CN115283015A - 一种有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)的制备方法 - Google Patents
一种有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)的制备方法 Download PDFInfo
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Abstract
一种有机金属骨架复合光催化剂BiVO4@NH2‑MIL‑125(Ti)的制备方法,其属于光催化材料领域。本发明先用水热法制备了NH2‑MIL‑125(Ti),再通过水热法制备得到了BiVO4@NH2‑MIL‑125(Ti)复合光催化剂。本发明方法制备工艺简单,使用设备少,能耗低。制备的BiVO4@NH2‑MIL‑125(Ti)稳定性强、光催化活性高、光电转化效率高,在模拟太阳光氙灯照射下,0.1g制备的复合光催化剂降解100mL浓度为10mg/L的罗丹明B溶液,光照120min降解率达99%。本发明制备出的产品可广泛用于光催化降解有机污染物的领域中。
Description
技术领域
本发明涉及一种有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)的制备方法,属于光催化材料技术领域。
背景技术
半导体光催化技术是近年来发展起来的对环境特别友好的水污染环境治理技术,利用光能即可达到降解有机污染物的目的。传统光催化剂TiO2载流子复合率高,量子效率较低、光吸收波长范围窄,吸收波长阀值大都在紫外光区,且太阳光利用率低(仅占3%~5%)。研究发现,钒酸铋是一种极具潜力的光催化剂,它具有可见光吸收带隙窄、化学和热稳定性高、对环境友好、成本低等优点。然而,到目前为止,BiVO4实际转换的光电效率远低于预期。一是BiVO4电子传输效率太缓慢,约60%-80%的电子-空穴对在到达界面之前便重新组合,二是BiVO4导带(CB)边缘在可逆氢电极(RHE)水平以下严重限制了光催化性能。NH2-MIL-125(Ti)是由Ti8O8八面体笼和2-氨基对苯二甲酸组成的金属-有机骨架,具有强稳定性、高太阳能转换效率、优异的吸附和光催化性能,广泛应用于催化、传感器、气体储存分离、有机废水治理、光解制H2和CO2还原中。其制备的方法包括自牺牲模板法、溶剂热法、界面扩散法和微波法。
目前,构建半导体复合材料是提高光催化效率的有效策略。如“AppliedOrganometallic Chemistry”2018年4月第32卷第四期“Preparation of BiVO4/MIL-125(Ti)composite with enhanced visible-light photocatalytic activity for dyedegradation”一文中,先以钛酸四丁酯、对苯二甲酸,N,N-二甲基甲酰胺和甲醇为原材料通过热溶剂法合成MIL-125(Ti),再将MIL-125(Ti)与BiCl3和NH4VO3形成混合溶液二次水热制备出BiVO4/MIL-125(Ti)催化剂。该方法的不足之处是:(1)该复合催化剂催化活性低,在500W氙灯模拟太阳光下180min对罗丹明B的降解率仅为92%;(2)制备出的BiVO4/MIL-125(Ti)催化剂稳定性较差,4次循环回收实验后降解率仅为79%。又如“Separation AndPurification Technology”2020年10月第248卷“Novel z-scheme In2S3/BiVO4composites with improved visible-light photocatalytic performance andstability for glyphosate degradation”一文中,首先以硫脲作为硫源,与In(NO3)3·4.5H2O形成均匀混合溶液,通过水热反应合成In2S3,再向In2S3与Bi(NO3)3·5H2O形成的混合溶液中添加NH4VO3在180℃下水热24h合成了In2S3/BiVO4。该方法的不足之处是:(1)In2S3单样制备过程工艺复杂,硫脲与In(NO3)3·4.5H2O的混合溶液被转移到两个50mL的特氟龙高压釜中,难以控制两个反应釜所得的In2S3单样是一致的,进而影响In2S3/BiVO4光催化活性;(2)通过该方法制备的In2S3/BiVO4光催化活性不高,在模拟太阳光下180min对草甘膦的降解率仅为78%;(3)In2S3/BiVO4复合光催化材料光电转化效率低,复合材料受光激发产生的瞬时光电流仅为1.5μA/cm2。
发明内容
本发明的目的是针对制备BiVO4、NH2-MIL-125(Ti)光催化活性不佳以及催化剂稳定性差等问题,提出采用两步水热法制备新型复合光催化材料BiVO4@NH2-MIL-125(Ti),提高复合光催化剂的活性和光电转化效率,该制备工艺方法简单、周期短,催化剂活性高、稳定性强,本发明BiVO4@NH2-MIL-125(Ti)复合光催化材料的制备方法如下:
(1)有机金属骨架NH2-MIL-125(Ti)的制备
准确称取2-氨基对苯二甲酸2.86g,溶解于40mL的N,N-二甲基甲酰胺和10mL甲醇的混合溶液中,磁力搅拌20min,向混合溶液中滴加2.86mL异丙醇钛,持续搅拌30min,将所得的粘稠溶液转入100mL高压反应釜,密封完好,在110℃的烘箱中水热反应72h;反应完成后取出高压反应釜自然冷却至室温,过滤,滤饼分别用N,N-二甲基甲酰胺和甲醇在高速离心机中离心洗涤3次后置于60℃的烘箱中烘12h,取出后用石英研钵磨细成粉末状,得到的淡黄色粉末即为NH2-MIL-125(Ti)。
(2)有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)的制备
称取五水硝酸铋2.43g充分溶解于25mL的2mol/L稀硝酸中,将偏钒酸铵0.58g添加至混合溶液中,搅拌10min,缓慢滴加2mol/L的氢氧化钠溶液调节pH值至6.0,得到BiVO4前驱体溶液;按BiVO4:NH2-MIL-125(Ti)的质量比为100:3-15的比例称取制备的NH2-MIL-125(Ti)加入BiVO4前驱体溶液中,继续搅拌30min,将溶液转入100mL水热反应釜,在160℃下水热反应24h;待其冷却至室温后过滤,滤饼用蒸馏水和乙醇分别抽滤洗涤3次,放入烘箱60℃下干燥12h,取出后用石英研钵磨细成粉末状,得到的亮黄色粉末即为有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)。
本发明采用上述技术方案,主要有以下效果:
(1)本发明方法制备的有机金属骨架复合光催化材剂BiVO4@NH2-MIL-125(Ti)具有较高的光催化活性,0.1g制备的BiVO4@NH2-MIL-125(Ti)复合光催化剂分散于100mL浓度为10mg/L罗丹明B溶液中,在模拟太阳光300W氙灯光照120min,降解率达到了99%。
(2)本发明采用两步水热法制备,复合光催化剂的瞬时光电流达到2.53μA/cm2,且稳定性强,制备操作简单,所需设备少,能耗低。
附图说明
图1为BiVO4、NH2-MIL-125(Ti)和BiVO4@NH2-MIL-125(Ti)的X射线衍射图。
图2为BiVO4、NH2-MIL-125(Ti)和BiVO4@NH2-MIL-125(Ti)的SEM图。
图3为复合光催化剂BiVO4@NH2-MIL-125(Ti)的XPS图。
图4为BiVO4、NH2-MIL-125(Ti)和BiVO4@NH2-MIL-125(Ti)的降解率对比图。
具体实施方式
下面结合具体实施方式,进一步说明本发明。
实施例1
一种有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)的制备方法,具体步骤如下:
(1)有机金属骨架NH2-MIL-125(Ti)的制备
准确称取2-氨基对苯二甲酸2.86g,溶解于40mL的N,N-二甲基甲酰胺和10mL甲醇的混合溶液中,磁力搅拌20min,向混合溶液中滴加2.86mL异丙醇钛,持续搅拌30min,将所得的粘稠溶液转入100mL高压反应釜,密封完好,在110℃的烘箱中水热反应72h;反应完成后取出高压反应釜自然冷却至室温,过滤,滤饼分别用N,N-二甲基甲酰胺和甲醇在高速离心机中离心洗涤3次后置于60℃的烘箱中烘12h,取出后用石英研钵磨细成粉末状,得到的淡黄色粉末即为NH2-MIL-125(Ti)。
(2)有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)的制备
称取五水硝酸铋2.43g充分溶解于25mL的2mol/L稀硝酸中,将偏钒酸铵0.58g添加至混合溶液中,搅拌10min,缓慢滴加2mol/L的氢氧化钠溶液调节pH值至6.0,得到BiVO4前驱体溶液;按BiVO4:NH2-MIL-125(Ti)的质量比为100:3的比例称取制备的NH2-MIL-125(Ti)加入BiVO4前驱体溶液中,继续搅拌30min,将溶液转入100mL水热反应釜,在160℃下水热反应24h;待其冷却至室温后过滤,滤饼用蒸馏水和乙醇分别抽滤洗涤3次,放入烘箱60℃下干燥12h,取出后用石英研钵磨细成粉末状,得到的亮黄色粉末即为有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)。
实施例2
一种有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)的制备方法,具体步骤如下:
(1)同实施例1中(1)。
(2)有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)的制备
称取五水硝酸铋2.43g充分溶解于25mL的2mol/L稀硝酸中,将偏钒酸铵0.58g添加至混合溶液中,搅拌10min,缓慢滴加2mol/L的氢氧化钠溶液调节pH值至6.0,得到BiVO4前驱体溶液;按BiVO4:NH2-MIL-125(Ti)的质量比为100:5的比例称取制备的NH2-MIL-125(Ti)加入BiVO4前驱体溶液中,继续搅拌30min,将溶液转入100mL水热反应釜,在160℃下水热反应24h;待其冷却至室温后过滤,滤饼用蒸馏水和乙醇分别抽滤洗涤3次,放入烘箱60℃下干燥12h,取出后用石英研钵磨细成粉末状,得到的亮黄色粉末即为有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)。
实施例3
一种有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)的制备方法,具体步骤如下:
(1)同实施例1中(1)。
(2)有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)的制备
称取五水硝酸铋2.43g充分溶解于25mL的2mol/L稀硝酸中,将偏钒酸铵0.58g添加至混合溶液中,搅拌10min,缓慢滴加2mol/L的氢氧化钠溶液调节pH值至6.0,得到BiVO4前驱体溶液;按BiVO4:NH2-MIL-125(Ti)的质量比为100:7的比例称取制备的NH2-MIL-125(Ti)加入BiVO4前驱体溶液中,继续搅拌30min,将溶液转入100mL水热反应釜,在160℃下水热反应24h;待其冷却至室温后过滤,滤饼用蒸馏水和乙醇分别抽滤洗涤3次,放入烘箱60℃下干燥12h,取出后用石英研钵磨细成粉末状,得到的亮黄色粉末即为有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)。
实施例4
一种有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)的制备方法,具体步骤如下:
(1)同实施例1中(1)。
(2)有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)的制备
称取五水硝酸铋2.43g充分溶解于25mL的2mol/L稀硝酸中,将偏钒酸铵0.58g添加至混合溶液中,搅拌10min,缓慢滴加2mol/L的氢氧化钠溶液调节pH值至6.0,得到BiVO4前驱体溶液;按BiVO4:NH2-MIL-125(Ti)的质量比为100:10的比例称取制备的NH2-MIL-125(Ti)加入BiVO4前驱体溶液中,继续搅拌30min,将溶液转入100mL水热反应釜,在160℃下水热反应24h;待其冷却至室温后过滤,滤饼用蒸馏水和乙醇分别抽滤洗涤3次,放入烘箱60℃下干燥12h,取出后用石英研钵磨细成粉末状,得到的亮黄色粉末即为有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)。
实施例5
一种有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)的制备方法,具体步骤如下:
(1)同实施例1中(1)。
(2)有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)的制备
称取五水硝酸铋2.43g充分溶解于25mL的2mol/L稀硝酸中,将偏钒酸铵0.58g添加至混合溶液中,搅拌10min,缓慢滴加2mol/L的氢氧化钠溶液调节pH值至6.0,得到BiVO4前驱体溶液;按BiVO4:NH2-MIL-125(Ti)的质量比为100:15的比例称取制备的NH2-MIL-125(Ti)加入BiVO4前驱体溶液中,继续搅拌30min,将溶液转入100mL水热反应釜,在160℃下水热反应24h;待其冷却至室温后过滤,滤饼用蒸馏水和乙醇分别抽滤洗涤3次,放入烘箱60℃下干燥12h,取出后用石英研钵磨细成粉末状,得到的亮黄色粉末即为有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)。
实验结果
实施例3制备的复合光催化材料BiVO4@NH2-MIL-125(Ti)催化降解活性最佳。为了便于比较,制备了BiVO4样品。BiVO4制备方法为实施例3步骤(2)中不加入NH2-MIL-125(Ti)。
BiVO4的XRD如图1(b)所示,BiVO4样品在2θ为18.67°、18.99°、28.95°、30.55°、34.50°、35.22°、39.78°、40.04°、46.71°、47.31°、53.24°和53.31°处出现单斜白钨矿类型钒酸铋的特征衍射峰(JCPDS#14-0688),分别对应(110)、(011)、(-121)、(121)、(200)、(002)、(-141)、(141)、(240)、(042)、(-161)和(161)晶面。衍射峰窄而尖锐且无杂峰,样品结晶度高,纯度高。
NH2-MIL-125(Ti)的XRD图如图1(c),NH2-MIL-125(Ti)样品在2θ为6.77°、9.71°、11.60°、16.54°、17.85°和19.51°处都观察到了NH2-MIL-125(Ti)的特征衍射峰,这与前人制备的NH2-MIL-125(Ti)特征衍射峰一致,衍射峰尖锐且无其他的杂峰,说明制备的NH2-MIL-125(Ti)结晶度良好,样品纯度高。
BiVO4@NH2-MIL-125(Ti)的XRD衍射图谱如图1(a)所示,从图中观察到BiVO4的特征衍射峰,这些峰与BiVO4单样的特征峰2θ完美对应,说明BiVO4的特征衍射峰没有因NH2-MIL-125(Ti)的引入而改变,且由于NH2-MIL-125(Ti)在复合样品中含量太少,图中没有观察到明显的NH2-MIL-125(Ti)特征峰。而复合光催化材料中属于BiVO4晶面指数(020)、(121)、(051)和(-161)的强度有增加的趋势,特别是(121)晶面明显增强,这将有利于罗丹明B污染物分子氧化分解。
BiVO4、NH2-MIL-125(Ti)和BiVO4@NH2-MIL-125(Ti)的SEM如图2所示。从图2(a)可以看出BiVO4呈两头偏大、中间偏小的哑铃型形貌,边界分明,表面光滑,不规则块状BiVO4分布较均匀,结合不很紧密,晶体之间存在较大孔隙。图2(b)NH2-MIL-125(Ti)则为一定厚度的圆形片状晶体,许多圆形片状晶体团聚在一起,这些规则圆片分布均匀,结合紧密,晶体之间孔隙很小。图2(c)为BiVO4@NH2-MIL-125(Ti)的形貌图,具有哑铃型形貌的BiVO4和团聚圆片状形貌的NH2-MIL-125(Ti)组成,二者堆叠在一起,团聚的NH2-MIL-125(Ti)圆片穿插在BiVO4的孔隙中,使得孔隙变小,证明BiVO4@NH2-MIL-125(Ti)制备成功。
BiVO4@NH2-MIL-125(Ti)的XPS如图3所示。从图3可看出,BiVO4@NH2-MIL-125(Ti)中有C、N、Bi、Ti、O和V元素,在图3c中V2p谱图中出现了523.78eV和516.44eV两处特征峰,分别对应于BiVO4的V2p1/2和V2p3/2,说明V元素处于V5+的价态;图3a的Bi4f谱图中,164.06eV与158.77eV处的特征峰对应于Bi4f5/2和Bi4f7/2结合能,表明Bi元素以Bi3+的形式存在;图3b中529.11eV、529.62eV和530.16eV处的峰值证实了O1s的结合能,其中,特征峰529.11eV处对应的是BiVO4的Bi-O键,特征峰529.62eV来源于NH2-MIL-125的Ti-O键,530.16eV处的峰值对应羟基;图3f中,Ti2p在465.46eV和458.79eV处有两个特征峰,这两个峰对应Ti2p3/2和Ti2p1/2结合能,表明Ti以Ti4+化学状态存在;图3e为C1s的高分辨谱图,288.24eV、285.97eV、284.63eV处分别对应碳氧双键官能团(C=O)、碳氮键官能团(C-N)和碳碳双键官能团(C=C),表明NH2-MIL-125(Ti)的官能团成功引入BiVO4@NH2-MIL-125(Ti)样品中;图3dN1s在399.5 4eV处发现一个尖锐的峰,这个峰对应碳氮键和氮氢键(C-N/N-H)。XPS分析结果显示出,BiVO4@NH2-MIL-125(Ti)样品制备成功。
如图4所示,BiVO4与NH2-MIL-125(Ti)质量比为100:7时制备的BiVO4@NH2-MIL-125(Ti)降解效果最佳,在光照120min时RhB溶液降解率达99%,此时瞬时光电流最大(2.53μA/cm2),是BiVO4的21倍;稳定性施压表明,BiVO4@NH2-MIL-125(Ti)光催化剂使用后回收再利用,4次循环利用光催化降解RhB溶液,降解率达92%。
Claims (2)
1.一种有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)的制备方法,其包括以下步骤:
(1)有机金属骨架NH2-MIL-125(Ti)的制备
准确称取2-氨基对苯二甲酸2.86g,溶解于40mL的N,N-二甲基甲酰胺和10mL甲醇的混合溶液中,磁力搅拌20min,向混合溶液中滴加2.86mL异丙醇钛,持续搅拌30min,将所得的粘稠溶液转入100mL高压反应釜,密封完好,在110℃的烘箱中水热反应72h;反应完成后取出高压反应釜自然冷却至室温,过滤,滤饼分别用N,N-二甲基甲酰胺和甲醇在高速离心机中离心洗涤3次后置于60℃的烘箱中烘12h,取出后用石英研钵磨细成粉末状,得到的淡黄色粉末即为NH2-MIL-125(Ti);
(2)有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)的制备
称取五水硝酸铋2.43g充分溶解于25mL的2mol/L稀硝酸中,将偏钒酸铵0.58g添加至混合溶液中,搅拌10min,缓慢滴加2mol/L的氢氧化钠溶液调节pH值至6.0,得到BiVO4前驱体溶液;按BiVO4:NH2-MIL-125(Ti)的质量比为100:3-15的比例称取制备的NH2-MIL-125(Ti)加入BiVO4前驱体溶液中,继续搅拌30min,将溶液转入100mL水热反应釜,在160℃下水热反应24h,待其冷却至室温后过滤,滤饼用蒸馏水和乙醇分别抽滤洗涤3次,放入烘箱60℃下干燥12h,取出后用石英研钵磨细成粉末状,得到的亮黄色粉末即为有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)。
2.根据权利要求1所述的一种有机金属骨架复合光催化剂BiVO4@NH2-MIL-125(Ti)的制备方法,其特征在于两步水热法制备,实现了BiVO4和NH2-MIL-125(Ti)间的牢固结合和光催化活性的提高。
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