CN112547077B - 一种宽光谱响应软铋矿基高效光催化剂及其制备方法 - Google Patents
一种宽光谱响应软铋矿基高效光催化剂及其制备方法 Download PDFInfo
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
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Abstract
本发明公开了一种宽光谱响应软铋矿基高效光催化剂及其制备方法，属于环境科学与无机材料制备领域。本发明采用水热法制备一种用于高效光催化降解有机污染物的新型宽光谱响应软铋矿基光催化剂Bi24(Bi2‑xCox)O39+x(0＜x≤1)，具体将铋盐和钴盐溶于特定浓度的碱液中，在较温合的温度与时间下进行水热反应，制得光催化剂Bi24(Bi2‑xCox)O39+x。本发明制备方法成本低、工艺简单、易于控制，为其他类似结构的软铋矿光催化剂制备提供新的制备思路；所得催化剂具有禁带宽度窄、结晶性好、纯度高的特点，对染料和酚类等水中有机污染物表现出良好的可见光催化降解活性，在可见光有机污染物降解领域拥有广泛的潜在应用前景。
Description
技术领域
本发明涉及一种宽光谱响应软铋矿基高效光催化剂及其制备方法，属于环境科学与无机材料制备领域。
背景技术
近年来，半导体光催化技术在污染物降解、光解水制氢等领域得到广泛运用。商用最广泛的二氧化钛由于禁带宽度大于3.0eV，只能利用占太阳光4％的紫外线，对占太阳光57％的可见光利用率较低。同时其紫外光污染物去除速率并不能满足实际应用的需求，因而实用化受到较大限制。开发新型、高效利用可见光的光催化剂，是目前光催化研究的主要方向。
铋盐是非二氧化钛系光催化剂中最重要的一类，可将光催化剂的光响应波长拓展至可见光区。软铋矿做为铋盐的一种，其具有可见光光催化活性是近年来刚刚被发现的，还有较大的提升空间。目前软铋矿光催化剂的制备多采用高温固相反应、水热合成等方法，其禁带宽度处在2.2-3.2eV之间，在可见光下对染料等有机然污染物表现出一定的降解活性。例如中国专利CN101147859A提出了一种溶剂热制备钛酸铋软铋矿的方法，但钛酸铋软铋矿的禁带宽度大于3.0eV，对可见光利用不足。美国专利US8709304B2提出一种水热法合成钛酸铋软铋矿纳米立方的方法，但其禁带宽度同样大于3.0eV。中国专利CN101723467A提出一种水热法合成铁酸铋软铋矿的方法，但其存在铁位缺陷较多、活性较差，可见光下照射14h对甲基橙去除率仅为78％。俄罗斯专利RU2463394C1提出一种以+5价铋盐为原料水热法合成铋、钐、钒复合软铋矿单晶材料，其缺陷较多。在文献报导中的软铋矿光催化剂(比如：AndréE.Nogueira et al.Colloid Interf.Sci.2014,415,89,Tae Hoon Noh etal.Ceram.Int.43,2017,12102–12108；Lin Xinping et al.Catal.Commun.9,2008,572–576.)，多用高温固相反应方法，普遍存在禁带宽度过宽、缺陷多、可见光活性低的问题。
发明内容
为了解决上述问题，本发明首次提出了一种宽光谱响应软铋矿Bi24(Bi2-xCox)O39+x光催化剂，其禁带宽度窄、缺陷少、降解污染物活性好，有很好的工业应用前景。
本发明的第一个目的是提供一种制备钴基软铋矿基光催化剂Bi24(Bi2-xCox)O39+x的方法，所述x大于0且不超过1；所述方法包括如下步骤：
(1)利用强碱溶于水中，配置0.3～4mol/L的碱液A；
(2)将铋盐和钴盐加入到碱液A中进行水热反应，反应结束后，固液分离，收集固体沉淀，洗涤、干燥。
在本发明的一种实施方式中，所述步骤(1)中强碱包括如下任意一种或多种：氢氧化钠、氢氧化钾、氨水。
在本发明的一种实施方式中，所述步骤(2)中铋盐与钴盐中Bi3+与Co2+的摩尔比为(0.1～2.5)：0.1。
在本发明的一种实施方式中，所述步骤(2)中铋盐相对碱液A的摩尔浓度为0.03-0.1mol/L；优选0.033-0.083mol/L。
在本发明的一种实施方式中，所述步骤(2)中铋盐为水溶性铋盐，选自如下任意一种或多种：硝酸铋、氯化铋、醋酸铋。
在本发明的一种实施方式中，所述步骤(2)中钴盐为水溶性钴盐，选自如下任意一种或多种：硝酸钴、六水合硝酸钴、醋酸钴、氯化钴。
在本发明的一种实施方式中，所述步骤(2)中水热反应的反应温度为120℃～270℃。
在本发明的一种实施方式中，所述步骤(2)中水热反应的反应时间为12～72h。
在本发明的一种实施方式中，所述步骤(2)中洗涤是将固体沉淀洗涤至中性。
在本发明的一种实施方式中，所述步骤(2)中干燥是采用60℃鼓风烘箱干燥。
在本发明的一种实施方式中，上述的宽光谱响应软铋矿基高效光催化剂Bi24(Bi2- xCox)O39+x的制备方法，所述方法具体包括如下步骤：
(1)碱溶液配制：将0.009～0.12mol强碱用30ml去离子水溶液溶解得到碱液A；碱液A浓度为0.3～4mol/L；
(2)铋-钴混合盐溶液配制：将0.1～2.5mmol铋盐和0.1mmol钴盐混合加入碱液A中，得到混合溶液B；溶液B搅拌30min后，将得到的淡黄色沉淀转移至对位聚苯(PPL)内衬的水热釜内120℃～270℃水热反应12～72h；离心、用去离子水和乙醇洗涤步骤3得到的固体颗粒至pH为7，转移至60℃鼓风烘箱干燥即得产物。
本发明的第二个目的是利用上述方法提供一种钴基软铋矿基光催化剂Bi24(Bi2- xCox)O39+x。
在本发明的一种实施方式中，所述钴基软铋矿基光催化剂的禁带宽度为1.7～2.2eV。
本发明的第三个目的是将上述的钴基软铋基矿光催化剂Bi24(Bi2-xCox)O39+x应用于污染物降解中。
有益效果：
与现有技术相比，本发明提出的宽光谱响应钴基软铋矿基高效光催化剂Bi24(Bi2- xCox)O39+x具有如下优点：本发明合成的光催化剂具有带隙窄、光催化活性高等优点。本发明的催化剂禁带宽度在1.7～2.2eV，显著小于现有报道的软铋矿基光催化剂如Bi25FeO40(2.72eV)、Bi24AlO39(2.46eV)等。本发明的软铋矿光催化剂可见光响应波长可达730nm，对可见光(400－800nm)利用率更高，在可见光下照射4h对亚甲基蓝的去除率达到84％。
本发明提出的制备宽光谱响应软铋矿基高效光催化剂Bi24(Bi2-xCox)O39+x的方法是水热合成法，本发明的方法工艺简单、温度合适、条件可控。高温固相制备软铋矿光催化剂缺陷和杂质较多，本发明的方法制备的软铋矿光催化剂结晶性好，缺陷和杂质少(从X射线衍射谱图可以得到证实)，活性高。本发明为其它类似软铋矿基光催化剂的制备提供了借鉴。
附图说明
图1为本发明制备的宽光谱响应软铋矿基高效光催化剂Bi24(Bi2-xCox)O39+x(x＝0、0.1、1)的X射线衍射谱图；(x＝0为不添加Co盐的对比实照)
图2为本发明制备的宽光谱响应软铋矿基高效光催化剂Bi24(Bi2-xCox)O39+x(x＝1)的扫描电子显微镜图像；
图3为本发明制备的宽光谱响应软铋矿基高效光催化剂Bi24(Bi2-xCox)O39+x(x＝1)的X射线能量色散光谱图；
图4为本发明制备的宽光谱响应软铋矿基高效光催化剂Bi24(Bi2-xCox)O39+x(x＝1、0.1、0)的紫外-可见光漫反射吸收光谱；(x＝0为不添加Co盐的对照)
图5为本发明制备的宽光谱响应软铋矿基高效光催化剂Bi24(Bi2-xCox)O39+x(x＝1、0.65、0.1)可见光催化降解亚甲基蓝曲线；
图6为本发明制备的宽光谱响应软铋矿基高效光催化剂Bi24(Bi2-xCox)O39+x(x＝1)对亚甲基蓝、罗丹明B(2×10-5mol/L、100ml)、4-氯苯酚(5ppm、50ml)、苯酚(5ppm、50ml)染料的去除率(统一采用300W氙灯，酚类检测采用超高效液相色谱)。
具体实施方式
实施例1：
将0.009mol NaOH溶于30ml去离子水中(即0.3M)，加入2.5mmol的Bi(NO3)3·5H2O(即0.083M)和0.1mmol的Co(NO3)2·6H2O(即0.0033M)，搅拌30min，将淡黄色沉淀转移至50ml对位聚苯(PPL)内衬的水热釜内，在270℃水热12h，冷却至室温，产物离心，用去离子水和乙醇洗涤至pH为7，在60℃烘干，得到产物Bi24(Bi2-xCox)O39+x(x＝1)。
实施例2：
将1mL浓氨水加入30ml去离子水中(即0.4M)，加入1mmol的(CH3CO2)3Bi(即0.033M)和1mmol的CoCl2(即0.033M)，搅拌30min，将淡黄色沉淀转移至50ml对位聚苯(PPL)内衬的水热釜内，在120℃水热72h，冷却至室温，产物离心，用去离子水和乙醇洗涤至pH为7，在60℃烘干，得到产物Bi24(Bi2-xCox)O39+x(x＝0.65)。
实施例3：
将0.12mol KOH溶于30ml去离子水中(即4M)，加入1.6mmol的BiCl3(即0.053M)和0.1mmol的C4H6CoO4(即0.0033M)，搅拌30min，将淡黄色沉淀转移至50ml对位聚苯(PPL)内衬的水热釜内，在180℃水热24h，冷却至室温，产物离心，用去离子水和乙醇洗涤至pH为7，在60℃烘干，得到产物Bi24(Bi2-xCox)O39+x(x＝0.1)。
对比例1：不添加Co盐的对照
参照实施例1，不添加Co盐，其他条件不变，制得相应的催化剂Bi24Bi2O39(即相当于x＝0的情形)。
对实施例1-3和对比例1所得催化剂进行结构表征：
图1为本发明制备的宽光谱响应软铋矿基高效光催化剂Bi24(Bi2-xCox)O39+x(x＝0、0.1、1)的X射线衍射谱图，可以用来分析样品的晶型和结晶性。由X射线衍射结果可以看出，当x＝0时，所制得样品为γ-Bi2O3(图1中PDF No.45-1344)，且无不纯相。随着Co掺入γ-Bi2O3的晶格中，开始形成软铋矿相。当x分别为0.1和1时，所制得样品分别对应于图1中PDFNo.51-1015和PDF No.39-0871。且都无不纯相。
图2为本发明制备的宽光谱响应软铋矿基高效光催化剂Bi24(Bi2-xCox)O39+x(x＝1)的扫描电子显微镜图像，可以用来分析催化剂的形貌和颗粒粒径的大小。由扫描结果可以看出，催化剂颗粒粒径处于10-40μm，呈现出三角形和板状结构。且出现颗粒聚集现象。
图3为本发明制备的宽光谱响应软铋矿基高效光催化剂Bi24(Bi2-xCox)O39+x(x＝1)的X射线能量色散光谱图，可以用来分析催化剂中元素含量。由谱图结果可以看出，所得催化剂中Bi元素含量明显高于Co，分析结果与原料的加入比例一致。
图4为本发明制备的宽光谱响应软铋矿基高效光催化剂Bi24(Bi2-xCox)O39+x(x＝1、0.1、0)的紫外-可见光漫反射吸收光谱，可以用来研究物质的吸光特性。由漫反射结果可以看出随着Co含量的增加，催化剂的吸收带边逐渐向高波数偏移(红移)，原因在于Co的3d轨道电子跃迁发生在较高的波数。表明所制得催化剂对可见光(400-800nm)利用逐渐增强。此外，更宽的光谱吸收意味着更窄的带隙。
实施例4钴基软铋矿基高效光催化剂的应用
以亚甲基蓝为典型污染物代表：准确称取0.05g催化剂粉末，将其加入到100ml浓度为2×10-5mol/L的亚甲基蓝水溶液中，超声波作用下制成悬浮液，黑暗下搅拌处理30min，达到吸附平衡，用300W氙灯作为光源，420nm截止滤光片滤除紫外光，可见光照射下进行反应。开始前1h每30min取4ml的样品，此后每1h取4ml样品，离心去除催化剂，用紫外分光光度计分析剩余溶液的亚甲基蓝浓度。
相应的，将2×10-5mol/L的亚甲基蓝水溶液替换为罗丹明B(2×10-5mol/L、100ml)、4-氯苯酚(5ppm、50ml)、苯酚(5ppm、50ml)，分别测定相应的去除效果。
结果如图5、6所示，具体结果见表1。
表1实施例1-3所得光催化剂对四种目标污染物的降解去除效果
其中，去除率的含义为：C/Co(C表示取点时样品浓度；Co表示污染物初始浓度)
对比例2
参照实施例1，将NaOH的用量由0.009mol替换为0.15mol(即碱液浓度为5M)，其他条件不变，碱浓度过高会导致Bi2O3杂相的出现，无法制得相应的纯相复合氧化物光催化剂。
参照实施例4中的应用过程，结果发现：在同等条件下降解MB，5M碱液所制得的样品对亚甲基蓝的去除率不超过20％，基本没有光催化活性。
对比例3
参照实施例1，将Co(NO3)2·6H2O的替换等摩尔量的为Fe(NO3)3，其他条件不变，制得相应的铁基复合氧化物光催化剂。
参照实施例4中的应用过程，结果发现：在同等条件下降解MB，铁基复合氧化物光催化剂的去除率仅为30％，远小于本专利涉及的钴基光催化剂。
Claims (9)
1.一种制备钴基软铋矿基光催化剂Bi24(Bi2-xCox)O39+x的方法，其特征在于，所述x大于0且不超过1；所述方法包括如下步骤：
(1)利用强碱溶于水中，配置0.3～4mol/L的碱液A；
(2)将铋盐和钴盐加入到碱液A中进行水热反应，其中铋盐与钴盐中Bi3+与Co2+的摩尔比为(0.1～2.5)：0.1；反应结束后，固液分离，收集固体沉淀，洗涤、干燥。
2.根据权利要求1所述的方法，其特征在于，所述步骤(2)中铋盐相对碱液A的摩尔浓度为0.03-0.1mol/L。
3.根据权利要求1所述的方法，其特征在于，所述步骤(2)中铋盐选自如下任意一种或多种：硝酸铋、氯化铋、醋酸铋。
4.根据权利要求1所述的方法，其特征在于，所述步骤(2)中钴盐选自如下任意一种或多种：硝酸钴、六水合硝酸钴、醋酸钴、氯化钴。
5.根据权利要求1所述的方法，其特征在于，所述步骤(2)中水热反应的反应温度为120℃～270℃。
6.根据权利要求1所述的方法，其特征在于，所述步骤(2)中水热反应的反应时间为12～72h。
7.根据权利要求1所述的方法，其特征在于，所述步骤(1)中强碱包括如下任意一种或多种：氢氧化钠、氢氧化钾、氨水。
8.权利要求1-7任一项所述方法制备得到的一种钴基软铋矿基光催化剂Bi24(Bi2-xCox)O39+x，其特征在于，所述x大于0且不超过1。
9.权利要求8所述的钴基软铋基矿光催化剂Bi24(Bi2-xCox)O39+x在污染物降解中的应用。
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