CN106861755B - 一种刺激响应性材料负载的Pd催化剂及其制备方法和应用研究 - Google Patents
一种刺激响应性材料负载的Pd催化剂及其制备方法和应用研究 Download PDFInfo
- Publication number
- CN106861755B CN106861755B CN201710109913.0A CN201710109913A CN106861755B CN 106861755 B CN106861755 B CN 106861755B CN 201710109913 A CN201710109913 A CN 201710109913A CN 106861755 B CN106861755 B CN 106861755B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- aam
- reaction
- preparation
- thermo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000004936 stimulating effect Effects 0.000 title claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000011557 critical solution Substances 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 claims 2
- 239000010970 precious metal Substances 0.000 claims 2
- 229920002521 macromolecule Polymers 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 claims 1
- 230000004044 response Effects 0.000 claims 1
- 230000004043 responsiveness Effects 0.000 claims 1
- 230000000638 stimulation Effects 0.000 claims 1
- 238000007172 homogeneous catalysis Methods 0.000 abstract description 11
- 238000005191 phase separation Methods 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- KSSNXJHPEFVKHY-UHFFFAOYSA-N phenol;hydrate Chemical compound O.OC1=CC=CC=C1 KSSNXJHPEFVKHY-UHFFFAOYSA-N 0.000 abstract description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 3
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/006—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenation of aromatic hydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/646—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of aromatic or heteroaromatic rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种刺激响应性材料负载的Pd催化剂及其制备方法和应用,以具有温敏性的高聚物聚(丙烯酰胺‑co‑丙烯酸)(P(AAm‑co‑AA))为载体制备负载型Pd催化剂,并将P(AAm‑co‑AA)‑Pd催化剂应用于苯酚水相加氢反应,以普遍使用的多相催化剂Pd/γ‑Al2O3做为参比催化剂,本发明的优点在于利用P(AAm‑co‑AA)在水溶液中的温敏性,实现了P(AAm‑co‑AA)‑Pd催化剂在反应体系中的均相催化和反应后的多相分离,得到了均相催化的优点同时又实现了催化剂的回收利用,具有广阔的应用前景。
Description
技术领域
本发明提供了一种刺激响应性高聚物负载Pd催化剂、制备方法及其在水溶液催化加氢反应并实现反应中均相催化和多相分离的方法。
背景技术
均相催化具有反应条件温和、高活性和高选择性等优点,然而反应后的催化剂分离非常困难,造成了催化活性组分的浪费。多相催化中,催化剂能通过过滤、离心等简单方式进行分离、回收,然而受扩散控制影响,催化活性位点不能充分被反应底物接触,导致活性差和选择性低等问题。随着科学技术的不断发展,考虑到多相催化与均相催化优点,实现催化剂在反应中的均相催化和多相分离,具有重大意义。
温敏性高聚物聚研究较多的是PNIPAM,PNIPAM在水溶液中具有低临界溶液温度(~32℃)。1997年Chen等人采用醇还原方法成功制备了PNIPAM作为稳定剂的Pt纳米颗粒,并将其成功应用于烯丙醇的加氢反应中(Chen C W,Akashi M.Langmuir,1997,13,6465-6472.)。在温度低于LCST值的情况下,反应体系为均相体系具有均相催化优点。在温度高于低溶液临界温度(LCST)值的情况下,催化剂与反应体系发生相分离,使得催化剂可以分离、回收。然而,反应速率与温度成正相关,大多数反应在较高温下有利,因此PNIPAM的适用体系十分有限。
魏清渤等人在《化学与生物工程》2011,Vol.28,NO.,发表的“pH敏感性P(AAm-co-AA)半互穿网络水凝胶的制备、表征及溶胀动力学研究”对P(AAm-co-AA)制备及其影响因素进行了研究,魏清渤等人在《应用化工》2013年第01期上发表了“P(AAm-co-AA)/Ag复合材料制备及表征”,公开了利用自组装制备P(AAm-co-AA)/Ag水凝胶复合材料的研究,以水凝胶P(AAm-co-AA)网络结构作为纳米反应器制备了P(AAm-co-AA)/Ag复合材料,指出该材料可以作为潜在的抗菌材料。
发明内容
本发明提出以温敏性型高聚物聚(丙烯酰胺-co-丙烯酸)(P(AAm-co-AA))为载体制备负载型Pd催化剂。并将P(AAm-co-AA)-Pd催化剂应用于苯酚水相的加氢反应,利用P(AAm-co-AA)在水溶液中的温敏性,实现P(AAm-co-AA)-Pd催化剂在反应体系中的均相催化和反应后的多相分离。
本发明的技术方案:
本发明一种温敏材料负载Pd催化剂的制备方法:其特点在于所研制的催化剂均以Pd为活性组分,以温敏性高聚物聚(丙烯酰胺-co-丙烯酸)(P(AAm-co-AA))为载体。将其应用于水相苯酚加氢实现了反应中的均相催化与反应后的多相分离。
催化剂的制备步骤如下:
首先是载体P(AAm-co-AA)的制备:将0.2124g丙烯酰胺、0.4269g丙烯酸和0.0118g过硫酸铵,溶解在20mL水中。常温下,连续通N230min,除去系统内空气。然后将体系升温至60℃后反应1h。反应完成后,后将体系在冰水浴中迅速冷却,此时有白色沉淀析出,并离心除去上层清液。离心、洗涤的过程重复3次。获得的产物在真空干燥箱内烘干。
P(AAm-co-AA)-Pd催化剂的制备:将0.0805g P(AAm-co-AA)加入到30mL蒸馏水中,40℃下搅拌直至完全溶解,加入1.0mL PdCl2(0.0114mol/L)溶液,然后逐滴加入6.0mL25mmol/L现配制的NaBH4溶液,搅拌3h后即可得到P(AAm-co-AA)-Pd催化剂。
所述载体P(AAm-co-AA)的最高临界溶液温度为14℃。
所述催化剂用于水相苯酚加氢反应,实现了反应中的均相催化与反应后的多相分离,提高了反应环己酮的选择性和苯酚的转化率。
附图说明
图1为本发明制备的P(AAm-co-AA)-Pd催化剂的TEM图。
图2为Pd/γ-Al2O3和P(AAm-co-AN)-Pd在65℃下催化水相苯酚加氢反应转化率随时间变化图。
图3为P(AAm-co-AA)-Pd在不同温度下的溶解现象图。
图4为本发明制备的催化剂P(AAm-co-AA)-Pd在回收利用中的苯酚转化率和环己酮选择性图。
具体实施方式
本例说明催化剂的制备过程。
实施例1-6
这些实例说明P(AAm-co-AA)-Pd催化剂在催化水相苯酚加氢中均相催化与反应后的多相分离的研究。
实施例1:
采用P(AAm-co-AA)-Pd为催化剂,反应温度为65℃,氢气压力为0.1MPa,搅拌为1000rpm,底物与Pd物质的量比为20∶1,底物量为1mmol。在25mL玻璃管内,加入2mL蒸馏水和一定量的催化剂,通氢气三次排尽空气,待升温到65℃,打开搅拌开始反应。反应9h后苯酚的转化率为100%,环己酮的选择性为98%。本申请中所述的底物为苯酚。
原料和产物的分析采用气相色谱福立9790,色谱柱固定相为聚乙二醇,采用火焰离子检测器,具体分析条件如下:检测器温度为220℃、进样器温度为220℃、柱温为60℃保留5min,随后以10℃/min升温至200℃并保留5min、空气压力为0.1MPa、氢气压力为0.1MPa、柱前压为0.04MPa。
实施例2:
按照实施例1反应的反应条件,将温敏性催化剂P(AAm-co-AA)-Pd替换为多相催化剂物Pd/γ-Al2O3,底物与Pd物质的量比为20∶1,底物量为1mmol。在25mL玻璃管内,加入2mL蒸馏水和一定量的催化剂,通氢气3次排尽空气,待升温到65℃后,打开搅拌开始反应。反应9h后苯酚的转化率为70.5%。本实施例用于对比说明P(AAm-co-AA)-Pd催化剂的催化化加氢催化性能优于常用的多相催化剂Pd/γ-Al2O3。
实施例3:
采用P(AAm-co-AA)-Pd为催化剂,反应温度为65℃,氢气压力为0.5MPa,搅拌为1000rpm,底物与Pd物质的量比为20∶1,底物量为1mmol。在25mL玻璃管内,加入2mL蒸馏水搅拌条件下,加入一定量的催化剂,通氢气3次排尽空气,待升温到65℃,打开搅拌开始反应。反应3h后苯酚的转化率为100%,环己酮的选择性为97.6%。
本例用于说明P(AAm-co-AA)-Pd在高压下仍然适用。
实施例4:
采用P(AAm-co-AA)-Pd为催化剂,反应温度为90℃,氢气压力为1.0MPa,搅拌为1000rpm,底物与Pd物质的量比为20∶1,底物量为1mmol。在25mL玻璃管内,加入2mL蒸馏水搅拌条件下,加入一定量的催化剂,通氢气3次排尽空气,待升温到65℃,打开搅拌开始反应。反应1h后苯酚的转化率为100%,环己酮的选择性为98%。
本例用于说明P(AAm-co-AA)-Pd,在高温、高压下仍然适用。
实施例5:
由于P(AAm-co-AA)的温敏性则使得P(AAm-co-AA)-Pd催化剂存在浊点。在温度高于浊点情况下,催化剂会溶解在水中形成均相反应体系。将上述反应体系温度降低至低于UCST值,通过过滤或离心等简单方法分离催化剂,将其回收利用。我们将反应液除去后,加入新的反应原料和溶剂,在温度为65℃、氢气压力为0.1MPa下重新评价催化剂的活性。P(AAm-co-AA)-Pd催化剂循环利用3次之后,苯酚的转化率在催化剂每次重新利用后只有因合理机械损失造成的微小降低,循环利用3次的苯酚转化率分别为64.8%,62.7%,60.4%。
本施例用于说明P(AAm-co-AA)-Pd具有良好的回收活性。
对比例1:
将实施例1中的活性组分Pd替换为等摩尔量的Pt,其余步骤与实施例1相同。经测试,反应9h后苯酚的转化率为89.4%,环己酮的选择性为88.2%。
对比例2:
将实施例1中的P(AAm-co-AA)替换为等量的PNIPAM,其余步骤与实施例1相同。经测试,反应9h后苯酚的转化率为80.7%,环己酮的选择性为85.3%。
对比例3:
将实施例1中的P(AAm-co-AA)替换为等量的PNIPAM,活性组分Pd替换为等摩尔量的Pt,其余步骤与实施例1相同。经测试,反应9h后苯酚的转化率为74.9%,环己酮的选择性为81.0%。
Claims (5)
1.一种刺激响应性材料负载贵金属的苯酚加氢反应的催化剂,其特征在于:所述刺激响应性材料为温敏性水溶高分子材料聚丙烯酰胺-co-丙烯酸P(AAm-co-AA),所述高分子材料为载体,活性组分为贵金属Pd;
P(AAm-co-AA)-Pd催化剂的制备方法如下:将0.0805gP(AAm-co-AA)加入到30mL蒸馏水中,40℃下搅拌直至完全溶解,加入1.0mL的0.0114mol/LPdCl2溶液,然后逐滴加入6.0mL25mmol/L现配制的NaBH4溶液,搅拌3h后即得到P(AAm-co-AA)-Pd催化剂。
2.根据权利要求1所述的催化剂,其特征在于:催化活性金属为贵金属Pd,由于载体的温敏性,P(AAm-co-AA)-Pd具有相应的临界溶液温度。
3.权利要求1所述的催化剂的应用,其特征在于,所述催化剂用于水相苯酚加氢制环己酮的反应。
4.根据权利要求3所述的应用,其特征在于:应用反应为水相苯酚加氢反应,底物苯酚与催化剂中活性金属组分的摩尔比例为20∶1。
5.根据权利要求3或4所述的应用,其特征在于:P(AAm-co-AA)-Pd在反应后能通过调节温度的方式实现循环利用3次。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710109913.0A CN106861755B (zh) | 2017-02-24 | 2017-02-24 | 一种刺激响应性材料负载的Pd催化剂及其制备方法和应用研究 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710109913.0A CN106861755B (zh) | 2017-02-24 | 2017-02-24 | 一种刺激响应性材料负载的Pd催化剂及其制备方法和应用研究 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106861755A CN106861755A (zh) | 2017-06-20 |
CN106861755B true CN106861755B (zh) | 2019-11-29 |
Family
ID=59168848
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710109913.0A Active CN106861755B (zh) | 2017-02-24 | 2017-02-24 | 一种刺激响应性材料负载的Pd催化剂及其制备方法和应用研究 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106861755B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA3037270A1 (en) * | 2016-09-20 | 2018-03-29 | Rohm And Haas Company | Method of hydrogenation of phenol |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1519052A (zh) * | 2003-01-24 | 2004-08-11 | 上海师范大学 | 负载Pd氢化催化剂及其制备方法,使用该催化剂的苯酚制备环己酮的方法 |
CN1850330A (zh) * | 2006-05-23 | 2006-10-25 | 上海师范大学 | 一种负载型非晶态合金氢化催化剂及其制备方法 |
CN102827330A (zh) * | 2012-09-11 | 2012-12-19 | 华东理工大学 | 一种温敏性核壳结构凝胶纳米粒子的制备方法及其产物的应用 |
CN103769216A (zh) * | 2014-01-16 | 2014-05-07 | 陕西师范大学 | 一种具有温敏性和磁性能的纳米银催化剂及其制备方法 |
CN104841483A (zh) * | 2015-04-21 | 2015-08-19 | 南开大学 | 一种温敏材料负载的Pd催化剂的制备方法及其应用研究 |
-
2017
- 2017-02-24 CN CN201710109913.0A patent/CN106861755B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1519052A (zh) * | 2003-01-24 | 2004-08-11 | 上海师范大学 | 负载Pd氢化催化剂及其制备方法,使用该催化剂的苯酚制备环己酮的方法 |
CN1850330A (zh) * | 2006-05-23 | 2006-10-25 | 上海师范大学 | 一种负载型非晶态合金氢化催化剂及其制备方法 |
CN102827330A (zh) * | 2012-09-11 | 2012-12-19 | 华东理工大学 | 一种温敏性核壳结构凝胶纳米粒子的制备方法及其产物的应用 |
CN103769216A (zh) * | 2014-01-16 | 2014-05-07 | 陕西师范大学 | 一种具有温敏性和磁性能的纳米银催化剂及其制备方法 |
CN104841483A (zh) * | 2015-04-21 | 2015-08-19 | 南开大学 | 一种温敏材料负载的Pd催化剂的制备方法及其应用研究 |
Also Published As
Publication number | Publication date |
---|---|
CN106861755A (zh) | 2017-06-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Schrader et al. | Functionalization of platinum nanoparticles with L-proline: simultaneous enhancements of catalytic activity and selectivity | |
Miyamura et al. | Aerobic oxidation of amines catalyzed by polymer-incarcerated Au nanoclusters: Effect of cluster size and cooperative functional groups in the polymer | |
Amara et al. | Enabling the scale-up of a key asymmetric hydrogenation step in the synthesis of an API using continuous flow solid-supported catalysis | |
Xu et al. | One-stage synthesis of cagelike porous polymeric microspheres and application as catalyst scaffold of Pd nanoparticles | |
Widegren et al. | Anisole hydrogenation with well-characterized polyoxoanion-and tetrabutylammonium-stabilized Rh (0) nanoclusters: effects of added water and acid, plus enhanced catalytic rate, lifetime, and partial hydrogenation selectivity | |
Hagiwara et al. | Sustainable Mizoroki–Heck reaction in water: remarkably high activity of Pd (OAc) 2 immobilized on reversed phase silica gel with the aid of an ionic liquid | |
CN103483381A (zh) | 一类膦功能化离子液体的制备及其在氢甲酰化反应中的应用 | |
CN104841483B (zh) | 一种温敏材料负载的Pd催化剂的制备方法及其应用研究 | |
Drinkel et al. | Zwitterionic-surfactant-stabilized palladium nanoparticles as catalysts in the hydrogen transfer reductive amination of benzaldehydes | |
CN107188849B (zh) | 用于苯羟基化反应的介孔离子液体杂多酸盐催化剂及其制备方法和应用 | |
Upadhyay et al. | Synthesis of monometallic Ru/TiO 2 catalysts and selective hydrogenation of CO 2 to formic acid in ionic liquid | |
CN106861755B (zh) | 一种刺激响应性材料负载的Pd催化剂及其制备方法和应用研究 | |
Keilitz et al. | Chirally Modified Platinum Nanoparticles Stabilized by Dendritic Core‐Multishell Architectures for the Asymmetric Hydrogenation of Ethyl Pyruvate | |
Zhao et al. | Novel continuous process for methacrolein production in numerous droplet reactors | |
CN103285922A (zh) | 环氧聚合物微球固载四甲基哌啶氮氧自由基催化剂及其制备方法和应用方法 | |
Ye et al. | Support and size effects of ruthenium catalysts with a chiral modifier for asymmetric hydrogenation of aromatic ketones | |
CN103769164B (zh) | 一种不锈钢丝网负载铂催化剂及其应用 | |
CN109999893A (zh) | 一种苯加氢制环己基苯用催化剂的制备方法 | |
CN108465487B (zh) | 一种用于烯烃环氧化反应的聚离子液体基杂多酸催化剂、制备方法及其应用 | |
CN114477112B (zh) | 一种交联酸性聚合离子液体催化环己酮肟制备羟胺的方法 | |
CN109365002A (zh) | 一种磁性离子液体固载型催化剂在二氧化碳环加成反应中的应用 | |
CN109622031A (zh) | 2-羟基膦酰基乙酸锆的制备方法及其在糠醇合成中的应用 | |
CN113105321B (zh) | 一种铜基金属有机框架化合物、制备方法及其应用 | |
CN101139332A (zh) | 用负载型纳米金催化剂催化制备γ-丁内酯的方法 | |
CN112657553B (zh) | 一种可自分离的Pickering乳液催化剂制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |