CN114849785B - 一种三嗪环共价有机框架材料掺杂卟啉钴光催化剂的制备 - Google Patents
一种三嗪环共价有机框架材料掺杂卟啉钴光催化剂的制备 Download PDFInfo
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- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
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- -1 cobalt porphyrin carbon dioxide Chemical compound 0.000 claims abstract description 28
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 48
- 239000001569 carbon dioxide Substances 0.000 abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 4
- 229910052724 xenon Inorganic materials 0.000 abstract description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 abstract description 3
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
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- 150000004032 porphyrins Chemical class 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 32
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- SSJXIUAHEKJCMH-PHDIDXHHSA-N (1r,2r)-cyclohexane-1,2-diamine Chemical compound N[C@@H]1CCCC[C@H]1N SSJXIUAHEKJCMH-PHDIDXHHSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
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- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
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- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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Abstract
一种三嗪环共价有机框架材料掺杂卟啉钴光催化剂的制备方法,它涉及一种二氧化碳还原为一氧化碳光催化剂的制备方法。本发明的目的是要解决现有共价有机框架材料本身作为二氧化碳催化剂吸光能力不高,对大气中的二氧化碳利用率不高,导致其还原效率低,太阳光利用率低,从而光催化剂还原二氧化碳速率低。方法:一、利用有机溶剂热法制备THFB‑COF‑2‑Zn;二、通过超声波振荡分散法和有机溶剂热法将卟啉钴与THFB‑COF‑2‑Zn材料混合分散均匀,得到含有THFB‑COF‑2‑Zn掺杂卟啉钴二氧化碳还原光催化剂材料。本发明制备的含有THFB‑COF‑2‑Zn掺杂卟啉钴二氧化碳还原光催化剂材料在300W氙灯可见光照射下二氧化碳还原产一氧化碳速率最高可达352.8μmol·g‑1~700μmol·g‑1。本发明可以获得一种THFB‑COF‑2‑Zn共价有机框架材料掺杂卟啉钴二氧化碳还原光催化剂材料。
Description
技术领域
本发明涉及一种光催化二氧化碳还原催化剂的制备方法以及光催化性能测试。
背景技术
随着人类社会的进步和工业的发展,煤、石油、天然气等化石能源被广泛的开发和利用,导致了严重的能源危机和环境危机。其中,温室效应问题日趋严重,大气中二氧化碳含量屡创新高,严重危害我们的身体健康及生存环境。因此将二氧化碳转换为能源以实现能源的绿色循环利用被认为是解决能源问题和环境问题的最理想方式。全世界学者争相报道,目前将二氧化碳转换为能源的方法主要通过催化剂的作用将二氧化碳还原为低碳能源,转换方法分为传统催化、电催化和光催化三种。传统催化反应条件苛刻,需要提供大量的热能;电催化反应条件虽温和,但仍需要提供电能。光催化即以太阳能为反应动力,在催化剂的作用下将二氧化碳还原,其过程模拟绿色植物光合作用,被认为是最理想的二氧化碳转换利用途径。传统的光催化剂如二氧化钛、硫化镉和氧化锌等材料,他们的比表面积小、光生电子—空穴易复合、易光腐蚀且可见光利用率低,从而导致他们的CO2还原效率低。而理想的光催化剂应该具有比表面积大、光生电子—空穴不易复合、可见光利用率高、不易光腐蚀等要求。
酞菁系列是一种强有力的候选材料,得到了广泛的研究。特别是,卟啉钴因为其具有促进电子转移和二氧化碳吸附的作用。然而,卟啉钴钴倾向于团聚,从而减少表面积和高的光诱导电子、空穴重组率。为了解决这些问题,我们我们希望能限制卟啉钴粒子的团聚,从而提高卟啉钴粒子的光催化活性。共价有机框架(COFs)是一种由与有机配体自组装形成的新型网络状结构的类沸石材料。目前COFs已被用到了多个不同的领域,如气体分离与储存、催化、化学传感和荧光材料等。共价有机骨架材料(Covalent Organic Frameworks)是由C、B、O、N和Si等轻元素通过强共价键连接,经过热力学控制的可逆反应聚合而成的晶态多孔材料。由于质量轻,密度低,高比表面积,孔道规整均一,结构相对稳定,片层内部有强的π-π作用,光吸收和利用能力强,易功能化修饰和构筑基元多种多样等优点,被认为是理想的光催化剂。THFB-COF-2-Zn被认为是一种非常有发展潜力的复合载体。因此,我们提出了用搅拌法将卟啉钴掺杂到THFB-COF-2-Zn孔道中,利用COFs孔道提供的有限的空间作为一个微反应器,来限制卟啉钴粒子的团聚,从而提高卟啉钴粒子的光催化活性。
发明内容:
本发明的目的是要解决现有的纯卟啉钴光催化剂易团聚的问题,从而减少表面积和高的光生电子、空穴重组率的问题,而提供一种THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂的制备方法。
本发明的一种三嗪环共价有机框架材料掺杂卟啉钴二氧化碳还原光催化剂的制备方法是按以下步骤完成的:
步骤一、将干燥活化好的THFB-COF-2-Zn分散到四氢呋喃溶液中,在超声频率为30-50KHz的数控超声波清洗器上超声分散30min~60min后转移到搅拌速度为100r/min~300r/min磁力搅拌器上搅拌1h~5h后投加卟啉钴固体粉末,继续搅拌1h~2h,待溶液混合均匀,60℃加热持续搅拌10h~12h;抽滤得到沉淀,先用四氢呋喃对沉淀物洗涤2次~3次,再用无水乙醇洗涤2次~3次,50℃~70℃真空干燥6h~8h得到THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂粗产品;将上述粗产品置于史朗克管中,加入在均三甲苯中温度为100℃~120℃条件下保持18h~24h,再自然冷却至室温;离心得到沉淀,先用四氢呋喃对沉淀物洗涤1次~2次,再用无水乙醇洗涤1次~2次;将洗涤后的沉淀物在温度为50℃~70℃下真空干燥6h~8h得到THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂。
所述步骤一中干燥活化好的THFB-COF-2-Zn的质量与四氢呋喃体积比为1mg:0.05mL~1mg:1.5mL;
步骤一中干燥活化好的THFB-COF-2-Zn的质量与投加卟啉钴体积比为100mg:10mg~100mg:20mg;
步骤一中掺杂卟啉钴的粗产品质量与均三甲苯的体积比为1mg:0.05mL~1mg:0.5mL。
为考察THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂材料在可见光下催化二氧化碳还原效果,按以下方法对其可见光二氧化碳还原性能进行测试,测试过程如下:将制备好的复合催化剂薄膜置于自制的光催化气固相CO2还原反应器中,并加入0.2mL蒸馏水,并保证蒸馏水在光催化反应过程中不会触碰到复合催化剂薄膜。向体系中通入水蒸气和CO2以除去空气,30分钟后关闭体系,开启光源后,光照条件下每隔1h进行采样,利用气相色谱仪(GC112A)进行分析,反应时长共计5h。
本发明的有益处效果为:
本发明使用四氢呋喃溶液将卟啉钴掺杂到THFB-COF-2-Zn孔道中,利用THFB-COF-2-Zn孔道提供的有限的空间的孔道作为一个微反应器来限制卟啉钴粒子的团聚,并且,由于THFB-COF-2-Zn的包裹作用,又一定程度上减轻了卟啉钴粒子的光腐蚀现象,从而综合提高卟啉钴粒子的光催化活性。本发明制备的THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂在300W氙灯照射下进行光催化二氧化碳还原反应。本发明制备的THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂在300W氙灯照射下一氧化碳产生速率可达到352.8μmol·g-1~700μmol·g-1。
附图说明
图1为THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂材料X射线粉末衍射图;
图2为THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂材料可见光光催化二氧化碳还原速率柱状图。
图3为THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂材料可见光光催化二氧化碳还原速率点线图。
具体实施方式
下面结合具体的实施例对本发明作更详尽的说明。
实施例1:本实施方式的一种THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂的制备方法是按以下步骤完成的:
步骤一、称取1,3,5-三嗪-2,4,6-三(4’-羟基-5’-甲酰基苯基)苯(THFB)并加入到史朗克真空管中,随后向管中加入2ml均三甲苯,将管封闭后进行超声处理直至THFB在均三甲苯体系中混合均匀且无大颗粒;称取(1R,2R)-(-)-1,2-环己二胺置于另外的烧杯中,并加入2mL乙醇,超声使其全部溶解后加入Zn(ClO4)2·6H2O,产生的白色絮状沉淀是环己二胺和高氯酸锌的配合物。将白色沉淀加入到史朗克真空管中继续超声直至体系均一。随后相反应体系中加入乙酸水溶液并摇动真空管使酸混合均匀,通过在液氮浴中冷冻-脱气-融化的循环三次,自然冷却后置于自然升温至120℃的烘箱中静置反应,72小时后关闭烘箱使其自然降温至室温,收集过滤得到的固体。
步骤二、将步骤一中得到的0.25g THFB-COF-2-Zn固体,用N,N二甲基甲酰胺溶剂索提直至流出液无色,最后用甲醇索提8小时后真空干燥处理10小时。干燥后用乙醇浸泡12小时,期间多次更换乙醇,最后将得到的固体置于100℃真空干燥箱中12小时,得到100mg干燥活化好的THFB-COF-2-Zn黄色粉末固体。
步骤三、将步骤二中100mg干燥活化好的THFB-COF-2-Zn分散到四氢呋喃溶液中,超声分散30min~60min后转移到磁力搅拌器上在搅拌速度为100r/min~300r/min下搅拌1h~5h;后投加卟啉钴固体粉末,继续搅拌1h~2h,待溶液混合均匀,60℃加热持续搅拌10h~12h;抽滤得到沉淀,先用四氢呋喃对沉淀物洗涤2次~3次,再用无水乙醇洗涤2次~3次,50℃~70℃真空干燥6h~8h得到THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂粗产品;
步骤四、将步骤三中得到的80mg THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂粗产品置于史朗克管中,加入在温度为100℃~120℃条件下保持18h~24h,再自然冷却至室温;离心得到沉淀,先用四氢呋喃对沉淀物洗涤1次~2次,再用无水乙醇洗涤1次~2次;将洗涤后的沉淀物在温度为50℃~70℃下真空干燥6h~8h得到THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂;
THFB-COF-2-Zn/卟啉钴复合材料光催化剂的表征及性能检测:
图1对实施例1得到的THFB-COF-2-Zn掺杂不同含量卟啉钴二氧化碳还原光催化剂材料进行可见光光催化二氧化碳还原速率对比,得到如图1所示的THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂材料二氧化碳还原速率对比图。本发明制备的THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂材料最大平均一氧化碳产生速率可达692.2μmol·g-1。
图2对实施例1得到的THFB-COF-2-Zn掺杂不同含量卟啉钴二氧化碳还原光催化剂材料进行可见光光催化二氧化碳还原5h总产量数据,得到如图2所示的THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂材料二氧化碳还原速率对比图。本发明制备的THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂材料最大平均一氧化碳产生速率可达692.2μmol·g-1。
本具体实例所得的THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂材料,有良好的光催化二氧化碳还原能力,能够光催化二氧化碳还原,可作为光催化剂。
Claims (1)
1.一种THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂的制备方法,其特征在于该方法按以下步骤进行:
将干燥活化好的THFB-COF-2-Zn分散到四氢呋喃溶液中,在超声频率为30-50kHz的数控超声波清洗器上超声分散30min~60min后转移到搅拌速度为100r/min~300r/min磁力搅拌器上搅拌1h~5h后投加卟啉钴固体粉末,继续搅拌1h~2h,待溶液混合均匀,60℃加热持续搅拌10h~12h;抽滤得到沉淀,先用四氢呋喃对沉淀物洗涤2次~3次,再用无水乙醇洗涤2次~3次,50℃~70℃真空干燥6h~8h得到THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂粗产品;将上述粗产品置于史朗克管中,加入在均三甲苯中温度为100℃~120℃条件下保持18h~24h,再自然冷却至室温;离心得到沉淀,先用四氢呋喃对沉淀物洗涤1次~2次,再用无水乙醇洗涤1次~2次;将洗涤后的沉淀物在温度为50℃~70℃下真空干燥6h~8h得到THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂;
所述干燥活化好的THFB-COF-2-Zn的质量与四氢呋喃体积比为1mg:0.05mL~1mg:1.5mL;
所述干燥活化好的THFB-COF-2-Zn的质量与投加卟啉钴质量比为100mg:10mg~100mg:20mg;
所述THFB-COF-2-Zn掺杂卟啉钴二氧化碳还原光催化剂粗产品质量与均三甲苯的体积比为1mg:0.05mL~1mg:0.5mL。
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