CN110612159A - 沉积pd纳米粒子的改进方法 - Google Patents
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 17
- 238000000151 deposition Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- 238000000527 sonication Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000000523 sample Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- 238000002525 ultrasonication Methods 0.000 claims description 3
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 101150003085 Pdcl gene Proteins 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000004675 formic acid derivatives Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011981 lindlar catalyst Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RKWGIWYCVPQPMF-UHFFFAOYSA-N Chloropropamide Chemical compound CCCNC(=O)NS(=O)(=O)C1=CC=C(Cl)C=C1 RKWGIWYCVPQPMF-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- 235000019253 formic acid Nutrition 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013580 millipore water Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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Abstract
本发明涉及制备Pd纳米粒子并将其沉积在金属氧化物上的改进方法。
Description
本发明涉及一种制备Pd纳米粒子并将其沉积到金属氧化物上的改进方法。
带有Pd纳米粒子的催化剂是众所周知的且被广泛使用的催化剂。
这种催化剂中非常突出的一类是所谓的Lindlar催化剂。
Lindlar催化剂是一种非均相催化剂，其由沉积在碳酸钙载体上的钯组成，该载体也用各种形式的铅处理。
还有其他种类的类似催化剂，其中仅沉积钯纳米粒子且不含铅。
有一些方法已知如何用Pd纳米粒子沉积(掺杂)金属氧化物(它是催化体系的一部分)。现有技术中已知的沉积方法具有如下缺点：
·就尺寸和形状而言，通过用H2还原而形成的Pd纳米粒子(这是常见且平常的方式)不是规整的纳米粒子。
·为了H2还原，使H2-气体鼓泡通过Pd盐溶液，这意味着使用了过量的还原剂。
·对于H2方法，PdCl2用作Pd源。为了将这种盐溶解在水中，需要使用Na2MoO4形成水溶性的Pd络合物，这意味着更长的制备时间以及将钼负载在催化剂表面上。使用其他Pd盐效果不佳，反之亦然。
现在发现，当沉积Pd纳米粒子的过程包括超声处理步骤时，克服了这些缺点。
因此，本发明涉及在金属氧化物(或金属氧化物的混合物)上沉积Pd-纳米粒子的方法，其中该方法包括超声处理步骤。
此外，发现了当Pd-盐溶液包含表面活性剂时，也克服了这些缺点。
因此，本发明涉及在金属氧化物(或金属氧化物的混合物)上沉积Pd-纳米粒子的方法，其中该方法包括超声处理步骤以及表面活性剂。
新方法的优点例如在于
·通过新方法形成的Pd纳米粒子几乎是球形的，并且尺寸规整。
·不使用H2-气体。
·这是一个非常快速和有效的方法。
掺杂的钯纳米粒子可以在表面上彼此分离，或者也可以附聚形成不同尺寸的钯纳米粒子簇。
掺杂有Pd纳米粒子的金属氧化物可以是粉末形式(或其他固体形式)，或者金属氧化物可以是用于包衣另一种材料的层。金属氧化物可以是一种金属氧化物(来自一种金属)，也可以是各种金属氧化物的混合物。
超声处理是根据本发明的方法的必要部分。
超声处理是施加声能以搅动样品中的颗粒的行为。通常使用超声频率(>20kHz)，该过程也被称为超声处理或超级-声处理。
通常使用超声波浴或超声波探头来进行应用。
根据本发明的方法通常包括(并且优选)以下步骤：
(a)制备Pd-盐水溶液，可选地加入聚乙二醇，
(b)加热步骤(a)的溶液并使溶液经受超声处理，
(c)将还原剂，优选甲酸盐溶液，加入到Pd溶液中，
(d)添加金属氧化物粉末，
(e)将步骤(d)中获得的悬浮液进行过滤并干燥
这样得到的粉末具有优异的催化剂性能。
步骤(a)
将Pd盐溶于水(或水性溶剂，这意味着将水与至少一种其他溶剂混合)。可以使用任何通常已知使用的Pd盐。合适的盐是PdCl2或Na2PdCl4。它可以是一种Pd盐，也可以是两种或更多种Pd盐的混合物。此外，向溶液中添加至少一种表面活性剂是有利的。合适的是聚乙二醇(PEG)、聚乙烯吡咯烷酮(PVP)或葡糖酰胺。
步骤(b)
通常将步骤(a)的溶液加热至高温。通常不加热至溶剂(或所用溶剂混合物)的沸点那样的较高温度。通常将其加热到30–80℃之间的温度。通常在30–50kHz的频率下进行超声处理。超声处理步骤的持续时间通常至少为10分钟，最好超过20分钟(合适的优选范围是30–120分钟)。超声处理步骤的持续时间的最大长度并不关键。可以通过使用超声波浴或浸没探针来进行超声处理步骤。甚至两种方法都可以结合使用。
步骤(c)
向步骤(b)的溶液中添加还原剂。通常，还原剂是甲酸钠溶液。但也可以使用其他甲酸盐(或甲酸盐的混合物)。任选地(代替或补充地)，也可以添加H2气体、L-抗坏血酸和/或甲酸。
步骤(d)
向步骤(c)的溶液中加入金属氧化物粉末(或金属氧化物粉末的混合物)。通常搅拌反应混合物。
步骤(e)
最后，过滤步骤(d)的悬浮液，通常洗涤并干燥所获得的掺杂的金属氧化物粉末。
显然，某些步骤可以执行多次。例如，超声处理也可能在除了仅步骤(b)中以外的其他步骤中进行。然后将如此获得的催化剂在使用前活化。
下列实施例用于说明本发明。如果没有另外说明，所有百分比均与重量有关，温度以摄氏度为单位。
实施例
氧化物粉末催化剂的制备
将四氯钯酸钠(sodium tetrachloropalladate)(II)(0.48mmol)溶解在133mL的密理博水中，并加入PEG-MS40(3.2mmol)。将该溶液加热至60℃，并在该温度下开始超声处理。添加新鲜制备的甲酸钠溶液(16mM，67mL)。在该温度下将溶液再超声处理60分钟，然后冷却至室温，接着添加所需的氧化物粉末。
已使用以下来自Sasol Performance Chemical的市售混合氧化物：
SCFa-160/Ce20(81.0％Al2O3/19.0％CeO2)
TH100/150 Ti10(89.6％Al2O3/10.4％TiO2)
SCFa-190 Zr20(78.8％Al2O3/21.2％ZrO2)
Mg28/100(71.2％Al2O3/28.8％MgO)
炔烃到烯烃的选择性半氢化的结果
在典型的氢化实验中，将40.0g 2-甲基-3-丁炔-2-醇(MBY)、所需量的氧化物粉末催化剂以及6mg含硫催化剂毒物/mgPd添加到125mL高压釜反应器中。通过加热/冷却夹套维持氢化反应期间的等温条件(338K)。反应器装有气体夹带搅拌器。在氮气气氛下以所需值提供纯氢。用氮气吹扫后，用氢气吹扫反应器并将其加热至所需温度。在实验过程中，通过从外部储罐供应氢气来维持反应器中的压力(3.0bar)。以1000rpm搅拌反应混合物。从最低95％的MBY转化率开始定期从反应器中取出液体样品(200μL)，并通过气相色谱法(HP 6890series，GC-system)对其进行分析。选择性被报道为，与所有反应产物相比，所需半氢化产物(2-甲基-3-丁烯-2-醇(MBE))的量。
表1：氢化的结果(实施例1是采用市售Lindlar催化剂的对比试验)
反应条件：40.0MBY，1000rpm，3.0bar H2，65℃，6mg含硫催化剂毒物/mgPd
a在碳酸钙上5％钯由Evonik获得。
可以看出，使用新方法生产的催化剂显示出更好的选择性。
Claims (7)
1.一种将Pd纳米粒子沉积在至少一种金属氧化物上的方法，其中所述方法包括超声处理步骤。
2.根据权利要求1的方法，其中所述至少一种金属氧化物为粉末形式(或其他固体形式)或用于包衣另一种材料的层状。
3.根据前述权利要求中任一项的方法，其中PdCl2和/或Na2PdCl4。
4.根据前述权利要求中任一项的方法，其中，所述超声处理以30-50kHz的频率进行。
5.根据前述权利要求中任一项的方法，其中通过使用超声浴和/或浸没探针来进行所述超声处理。
6.根据前述权利要求中任一项的方法，其中将至少一种还原剂(优选甲酸钠)添加到所述Pd-盐溶液中。
7.根据前述权利要求中任一项的方法，其中将至少一种表面活性剂(优选聚乙二醇)添加到所述Pd-盐溶液中。
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