CN111545235A - 一种2D/2Dg-C3N4CoAl-LDH产氢异质结材料及其制备方法与应用 - Google Patents
一种2D/2Dg-C3N4CoAl-LDH产氢异质结材料及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种2D/2D g‑C3N4/CoAl‑LDH异质结材料的制备与光催化分解水产氢的应用,属于材料制备及可再生清洁能源利用技术领域。所述异质结材料的制备以g‑C3N4纳米片为模板,通过原位一步水热法将CoAl‑LDH负载在C3N4纳米片表面形成二维/二维平面异质结复合材料。所得的平面异质结构的更大的接触界面积为光生载流子的迁移和分离提供更多的高速通道;同时2D纳米片的表面特性使其近似于分子层间的修饰,保持了尽可能大的表面原子的占比,为光催化反应提供更多的活性位点。因此复合异质结样品在光催化产氢反应中表现出优异性能。本发明制备方法操作简单,催化剂活性和稳定性高,有较大的应用潜力。
Description
技术领域
本发明属于材料制备及可再生清洁能源利用技术领域,具体涉及一种2D/2Dg-C3N4/CoAl-LDH异质结材料的制备与光催化分解水产氢应用。
背景技术
氢能作为一种无污染的清洁能源在近些年受到研究者们的广泛关注。氢气燃烧产生的能量高达122KJ·g-1,是碳氢燃料的2.75倍和甲醇乙醇的5倍。因此,氢气被认为是未来最理想的燃料和能源载体。然而,目前氢能的来源还主要是通过化石燃料的蒸馏重整和天然气、煤气的热解和电解。这些方法都需要消耗大量的化石燃料,从长远角度看来不利于人类的可持续发展。而光催化分解水产氢技术,可直接以太阳光为驱动力,在光催化剂存在的条件下,直接将水分解产生氢气而被认为是一种最理想的获取H2途径。但是,受光催化材料的限值,目前光催化产氢效率依然不高,因此寻找制备简单和高效的催化剂是光催化产氢领域的重点。
在目前已开发的众多光催化材料中,氮化碳由于其独特的电子能带结构和优异的化学稳定性,被广泛应用于光催化分解水产氢。然而,体相g-C3N4光催化剂的一般制备方法是通过高温热聚合,这导致其存在比表面积小、激子结合能高、光生载流子复合严重以及光吸收能力不足等问题,严重制约了g-C3N4光催化产氢性能。将两种或多种半导体材料以不同形貌或电子排布结构在其界面形成纳米尺度的异质结已成为复合半导体光催化剂研究领域的热点。复合异质结材料在热力学上具有合适的能带结构来驱动H2O分子转化或诱导其产生激发态;动力学上其光生载流子能迅速迁移分离,并有效地与表面吸附物发生氧化还原反应。因此,对C3N4进行表面修饰和改进对于实现更高效的产氢性能意义重大。
C3N4基复合光催化剂的一般制备方法是直接以石墨相氮化碳为原料,通过原位生长的方法在其表面修饰第二组分。如专利CN108636436A公开了用水热法直接将将g-C3N4分散在去离子水中,依次加入Na2MoO4·2H2O、CH3CSNH2后通过一步水热法制备得到g-C3N4/MoS2复合光催化剂。专利CN110624583A公开了直接将硝酸银、醋酸锌、醋酸铟、硫代乙酰胺和石墨相氮化碳按照比例在水热条件下反应,获得Ag:ZnIn2S4/g-C3N4光催化剂。但是,上述合成g-C3N4基复合光催化剂的方法,由于体相g-C3N4颗粒尺寸大、比表面积小而导致所得到的复合结构中g-C3N4基和第二组分的接触面积小,不利于界面间的光生载流子的迁移和分离。
发明内容
为了解决上述问题,本发明的目的在于提供一种2D/2D g-C3N4/CoAl-LDH异质结材料的制备与光催化分解水产氢应用,解决了传统C3N4基复合光催化剂之间的接触界面积小,反应活性低的问题。
为实现上述目的,本发明采用如下技术方案:
以三聚氰胺为前驱体,通过热聚合法得到g-C3N4前驱体;然后将制备得到的g-C3N4分散在去离子水中,超声剥离得到g-C3N4纳米片;向上述g-C3N4纳米片水溶液中按比例加入Co(NO3)2、Al(NO3)2和尿素,通过水热法制备得到2D/2D g-C3N4/CoAl-LDH复合光催化剂。其具体包括以下步骤:
(1)取10 g的三聚氰胺于坩埚中,置于马弗炉中550 oC下煅烧4 h(升温速率2.3 oC/min)待自然冷却至室温后,取出样品研磨得到黄色氮化碳前驱体,标记为g-C3N4备用;
(2)取0.5 g的g-C3N4于50 mL去离子水中超声2 h,得到的悬浊液在3000转/分钟的转速下离心,去除底部的g-C3N4沉淀物,得到g-C3N4纳米片悬浊液;
(3)取一定量的Co(NO3)2和Al(NO3)2按3:1摩尔比和0.5 g尿素加入到(2)中的g-C3N4纳米片悬浊液,搅拌0.5 h后于120 oC下水热反应12 h,冷却至室温后离心分离,沉淀物分别用蒸馏水和乙醇洗涤,60 oC真空干燥得到2D/2D g-C3N4/CoAl-LDH异质结催化剂。
光催化分解水产氢反应条件为:向水和三乙醇胺溶液中加入制备得到的复合光催化剂,在可见光(420-800 nm)照射下,可以进行光催化分解水产氢反应。
本发明的显著优点在于:
(1)本发明创造了一种2D/2D g-C3N4/CoAl-LDH的新型制备方法。
(2)通过本发明制备得到的样品相较于传统的复合材料,其组成更均匀,且制备条件温和、合成产率较高,这些操作均能显著降低生产成本,且获得的材料纯度高,稳定性好,具有较大的应用潜力。
(3)本发明制备得到2D/2D g-C3N4/CoAl-LDH材料,面/面型的接触界面为为光生载流子的迁移和分离提供了更多的迁移高速通道,光电性能较好,在光催化反应体系中的稳定性和可再生能力强,重复利用率高,具有很高的实用价值和应用前景。
附图说明
图1为实施例1-6所得2D/2D g-C3N4/CoAl-LDH材料的X射线粉末衍射图(XRD)。
图2为实施例4所得2D/2D g-C3N4/CoAl-LDH的扫描电镜图。
图3为实施例1-5所得2D/2D g-C3N4/CoAl-LDH材料的光电流图。
图4为实施例1-5所得2D/2D g-C3N4/CoAl-LDH材料的光催化产氢活性图。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1
取10 g的三聚氰胺于坩埚中,盖上盖子后置于马弗炉中550 oC下煅烧4 h(升温速率2.3 oC/min)待自然冷却至室温后,取出样品研磨得到黄色氮化碳前驱体,标记为g-C3N4;取0.5 g的g-C3N4于50 mL去离子水中超声2 h,得到的悬浊液在3000转/分钟的转速下离心,去除底部的g-C3N4沉淀物,得到g-C3N4纳米片悬浊液。
实施例2
取10 g的三聚氰胺于坩埚中,盖上盖子后置于马弗炉中550 oC下煅烧4 h(升温速率2.3 oC/min)待自然冷却至室温后,取出样品研磨得到黄色氮化碳前驱体,标记为g-C3N4;取0.5 g的g-C3N4于50 mL去离子水中超声2 h,得到的悬浊液在3000转/分钟的转速下离心,去除底部的g-C3N4沉淀物,得到g-C3N4纳米片悬浊液。向悬浊液中加入0.003 mol Co(NO3)2和0.001 mol Al(NO3)2、0.5 g尿素搅拌0.5 h后于120 oC下水热反应12 h,冷却至室温后离心分离,沉淀物分别用蒸馏水和乙醇洗涤,60 oC真空干燥得到的粉末固体标记为CN-CoAl0.003。
实施例3
取10 g的三聚氰胺于坩埚中,盖上盖子后置于马弗炉中550 oC下煅烧4 h(升温速率2.3 oC/min)待自然冷却至室温后,取出样品研磨得到黄色氮化碳前驱体,标记为g-C3N4;取0.5 g的g-C3N4于50 mL去离子水中超声2 h,得到的悬浊液在3000转/分钟的转速下离心,去除底部的g-C3N4沉淀物,得到g-C3N4纳米片悬浊液。向悬浊液中加入0.006 mol Co(NO3)2和0.002 mol Al(NO3)2、0.5 g尿素搅拌0.5 h后于120 oC下水热反应12 h,冷却至室温后离心分离,沉淀物分别用蒸馏水和乙醇洗涤,60 oC真空干燥得到的粉末固体标记为CN-CoAl0.006。
实施例4
取10 g的三聚氰胺于坩埚中,盖上盖子后置于马弗炉中550 oC下煅烧4 h(升温速率2.3 oC/min)待自然冷却至室温后,取出样品研磨得到黄色氮化碳前驱体,标记为g-C3N4;取0.5 g的g-C3N4于50 mL去离子水中超声2 h,得到的悬浊液在3000转/分钟的转速下离心,去除底部的g-C3N4沉淀物,得到g-C3N4纳米片悬浊液。向悬浊液中加入0.009 mol Co(NO3)2和0.003 mol Al(NO3)2、0.5 g尿素搅拌0.5 h后于120 oC下水热反应12 h,冷却至室温后离心分离,沉淀物分别用蒸馏水和乙醇洗涤,60 oC真空干燥得到的粉末固体标记为CN-CoAl0.009。
实施例5
取10 g的三聚氰胺于坩埚中,盖上盖子后置于马弗炉中550 oC下煅烧4 h(升温速率2.3 oC/min)待自然冷却至室温后,取出样品研磨得到黄色氮化碳前驱体,标记为g-C3N4;取0.5 g的g-C3N4于50 mL去离子水中超声2 h,得到的悬浊液在3000转/分钟的转速下离心,去除底部的g-C3N4沉淀物,得到g-C3N4纳米片悬浊液。向悬浊液中加入0.012 mol Co(NO3)2和0.004 mol Al(NO3)2、0.5 g尿素搅拌0.5 h后于120 oC下水热反应12 h,冷却至室温后离心分离,沉淀物分别用蒸馏水和乙醇洗涤,60 oC真空干燥得到的粉末固体标记为CN-CoAl0.012。
实施例6
取0.06 mol Co(NO3)2和0.02 mol Al(NO3)2、0.5 g尿素于50 mL H2O中搅拌0.5 h后于120 oC下水热反应12 h,冷却至室温后离心分离,沉淀物分别用蒸馏水和乙醇洗涤,60 oC真空干燥得到的粉末固体标记为CoAl-LDH。
图1为实施例1-6所得g-C3N4/CoAl-LDH材料的X射线粉末衍射图,从图1可以看出,制备得到的复合材料由g-C3N4和CoAl-LDH组成。
图2为实施例4所得2D/2D g-C3N4/CoAl-LDH的扫描电镜图。从图中可看出所制备的g-C3N4/CoAl-LDH复合材料表现为纳米片组装结构。
图3为实施例1-5所得2D/2D g-C3N4/CoAl-LDH材料的光电流图,从图中可以看出所制备得到的复合材料相比于纯g-C3N4具有更强的光电响应。
图4为实施例1-5所得2D/2D g-C3N4/CoAl-LDH材料的光催化产氢活性。从图中可以看出,复合材料相比于纯g-C3N4具有显著提高的光催化产氢活性,其中CN/CoAl-LDH0.009表现出最佳的产氢性能,是未修饰g-C3N4的8.8倍。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (6)
1.一种产氢异质结材料,其特征在于:化学式为2D/2D g-C3N4/CoAl-LDH。
2.制备一种如权利要求1所述2D/2Dg-C3N4CoAl-LDH产氢异质结材料的方法,其特征在于:以三聚氰胺为起始物,通过热聚合法合成石墨相氮化碳前驱体;取氮化碳粉末于蒸馏水中超声剥离,离心之后得到氮化碳纳米片,并加入硝酸钴、硝酸铝和尿素,再采用水热法制得到2D/2D g-C3N4/CoAl-LDH复合异质结材料。
3.根据权利要求2所述2D/2Dg-C3N4CoAl-LDH产氢异质结材料的制备方法,其特征在于:
(1)取10 g的三聚氰胺于坩埚中,550 oC下煅烧4 h,待自然冷却至室温后,取出样品研磨得到黄色氮化碳前驱体,标记为g-C3N4备用;
(2)取0.5 g的C3N4于50 mL去离子水中超声2 h,得到的悬浊液在3000转/分钟的转速下离心,去除底部的g-C3N4沉淀物,得到g-C3N4纳米片悬浊液;
(3)取Co(NO3)2和Al(NO3)2按3:1摩尔比和0.5 g尿素加入到步骤(2)中制备好的g-C3N4纳米片悬浊液重,搅拌0.5 h后于120 oC下水热反应12 h,冷却至室温后离心分离,沉淀物分别用蒸馏水和乙醇洗涤后,于60 oC真空干燥得到2D/2D g-C3N4/CoAl-LDH异质结催化剂。
4.根据权利要求3所述2D/2Dg-C3N4CoAl-LDH产氢异质结材料的制备方法,其特征在于:所述步骤(1)中煅烧的升温速率为2.3 oC/min。
5.根据权利要求3所述2D/2Dg-C3N4CoAl-LDH产氢异质结材料的制备方法,其特征在于:所述Co(NO3)2的用量为0.001-0.012mol。
6.一种如权利要求1-5任一项所述制备得到的异质结催化剂在光催化上的应用,其特征在于:在以三乙醇胺为牺牲剂的水体系中,用420 nm-800 nm模拟可见光照射下,采用2D/2D g-C3N4/CoAl-LDH材料进行光催化分解水制氢。
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