CN112570030A - 一种Bi4O5Br2/Fe-MIL复合材料光催化剂的制备方法及其用途 - Google Patents
一种Bi4O5Br2/Fe-MIL复合材料光催化剂的制备方法及其用途 Download PDFInfo
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Abstract
本发明提供了一种合成Bi4O5Br2/Fe‑MIL棒状结构复合材料的制备方法,用于在模拟太阳光下光催化还原二氧化碳研究。具体技术方案:利用在合成NH2‑MIL‑101(Fe)的过程中加入中空球状Bi4O5Br2作为固体酸调节了NH2‑MIL‑101(Fe)向NH2‑MIL‑88B(Fe)的晶型转变;Bi4O5Br2材料与晶型转变后的NH2‑MIL‑88B(Fe)形成异质结构,加快了电子传输速率,有效促进了电子空穴分离,提高了光催化性能。本发明制备过程简单,催化剂稳定性高,利用卤氧化铋取代贵金属光敏剂形成复合材料,将CO2光催化还原为可利用的有机物质CH4,为环境问题和能源短缺提供了解决方案,具有显著的经济效益和应用前景。
Description
技术领域
本发明属于催化材料技术领域,具体地说涉及一种应用于光催化还原CO2的复合催化剂的制备方法及其应用。
背景技术
随着科学技术的日新月异和工业生产的迅猛发展,以及人们对能源需求量的逐年增加,化石燃料燃烧排放的CO2成为引起温室效应的重要因素。由IPCC(国际气候变化委员会)发布数据表明2100年大气中的二氧化碳浓度可能由工业革命前的280ppm增加至590ppm,为工业前水平的211%,全球气温将普遍升高1.5℃,因此“温室效应”的产生将对人类的生存和发展造成一定的威胁,环境问题成为世界各国关注的焦点。由于人们对化石能源的依赖,直接减少化石燃料的燃烧是难以实现的,通过光催化技术将CO2光还原为增值燃料或可利用的化学物质可以同时解决环境问题和能源挑战。
近年来金属有机骨架(MOFs)由于其独特的物理化学特性(例如大表面积,可调节的多孔结构和强大的CO2吸附能力)和易改性的结构特征而受到广泛关注,且MOFs已经很好地应用于光催化CO2RR。然而,由于光生电荷载流子的快速重组和太阳光利用率低,原始MOFs的光催化效率仍不令人满意。因此,需要尝试一系列改性策略来解决上述障碍,包括MOFs衍生物的合成,杂原子掺杂,形态控制,异质结的构建等。其中,通过调控材料的形态来提高光催化性能的研究已有报道,而将MOFs与半导体形成异质结来增加电子空穴分离速率的改性方法是目前研究最多的方法。
氨基功能化的Fe-MIL系列的MOF具有良好的可见光吸收效果,活性位点较多,比表面积较大,疏松多孔,可以吸附更多的CO2,更重要的是结构更易调控,对其进行半导体复合,构建异质结构,通过半导体与MOF的界面作用,加快光生电子的传输速率,促进电子和空穴的分离,进而提高光催化反应活性。
发明内容
本发明提供了一种新型光催化剂的制备方法和应用,该催化剂避免使用贵金属光敏剂,对还原CO2为CH4具有较高的活性,在循环测试后保持良好的稳定性,且制备工艺简单,成本低,为新能源和新型催化剂的开发提供了新的研发思路。
为解决上述技术问题,本发明采用以下技术方案予以实现:
技术方案:
一、本发明提供了新型光催化剂的制备方法,包括以下步骤:
(1)利用溶剂热法合成空心球状Bi4O5Br2纳米材料
将Bi(NO3)3·5H2O和CTAB以摩尔比为2∶1-2.55∶1的比例溶解在一定量的甘油中,分别记为溶液A和B。将B溶液滴加到A溶液中不断搅拌,随后将悬浮液转移至聚四氟乙烯内衬的不锈钢高压釜中,加热至120-160℃后反应12-16h,冷却后用乙醇洗涤数次,于60℃干燥过夜得到前驱体。之后将0.2-0.4g的前驱体放入200-300mL的去离子水中,油浴加热一定时间,其沉淀物用水和乙醇洗涤,将收集的固体在60℃烘箱中干燥过夜,即得到空心球状Bi4O5Br2材料。
(2)利用溶剂热法合成Bi4O5Br2/Fe-MIL复合材料
在含有45mL的DMF溶液中加入不同量Bi4O5Br2材料,超声一定时间后分别加入摩尔比为2∶1的FeCl3·6H2O和NH2-BDC,将混合溶液转移至高压反应釜中,在110℃下反应20h,冷却至室温后,将悬浮液离心,用DMF,去离子水和乙醇洗涤数次,即得到Bi4O5Br2/Fe-MIL复合材料,将复合材料命名为BMFe-X。
二、纳米光催化剂Bi4O5Br2/Fe-MIL的光催化还原CO2性能评价,方法如下:
光催化还原CO2反应是以异丙醇为溶剂,在一个密闭的高压反应***中进行的。装置分为五部分:CO2气体钢瓶、载气N2钢瓶、光催化不锈钢反应釜、均匀光氙灯光源、气相色谱仪。反应釜顶部是可透光的石英玻璃,釜的一端连接CO2气体钢瓶,另一端接气相色谱仪的进样口,外侧有循环冷凝水以控制反应温度保持在30℃左右。
其具体实验步骤为:首先取20mg样品和20mL异丙醇于光催化反应釜中,向反应釜中通入高纯CO2气体至釜内压力为0.2MPa,封闭反应体系。然后打开氙灯光源照射。反应进行5h后,关闭灯源。用气相色谱仪检测分析其气体产物。将回收的样品重复以上步骤评价其稳定性。
附图说明
图1为本发明制备的Bi4O5Br2/Fe-MIL复合材料光催化剂的X射线衍射(XRD)图,即实施例2的XRD图;
图2为本发明制备的中空球状Bi4O5Br2光催化剂的扫描电镜(SEM)图,即实施例1的SEM图;
图3为本发明制备的复合材料BMFe-5光催化剂的(a)扫描电镜图和(b)透射电镜图,即实施例2的SEM和TEM图;
图4为本发明制备的不同比例的Bi4O5Br2/Fe-MIL复合材料光催化还原CO2为CH4的产率,即实施例1和实施例2的性能测试图;
图5为本发明制备的复合材料BMFe-5光催化剂的活性循环测试结果图,即实施例2的复合材料性能测试图;
具体实施方式
本发明针对现有技术的不足,提供了一种具有异质结构的Bi4O5Br2/Fe-MIL复合材料用于光催化还原CO2的制备方法。下面通过具体的实施例对本发明给予进一步的说明。
实施例1
具有光催化还原CO2性能的Bi4O5Br2材料的制备与性能测试。
(1)利用溶剂热法合成空心球状Bi4O5Br2纳米材料
将Bi(NO3)3·5H2O和CTAB以摩尔比为2∶1-2.55∶1的比例溶解在一定量的甘油中,分别记为溶液A和B。将B溶液滴加到A溶液中不断搅拌,随后将悬浮液转移至聚四氟乙烯内衬的不锈钢高压釜中,加热至120-160℃后反应12-16h,冷却后用乙醇洗涤数次,于60℃干燥过夜得到前驱体。之后将0.2-0.4g的前驱体放入200-300mL的去离子水中,油浴加热一定时间,其沉淀物用水和乙醇洗涤,将收集的固体在60℃烘箱中干燥过夜,即得到空心球状Bi4O5Br2材料。
(2)纳米光催化剂Bi4O5Br2的光催化还原CO2性能研究
取20mg的Bi4O5Br2样品和20mL异丙醇于光催化反应釜中,向反应釜中通入高纯CO2气体至釜内压力为0.2MPa,封闭反应体系。然后打开氙灯光源照射,反应进行5h后,关闭灯源。用气相色谱仪分析其气体产物。
实施例2
具有优异光催化还原CO2性能的纳米复合光催化剂Bi4O5Br2/Fe-MIL的制备及性能测试。
(1)利用溶剂热法合成Bi4O5Br2/Fe-MIL复合材料
在含有45mL的DMF溶液中加入不同量Bi4O5Br2材料,超声一定时间后分别加入摩尔比为2∶1的FeCl3·6H2O和NH2-BDC,将混合溶液转移至高压反应釜中,在110℃下反应20h,冷却至室温后,将悬浮液离心,用DMF,去离子水和乙醇洗涤数次,即得到Bi4O5Br2/Fe-MIL复合材料,将复合材料命名为BMFe-X。
(2)纳米光催化剂Bi4O5Br2/Fe-MIL的光催化还原CO2性能研究取20mg的Bi4O5Br2/Fe-MIL样品和20mL异丙醇于光催化反应釜中,向反应釜中通入高纯CO2气体至釜内压力为0.2MPa,封闭反应体系。然后打开氙灯照射,反应进行5h后,关闭灯源。用气相色谱仪分析其气体产物。选择活性最高的催化剂,将回收的样品重复以上步骤评价其稳定性。
图1为实施例1和实施例2中通过溶剂热法制备的Bi4O5Br2纳米材料及复合材料Bi4O5Br2/Fe-MIL,随着Bi4O5Br2材料量的增多,其晶体结构发生了变化。
图2为实施例1中得到的中空球状Bi4O5Br2纳米材料的扫描电镜图像,从图中可以看出其结构为超薄纳米片堆积形成,具有疏松多孔的结构,有利于CO2的吸附。
图3为实施例2中得到BMFe-5复合材料的SEM和TEM图像,可以看到的Bi4O5Br2纳米材料的晶格间距,表明复合材料的成功合成。
图4为实施例2中得到的复合材料Bi4O5Br2/Fe-MIL的活性测试结果,图中BMFe-X(X=1,2,3,4,5,6)分别代表不同Bi4O5Br2含量的复合材料,由图可知复合材料BMFe-5的活性明显高于其他催化剂的光催化还原CO2的活性,产甲烷的反应速率达到最大值7.96μmol/h/g。
图5为BMFe-5复合材料经四次活性循环测试结果,其产甲烷的速率几乎没变,表明该催化剂具有良好的稳定性。
以上所述,仅是本发明的较佳实施例而已,并非是对本发明作其它形式的限制,任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何修改、等同变化与改型,仍属于本发明技术方案的保护范围。
Claims (3)
1.一种具有光催化还原CO2性能的Bi4O5Br2/Fe-MIL复合材料的制备方法,复合材料的异质结结构有利于促进光生电子和空穴的分离,加快光生电子传输速率,大幅度提高了光催化还原CO2性能。
2.根据权利要求1所述的一种Bi4O5Br2/Fe-MIL复合材料的制备方法,其特征在于,包括以下步骤:
(1)利用溶剂热法合成空心球状Bi4O5Br2纳米材料
将Bi(NO3)3·5H2O和CTAB以摩尔比为2∶1-2.55∶1的比例溶解在一定量的甘油中,分别记为溶液A和B。将B溶液滴加到A溶液中不断搅拌,随后将悬浮液转移至聚四氟乙烯内衬的不锈钢高压釜中,加热至120-160℃后反应12-16h,冷却后用乙醇洗涤数次,于60℃干燥过夜得到前驱体。之后将0.2-0.4g的前驱体放入200-300mL的去离子水中,油浴加热一定时间,其沉淀物用水和乙醇洗涤,将收集的固体在60℃烘箱中干燥过夜,即得到空心球状Bi4O5Br2材料。
(2)利用溶剂热法合成Bi4O5Br2/Fe-MIL复合材料
在含有45mL的DMF溶液中加入不同量的Bi4O5Br2材料,超声一定时间后分别加入摩尔比为2∶1的FeCl3·6H2O和NH2-BDC,将混合溶液转移至高压反应釜中,在110℃下反应20h,冷却至室温后,将悬浮液离心,用DMF,去离子水和乙醇洗涤数次,即得到Bi4O5Br2/NH2-MIL-88B(Fe)复合材料,将复合材料命名为BMFe-X。
3.根据权利要求1所述Bi4O5Br2/Fe-MIL复合材料的合成方法及在模拟太阳光下具有光催化还原CO2产CH4性能方面的应用。
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