CN114505086A - 一种异质结光催化剂BaSb2O6/g-C3N4的制备方法 - Google Patents
一种异质结光催化剂BaSb2O6/g-C3N4的制备方法 Download PDFInfo
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Abstract
本发明公开了一种二维异质结光催化剂BaSb2O6/g‑C3N4的制备方法。该方法包括:采用固相烧结法分别制得BaSb2O6和g‑C3N4,然后将BaSb2O6、g‑C3N4和无水乙醇混合,研磨,在480℃恒温烧结2h,自然降温至室温后即得到异质结BaSb2O6/g‑C3N4光催化剂。该异质结BaSb2O6/g‑C3N4可以有效催化苯甲醇脱氢生产苯甲醛,实现高效、绿色催化有机合成反应。另外,该异质结在降解四环素方面具有良好的光催化效果,且光催化性质稳定。
Description
技术领域
本发明属于有机化学和环保领域、具体涉及一种异质结光催化剂BaSb2O6/g-C3N4的制备及其在可见光光催化苯甲醇脱氢生产苯甲醛和降解四环素的用途。
背景技术
作为重要的有机化工原料中间体苯甲醛,一直以来被广泛应用于食品、塑料、香料、农药、医药、农药等领域、目前工业上生产苯甲醛传统的方法主要是二氯甲烷水解及甲苯直接氧化等方法,缺点是产物苯甲醛中含氯离子或是苯甲醛产率低,使得其应用受到了限制。因此,实现高效、绿色催化苯甲醇催化氧化生产苯甲醛一直以来备受科研工作者的关注。另外,近年来,环境中残留的抗生素四环素对人类的健康及生态环境造成了极大的威胁,有效去除四环素是亟待解决的重要的环境问题,作为一种有效的高级氧化技术,可见光光催化技术是一种绿色有效的催化及降解抗生素的重要手段。在可见光照射下,利用半导体表面产生的活性自由基(和)可以氧化降解有机污染物分子。开发与寻找高效稳定的新型半导体光催化剂是实现光催化降解有机抗生素分子的重要前提。
当前,人们已对TiO2,ZnO和WO3等金属氧化物半导体进行了广泛研究。然而,由于可见光吸收差、量子效率低等本征缺陷,在很大程度上限制了其光催化方面的发展。提升光生载流子的有效分离程度是增强其光催化效率的核心问题。在这方面,构筑半导体异质结是解决上述问题的有效手段。因此,二维材料因其独特的结构和光学性能,在光催化领域得到了广泛的研究。然而,BaSb2O6/g-C3N4用于光催化苯甲醇氧化生产苯甲醛以及降解四环素还未见报道。
本发明人采用固相烧结方法合成异质结光催化剂BaSb2O6/g-C3N4。研究结果表明,在可见光下,制备的BaSb2O6/g-C3N4异质结对催化苯甲醇脱氢生产苯甲醛以及降解四环素溶液的光降解性均优于母体化合物BaSb2O6和g-C3N4,且4小时内质量比为5wt%的异质结光催化降解效率为80%,通过光催化机制分析,研究表明光催化效率的提升可能源自于g-C3N4与BaSb2O6形成的Type-II型异质结提升了光生载流子的分离效率所致。
发明内容
本发明的目的在于提供了一种异质结光催化剂BaSb2O6/g-C3N4的制备方法,以及该方法制得的异质结BaSb2O6/g-C3N4在可见光下在催化苯甲醇生产苯甲醛、降解四环素等方面的应用。
为实现本发明的目的,提供如下实施方案。
在一实施方案中,本发明的一种二维异质结光催化剂BaSb2O6/g-C3N4的制备方法,包含以下步骤:
1)将BaCl2和Sb2O3按摩尔比1:(1.05-1.5)混合、研磨均匀后,在850-900℃温度下烧结7-15h,冷却至室温后得到粉末状BaSb2O6前驱体;
2)将三聚氰胺在520-600℃下烧结1.5-2.5h,自然冷却至室温,即得粉末g-C3N4前驱体;
3)将步骤1)的BaSb2O6前驱体和步骤2)的g-C3N4前驱体与无水乙醇以质量比混合研磨均匀,置于马弗炉中,在450-500℃恒温下煅烧1.5-2.5h;
4)煅烧反应结束后,自然冷却至室温,制得异质结光催化剂BaSb2O6/g-C3N4。
优选的,上述本发明的制备方法,步骤1)中,BaCl2与Sb2O3的摩尔比为1:1.05,烧结温度为870℃,烧结时间为10h;步骤2)中,所述烧结,以4℃/min的速率加热至560℃,并保温2h,进一步包括将制得的g-C3N4用0.1mol/L稀HNO3洗涤、再用无水乙醇洗涤、烘干;步骤3)中,BaSb2O6前驱体与g-C3N4前驱体的质量比为1:6~1:50,优选为1:19,所述研磨,BaSb2O6、g-C3N4和无水乙醇混合研磨时间为30min,所述煅烧,锻烧温度为480℃,锻烧时间为2h。
优选的,上述本发明的制备方法,步骤4)中,获得的BaSb2O6/g-C3N4,其中,BaSb2O6占异质结BaSb2O6/g-C3N4重量的质量百分比为2-15wt%,更优选的,BaSb2O6的质量百分比为5wt%。
本发明还提供了本发明的方法制备的BaSb2O6/g-C3N4用于光催化降解四环素的用途,以及用作苯甲醇催化脱氢生产苯甲醛的催化剂的用途。
在一具体实施方案中,本发明的一种异质结光催化剂BaSb2O6/g-C3N4的制备方法,包含以下步骤:
1)将BaCl2和Sb2O3按照一定摩尔比1:(1.05-1.5)混合、研磨均匀后,放入高温马弗炉在850-900℃烧结7-15h,冷却至室温后得到白色粉末状BaSb2O6前驱体;
2)将三聚氰胺放入高温马弗炉中,在520-600℃下烧结1.5-2.5h,待其自然冷却至室温后,即得黄色粉末g-C3N4(类石墨相氮化碳)前驱体;
3)将得到的BaSb2O6、g-C3N4前驱体和无水乙醇一定质量比混合研磨均匀;
4)将上步研磨后的混合样品转移至马弗炉中,加热升温至450-500℃恒温煅烧1.5-2.5h;
5)待反应结束后,自然冷却至室温,制得异质结光催化剂BaSb2O6/g-C3N4,
其中,BaSb2O6前驱体与g-C3N4前驱体的质量比足以使煅烧反应获得的异质结BaSb2O6/g-C3N4催化剂,其BaSb2O6占异质结重量的质量百分比为2-15wt%,更优选的,质量百分比为5wt%。
在上述实施方案中,本发明的方法,进一步包括将步骤2)中制得的g-C3N4用0.1mol/L稀HNO3洗涤、搅拌,再用无水乙醇洗涤,最后水洗,60℃烘干即可。
在上述实施方案中,本发明的方法,步骤1)中,BaCl2·2H2O和Sb2O3的摩尔比为1:1.05,研磨时间为30min,烧结温度为870℃,烧结时间为10h;步骤2)中,三聚氰胺的量为3g,烧结温度为560℃,烧结时间为2h;步骤3)中,无水乙醇的用量是1ml,研磨时间为30min;步骤4)中,升温过程中,其升温速率为5℃/min,烧结温度恒温为480℃,煅烧时间为2h。
本发明的一种异质结光催化剂BaSb2O6/g-C3N4的制备方法,包含以下步骤:
1)将BaCl2和Sb2O3按照一定摩尔比(1mmol:1.05mmol)混合、研磨均匀后,放入高温马弗炉在870℃烧结10h,冷却至室温后得到白色粉末状BaSb2O6前驱体;
2)将3g三聚氰胺混合均匀后放入高温马弗炉,在560℃烧结2h,待其冷却至室温后即得黄色粉末g-C3N4前驱体,用0.1mol/L的稀HNO3搅拌10min,再用无水乙醇洗涤10min,最后60℃烘干;
3)将所得BaSb2O6前驱物与g-C3N4前驱体混合、研磨均匀后,以5℃/min的升温速率加热至480℃,保温煅烧反应2h;
4)待反应结束,自然冷却至室温,即得异质结光催化剂BaSb2O6/g-C3N4,
其中,在BaSb2O6/g-C3N4中,BaSb2O6的质量百分含量为5%。
本发明利用固相烧结法制得的二维异质结光催化剂BaSb2O6/g-C3N4在催化苯甲醇催化制备苯甲醛以及催化降解四环素中的用途,特别是用于光催化降解环境水体中残存的四环素。
在具体实施方案中,本发明的一种二维异质结光催化剂BaSb2O6/g-C3N4的制备方法,包含以下步骤
1)分别称取1mmol BaCl2·2H2O、1.05mmol Sb2O3混合研磨40min后,转移至刚玉坩埚中;
2)将刚玉坩埚放入高温马弗炉中,于870℃烧结10h,自然降温后,最终制得BaSb2O6前驱体;
3)称取1g三聚氰胺混合均匀后,转移至刚玉坩埚中,将刚玉坩埚放入马弗炉中,以4℃/min的升温速率于560℃烧结2h,自然降温后即得g-C3N4前驱体;
4)制得的g-C3N4用150mL 0.1mol/L稀HNO3洗涤、搅拌,再用150mL无水乙醇洗涤、搅拌,烘干即可;
5)将上述两前驱体BaSb2O6、g-C3N4和1mL无水乙醇混合研磨30min后,所得样品转移至刚玉坩埚中;
6)将刚玉坩埚转移至高温马弗炉中,以5℃/min的升温速率与480℃烧结2h,自然冷却至室温,最终制得二维异质结光催化剂BaSb2O6/g-C3N4,其中,BaSb2O6的质量百分比为5wt%。
本发明的有益效果是:用固相烧结法获得的异质结光催化剂BaSb2O6/g-C3N4对催化苯甲醇氧化生产苯甲醛、降解抗生素取得良好的作用效果,该催化剂可以高效催化苯甲醇脱氢生产苯甲醛。另外,特别是对四环素类药物具有良好的催化降解作用,特别是BaSb2O6质量百分比为5wt%的异质结BaSb2O6/g-C3N4光催化降解效率达80%,可用于水体污染物中抗生素如四环素类药物的降解,有利于环保处理,且可以循环使用,催化特性稳定。
附图说明
图1为g-C3N4,BaSb2O6及光催化剂异质结BaSb2O6/g-C3N4的XRD图;
图2(a)为合成的BaSb2O6/g-C3N4催化剂在可见光(λ≥420nm)下光催化降解TC曲线、(b)为TC溶液的特征吸收曲线;
图3(a)为BSO-CN-2循环实验的光降解TC图谱、(b)为异质结BaSb2O6/g-C3N4(5wt%)粉末循环实验后的XRD图谱;
图4为BSO-CN-2光催化剂在可见光(λ≥420nm)下光催化苯甲醇转化为苯甲醛的选择性和转化率的效果对比图;
图5(a)为BSO-CN-2与SSO-CN-2在可见光下对TC光降解的效果对比图、(b)为BSO-CN-2与SSO-CN-2在可见光下对苯甲醇的转化效果对比图。
具体实施方式
以下实施例为典型的,用于帮助理解和进一步阐明本发明的实质,但不以此限制本发明的范围。
实施例1固相法制备BaSb2O6/g-C3N4异质结
制备工艺如下:
1)分别称取1mmol BaCl2·2H2O、1.05mmol Sb2O3混合研磨40min后,转移至刚玉坩埚中;
2)将刚玉坩埚放入高温马弗炉中,于870℃烧结10h,自然降温后,最终制得BaSb2O6前驱体;
3)称取3g三聚氰胺混合均匀后,转移至刚玉坩埚中,将刚玉坩埚放入马弗炉中,以4℃/min的升温速率于560℃烧结2h,自然降温后即得g-C3N4前驱体;
4)制得的g-C3N4用0.1mol/L稀HNO3洗涤、搅拌,再用无水乙醇洗涤搅拌,最后60℃烘干即可;
5)将前驱体BaSb2O6、g-C3N4和无水乙醇(1ml)混合研磨30min后,转移至刚玉坩埚中,将刚玉坩埚放入高温马弗炉中,以5℃/min的升温速率于480℃烧结2h,自然降温后,得到光催化剂BaSb2O6/g-C3N4异质结,BaSb2O6质量百分比为2%,5%,10%和15%的样品,并分别标记为BSO-CN-1、BSO-CN-2、BSO-CN-3和BSO-CN-4。(见下表1)。所得样品用于物相表征。
表1前驱体BaSb2O6和g-C3N4的投料量及产品中BaSb2O6百分比
XRD测试:取所制得的BaSb2O6/g-C3N4异质结少量产物在玛瑙研钵中充分研磨后,样品在岛津7000-X射线衍射仪进行物相表征,结果如图1(a)所示。图1(a)表明,实验获得的图谱与标准PDF卡片(JCPDS 46-1494)的X射线(XRD)图谱一致,表明获得的样品为纯相。
FT-IR测试:采用KBr压片方法,将1mg合成样品加入到200mg KBr中混合研磨均匀,以15兆帕的压力压制30s,形成直径为13毫米的圆片。在Nicolet360光谱仪上收集样品的红外反射数据,结果见如图1的(b)所示,分辨率为2cm-1,扫描范围为500~4000cm-1。图1(b)表明,BaSb2O6和g-C3N4的所有主要特征峰均在BaSb2O6/g-C3N4异质结中被观察到,也表明获得的样品为纯相。
实施例2应用效果试验
1、通过实施本发明的异质结光催化降解抗生素四环素的实验,可知固相烧结制备的异质结光催化剂BaSb2O6/g-C3N4对抗生素四环素有良好的降解作用。以20mg/L四环素溶液为模拟污染物来评价异质结BaSb2O6/g-C3N4及母体的光催化性能。如图2所示,空白TC溶液的吸光度是稳定的,表明自然光降解是可以忽略不计。母体g-C3N4和BaSb2O6光催化降解率较低,240min的催化效率达到30%。有趣的是,制备异质结光催化剂样品BaSb2O6/g-C3N4的光催化性能均得到了显著提升。其中,BaSb2O6质量百分比占5%的样品BaSb2O6/g-C3N4(5wt%)的光催化活性最高,240min内光催化降解率可以达到80%。以上结果表明,g-C3N4和BaSb2O6形成了异质结,提升了光催化降解效率。
实验具体步骤如下:
取50mg制得的光催化剂BaSb2O6/g-C3N4加入到100ml浓度为20mg/L的抗生素四环素溶液中,暗吸附120min建立吸附-脱附平衡。在300W氙灯下光照240min,每隔30min取上清液5ml,离心后用UV-Vis分光光度计(岛津UV-2550)测定其吸光度。结果表明,在240min内,光催化降解效率达到60%,降解效果良好。结果见图3。
图3(a)为BaSb2O6/g-C3N4(5wt%)异质结在可见光下催化降解TC溶液的循环降解实验图。从图中可以看出,光催化降解循环实验具有较高的稳定性。图3(b)显示的是光催化前后样品BaSb2O6/g-C3N4(5wt%)的XRD对比图。从图中可以看出光催化循环三次之后的XRD图谱与最初制备样品的XRD图谱保持一致。经过三次光催化循环实验后,样品BaSb2O6/g-C3N4(5wt%)具有较高的光催化降解和物相稳定性。
2、通过实施本品BaSb2O6/g-C3N4光催化苯甲醇氧化生产苯甲醛的实验,可知固相烧结制备的异质结光催化剂BaSb2O6/g-C3N4对光催化苯甲醇氧化生产苯甲醛有良好的转化率。根据该异质结光催化剂材料BaSb2O6/g-C3N4可见光下降解TC的结论,以含有25μL(0.24mmol)苯甲醇的10mL乙腈来评价异质结BaSb2O6/g-C3N4(5wt%)的光催化性能。实验结果表明6h内光催化苯甲醇氧化生产苯甲醛转化率可以达到13%,选择性达到70%。以上结果表明,g-C3N4和BaSb2O6形成的Type-II型异质结,有效地提升了苯甲醇催化氧化生产苯甲醛的转化率。
实验具体步骤如下:
取50mg制得的光催化剂BaSb2O6/g-C3N4(5wt%)加入到含有25μL(0.24mmol)苯甲醇的10mL乙腈中,在双壁石英反应器中进行,通过循环水流动将溶液温度保持在25℃。首先用氧气净化反应悬浮液30min,然后在300W氙灯下光照6h,采用高效液相色谱(HPLC)分析液体产物。结果表明,BaSb2O6/g-C3N4光催化剂在可见光下有良好的光催化氧化苯甲醇的活性,结果见图4。
图4为BaSb2O6/g-C3N4(5wt%)异质结在可见光下催化含有25μL(0.24mmol)苯甲醇的10mL乙腈溶液的催化氧化实验图(图中BSO-CN-2表示BaSb2O6/g-C3N4(5wt%)的样品)。从图4的结果表明,该异质结型材料对苯甲醇选择性催化氧化具有较高的转化率和选择性。
3、应用效果试验对比
根据调研文献和实验结果,我们对比了最优效果下的BaSb2O6/g-C3N4(5wt%)与同族金属Sr和g-C3N4的二维异质结光催化剂SrSb2O6/g-C3N4(5wt%)在可见光下用于光催化降解四环素(化学通报2021.84.7DOI:10.14159/j.cnki.0441-3776.2021.07.009)和催化氧化苯甲醇的效率。结果表明,BaSb2O6/g-C3N4光催化剂的光催化降解TC和催化苯甲醇的性能优于SrSb2O6/g-C3N4光催化剂,结果见图5。
图5(a)为BaSb2O6、SrSb2O6、BaSb2O6/g-C3N4(5wt%)异质结与SrSb2O6/g-C3N4(5wt%)在可见光下对20mg/mL四环素溶液的催化效果对比图(图中BSO-CN-2表示BaSb2O6/g-C3N4(5wt%)的样品;SSO-CN-2表示SrSb2O6/g-C3N4(5wt%)的样品)。图5(b)为BaSb2O6/g-C3N4(5wt%)异质结与SrSb2O6/g-C3N4(5wt%)在可见光下对含有25μL(0.24mmol)苯甲醇的10mL乙腈溶液的催化效果对比图。图5的结果表明,该BaSb2O6/g-C3N4异质结在可见光下对四环素溶液和催化苯甲醇有着更优异的光催化性能。
同时,根据实验结果,在催化苯甲醇转化成苯甲醛的反应中,6小时,同族金属光催化剂CaSb2O6/g-C3N4催化苯甲醇转化活性(选择性45.2%,转化率3.2%)弱于BaSb2O6/g-C3N4(5wt%)的催化活性(选择性70%,转化率12.8%)。
Claims (10)
1.一种二维异质结光催化剂BaSb2O6/g-C3N4的制备方法,包含以下步骤:
1)将BaCl2和Sb2O3按摩尔比1:(1.05-1.5)混合、研磨均匀后,在850-900℃温度下烧结7-15h,冷却至室温后得到粉末状BaSb2O6前驱体;
2)将三聚氰胺在520-600℃下烧结1.5-2.5h,自然冷却至室温,即得粉末g-C3N4前驱体;
3)将步骤1)的BaSb2O6前驱体和步骤2)的g-C3N4前驱体与无水乙醇以质量比混合研磨均匀,置于马弗炉中,在450-500℃恒温下煅烧1.5-2.5h;
4)煅烧反应结束后,自然冷却至室温,制得异质结光催化剂BaSb2O6/g-C3N4。
2.如权利要求1的制备方法,步骤1)中,BaCl2与Sb2O3的摩尔比为1:1.05,烧结温度为870℃,烧结时间为10h。
3.如权利要求1的制备方法,步骤2)中,所述烧结,以4℃/min的速率加热至560℃,并保温2h。
4.如权利要求1的制备方法,步骤2)中,进一步包括将制得的g-C3N4用0.1mol/L稀HNO3洗涤、再用无水乙醇洗涤、烘干。
5.如权利要求1的制备方法,步骤3)中,所述煅烧,锻烧温度为480℃,锻烧时间为2h。
6.如权利要求1所述的方法,步骤3)中,BaSb2O6、g-C3N4和无水乙醇混合研磨时间为30min。
7.如权利要求1的制备方法,步骤4)中,获得的二维异质结光催化剂BaSb2O6/g-C3N4,其中,BaSb2O6占BaSb2O6/g-C3N4重量的质量比为2-15%。
8.如权利要求7的制备方法,所述质量比为5wt%。
9.权利要求1-7的方法制备的BaSb2O6/g-C3N4用于光催化降解四环素的用途。
10.权利要求1-7的方法制备的BaSb2O6/g-C3N4用作苯甲醇催化脱氢生产苯甲醛的催化剂的用途。
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