CN112588310A - 一种可见光响应的镍-磷化氮化碳光催化剂的制备方法 - Google Patents
一种可见光响应的镍-磷化氮化碳光催化剂的制备方法 Download PDFInfo
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Abstract
本发明属于光催化材料的制备方法技术领域,公开了一种可见光响应的镍‑磷化氮化碳光催化剂的制备方法。该方法首先三聚氰胺高温共聚合的方案得到氮化碳,之后通过次亚磷酸钠与氮化碳混合煅烧的方案得到磷化的氮化碳材料,最后通过原位光沉积的方法原位修饰金属镍。镍‑磷化氮化碳光催化具有良好的可见光吸收以及不含贵金属的特点,提高了制氢活性并且降低了催化剂成本。
Description
技术领域
本发明属于光催化材料的制备方法技术领域,涉及一种可见光响应的镍-磷化氮化碳光催化剂的制备方法及其光催化制氢应用。
背景技术
石墨相氮化碳是一种一种非金属半导体材料,具有合适的能带位置,可以进行可见光催化反应,而且物理化学性质稳定,制备方法简单,可见光吸收的特点。因此,石墨相氮化碳被广泛的应用于光解水制氢、光催化二氧化碳还原及可污染物降解领域。然而,普通的氮化碳因其存在的一些缺点限制了其活性,例如光吸收范围不够宽、载流子复合率高、析氢活性位点少以及需要负载铂等贵金属助催化剂等。研究人员已经证明可以通过一些纳米设计的方法提高氮化碳的光催化性能,例如纳米形貌调控、元素掺杂、以及与其他半导体材料构筑异质结形成复合光催化材料等。针对氮化碳进行元素掺杂或修饰是一种改性氮化碳光催化活性的有效方案,主要包含,金属掺杂和非金属掺杂以及共掺杂等。对于普通氮化碳进行磷化改性,极大地拓展了氮化碳可见光吸收能力、提供了大量的路易斯碱活性位点、更低的价带位置和更低的光生电子空穴对复合率。目前氮化碳掺杂主要制备方法包括溶剂热法、固相烧结法等。针对特定的元素改性寻找一种简单高产方法来制备氮化碳是十分必要的。
非金属改性氮化碳是一种制备高活性氮化碳的有效方法,其具有以下特点:首先是非金属元素能够取代到氮化碳中的氮或碳原子,从而不会破坏氮化碳的共轭结构,并且掺入的非金属元素可以作为路易斯碱位点,能够为助催化剂的附着提供位点。而金属掺杂只能修饰在氮化碳边缘或者络合在三嗪环之间,这种掺杂元素不能进入晶格,具有位置不确定性,最终导致可能形成新的复合中心。
发明内容
本发明目的是研发一种可见光响应的镍-磷化氮化碳光催化剂的制备方法,并将该光催化材料用于光催化产氢应用。本发明采用的改进的固相-气相界面掺杂法,可以在反应气体分子的逐渐释放的过程中,通过氮化碳聚合的方式掺入到晶格中形成磷化氮化碳材料。新的氮化碳共轭面由氮、碳、磷组成,磷作为路易斯碱位点能够锚定路易斯酸Ni2+,最终原位光还原形成金属团簇,作为助催化剂促进产氢活性的提升。
本发明首先以三聚氰胺高温共聚合的方案得到普通氮化碳,之后通过次亚磷酸钠与普通氮化碳混合煅烧的方案得到磷化的氮化碳材料,最后通过原位光沉积的方法原位修饰金属镍。镍-磷化氮化碳光催化具有良好的可见光吸收以及不含贵金属的特点,提高了制氢活性并且降低了催化剂成本。
实现本发明目的的技术解决方案为:
一种可见光响应的镍-磷化氮化碳光催化剂的制备方法,包括如下步骤:
(1)制备氮化碳,备用;
(2)按比例将氮化碳和次亚磷酸钠研磨混合均匀,在氩气气氛中,程序升温至煅烧温度,并保温一段时间,然后自然降温后用去离子水清洗,最终真空干燥得到磷化氮化碳;
(3)将步骤(2)得到的磷化氮化碳和氯化镍加入到三乙醇胺溶液中,超声分散后,氙灯光照一段时间,最后分离沉淀,真空干燥,得到镍-磷化氮化碳光催化剂。
步骤(1)中,氮化碳的制备步骤为:将2克三聚氰胺至于坩埚中,以每分钟7℃的升温速度升温至530℃,并保温4小时,随后立即取出自然冷却降温,得到粉体研磨半小时得到氮化碳。
步骤(2)中,氮化碳和次亚磷酸钠的质量比为1:1-4;程序升温的速率为5℃/min。煅烧温度为400-500℃,保温2小时。
步骤(3)中,磷化氮化碳和三乙醇胺溶液用量比例为50mg:50mL;其中,三乙醇胺溶液的体积百分浓度为10%,超声分散的时间为半小时,氙灯光照的时间为1-5小时,真空干燥的温度为60℃。
步骤(3)中,镍的负载量为质量分数1%-10%。
将本发明制得的可见光响应的镍-磷化氮化碳光催化剂用于可见光分解水制氢的用途。
本发明与现有技术相比有着显著地优点:
磷化氮化碳相比于普通的氮化碳具有更优越的光吸收范围,磷元素取代了特定位置的碳原子进入了氮化碳共轭骨架,磷原子具有孤对电子,作为路易斯碱能够影响价带顶位置,并且能够与Ni2+通过路易斯酸碱络合锚定助催化。该制备方法简单,产物产率,操作简单,重复性好,适合规模化制备。
附图说明
图1为本发明实施例所制备的镍-磷化氮化碳光催化剂与普通氮化碳的X-射线衍射图谱。
图2为本发明实施例所制备的镍-磷化氮化碳光催化剂的扫描电镜图片。
图3为发明本实施例所制备的镍-磷化氮化碳光催化剂与普通氮化碳的紫外-可见漫反射吸收光谱对比图。
图4为本发明实施例所制备出的镍-磷化氮化碳光催化剂的价带x射线光电子能谱。
图5为本发明实施例所制备出的镍-磷化氮化碳光催化剂的活性图。
具体实施方式
下面结合说明书附图和具体实施例对本发明作进一步的阐述。
实施例1
本发明的镍磷化氮化碳光催化剂的制备方法,具体包括以下步骤:
(1)将2克三聚氰胺至于坩埚中,以每分钟7℃的升温速度升温至530℃,并保温4小时,随后立即取出自然冷却降温,得到粉体研磨半小时得到氮化碳;
(2)将1克氮化碳和0.5克次亚磷酸钠研磨混合均匀,在氩气煅烧反应中以每分钟5℃的升温速度升温至430℃,保温2小时,然后自然降温后用其离子水清洗,最终真空干燥得到磷化氮化碳;
(3)磷化氮化碳和氯化镍(镍原子的负载量为质量分数3%)加入到50毫升10%体积分数的三乙醇胺溶液中,的超声分散半小时后,氙灯光照2小时,最后6000-8000转/分钟离心5-10分钟分离沉淀,最后60℃真空干燥,得到镍-磷化氮化碳光催化剂。
图1为本实施例所制备的镍-磷化氮化碳光催化剂与普通氮化碳的X-射线衍射图谱。普通的氮化碳在13.1°的衍射峰为氮化碳的(100)晶面,在27.3°的强的衍射峰为氮化碳的(002)晶面,这分别是由于氮化碳平面结构上的重复单元和夹层叠加反射引起的。与普通的氮化碳相比镍-磷化氮化碳光催化剂的衍射峰没有发生明显的变化,说明制备的镍-磷化氮化碳光催化剂并没有发生组分和成分的变化。
图2为本实施例所制备的镍-磷化氮化碳光催化剂的扫描电镜图片,由图2可知所得到的镍-磷化氮化碳光催化剂为无规则的块状结构。
图3为本实施例所制备的镍-磷化氮化碳光催化剂与普通氮化碳的紫外-可见漫反射吸收光谱对比图,从图3可知镍-磷化氮化碳光催化剂相比于普通氮化碳拥有更好的可见光吸收,这种更好的光吸收能力有利于镍-磷化氮化碳光催化剂的光催化产氢性能。
图4为本实施例所制备出的镍-磷化氮化碳光催化剂的价带x射线光电子能谱。普通氮化碳价带EVB的值被测定大约是1.87eV,而镍-磷化氮化碳光催化剂催化剂的EVB为2.10eV。镍-磷化氮化碳光催化剂催化剂的价带位置更正,表明镍-磷化氮化碳光催化剂催化剂拥有更强的氧化能力,这有利于催化反应的进行。
图5为本实施例所制备出的镍-磷化氮化碳光催化剂的活性图。如图5所示,20毫克镍-磷化氮化碳光催化剂在可见光照射下2.5小时产氢量为13.6微摩尔,而负载1%铂的普通氮化碳产氢量为2.1微摩尔,活性提高了越3.4倍。这种优越的活性充分体现了本材料设计的先进性。
实施例2
本发明的镍磷化氮化碳光催化剂的制备方法,具体包括以下步骤:
(1)将2克三聚氰胺至于坩埚中,以每分钟10℃的升温速度升温至550℃,并保温4小时,随后立即取出自然冷却降温,得到粉体研磨半小时得到普通氮化碳;
(2)1克普通氮化碳和0.5克次亚磷酸钠研磨混合均匀,在氩气煅烧反应中以每分钟5℃的升温速度升温至450℃,保温2小时,然后自然降温后用其离子水清洗,最终真空干燥得到磷化氮化碳;
(3)磷化氮化碳和氯化镍(镍原子的负载量为质量分数5%)加入到50毫升10%体积分数的三乙醇胺溶液中,超声分散半小时后,氙灯光照2小时,最后6000-8000转/分钟离心5-10分钟分离沉淀,最后60℃真空干燥得到镍-磷化氮化碳光催化剂。
实施例3
本发明的镍磷化氮化碳光催化剂的制备方法,具体包括以下步骤:
(1)将2克三聚氰胺至于坩埚中,以每分钟10℃的升温速度升温至550℃,并保温4小时,随后立即取出自然冷却降温,得到粉体研磨半小时得到普通氮化碳;
(2)1克普通氮化碳和1克次亚磷酸钠研磨混合均匀,在氩气煅烧反应中以每分钟5℃的升温速度升温至430℃,保温2小时,然后自然降温后用其离子水清洗,最终真空干燥得到磷化氮化碳;
(3)磷化氮化碳和氯化镍(镍原子的负载量为质量分数1%)加入到50毫升10%体积分数的三乙醇胺溶液中,超声分散半小时后,氙灯光照2小时,最后6000-8000转/分钟离心5-10分钟分离沉淀,最后60℃真空干燥得到镍-磷化氮化碳光催化剂。
Claims (6)
1.一种可见光响应的镍-磷化氮化碳光催化剂的制备方法,其特征在于,包括如下步骤:
(1)制备氮化碳,备用;
(2)按比例将氮化碳和次亚磷酸钠研磨混合均匀,在氩气气氛中,程序升温至煅烧温度,并保温一段时间,然后自然降温后用去离子水清洗,最终真空干燥得到磷化氮化碳;
(3)将步骤(2)得到的磷化氮化碳和氯化镍加入到三乙醇胺溶液中,超声分散后,氙灯光照一段时间,最后分离沉淀,真空干燥,得到镍-磷化氮化碳光催化剂。
2.如权利要求1所述的制备方法,其特征在于,步骤(1)中,氮化碳的制备步骤为:将2克三聚氰胺至于坩埚中,以每分钟7℃的升温速度升温至530℃,并保温4小时,随后立即取出自然冷却降温,得到粉体研磨半小时得到氮化碳。
3.如权利要求1所述的制备方法,其特征在于,步骤(2)中,氮化碳和次亚磷酸钠的质量比为1:1-4;程序升温的速率为5℃/min,煅烧温度为400-500℃,保温2小时。
4.如权利要求1所述的制备方法,其特征在于,步骤(3)中,磷化氮化碳和三乙醇胺溶液用量比例为50mg:50mL;其中,三乙醇胺溶液的体积百分浓度为10%,超声分散的时间为半小时,氙灯光照的时间为1-5小时,真空干燥的温度为60℃。
5.如权利要求1所述的制备方法,其特征在于,步骤(3)中,镍的负载量为质量分数1%-10%。
6.将权利要求1~5任一项所述制备方法制得的可见光响应的镍-磷化氮化碳光催化剂用于可见光分解水制氢的用途。
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