CN116139867A - 一种MOFs衍生的ZnO@CDs@Co3O4复合光催化剂及其制备方法和应用 - Google Patents
一种MOFs衍生的ZnO@CDs@Co3O4复合光催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于纳米材料领域,具体涉及一种MOFs衍生的ZnO@CDs@Co3O4复合光催化剂及其制备方法和应用。本发明通过先合成ZIF‑8结构,再负载碳点,最后再原位合成ZIF‑67,经煅烧制备的ZnO@CDs@Co3O4复合光催化剂形成了独特的核壳结构。根据结构表征和性能表征实验,可以发现所制备的ZnO@CDs@Co3O4复合光催化剂具有化学性质稳定,形貌均匀,催化效率高等优点,又因其具有原料易得,且制备成本低廉等优点,具有一定的研究和应用价值。
Description
技术领域
本发明属于纳米材料领域,特别涉及一种MOFs衍生的ZnO@CDs@Co3O4复合光催化剂及其制备方法和应用。
背景技术
能源短缺和环境问题已成为当今人类社会所面临的重大挑战。当前世界能源消耗的80%仍来自于以石油、煤、天然气等为主的化石能源。随着人类社会活动的增加,不仅加快了对化石能源的消耗,还造成大气中以CO2为主的温室气体排放量的增加,严重干扰了自然界的碳循环,导致全球气候变暖。
近年来,半导体材料包括金属氧化物(ZnO和Co3O4)、金属硫化物(CdS和In2S3),碳基材料(C3N4和碳量子点),金属有机框架(UIO-66-NH2和MIL-125氨基)等等,已经报道了CO2光转换。其中,ZnO一直被称为是一种大多数有前途的半导体都因其高稳定性,成本低,具有合理的氧化还原二氧化碳能力。但是,宽频带隙高达3.2eV,充电速度快复合限制了光催化CO2转化,裸ZnO用作光催化剂时的效率来提高光催化性能,有许多策略采用了包括表面工程、各种形态调节、助催化剂负载,杂原子掺杂,异质结建筑等等。
金属-有机骨架材料(MOFs)由于具有高的比表面积、半导体性质和丰富的活性位点,在光催化领域得到了广泛的应用,其中,以ZIF-67和ZIF-8为代表的沸石型咪唑酸骨架结构具有金属位点暴露、碳氮配体易接近、化学稳定性好等特点,是太阳能制氢的理想材料。Wang等人报道了ZIF-67/Ni-Fe LDHs复合材料,其中ZIF-67具有较高的比表面积和匹配良好的能带结构,从而表现出更高的光催化氢率。ZIF-8/ZIF-67与其他MOFs相比具有更好的稳定性和附着力。此外,当光催化体系释放大量二氧化碳时,二氧化碳可以快速通过多孔层,从而加速化学反应动力学。
在我们之前的工作中,我们通过多步骤合成的CD-修饰的金属有机框架(MOF)形成的Co3O4/In2O3纳米管(CDs-M-CIO)异质结构在没有牺牲剂的情况下表现出较高的太阳能驱动CO生成速率,达到2.05μmol h-1g-1。本发明中我们通过一步热解制备ZIF-8@CDs@ZIF-67衍生的具有独特的核壳结构的ZnO@CDs@Co3O4,首次应用于光催化领域且能极大地提高光催化二氧化碳还原性能。
发明内容
本发明要解决的技术问题是:基于上述问题,本发明的目的是提供一种MOFs衍生的ZnO@CDs@Co3O4复合光催化剂及其制备方法和应用。
本发明为解决其技术问题所采用的一个技术方案是:一种MOFs衍生的ZnO@CDs@Co3O4复合光催化剂,以ZnO为核,在ZnO的表面分布碳点,以Co3O4为壳的核壳结构的复合光催化剂,其制备方法包括以下步骤:
(1)ZIF-8的制备:将六水合硝酸锌(Zn(NO3)2·6H2O)加入甲醇中,再加入含2-甲基咪唑的甲醇溶液,搅拌使混合均匀后,甲醇洗涤数次,干燥,得到ZIF-8;
(2)ZIF-8@CDs@ZIF-67的制备:将制备好的ZIF-8溶于甲醇中,加入碳点的乙醇溶液,再加入氯化钴,将含2-甲基咪唑的甲醇溶液缓慢放入上述悬浮液中,搅拌使反应完全,用甲醇洗涤数次得到ZIF-8@CDs@ZIF-67;
(3)ZnO@CDs@Co3O4的制备:将制备好的ZIF-8@CDs@ZIF-67放入坩埚中,在马弗炉中煅烧,得到产品ZnO@CDs@Co3O4。
进一步地,步骤(1)中Zn(NO3)2·6H2O和2-甲基咪唑物质的量的比为2~3:5~7;优选为2.7:6.4。在该比例下制备得到的ZIF-8的尺寸在2μm左右,而不同的比例会影响ZIF-8的形貌和尺寸,进而影响复合和催化效果。
进一步地,所述的步骤(2)中ZIF-8、CoCl2、2-甲基咪唑的物质的量比为0.1~0.3:1~1.5:10~11;优选0.1~0.3:1.4:10.9;进一步优选为0.2:1.4:10.9。在该比例下,形成的ZIF-67的形貌和尺寸可以确保能把ZIF-8和CDs包裹进去,从而形成核壳结构。
进一步地,所述的步骤(2)中将CDs分散在乙醇溶液中以是CDs能均匀分散为宜,优选的,CDs的乙醇溶液的浓度为1mg/ml;CDs的加入量为ZIF-8质量的1%~5%;进一步优选CDs的加入量为ZIF-8质量的3%。
进一步地,所述步骤(3)中煅烧温度为450℃,煅烧时间为2h。煅烧温度和时间会影响煅烧出来的形貌和粒径,优选450℃下煅烧2h,使最终ZnO@CDs@Co3O4复合光催化剂的形貌为形状规整,大小均匀的褶皱的十二面体。
本发明制备的ZnO@CDs@Co3O4复合光催化剂用于光催化二氧化碳还原,进一步的本发明制备的ZnO@CDs@Co3O4复合光催化剂用于光催化二氧化碳还原产一氧化碳。
相比于现有技术,本发明的有益效果是:
(1)本发明先合成了ZIF-8结构,再通过机械搅拌负载碳点,最后再原位生产上ZIF-67,制备的ZnO@CDs@Co3O4复合光催化剂以ZnO为核,在ZnO的表面分布了CDs的粒子,最后包覆Co3O4作为整个结构的壳,形成了独特的核壳结构。通过本发明方法制备的ZIF-8@CDs@ZIF-67复合光催化剂的形貌为形状规整,大小均匀的十二面体;ZnO@CDs@Co3O4复合光催化剂的形貌为形状规整,大小均匀的褶皱的十二面体;
(2)本发明中负载的碳点(CDs)不仅具有良好的电子转移特性,从而抑制光激发电子-空穴对的复合,且CDs具有共轭p结构可以优先吸附和激活二氧化碳,因此具有优异的光催化活性;
(3)与现有技术的立方体结构相比,本发明的ZnO@CDs@Co3O4复合光催化剂比表面积明显增大,具有较好的稳定性,无二次污染,且催化效率,能在180min中ZnO@CDs@Co3O4光催化二氧化碳速率可以达到2123μmol g-1h-1;
(4)本发明的ZnO@CDs@Co3O4复合光催化剂的制备方法简单,制备条件易于控制,无二次污染等优点,具有一定的研究和应用价值。
附图说明:
下面结合附图对本发明进一步说明。
图1是本发明实施例1制备得到的纯ZIF-67,纯ZIF-8,ZIF-8@ZIF-67,ZIF-8@CDs@ZIF-67,纯Co3O4,纯ZnO,ZnO@Co3O4,和ZnO@CDs@Co3O4复合光催化剂的X射线衍射图;
图2是本发明实施例1制备得到的纯ZIF-67(图2a),纯ZIF-8(图2b),ZIF-67@ZIF-8(图2c),ZIF-8@CDs@ZIF-67(图2d),纯Co3O4(图2e),纯ZnO(图2f),Co3O4@ZnO(图2g),和ZnO@CDs@Co3O4(图2h)复合光催化剂的扫描电镜图;ZIF-8@CDs@ZIF-67(图2i)和ZnO@CDs@Co3O4(图2j)的透射电镜图;ZnO@CDs@Co3O4(图2k)的高倍透射电镜图;ZnO@CDs@Co3O4(图2l)的EDX能谱图;
图3是本发明实施例1制备得到的ZnO@Co3O复合光催化剂光催化二氧化碳速率图;
图4是本发明实施例1制备得到的ZnO@CDs@Co3O复合光催化剂光催化二氧化碳速率图;
图5是本发明实施例1制备得到的3%-ZnO@CDs@Co3O与3%-ZnO@Co3O@CDs复合光催化剂光催化二氧化碳速率对比图。
具体实施方式
现在结合具体实施例对本发明作进一步说明,以下实施例旨在说明本发明而不是对本发明的进一步限定。
本发明中复合光催化剂进行光催化二氧化碳还原的通常方法是:10mg的样本和10mg吡啶钌添加到20ml乙腈,5ml水,5ml三乙醇胺中,再超声30分钟以制备出均匀分散的催化剂样品。然后,将制备好的催化剂样品和30ml溶液放入120ml的Pyrex玻璃反应器中与二氧化碳***鼓泡30min,确保30分钟的厌氧条件。光催化实验使用300W氙灯(模拟太阳光全光谱,波长范围是200-2500nm)。在反应进行三个小时后取样用气相色谱法(GC-7860Plus,TCD检测器)检测。
本发明所用试剂如无特殊说明,均为分析纯。
实施例1
(1)CDs的制备:
以两根石墨棒作为碳源,先在去离子水中超声清洗15min,以去除表面杂质。两根石墨棒分别与正负极连接后***装有超纯水的烧杯中,作为阳极和阴极。两电极相距7.5cm左右,并从电解液液面向外突出3-5cm,用直流电源在两个电极之间施加30V的电压。电解石墨棒半个月左右,待烧杯中的水溶液变成棕黑色时,用慢性定量滤纸过滤三次,或离心机22000rpm离心15-30min左右,以去除沉淀的氧化石墨和较大石墨颗粒,最终得到纯CDs的水溶液。通过取一定量的CDs水溶液进行冷冻干燥,获得CDs粉末。最后将CDs粉末分散在乙醇溶液中备用,CDs的乙醇溶液的浓度为1mg/ml。
(2)ZIF-67和ZIF-8的制备:将0.177g CoCl2溶于15ml甲醇中,然后将15mL含0.895g 2-甲基咪唑的甲醇溶液缓慢放入上述悬浮液中,搅拌3h后,用甲醇洗涤数次,所得样品为ZIF-67;将0.810g Zn(NO3)2·6H2O加入15mL甲醇中,然后将40mL含0.526g 2-甲基咪唑的甲醇溶液加入上述混悬液中,搅拌3h后,用甲醇洗涤3次,60℃干燥,所得样品为ZIF-8。
(3)ZnO@Co3O4复合光催化剂的制备:
将40mg ZIF-8或50mg ZIF-8或60mg ZIF-8溶于15ml甲醇中,再加入0.177gCoCl2。然后,将15mL含0.895g 2-甲基咪唑的甲醇溶液缓慢放入上述悬浮液中,搅拌3h后,用甲醇洗涤数次得到产品ZIF-8@ZIF-67;将制备好的ZIF-8@ZIF-67放入坩埚中,在马弗炉中450℃煅烧2h,得到产品分别标记为40mg-ZnO@Co3O4、50mg-ZnO@Co3O4、60mg-ZnO@Co3O4。
从图3可以看出,50mg-ZnO@Co3O4催化二氧化碳产CO的效率最高,达1032μmol g-1h-1相比于ZnO和Co3O4分别提高了2.96、2.30倍。
(4)ZnO@CDs@Co3O4复合光催化剂的制备:
1%-ZnO@CDs@Co3O4复合光催化剂的制备:将50mg ZIF-8溶于15ml甲醇中,加入0.5ml CDs的乙醇溶液(1mg/ml),再加入0.177g CoCl2。然后,将15mL含0.895g 2-甲基咪唑的甲醇溶液缓慢放入上述悬浮液中。搅拌3h后,用甲醇洗涤数次得到产品ZIF-8@CDs@ZIF-67;将制备好的ZIF-8@CDs@ZIF-67放入坩埚中,在马弗炉中450℃煅烧,2h后得到产品1%-ZnO@CDs@Co3O4。
3%-ZnO@CDs@Co3O4复合光催化剂的制备:与1%-ZnO@CDs@Co3O4复合光催化剂制备方法不同的是,1mg/ml CDs的乙醇溶液的加入量为1.5ml。
5%-ZnO@CDs@Co3O4复合光催化剂的制备:与1%-ZnO@CDs@Co3O4复合光催化剂制备方法不同的是,1mg/ml CDs的乙醇溶液的加入量为2.5ml。
从图4可见,在180min内,1%-ZnO@CDs@Co3O4、3%-ZnO@CDs@Co3O4、5%-ZnO@CDs@Co3O4复合光催化剂相比于50mg-ZnO@Co3O4分别提高了1.22、2.06、1.35倍,其中3%-ZnO@CDs@Co3O4光催化二氧化碳还原生产CO的速率可以达到2123μmol g-1h-1,CO选择性为62%。由此可见所制备的ZnO@CDs@Co3O4复合光催化剂具有很高的光催化活性。
(5)制备3%-ZnO@Co3O4@CDs,考察CDs的掺杂方式对光催化剂的活性的影响
按步骤(3)ZnO@Co3O4复合光催化剂的制备方法,称取50mg ZIF-8,制备50mg-ZnO@Co3O4;将50mg-ZnO@Co3O4溶于15ml甲醇中,加入1.5ml CDs的乙醇溶液(1mg/ml),搅拌24h后,用甲醇洗涤数次得到产品3%-ZnO@Co3O4@CDs。
从图5可见CDs的掺杂方式对光催化剂的活性会有明显影响,先制备ZnO@Co3O4再负载CDs制备的3%-ZnO@Co3O4@CDs的CO生成速率为1528μmol g-1h-1;先负载CDs制备的3%-ZnO@CDs@Co3O4的CO生成速率为2123μmol g-1h-1;二者相比,先掺杂的方式制备的复合光催化其催化二氧化碳产生CO的速率提高了1.39倍。
采用日本D/MAX2500的X-射线衍射仪分析实施例1所制备的纯ZIF-67,纯ZIF-8,ZIF-8@ZIF-67,ZIF-8@CDs@ZIF-67,纯Co3O4,纯ZnO,Co3O4@ZnO,和ZnO@CDs@Co3O4复合光催化剂的晶相结构,其中,X射线为Cu靶Kα电压40kV,电流100mA,步长为0.02°,扫描范围5°~80°。X射线衍射图谱如图1所示,由图可知,制备的ZIF-8@CDs@ZIF-67复合光催化剂的XRD衍射图中可看到在7.4°,10.4°,12.8°,14.7°,16.4°和17.8°出现ZIF-8的特征衍射峰分别对应ZIF-8的(011),(002),(112),(022),(013),以及(222)晶面,7.4°,10.4°,12.8°,14.7°,16.4°和17.8°是ZIF-67的特征衍射峰分别对应ZIF-67的(011),(002),(112),(022),(013),以及(222)晶面。22.5°和42.3°是CDs的特征衍射峰分别对应CDs的(002)和(100)晶面。但是在X射线衍射图谱中ZIF-8@CDs@ZIF-67复合材料没有明显的CDs峰,这与CDs加载量低、体积小、分散性好有关。因此,该复合光催化剂中只含有ZIF-8和ZIF-67,并且在复合过程中未改变二者的化学结构和晶型。同样的,制备的ZnO@CDs@Co3O4复合光催化剂的XRD衍射图中可看到在31.2°,37.1°,44.7°,59.3°,和65.3°出现Co3O4的特征衍射峰分别对应Co3O4的(220),(311),(400),(511),以及(440)晶面,31.9°,34.5°,36.3°,47.5°,56.6°,62.9°,66.4°,68.0°和69.1°是ZnO的特征衍射峰分别对应ZnO的(100),(002),(101),(102),(110),(103),(200),(112)以及(201)晶面。22.5°和42.3°是CDs的特征衍射峰分别对应CDs的(002)和(100)晶面。但是在X射线衍射图谱中ZnO@CDs@Co3O复合材料没有明显的CDs峰,这与CDs加载量低、体积小、分散性好有关。因此,该复合光催化剂中只含有Co3O4和ZnO,并且在复合过程中未改变二者的化学结构和晶型。
采用Quanta 200F型场发射扫描电子显微镜观察实施例1制备的ZIF-8@CDs@ZIF-67和ZnO@CDs@Co3O4复合光催化剂的形貌,扫描电镜图如图2所示,从图可以看出,本实施方式制备的ZIF-8@CDs@ZIF-67复合光催化剂的形貌为形状规整,大小均匀的十二面体;而ZnO@CDs@Co3O4复合光催化剂的形貌为形状规整,大小均匀的褶皱的十二面体。这也可以由图2中的TEM图进一步表明。
Claims (8)
1.一种MOFs衍生的ZnO@CDs@Co3O4复合光催化剂,其特征在于,所述MOFs衍生的ZnO@CDs@Co3O4复合光催化剂是以表面分布碳点的ZnO为核,以Co3O4为壳的核壳结构的复合光催化剂。
2.根据权利要求1所述的MOFs衍生的ZnO@CDs@Co3O4复合光催化剂的制备方法,其特征是:包括以下步骤:
(1)ZIF-8的制备:将六水合硝酸锌加入甲醇中,再加入含2-甲基咪唑的甲醇溶液,搅拌使混合均匀后,甲醇洗涤数次,干燥,得到ZIF-8;
(2)ZIF-8@CDs@ZIF-67的制备:将制备好的ZIF-8溶于甲醇中,加入碳点的乙醇溶液,再加入氯化钴,将含2-甲基咪唑的甲醇溶液缓慢放入上述悬浮液中,搅拌使反应完全,用甲醇洗涤数次得到ZIF-8@CDs@ZIF-67;
(3)ZnO@CDs@Co3O4的制备:将制备好的ZIF-8@CDs@ZIF-67放入坩埚中,在马弗炉中煅烧,得到产品ZnO@CDs@Co3O4。
3.根据权利要求2所述的MOFs衍生的ZnO@CDs@Co3O4复合光催化剂的制备方法,其特征在于,所述步骤(1)中六水合硝酸锌与2-甲基咪唑物质的量的比为2~3:5~7。
4.根据权利要求2所述的MOFs衍生的ZnO@CDs@Co3O4复合光催化剂的制备方法,其特征在于,所述步骤(2)中ZIF-8、氯化钴、2-甲基咪唑物质的量比为0.1~0.3:1~1.5:10~11。
5.根据权利要求2所述的MOFs衍生的ZnO@CDs@Co3O4复合光催化剂的制备方法,其特征在于,所述步骤(2)中碳点的加入量为ZIF-8质量的1%~5%。
6.根据权利要求2所述的MOFs衍生的ZnO@CDs@Co3O4复合光催化剂的制备方法,其特征在于,所述步骤(3)中煅烧温度为450℃,煅烧时间为2h。
7.根据权利要求1所述的MOFs衍生的ZnO@CDs@Co3O4复合光催化剂的应用,其特征在于,所述复合光催化剂在光催化二氧化碳还原中的应用。
8.根据权利要求7所述的MOFs衍生的ZnO@CDs@Co3O4复合光催化剂的应用,其特征在于,所述复合光催化剂在光催化二氧化碳还原产一氧化碳中的应用。
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