CN101362105A - 一种高性能纳米金属催化剂的制备方法 - Google Patents
一种高性能纳米金属催化剂的制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003863 metallic catalyst Substances 0.000 title claims description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 29
- 239000012266 salt solution Substances 0.000 claims abstract description 25
- 239000000084 colloidal system Substances 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 14
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 12
- 229910010277 boron hydride Inorganic materials 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 239000012448 Lithium borohydride Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 238000011946 reduction process Methods 0.000 abstract description 2
- 239000013049 sediment Substances 0.000 abstract 2
- -1 hydroxide ions Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 4
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
本发明公开了一种高性能纳米金属催化剂的制备方法。它是将100毫升0.001~5M的金属盐溶液和100毫升硼氢化物和氢氧化物溶液加入反应器中进行反应,硼氢化物的浓度为0.001~10M,金属盐溶液中金属离子的摩尔数与硼氢化物溶液中氢氧根离子的摩尔数之比为1/3~2/3,反应首先生成该金属的氢氧化物胶体,然后生成纳米金属或纳米金属硼化物沉淀;经过滤、清洗、干燥,得到粒径为10~20纳米的金属或金属硼化物催化剂。本发明在水溶液中先生成催化金属的氢氧化物胶体溶液,由于胶体粒子在还原过程中作为金属或金属硼化物沉淀的核心,并且胶体能有效地阻止颗粒的合并和长大,因此得到了粒径为10纳米左右的具有高比表面和高催化活性的纳米金属或金属硼化物。
Description
技术领域
本发明涉及催化剂的制备方法,尤其涉及一种高性能纳米金属催化剂的制备方法。
背景技术
纳米金属催化剂是指粒径在数纳米至数百纳米的金属催化剂,具有比表面积高,催化活性好等特点,在化工,材料,能源等行业起着十分重要的作用。常用的纳米催化剂的制备方法有含浸法,沉淀法,溶胶凝胶法,水热法等。
在此背景下,如何制备粒度小、比表面积高的纳米催化剂是纳米催化剂研究开发的重要内容。用硼氢化物(MBH4,M=Li,Na,K)在水溶液中还原金属盐是一种制备纳米金属或金属硼化物的方法。在该方法中,金属离子在水溶液中被硼氢根离子所还原,形成纳米级的黑色金属或金属硼化物。制备过程通常把金属盐溶液与硼氢化物溶液混合,或者把金属盐固体加入硼氢化物溶液,也可以把固体硼氢化物加入到金属盐溶液中。这种方法获得的金属或金属硼化物的粒度易受多种反应条件的影响,粒度通常在20和500纳米,不易控制。本发明通过在硼氢化物溶液中加入适量氢氧化物,使之与金属盐溶液混合后先生成该金属的亚稳态氢氧化物胶体溶液,再使胶体还原成纳米金属或金属硼化物。由于胶体粒子可作为金属纳米粒子沉淀的核心,并且胶体能有效地阻止粒子的长大,因此能获得粒径为10~20纳米的金属或金属硼化物催化剂。
发明内容
本发明的目的是克服现有技术的不足,提供一种高性能纳米金属催化剂的制备方法。
高性能纳米金属催化剂的制备方法是将100毫升0.001~5M的金属盐溶液和100毫升硼氢化物和氢氧化物溶液加入反应器中进行反应,硼氢化物的浓度为0.001~10M,金属盐溶液中金属离子的摩尔数与硼氢化物溶液中氢氧根离子的摩尔数之比为1/3~2/3,反应首先生成该金属的氢氧化物胶体,然后生成纳米金属或金属硼化物沉淀;经过滤、清洗、干燥,得到粒径为10~20纳米的金属或金属硼化物催化剂。
所述的金属盐溶液为铁盐溶液、钴盐溶液、镍盐溶液或铜盐溶液。同时金属盐溶液为卤化物溶液、硫酸盐溶液或硝酸盐溶液。硼氢化物为硼氢化锂、硼氢化钠或硼氢化钾。氢氧化物为氢氧化锂、氢氧化钠或氢氧化钾。
本发明通过在水溶液中先生成催化金属的亚稳态氢氧化物胶体溶液,再使其在硼氢化物还原剂的作用下还原成金属态。由于胶体是由极微小的胶体粒子组成,在还原过程中作为金属或金属硼化物沉淀的核心,并且胶体的性质能有效地阻止颗粒的合并和长大,使得生成的催化金属或其硼化物具有10纳米左右的微小粒经,因此具有高比表面积和高催化活性。在制备过程中,氢氧化物的添加量具有决定性的作用。如果添加量小,不足以生成氢氧化物胶体溶液,则得不到超细纳米粒径的催化剂。如果添加量过大,则产生稳定的氢氧化物沉淀,硼氢化物无法使之还原成金属态,也无法得到高性能的纳米金属催化剂。
具体实施方式
实施例1
将100毫升0.1M氯化钴溶液加到100毫升0.5M硼氢化钠和0.2M氢氧化钠溶液中,反应首先生成蓝色氢氧化钴胶体,然后生成黑色硼化钴沉淀。经过滤,清洗,干燥,得到粒径为10~20纳米的硼化钴催化剂。
实施例2
将100毫升0.05M硫酸镍溶液加到100毫升0.1M硼氢化钾和0.09M氢氧化钾溶液中,反应首先生成绿色氢氧化镍胶体,然后生成黑色硼化镍沉淀。经过滤,清洗,干燥,得到粒径为10~20纳米的硼化镍催化剂。
实施例3
将100毫升0.1M氯化亚铁溶液加到100毫升0.3M硼氢化锂和0.2M氢氧化锂溶液中,反应首先生成氢氧化亚铁胶体,然后生成黑色硼化铁沉淀。经过滤,清洗,干燥,得到粒径为10~20纳米的硼化铁催化剂。
实施例4
将100毫升0.2M硫酸铜溶液加到100毫升0.6M硼氢化钾和0.3M氢氧化钾溶液中,反应首先生成氢氧化铜胶体,然后生成微细金属铜沉淀。经过滤,清洗,干燥,得到粒径为20纳米的铜催化剂。
实施例5
将100毫升0.05M硝酸钴溶液加到100毫升0.2M硼氢化钾和0.15M氢氧化钾溶液中,反应首先生成蓝色氢氧化钴胶体,然后生成黑色硼化钴沉淀。经过滤,清洗,干燥,得到粒径为10~20纳米的硼化钴催化剂。
实施例6
将100毫升0.1M氯化镍溶液加到100毫升0.4M硼氢化钠和0.2M氢氧化钠溶液中,反应首先生成绿色氢氧化镍胶体,然后生成黑色硼化镍沉淀。经过滤,清洗,干燥,得到粒径为10~20纳米的硼化镍催化剂。
实施例7
将100毫升0.001M的钴盐溶液和100毫升硼氢化钠和氢氧化钠溶液加入反应器中进行反应,硼氢化钠的浓度为0.001M,钴盐溶液中钴金属离子与硼氢化钠溶液中氢氧根离子的摩尔数之比为1/3,反应首先生成蓝色氢氧化钴胶体,然后生成黑色硼化钴沉淀;经过滤,清洗,干燥,得到粒径为10纳米的硼化钴催化剂。
实施例8
将100毫升5M的钴盐溶液和100毫升硼氢化钠和氢氧化钠溶液加入反应器中进行反应,硼氢化钠的浓度为10M,钴盐溶液中钴金属离子与硼氢化钠溶液中氢氧根离子的摩尔数与之比为2/3,反应首先生成蓝色氢氧化钴胶体,然后生成黑色硼化钴沉淀;经过滤,清洗,干燥,得到粒径为20纳米的硼化钴催化剂。
Claims (5)
1.一种高性能纳米金属催化剂的制备方法,其特征在于将100毫升0.001~5M的金属盐溶液和100毫升硼氢化物和氢氧化物溶液加入反应器中进行反应,硼氢化物的浓度为0.001~10M,金属盐溶液中金属离子的摩尔数与硼氢化物溶液中氢氧根离子的摩尔数之比为1/3~2/3,反应首先生成该金属的氢氧化物胶体,然后生成纳米金属或纳米金属硼化物沉淀;经过滤、清洗、干燥,得到粒径为10~20纳米的金属或金属硼化物催化剂。
2.根据权利要求1所述的一种高性能纳米金属催化剂的制备方法,其特征在于所述的金属盐溶液为铁盐溶液、钴盐溶液、镍盐溶液或铜盐溶液。
3.根据权利要求1所述的一种高性能纳米金属催化剂的制备方法,其特征在于所述的金属盐溶液为卤化物溶液、硫酸盐溶液或硝酸盐溶液。
4.根据权利要求1所述的一种高性能纳米金属催化剂的制备方法,其特征在于所述的硼氢化物为硼氢化锂、硼氢化钠或硼氢化钾。
5.根据权利要求1所述的一种高性能纳米金属催化剂的制备方法,其特征在于所述的氢氧化物为氢氧化锂、氢氧化钠或氢氧化钾。
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CN107243646A (zh) * | 2017-06-08 | 2017-10-13 | 桂林电子科技大学 | 一种高比表面Co‑B合金纳米片及其制备方法与应用 |
CN113774217A (zh) * | 2021-08-19 | 2021-12-10 | 南方科技大学 | 电子产品浸出液中多种金属离子的同步回收方法 |
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CN107243646A (zh) * | 2017-06-08 | 2017-10-13 | 桂林电子科技大学 | 一种高比表面Co‑B合金纳米片及其制备方法与应用 |
CN113774217A (zh) * | 2021-08-19 | 2021-12-10 | 南方科技大学 | 电子产品浸出液中多种金属离子的同步回收方法 |
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