CN110038639A - 一种壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂的制备方法 - Google Patents
一种壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂的制备方法 Download PDFInfo
- Publication number
- CN110038639A CN110038639A CN201910454168.2A CN201910454168A CN110038639A CN 110038639 A CN110038639 A CN 110038639A CN 201910454168 A CN201910454168 A CN 201910454168A CN 110038639 A CN110038639 A CN 110038639A
- Authority
- CN
- China
- Prior art keywords
- montmorillonite
- composite
- pillared
- preparation
- chitosan
- 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.)
- Withdrawn
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 89
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 35
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 238000009830 intercalation Methods 0.000 title claims abstract description 30
- 230000002687 intercalation Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 239000008236 heating water Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000011229 interlayer Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 235000021419 vinegar Nutrition 0.000 claims description 4
- 239000000052 vinegar Substances 0.000 claims description 4
- 229920002101 Chitin Polymers 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000005859 coupling reaction Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 229920000620 organic polymer Polymers 0.000 abstract description 6
- 230000000536 complexating effect Effects 0.000 abstract description 5
- 125000002524 organometallic group Chemical group 0.000 abstract description 5
- 238000010668 complexation reaction Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000007812 deficiency Effects 0.000 abstract description 3
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 229910052723 transition metal Inorganic materials 0.000 description 8
- 150000003624 transition metals Chemical class 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 5
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- YVKOUANNKYWVHL-UHFFFAOYSA-N C1=CC=CC2=CC=CC=C12.[I] Chemical compound C1=CC=CC2=CC=CC=C12.[I] YVKOUANNKYWVHL-UHFFFAOYSA-N 0.000 description 3
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 3
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- -1 Al/Fe Chemical class 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- GHUURDQYRGVEHX-UHFFFAOYSA-N prop-1-ynylbenzene Chemical group CC#CC1=CC=CC=C1 GHUURDQYRGVEHX-UHFFFAOYSA-N 0.000 description 2
- XQFARSXVMYNQRL-UHFFFAOYSA-N acetylene chlorobenzene Chemical group C#C.ClC1=CC=CC=C1 XQFARSXVMYNQRL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
- C07B37/04—Substitution
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
- C07C2531/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of the platinum group metals, iron group metals or copper
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种用于有机偶联反应非均相催化的一种壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂的制备方法，属于催化剂材料制备工艺技术领域。本发明包括以下步骤：（1）Al/Fe复合柱撑液的制备；（2）Al/Fe复合柱撑蒙脱土的制备；（3）通过溶液插层与化学络合制备壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂。本发明的一种壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂的制备方法有效改善了单一采用有机高分子改性或无机柱撑改性蒙脱土在性能提升上的不足，制备的Pd@CS‑Al/Fe‑pillared MMT催化剂不仅有较高的比表面积和吸附性能，钯活性组分与载体的络合强度高，在有机偶联反应催化应用中表现出优异的综合性能。
Description
技术领域
本发明涉及一种用于有机偶联反应非均相催化的一种壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂的制备方法，属于催化剂材料制备工艺技术领域。
背景技术
蒙脱土是一种天然粘土矿物，具有层状片晶结构，具有良好的机械稳定性和热稳定性，可以作为过渡金属钯催化剂的载体材料，但是纯蒙脱土具有亲水疏油的特点，其与有机分子的亲和性较低，与过渡金属的络合强度一般，直接以蒙脱土为载体负载过渡金属制成的非均相催化剂综合性能一般，在有机反应催化应用过程中过渡金属组分流失较快，催化剂只能重复套用 3次左右（ Dutta, D.; Dutta, D.K. Appl.Catal.A:Gen.2014,487,158-1640）。极性有机高分子，如壳聚糖(Zeng, M.F.; Wang, Y.D.; Liu, Q.; Yuan, X.;Zuo, S.F.; Feng, R.K.; Yang, J.; Wang, B.Y.; Qi, C.Z.; Lin, Y. ACS Appl.Mater. Interfaces 2016, 8, 33157–33164. )，聚乙烯醇(Zhao, J.; Xu, M.D.; Shu,G.Q.; Yang, Z.; Liu, Q.; Zeng, M.F.; Qi, C.Z.; Cao, X.Z.; Wang, B.Y. Radiat.Phys.Chem. 2018, 153, 164–172)、聚乙烯吡咯烷酮(Xu, M.D.; Zhao, J.; Shu, G.Q.;Liu, Q.; Zeng, M.F. Polymers 2018, 10, 669)等，可有效插层进入蒙脱土的晶片层间，可极大的改善载体与过渡金属钯的络合强度，使制备的高分子插层改性蒙脱土负载钯催化剂的可重复套用次数达到10次以上。但是，有机高分子插层改性蒙脱土属于柔性插层，对载体的比表面积和吸附性能提升效果不大，比如，文献报道(Zeng, M.F.; Wang, Y.D.; Liu,Q.; Yuan, X.; Zuo, S.F.; Feng, R.K.; Yang, J.; Wang, B.Y.; Qi, C.Z.; Lin, Y.ACS Appl. Mater. Interfaces 2016, 8, 33157–33164. )的壳聚糖插层蒙脱土负载钯催化材料的比表面积只有21.88 m2/g。
近年来，利用复合多核羟基金属阳离子柱撑改性蒙脱土得到了广泛的关注，无机柱撑改性的实质是在蒙脱土晶片层间引入无机氧化物“柱子”，使蒙脱土晶片层间空间形成稳定的无机“柱子”使晶片层有效撑开，可诱发大量的、稳定的微孔/介孔结构，载体的比表面积和孔隙率可大幅提升，对于制备催化剂载体十分有利。常采用羟基铝阳离子和其他金属阳离子一起对粘土进行柱撑，如Al/Fe, A1/Ni, Al/Mn, Al /Si，Al/Cr等。但是，无机柱撑改性对于蒙脱土载体与有机分子的亲和性以及与过渡金属的络合强度影响不大
为了改善单一采用有机高分子改性或无机柱撑改性蒙脱土在性能提升上的不足，本发明拟采用的协同运用Al/Fe无机刚性柱撑与壳聚糖高分子柔性插层手段是一个很好的催化剂制备工艺改进策略，可望实现改性蒙脱土负载钯催化剂综合性能的大幅提升。Al/Fe无机柱撑的引入可以使蒙脱土晶片层间距有效增大，层与层之间的柱撑结构更加稳定，并使材料的比表面积得到大幅度的提升；柔性壳聚糖分子链的引入，一方面可以提高蒙脱土载体的亲油性，更是起到蒙脱土的层间络合、锚固过渡金属活性组分钯的作用。
有基于此，提出本发明。
发明内容
本发明的目的是提供一种壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂的制备方法，具体方案如下：
一种壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂的制备方法，包括以下步骤：
（1）50- 60 ºC水浴加热条件下，将0.2mol/L的AlCl3与0.2mol/L的FeCl3溶液按照一定的比例混合，再与0.4mol/L的NaOH按照摩尔比n (Al 3+ /Fe 3+ ):n (OH -= )=1:2.4混合均匀，50- 60 ºC下老化10-30小时，得到Al/Fe复合柱撑液；
（2）按一定比例，将步骤（1）得到的Al/Fe复合柱撑液滴加到浓度为10%的钠型蒙脱土悬浮液中， 50-60 ºC水浴加热搅拌12-24小时，离心、去离子水洗涤至无Cl-，100-120ºC烘干，氮气气氛下400-600°C高温焙烧2-8小时，得到Al/Fe复合柱撑蒙脱土；
（3）将壳聚糖溶解于2%稀醋酸配成均一溶液，向壳聚糖溶液滴加浓度为0.3%的Pd2+溶液，将步骤得到的Al/Fe复合柱撑蒙脱土分散于去离子水，将CS-Pd复合物溶液加到Al/Fe复合柱撑蒙脱土悬浮液中，50ºC-60ºC水浴加热搅拌4-12小时，使CS-Pd复合物充分插层进入到Al/Fe复合柱撑蒙脱土的层间，用去离子水离心洗涤至中性，60ºC烘干，得到最终壳聚糖改性Al/Fe复合柱撑蒙脱土负载钯催化剂。
所述步骤（1）中，AlCl3与FeCl3的摩尔比例为15：1-3：1。
所述步骤（2）中的Al/Fe复合柱撑液与MMT的比例为10-50mmol Al/Fe复合柱撑液含有1g蒙脱土。
所述步骤（3）中，CS浓度为1-3%，CS与Al/Fe复合柱撑蒙脱土的质量比为9/1-5/5，；制备的壳聚糖改性Al/Fe复合柱撑蒙脱土负载钯催化剂中钯的含量为0.1-3%，比表面积100-300 m2/g。
本发明提供一种壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂的制备方法，改善单一采用有机高分子改性或无机柱撑改性蒙脱土在性能提升上的不足，一方面，Al/Fe复合柱撑在蒙脱土层间引入无机刚性“柱子”，大幅提升载体的孔隙率与比表面积，另一方面，壳聚糖插层进入Al/Fe复合柱撑改性后的蒙脱土的晶片层间，过渡金属离子与壳聚糖分子形成强络合而固载。通过合理调控柱撑液组成配比、插层高分子比例、过渡金属含量等工艺条件，所制得的壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂，具有比表面积大，吸附性能好，钯活性组分在改性蒙脱土层间分散均匀，与载体络合强等特点，在有机偶联反应的催化应用中表现出优异的综合性能。
在制备过程中，Al/Fe柱撑液与钠型蒙脱土发生离子交换进入层间，氮气气氛高温焙烧后，形成Al/Fe氧化物复合柱撑蒙脱土结构，壳聚糖-钯复合物分子溶液插层进入Al/Fe氧化物复合柱撑蒙脱土的层间，经离心、洗涤、烘干、活化后得到具有优异综合性能的壳聚糖改性与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂（Pd@CS- Al/Fe-pillared MMT），在有机偶联反应应用中有良好的综合性能。
本发明壳聚糖改性与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂的制备方法具有如下有益效果：
1、原料易得，工艺过程简单与绿色性好。
2、把无机 “刚性”柱撑与有机高分子“柔性”插层有效协同起来，制得的催化剂既具较大的比表面积，又有较强的过渡金属络合能力，在催化有机反应应用中表现出较高的催化活性，催化剂可重复循环使用15次以上。
附图说明
图1 为本发明实施例1的Pd@CS- Al/Fe-pillared MMT催化剂与MMT原土的X射线粉末衍射分析结果图；
图2为本发明实施例1的Pd@CS- Al/Fe-pillared MMT的透射电镜示意图；
图3为本发明实施例1的Pd@CS- Al/Fe-pillared MMT催化剂与MMT原土的氮气吸脱附曲线。
具体实施方式
下面结合实例对本发明作进一步说明，本发明并不限于以下实施例。
实施例1
（1）取定量NaOH，溶于去离子水，配成NaOH浓度为0.4mol/L的溶液，取定量的AlCl3·6H2O，溶于去离子水，配成AlCl3浓度为0.2mol/L的溶液，取定量的FeCl3·6H2O，溶于去离子水，配成FeCl3的浓度为0.2mol/L的溶液；在60℃水浴中，按照比例Al3+：Fe3+=15:1（mol）比例，取150ml的上述AlCl3溶液与10ml的上述FeCl3溶液混合，搅拌30min后，按照（Al3+-Fe3+）：OH-=1:2.4（mol）的比例向混合溶液中滴加192mL的NaOH溶液，搅拌至该体系为红棕色透明液体，在60℃的烘箱中老化12h，备用。
（2）60°C水浴加热并搅拌条件下，取2.5gMMT（蒙脱土）分散于250ml蒸馏水，形成悬浮液，按照（Al3+- Fe3+）：MMT=20mmol：1g的比例向悬浮液中滴加铝铁柱撑液，搅拌12h，去离子水洗涤至无Cl-，100ºC烘干，在氮气气氛下500°C焙烧3小时，得到Al/Fe复合柱撑MMT(Al/Fe-pillared MMT)。研磨成粉状。
（3）将0.5g壳聚糖(CS)溶解于50mL2%稀醋酸配成均一溶液，向CS溶液滴加浓度为0.3%的Pd2+溶液2mL；60°C水浴加热并搅拌条件下，取2gAl/Fe复合柱撑MMT分散于50ml去离子水，形成均一悬浮液；将将上述CS-Pd复合物溶液加到Al/Fe复合柱撑蒙脱土悬浮液中，60ºC水浴加热搅拌12小时，用去离子水离心洗涤至中性，60ºC烘干，得到壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂(Pd@CS- Al/Fe-pillared MMT)。
效果检测：
对上述实施例1所制得的Pd@CS- Al/Fe-pillared MMT催化剂进行物性表征与催化性能评价，其过程和结果如下所述：
（1）如图1，X射线粉末衍射结果显示，Pd@CS- Al/Fe-pillared MMT载体的层间距为1.79 nm, MMT原土层间距约为1.25nm，说明Al/Fe复合刚性柱撑使MMT的层间距明显增大；如图2，Pd@CS- Al/Fe-pillared MMT的透射电镜结果表明，钯活性组分受插入MMT层间的壳聚糖分子的强络合，稳定夹杂在Al/Fe柱撑MMT的层间，ICP结果表明钯的负载量约为0.2%；如图3氮气吸附结果表明，Pd@CS- Al/Fe-pillared MMT的BET比表面积为156.3 m2/g，而MMT原土的BET比表面积只有6.7m2/g。
（2）Pd@CS- Al/Fe-pillared MMT催化剂应用于Sonogashira偶联反应的催化：
| 编号 | 芳基卤代物 | 苯乙炔及其衍生物 | 产率（%） |
| 1 | 碘苯 | 苯乙炔 | 99 |
| 2 | 邻氯甲苯 | 苯乙炔 | 98 |
| 3 | 对甲氧基碘苯 | 苯乙炔 | 99 |
| 4 | 碘苯 | 对甲基苯乙炔 | 98 |
| 5 | 碘萘 | 苯乙炔 | 98 |
| 6 | 碘萘 | 对甲基苯乙炔 | 97 |
| 7 | 碘萘 | 对氯苯乙炔 | 98 |
反应结果如上表，实施例1的催化剂不仅对于取代碘苯与取代苯乙炔的Sonogashira偶联反应有很高的催化活性，对于较大分子尺寸的碘萘与取代苯乙炔的Sonogashira偶联反应也有很高的催化活性，产率都接近100%；以催化碘苯与苯乙炔偶联反应为模板反应，1次反应完成后，实施例1的催化剂可简单过滤分离，用乙醇洗涤烘干后，再投入同一反应催化，产率仍高于95%，并且可继续重复套用，第15次的反应产率74%，表明此催化剂的可循环利用性能优异。
实施例2
（1）取定量NaOH，溶于去离子水，配成NaOH浓度为0.4mol/L的溶液，取定量的AlCl3·6H2O，溶于去离子水，配成AlCl3浓度为0.2mol/L的溶液，取定量的FeCl3·6H2O，溶于去离子水，配成FeCl3的浓度为0.2mol/L的溶液；在60℃水浴中，按照比例Al3+：Fe3+=7.5:1（mol）比例，取150ml的上述AlCl3溶液与10ml的上述FeCl3溶液混合，搅拌30min后，按照（Al3+-Fe3+）：OH-=1:2.4（mol）的比例向混合溶液中滴加192mL的NaOH溶液，搅拌至该体系为红棕色透明液体，在60℃的烘箱中老化12h，备用。
（2）60°C水浴加热并搅拌条件下，取2.5gMMT分散于250ml蒸馏水，形成悬浮液，按照（Al3+- Fe3+）：MMT=20mmol：1g的比例向悬浮液中滴加铝铁柱撑液，搅拌12h，去离子水洗涤至无Cl-，100ºC烘干，在氮气气氛下600°C焙烧5小时，得到Al/Fe复合柱撑MMT。研磨成粉状。
（3）将1g壳聚糖(CS)溶解于50mL2%稀醋酸配成均一溶液，向CS溶液滴加浓度为0.3%的Pd2+溶液2mL；60°C水浴加热并搅拌条件下，取1.5gAl/Fe复合柱撑MMT分散于50ml去离子水，形成均一悬浮液；将将上述CS-Pd复合物溶液加到Al/Fe复合柱撑蒙脱土悬浮液中，60ºC水浴加热搅拌12小时，用去离子水离心洗涤至中性，60ºC烘干，得到壳聚糖插层与Al/Fe复合柱撑协同改性(Pd@CS- Al/Fe-pillared MMT)。
效果监测：
对上述实施例2所制得的Pd@CS- Al/Fe-pillared MMT催化剂进行物性表征与催化性能评价，其过程和结果如下所述：
（1）实施例2所制得的Pd@CS- Al/Fe-pillared MMT载体的层间距为1.75 nm, BET比表面积为106.7 m2/g。
（2）实施例2所制得的Pd@CS- Al/Fe-pillared MMT催化剂应用于Sonogashira偶联反应的催化时，也表现出与实施例1相似优异的综合性能，相同条件，催化碘苯与苯乙炔的的Sonogashira偶联反应产率98%，并且可继续重复套用，第15次的反应产率66%。
上述实施例仅用于解释说明本发明的发明构思，而非对本发明权利保护的限定，凡利用此构思对本发明进行非实质性的改动，均应落入本发明的保护范围。
Claims (4)
1.一种壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂的制备方法，其特征在于，包括以下步骤：
（1）50- 60 ºC水浴加热条件下，将0.2mol/L的AlCl3与0.2mol/L的FeCl3溶液按照一定的比例混合，再与0.4mol/L的NaOH按照摩尔比n (Al 3+ /Fe 3+ ):n (OH -= )=1:2.4混合均匀，50- 60 ºC下老化10-30小时，得到Al/Fe复合柱撑液；
（2）按一定比例，将步骤（1）得到的Al/Fe复合柱撑液滴加到浓度为10%的钠型蒙脱土悬浮液中，50-60 ºC水浴加热搅拌12-24小时，离心、去离子水洗涤至无Cl-，100-120ºC烘干，氮气气氛下400-600°C高温焙烧2-8小时，得到Al/Fe复合柱撑蒙脱土；
（3）将壳聚糖溶解于2%稀醋酸配成均一溶液，向壳聚糖溶液滴加浓度为0.3%的Pd2+溶液，将步骤（2）得到的Al/Fe复合柱撑蒙脱土分散于去离子水配成悬浮液，将CS-Pd复合物溶液加到Al/Fe复合柱撑蒙脱土悬浮液中，50ºC-60ºC水浴加热搅拌4-12小时，使CS-Pd复合物充分插层进入到Al/Fe复合柱撑蒙脱土的层间，用去离子水离心洗涤至中性，60ºC烘干，得到最终壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂。
2.如权利要求1所述的一种壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂的制备方法，其特征在于：所述步骤（1）中，AlCl3与FeCl3的摩尔比例为15：1-3：1。
3.如权利要求1所述的一种壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂的制备方法，其特征在于：所述步骤（2）中的Al/Fe复合柱撑液与MMT的比例为10-50mmolAl/Fe复合柱撑液含有1g蒙脱土。
4.如权利要求1所述的一种壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂的制备方法，其特征在于：所述步骤（3）中，CS浓度为1-3%，CS与Al/Fe复合柱撑蒙脱土的质量比为9/1-5/5，；制备的壳聚糖改性Al/Fe复合柱撑蒙脱土负载钯催化剂中钯的含量为0.1-3%，比表面积100-300 m2/g。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910454168.2A CN110038639A (zh) | 2019-05-29 | 2019-05-29 | 一种壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910454168.2A CN110038639A (zh) | 2019-05-29 | 2019-05-29 | 一种壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂的制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110038639A true CN110038639A (zh) | 2019-07-23 |
Family
ID=67283967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910454168.2A Withdrawn CN110038639A (zh) | 2019-05-29 | 2019-05-29 | 一种壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110038639A (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225224A (zh) * | 2020-09-15 | 2021-01-15 | 绍兴文理学院 | 一种基于蒙脱土和壳聚糖的三维纳米复合材料的制备方法 |
| CN112958090A (zh) * | 2021-02-05 | 2021-06-15 | 长春工业大学 | 高效稳定的铁铜蒙脱土非均相芬顿催化剂及其制备方法和应用 |
-
2019
- 2019-05-29 CN CN201910454168.2A patent/CN110038639A/zh not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225224A (zh) * | 2020-09-15 | 2021-01-15 | 绍兴文理学院 | 一种基于蒙脱土和壳聚糖的三维纳米复合材料的制备方法 |
| CN112958090A (zh) * | 2021-02-05 | 2021-06-15 | 长春工业大学 | 高效稳定的铁铜蒙脱土非均相芬顿催化剂及其制备方法和应用 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Cu-Al2O3-g-C3N4 and Cu-Al2O3-C-dots with dual-reaction centres for simultaneous enhancement of Fenton-like catalytic activity and selective H2O2 conversion to hydroxyl radicals | |
| Chen et al. | In-situ growth of Ag3PO4 on calcined Zn-Al layered double hydroxides for enhanced photocatalytic degradation of tetracycline under simulated solar light irradiation and toxicity assessment | |
| Liu et al. | Boron doped C3N4 nanodots/nonmetal element (S, P, F, Br) doped C3N4 nanosheets heterojunction with synergistic effect to boost the photocatalytic hydrogen production performance | |
| Xue et al. | In situ synthesis of visible-light-driven Z-scheme AgI/Bi2WO6 heterojunction photocatalysts with enhanced photocatalytic activity | |
| Chen et al. | Metallic NiSe cocatalyst decorated g-C3N4 with enhanced photocatalytic activity | |
| CN107008326B (zh) | 一种碳量子点负载铁基材料高效异相类芬顿催化剂的制备方法 | |
| Che et al. | Synthesis of mesoporous g-C3N4/S-PAN π-conjugation heterojunction via sulfur-induced cyclization reaction for enhanced photocatalytic H2 production | |
| Gao et al. | Construction of novel MWCNTs/Bi4O5I2 nanosheets with enhanced adsorption and photocatalytic performance for the degradation of tetracycline: Efficiency, mechanism and regeneration | |
| Xu et al. | Facile synthesis of nitrogen deficient g-C3N4 by copolymerization of urea and formamide for efficient photocatalytic hydrogen evolution | |
| Zhang et al. | Construction of ultra-stable and Z-scheme Fe-Graphdiyne/MIL-100 (Fe) photo-Fenton catalyst with C= C-Fe| O interface for the highly enhanced catalytic degradation of Dinotefuran | |
| Zhao et al. | Boron doped graphitic carbon nitride dots dispersed on graphitic carbon nitride/graphene hybrid nanosheets as high performance photocatalysts for hydrogen evolution reaction | |
| CN103801284B (zh) | 一种钒酸铋-石墨烯复合光催化剂的制备方法 | |
| Gao et al. | A regenerable Cu2O/BiOBr S-scheme heterojunction photocatalysts for efficient photocatalytic degradation of mixed organic pollutants | |
| CN102992306A (zh) | 高比表面积多级孔石墨化碳及其制备方法 | |
| Ding et al. | Construction of carbon dots modified hollow g-C3N4 spheres via in situ calcination of cyanamide and glucose for highly enhanced visible light photocatalytic hydrogen evolution | |
| CN110038639A (zh) | 一种壳聚糖插层与Al/Fe复合柱撑协同改性蒙脱土负载钯催化剂的制备方法 | |
| Zhai et al. | 2D/2D black-BiOCl/Fe2O3 heterojunction photo-Fenton catalytic system for enhanced visible-light tetracycline degradation | |
| Yang et al. | Lanthanide-based dual modulation in hematite nanospindles for enhancing the photocatalytic performance | |
| He et al. | Design and synthesis of La 3+-, Sb 3+-doped MOF-In 2 S 3@ FcDc-TAPT COFs hybrid materials with enhanced photocatalytic activity | |
| An et al. | Cr (VI) reduction over Ag3PO4/g-C3N4 composite with pn heterostructure under visible-light irradiation | |
| Yuan et al. | Flower spherical-like Bi7O9I3/AgI S-scheme heterojunction for phenol photodegradation: The synergetic effect of dual surface plasmon resonance and photothermal property | |
| CN110302837B (zh) | 一种用于高级氧化工艺处理染料废水的纤维素基催化膜及其制备方法 | |
| CN107008496B (zh) | 一种亲油性改性石墨相氮化碳的制备方法 | |
| CN106517161B (zh) | 一种水热法合成氧化铜掺氮石墨烯气凝胶的制备 | |
| Chen et al. | Preparation of Fe3O4@ SiO2@ BiO1. 8· 0.04 H2O/Ag3PO4 magnetic nanocomposite and its photocatalytic performance |
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 | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190723 |