CN110180543A - A kind of solid-carrying type Cu2The preparation method and applications of O/Cu@ACSs photochemical catalyst - Google Patents
A kind of solid-carrying type Cu2The preparation method and applications of O/Cu@ACSs photochemical catalyst Download PDFInfo
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- CN110180543A CN110180543A CN201910514517.5A CN201910514517A CN110180543A CN 110180543 A CN110180543 A CN 110180543A CN 201910514517 A CN201910514517 A CN 201910514517A CN 110180543 A CN110180543 A CN 110180543A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 23
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000005011 phenolic resin Substances 0.000 claims abstract description 17
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 150000003624 transition metals Chemical class 0.000 claims abstract description 12
- 230000001699 photocatalysis Effects 0.000 claims abstract description 11
- 238000007540 photo-reduction reaction Methods 0.000 claims abstract description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 6
- 150000002989 phenols Chemical class 0.000 claims abstract description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 6
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims description 56
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 238000007146 photocatalysis Methods 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- -1 aldehyde compounds Chemical class 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical class CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical class OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 2
- 229940100630 metacresol Drugs 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000004913 activation Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 150000001298 alcohols Chemical class 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 22
- 239000000047 product Substances 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 7
- 238000011056 performance test Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 210000001367 artery Anatomy 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- MNEVGNCIZWZKLR-UHFFFAOYSA-N copper;phenol Chemical compound [Cu].OC1=CC=CC=C1.OC1=CC=CC=C1 MNEVGNCIZWZKLR-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- WXYNCCWBUXKSBG-UHFFFAOYSA-N copper;nitric acid Chemical compound [Cu].O[N+]([O-])=O WXYNCCWBUXKSBG-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of solid-carrying type Cu2The preparation method and applications of O/Cu@ACSs photochemical catalyst belong to field of photocatalytic material, and it is an object of the present invention to provide a kind of be applied to photo catalytic reduction CO2Reaction, shows the solid-carrying type Cu of high absorption capacity, high activity, high stability2The preparation method of O/Cu@ACSs photochemical catalyst, the present invention is using phenols, aldehydes and mantoquita as raw material, and alcohols and triethylamine are surfactant, and polyvinyl alcohol is dispersing agent, using one pot process metallic copper-phenolic resin ball complex.After carbonization-activation, on the one hand, transition metal organic coordination key breaks to form Cu2Cuprous oxide is reduced into simple substance Cu by O, on the other hand, the process of high-temperature activation charing, to obtain high absorption-photo-reduction CO2Solid-carrying type Cu2O/Cu@ACSs spherical shape photochemical catalyst.The present invention relates to raw materials to be easy to get at a low price, preparation process is simple, mild condition, product are stable, is suitble to industrialized production.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of solid-carrying type Cu2O/Cu@ACSs photochemical catalyst
Preparation method and applications.
Background technique
Final product one of of the carbon dioxide as burning, has resulted in energy crisis and a series of environmental pollutions etc. and asks
Topic.Reduce CO2Discharge and realization CO2Resourcable transformation has become and promotes global economic development, new energy and high-tech environmental protection
One of technological development and the strategic project of realization.Photocatalysis CO2Reduction is to utilize high efficiency semiconductor by CO under solar energy effect2
It is reduced into hydrocarbon fuel (such as CO, CH4Or CH3OH) etc..Global warming can not only be alleviated, and sustainable development can be met
Demand.
Polymer-based active carbon, which has, stablizes chemical structure, high surface area and mechanical strength, the pore structure of prosperity and strong suction
The advantages that attached ability, it has also become one of the optimum carrier of high efficiency composition catalysis material system construction.Wherein, phenolic resin conduct
The presoma of polymer-based active carbon ball (ACSs) shows good application prospect.The study found that Cu2O is as a kind of typical
Transition metal oxide, band gap magnitude are about 2.1 eV, have good visible light-responded ability [Journal of Nano
Research, 2011,15 (41): 69-74], it is easy in Cu+And Cu2+Mutually converting between oxidation state effectively realizes oxidation
The progress of reduction reaction, thus in photocatalytic degradation water pollutant (such as MB, Cr (VI)), water hydrogen manufacturing, CO2Reduction etc.
Show superperformance [Chemical Engineering Journal, 2014,255:394-402; Materials
Letters, 2016, 184: 148-151; Nano letters, 2016, 16(3): 1848-1857;
ChemSusChem, 2014, 7(4): 1086-1093】。
Summary of the invention
The purpose of the present invention is to provide one kind to be applied to photo catalytic reduction CO2It is living to show high absorption capacity, height for reaction
The solid-carrying type Cu of property, high stability2The preparation method of O/Cu@ACSs photochemical catalyst, the preparation method cheap, technique with raw material
Simply, be easily manipulated, mild condition the advantages that, loading density is uniform, wear-resistant, corrosion-resistant, regeneration is easy, and solves existing powder
Last catalyst there are the problem of, be convenient for industrialized production.Obtained solid-carrying type Cu2O/Cu@ACSs catalysis material possesses more
Grade cellular structure is CO absorption2Channel and dynamic performance are provided.
The present invention is using phenols, aldehydes and mantoquita as raw material, and alcohols and triethylamine are surfactant, and polyvinyl alcohol is dispersion
Agent synthesizes transition metal-phenolic resin ball complex using one pot process technology, after tube furnace carbonization-activation, transition gold
Belong to Cu organic coordination key and breaks to form Cu2O finally obtains the Cu of multi-stage artery structure, high catalytic activity2O/Cu@ACSs solid-carrying type
Photochemical catalyst.
The present invention adopts the following technical scheme:
A kind of solid-carrying type Cu2The preparation method of O/Cu@ACSs photochemical catalyst, includes the following steps:
The first step is added and contains according to 30~60 parts of phenols of poidometer part, 40-80 parts of aldehyde compounds and 15~35 parts of ethylene glycol
Have a three-necked flask of 200~300 parts of water, stir 0.5~1.5 h, be added 2~5 parts of triethylamines, oil bath pan controlled at 70~
120 DEG C, 0.5~2 h is stirred, mixed solution is obtained；
Second step is added in the mixed solution of the first step according to 5~10 parts of mantoquitas and 1~9 part of polyvinyl alcohol of poidometer part,
60~120 DEG C are maintained the temperature at, the reaction was continued 0.5~2 h, finally, 1~3 part of hexa is added in the above solution,
It filters after 4~8 h of reaction, and is washed with dilute alkaline soln, dry 10~24 h under conditions of 60~100 DEG C obtain transition gold
Belong to copper-phenolic resin ball；
Third step, transition metal copper-phenolic resin ball that second step is obtained be placed in tube furnace select 500 under nitrogen protection~
1000 DEG C are carbonized, and then switching is passed through vapor and activates 1~3 at 700~1000 DEG C with 1.5~5 DEG C/min heating rate
H is down to room temperature after reaction, collects sample, dilute acid wash 3 times, reuses after distilling water washing to neutrality, drying at room temperature
Up to Cu2O/Cu@ACSs solid-carrying type photochemical catalyst.
Phenols described in the first step is phenol, metacresol, to any one in phenyl phenol and 6- tert-butyl-m-cresol
Or two kinds, aldehyde compound is formaldehyde or furfural.
Dilute alkaline soln described in second step is any one in potassium hydroxide, sodium hydroxide and ammonium hydroxide, and mantoquita is nitre
Any one in sour copper, copper acetate and copper chloride.
Diluted acid described in third step is any one in dust technology, sulfuric acid and person's hydrochloric acid.
A kind of solid-carrying type Cu2O/Cu@ACSs photocatalyst applications are in photo-reduction CO2。
The principle of the present invention is as follows:
Transition metal is introduced in the synthesis process of phenolic resin, forms metallic copper-phenolic resin ball complex.In high-temperature activation
Cu2O, and N are formed during charing2By the control for activation temperature under atmosphere, promotes copper and further restore, thus
Lead to the appearance of elemental copper.Ultimately form Cu2O/Cu@ACSs photochemical catalyst.
Beneficial effects of the present invention are as follows:
Present invention containing transition metal Cu in the preparation process of phenolic resin ball forms Cu- phenolic resin ball complex, utilizes
Its unique metal-organic framework structure improves Cu degree of scatter, then its coordinate bond is broken to form Cu by activated charing2O or
It is reduced into simple substance Cu, forms efficient solid-carrying type Cu2O/Cu@active carbon ball (ACSs) visible light catalytic material.It on the one hand, can be by
Vapor catalyst activation procedure pore-creating improves porosity, effective adjustment aperture and cellular structure distribution；On the other hand, Cu2O/
Its high-specific surface area of Cu@ACSs spherical catalyst material use, hierarchical porous structure promote CO2Adsorption activation, own electronic in addition
Conducting power facilitates photo-generated carrier transmitting and conveying, and then enhances its photo-catalysis capability.Importantly, solid-carrying type
Cu2O/Cu@ACSs system had not only solved fine catalyst and has been difficult to the sciences problems recycled but also can promote CO2Resourcable transformation institute
Need the development of industrial catalyst.
Compared with prior art, the present invention has the advantage that
1) catalyst method prepared by the present invention is simple, reacts easily controllable.
2) catalyst prepared by the present invention is solid-carrying type Cu2O/Cu@ACSs has multi-stage artery structure.
3) catalyst prepared by the present invention has excellent photo catalytic reduction CO2Performance.
4) preparation process of the invention and CO2Reduction process is all laboratory commonly used equipment, and process flow is simple, it is low at
This, low energy consumption.
5) catalyst prepared by the present invention is suitble to industrial production, to solution CO2Environmental problem caused by excessive discharge
With good actual application prospect.For photo-reduction CO2Performance test, the selectivity 100% of gas-phase product CO, ultraviolet light,
The CO yield that visible light and simulated solar irradiation irradiate lower 4 h is 10-67 μm of olg-1。
Detailed description of the invention
Fig. 1 is the solid-carrying type Cu prepared in embodiment 12X-ray diffraction (XRD) figure of O/Cu@ACSs photochemical catalyst；
Fig. 2 is the solid-carrying type Cu prepared in embodiment 12Scanning electron microscope (SEM) figure of O/Cu@ACSs photochemical catalyst；
Fig. 3 is the solid-carrying type Cu prepared in embodiment 12The hierarchical porous structure SEM of O/Cu@ACSs photochemical catalyst schemes；
Fig. 4 is the solid-carrying type Cu prepared in embodiment 12The SEM mapping of O/Cu@ACSs photochemical catalyst schemes；
Fig. 5 is the solid-carrying type Cu prepared in embodiment 1-42O/Cu@ACSs photochemical catalyst is used for photo-reduction CO2Performance test is in purple
Outer light, visible light and simulated solar irradiation irradiate the CO yield histogram of lower 4 h.
Specific embodiment
Embodiment 1
(1) the three of 200 parts of water is filled according to 35 parts of phenol of poidometer part, 50 parts of Furnan products and 15 parts of ethylene glycol additions
3 parts of triethylamines are added in mouth flask, 0.5 h of stir about, and oil bath pan stirs 0.5 h controlled at 95 DEG C.It (2) will be according to 5 parts
Copper acetate and 4 parts of polyethylene sodium alkoxide are added in the mixed solution of above-mentioned steps (1), maintain the temperature at 95 DEG C, and the reaction was continued 0.5
H is filtered, and washed with ammonia spirit, 70 finally, 1.5 parts of hexas are added in the above solution after reacting 5 h
Dry 12 h, obtain transition metal copper-phenolic resin ball under conditions of DEG C.(3) transition metal copper-phenol for obtaining above-mentioned (2)
Urea formaldehyde ball is placed in tube furnace and selects 550 DEG C to be carbonized under nitrogen protection, and then switching is passed through vapor with 1.5 DEG C/min
Heating rate is down to room temperature after reaction, collects sample, washed 3 times with dust technology, reuse steaming in 750 DEG C of 1.5 h of activation
Distilled water is washed to neutrality, and drying at room temperature is up to Cu2O/Cu@ACSs solid-carrying type photochemical catalyst.It (4) will be solid made from above-mentioned (3)
Load type Cu2O/Cu@ACSs photochemical catalyst is used for photo-reduction CO2Performance test, the photocatalysis CO2The condition of reduction are as follows: catalysis
Agent dosage is 0.3 g, 50 mL of amount of aqueous solution used, apart from 20 cm of reaction interface.The selectivity 100% of its gas-phase product CO, in purple
The CO yield that outer light, visible light and simulated solar irradiation irradiate the CO yield of lower 4 h is 66.8,27.9,47.2 μm of olg-1。
It can be found that the catalyst is made of tri- kinds of elements of C, O, Cu from Fig. 4, and Cu is evenly distributed on active carbon ball
Surface.
Embodiment 2
(1) the three of 200 parts of water is filled according to 30 parts of phenol of poidometer part, 40 parts of Furnan products and 15 parts of ethylene glycol additions
2 parts of triethylamines are added in mouth flask, 0.5 h of stir about, and oil bath pan stirs 0.5 h controlled at 80 DEG C.It (2) will be according to 5 parts
Copper nitrate and 2 parts of polyvinyl alcohol are added in the mixed solution of above-mentioned steps (1), maintain the temperature at 90 DEG C, and the reaction was continued 0.5
H is filtered, and washed with potassium hydroxide solution finally, 1 part of hexa is added in the above solution after reacting 4h,
Dry 10 h, obtain transition metal copper-phenolic resin ball under conditions of 60 DEG C.(3) transition metal copper-for obtaining above-mentioned (2)
Phenolic resin ball is placed in tube furnace and selects 500 DEG C to be carbonized under nitrogen protection, then switching be passed through vapor with 1.5 DEG C/
Min heating rate is down to room temperature after reaction, collects sample, washed 3 times, reused with dilute hydrochloric acid in 700 DEG C of 1 h of activation
After distilling water washing to neutrality, drying at room temperature is up to Cu2O/Cu@ACSs solid-carrying type photochemical catalyst.(4) above-mentioned (3) are obtained
Solid-carrying type Cu2O/Cu@ACSs photochemical catalyst is used for photo-reduction CO2Performance test, the photocatalysis CO2The condition of reduction are as follows: urge
Agent dosage is 0.3 g, 50 mL of amount of aqueous solution used, apart from 20 cm of reaction interface.The selectivity 100% of its gas-phase product CO,
The CO yield that ultraviolet light, visible light and simulated solar irradiation irradiate lower 4 h is 42.1,12.9,29.3 μm of olg-1。
Embodiment 3
(1) the three of 250 parts of water is filled according to 40 parts of phenol of poidometer part, 60 parts of Furnan products and 15 parts of ethylene glycol additions
3 parts of triethylamines are added in mouth flask, 1 h of stir about, and oil bath pan stirs 1h controlled at 100 DEG C.It (2) will be according to 5 parts of nitric acid
Copper and 5 parts of polyvinyl alcohol are added in the mixed solution of above-mentioned steps (1), maintain the temperature at 100 DEG C, the reaction was continued 1 h, most
Afterwards, 2 parts of hexas are added in the above solution, are filtered after reacting 5 h, and washed with diluted sodium hydroxide solution, 60
Dry 15 h, obtain transition metal copper-phenolic resin ball under conditions of DEG C.(3) transition metal copper-phenol for obtaining above-mentioned (2)
Urea formaldehyde ball is placed in tube furnace and selects 600 DEG C to be carbonized under nitrogen protection, and then switching is passed through vapor with 2 DEG C/min liter
Warm rate is down to room temperature after reaction, collects sample, washed 3 times with dilute hydrochloric acid, reuse distillation in 800 DEG C of 1.5 h of activation
After water washing to neutrality, drying at room temperature is up to Cu2O/Cu@ACSs solid-carrying type photochemical catalyst.It (4) will be immobilized made from above-mentioned (3)
Type Cu2O/Cu@ACSs photochemical catalyst is used for photo-reduction CO2Performance test, the photocatalysis CO2The condition of reduction are as follows: catalyst
Dosage is 0.3 g, 50 mL of amount of aqueous solution used, apart from 20 cm of reaction interface.The selectivity 100% of its gas-phase product CO, ultraviolet
The CO yield that light, visible light and simulated solar irradiation irradiate lower 4 h is 33.6,10.2,19.3 μm of olg-1。
Embodiment 4
(1) the three of 300 parts of water is filled according to 50 parts of phenol of poidometer part, 70 parts of Furnan products and 30 parts of ethylene glycol additions
4 parts of triethylamines are added in mouth flask, 1.5 h of stir about, and oil bath pan stirs 1.5h controlled at 110 DEG C.It (2) will be according to 8 parts
Copper nitrate and 7 parts of polyethylene sodium alkoxide are added in the mixed solution of above-mentioned steps (1), maintain the temperature at 110 DEG C, and the reaction was continued 1
H is filtered, and washed with diluted sodium hydroxide solution finally, 3 parts of hexas are added in the above solution after reacting 6 h,
Dry 18 h, are obtained modeling metallic copper-phenolic resin ball under conditions of 60 DEG C.(3) transition metal for obtaining above-mentioned (2)
Copper-phenolic resin ball is placed in tube furnace and selects 650 DEG C to be carbonized under nitrogen protection, then switching be passed through vapor with 2 DEG C/
Min heating rate is down to room temperature after reaction, collects sample, washed 3 times, reused with dilute hydrochloric acid in 850 DEG C of 2 h of activation
After distilling water washing to neutrality, drying at room temperature is up to Cu2O/Cu@ACSs solid-carrying type photochemical catalyst.(4) above-mentioned (3) are obtained
Solid-carrying type Cu2O/Cu@ACSs photochemical catalyst is used for photo-reduction CO2Performance test, the photocatalysis CO2The condition of reduction are as follows: urge
Agent dosage is 0.3 g, 50 mL of amount of aqueous solution used, apart from 20 cm of reaction interface.The selectivity 100% of its gas-phase product CO,
The CO yield that ultraviolet light, visible light and simulated solar irradiation irradiate lower 4 h is 46.5,22.5,31.7 μm of olg-1。
Claims (5)
1. a kind of solid-carrying type Cu2The preparation method of O/Cu@ACSs photochemical catalyst, characterized by the following steps:
The first step is added and contains according to 30~60 parts of phenols of poidometer part, 40-80 parts of aldehyde compounds and 15~35 parts of ethylene glycol
Have a three-necked flask of 200~300 parts of water, stir 0.5~1.5 h, be added 2~5 parts of triethylamines, oil bath pan controlled at 70~
120 DEG C, 0.5~2 h is stirred, mixed solution is obtained；
Second step is added in the mixed solution of the first step according to 5~10 parts of mantoquitas and 1~9 part of polyvinyl alcohol of poidometer part,
60~120 DEG C are maintained the temperature at, the reaction was continued 0.5~2 h, finally, 1~3 part of hexa is added in the above solution,
It filters after 4~8 h of reaction, and is washed with dilute alkaline soln, dry 10~24 h under conditions of 60~100 DEG C obtain transition gold
Belong to copper-phenolic resin ball；
Third step, transition metal copper-phenolic resin ball that second step is obtained be placed in tube furnace select 500 under nitrogen protection~
1000 DEG C are carbonized, and then switching is passed through vapor and activates 1~3 at 700~1000 DEG C with 1.5~5 DEG C/min heating rate
H is down to room temperature after reaction, collects sample, dilute acid wash 3 times, reuses after distilling water washing to neutrality, drying at room temperature
Up to Cu2O/Cu@ACSs solid-carrying type photochemical catalyst.
2. a kind of solid-carrying type Cu according to claim 12The preparation method of O/Cu@ACSs photochemical catalyst, it is characterised in that:
Phenols described in the first step is phenol, metacresol, to any one or two kinds in phenyl phenol and 6- tert-butyl-m-cresol, aldehyde
Class compound is formaldehyde or furfural.
3. a kind of solid-carrying type Cu according to claim 12The preparation method of O/Cu@ACSs photochemical catalyst, it is characterised in that:
Dilute alkaline soln described in second step is any one in potassium hydroxide, sodium hydroxide and ammonium hydroxide, and mantoquita is copper nitrate, acetic acid
Any one in copper and copper chloride.
4. a kind of solid-carrying type Cu according to claim 12The preparation method of O/Cu@ACSs photochemical catalyst, it is characterised in that:
Diluted acid described in third step is any one in dust technology, sulfuric acid and person's hydrochloric acid.
5. a kind of solid-carrying type Cu using the preparation of preparation method described in claim 1 ~ 4 any one2O/Cu@ACSs photocatalysis
Agent is applied to photo-reduction CO2。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111992218A (en) * | 2020-03-17 | 2020-11-27 | 武汉纺织大学 | Copper-based catalyst for degrading antibiotics and preparation method thereof |
| CN116459858A (en) * | 2023-04-27 | 2023-07-21 | 天津工业大学 | Cu (I) single-site solid catalyst and preparation method and application thereof |
| CN116651453A (en) * | 2023-05-31 | 2023-08-29 | 南京工业大学 | Cu synthesized by thermal decomposition 2 O/Cu heterostructure nano material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003088753A (en) * | 2001-09-19 | 2003-03-25 | Sumitomo Electric Ind Ltd | REDOX REACTION APPARATUS, HYDROGEN AND OXYGEN PRODUCTION METHOD, CARBON DIOXIDE FIXATION METHOD, COMPOUND PRODUCTION METHOD, Cu2O STABILIZATION METHOD, AND Cu2O STABILIZED SOLUTION |
| CN105170189A (en) * | 2015-09-23 | 2015-12-23 | 太原理工大学 | Preparation method of spherical BiOBr/NiO@ACSs composite photocatalyst |
| CN105521783A (en) * | 2016-01-05 | 2016-04-27 | 北京林业大学 | Biomass carbon base and copper and/or cuprous oxide hybrid material, and preparation method thereof |
| CN106540694A (en) * | 2016-11-01 | 2017-03-29 | 辽宁石油化工大学 | Copper-based MOF materials prepare the Cu of porous carbon load2The method of O/Cu composites and its application |
-
2019
- 2019-06-14 CN CN201910514517.5A patent/CN110180543A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003088753A (en) * | 2001-09-19 | 2003-03-25 | Sumitomo Electric Ind Ltd | REDOX REACTION APPARATUS, HYDROGEN AND OXYGEN PRODUCTION METHOD, CARBON DIOXIDE FIXATION METHOD, COMPOUND PRODUCTION METHOD, Cu2O STABILIZATION METHOD, AND Cu2O STABILIZED SOLUTION |
| CN105170189A (en) * | 2015-09-23 | 2015-12-23 | 太原理工大学 | Preparation method of spherical BiOBr/NiO@ACSs composite photocatalyst |
| CN105521783A (en) * | 2016-01-05 | 2016-04-27 | 北京林业大学 | Biomass carbon base and copper and/or cuprous oxide hybrid material, and preparation method thereof |
| CN106540694A (en) * | 2016-11-01 | 2017-03-29 | 辽宁石油化工大学 | Copper-based MOF materials prepare the Cu of porous carbon load2The method of O/Cu composites and its application |
Non-Patent Citations (2)
| Title |
|---|
| CHANGMING ZHANG ET AL.，: "Synthesis of CeO2-modified activated carbon spheres by grafting and coordinating reactions for elemental mercury removal", 《J MATER SCI》 * |
| YINHUI LI ET AL.，: "Synthesis and photocatalytic activity of carbon spheres loaded Cu2O/Cu composites", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111992218A (en) * | 2020-03-17 | 2020-11-27 | 武汉纺织大学 | Copper-based catalyst for degrading antibiotics and preparation method thereof |
| CN116459858A (en) * | 2023-04-27 | 2023-07-21 | 天津工业大学 | Cu (I) single-site solid catalyst and preparation method and application thereof |
| CN116651453A (en) * | 2023-05-31 | 2023-08-29 | 南京工业大学 | Cu synthesized by thermal decomposition 2 O/Cu heterostructure nano material and preparation method and application thereof |
| CN116651453B (en) * | 2023-05-31 | 2024-10-15 | 南京工业大学 | Cu synthesized by thermal decomposition2O/Cu heterostructure nano material and preparation method and application thereof |
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