有机染料包括罗丹明B。
6.根据权利要求4所述的应用,其特征在于:所述抗生素包括四环素。
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