CN107715901B - 一种氧化银/碳酸氧铋复合光催化剂一锅水热制备的方法 - Google Patents
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Abstract
本发明公开了一种Ag2O/Bi2O2CO3复合光催化剂一锅水热的制备方法。它是以Bi(NO3)3和AgNO3作为盐源，巧妙利用Na2CO3既可以提供CO3 2‑离子，又因水解产生弱碱性OH‑的双重作用，经过60℃低温水热反应4h成功合成了Ag2O表面修饰的Bi2O2CO3光催化剂。结果表明微量Ag2O的修饰不但可以拓宽Bi2O2CO3对太阳光的吸收范围，而且半导体的光生载流子复合得到了有效抑制。在Ag2O质量百分比为0.05‑2.0%范围内，复合材料的光催化活性均明显提高，其中Ag2O质量百分含量为0.52%时光催化活性最佳，其降解罗丹明B的动力学常数为纯Bi2O2CO3的2.7倍，且表现出良好的循环利用性。该制备方法简单可行、低能短时，预示了该复合光催化剂良好的应用前景。
Description
技术领域
本发明属于水体污染保护技术领域，涉及工业废水的处理技术，更具体地说是一种高性能Ag2O/Bi2O2CO3复合光催化剂一锅水热制备的方法。
背景技术
随着全球经济和现代工业迅猛发展，由此带来的能源与环境问题也日益显露。由工业生产所引起的水体污染是当今社会亟待解决的问题之一。近年来，光催化技术作为一种“绿色”技术，因其能源消耗低、氧化能力强、反应条件温和等优点，倍受广大科研工作者关注，成为解决环境水污染问题的关键技术。
近几年，具有Sillén层状结构的铋系碳酸盐Bi2O2CO3（BOC）因其优异的光催化性能受到广泛关注。但为了满足该催化剂的实用化要求，仍然存在两个需要解决的问题：一是其带隙较宽（约3.2 eV）,只能吸收占太阳光不足5%的紫外光，对太阳能的利用率太低；二是单一体系半导体中的光生电子-空穴复合速率快，使其光量子效率仍相对较低。因此，有效改善上述问题，进一步提高BOC的光催化活性并实现实用化，是目前该催化剂研究中需要解决的关键问题。
研究表明对BOC进行金属氧化物半导体复合，可以有效拓宽对可见光的吸收范围，并利用半导体间的带隙耦合效应促进光生载流子有效分离，从而提高其光催化活性。Ag2O是一种窄带隙（1.2eV）半导体，在整个可见光区甚至近红外区均有光吸收。而且，根据“绝对电负性”的理论计算预测，该半导体与BOC具有匹配的带隙位置，因此研究Ag2O对BOC的修饰，对于解决上述两大科学问题，并提高其光催化活性，具有重要的理论和实际意义。有文献报道将商业化的BOC浸渍在AgNO3溶液中，再用300 W的氙弧灯光照可使其分解出Ag2O，从而合成Ag2O修饰BOC的复合光催化剂。该方法实际为两步合成，需要首先制得BOC前驱体，并且复合过程中用到了高能氙灯的辐照，操作繁琐而耗能，难于规模化生产。该文献中最佳Ag2O的质量百分比为23%，因AgNO3用量较大而并不经济实用。此外，根据理论知识，AgNO3经光照后的产物通常为Ag单质而非Ag2O。因此，有必要探索操作简单、易于规模化、经济可行的方法，对BOC光催化剂进行Ag2O的复合。
本发明本着简化制备工艺、节约能源、并提高性能的角度，巧妙利用Na2CO3既可以提供CO32-离子，又因水解产生弱碱性的双重作用，仅通过在合成BOC的反应体系中加入AgNO3，利用AgOH的极不稳定性，通过一步水热法合成了Ag2O修饰的BOC光催化剂。发现Ag2O质量百分比在0.05-2.0%的范围内光催化活性均得到提高，其中复合含量0.52%时光催化活性最佳，其动力学常数达到纯BOC样品的2.7倍。
发明内容
为实现上述目的，本发明公开了如下的技术内容：
一种高性能Ag2O/Bi2O2CO3复合光催化剂的制备方法，其特征在于它是通过低温、短时的一锅水热法制备而成，其方法如下：
称取1.0 mmol Bi(NO3)3•5H2O于25.0 mL 水热反应釜中，加入7.0 mL蒸馏水并剧烈搅拌10 min，再称取6.0 mmol Na2CO3用蒸馏水溶解；将Na2CO3溶液缓慢滴加于反应釜中，继续搅拌30 min后，再缓慢滴加不同体积的AgNO3储备液（0.0011 mol/L），充分反应后将所得悬浊液于60 ℃恒温水热反应4 h，将产物分离并多次洗涤后于60℃干燥，得到Ag2O/Bi2O2CO3复合光催化剂；其中复合光催化剂中Ag2O的质量百分比为0.05-2.0%。优选复合光催化剂中Ag2O的质量百分比为0.52%。
本发明所述的滴加不同体积的AgNO3储备液指的是：滴加0.1-4.0 mL 的0.0011mol/L 的AgNO3储备液。
本发明所述的复合光催化剂，Na2CO3既提供基质产物Bi2O2CO3所需的CO32-离子，又通过水解提供生成Ag2O所需的OH-离子，其中反应温度为60℃，反应时间为4h。
本发明进一步公开了高性能Ag2O/BOC复合光催化剂在降解有机染料方面的应用。特别是在在降解印染车间所排污水中含有的难降解性芳香类化合物中的应用。
该复合光催化剂在降解有机染料方面表现出良好的循环利用性。该合成方法为简单一锅水热法，具有痕量的Ag2O负载量和优异的光催化性能，这些优势预示着该光催化剂在工业废水处理领域的良好应用前景。
附图说明
图1为总的不同样品的XRD图谱；其中
图1A为不同样品的XRD图谱、1B为最佳样品的EDS图谱：A图中所有样品的衍射峰均与BOC的标准卡片（JCPDS No. 41-1488）吻合，表明产物为高纯度的BOC。同时说明在该低温水热反应过程中，Ag2O的修饰并没有影响BOC基质的晶相结构。但由于Ag2O的主强峰与BOC的次强峰位置基本相同，且所复合的Ag2O含量较少，因而在衍射图谱中不能明显观察到Ag2O晶相。进一步对Ag2O/BOC-0.52%样品进行了电子能谱（EDS）的分析，如图1B所示，除了Bi、C和O三种元素外，从能谱图中可清楚检测到Ag2O中Ag元素的存在；
图2为BOC及不同复合比例Ag2O/BOC的紫外-可见漫反射光谱。BOC陡峭的吸收光谱说明来自本征带隙跃迁，但由于其带隙能较大，仅能吸收波长小于391 nm的紫外光，对太阳能的利用率较低。而Ag2O在整个检测光区都表现出较强吸收。当对BOC进行Ag2O的表面修饰后，Ag2O/BOC复合光催化剂的吸收带边明显红移。而且随着Ag2O复合比例的增加，在可见光的吸收程度逐渐增强，说明复合光催化剂能够更加有效地利用太阳能；
图3为在280 nm紫外光激发下系列BOC的荧光光谱。荧光光谱常用来考察光生载流子的分离和复合过程，荧光强度的减弱通常意味着载流子的复合几率降低。BOC在350-400nm表现出较宽的荧光发射带，其中385 nm的最强荧光峰归属于激发电子从导带跃迁回价带，从而引起光生载流子复合而释放出的能量。Ag2O/BOC复合光催化剂的荧光峰形与BOC基本一致，但荧光强度明显下降，尤其Ag2O含量为0.52%时，样品的荧光强度最低。说明Ag2O的复合可有效抑制光生载流子的复合，从而提高了光量子效率；
图4 为各光催化剂（5.0 mg）在250W Xe灯辐照下，光催化降解10 ml RhB（10-5 M）溶液的性能对比图；其中（A）为降解效率，（B）为相应的准一级反应速率常数。空白实验表明在RhB的光解和BOC对染料分子的吸附均较弱，不影响光催化的性能对比。对于纯BOC，光照40min后对RhB的降解率为87%，准一级降解反应速率常数为0.050 min-1；而复合Ag2O后BOC的光催化活性均明显提高。其中Ag2O/BOC-0.52%的样品性能最佳，辐照40min后已经将RhB完全脱色，其反应速率常数可达0.136 min-1，为复合前样品的2.7倍。复合比例过高时，反应速率虽有所降低，但仍均高于纯BOC。说明二者之间的最佳复合比例为Ag2O-0.52%，过高的复合含量将因缺陷效应而产生逆向抑制作用。
光催化剂的循环稳定性是影响其实用化的重要因素之一；图5为Ag2O/BOC-0.52%的循环效果图，经过五个周期的循环后，经40 min辐照对RhB的降解效率仍然可以达到92%。说明该催化剂具有良好的光热稳定性，具有广阔的应用前景。
具体实施方式
为了进一步解释本发明，提供下述制备方法实施实例。以下实施例的表述不限制本发明，本领域的专业人员可按照本发明的精神对其进行改进和变化，所述的这些改进和变化都应视为在本发明新型的范围内。本发明所述的各种原料例如Bi(NO3)3•5H2O、Na2CO3、AgNO3均有市售。
实施例1
称取0.4851 g Bi(NO3)3•5H2O于25.0 mL 水热反应釜中，加入7.0 mL蒸馏水并磁力搅拌10 min，再称取6.0 mmol Na2CO3用蒸馏水溶解。将Na2CO3溶液缓慢滴加于反应釜中，继续搅拌30 min后，再缓慢滴加0.1 mL AgNO3储备液（0.0011 mol/L），充分反应后将所得白色悬浊液于60℃恒温水热反应4 h。自然冷却至室温后将产物离心分离、洗涤并干燥，得到Ag2O/BOC-0.05%的复合光催化剂。
实施例2
称取1.0 mmol Bi(NO3)3•5H2O于25.0 mL 水热反应釜中，加入7.0 mL蒸馏水并磁力搅拌8 min，再称取6.0 mmol Na2CO3用蒸馏水溶解。将Na2CO3溶液缓慢滴加于反应釜中，继续搅拌30 min后，再缓慢滴加1.04 mL AgNO3储备液（0.0011 mol/L），将充分反应后的悬浊液于60℃恒温水热反应4 h。自然冷却至室温后将产物分离、洗涤并干燥，得到Ag2O/BOC-0.52%的复合光催化剂。
实施例3
称取0.4851 g Bi(NO3)3•5H2O于25.0 mL 水热反应釜中，加入7.0 mL蒸馏水并磁力搅拌10 min，再称取6.0 mmol Na2CO3用蒸馏水溶解。将Na2CO3溶液缓慢滴加于反应釜中，继续搅拌30 min后，再缓慢滴加2.08 mL AgNO3储备液（0.0011 mol/L），充分反应后将所得白色悬浊液于60℃水热反应4 h。自然冷却至室温后将产物离心分离、洗涤并于60℃干燥，得到Ag2O/BOC-1.04%的复合光催化剂。
实施例4
称取1.0 mmol Bi(NO3)3•5H2O于25.0 mL水热反应釜中，加入7.0 mL蒸馏水并搅拌10 min，再称取6.0 mmol Na2CO3用蒸馏水溶解。将Na2CO3溶液缓慢滴加于反应釜中，继续搅拌30 min后，再缓慢滴加4.0 mL AgNO3储备液（0.0011 mol/L），充分反应后将所得白色悬浊液于60℃水热反应4 h。将所得产物离心分离、洗涤并于60℃干燥，得到Ag2O/BOC-2.0%的复合光催化剂。
实施例5
印染车间所排污水中含有的难降解性芳香类化合物的降解实例：
罗丹明B是印染工业常用的难降解芳香类红色染料，从印染车间取含有RhB染料4.8 mg/L的废水500 mL，加入Ag2O/BOC-0.52%的光催化剂250 mg，在XPA-7型光化学反应仪暗箱中磁力搅拌达到吸-脱附平衡，经250W氙灯模拟日光辐照40 min后，立即过滤分离，测上清液的吸光度，并计算罗丹明B的降解率为100%，而同等条件下纯BOC的光催化降解效率仅为87%
实施例6
选定性能最佳的Ag2O/BOC-0.52%样品，对除RhB外的其它染料，包括亚甲基蓝和甲基橙也分别进行了相同条件下的光降解实验，并和未经复合的纯BOC样品进行了对比，所得不用时间的降解率数据列表如下：
从上表数据可以看出，Ag2O/BOC-0.52%光催化剂不但对RhB的降解效率明显高于未经复合的BOC，对其它染料如亚甲基蓝和甲基橙的降解表现出同样地优势。说明该发明中的复合光催化剂在降解印染车间所排含芳香类化合物的污水中确实具有良好的应用前景。
Claims (4)
1.一种高性能Ag2O/Bi2O2CO3复合光催化剂的制备方法，其特征在于它是通过低温、短时的一锅水热法制备而成，其方法如下：
称取1.0 mmol Bi(NO3)3•5H2O于25.0 mL 水热反应釜中，加入7.0 mL蒸馏水并剧烈搅拌10 min，再称取6.0 mmol Na2CO3用蒸馏水溶解；将Na2CO3溶液缓慢滴加于反应釜中，继续搅拌30 min后，再缓慢滴加不同体积的0.0011 mol/L 的AgNO3储备液，充分反应后将所得悬浊液于60℃ 恒温水热反应4 h，将产物分离并多次洗涤后于60℃干燥，得到Ag2O/Bi2O2CO3复合光催化剂；其中复合光催化剂中Ag2O的质量百分比为0.05-2.0%。
2.权利要求1所述的制备方法，其中滴加不同体积的AgNO3储备液指的是滴加0.1 ~ 4.0mL的0.0011 mol/L 的AgNO3储备液。
3.权利要求1所述的制备方法，其中复合光催化剂中Ag2O的质量百分比为0.52%。
4.权利要求1所述Ag2O/ Bi2O2CO3复合光催化剂在降解罗丹明B、亚甲基蓝和甲基橙方面的应用。
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