CN105798323A - 球磨辅助界面制备大比表面积过渡金属-硼合金材料的方法 - Google Patents
球磨辅助界面制备大比表面积过渡金属-硼合金材料的方法 Download PDFInfo
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明提供了一种球磨辅助界面制备大比表面积过渡金属‑硼合金材料的方法，是将与水不互溶的有机溶剂加入含有球磨珠的球磨罐中，再将过渡金属盐分散于球磨罐的有机溶剂中，并将强还原剂溶液滴加至上述体系形成两相液液界面；然后转动球磨机进行球磨辅助界面反应；反应产物依次用蒸馏水、无水乙醇洗涤，真空干燥即得。本发明通过球磨辅助界面反应，直接用还原剂溶液在常温下还原过渡金属盐及其过渡金属的复合金属盐，得到的过渡金属‑硼合金具有比表面积大、成本低、无遮蔽剂参与反应、活性高等优点，对化合物水解产氢、燃料电池、表面催化等多种领域的催化活性较高，因此是用于清洁能源的开发与制备的优良高性能催化剂。
Description
技术领域
本发明属于功能材料技术领域，涉及一种大比表面积过渡金属合金材料的制备方法，尤其涉及一种球磨辅助界面法制备大比表面积过渡金属-硼合金材料的方法，主要用于催化NaBH4水解产氢。
背景技术
随着化石燃料的日益减少以及人类对环境保护意识的逐渐提高，开发新的能源已成为人类十分关注的问题。氢能是21世纪的主要清洁能源之一，储氢材料的研究引起了人们的关注。NaBH4具有良好的可逆性、相对较高的氢含量（10.8%）以及良好的热力学性质，被认为是一种极具有前景的储氢化合物。但NaBH4自身水解产氢速率慢，不能满足需要，因此采用催化剂促进产氢速率的提高显得尤为重要。
近些年，已有许多使用催化剂水解NaBH4产氢的研究。早期研究的水解NaBH4产氢的催化剂CoCl2、CoB、NiCl2、FeCl2、NiB等，催化活性均较低。研究发现，过渡金属-硼合金对于水解NaBH4产氢具有较高的催化活性。研究还表明，影响过渡金属-硼合金活性的重要参数之一是比表面积。因此，寻求一种大比表面积过渡金属-硼合金催化剂的制备方法具有十分重要的意义。
发明内容
本发明的目的是提供一种球磨辅助界面法制备大比表面积过渡金属-硼合金材料的方法。
本发明球磨辅助界面制备大比表面积过渡金属-硼合金材料的方法，是将与水不互溶的有机溶剂加入含有球磨珠的球磨罐中，再将过渡金属盐分散于球磨罐的有机溶剂中，并将强还原剂溶液滴加至上述体系形成两相液液界面；然后转动球磨机进行球磨辅助界面反应；反应产物依次用蒸馏水、无水乙醇洗涤，真空干燥，即得大比表面积过渡金属-硼合金材料。
所述有机溶剂为密度大于水的氯代烃，如氯仿、四氯化碳等。
所述球磨罐中的球磨珠的量为5~20个，直径为5~10 mm；所述球磨机的转速为250~750 rpm。
所述过渡金属盐为铁、钴、镍金属的氯化盐或硝酸盐；所述强还原剂为NaBH4，其与过渡金属盐的物质量比为4:1~8:1。
所述球磨辅助界面反应时间为1~6h。所述的真空干燥温度为40~60℃。
下面对本发明制备的过渡金属-硼合金材料的结构和性能作进一步分析说明。
图1为球磨辅助界面反应方法制备的大比表面积Me-B合金的N2-吸脱附曲线图（采用全自动比表面积及孔隙度分析仪，美国康塔公司）。经测试表明，球磨辅助界面还原制备的Me-B合金的比表面积为150~250m2·g-1，是普通方法还原制备的Me-B合金的7~10倍（普通方法还原制备的Me-B合金的比表面积仅为20~30 m2·g-1），为催化储氢化合物水解产氢具有高的活性提供了保证。
图2为球磨辅助界面法制备的大比表面积Me-B合金的孔径分布图（根据N2-脱附曲线通过BJH算法计算得到）。经测试表明，本发明球磨辅助界面还原制备的Me-B合金的孔径均处于介孔范围，并且孔径主要集中于7 nm左右，孔道相对较小，这对Me-B合金催化剂具有大比表面积提供了理论依据。
图3为球磨辅助界面还原制备的大比表面积Me-B合金的SEM图。从图3可以清楚的看到，该Me-B合金材料呈现疏松絮状结构，增大了Me-B合金的比表面积，从而有利于催化剂与催化底物的接触使其催化NaBH4水解产氢具有较高的催化活性。
图4为球磨辅助界面还原制备的大比表面积Me-B合金的X射线电子衍射图（XRD）。从图4可以清楚的看到，在2θ= 45.5°附近有一个较大的衍射峰，说明球磨辅助界面还原制备的Me-B合金是短程有序、长程无序的非晶态结构，没有明显的结构缺陷。与其具有大比表面积相辅相成。正是由于其非晶态结构及大比表面积使得催化NaBH4水解产氢具有较高的催化活性。
图5为球磨辅助界面还原制备的大比表面积Me-B合金与普通还原制备的Me-B合金对催化储氢化合物水解产氢量的对比图。从图中曲线的斜率看出，本发明球磨辅助界面还原制备的Me-B合金催化活性明显优于普通还原方法制备的Me-B合金。
综上所述，本发明通过球磨辅助界面反应，直接用还原剂溶液在常温下还原过渡金属盐及其过渡金属的复合金属盐，得到的过渡金属-硼合金材料Me-B具有比表面积大、成本低、无遮蔽剂参与反应、活性高等优点，对化合物水解产氢、燃料电池、表面催化等多种领域的催化活性较高，因此是用于清洁能源的开发与制备的优良高性能催化剂。
附图说明
图1为大比表面积Me-B合金的N2-吸脱附曲线图；
图2为大比表面积Me-B合金的孔径-孔容分布图；
图3为大比表面积Me-B合金的SEM图；
图4为大比表面积Me-B合金的XRD图；
图5为两种不同方法制备的Me-B合金催化储氢化合物产氢量对比图。
具体实施方式
下面通过具体实施例对本发明球磨辅助界面还原制备大比表面积Me-B的方法及对NaBH4水解产氢的催化活性作进一步说明。
实施例1
将4 mL CHCl3加入至含有20个直径为5 mm球磨珠的球磨罐中；再将0.6 mmolCoCl2·6H2O分散于有机相，再将4 mL 3.6mmol NaBH4溶液滴加至上述体系形成两相液液界面；随即将体系在转速750 rpm 进行球磨辅助界面反应2 h；反应产物用蒸馏水洗涤，无水乙醇洗涤，真空40~60 ℃干燥即得Me-B(Co-B)合金催化剂，其比表面积为224.7m2·g-1。
通过催化NaBH4水解产氢测试发现，上述制备的Me-B(Co-B)合金催化NaBH4水解产氢的速率为16 mL·min-1，比用NaBH4直接还原制备的催化剂产氢速率提高了3 mL·min-1。
实施例2
将40 mL CHCl3加入至含有15个直径为10 mm球磨珠的球磨罐中；再将0.5mmol FeCl3·6H2O分散于有机相，再40mL
2mmol NaBH4溶液滴加至上述体系形成两相液液界面；随即将体系在转速250
rpm 下进行球磨辅助界面反应1 h；反应液用蒸馏水洗涤，无水乙醇洗涤，真空40~60
℃干燥，即得大比表面积Me-B(Fe-B)合金催化剂，其比表面积为160.8
m2·g-1。
通过催化NaBH4水解产氢测试发现，上述制备的Me-B(Fe-B)合金催化NaBH4水解产氢速率为13 mL·min-1，比用NaBH4直接还原方法制备的催化剂产氢速率提高了5 mL·min-1。
实施例3
将20 mL CCl4加入至球磨罐中，其中球磨罐含有的球磨珠的个数是直径为5 mm及10 mm的各10个；再将0.6mmolNi(NO3)2分散于有机相，再20 mL 4.2mmol NaBH4溶液滴加至上述体系形成两相液液界面；随即将体系在转速550
rpm 下进行球磨辅助界面反应1.5 h；反应液用蒸馏水洗涤，无水乙醇洗涤，真空40~60
℃干燥，即得大比表面积Me-B(Ni-B)合金催化剂，其比表面积为208 m2·g-1。
通过催化NaBH4水解产氢测试发现，上述制备的Me-B(Ni-B)合金催化NaBH4水解产氢速率为15 mL·min-1，比用NaBH4直接还原方法制备的催化剂产氢速率提高了6 mL·min-1。
实施例4
将10 mL CHCl3加入至含有20个直径为10 mm球磨珠的球磨罐中；再将0.5 mmol CoSO4分散于有机相，再将10 mL 3mmol NaBH4溶液滴加至上述体系形成两相液液界面；随即将体系在转速750
rpm 下进行球磨辅助界面反应2 h；反应液用蒸馏水洗涤，无水乙醇洗涤，真空50~60
℃干燥，即得大比表面积Me-B(Co-B)合金催化剂，其比表面积为196 m2·g-1。
通过催化NaBH4水解产氢测试发现，上述制备的Me-B(Co-B)合金催化NaBH4水解产氢速率为16 mL·min-1，比用NaBH4直接还原方法制备的催化剂产氢速率提高了3 mL·min-1。
实施例5
将2 mL CCl4加入至含有20个直径为10 mm球磨珠的球磨罐中；再将0.4 mmol NiSO4分散于有机相，再将2 mL 1.6 mmol
NaBH4溶液滴加至上述体系形成两相液液界面；随即将体系在转速500
rpm 下进行球磨辅助界面反应1 h；反应液用蒸馏水洗涤，无水乙醇洗涤，真空40~60
℃干燥，即得大比表面积Me-B(Ni-B)合金催化剂，其比表面积为189.7
m2·g-1。
通过催化NaBH4水解产氢测试发现，上述制备的Me-B(Ni-B)合金催化NaBH4水解产氢速率为15 mL·min-1，比用NaBH4直接还原方法制备的催化剂产氢速率提高了6 mL·min-1。
实施例6
将25 mL CHCl3有机溶剂加入至含有20个直径为5 mm球磨珠的球磨罐中；再将0.5mmol Fe(NO3)3分散于有机相，再将25 mL 3.5 mmol
NaBH4溶液滴加至上述体系形成两相液液界面；随即将体系在转速350
rpm 下进行球磨辅助界面反应2 h；反应液用蒸馏水洗涤，无水乙醇洗涤，真空40~60
℃干燥，即得大比表面积Me-B(Fe-B)合金催化剂，其比表面积为206.9
m2·g-1。
通过催化NaBH4水解产氢测试发现，上述制备的Me-B(Fe-B)合金催化NaBH4水解产氢速率为12 mL·min-1，比用NaBH4直接还原方法制备的催化剂产氢速率提高了2 mL·min-1。
实施例7
将15 mL CHCl3有机溶剂加入球磨罐中，其中球磨罐中含有的球磨珠的个数是直径为5 mm及10 mm的各10个；再将0.5mmol Fe(NO3)3分散于有机相，再将15 mL 2 mmol
NaBH4溶液滴加至上述体系形成两相液液界面；随即将体系在转速500
rpm 下进行球磨辅助界面反应2 h；反应液用蒸馏水洗涤，无水乙醇洗涤，真空40~60℃干燥，即得大比表面积Me-B(Fe-B)合金催化剂。其比表面积为162.5
m2·g-1。
通过催化NaBH4水解产氢测试发现，上述制备的Me-B(Fe-B)合金催化NaBH4水解产氢速率为15 mL·min-1，比用NaBH4直接还原方法制备的催化剂产氢速率提高了4 mL·min-1。
实施例8
将35 mL CHCl3有机溶剂加入至含有20个直径为5 mm球磨珠的球磨罐中；再将0.5mmol Co(NO3)2分散于有机相，再将35 mL 4mmol NaBH4溶液滴加至上述体系形成两相液液界面；随即将体系在转速400
rpm 下进行球磨辅助界面反应2 h；反应液用蒸馏水洗涤，无水乙醇洗涤，真空40~60℃干燥，即得大比表面积Me-B(Co-B)合金催化剂。其比表面积为246.1
m2·g-1。
通过催化NaBH4水解产氢测试发现，上述制备的Me-B(Co-B)合金催化NaBH4水解产氢速率为11 mL·min-1，比用NaBH4直接还原方法制备的催化剂产氢速率提高了3 mL·min-1。
Claims (8)
1.球磨辅助界面制备大比表面积过渡金属-硼合金材料的方法，是将与水不互溶的有机溶剂加入含有球磨珠的球磨罐中，再将过渡金属盐分散于球磨罐的有机溶剂中，并将强还原剂溶液滴加至上述体系形成两相液液界面；然后转动球磨机进行球磨辅助界面反应；反应产物依次用蒸馏水、无水乙醇洗涤，真空干燥，即得大比表面积过渡金属-硼合金材料。
2.如权利要求1所述球磨辅助界面制备大比表面积过渡金属-硼合金材料的方法，其特征在于：所述有机溶剂为密度大于水的氯代烃。
3.如权利要求1所述球磨辅助界面制备大比表面积过渡金属-硼合金材料的方法，其特征在于：所述球磨罐中的球磨珠的量为5~20个，直径为5~10 mm。
4.如权利要求1所述球磨辅助界面制备大比表面积过渡金属-硼合金材料的方法，其特征在于：所述球磨机的转速为250~750 rpm。
5.如权利要求1所述球磨辅助界面制备大比表面积过渡金属-硼合金材料的方法，其特征在于：所述过渡金属盐为铁、钴、镍金属的氯化盐或硝酸盐。
6.如权利要求1所述球磨辅助界面制备大比表面积过渡金属-硼合金材料的方法，其特征在于：所述强还原剂为NaBH4，其与过渡金属盐的物质量比为4:1~8:1。
7.如权利要求1所述球磨辅助界面制备大比表面积过渡金属-硼合金材料的方法，其特征在于：所述球磨辅助界面反应时间为1~6h。
8.如权利要求1所述球磨辅助界面制备大比表面积过渡金属-硼合金材料的方法，其特征在于：所述的真空干燥温度为40~60℃。
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