CN108855160A - 一种超薄二维磷化镍纳米片及其制备和光催化产氢的应用 - Google Patents
一种超薄二维磷化镍纳米片及其制备和光催化产氢的应用 Download PDFInfo
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- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 claims abstract description 5
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical class [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
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- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 abstract description 6
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- AIBQNUOBCRIENU-UHFFFAOYSA-N nickel;dihydrate Chemical compound O.O.[Ni] AIBQNUOBCRIENU-UHFFFAOYSA-N 0.000 abstract description 2
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- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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Abstract
本发明公开了一种超薄二维磷化镍纳米片材料及其制备和光催化产氢的应用。先通过溶剂热的方法制备了超薄氢氧化镍(Ni(OH)2)前驱体,通过静电自组装的方法将合成的Ni(OH)2分散在单层石墨烯(FGR)上,最后通过气固相磷化的方法合成超薄二维Ni2P纳米材料。在可见光照射下,该催化剂表现出良好的曙红(Eosin Y)敏化分解水产氢活性和稳定性。由于制备方法简单、可批量化,反应条件温和,能够高效分离回收并重复利用,该复合型催化材料在材料制备技术领域以及水分解制氢气方面具有重要的实际应用价值,有利于环境和能源的可持续发展。
Description
技术领域
本发明属于催化剂制备以及环境和能源的可持续发展领域,具体涉及一种超薄二维磷化镍纳米片材料及其制备和光催化产氢的应用。
背景技术
能源危机和环境污染是人类目前面临的两大社会问题。光解水产氢技术被认为是一种理想的途径来缓解能源和环境问题,受到了广泛的关注和研究。选择合适的催化材料并进行合理的结构设计,是提高光解水产氢效率的一种有效策略。超薄二维(2D)过渡金属磷化物(TMPs)为能量转换和储存提供了新选择,因其超高的比表面积和量子限制效应而具有独特的电、机械和催化性能。低成本、多功能的TMPs,具有合适的电荷从金属原子到磷原子的转移,已被广泛地研究用于水分解产氢的光电催化剂和电催化剂。特别,磷化镍(Ni2P)是最佳候选之一。尽管目前已经合成了许多有载体支撑和无载体支撑的2D Ni2P纳米片或纳米盘,但超薄Ni2P纳米片的控制合成仍然具有挑战性。
发明内容
本发明的目的在于针对现有技术的不足,提供一种超薄二维磷化镍纳米片材料及其制备和光催化产氢的应用。所制备催化剂具有优良的光解水产氢性能和稳定性。
为实现上述目的,本发明采用如下技术方案:
一种超薄二维磷化镍纳米片材料的制备方法:先通过溶剂热的方法制备了超薄氢氧化镍前驱体,通过静电自组装的方法将合成的超薄氢氧化镍前驱体分散在功能化单层石墨烯上,最后通过气固相磷化的方法合成超薄二维Ni2P纳米材料。
具体的,该制备方法包括以下步骤:
(1)超薄氢氧化镍纳米片的制备;
(2)超薄氢氧化镍-功能化单层石墨烯前驱体的制备:往功能化单层石墨烯水溶液中加入表面活性剂,超声处理后,得到功能化单层石墨烯分散体溶液;将功能化单层石墨烯分散体溶液逐滴加入到超薄氢氧化镍纳米片悬浮液中,搅拌30-40min,老化24h,过滤,将产物经洗涤、干燥处理后,得到超薄氢氧化镍-功能化单层石墨烯前驱体;
(3)将装有NaH2PO2粉末的瓷舟放置在管式炉的上游端,将装有超薄氢氧化镍-功能化单层石墨烯前驱体的另一个舟放置在管式炉的下游端,将它们分开放置,将管密封,抽真空,冲入高纯Ar气以提供无氧环境;然后将管式炉预热至150 ℃保持30 min,然后在Ar气氛下以5 ℃min−1的升温速率升温至300 ℃;每个样品在设定温度下保持15 min;管式炉自然冷却至室温后,收集所制备的超薄二维磷化镍纳米片材料。
步骤1)具体为:将2.2 g十六烷基三甲基溴化铵和2.4 mmol四水合醋酸镍,加入到60 mL乙醇和11 mL水的混合溶液中,超声搅拌上述混合物形成均匀溶液,进一步搅拌1 h;然后将该溶液转移到聚四氟乙烯内衬的100 mL不锈钢高压釜中,并在180 ℃下加热24 h;反应器自动冷却至室温,离心收集最终的浅绿色产物,洗涤并随后冻干。
步骤(2)所述的表面活性剂为十二烷基硫酸钠。
步骤(2)所述的功能化单层石墨烯分散体溶液中,功能化单层石墨烯的浓度为0.5mg/mL,表面活性剂的质量分数为0.1wt%。
步骤(2)所述的超薄氢氧化镍纳米片悬浮液的制备方法为:将超薄氢氧化镍纳米片分散在甲酰胺溶液中。
步骤(2)中功能化单层石墨烯和超薄氢氧化镍纳米片的质量比为:0.05:1。
步骤(2)中功能化单层石墨烯是通过高温热膨胀氧化石墨的方法制得。
一种如上所述的制备方法制得的超薄二维磷化镍纳米片材料,厚度小于3 纳米,边缘尺寸约为400 纳米,具有优异的催化产氢性能。
一种如上所述的超薄二维磷化镍纳米片材料在曙红敏化光解水产氢反应中的应用。
本发明的显著优点在于:
(1)本发明采用热膨胀氧化石墨制得的功能化单层石墨烯(FGR)作为基底,超薄Ni(OH)2作为前驱体,控制合成了超薄Ni2P纳米片;
(2)本发明将Ni2P-FGR复合光催化材料应用于曙红(Eosin Y)敏化光解水产氢反应,具有较高的光催化效率,有利于环境和能源的可持续发展。
附图说明
图1是超薄氢氧化镍(Ni(OH)2)的a)扫描电镜(SEM)图和b)原子力显微镜(AFM)图;
图2是超薄氢氧化镍-单层石墨烯(Ni(OH)2-FGR)的SEM图;
图3是超薄磷化镍-单层石墨烯(Ni2P-FGR)复合物的a) SEM图和b) AFM图;
图4是单层石墨烯的AFM图;
图5是单组份磷化镍(Ni2P)材料的SEM图;
图6是超薄Ni(OH)2和FGR样品实物图以及气固相磷化反应机理示意图;
图7是可见光照射2 h,曙红(Eosin Y)敏化不同催化剂的产氢活性对比。
具体实施方式
本发明用下列实施例来进一步说明本发明,但本发明的保护范围并不限于下列实施例。
实施例1
(1)超薄氢氧化镍纳米片的制备:
将2.2 g十六烷基三甲基溴化铵和2.4 mmol四水合醋酸镍,加入到60 mL乙醇和11 mL水的混合溶液中,超声搅拌上述混合物形成均匀溶液,进一步搅拌1 h;然后将该溶液转移到聚四氟乙烯(PTFE)内衬的100 mL不锈钢高压釜中并在180 ℃下加热24 h。反应器自动冷却至室温,离心收集最终的浅绿色产物,洗涤并随后冻干。
在与玻璃封闭气体循环系统连接的Pyrex顶部辐照容器中,进行光催化产氢反应。使用装备有420nm截止滤光片的300W氙灯(420 nm ≤ λ)(PLS-SXE300C,Perfectlight)作为可见光源。照射面积被控制为18.1 cm−2。典型地,通过超声处理15 min,将20 mg制备的催化剂和15 mg曙红(Eosin Y)分散在80 mL的15%(v/v)三乙醇胺-水(TEOA-H2O)溶液中。使用装备有热导检测器的在线气相色谱仪(GC-2014C,MS-5A柱,Ar 作为载气,Shimadzu Co.,Ltd.)测定2 h产生的H2的量为445.6 μmol·g−1。
(2)超薄氢氧化镍-功能化单层石墨烯前驱体的制备:
将获得的超薄Ni(OH)2纳米片分散在甲酰胺溶液中;通过SDS辅助超声处理0.5 mg/mL的功能化单层石墨烯(FGR)水溶液,表面活性剂SDS (SDS/H2O 0.1wt.%)增强了层间静排斥力和亲水性,从而防止FGR聚集;然后,在连续搅拌下将一定体积的SDS修饰的FGR分散体逐滴加入到上述Ni(OH)2悬浮液中, FGR和Ni(OH)2的质量比为0.05:1,将复合材料再搅拌30min,然后老化24 h以完全絮凝,将产物滤出,用大量无水乙醇和水洗涤并干燥处理;
在与玻璃封闭气体循环系统连接的Pyrex顶部辐照容器中,进行光催化产氢反应。使用装备有420nm截止滤光片的300W氙灯(420 nm ≤ λ)(PLS-SXE300C,Perfectlight)作为可见光源。照射面积被控制为18.1 cm−2。典型地,通过超声处理15 min,将20 mg制备的催化剂和15 mg曙红(Eosin Y)分散在80 mL的15%(v/v)三乙醇胺-水(TEOA-H2O)溶液中。使用装备有热导检测器的在线气相色谱仪(GC-2014C,MS-5A柱,Ar 作为载气,Shimadzu Co.,Ltd.)测定Ni(OH)2-FGR 材料2 h产生的H2的量为1468.9 μmol·g−1,单组份FGR 2 h产生的H2的量为27.2 μmol·g−1。
(3)超薄二维磷化镍纳米片材料的制备:
将装有NaH2PO2粉末的瓷舟放置在管式炉的上游端,将装有Ni(OH)2-FGR前驱体样品的另一个舟放置在管式炉的下游端,将它们分开放置;将管密封,抽真空,并充入高纯Ar气以提供无氧环境;随后,首先将管式炉预热至150 ℃保持30 min,然后在Ar气氛下以5 ℃min−1的升温速率升温至300 ℃;每个样品在设定温度下保持15 min。管式炉自然冷却至室温后,收集所制备的Ni2P-FGR(NP-FG)材料,样品颜色由灰色变为黑色。
单组份Ni2P制备方法与NP-FG的制备方法相同,仅所使用的前驱体不同:合成单组份Ni2P,使用单组份超薄Ni(OH)2作为前驱体。
在与玻璃封闭气体循环系统连接的Pyrex顶部辐照容器中,进行光催化产氢反应。使用装备有420nm截止滤光片的300W氙灯(420 nm ≤ λ)(PLS-SXE300C,Perfectlight)作为可见光源。照射面积被控制为18.1 cm−2。典型地,通过超声处理15 min,将20 mg制备的催化剂和15 mg曙红(Eosin Y)分散在80 mL的15%(v/v)三乙醇胺-水(TEOA-H2O)溶液中。使用装备有热导检测器的在线气相色谱仪(GC-2014C,MS-5A柱,Ar 作为载气,Shimadzu Co.,Ltd.)测定Ni2P-FGR材料2 h产生的H2的量为3954.7 μmol·g−1,单组份Ni2P 2 h产生的H2的量为2298.2 μmol·g−1。
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 (10)
1.一种超薄二维磷化镍纳米片材料的制备方法,其特征在于:先通过溶剂热的方法制备了超薄氢氧化镍前驱体,通过静电自组装的方法将合成的超薄氢氧化镍前驱体分散在功能化单层石墨烯上,最后通过气固相磷化的方法合成超薄二维Ni2P纳米材料。
2.根据权利要求1所述的超薄二维磷化镍纳米片材料的制备方法,其特征在于:
包括以下步骤:
(1)超薄氢氧化镍纳米片的制备;
(2)超薄氢氧化镍-功能化单层石墨烯前驱体的制备:往功能化单层石墨烯水溶液中加入表面活性剂,超声处理后,得到功能化单层石墨烯分散体溶液;将功能化单层石墨烯分散体溶液逐滴加入到超薄氢氧化镍纳米片悬浮液中,搅拌30-40min,老化24h,过滤,将产物经洗涤、干燥处理后,得到超薄氢氧化镍-功能化单层石墨烯前驱体;
(3)将装有NaH2PO2粉末的瓷舟放置在管式炉的上游端,将装有超薄氢氧化镍-功能化单层石墨烯前驱体的另一个舟放置在管式炉的下游端,将它们分开放置,将管密封,抽真空,冲入高纯Ar气以提供无氧环境;然后将管式炉预热至150 ℃保持30 min,然后在Ar气氛下以5 ℃min−1的升温速率升温至300 ℃;每个样品在设定温度下保持15 min;管式炉自然冷却至室温后,收集所制备的超薄二维磷化镍纳米片材料。
3.根据权利要求2所述的超薄二维磷化镍纳米片材料的制备方法,其特征在于:步骤1)具体为:将2.2 g十六烷基三甲基溴化铵和2.4 mmol四水合醋酸镍,加入到60 mL乙醇和11mL水的混合溶液中,超声搅拌上述混合物形成均匀溶液,进一步搅拌1 h;然后将该溶液转移到聚四氟乙烯内衬的100 mL不锈钢高压釜中,并在180 ℃下加热24 h;反应器自动冷却至室温,离心收集最终的浅绿色产物,洗涤并随后冻干。
4.根据权利要求2所述的超薄二维磷化镍纳米片材料的制备方法,其特征在于:步骤(2)所述的表面活性剂为十二烷基硫酸钠。
5.根据权利要求2所述的超薄二维磷化镍纳米片材料的制备方法,其特征在于:步骤(2)所述的功能化单层石墨烯分散体溶液中,功能化单层石墨烯的浓度为0.5 mg/mL,表面活性剂的质量分数为0.1wt%。
6.根据权利要求2所述的超薄二维磷化镍纳米片材料的制备方法,其特征在于:步骤(2)所述的超薄氢氧化镍纳米片悬浮液的制备方法为:将超薄氢氧化镍纳米片分散在甲酰胺溶液中。
7.根据权利要求2所述的超薄二维磷化镍纳米片材料的制备方法,其特征在于:步骤(2)中功能化单层石墨烯和超薄氢氧化镍纳米片的质量比为:0.05:1。
8.根据权利要求2所述的超薄二维磷化镍纳米片材料的制备方法,其特征在于:步骤(2)中功能化单层石墨烯是通过高温热膨胀氧化石墨的方法制得。
9.一种如权利要求1-8任一项所述的制备方法制得的超薄二维磷化镍纳米片材料,其特征在于:厚度小于3 纳米,边缘尺寸为400±5纳米,具有优异的催化产氢性能。
10.一种如权利要求9所述的超薄二维磷化镍纳米片材料在曙红敏化光解水产氢反应中的应用。
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