CN114011467B - 一种巯基丙酸联结的二氧化钛共价有机框架复合材料及其制备方法和应用 - Google Patents
一种巯基丙酸联结的二氧化钛共价有机框架复合材料及其制备方法和应用 Download PDFInfo
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- 229910052802 copper Inorganic materials 0.000 claims description 4
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 4
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Abstract
本发明公开了一种巯基丙酸联结的二氧化钛共价有机框架复合材料在光催化CO2还原中的应用。该发明在缓解能源危机和解决温室效应等环境问题方面有一定的助益。TiO2作为光催化剂具有无毒、价格低廉易得、氧化还原电位合适、高抗光腐蚀性、优异的化学稳定性等特点。共价有机框架材料是以共价键相连的一类具有高比表面积、高孔隙率、高结晶度的结构多样性多孔材料,具有可设计性、易功能化的特点。本发明利用巯基丙酸作为联结剂将无机半导体TiO2和具有大的π共轭体系、优异的化学稳定性的COFs以共价键的形式相结合,合成复合材料催化剂,用于光催化CO2还原中,具有较大的研究价值和应用潜力。
Description
技术领域
本发明属于材料制备领域,具体是提出一种用于光催化CO2还原的巯基丙酸联结的二氧化钛共价有机框架复合材料。
背景技术
随着工业的快速发展和人们生活水平的提高,人类面临的能源需求和环境污染等问题日益严峻,其中,温室效应已经成为环境污染的重大难题之一,所以,将温室气体CO2还原为可用的化石燃料是人类面对的新挑战,但是CO2作为一种稳定性高的气体,将其还原有较大的难度,因此,研究可以通过收集取之不尽、用之不竭的太阳光能量来将还原CO2的光催化剂是解决温室效应的关键所在。作为合适的光催化剂,其应该具有稳定的化学结构,优异的吸光能力,高效的电子传输效率等特点。
自1972年AKIRA等人第一次将二氧化钛作为光催化剂报道以来,TiO2就以其无毒、价格低廉易得、合适的氧化还原电位、高的抗光腐蚀性、优异的化学稳定性等特点,得到了研究者们的青睐。然而,TiO2的宽带隙(3.0~3.2eV),只能吸收紫外光(λ<380nm),对占太阳能总能量的43%的可见光区域几乎无响应的特点限制了纯TiO2材料在光催化反应中的应用,同时,缓慢的电子转移和快速的载流子复合效率也阻碍了其发展的进程。
自2005年Yaghi课题组首次报道共价有机框架材料(COFs)以来, COFs就受到了研究者们的广泛关注,作为一种通过共价键相连的具有周期性和结晶性的有机多孔聚合物,其具有良好的热稳定性和化学稳定性、有序的孔道结构、结晶性好、单元结构可设计性等特点, 其设计性高、易功能化的孔道结构给研究者们提供了更多的科研思路, 通过“自上而下”或者后修饰策略将具有催化活性的官能团或金属颗粒嵌入到材料中成为了近年来研究的热点。
研究用巯基丙酸作联结剂,将无机半导体TiO2和具有大的π共轭体系、好的化学稳定性的有机框架材料COFs纳米片以共价键的形式相结合,制备复合材料用于光催化反应中,将CO2还原为可用的燃料,这对环境能源发展具有深远的意义。
发明内容
本发明提出用巯基丙酸(MPA)作联结剂,将无机半导体TiO2和具有大的π共轭体系、好的化学稳定性的有机材料COFs以共价键的形式相结合,制备复合材料用于光催化CO2还原反应中,结合二者优点,克服无机半导体TiO2在光催化应用中只能吸收紫外光的局限性,提高可见光利用率,为光催化技术领域的发展探索了一条新的道路。
为实现上述发明目的,本发明采用如下技术方案:
一种巯基丙酸联结的二氧化钛共价有机框架复合材料——TiO2-TT-por(Cu)-COFNSs,其利用5,10,15,20-四(4-氨基苯基)卟啉铜(TAPP-Cu)、噻吩并[3,2-b]噻吩-2,5-二羧醛(TT)和2, 4, 6-三甲基苯甲醛(TBA)通过席夫碱缩合反应合成共价有机框架纳米片材料TT-por(Cu)-COF NSs,再通过巯基丙酸(MPA)联结,将TiO2和TT-por(Cu)-COF NSs复合在一起,即TiO2-TT-por(Cu)-COF NSs,得到的复合材料呈现出良好的光催化CO2还原活性。
所述的TiO2-TT-por(Cu)-COF NSs的制备方法:
(1)在苯甲醇、正丁醇和醋酸的体系中分别加入5,10,15,20-四(4-氨基苯基)卟啉铜、噻吩并[3,2-b]噻吩-2,5-二羧醛和2, 4, 6-三甲基苯甲醛,从室温升温至120℃,保温3-7天,通过溶剂热法得到共价有机框架纳米片TT-por(Cu)-COF NSs;
(2)在N, N-二甲基甲酰胺(DMF)溶剂中加入二氧化钛,搅拌至其溶解,然后滴入适量巯基丙酸(MPA)溶剂,搅拌至溶液呈淡黄色,再将步骤(1)所得的TT-por-COF-Cu NSs加入到混合溶剂中,加热冷凝回流后,经DMF溶剂抽滤洗涤后,收集产物并在真空干燥箱中干燥过夜,得到巯基丙酸联结的二氧化钛共价有机框架复合材料TiO2-TT-por(Cu)-COF NSs。
进一步地,步骤(1)的苯甲醇、正丁醇和醋酸的体系中所使用的苯甲醇和正丁醇体积比例为12:1,醋酸的浓度为6mol/L,2, 4, 6-三甲基苯甲醛为40当量。
进一步地,步骤(2)加热冷凝回流反应温度为120℃,反应时间为5h。
进一步地,所述TiO2与 TT-por-COF-Cu NSs 的质量比为1:2。
本发明的有益效果在于
1)本发明通过使用5,10,15,20-四(4-氨基苯基)卟啉铜(TAPP-Cu)、噻吩并[3,2-b]噻吩-2,5-二羧醛(TT)和2, 4, 6-三甲基苯甲醛(TBA)合成一种新型共价有机框架纳米片材料,再通过巯基丙酸作联结剂与无机半导体TiO2结合制备新型光催化剂。卟啉铜(TAPP-Cu)由于其π共轭体系大,可见光吸收强,热稳定性高而成为一种优秀的光敏剂,TT-por(Cu)-COF NSs 其作为一种有机半导体,拥有合适的能带结构,在与无机半导体TiO2结合时,可以使光生电子从TT-por(Cu)-COF NSs的LUMO转移到TiO2的导带上,而巯基丙酸可以保证二者以共价键的形式稳定结合,从而可以有效提高电子转移速率,在反应中提高光催化还原CO2活性。
2)本发明中所用到的设备和化学试剂易得,工艺操作简便,工艺条件简单,工业应用价值高,易于推广利用。卟啉中的金属不仅限于Cu,也适用于Zn、Ni等。联结剂不仅限于巯基丙酸,也可用巯基乙酸、巯基丁酸等。同时本发明中的噻吩并[3,2-b]噻吩-2,5-二羧醛(TT)是在经过和对苯二甲醛(BDA)进行催化性能对比后优选得到的,与BDA相比,TT中的S在TT-por(Cu)-COF NSs中可以有效地向卟啉铜(TAPP-Cu)中心转移电子,提高电荷传输速率,从而提高光催化反应活性。
附图说明
图1是TiO2-TT-por(Cu)-COF NSs的合成示意图;
图2是TiO2-TT-por(Cu)-COF NSs的扫描电镜图;
图3是TiO2、TT-por(Cu)-COF NSs和TiO2-TT-por(Cu)-COF NSs的X射线粉末衍射图,XRD特征衍射峰证明了二者的成功合成;
图4是TiO2、TT-por(Cu)-COF NSs和TiO2-TT-por(Cu)-COF NSs的傅里叶变换红外光谱图,FT-IR红外吸收峰证明了二者的成功合成;
图5是TiO2、TT-por(Cu)-COF NSs和TiO2-TT-por(Cu)-COF NSs的紫外可见吸收光图谱,可见复合后材料TiO2-TT-por(Cu)-COF NSs的吸光范围相比于TiO2有较大提升;
图6是TiO2、TT-por(Cu)-COF NSs、TiO2-TT-por(Cu)-COF NSs、TiO2-COF-366-Cu和按比例通过研磨物理混合后的TiO2/TT-por(Cu)-COF NSs(质量比1:2)光催化还原CO2性能对比图,以及TiO2-TT-por(Cu)-COF NSs的循环实验性能图;
图7是TiO2、TT-por(Cu)-COF NSs和TiO2-TT-por(Cu)-COF NSs的光电流密度对比图,可见复合后的材料对于光的响应有较大提升。
具体实施方式
为了使本发明的目的、技术方案及优势更加清楚明白便于理解,以下结合实施例,对本发明进行进一步详细说明。可以理解,此处所描述的具体实施仅用于解释本发明,并不用于限定本发明。
实施例1
将5,10,15,20-四(4-氨基苯基)卟啉铜(TAPP-Cu)(14.8mg,0.02 mmol)、噻吩并[3,2-b]噻吩-2,5-二羧醛(TT)(8mg,0.04mmol)和2, 4, 6-三甲基苯甲醛(TBA)(0.12mL)置于Pyrex管中(体积约5 mL,长20 cm,直径1 cm),加入0.925mL苯甲醇和0.077mL正丁醇超声处理1分钟,使其分散均匀,然后加入 0.2 mL的6 M醋酸。然后把Pyrex管在液氮中冷冻解冻,抽真空三次,使其内部压力为0 mbar并进行火焰密封。然后将Pyrex管置于120 ℃的烘箱中反应7天。用四氢呋喃、丙酮洗涤三次,抽滤收集产物,将收集的紫色粉末在70℃真空干燥过夜,得到TT-por(Cu)-COF NSs。
称取10mg TiO2,加入装有20mL N, N-二甲基甲酰胺(DMF)的圆底烧瓶中,搅拌至其溶解,然后缓慢滴入6μL 巯基丙酸(MPA)溶剂,继续搅拌至溶液呈淡黄色,再将20mg 研磨好的TT-por(Cu)-COF NSs加入到混合溶剂中,120℃加热冷凝回流,反应5小时后,经DMF溶剂抽滤洗涤,收集产物并在真空干燥箱中干燥过夜,得到巯基丙酸联结的二氧化钛共价有机框架复合材料TiO2-TT-por(Cu)-COF NSs。
实施例2
称取10 mg TiO2-TT-por(Cu)-COF NSs、10mg TiO2、10mg TT-por(Cu)-COF NSs和10mgTiO2-COF-366-Cu,分别平铺在石英器皿中,在特制的玻璃反应器下层中加入50mL去离子水以产生水蒸气用于反应过程中,将盛有催化剂的石英器皿置于反应器上层,与水分离,将反应器抽真空后,通15分钟的CO2气体,以保证反应体系中无空气残留。在303~323 K下用300 W氙灯(装有AM1.5滤光片)照射,在光催化反应过程中,每隔2小时用气相色谱检测光催化反应后的气体成分,如图6所示,根据检测到的CH4和CO的含量来说明制备的催化剂的光催化性能,通过性能对比可以发现,复合后的TiO2-TT-por(Cu)-COF NSs的CO产率达到了28μmol•g-1•h-1,无CH4产生,说明催化剂具有良好的产物选择性。而TiO2的CO产率仅为1μmol•g-1•h-1、TT-por(Cu)-COF NSs的CO产率为1.5μmol•g-1•h-1、TiO2-COF-366-Cu的CO产率为13.5μmol•g-1•h-1,并且三者CH4产率均为0.5μmol•g-1•h-1,而未采用巯基丙酸联结的复合材料,即按比例通过研磨物理混合后的TiO2/TT-por(Cu)-COF NSs(质量比1:2)的CO产率仅为8μmol•g-1•h-1,CH4产率为1μmol•g-1•h-1。因此可以说明本发明中通过巯基丙酸联结后的复合材料TiO2-TT-por(Cu)-COF NSs可有效提高光催化活性和还原产物选择性。
尽管本发明的内容已经通过上述优选实施例作了详细介绍,但应当认识到上述的描述不应该被认为是对本发明的限制。在本领域技术人员阅读了上述内容后,对于本发明的多种修改和替代都是显而易见的。因此,本发明的保护范围应由所附的权利要求来限定。
Claims (7)
1.一种巯基丙酸联结的二氧化钛共价有机框架复合材料的制备方法,其特征在于:包括以下步骤:
(1)在苯甲醇、正丁醇和醋酸的体系中分别加入5,10,15,20-四(4-氨基苯基)卟啉铜、噻吩并[3,2-b]噻吩-2,5-二羧醛和2, 4, 6-三甲基苯甲醛,从室温升温至120℃,保温3-7天,通过溶剂热法得到共价有机框架纳米片TT-por(Cu)-COF NSs;
(2)在N, N-二甲基甲酰胺溶剂中加入二氧化钛,搅拌至其溶解,然后滴入适量巯基丙酸溶剂,搅拌至溶液呈淡黄色,再将步骤(1)所得的TT-por(Cu)-COF NSs加入到淡黄色溶液中,加热冷凝回流后,经DMF溶剂抽滤洗涤后,收集产物并在真空干燥箱中干燥过夜,得到巯基丙酸联结的二氧化钛共价有机框架复合材料TiO2-TT-por(Cu)-COF NSs。
2.根据权利要求1所述的巯基丙酸联结的二氧化钛共价有机框架复合材料的制备方法,其特征在于:步骤(1)的苯甲醇、正丁醇和醋酸的体系中所使用的苯甲醇和正丁醇体积比例为12:1,醋酸的浓度为6mol/L。
3.根据权利要求1所述的巯基丙酸联结的二氧化钛共价有机框架复合材料的制备方法,其特征在于:5,10,15,20-四(4-氨基苯基)卟啉铜、噻吩并[3,2-b]噻吩-2,5-二羧醛的摩尔比为1:2:40。
4.根据权利要求1所述的巯基丙酸联结的二氧化钛共价有机框架复合材料的制备方法,其特征在于:步骤(2)中所述TiO2与TT-por(Cu)-COF NSs的质量比为1:2。
5.根据权利要求1所述的巯基丙酸联结的二氧化钛共价有机框架复合材料的制备,其特征在于:步骤(2)的加热冷凝回流温度为120℃,反应时间5h。
6.一种如权利要求1~5任一项所述的制备方法制得巯基丙酸联结的二氧化钛共价有机框架复合材料。
7.一种如权利要求6所述巯基丙酸联结的二氧化钛共价有机框架复合材料在光催化CO2还原中的应用。
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