CN111701592B - Co/MIIFe层状双金属氢氧化物制备及氨硼烷产氢 - Google Patents
Co/MIIFe层状双金属氢氧化物制备及氨硼烷产氢 Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000001257 hydrogen Substances 0.000 title claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 55
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims description 36
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 22
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- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011941 photocatalyst Substances 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 8
- 229910017112 Fe—C Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002135 nanosheet Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000009830 intercalation Methods 0.000 claims description 4
- 230000002687 intercalation Effects 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
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- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 229910017116 Fe—Mo Inorganic materials 0.000 claims 3
- -1 solution B Chemical compound 0.000 claims 1
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 abstract description 2
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910015234 MoCo Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 230000000452 restraining effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种Co/MIIFe层状双金属氢氧化物制备及氨硼烷产氢催化体系,该催化剂制备方法为:采用稳定的半填充Fe3+来捕获光生电子,调整MII‑O‑Fe氧桥结构来优化短程定向电荷传输能力,并将金属氧酸盐插层到LDH中,进一步提高了LDH的光吸收和电子空穴分离性能;光催化氨硼烷水解制氢的方法为:将一定量的水滑石载体和CoCl2•6H2O水溶液置于双颈烧瓶中搅拌负载,当向上述混合物中添加一定量的纳米金属还原剂NaBH4和底物NH3BH3的水溶液,在298 K光照下立即开始催化反应。该催化剂制备方法简单易操作,可用于光催化氨硼烷高效水解产氢,反应条件温和,在优化条件下TOF可以达到113.2 min‑1,而且催化剂容易回收利用。
Description
技术领域
本发明涉及一种Co/MIIFe层状双金属氢氧化物制备及氨硼烷产氢。
背景技术
随着经济的不断发展和生活质量的提高,人们对能源的需求也在不断增加。然而,化石能源日益枯竭。氢能是全球公认的清洁能源,有助于解决能源危机,实现能源转型,遏制全球变暖和环境污染,因此氢能的开发利用已引起世界各国的关注。氢气难以压缩或液化的形式储存,已成为利用氢能源的主要困难。固态储氢是利用储氢材料与氢气之间的物理或化学变化来储存氢气的一种方法。其中,氨硼烷(NH3BH3, AB)因其含氢量高达19.6wt%而被认为是最有前途的储氢材料之一。在适当的催化作用下,氨硼烷的水解可以迅速进行,生成氢气。贵金属(如Rh、Pd、Ru和Pt)在氨硼烷催化水解制氢反应中有着广泛的研究。然而,贵金属催化剂是不经济的,开发物美价廉、地球资源丰富的廉价非贵金属催化制氢是迫切需要的。
层状双金属氢氧化物具有可调的电子结构、高度分散的金属离子、层间可交换的阴离子以及可控的拓扑变换等优点,可作为理想的光催化材料。
发明内容
本发明提供了一种Co/MIIFe层状双金属氢氧化物制备及氨硼烷产氢催化体系,本发明提供的制备方法简易、经济,可用于光催化氨硼烷水解产氢。Co/MIIFe层状双金属氢氧化物光催化剂在可见光下对催化氨硼烷高效水解产氢,不仅避免了贵金属的使用,反应条件温和,析氢活性较高,而且相较于暗反应其TOF值提高了很多。
所采用的技术方案是:采用稳定的半填充Fe3+来捕获光生电子,调整MII-O-Fe氧桥结构来优化短程定向电荷传输能力,并将金属氧酸盐插层到LDH中,进一步提高了LDH的光吸收和电子空穴分离性能,光催化氨硼烷水解制氢的方法包括:将一定量的载体水滑石和CoCl2•6H2O水溶液置于双颈烧瓶中搅拌负载,向上述混合物中添加一定量的纳米金属还原剂NaBH4和底物NH3BH3的水溶液,在298 K光照下立即开始催化反应,该催化剂制备方法简单易操作,可用于温和反应条件下光催化氨硼烷高效水解产氢,在优化条件下TOF可以达到113.2 min-1,而且催化剂容易回收利用。
上述的一种Co/MIIFe层状双金属氢氧化物制备及氨硼烷产氢,其特征在于采用共沉淀和水热法制备了不同的MIIFe-C层状双金属氢氧化物纳米片进而调整MII-O-Fe氧桥连结构来优化短程定向电荷传输能力,采用共沉淀法一步合成了钼酸盐插层CoFe-Mo层状双金属氢氧化物纳米片,进而提高了LDH的光吸收和电子空穴分离性能。
上述的一种Co/MIIFe层状双金属氢氧化物制备及氨硼烷产氢,其特征在于:非贵金属纳米粒子的负载使氨硼烷的光催化活性大幅度提高,非贵金属纳米粒子包含Co纳米粒子,Ni纳米粒子及其合金。
上述的一种Co/MIIFe层状双金属氢氧化物制备及氨硼烷产氢,其特征在于:在无光照时该催化体系催化活性较低,在光作用下催化活性大幅提高。
上述的一种Co/MIIFe层状双金属氢氧化物制备及氨硼烷产氢,其特征在于:催化剂的循环使用性能较好,经过20次循环使用,Co/CoFe-Mo光催化剂仍维持了很高的光催化活性。
上述的一种Co/MIIFe层状双金属氢氧化物制备及氨硼烷产氢,其特征在于:所用光源可以是氙灯、各种颜色的单色光、各种其他人造光源或太阳光。
为了实现上述目的,本发明采用以下技术方案:
一种Co/MIIFe层状双金属氢氧化物光催化剂的制备方法,所述制备方法包括以下步骤:
1、碳酸盐插层MIIFe-C层状双金属氢氧化物的制备
①Co/Fe摩尔比为3:1的Co(NO3)2•6H2O和Fe(NO3)3•9H2O溶解在去离子水中,形成0.6 M盐溶液(溶液A)。②将NaOH(0.4 g,10 mmol)和Na2CO3(2.1 g,20 mmol)在去离子水中搅拌溶解(溶液B)。③将溶液A和溶液B同时滴入含有去离子水的三颈瓶中,并在60℃水浴中剧烈搅拌。将pH值调整至9-9.5,然后连续搅拌0.5 h。④所得浆液放入水热反应釜,在80℃下加热48 h,然后用去离子水和乙醇离心彻底清洗,最后在60℃下干燥过夜,得到CoFe-C层状双金属氢氧化物样品。⑤用相同方法制备的NiFe-C层状双金属氢氧化物和ZnFe-C层状双金属氢氧化物。不同的是,NiFe-C层状双金属氢氧化物在120℃下,以pH=8.5结晶;ZnFe-C层状双金属氢氧化物在25℃下,以pH=10结晶。
2、钼酸盐插层CoFe-Mo层状双金属氢氧化物纳米片的合成
①用氮气对去离子水鼓泡30 min,去除CO2,整个实验在氮气保护下进行。②制备10 mL钼酸钠水溶液,n(MoO4 2-):n(Fe3+)=2:1。③用0.5 M NaOH调节pH至9-9.5(溶液C)。④将溶液A和溶液C同时滴入含有少量去离子水的三颈瓶中,并在60℃水浴中剧烈搅拌。⑤其余步骤与CoFe-C层状双金属氢氧化物相同,最后得到CoFe-Mo层状双金属氢氧化物样品。
3、 Co/CoFe-Mo的合成
①将CoFe-Mo(18.0 mg)和CoCl2•6H2O(0.034 mmol)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h。②将NaBH4(0.068 mmol)的水溶液(1.0 mL)注入上述混合物中,待反应完全后,用去离子水和乙醇分别洗涤几次,在60℃真空烘箱中干燥过夜。③采用与Co/CoFe-Mo相似的工艺合成了Co/CoFe-C、Co/NiFe-C和Co/ZnFe-C。
一种利用Co/CoFe-Mo层状双金属氢氧化物光催化剂光催化氨硼烷产氢的方法,包括如下步骤:
将CoFe-Mo(18.0 mg)和CoCl2•6H2O(0.034 mmol)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h。当向上述混合物中添加纳米金属还原剂NaBH4(0.068 mmol)和底物NH3BH3(1.0mmol)的水溶液(1.0 mL)时,在298 K下立即开始催化反应。在催化反应过程中,利用排水法监测了气体的生成量。为了比较不同层状双金属氢氧化物种类对催化剂析氢性能的影响,用同样方法检测了Co/CoFe-C、Co/NiFe-C和Co/ZnFe-C三种催化剂的析氢性能。
说明书附图
图1是实施案例1制备的CoFe-Mo、Co/CoFe-Mo的SEM图。
图2是实施案例1制备的Co/CoFe-Mo、CoFe-Mo、Co/CoFe-C、CoFe-C、Co/NiFe-C、NiFe-C、Co/ZnFe-C、ZnFe-C的X射线衍射图谱(X-ray diffraction,XRD)。
图3是实施案例1制备的Co/CoFe-Mo透射电镜图(transmission electronmicroscope,TEM)。
图4是实施案例1制备的Co/CoFe-Mo的X射线光电子能谱(X-ray photoelectronspectroscopy,XPS)图。
具体实施方式
下面结合具体实施案例对本发明进行详细说明。
实施案例1:
一种Co/MIIFe层状双金属氢氧化物光催化剂的制备方法,所述制备方法包括以下步骤:
(1)碳酸盐插层MIIFe-C层状双金属氢氧化物的制备
①Co/Fe摩尔比为3:1的Co(NO3)2•6H2O和Fe(NO3)3•9H2O溶解在去离子水中,形成0.6 M盐溶液(溶液A)。②将NaOH(0.4 g,10 mmol)和Na2CO3(2.1 g,20 mmol)在去离子水中搅拌溶解(溶液B)。③将溶液A和溶液B同时滴入含有去离子水的三颈瓶中,并在60℃水浴中剧烈搅拌。将pH值调整至9-9.5,然后连续搅拌0.5 h。④所得浆液放入水热反应釜,在80℃下加热48 h,然后用去离子水和乙醇离心彻底清洗,最后在60℃下干燥过夜,得到CoFe-C层状双金属氢氧化物样品。⑤用相同方法制备的NiFe-C层状双金属氢氧化物和ZnFe-C层状双金属氢氧化物。不同的是,NiFe-C层状双金属氢氧化物在120℃下,以pH=8.5结晶;ZnFe-C层状双金属氢氧化物在25℃下,以pH=10结晶。
(2)钼酸盐插层CoFe-Mo层状双金属氢氧化物纳米片的合成
①用氮气对去离子水鼓泡30 min,去除CO2,整个实验在氮气保护下进行。②制备10 mL钼酸钠水溶液,n(MoO4 2-):n(Fe3+)=2:1。③用0.5 M NaOH调节pH至9-9.5(溶液C)。④将溶液A和溶液C同时滴入含有少量去离子水的三颈瓶中,并在60℃水浴中剧烈搅拌。⑤其余步骤与CoFe-C层状双金属氢氧化物相同,最后得到CoFe-Mo层状双金属氢氧化物样品。
(3)Co/CoFe-Mo的合成
①将CoFe-Mo(18.0 mg)和CoCl2•6H2O(0.034 mmol)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h。②将NaBH4(0.068 mmol)的水溶液(1.0 mL)注入上述混合物中,待反应完全后,用去离子水和乙醇分别洗涤几次,在60℃真空烘箱中干燥过夜。③采用与Co/CoFe-Mo相似的工艺合成了Co/CoFe-C、Co/NiFe-C和Co/ZnFe-C。
图1是上述步骤制备的CoFe-Mo、Co/CoFe-Mo的SEM图,从图中可以看出CoFe-Mo具有层状结构,Co NPs负载后Co/CoFe-Mo的形貌没有明显变化。
对本实施案例制备的催化剂材料分别进行XRD分析如图2所示,在所有样品中都能清晰地观察到具有典型层状双金属氢氧化物结构的特征峰。以Co/CoFe-C为例,分别在11.4°、23.2°、34.0°、38.5°、46.0°、58.9°、60.4°和64.4°附近观察到(003),(006),(012),(015),(018),(110),(113)和(1013)的反射晶面。CoFe-C的结晶度明显高于NiFe-C和ZnFe-C。CoFe-C和NiFe-C的基间距为0.78nm,ZnFe-C为0.68nm。与Co/CoFe-C相比,Co/CoFe-Mo在(003),(006),(012),(018)和(110)晶面上有对应的峰,但这些峰明显减弱,衍射峰随钼酸盐插层到层状双金属氢氧化物上而略有偏移。所有Co/MIIFe 层状双金属氢氧化物均未发现新的特征峰,表明Co NPs具有良好的分散性。
图3是上述步骤所制备的CoFe-Mo、Co/CoFe-Mo的TEM图,从图中可以看出表明CoNPs在二维层状CoFe-Mo层状双金属氢氧化物上分散良好。HRTEM图像中间距为0.26和0.20nm的晶格条纹分别对应于CoFe-Mo LDH的(012)晶面和Co NPs的(111)晶面。
图4是对上述步骤所制备的Co/CoFe-Mo进行了X射线光电子能谱(XPS)表征,Co/CoFe-Mo的XPS总谱表明,催化剂主要含有Co、Fe、Mo和O元素。在Co 2p的XPS图谱中,Co 2p轨道谱图的峰位于780.4 eV和795.8 eV,分别属于Co2+的Co 2p3/2和Co 2p1/2,而位于778.3eV和793.6 eV附近的峰则属于Co NPs的Co 2p3/2和Co 2p1/2。在Fe 2p的XPS图谱中,约711.3 eV的峰值对应Fe3+的Fe 2p3/2,而717.9 eV的峰值则是Fe 2p3/2的卫星峰。在Mo 3d的XPS图谱,显示233.2和236.3 eV处的中的两个强峰对应于Mo6+的Mo 3d5/2和Mo 3d3/2。
实施案例2:
将CoFe-Mo(18.0 mg)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h,当向上述混合物中添加底物NH3BH3(1.0 mmol)的水溶液(1.0 mL)时,在298 K下立即开始催化反应,利用排水法监测了气体的生成量。在没有负载催化剂的情况下,氨硼烷在水中比较稳定,TOF值为0min-1,即使在可见光照射下,也没有观察到氢气产生。
实施案例3:
将CoFe-Mo(18.0 mg)和CoCl2•6H2O(0.034 mmol)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h,当向上述混合物中添加纳米金属还原剂NaBH4(0.068 mmol)和底物NH3BH3(1.0mmol)的水溶液(1.0 mL)时,在298 K下立即开始催化反应,利用排水法监测了气体的生成量。在无光照的条件下,TOF为35.1min-1,在光照下析氢活性提高了322.8%,TOF高达113.2min-1。在上一次析氢结束后,向反应中注入1.0 mmol NH3BH3的水溶液(1.0 mL),在可见光照射下,催化总循环次数为20次,在两个相邻的周期中,间隔为5分钟。在循环测试20次后光催化氨硼烷析氢活性仍然很高效,TOF值基本保持不变。
实施案例4:
将CoFe-C(18.0 mg)和CoCl2•6H2O(0.034 mmol)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h,当向上述混合物中添加纳米金属还原剂NaBH4(0.068 mmol)和底物NH3BH3(1.0mmol)的水溶液(1.0 mL)时,在298 K下立即开始催化反应,利用排水法监测了气体的生成量。在无光照的条件下,TOF为28.9min-1,在光照下的析氢活性提高了268.5%,TOF达到77.6min-1。在上一次析氢结束后,向反应中注入1.0 mmol NH3BH3的水溶液(1.0 mL),在可见光照射下,催化总循环次数为20次,在两个相邻的周期中,间隔为5分钟。在循环测试20次后光催化氨硼烷析氢活性仍然很高,TOF值基本保持不变。
实施案例5:
将NiFe-C(18.0 mg)和CoCl2•6H2O(0.034 mmol)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h,当向上述混合物中添加纳米金属还原剂NaBH4(0.068 mmol)和底物NH3BH3(1.0mmol)的水溶液(1.0 mL)时,在298 K下立即开始催化反应,利用排水法监测了气体的生成量。在无光照的条件下,TOF为27.6min-1,在光照下的析氢活性提高了246.7%,TOF达到68.2min-1。
实施案例6:
将ZnFe-C(18.0 mg)和CoCl2•6H2O(0.034 mmol)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h,当向上述混合物中添加纳米金属还原剂NaBH4(0.068 mmol)和底物NH3BH3(1.0mmol)的水溶液(1.0 mL)时,在298 K下立即开始催化反应,利用排水法监测了气体的生成量。在无光照的条件下,TOF为28.5min-1,在光照下的析氢活性提高了257.9%,TOF达到73.4min-1。
实施案例7:
将CoFe-Mo(18.0 mg)和CoCl2•6H2O(0.034 mmol)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h,当向上述混合物中添加纳米金属还原剂NaBH4(0.068 mmol)和底物NH3BH3(1.0mmol)的水溶液(1.0 mL)时,在298 K下立即开始催化反应,设定照射光的强度为200 mw/cm2,利用排水法监测了气体的生成量。氨硼烷的析氢速率相比无光照增大46%,TOF达到65min-1。
实施案例8:
将CoFe-Mo(18.0 mg)和CoCl2•6H2O(0.034 mmol)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h,当向上述混合物中添加纳米金属还原剂NaBH4(0.068 mmol)和底物NH3BH3(1.0mmol)的水溶液(1.0 mL)时,在298 K下立即开始催化反应,设定照射光的强度为300 mw/cm2,利用排水法监测了气体的生成量。氨硼烷的析氢速率相比无光照增大56%,TOF达到79.8min-1。
实施案例9:
将CoFe-Mo(18.0 mg)和CoCl2•6H2O(0.034 mmol)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h,当向上述混合物中添加纳米金属还原剂NaBH4(0.068 mmol)和底物NH3BH3(1.0mmol)的水溶液(1.0 mL)时,在298 K下立即开始催化反应,设定照射光的强度为400 mw/cm2,利用排水法监测了气体的生成量。氨硼烷的析氢速率相比无光照增大63%,TOF达到94.5min-1。
实施案例10:
将CoFe-Mo(18.0 mg)和CoCl2•6H2O(0.034 mmol)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h,当向上述混合物中添加纳米金属还原剂NaBH4(0.068 mmol)和底物NH3BH3(1.0mmol)的水溶液(1.0 mL)时,在298 K下立即开始催化反应,设定照射光的强度为500 mw/cm2,利用排水法监测了气体的生成量。氨硼烷的析氢速率相比无光照增大69%,TOF达到113.2 min-1。
实施案例11:
将CoFe-C(18.0 mg)和CoCl2•6H2O(0.034 mmol)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h,当向上述混合物中添加纳米金属还原剂NaBH4(0.068 mmol)和底物NH3BH3(1.0mmol)的水溶液(1.0 mL)时,在298 K下立即开始催化反应,设定照射光的强度为200 mw/cm2,利用排水法监测了气体的生成量。氨硼烷的析氢速率相比无光照增大41%,TOF达到49min-1。
实施案例12:
将CoFe-C(18.0 mg)和CoCl2•6H2O(0.034 mmol)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h,当向上述混合物中添加纳米金属还原剂NaBH4(0.068 mmol)和底物NH3BH3(1.0mmol)的水溶液(1.0 mL)时,在298 K下立即开始催化反应,设定照射光的强度为300 mw/cm2,利用排水法监测了气体的生成量。氨硼烷的析氢速率相比无光照增大50%,TOF达到57.8 min-1。
实施案例13:
将CoFe-C(18.0 mg)和CoCl2•6H2O(0.034 mmol)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h,当向上述混合物中添加纳米金属还原剂NaBH4(0.068 mmol)和底物NH3BH3(1.0mmol)的水溶液(1.0 mL)时,在298 K下立即开始催化反应,设定照射光的强度为400 mw/cm2,利用排水法监测了气体的生成量。氨硼烷的析氢速率相比无光照增大57%,TOF达到67.2 min-1。
实施案例14:
将CoFe-C(18.0 mg)和CoCl2•6H2O(0.034 mmol)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h,当向上述混合物中添加纳米金属还原剂NaBH4(0.068 mmol)和底物NH3BH3(1.0mmol)的水溶液(1.0 mL)时,在298 K下立即开始催化反应,设定照射光的强度为500 mw/cm2,利用排水法监测了气体的生成量。氨硼烷的析氢速率相比无光照增大61%,TOF达到74.1min-1。
实施案例15:
将CoFe-Mo(18.0 mg)和CoCl2•6H2O(0.034 mmol)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h,当向上述混合物中添加纳米金属还原剂NaBH4(0.068 mmol)、底物NH3BH3(1.0mmol)的水溶液(1.0 mL)及电子清除剂KBrO3(100μM)时,在298 K下立即开始催化反应,利用排水法监测了气体的生成量。相比没有加入电子清除剂,此时氨硼烷的析氢速率TOF大大降低到65.3 min-1,这表明光生电子在催化过程中的作用。
实施案例16:
将CoFe-Mo(18.0 mg)和CoCl2•6H2O(0.034 mmol)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h,当向上述混合物中添加纳米金属还原剂NaBH4(0.068 mmol)、底物NH3BH3(1.0mmol)的水溶液(1.0 mL)及空穴清除剂KI(100μM)时,在298 K下立即开始催化反应,利用排水法监测了气体的生成量。相比没有加入空穴清除剂,此时氨硼烷的析氢速率TOF大大降低到85.0 min-1,这表明光生空穴在催化过程中的作用。
实施案例17:
将CoFe-Mo(18.0 mg)和CoCl2•6H2O(0.034 mmol)的水溶液(1.0 mL)在双颈烧瓶中搅拌5 h,当向上述混合物中添加纳米金属还原剂NaBH4(0.068 mmol)和底物NH3BH3(1.0mmol)的水溶液(1.0 mL)及•OH清除剂异丙醇(IPA,100μL)时,在298 K下立即开始催化反应,利用排水法监测了气体的生成量。相比没有加入•OH清除剂,此时氨硼烷的析氢速率TOF大大降低到78.4 min-1,这表明•OH在催化过程中的作用。
Claims (3)
1.一种Co/MIIFe层状双金属氢氧化物光催化剂在光催化氨硼烷水解产氢上的应用,其特征在于:光催化氨硼烷水解产氢包括如下步骤:将MIIFe-C或MIIFe-Mo和CoCl2·6H2O的水溶液在双颈烧瓶中搅拌5h,当向上述混合物中添加纳米金属还原剂NaBH4和底物NH3BH3的水溶液,在298K下立即开始催化反应;其中MII为Zn2+、Co2+或Ni2+;该MIIFe-C或MIIFe-Mo层状双金属氢氧化物的制备方法包括:
1)碳酸盐插层MIIFe-C层状双金属氢氧化物的制备:①Co/Fe摩尔比为3:1的Co(NO3)2·6H2O和Fe(NO3)3·9H2O溶解在去离子水中,形成0.6M盐溶液,即溶液A,②将NaOH和Na2CO3在去离子水中搅拌溶解,即溶液B,③将溶液A和溶液B同时滴入含有去离子水的三颈瓶中,并在60℃水浴中剧烈搅拌,将pH值调整至9-9.5,然后连续搅拌0.5h,④所得浆液放入水热反应釜,在80℃下加热48h,然后用去离子水和乙醇离心彻底清洗,最后在60℃下干燥过夜,得到CoFe-C层状双金属氢氧化物样品,⑤用相同方法制备的NiFe-C层状双金属氢氧化物和ZnFe-C层状双金属氢氧化物,不同的是,NiFe-C层状双金属氢氧化物在120℃下,以pH=8.5结晶;ZnFe-C层状双金属氢氧化物在25℃下,以pH=10结晶;
2)钼酸盐插层MIIFe-Mo层状双金属氢氧化物纳米片的合成:①用氮气对去离子水鼓泡30min,去除CO2,整个实验在氮气保护下进行,②制备10mL钼酸钠水溶液,n(MoO4 2-):n(Fe3+)=2:1,③用0.5M NaOH调节pH至9-9.5,即溶液C,④将溶液A和溶液C同时滴入含有少量去离子水的三颈瓶中,并在60℃水浴中剧烈搅拌,⑤其余步骤与CoFe-C层状双金属氢氧化物相同,最后得到CoFe-Mo层状双金属氢氧化物样品,⑥用相同方法制备的NiFe-Mo层状双金属氢氧化物和ZnFe-Mo层状双金属氢氧化物。
2.如权利要求1所述的一种Co/MIIFe层状双金属氢氧化物光催化剂在光催化氨硼烷水解产氢上的应用,其特征在于:催化剂的循环使用性能较好,经过20次循环使用,光催化剂仍维持了高光催化产氢活性。
3.如权利要求1所述的一种Co/MIIFe层状双金属氢氧化物光催化剂在光催化氨硼烷水解产氢上的应用,其特征在于:该光催化氨硼烷水解制氢体系简单易操作,能够用于温和反应条件下光催化氨硼烷高效水解产氢,在优化条件下TOF能够达到113.2min-1。
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