CN106582841A - Sponge loaded photocatalyst and application thereof - Google Patents
Sponge loaded photocatalyst and application thereof Download PDFInfo
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- CN106582841A CN106582841A CN201611079952.2A CN201611079952A CN106582841A CN 106582841 A CN106582841 A CN 106582841A CN 201611079952 A CN201611079952 A CN 201611079952A CN 106582841 A CN106582841 A CN 106582841A
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- Prior art keywords
- sponge
- photocatalyst
- loads
- linker reagents
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Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 130
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 47
- 125000000524 functional group Chemical group 0.000 claims abstract description 9
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- -1 amino, carboxyl Chemical group 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001345 alkine derivatives Chemical class 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 4
- 229940073608 benzyl chloride Drugs 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- 150000002540 isothiocyanates Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 230000006340 racemization Effects 0.000 claims description 3
- 238000007704 wet chemistry method Methods 0.000 claims description 3
- 239000012327 Ruthenium complex Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 2
- 241000628997 Flos Species 0.000 claims 1
- 239000004793 Polystyrene Substances 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 229940068917 polyethylene glycols Drugs 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- 238000004381 surface treatment Methods 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical group O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229930187593 rose bengal Natural products 0.000 description 3
- 229940081623 rose bengal Drugs 0.000 description 3
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 3
- 238000002444 silanisation Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical group ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- JKYKXTRKURYNGW-UHFFFAOYSA-N 3,4-dihydroxy-9,10-dioxo-9,10-dihydroanthracene-2-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=C(O)C(S(O)(=O)=O)=C2 JKYKXTRKURYNGW-UHFFFAOYSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- BIOPPFDHKHWJIA-UHFFFAOYSA-N anthracene-9,10-dinitrile Chemical compound C1=CC=C2C(C#N)=C(C=CC=C3)C3=C(C#N)C2=C1 BIOPPFDHKHWJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- ZBQZBWKNGDEDOA-UHFFFAOYSA-N eosin B Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC([N+]([O-])=O)=C(O)C(Br)=C1OC1=C2C=C([N+]([O-])=O)C(O)=C1Br ZBQZBWKNGDEDOA-UHFFFAOYSA-N 0.000 description 1
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- VYXSBFYARXAAKO-UHFFFAOYSA-N ethyl 2-[3-(ethylamino)-6-ethylimino-2,7-dimethylxanthen-9-yl]benzoate;hydron;chloride Chemical compound [Cl-].C1=2C=C(C)C(NCC)=CC=2OC2=CC(=[NH+]CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 229960002143 fluorescein Drugs 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- VOFUROIFQGPCGE-UHFFFAOYSA-N nile red Chemical compound C1=CC=C2C3=NC4=CC=C(N(CC)CC)C=C4OC3=CC(=O)C2=C1 VOFUROIFQGPCGE-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 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
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/123—Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain
- B01J31/124—Silicones or siloxanes or comprising such units
-
- B01J35/39—
-
- 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
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a sponge loaded photocatalyst, which is prepared from sponge, a Linker reagent and a photocatalyst, wherein the sponge contains surface groups; the Linker reagent at least contains two active functional groups; the photocatalyst is an organic photocatalyst or a metal complex photocatalyst; the Linker reagent is chemically bonded with the surface groups of the sponge through the active functional groups, and is then loaded on the surface of the sponge; and the photocatalyst is connected onto the surface of the sponge through being bonded with the active functional groups of the Linker reagent.
Description
Technical field
The invention belongs to catalyst field, more particularly to a kind of photocatalyst and its application of sponge load.
Background technology
Photocatalyst is the chemical substance that catalytic action can be played under the exciting of photon, its generally using visible ray as
Light source, is a kind of green, efficient catalytic specie.Application of the photocatalyst in dehydrogenation coupling reaction is intersected increasingly is closed
Note.Photocatalyst is due to itself and is not involved in reaction, therefore, in principle the photocatalyst to trying can carry out reclaiming profit
With.But traditional homogeneous photochemical catalysis reaction, due to last handling process trouble, it will usually which used photocatalyst is given up
Process, so as to cause the very big waste of photocatalyst.Especially metal complex photocatalyst, it brings after giving up to environment
Very big pollution.Photocatalyst is loaded, is to reduce the effective way for wasting and polluting, be also the strategy for realizing recycling
One of.The catalyst being supported should be stable in properties, again non-inactivation, therefore, there is very high requirement in technology of preparing.
In the technical field of loaded optic catalyst, how to obtain that to be loaded with the product of photocatalyst be problem demanding prompt solution.
Although load of the photocatalyst on other carriers is it has been reported that such as silica gel and material silica gel composite, the stone of porous
The grapheme material of black alkene and functionalization, metal-organic framework, but some carriers itself light transmission and bad；And carrier is equal
It is small granule, be by filtration or centrifugal treating, it is impossible to meet industrial actual demand.Sponge is common life
Articles for use, the sponge with stiff stability and high light transmittance is especially suitable for doing the carrier of photocatalyst.The catalyst of sponge load can
To reuse, therefore, this will be a convenient, efficient, preferable catalytic reaction process.This technology is used for into industry raw
Produce, by with huge economic worth.At present, the research report also without other supported catalysts on sponge, only light
Load of the catalyst on other carriers is to be used for catalytic reaction in the form of powder or solid particle, not only affects catalysis anti-
The effect answered, and recycle still inconvenience.Therefore, the problem that currently need to urgently solve is to provide one kind reliably, just
Prompt, efficient photocatalyst product.
The content of the invention
It is an object of the invention to provide a kind of photocatalyst of sponge load and its application, it is intended to solve prior art not
Make the problem that recycling causes to waste and pollute to photocatalyst, and prior art is also not by photocatalyst in sponge
On research.
The present invention is achieved in that a kind of photocatalyst of sponge load, and the photocatalyst of the sponge load is by sea
Continuous, Linker reagents and photocatalyst are made, wherein, the sponge contains surface group, and the Linker reagents at least contain
Two active function groups, the photocatalyst is organic photocatalyst or metal complex photocatalyst, and the Linker is tried
Agent is supported on the sponge surface, the photocatalysis by the active function groups with the surface group chemical bonding of the sponge
Agent with the active function groups of the Linker reagents by being bonded, being connected to the sponge surface.
And, a kind of photocatalyst of sponge load is in racemization or the application of asymmetric intersection dehydrogenation coupling reaction.
The photocatalyst of the sponge load that the present invention is provided, by the surface to the sponge chemical treatment is carried out, and is introduced
, further, there is chemical reaction with the photocatalyst by the active function groups in specific active function groups, and with ion
The mode of key or covalent bond is connected to sponge surface, forms the sponge catalysts with photocatalytic activity.Thus the sponge for providing
The photocatalyst of load, its is stable in properties, does not affect the activity of catalytic reaction；And only need to inhale reactant liquor through simply extruding
Enter sponge, after the completion of question response, then reactant liquor extrusion can just be reached into the purpose of light-catalyzed reaction, and photocatalysis in catalytic process
Agent will not come off from the sponge, be conducive to the recovery of the photocatalyst.Secondly, the sponge surface can be loaded simultaneously
Various Linker reagents containing different activities functional group, and then react with different types of photocatalyst, so as to realize
Multiple catalysts are loaded while sponge surface, improve the scope of application of the photocatalyst.Again, the sponge is thin
Aqueous nature makes heterogeneous catalytic reaction just can carry out in water phase.Additionally, the photocatalyst that the sponge that the present invention is provided loads, tool
Have the advantages that carrying capacity is controllable, high recycling rate.
The application of the photocatalyst of the sponge load that the present invention is provided, has the advantages that stability and recuperability are strong.
Description of the drawings
Fig. 1 is the schematic diagram of the photocatalyst of the sponge load that the embodiment of the present invention 1 is provided；
Fig. 2 is the schematic diagram of the photocatalyst of the sponge load that the embodiment of the present invention 2 is provided；
Fig. 3 is the schematic diagram of the photocatalyst of the sponge load that the embodiment of the present invention 3 is provided.
Specific embodiment
In order that the technical problem to be solved in the present invention, technical scheme and beneficial effect become more apparent, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain
The present invention, is not intended to limit the present invention.
A kind of photocatalyst of sponge load is embodiments provided, the photocatalyst of the sponge load is by sea
Continuous, Linker reagents and photocatalyst are made, wherein, the sponge contains surface group, and the Linker reagents at least contain
Two active function groups, the photocatalyst is organic photocatalyst or metal complex photocatalyst, and the Linker is tried
Agent is supported on the sponge surface, the photocatalysis by the active function groups with the surface group chemical bonding of the sponge
Agent with the active function groups of the Linker reagents by being bonded, being connected to the sponge surface.
Specifically, in the embodiment of the present invention, the sponge is polymer, preferably polyurethaness, polyethylene kind, polyphenyl second
Alkenes, polydimethylsiloxanepolymer polymer, polystyrene-benzene divinyl crosslinked resin, polyacrylamide, polyethylene-ethylene glycol
At least one in class, polyethylene terephthalate.Preferred above-mentioned sponge, with stiff stability and high light transmittance, one
Aspect, it will not participate in chemical reaction in the reaction system of the photocatalyst of load effect, and on the other hand, its high light transmittance can
To ensure light-catalysed being smoothed out, it is to avoid because sponge light transmission difference causes the photocatalyst utilization rate for being supported on its surface low
Problem.
Further, the sponge contains surface group, provides for attachment of the Linker reagents on the sponge
Chemical bonding site.The surface group can be the surface group that the sponge contains itself, it is also possible to by described
Sponge carries out being surface-treated the surface group for obtaining.The quantity of the sponge surface group is not clearly limited.
In the embodiment of the present invention, on the one hand the Linker reagents are attached to the sponge surface, the opposing party as tie
There is chemical reaction in face, with the photocatalyst by chemical bonding indirectly by the photocatalyst in the sponge table
Face.Therefore, the Linker reagents at least containing two respectively with the photocatalyst, the surface group of the sponge
Learn the end active functional group of reaction.
In the embodiment of the present invention, the Linker reagents are supported on the sponge surface, can be tried by the Linker
Agent is realized with the sponge direct reaction, it is also possible to which the sponge surface is carried out into hydrophilic treated, and obtaining surface bond has hydrophilic
After the sponge system of group such as hydroxyl, further realize with the Linker reagent reactings.I.e. described sponge contains surface hydroxyl,
And the Linker reagents are supported on the sponge surface by being bonded with the hydroxy chemical.Thus obtained sponge-silane
Change system, with more preferable stability.Further, the surface hydroxyl of the sponge to the sponge by carrying out surface hydrophilic
Process is prepared, wherein, the method for the hydrophilic treated includes gas phase process, wet chemistry method or gas phase process and wet-chemical
Method mixed processing.The gas phase process includes but is not limited to plasma oxidation, ultraviolet light, chemical gas deposition, metallization
Compound is coated, and the wet chemistry method includes but is not limited to layer by layer deposition, colloidal sol coating, silanization, surfactant modified, albumen
Deposition.
In the embodiment of the present invention, the photocatalyst is the organic catalyst or gold that can cause electron transition by light irradiation
Metal catalyst.The photocatalyst includes organic photocatalyst, ruthenium complex photocatalyst, metal iridium complex photocatalysis
Agent.Specifically, organic photocatalyst includes Eosin B, Eosin Y, Rose Bengal, Rhodamine B,
Fluorescein, Tetraphenylporphine, Perylene, Rh-6G, Alizarin red S, Nile red, NKX-
2553,9,10-Dicyanoanthracene,Methylene Blue,DPZ,Diiodo-BODIPY-COCI；The metal Ru
Coordination compound photocatalyst includes Ru-1, Ru-2, Ru-3；The metal iridium complex photocatalyst includes Ir-1, Ir-2, Ir-3,
Ir-4, its structural formula difference is as follows：
Above-mentioned preferred photocatalyst, in the lower just energy catalytic reaction of visible ray (380-780nm, naked eyes are visible) irradiation.
Wherein, organic photocatalyst is cheap and easy to get, is adapted to commercial production；The scope of application of metal complex photocatalyst catalytic reaction
Extensively.After being supported on sponge, these photocatalysts are activity stabilized, high recycling rate.
Used as the preferred embodiment of the present invention, as shown in following formula 1, the structure of the Linker reagents is such as the structure of the sponge
Shown in following formula 2, the molecular formula of the photocatalyst as shown in following formula 3, wherein, R1、R2、R3、R4For active function groups, n >=0, institute
Linker reagents are stated by the R1With the R2Between chemical bonding, be supported on the sponge surface；The photocatalyst leads to
Cross and pass through the R with the Linker reagents3With the R4Between chemical bonding be connected,
And the R1、R2、R3、R4Be respectively selected from amino, carboxyl, halogen, cyano group, isocyanates, isothiocyanate, alkene,
Alkynes, hydroxyl, mercaptan, phenol, benzyl chloride, benzoic acid, expoxy propane, or
The R1、R2、R3、R4Be to amino, carboxyl, halogen, cyano group, isocyanates, isothiocyanate, alkene, alkynes,
Hydroxyl, mercaptan, phenol, benzyl chloride, benzoic acid, expoxy propane modified after group.Above-mentioned group can be carried out further
Moditied processing, to improve the reactivity of the Linker reagents and the photocatalyst, further improves the photocatalyst
Load capacity, a such as molecule L inker reagent can be combined with polymolecular photocatalyst.Above-mentioned preferred active function groups, Neng Gou
More stable chemistry is provided between the sponge and the Linker reagents, between the Linker reagents and the photocatalyst
Key.Specifically, the sponge surface after silanization is carried out can be adopted, radical polymerization in situ is carried out to the silylation groups,
It is end modified so as to realize, expose more reaction sites.
Further, in order to improve the bonding efficiency and bonding effect of the photocatalyst and the Linker reagents,
Carry out adding certain condensing agent during bonding reaction, the type of the condensing agent is according to specific Linker reagents and photocatalyst
Structure depending on.
In the embodiment of the present invention, the photocatalyst by way of ionic bond or covalent bond with the Linker reagents key
Close, and then be supported on the sponge surface.Preferably, load capacity of the photocatalyst on the sponge is 0.01-
2.00mmol/g.If the load capacity of the photocatalyst is very few, the effective rate of utilization of sponge is too low, the sponge energy of unit volume
The photocatalytic effect for bringing is limited；If the load capacity of the photocatalyst is excessive, photocatalyst surface may be caused mutually to hand over
Fork, the active group for producing catalytic reaction is hidden, so as to produce efficient catalytic action.
In the embodiment of the present invention, two or more in the Linker reagents containing different activities functional group is same
When be supported on same sponge surface, and the different active function groups and different photocatalyst bondings.Thus, further carry
The scope of application of the photocatalyst of high sponge load.
The photocatalyst of sponge load provided in an embodiment of the present invention, is carried out at silanization by the surface to the sponge
Reason, introduces specific active function groups, further, chemical reaction occurs with the photocatalyst by the active function groups,
And sponge surface is connected in the way of ionic bond or covalent bond, form the sponge catalysts with photocatalytic activity.Thus carry
For sponge load photocatalyst, its is stable in properties, does not affect the activity of catalytic reaction；And only need to through simply extrude by
Reactant liquor inspiration sponge, after the completion of question response, then can just reach the purpose of light-catalyzed reaction, and catalytic process by reactant liquor extrusion
Middle photocatalyst will not come off from the sponge, be conducive to the recovery of the photocatalyst.Secondly, the sponge surface can be with
The various Linker reagents containing different activities functional group are loaded simultaneously, and then are reacted with different types of photocatalyst,
So as to realize that multiple catalysts are loaded while sponge surface, the scope of application of the photocatalyst is improve.Again, it is described
The hydrophobic property of sponge makes heterogeneous catalytic reaction just can carry out in water phase.Additionally, sponge provided in an embodiment of the present invention is negative
The photocatalyst of load, has the advantages that carrying capacity is controllable, high recycling rate.
And, it is de- in racemization or asymmetric intersection that the embodiment of the present invention additionally provides a kind of photocatalyst of sponge load
The application of hydrogen coupling reaction.
The application of the photocatalyst of sponge provided in an embodiment of the present invention load, with strong excellent of stability and recuperability
Point.
Illustrate with reference to specific embodiment.
Embodiment 1
A kind of photocatalyst of sponge load, the photocatalyst of the sponge load is urged by sponge, silylating reagent and light
Agent is made, wherein, the sponge is the polydimethylsiloxane sponge (PDMS) containing surface hydroxyl, the Linker reagents
For the vinyltrimethoxy silane that end group is modified with trimethyl ammonium chloride, the photocatalyst is rose bengal
(Rose Bengal, RB), and the silylating reagent by with the surface hydroxyl reaction load of the sponge in the sponge table
Face, the photocatalyst is bonded, is connected to the sponge surface by ionic bond with the silylating reagent after modification.Its
In, the structure of the photocatalyst is as follows, and the design sketch of the photocatalyst of the sponge load is as shown in Figure 1：
Embodiment 2
A kind of photocatalyst of sponge load, the photocatalyst of the sponge load is urged by sponge, silylating reagent and light
Agent is made, wherein, the sponge is the polydimethylsiloxane sponge (PDMS) containing surface hydroxyl, the silylating reagent
For APTES, the photocatalyst is rose bengal (Rose Bengal, RB), and the silicon
Alkylators are by the way that, in the sponge surface, the photocatalyst passes through covalent bond with the surface hydroxyl reaction load of the sponge
Amino bonded with the silylating reagent, it is connected to the sponge surface.The design sketch of the photocatalyst of the sponge load
As shown in Figure 2.
Embodiment 3
A kind of photocatalyst of sponge load, the photocatalyst of the sponge load is urged by sponge, silylating reagent and light
Agent is made, wherein, the sponge is the polydimethylsiloxane sponge (PDMS) containing surface hydroxyl, the silylating reagent
For the vinyltrimethoxy silane that end group is modified with expoxy propane, the photocatalyst is rose bengal (Rose
Bengal, RB), and the surface hydroxyl reaction load of the sponge of the silylating reagent after with modification is in the sponge
Surface, the photocatalyst by covalent bond with modification after the silylating reagent amino bonded, be connected to the sponge
Surface.The design sketch of the photocatalyst of the sponge load is as shown in Figure 3.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (10)
1. the photocatalyst that a kind of sponge loads, it is characterised in that the photocatalyst of the sponge load is tried by sponge, Linker
Agent and photocatalyst are made, wherein, the sponge contains surface group, and the Linker reagents are at least containing two active senses
Group, the photocatalyst is organic photocatalyst or metal complex photocatalyst, and the Linker reagents are by the work
Property functional group and the surface group chemical bonding of the sponge are supported on the sponge surface, the photocatalyst by with it is described
The active function groups of Linker reagents are bonded, are connected to the sponge surface.
2. the photocatalyst that sponge as claimed in claim 1 loads, it is characterised in that the structure of the sponge such as institute of following formula 1
Show, the structure of the Linker reagents as shown in following formula 2, the molecular formula of the photocatalyst as shown in following formula 3, wherein, R1、R2、
R3、R4For active function groups, n >=0, the Linker reagents are by the R1With the R2Between chemical bonding, be supported on institute
State sponge surface；The photocatalyst with the Linker reagents by passing through the R3With the R4Between chemically bonded phase
Even,
And the R1、R2、R3、R4Be respectively selected from amino, carboxyl, halogen, cyano group, isocyanates, isothiocyanate, alkene, alkynes,
Hydroxyl, mercaptan, phenol, benzyl chloride, benzoic acid, expoxy propane, or
The R1、R2、R3、R4Be to amino, carboxyl, halogen, cyano group, isocyanates, isothiocyanate, alkene, alkynes, hydroxyl,
Mercaptan, phenol, benzyl chloride, benzoic acid, expoxy propane modified after group.
3. the photocatalyst that sponge as claimed in claim 1 loads, it is characterised in that the surface group of the sponge is by right
Sponge carries out surface treatment and obtains.
4. the photocatalyst that sponge as claimed in claim 1 or 2 loads, it is characterised in that the photocatalyst includes organic
Photocatalyst, ruthenium complex photocatalyst, metal iridium complex photocatalyst.
5. the photocatalyst that sponge as claimed in claim 4 loads, it is characterised in that the photocatalyst structure is as described below
Each compound：
6. the photocatalyst that sponge as claimed in claim 1 or 2 loads, it is characterised in that containing different activities functional group
Two or more in the Linker reagents is supported on same sponge surface, and the different active function groups simultaneously
It is bonded from different photocatalysts.
7. the photocatalyst that sponge as claimed in claim 1 or 2 loads, it is characterised in that the photocatalyst is in the sea
Load capacity on silk floss is 0.01-2.00mmol/g.
8. the photocatalyst that sponge as claimed in claim 1 or 2 loads, it is characterised in that the sponge is polyurethaness, gathers
Vinyl, polystyrene type, polydimethylsiloxanepolymer polymer, polystyrene-benzene divinyl crosslinked resin, polyacrylamide,
At least one in polyethylene-glycols, polyethylene terephthalate.
9. the photocatalyst that sponge as claimed in claim 2 loads, it is characterised in that the surface hydroxyl of the sponge is by right
The sponge carries out surface hydrophilic process and prepares, wherein, the method for the hydrophilic treated includes gas phase process, wet-chemical
Method or gas phase process and wet chemistry method mixed processing.
10. the photocatalyst of the sponge load as described in claim 1-9 is arbitrary is coupled in racemization or asymmetric intersection dehydrogenation
The application of reaction.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107349958A (en) * | 2017-06-15 | 2017-11-17 | 深圳大学 | The chiral organicatalyst of sponge load |
| CN108686639A (en) * | 2018-03-30 | 2018-10-23 | 南方科技大学 | Three-dimensional netted carbon-based composite photo-catalyst of metal organic framework derived material-and preparation method thereof, purposes |
| CN108686639B (en) * | 2018-03-30 | 2021-04-27 | 南方科技大学 | Metal organic framework derivative material-three-dimensional reticular carbon-based composite photocatalyst and preparation method and application thereof |
| CN108855214A (en) * | 2018-06-29 | 2018-11-23 | 深圳大学 | Metallic catalyst and preparation method thereof |
| CN108855214B (en) * | 2018-06-29 | 2021-01-29 | 深圳大学 | Metal catalyst and preparation method thereof |
| CN109364994A (en) * | 2018-09-10 | 2019-02-22 | 深圳大学 | Loaded photocatalyst and its application |
| CN109126878A (en) * | 2018-09-21 | 2019-01-04 | 深圳大学 | Metal combination chiral catalyst |
| CN112588321A (en) * | 2020-12-01 | 2021-04-02 | 华南理工大学 | Chitosan quaternary ammonium salt loaded dye photocatalyst and preparation method and application thereof |
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