CN114011398B - 3D花状Zn3In2S6@Bi2O4/β-Bi2O3双Z型异质结光电催化剂及应用 - Google Patents
3D花状Zn3In2S6@Bi2O4/β-Bi2O3双Z型异质结光电催化剂及应用 Download PDFInfo
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Abstract
本发明涉及3D花状Zn3In2S6@Bi2O4/β‑Bi2O3双Z型异质结光电催化剂及应用。将Bi(NO3)3·5H2O溶解在苯甲醇中，搅拌10‑20min后，加入Zn3In2S6，超声10‑20min后，再搅拌50min，将所得混合溶液转移到聚四氟乙烯衬里的不锈钢高压釜中，进行水热反应，反应结束后自然冷却至环境温度，产物用蒸馏水和无水乙醇洗涤，真空干燥后放入马弗炉中，于300‑350℃保持5小时，得目标产物。本发明构建的双Z型异质结光电催化剂，用于高效还原高毒性的Cr(VI)为无毒的Cr(III)，为含铬废水的处理提供理论基础，有助于推动光电催化技术在环境修复领域的应用。
Description
技术领域
本发明属于光电催化剂领域，特别涉及一种具有双Z型异质结结构的3D花状Zn3In2S6@Bi2O4/β-Bi2O3光电催化剂及其在光电催化Cr(VI)还原为Cr(III)中的应用。
背景技术
铬是一种典型的重金属污染物，主要来源于皮革鞣制、纺织制造、钢铁制造等行业。主要以Cr(VI)和Cr(III)两种价态存在，其中，Cr(VI)因其对生物体的急性毒性而被认为是高致癌物，而Cr(III)无毒，是人体必需的微量金属。因此，将Cr(VI)还原为Cr(III)被认为是一种行之有效的水处理方法。为此，研究人员已经开展了大量的研究工作，比如：微生物还原、化学还原和光催化还原、电催化还原、光电催化还原等等。其中，光电催化技术是近年来发展起来的一种高效的催化技术，它利用可再生的太阳光作为能源，结合电化学技术的优势，加快了光生载流子的分离，提高太阳能转换成化学能的转化效率，实现了节能、环保、高效催化等特性。目前，该技术已被广泛应用在析氢、加氢、CO2还原及合成氨等各种催化领域，其关键是合理设计和构建性能优异的催化剂。
具有Z-型电荷传导机制的半导体异质结，因其具有超高的氧化还原能力而备受关注，特别地，双Z型电荷传导模式使催化剂具有更好的电荷分离能力，从而获得更高的性能。
发明内容
本发明的目的是构建一种3D花状Zn3In2S6@Bi2O4/β-Bi2O3双Z型异质结光电催化剂，用于高效还原高毒性的Cr(VI)为无毒的Cr(III)，为含铬废水的处理提供理论基础，有助于推动光电催化技术在环境修复领域的应用。
为了实现上述目的，本发明采用的技术方案是：3D花状Zn3In2S6@Bi2O4/β-Bi2O3双Z型异质结光电催化剂，制备方法包括如下步骤：将Bi(NO3)3·5H2O溶解在苯甲醇中，搅拌10-20min后，加入Zn3In2S6，超声10-20min后，再搅拌50min，将所得混合溶液转移到聚四氟乙烯衬里的不锈钢高压釜中，进行水热反应，反应结束后自然冷却至环境温度，产物用蒸馏水和无水乙醇洗涤，真空干燥后放入马弗炉中，于300-350℃保持5小时，得3D花状Zn3In2S6@Bi2O4/β-Bi2O3双Z型异质结光电催化剂。
进一步的，所述Zn3In2S6的制备方法包括如下步骤：将ZnSO4·7H2O和硫代乙酰胺溶于去离子水中后，加入InCl3水溶液，搅拌30-40min，所得混合溶液转移至高压釜中在160℃水热反应12h，洗涤，干燥，得到Zn3In2S6。
进一步的，所述水热反应是，在120℃下水热反应24h。
本发明提供的3D花状Zn3In2S6@Bi2O4/β-Bi2O3双Z型异质结光电催化剂在光电催化Cr(VI)还原为Cr(III)中的应用。
进一步的，方法如下：将Zn3In2S6@Bi2O4/β-Bi2O3涂覆在导电玻璃上作为工作电极，铂片为对电极，Ag/AgCl为参比电极组成三电极体系，将三电极体系置于含Cr(VI)的电解质溶液中，进行光电催化还原。
进一步的，光电催化还原的条件为：偏压为-0.6V，光源为300W氙灯(λ>420 nm)，平均光强为100mW·cm-2。
进一步的，所述电解质溶液是pH＝3.0-5.0的浓度为0.1mol L-1的Na2SO4电解质溶液。
更进一步的，所述电解质溶液是pH＝3.0的浓度为0.1mol L-1的Na2SO4电解质溶液。
进一步的，调节含Cr(VI)的电解质溶液中，Cr(VI)的浓度为3-4mg·L-1，每50mL含Cr(VI)的电解质溶液中加入2-5mg Zn3In2S6@Bi2O4/β-Bi2O3。
本发明的有益效果是：
1、Zn3In2S6、Bi2O4和β-Bi2O3三种半导体都是非常优秀的n型半导体，具有合适的带隙宽度和良好的稳定性，本发明成功将n型半导体Bi2O4和β-Bi2O3纳米粒子负载到三维花状Zn3In2S6上，形成稳定的n-n-n三元异质结。该复合材料具有大的比表面积，超高的可见光吸收能力，增强的电子-空穴对分离效率，展现了优异的可见光催化性能。并且，通过材料的能带结构及能带弯曲理论推断，该Zn3In2S6@Bi2O4/β-Bi2O3异质结的光催化过程是一种新颖的双Z型载流子传导方式。
2、本发明设计并构建的三维分级结构的花状Zn3In2S6@Bi2O4/β-Bi2O3三元半导体异质结。由二维纳米片自组装形成的三维花状结构，不仅具有大的比表面积及丰富的多孔结构，而且利于入射光在材料表面和内部的多次反射和散射，从而提高了对可见光的利用率。在可见光照射下，构建的Zn3In2S6@Bi2O4/β-Bi2O3异质结材料对Cr(VI)展现了较好的催化还原效果(>80％)。
3、本发明Zn3In2S6@Bi2O4/β-Bi2O3复合材料形成了双Z型电荷传导路径，不仅有效抑制光生电子-空穴对的复合，还保留半导体材料突出的氧化还原能力。
附图说明
图1是Zn3In2S6(a)和Zn3In2S6@Bi2O4/β-Bi2O3(b)的SEM图。
图2是Bi2O4/β-Bi2O3，Zn3In2S6和Zn3In2S6@Bi2O4/β-Bi2O3的XRD图。
图3是Bi2O4/β-Bi2O3，Zn3In2S6和Zn3In2S6@Bi2O4/β-Bi2O3催化活性对比图。
图4是Zn3In2S6@Bi2O4/β-Bi2O3在纯光、纯电、光/电协同作用下及在无催化剂条件下还原效果对比。
图5是溶液的pH对催化还原Cr(VI)活性的影响。
图6是不同Zn3In2S6@Bi2O4/β-Bi2O3用量对Cr(VI)还原效果的影响(pH＝3)。
图7是本发明Zn3In2S6@Bi2O4/β-Bi2O3光电催化Cr(VI)还原为Cr(III)的反应动力曲线。
图8是Zn3In2S6@Bi2O4/β-Bi2O3在光/电协同作用下催化Cr(VI)还原反应机理。
具体实施方式
实施例1 3D花状Zn3In2S6@Bi2O4/β-Bi2O3双Z型异质结光电催化剂 (一)制备方法如下：
1、0.5865g InCl3·4H2O溶于25mL去离子水，0.8711g ZnSO4·7H2O和0.4545g硫代乙酰胺溶于45mL去离子水，将两溶液合并后搅拌30min，将所得混合溶液转移至高压釜中在160℃水热反应12h，洗涤，干燥，得到黄色粉末状固体Zn3In2S6。
2、将0.0312g Bi(NO3)3·5H2O溶解在30mL的苯甲醇中，搅拌10min后，加入0.0851gZn3In2S6，超声10min后，再搅拌50min。将所得混合溶液转移到聚四氟乙烯衬里的不锈钢高压釜，在120℃下水热反应24h，然后将反应釜自然冷却至环境温度。产物用蒸馏水和无水乙醇分别洗涤3次，真空干燥，然后在马弗炉中以5℃/min速度升温至300℃保持5小时，获得3D花状双Z型异质结光电催化剂Zn3In2S6@Bi2O4/β-Bi2O3。
对比例——Bi2O4/β-Bi2O3复合物的制备：将0.0312g Bi(NO3)3·5H2O溶解在30mL的苯甲醇中，搅拌10min后，超声10min，再搅拌50min，将所得物转移到聚四氟乙烯衬里的不锈钢高压釜，在120℃下水热反应24h，然后将反应釜自然冷却至环境温度。产物用蒸馏水和无水乙醇分别洗涤3次，真空干燥，然后在马弗炉中以5℃/min速度升温至300℃保持 5小时，获得Bi2O4/β-Bi2O3复合物。
(二)检测
图1是Zn3In2S6(a)和Zn3In2S6@Bi2O4/β-Bi2O3(b)的SEM图。由图1中(a)可见，Zn3In2S6展现了由2D纳米片组成了3D分级花状结构，这种分层级结构有利于可见光的吸收及目标物/反应中间产物的传质。由图1中(b)可见，大量Bi2O4/β-Bi2O3纳米粒状被成功镶嵌在Zn3In2S6花片里，形成稳定的复合物。
图2是Bi2O4/β-Bi2O3，Zn3In2S6和Zn3In2S6@Bi2O4/β-Bi2O3的XRD图。由图2可见，在Bi2O4/β-Bi2O3的谱图中，2θ＝29.35°，34.23°，41.34°，48.51°的衍射峰归因于Bi2O4(JCPDSno.50-0864)，2θ＝24.04°，28.34°，32.09°，45.71°，54.69°，58.94°处的衍射峰归因于β-Bi2O3(JCPDS no.78-1793)。对于单独的Zn3In2S6样品，其2θ＝28.23°，46.92°和56.44°处的衍射峰归因于Zn3In2S6(JCPDS no.65-4003)。Bi2O4/β-Bi2O3结构在Zn3In2S6@Bi2O4/β- Bi2O3复合材料中仅显示了较弱的特征峰，这是因为在该复合材料中的含量较低。
实施例2 Zn3In2S6@Bi2O4/β-Bi2O3光电催化剂在光电催化Cr(VI)还原为Cr(III)中的应用 (一)催化活性评价
方法：将K2Cr2O7溶解于浓度为0.1mol L-1，pH＝3.0的Na2SO4电解质溶液中，获得Cr(VI)浓度为3.5mg·L-1的Cr(VI)电解质溶液。将3mg Zn3In2S6@Bi2O4/β-Bi2O3涂覆在导电玻璃上作为工作电极，铂片为对电极，Ag/AgCl为参比电极组成三电极体系，偏压为- 0.6V，光源为300W氙灯(λ>420nm)，平均光强为100mW·cm-2。将三电极体系置于50 mL浓度为3.5mg·L-1的Cr(VI)电解质溶液中，评价Zn3In2S6@Bi2O4/β-Bi2O3催化Cr(VI)还原为Cr(III)的活性。电/光开始前，在黑暗中搅拌20min以达吸附和解吸平衡。采用显色法在 540nm处的紫外可见吸收进行定量分析，每隔20min测定一次目标物浓度。
图3是Zn3In2S6、Bi2O4/β-Bi2O3和Zn3In2S6@Bi2O4/β-Bi2O3催化Cr(VI)还原为Cr(III)的对比图。由图3可见，相比于单独的Zn3In2S6和Bi2O4/β-Bi2O3，Zn3In2S6@Bi2O4/β-Bi2O3光电催化剂展示了更高的催化还原活性，在光电催化120min时，还原率达到81.2％。
(二)催化还原条件对Cr(VI)还原为Cr(III)的影响
方法同(一)，分别对比了Zn3In2S6@Bi2O4/β-Bi2O3在单纯的光催化、电催化和在光电催化协同催化下，对Cr(VI)还原为Cr(III)的影响。
图4是Zn3In2S6@Bi2O4/β-Bi2O3在纯光、纯电、光/电协同作用下及在无催化剂条件下还原效果对比。由图4可见，在没有催化剂下Cr(VI)的还原效率很低，并且，相比于单纯的光催化和电催化，Zn3In2S6@Bi2O4/β-Bi2O3在光电催化协同作用下也展示了明显增强的催化活性，证明了光电的协同作用。
(三)pH对Cr(VI)还原为Cr(III)的影响
方法：将K2Cr2O7分别溶解于浓度为0.1mol L-1，pH＝3.0、4.0、5.0的Na2SO4电解质溶液中，获得不同pH的Cr(VI)浓度为3.5mg·L-1的Cr(VI)电解质溶液。将3mg Zn3In2S6@Bi2O4/β-Bi2O3涂覆在导电玻璃上作为工作电极，铂片为对电极，Ag/AgCl为参比电极组成三电极体系，偏压为-0.6V，光源为300W氙灯(λ>420nm)，平均光强为100 mW·cm-2，将三电极体系置于50mL浓度为3.5mg·L-1的Cr(VI)电解质溶液中，评价Zn3In2S6@Bi2O4/β-Bi2O3催化Cr(VI)还原为Cr(III)的活性。电/光开始前，在黑暗中搅拌20 min以达吸附和解吸平衡。采用显色法在540nm处的紫外可见吸收进行定量分析，每隔 20min测定一次目标物浓度。
图5是溶液pH对催化还原Cr(VI)活性的影响。由图5可见，pH值对Cr(VI)还原有明显影响，pH＝5时，还原效率较低，随着pH值降低催化活性明显增强，说明酸性条件有利于Cr(VI)的还原，本发明优选，采用pH＝3作为优选条件。
(四)不同Zn3In2S6@Bi2O4/β-Bi2O3用量对Cr(VI)还原效果的影响(pH＝3)
方法：将K2Cr2O7溶解于浓度为0.1mol L-1，pH＝3.0的Na2SO4电解质溶液中，获得Cr(VI)浓度为3.5mg·L-1的Cr(VI)电解质溶液。分别将2mg、3mg、4mg和5mg Zn3In2S6@Bi2O4/β-Bi2O3涂覆在导电玻璃上作为工作电极，铂片为对电极，Ag/AgCl为参比电极组成三电极体系，偏压为-0.6V，光源为300W氙灯(λ>420nm)，平均光强为100 mW·cm-2，将三电极体系置于50mL浓度为3.5mg·L-1的Cr(VI)电解质溶液中，评价Zn3In2S6@Bi2O4/β-Bi2O3催化Cr(VI)还原为Cr(III)的活性。电/光开始前，在黑暗中搅拌20 min以达吸附和解吸平衡。采用显色法在540nm处的紫外可见吸收进行定量分析，每隔 20min测定一次目标物浓度。
图6是不同Zn3In2S6@Bi2O4/β-Bi2O3用量对Cr(VI)还原效果的影响(pH＝3)。由图6可见，催化剂用量从2mg增大到3mg时，催化活性得到了明显提升，进一步增大催化剂用量，催化活性没有提升，而是些微降低，这可能是由于过多的催化剂降低了光的吸收及电荷传导速率，本发明优选每50mL浓度为3.5mg·L-1的Cr(VI)的溶液中加入3mg Zn3In2S6@Bi2O4/β-Bi2O3作为工作电极。
图7是本发明Zn3In2S6@Bi2O4/β-Bi2O3光电催化Cr(VI)还原为Cr(III)的反应动力曲线。由图7可见，表明该反应过程符合准一级动力学，相比于纯光和纯电条件， Zn3In2S6@Bi2O4/β-Bi2O3在光电协同作用下展现了更高的速率常数(速率常数为k＝0.01196 min-1)。
图8是Zn3In2S6@Bi2O4/β-Bi2O3在光/电协同作用下催化Cr(VI)还原反应机理。Zn3In2S6、Bi2O4及β-Bi2O3三种半导体均是n-型半导体，根据其带隙结构及能带弯曲理论，Zn3In2S6、Bi2O4及β-Bi2O3组成的三元异质结更易形成双Z型电荷传导模式，使复合材料具有更高的催化氧化/还原能力及更好的电荷分离效率。
Claims (7)
1.3D花状Zn3In2S6@Bi2O4/β-Bi2O3双Z型异质结光电催化剂，其特征在于，制备方法包括如下步骤：将Bi(NO3)3·5H2O溶解在苯甲醇中，搅拌10-20 min后，加入Zn3In2S6，超声10-20min后，再搅拌50 min，将所得混合溶液转移到聚四氟乙烯衬里的不锈钢高压釜中，在120℃下水热反应24h，反应结束后自然冷却至环境温度，产物用蒸馏水和无水乙醇洗涤，真空干燥后放入马弗炉中，于300-350 ℃保持5小时，得3D花状Zn3In2S6@Bi2O4/β-Bi2O3双Z型异质结光电催化剂。
2.根据权利要求1所述的3D花状Zn3In2S6@Bi2O4/β-Bi2O3双Z型异质结光电催化剂，其特征在于，所述Zn3In2S6的制备方法包括如下步骤：将ZnSO4·7H2O和硫代乙酰胺溶于去离子水中后，加入InCl3水溶液，搅拌30-40 min，所得混合溶液转移至高压釜中在160 ℃水热反应12 h，洗涤，干燥，得到Zn3In2S6。
3.权利要求1所述的3D花状Zn3In2S6@Bi2O4/β-Bi2O3双Z型异质结光电催化剂在光电催化Cr(VI)还原为Cr(III)中的应用。
4.根据权利要求3所述的应用，其特征在于，方法如下：将Zn3In2S6@Bi2O4/β-Bi2O3涂覆在导电玻璃上作为工作电极，铂片为对电极，Ag/AgCl为参比电极组成三电极体系，将三电极体系置于含Cr(VI)的电解质溶液中，进行光电催化还原。
5.根据权利要求4所述的应用，其特征在于，光电催化还原的条件为：偏压为-0.6V，光源为 300 W 氙灯，λ> 420 nm，平均光强为100 mW·cm-2。
6.根据权利要求4或5所述的应用，其特征在于，所述电解质溶液是pH=3.0的浓度为0.1mol·L-1的Na2SO4电解质溶液。
7.根据权利要求4或5所述的应用，其特征在于，调节含Cr(VI)的电解质溶液中，Cr(VI)的浓度为3-4mg·L-1，每50 mL含Cr(VI)的电解质溶液中加入2-5 mg Zn3In2S6@Bi2O4/β-Bi2O3。
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