CN114984979B - 一种高性能NiS2@C纳米材料及其制备方法和应用 - Google Patents
一种高性能NiS2@C纳米材料及其制备方法和应用 Download PDFInfo
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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Abstract
本发明公开了一种高性能NiS2@C纳米材料,它以甲醇为溶剂,首先将有机配体溶液滴加至镍盐溶液中进行溶剂热反应得花状Ni‑ZIF;然后将其与单质硫粉混合均匀,在流动的保护气氛下进行热处理得到。本发明所得NiS2@C纳米材料的形貌均一,具有较大的比表面积,且NiS2均匀分布在碳材料中,有利于增加光催化反应过程中的活化位点并增强光生载流子的转移,可显著提高其光催化析氢性能;且涉及的制备方法较简单,绿色环保,适合推广应用。
Description
技术领域
本发明属于光催化材料技术领域,具体涉及一种高性能NiS2@C纳米材料及其制备方法和应用。
背景技术
1972年首次报道了TiO2半导体吸收紫外光,催化解水产氢。迄今,众多类型的半导体催化剂被开发出来用于光催化分解水制氢。目前,高效的分解水产氢催化剂仍离不开Pt、Au和Ag等贵金属。避免使用贵金属,开发高效、低成本的太阳能制氢光催化剂已经引起研究者们极大的兴趣,但迄今为止仍然是一个巨大的挑战。
近些年,具有可见光吸收特性的过渡金属硫化物二硫化镍(NiS2)被广泛应用于光催化领域。然而由于其较低的表面活性和光生电子-空穴对的快速复合,纯NiS2的光催化活性仍然有限。同时,NiS2的合成条件较为苛刻,不利于规模化合成。如,专利CN 114149035 A采用砂磨-煅烧法,虽成功合成了比热容较高的NiS2材料,但涉及的耗时长、能耗高,不利于大规模生产。
发明内容
本发明的主要目的在于针对现有技术存在的问题和不足,提供一种高性能NiS2@C纳米材料,其形貌均一,具有较大的比表面积,且NiS2均匀分布在碳材料中,有利于增加光催化反应过程中的活化位点和增强光生载流子的转移,从而显著提高光催化析氢的效果;且涉及的制备方法较简单,绿色环保,适合推广应用。
为实现上述目的,本发明采用的技术方案为:
一种高性能NiS2@C纳米材料的制备方法,包括如下步骤:
1)花状Ni-ZIF的制备
以甲醇为溶剂,将有机配体溶液滴加至镍盐溶液中,混合均匀得绿色溶液;然后进行溶剂热反应,再经冷却、洗涤、干燥,得花状Ni-ZIF;
2)NiS2@C纳米材料的制备
将花状Ni-ZIF与单质硫粉混合均匀,在流动的保护气氛下,进行热处理,冷却,即得所述NiS2@C纳米材料。
上述方案中,所述单质硫粉可选用升华硫粉等。
上述方案中,所述花状Ni-ZIF与单质硫粉质量比为1:(0.5-1.5)。
上述方案中,所述热处理温度为250-350℃,时间为2-4h。
上述方案中,所述保护气氛可选用氩气或氮气等。
上述方案中,所述保护气氛的流动速率为2-10mL/min.
上述方案中,所述镍盐可选用硫酸镍、醋酸镍、硝酸镍等中的一种或几种;有机配体选用2-甲基咪唑。
上述方案中,所述镍盐与有机配体的摩尔比为1:(1-6)。
上述方案中,步骤1)中所得绿色溶液中镍盐的浓度为12.5-50mmol/L。
上述方案中,所述溶剂热反应温度为120-160℃,时间为4-12h。
优选的,步骤1)所述溶剂热反应温度为140-150℃
优选的,步骤1)所述搅拌时间为30-90min。
根据上述方案制备的NiS2@C纳米材料,其具有花球状结构,花球直径为1-2μm;NiS2颗粒均匀分布在花瓣上,NiS2的粒径在10-20nm。
将上述方案所得NiS2@C纳米材料应用于光催化析氢领域,其3h产生的氢气可高达7940μmol/g。
本发明的原理为:
本发明首先以镍盐、2-甲基咪唑有机配体为主要原料,以甲醇为溶剂,通过调控镍盐与有机配体的比例、加料顺序和反应温度,制备出花状Ni-ZIF前驱体材料;然后将其与单质硫粉混合均匀,在流动的保护气氛和加热条件下,单质硫粉末由固态升华为气态且被Ni-ZIF吸附,被吸附的单质硫与Ni-ZIF中均匀分布的Ni金属节点发生反应生成NiS2,同时有效保留Ni-ZIF前驱体的形貌。
与现有技术相比,本发明的有益效果为:
1)本发明所述NiS2@C纳米材料具有较大的比表面积,并可实现NiS2纳米颗粒在碳材料中的分布均匀,有效克服传统光催化剂催化活性不足以及光生电荷效率不高的问题;
2)本发明涉及的制备方法较简单,条件温和,绿色环保,所得产物稳定性高,并可显著提升光催化析氢性能,可为高性能硫基复合催化剂的制备提供一条新思路。
附图说明
图1为本发明实施例1所得产物的XRD图;
图2为本发明实施例1所得产物的SEM图;
图3为本发明实施例1所得产物的TEM图;
图4为本发明实施例2所得产物的XRD图;
图5为本发明对比例1所得产物的XRD图;
图6为本发明实施例1所得产物的光催化分解水产氢性能图。
具体实施方式
下面将结合本发明实施例,对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
一种高性能NiS2@C纳米材料,其制备方法包括如下步骤:
1)花状Ni-ZIF的制备
将0.5816g镍盐(六水合硝酸镍)溶解于40mL无水甲醇中,超声至溶质充分溶解,得镍盐溶液;将0.6568g 2-甲基咪唑溶于40mL无水甲醇中,超声至充分溶解后,得有机配体溶液;将所得有机配体溶液逐滴加入镍盐溶液中并搅拌60min得到绿色混合溶液;将所得绿色溶液转移至聚四氟乙烯内衬的高压反应釜中,在140℃条件下反应12h,反应结束后冷却至室温,将产物离心洗涤干燥,得到具有花状结构的Ni-ZIF;
2)NiS2@C材料的制备
将所得花状Ni-ZIF与升华硫粉按1:1的质量比研磨均匀并置于管式炉中,在氩气流动的条件下,以2℃/min的升温速率升温至300℃,并保温2h,自然冷却至室温后,即得所述NiS2@C纳米材料。
将本实施例所得产物进行X射线衍射分析,结果见图1,图中所得产物特征峰与NiS2的标准图谱一致,说明采用上述方案可成功引入硫元素并反应得到NiS2@C复合材料。
本实施例所得产物的扫描电镜图见图2,可以看出,所得产物形貌均匀,呈现花球状结构,花球直径在1-2μm且Ni-ZIF的结构并未被破坏。
本实施例所得产物的透射电镜图见图3,可以看出,NiS2纳米颗粒可均匀分布在花状微球的花瓣上,颗粒粒径为10-20nm。
实施例2
一种高性能NiS2@C纳米材料,其制备方法包括如下步骤:
1)花状Ni-ZIF的制备
将0.5816g镍盐(六水合硝酸镍)溶解于40mL无水甲醇中,超声至溶质充分溶解,得镍盐溶液;将1.3136g 2-甲基咪唑溶于40mL无水甲醇中,超声至充分溶解后,得有机配体溶液;将所得有机配体溶液逐滴加入镍盐溶液中并搅拌60min得到绿色混合溶液;将所得绿色溶液转移至聚四氟乙烯内衬的高压反应釜中,在140℃条件下反应12h,反应结束后冷却至室温,将产物离心洗涤干燥,得到具有花状结构的Ni-ZIF;
2)NiS2@C材料的制备
将所得花状Ni-ZIF与升华硫粉按1:1的质量比研磨均匀并置于管式炉中,在氩气流动的条件下,以2℃/min的升温速率升温至350℃,并保温2h,自然冷却至室温后,即得所述NiS2@C纳米材料。
将本实施例所得产物进行X射线衍射分析,结果见图4,图中所得到的产物特征峰与NiS2的标准图谱一致,说明采用上述方案可成功引入硫元素并反应得到NiS2@C复合材料。
应用例
将实施例1所得NiS2@C纳米材料应用于光催化分解水析氢实验,其具体操作包括如下步骤:
称取30mg实施例1所获得的NiS2@C材料分散于100mL含15vol%三乙醇胺的水溶液中,然后加入120mg的曙红Y染料,分散均匀后置于光催化反应器中;使用500W的氙灯作为光源,用装备热导检测器的气相色谱仪测定磷化镍-碳材料光催化分解水产生氢气的量;同时采用步骤1)所得花状Ni-ZIF作为对比实验。
图6为实施例1所得NiS2@C纳米材料和花状Ni-ZIF的分解水产氢性能对比图,可以看出NiS2@C材料光解水析氢性能高于Ni-ZIF,3h产生的氢气能达7940μmol/g,且相较于已报道的基于氧化石墨烯和贵金属Pt的复合材料的光催化效率得到明显提高(S.Min,G.Lu,Dye-Sensitized Reduced Graphene Oxide Photocatalysts for Highly EfficientVisible-Light-Driven Water Reduction,The Journal of Physical Chemistry C,115(2011)13938-13945.)。
对比例
一种NiS2@C纳米材料,其制备方法包括如下步骤:
1)花状Ni-ZIF的制备
将0.5816g镍盐(六水合硝酸镍)溶解于40mL无水甲醇中,超声至溶质充分溶解,得镍盐溶液;将0.6568g 2-甲基咪唑溶于40mL无水甲醇中,超声至充分溶解后,得有机配体溶液;将所得有机配体溶液逐滴加入镍盐溶液中并搅拌60min得到绿色混合溶液;将所得绿色溶液转移至聚四氟乙烯内衬的高压反应釜中,在140℃条件下反应12h,反应结束后冷却至室温,将产物离心洗涤干燥,得到具有花状结构的Ni-ZIF;
2)NiS2@C材料的制备
将所得花状Ni-ZIF与升华硫粉按1:2的质量比研磨均匀并置于管式炉中,在氩气流动的条件下,以2℃/min的升温速率升温至300℃,并保温2h,自然冷却至室温后,即得所述NiS2@C纳米材料。
将本对比例所得产物进行X射线衍射分析,结果见图5,图中所得到的产物特征峰中出现了NiS2和NiS的标准峰,无法保证形成单相的NiS2负载相。
上述实施例仅是为了清楚地说明所做的实例,而并非对实施方式的限制。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其他不同形式的变化或者变动,这里无需也无法对所有的实施方式予以穷举,因此所引申的显而易见的变化或变动仍处于本发明创造的保护范围之内。
Claims (7)
1.一种光催化析氢高性能NiS2@C纳米材料的制备方法,其特征在于,包括如下步骤:
1)花状Ni-ZIF的制备
以甲醇为溶剂,将有机配体溶液滴加至镍盐溶液中,混合均匀得绿色溶液;然后进行溶剂热反应,再经冷却、洗涤、干燥,得花状Ni-ZIF;
2)NiS2@C纳米材料的制备
将花状Ni-ZIF与单质硫粉混合均匀,在流动的保护气氛下,进行热处理,冷却,即得所述NiS2@C纳米材料;其具有花球状结构,花球直径为1-2 μm;NiS2颗粒均匀分布在花瓣上,NiS2的粒径为10-20 nm;
所述单质硫粉为升华硫粉;
所述花状Ni-ZIF与单质硫粉质量比为1:(0.5-1.5)。
2.根据权利要求1所述的制备方法,其特征在于,所述热处理温度为250-350℃,时间为2-4 h。
3.根据权利要求1所述的制备方法,其特征在于,所述保护气氛的流动速率为2-10 mL/min。
4.根据权利要求1所述的制备方法,其特征在于,所述镍盐为硫酸镍、醋酸镍、硝酸镍中的一种或几种;有机配体为2-甲基咪唑。
5.根据权利要求1所述的制备方法,其特征在于,所述镍盐与有机配体的摩尔比为1:(1-6)。
6.根据权利要求1所述的制备方法,其特征在于,所述溶剂热反应温度为120-160℃,时间为4-12h。
7.权利要求1~6任一项所述制备方法制备的NiS2@C纳米材料在光催化析氢领域中的应用。
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