CN108855214B - Metal catalyst and preparation method thereof - Google Patents
Metal catalyst and preparation method thereof Download PDFInfo
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- CN108855214B CN108855214B CN201810699012.6A CN201810699012A CN108855214B CN 108855214 B CN108855214 B CN 108855214B CN 201810699012 A CN201810699012 A CN 201810699012A CN 108855214 B CN108855214 B CN 108855214B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 117
- 239000002184 metal Substances 0.000 title claims abstract description 117
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims description 6
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 160
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 151
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 151
- 125000003277 amino group Chemical group 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims description 47
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 38
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 26
- 230000008878 coupling Effects 0.000 claims description 21
- 238000010168 coupling process Methods 0.000 claims description 21
- 238000005859 coupling reaction Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 229910052737 gold Inorganic materials 0.000 claims description 12
- 239000010931 gold Substances 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 11
- 238000004381 surface treatment Methods 0.000 claims description 10
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims description 7
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 150000002940 palladium Chemical class 0.000 claims description 3
- 150000003057 platinum Chemical class 0.000 claims description 3
- 238000002444 silanisation Methods 0.000 claims description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000010944 silver (metal) Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 3
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 15
- 239000000126 substance Substances 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000009832 plasma treatment Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
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- 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
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明提供了一种金属催化剂，所述金属催化剂为海绵负载纳米金属催化剂，所述海绵负载纳米金属催化剂包括聚二甲基硅氧烷海绵载体以及负载在所述聚二甲基硅氧烷海绵载体上的催化剂活性组分，所述催化剂活性成分为纳米金属，所述聚二甲基硅氧烷海绵载体表面含有氨基，且所述纳米金属通过所述氨基与所述聚二甲基硅氧烷海绵载体连接。
The invention provides a metal catalyst, the metal catalyst is a sponge-supported nano-metal catalyst, and the sponge-supported nano-metal catalyst comprises a polydimethylsiloxane sponge carrier and a polydimethylsiloxane sponge supported on the polydimethylsiloxane sponge. The catalyst active component on the carrier, the catalyst active component is nano metal, the surface of the polydimethylsiloxane sponge carrier contains amino groups, and the nano metal is connected to the polydimethylsiloxane through the amino group alkane sponge carrier attachment.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a polydimethylsiloxane sponge supported nano metal catalyst and a preparation method thereof.
Background
The metal catalyst is a solid catalyst with metal as main active component, and mainly takes noble metal and transition elements such as iron, cobalt, nickel and the like as catalytic active components, which are related to the structure and surface chemical bonds of the metal. The metal catalyst is divided into single metal catalyst and multi-metal catalyst, and is a kind of industrial catalyst with wide application and importance. In the using process of the metal oxidant, on one hand, the dispersibility is relatively poor, and the catalytic efficiency is low; on the other hand, the metal catalyst is difficult to effectively recycle in the using process, and is generally purchased and used as a loss product, so that the using rate or the service life of the catalytic material is low.
Disclosure of Invention
The invention aims to provide a metal catalyst, and aims to solve the problems that the catalytic efficiency of a pure-phase metal catalyst needs to be improved and the catalytic life is short.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a metal catalyst, wherein the metal catalyst is a sponge supported nano metal catalyst, the sponge supported nano metal catalyst comprises a polydimethylsiloxane sponge carrier and a catalyst active component loaded on the polydimethylsiloxane sponge carrier, the catalyst active component is a nano metal, the surface of the polydimethylsiloxane sponge carrier contains amino, and the nano metal is connected with the polydimethylsiloxane sponge carrier through the amino.
In another aspect, the present invention provides a method for preparing a metal catalyst, comprising the steps of:
providing polydimethylsiloxane sponge, and carrying out surface treatment on the polydimethylsiloxane sponge to obtain polydimethylsiloxane sponge containing surface groups;
coupling an amino coupling reagent on the surface of the polydimethylsiloxane sponge containing the surface groups to obtain a polydimethylsiloxane sponge carrier with amino connected to the surface;
providing a metal salt solution, and placing the polydimethylsiloxane sponge carrier with the surface connected with amino in the metal salt solution to obtain a polydimethylsiloxane sponge carrier solution loaded with metal salt;
and adding a reducing agent into the polydimethylsiloxane sponge carrier solution loaded with the metal salt, and reducing the metal salt into a nano metal simple substance to obtain the sponge-loaded nano metal catalyst.
The metal catalyst provided by the invention is a sponge supported nano metal catalyst, and comprises a polydimethylsiloxane sponge carrier with amino on the surface and nano metal loaded on the polydimethylsiloxane sponge carrier through the amino. The sponge supported nano Metal catalyst is constructed and formed through Metal-carrier Strong interaction (Classic Structure-Support Interactions), has good dispersibility, higher catalytic activity, easy recovery, reusability and high catalyst utilization rate, and can reduce the cost of industrial production. In addition, polydimethylsiloxane sponge is used as a sponge carrier matrix substance, and due to the hydrophobic characteristic of polydimethylsiloxane, the polydimethylsiloxane sponge is used as a carrier of transition nano metal in organic catalytic reaction in a water environment system, and due to the better compatibility between polydimethylsiloxane and an organic solvent, the contact efficiency of the polydimethylsiloxane sponge and the organic solvent is improved, and the organic catalytic activity can be obviously improved.
The metal catalyst provided by the invention is a sponge supported nano metal catalyst, a polydimethylsiloxane sponge carrier with amino groups connected to the surface is obtained on polydimethylsiloxane sponge through surface modification treatment, metal salt is further loaded on the polydimethylsiloxane sponge carrier with amino groups connected to the surface, and the sponge supported nano metal catalyst is obtained through reduction treatment by a reducing agent. The method is simple to operate, the reaction conditions are mild, and the prepared metal catalyst has the advantages of high catalytic activity and long service life.
Drawings
FIG. 1 is a schematic diagram of a reaction scheme provided in example 1 of the present invention;
FIG. 2 is a schematic diagram of the reaction scheme provided in example 2 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The embodiment of the invention provides a metal catalyst, wherein the metal catalyst is a sponge supported nano metal catalyst, the sponge supported nano metal catalyst comprises a polydimethylsiloxane sponge carrier and a catalyst active component loaded on the polydimethylsiloxane sponge carrier, the catalyst active component is a nano metal, the surface of the polydimethylsiloxane sponge carrier contains amino, and the nano metal is connected with the polydimethylsiloxane sponge carrier through the amino.
The metal catalyst provided by the embodiment of the invention is a sponge supported nano metal catalyst, and comprises a polydimethylsiloxane sponge carrier with amino on the surface and nano metal supported on the polydimethylsiloxane sponge carrier through the amino. The sponge supported nano Metal catalyst is constructed and formed through Metal-carrier Strong interaction (Classic Structure-Support Interactions), has good dispersibility, higher catalytic activity, easy recovery, reusability and high catalyst utilization rate, and can reduce the cost of industrial production. In addition, polydimethylsiloxane sponge is used as a sponge carrier matrix substance, and due to the hydrophobic characteristic of polydimethylsiloxane, the polydimethylsiloxane sponge is used as a carrier of transition nano metal in organic catalytic reaction in a water environment system, and due to the better compatibility between polydimethylsiloxane and an organic solvent, the contact efficiency of the polydimethylsiloxane sponge and the organic solvent is improved, and the organic catalytic activity can be obviously improved.
The surface of a common polydimethylsiloxane sponge does not contain amino groups. In order to enable the catalyst active ingredient, i.e., the nanometal, to be attached to the polydimethylsiloxane sponge, a sponge-supported nanometal catalyst is formed. In the embodiment of the invention, the polydimethylsiloxane sponge carrier is a polydimethylsiloxane sponge subjected to modification treatment, and the surface of the polydimethylsiloxane sponge contains amino. The nano metal is connected with the polydimethylsiloxane sponge carrier through amino on the surface of the modified polydimethylsiloxane sponge, and specifically, the nano metal is connected with nitrogen atoms on the amino on the surface of the polydimethylsiloxane sponge carrier through adsorption or a formula.
There are various ways of modifying polydimethylsiloxane sponge to obtain polydimethylsiloxane sponge carrier with surface containing cases. In a preferred embodiment, a silane coupling agent containing an amino group is bonded to the surface of the polydimethylsiloxane sponge carrier. Specifically, the polydimethylsiloxane sponge can contain surface hydroxyl after surface treatment, alkoxy of the silane coupling agent containing amino can react with the surface hydroxyl of the polydimethylsiloxane sponge after surface treatment, and the silane coupling agent with the alkoxy removed is connected to the surface of the polydimethylsiloxane sponge, so that the amino on the silane coupling agent is introduced, and a site is provided for the attachment of the nano metal.
As another preferred embodiment, the polydimethylsiloxane sponge carrier is bonded with a coupling unit shown in the following structural formula 1 on the surface,
in the formula 1, R1Selected from alkyl groups with a carbon number of 1-6, and n is more than or equal to 2.
Specifically, the polydimethylsiloxane sponge can contain surface hydroxyl after surface treatment, a silane coupling agent containing a terminal unsaturated bond reacts with the surface hydroxyl, and the silane coupling agent with alkoxy removed is connected to the surface of the polydimethylsiloxane sponge to realize the connection of the polydimethylsiloxane sponge and the surface hydroxyl. Further, by introducing a polymerized monomer containing a terminal epoxy group into the unsaturated terminal of the silane coupling agent with alkoxy groups removed, polymer molecules with a plurality of epoxy groups are formed on polydimethylsiloxane sponge after polymerization. Furthermore, the epoxy group and diethylenetriamine are subjected to a ring-opening reaction to obtain the coupling unit shown in the formula 1. The coupling unit with the structure can introduce a large amount of active amino groups on the polydimethylsiloxane sponge, so that more sites are provided for the attachment of nano metal, and the catalytic activity and the catalytic efficiency are further improved.
In the coupling unit of formula 1, R1Selected from alkyl groups having a carbon number of 1 to 6. If R is1The carbon atoms are too many, the branched structure is complex or the carbon chain is too long, the steric hindrance is obviously increased, the active amino group is covered, the contact between the nano metal and the active amino group becomes difficult, and the attachment of the nano metal is not facilitated. Particularly preferably, R is1is-CH2CH2-. At this time, the benefitIntroducing subsequent active fragments on the surface of the polydimethylsiloxane sponge through a silane coupling agent containing terminal alkenyl.
Preferably, n is less than or equal to 50, more preferably less than or equal to 20, so as to avoid overlong single polymer molecules, entanglement of simple substance molecules, increase of steric hindrance, hiding of active amino groups, difficulty in contact of the nano metal and the active amino groups and also unfavorable for attachment of the nano metal.
Based on the above examples, the loading amount of the catalyst active component on the polydimethylsiloxane sponge carrier is 1.34 × 10-5-1.34×10-4mmol/g. If the load capacity of the catalyst active component on the polydimethylsiloxane sponge carrier is too small, the utilization rate of the polydimethylsiloxane sponge carrier is too low, and the catalytic effect brought by the sponge in unit volume is limited. The loading amount of the catalyst active component is related to the number of amino groups in an organic unit, particularly an organic unit, on the surface of the polydimethylsiloxane sponge, but when the number of the organic units is too large, the organic units are easy to intersect with each other on the surface of the sponge, and the attachment of nano metal is not facilitated. Even if the nano metal passes through the steric hindrance and is attached to the polydimethylsiloxane sponge through the amino, the catalytic effect cannot be linearly increased along with the increase of the nano metal due to the hiding of the nano metal generating the catalytic reaction. Particularly preferably, when a silane coupling agent containing amino groups is bonded to the surface of the polydimethylsiloxane sponge carrier, the loading amount of the catalyst active component on the polydimethylsiloxane sponge carrier is 1.34 x 10-5-1.34×10-4mmol/mg. When the surface of the polydimethylsiloxane sponge carrier is bonded with the coupling unit shown in the structural formula 1, the loading amount of the catalyst active component on the polydimethylsiloxane sponge carrier is 1.34 multiplied by 10-5-1.34×10-4mmol/mg。
In the embodiment of the invention, the nano metal is at least one selected from Au, Ag, Ni, Cu, Pd, Zn, Fe and Pt. Specifically, the metal may be a simple metal, an alloy, or a metal ion of the above-mentioned metals.
The metal catalyst of the embodiment of the invention can be prepared by the following method.
Accordingly, another aspect of the embodiments of the present invention provides a method for preparing a metal catalyst, including the following steps:
s01, providing polydimethylsiloxane sponge, and carrying out surface treatment on the polydimethylsiloxane sponge to obtain polydimethylsiloxane sponge containing surface groups;
s02, coupling an amino coupling reagent on the surface of the polydimethylsiloxane sponge containing the surface groups to obtain a polydimethylsiloxane sponge carrier with the surface connected with amino;
s03, providing a metal salt solution, and placing the polydimethylsiloxane sponge carrier with the surface connected with amino in the metal salt solution to obtain a polydimethylsiloxane sponge carrier solution loaded with metal salt;
s04, adding a reducing agent into the polydimethylsiloxane sponge carrier solution loaded with the metal salt, and reducing the metal salt into a nano metal simple substance to obtain the sponge-loaded nano metal catalyst.
The metal catalyst provided by the embodiment of the invention is a sponge supported nano metal catalyst, a polydimethylsiloxane sponge carrier with amino groups connected to the surface is obtained on polydimethylsiloxane sponge through surface modification treatment, metal salt is further loaded on the polydimethylsiloxane sponge carrier with amino groups connected to the surface, and the sponge supported nano metal catalyst is obtained through reduction treatment by a reducing agent. The method is simple to operate, the reaction conditions are mild, and the prepared metal catalyst has the advantages of high catalytic activity and long service life.
Specifically, in step S01, the polydimethylsiloxane sponge is a conventional polydimethylsiloxane sponge. Conventional polydimethylsiloxane sponges generally have difficulty in attaching other modifying materials, particularly organic modifying materials, to their surfaces because they do not contain surface active groups. Based on this, in the embodiment of the present invention, the polydimethylsiloxane sponge is subjected to surface treatment to obtain a polydimethylsiloxane sponge containing surface groups. Preferably, the surface treatment may be plasma treatment, wherein the polydimethylsiloxane sponge is cleaned by plasma to increase the surface roughness thereof, and hydrophilic groups such as hydroxyl groups are grafted on the surface of the polydimethylsiloxane sponge by plasma treatment to realize surface hydrophilization. Specifically, the dried polydimethylsiloxane sponge is put into a plasma cleaning machine for plasma treatment for 1 to 10 minutes, preferably 3 to 5 minutes (e.g., 4 minutes), and hydrophilic groups such as hydroxyl groups are attached to the surface of the sponge. It should be noted that, in the surface treatment, especially the plasma treatment, performed in the embodiment of the present invention, it is required to ensure that the polydimethylsiloxane sponge is dry, so as to prevent the sponge from containing water to affect the effect of the plasma treatment, and further affect the generation of hydrophilic groups on the surface of the sponge.
Preferably, before the surface treatment, the surface cleaning treatment is performed to remove dust. Particularly preferably, the surface cleaning treatment is ultrasonic cleaning for 1 to 10 minutes, preferably 3 to 5 minutes. The solvent for ultrasonic cleaning may be an organic solvent including, but not limited to, ethanol. The washed sponge is dried, preferably in a forced air oven at 70-90 deg.C, for example 80 deg.C.
In the step S02, the polydimethylsiloxane sponge containing the surface group is further modified, and an amino group is introduced on the surface of the polydimethylsiloxane sponge to provide a nitrogen atom site for the attachment of the nano metal.
As a preferred embodiment, the method for coupling an amino coupling reagent on the surface of the polydimethylsiloxane sponge containing the surface groups to obtain the polydimethylsiloxane sponge carrier with the surface connected with amino comprises the following steps:
providing a silane coupling agent solution containing amino, placing the polydimethylsiloxane sponge containing surface groups into the silane coupling agent solution containing amino, and reacting the silane coupling agent containing amino with the surface groups of the polydimethylsiloxane sponge to prepare the polydimethylsiloxane sponge carrier connected with the amino.
Wherein, in the silane coupling agent solution containing amino, the silane coupling agent containing amino includes but is not limited to 3-aminopropyl triethoxysilane, and the solvent can be selected from but is not limited to toluene. Preferably, the amino group-containing silane coupling agent solution has a 3% to 10% by volume, and more preferably 5% by volume of the amino group-containing silane coupling agent, so that an appropriate amount of amino groups can be introduced.
The silane coupling agent containing amino groups reacts with surface groups of the polydimethylsiloxane sponge, preferably by stirring, and more preferably by heating and refluxing to accelerate the reaction.
As another preferred embodiment, the method for coupling an amino coupling reagent on the surface of the polydimethylsiloxane sponge containing the surface groups to obtain the polydimethylsiloxane sponge carrier with the surface connected with amino comprises the following steps:
s021, providing a silane coupling agent solution containing double bonds, placing the polydimethylsiloxane sponge containing surface groups into the silane coupling agent solution containing double bonds, and performing silanization treatment to obtain the polydimethylsiloxane sponge containing double bonds on the surface.
In this step, the double bond-containing silane coupling agent solution includes but is not limited to VTMS (vinyl trimethoxy silane), and the solvent includes but is not limited to ethanol, preferably an ethanol solution of VTMS. Particularly preferably, the mass part of the ethanol solution of the VTMS is 1% to 5%, and more preferably 3%, so as to form sites with a suitable spatial distance.
The silanization treatment can be directly realized by soaking the polydimethylsiloxane sponge containing the surface groups in the silane coupling agent solution containing the double bonds, preferably soaking for 2-3 hours, and washing with deionized water.
S022, placing the polydimethylsiloxane sponge with double bonds on the surface into a methacryloyloxyethyl trimethyl ammonium chloride solution, and carrying out free polymerization reaction to prepare the polydimethylsiloxane sponge with the polymer brush formed on the surface.
In the step, the polydimethylsiloxane sponge with double bonds on the surface is placed in a methacryloyloxyethyl trimethyl ammonium chloride solution and heated to 70-90 ℃ to carry out free polymerization reaction. Preferably, the mass portion of the methacryloyloxyethyl trimethyl ammonium chloride solution is 3% -8%, more preferably 5%,i.e., 60 g/L. The solvent of the methacryloyloxyethyl trimethyl ammonium chloride solution is preferably H with the volume ratio of 1:22O/DMF. Through free radical polymerization, a polymer brush grows on the surface of the sponge, and the sponge is washed clean by deionized water. By growing the polymer brush on the surface of the polydimethylsiloxane sponge, more amino sites are provided, so that the contact area of the sponge and the nano metal is increased.
S023, reacting the polydimethylsiloxane sponge with the polymer brush formed on the surface with diethylenetriamine to prepare the polydimethylsiloxane sponge carrier connected with amino.
In this step, the polydimethylsiloxane sponge with the polymer brush formed on the surface is reacted with diethylenetriamine, preferably at 65 to 75 ℃, in particular 70 ℃ overnight. The diethylenetriamine is a 1, 4-dioxane solution of the diethylenetriamine, and the solubility is preferably 0.02-0.06mmol/ml, and particularly preferably 0.04 mmol/ml.
In the step S03, a metal salt solution is provided, in which the metal salt is selected from one of gold salt, platinum salt, iron salt, zinc salt, silver salt, nickel salt, copper salt, and palladium salt, such as chloroauric acid. Placing the polydimethylsiloxane sponge carrier with the amino groups connected to the surface in the metal salt solution, and preferably placing the polydimethylsiloxane sponge carrier in the metal salt solution. The mass of the gold salt is 2 wt% relative to the mass of the sponge. Further, the reaction can be carried out under room temperature (15-35 ℃) by magnetic stirring, so that metal ions enter the polydimethylsiloxane sponge.
In the step S04, a reducing agent is added to the metal salt-supported polydimethylsiloxane sponge carrier solution, and the metal ions are reduced to nano-metal particles by utilizing the reducibility of the reducing agent and are dissociated in the solution. Further, the reduced nano metal particles and nitrogen atoms on the active group amino on the surface of the polydimethylsiloxane sponge carrier are adsorbed or coordinated to complete the loading.
Wherein, the metal salt in the metal salt solution is selected from one of gold salt, platinum salt, iron salt, zinc salt, silver salt, nickel salt, copper salt and palladium salt. Preferably, the reducing agent is selected from one of sodium citrate and formaldehyde, and is selected specifically for different gold salt types.
More preferably, the addition amount of the reducing agent is 15 to 35 times the molar mass of the gold salt.
The following description will be given with reference to specific examples.
Example 1
A method for preparing a metal catalyst, as shown in fig. 1, comprising the steps of:
the polydimethylsiloxane sponge is cleaned with a solvent (e.g., ethanol) in an ultrasonic cleaner for 1-10 minutes. And then putting the cleaned sponge into a blast oven at 70-90 ℃ for drying. And (3) placing the dried sponge into a plasma cleaning machine for plasma treatment for 1-10 minutes, and connecting hydrophilic groups such as hydroxyl groups on the surface of the sponge.
Dissolving 3-aminopropyltriethoxysilane in toluene (5%, v/v), stirring for 5 minutes, placing polydimethylsiloxane sponge in toluene, and stirring at room temperature for 3-5 hours to complete the surface modification of the sponge.
Adding 8-12ml of chloroauric acid solution with the concentration of 10mg/ml into 20ml of ultrapure water, adding 3-5g of polydimethylsiloxane sponge after the solution is uniformly mixed, and magnetically stirring for 20-40 minutes at room temperature to allow gold ions to enter the sponge.
16 to 24ml of a sodium citrate solution having a concentration of 50mg/ml was added to the above mixed solution, and heated in an oil bath at 80 ℃ for 30 minutes. And reducing the + 3-valent gold ions into gold nano simple substances by utilizing the reducibility of the sodium citrate, and dissociating the gold nano simple substances in the solution. Then, the nitrogen atom on the primary amine of the active group on the surface of the sponge is loaded on the surface of the sponge through chemical coordination, and the sponge loaded with the nano-gold is changed into purple black from white.
Example 2
A method for preparing a metal catalyst, as shown in fig. 2, comprising the steps of:
the polydimethylsiloxane sponge is cleaned with a solvent (e.g., ethanol) in an ultrasonic cleaner for 1-10 minutes. And (3) putting the cleaned sponge into a blast oven at 70-90 ℃ for drying. And (3) placing the dried sponge into a plasma cleaning machine for plasma treatment for 1-10 minutes, and connecting hydrophilic groups such as hydroxyl groups on the surface of the sponge.
Soaking the hydrophilic polydimethylsiloxane sponge in a silane molecular solution containing double bonds for 2-3h, and then washing the sponge clean with deionized water. The double-bond-containing silane molecular solution is a VTMS solution, the mass fraction of the VTMS solution is 1% -5%, and the VTMS solution is an ethanol solution of VTMS.
Soaking the silanized polydimethylsiloxane sponge in a methacryloyloxyethyl trimethyl ammonium chloride solution (containing KPS 60g/L) at the temperature of 70-90 ℃ for 6-9h, carrying out free radical polymerization on the surface of the polydimethylsiloxane sponge, growing a polymer brush on the surface of the sponge, and then washing the sponge clean with deionized water. Wherein the mass fraction of the methacryloyloxyethyl trimethyl ammonium chloride solution is 3% -8%, and the volume ratio of the solution solvent is 1: 2H2O/DMF。
The polydimethylsiloxane sponge with the polymer brush attached is soaked in a diethylenetriamine solution with the concentration of 0.04 mmol/ml. The concrete conditions are as follows: 1, 4-dioxane is used as a solvent for reaction, and the temperature of reaction liquid is 70 ℃ for overnight reaction. The sponge is taken out the next day, the unreacted raw materials of the sponge are washed by ethanol and then dried for 12 hours in a vacuum drying oven at 50 ℃.
Adding 8-12ml of chloroauric acid solution with the concentration of 10mg/ml into 20ml of ultrapure water, adding 3-5g of polydimethylsiloxane sponge after the solution is uniformly mixed, and magnetically stirring for 20-40 minutes at room temperature to allow gold ions to enter the sponge.
16 to 24ml of a sodium citrate solution having a concentration of 50mg/ml was added to the above mixed solution, and heated in an oil bath at 80 ℃ for 30 minutes. And reducing the + 3-valent gold ions into gold nano simple substances by utilizing the reducibility of the sodium citrate, and dissociating the gold nano simple substances in the solution. Then, the nitrogen atom on the primary amine of the active group on the surface of the sponge is loaded on the surface of the sponge through chemical coordination, and the sponge loaded with the nano-gold is changed into purple black from white.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
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