CN110327956A - A kind of preparation method of copper oxide and the compound heterojunction photocatalyst of carbonitride - Google Patents
A kind of preparation method of copper oxide and the compound heterojunction photocatalyst of carbonitride Download PDFInfo
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- CN110327956A CN110327956A CN201910511587.5A CN201910511587A CN110327956A CN 110327956 A CN110327956 A CN 110327956A CN 201910511587 A CN201910511587 A CN 201910511587A CN 110327956 A CN110327956 A CN 110327956A
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 16
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 12
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 title claims abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000013148 Cu-BTC MOF Substances 0.000 claims abstract description 34
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 claims abstract description 34
- 238000009833 condensation Methods 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 230000005494 condensation Effects 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000005286 illumination Methods 0.000 abstract description 4
- 229960002163 hydrogen peroxide Drugs 0.000 description 32
- 239000000243 solution Substances 0.000 description 17
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 16
- 238000005070 sampling Methods 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 14
- 229960004756 ethanol Drugs 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000013084 copper-based metal-organic framework Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229960000789 guanidine hydrochloride Drugs 0.000 description 1
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- -1 melamine Amine Chemical class 0.000 description 1
- 229920005588 metal-containing polymer Polymers 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002760 rocket fuel Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention provides the preparation method of a kind of copper oxide and the compound heterojunction photocatalyst of carbonitride, and steps are as follows for the preparation method: preparing Cu-BTC first, then using melamine as presoma, prepares g-C with the method for thermal condensation3N4；Then using oxygen to blocky g-C3N4It is removed, obtains the g-C of sheet3N4；Finally by the g-C of Cu-BTC and sheet3N4After mixing, it is treated thermally to produce CuO/g-C under inert gas protection3N4Heterojunction composite.The high, light induced electron with specific surface area and the separation rate in hole of the heterojunction photocatalyst of the method for the present invention preparation are high, forbidden bandwidth is small, and the advantages that visible light illumination utilization rate, it is a kind of catalysis material of environment-friendly type, the photocatalysis that can be used under visible light prepares hydrogen peroxide.
Description
[technical field]
The present invention relates to a kind of preparation methods of carbonitride base composite photocatalyst, and in particular to a kind of copper oxide and nitridation
The preparation method of the compound heterojunction photocatalyst of carbon.
[background technique]
Hydrogen peroxide has important answer as a kind of Green Oxidant, in fields such as organic synthesis, water process, catalysis
With.It is anthraquinone to be widely used to industrial production hydrogen peroxide.But this method energy consumption is big, is not suitable for current chemical industry and uses
The technology of " green, energy-saving and environmental protection ".In recent years, photocatalysis hydrogen phosphide production technology causes the great interest of researcher.
It is a kind of height with broad prospect of application that oxygen, which is reacted by Double electron reduction and reacts generation hydrogen peroxide with the hydrogen ion in water,
Energy product, is widely used in various fields, has both the double action of Oxidizing and Reducing Agents.It is a kind of ring in environment remediation
The oxidant (its byproduct is only water and oxygen) of border safety, is usually used in removing organic impurities in wastewater treatment process.In medical treatment
Field, it can be used for sterilizing wound and Surigical tool.Importantly, hydrogen peroxide can be used as rocket fuel, it can also
For fuel cell, generate electricity using water and oxygen as byproduct.In order to meet the needs of to hydrogen peroxide, conventional production methods are eliminated
Deficiency, exploitation efficiently, economic, green hydrogen peroxide manufacture technology be particularly important, solar energy is converted into chemical fuel
As a kind of very important approach.Recently, researcher's discovery can produce hydrogen peroxide by conductor photocatalysis process.
During these, in presence of water, the photo-reduction of oxygen can produce hydrogen peroxide.Due to related driving force, sun
Abundant and reproducibility, the conductor photocatalysis process of light cause the extensive concern of people.However, due to their broadband
Gap, their photoresponse is only limitted to ultraviolet region, and ultraviolet light only accounts for the 4% of solar spectrum.Recently, many researcher's hairs
Existing, under visible light, oxygen reduction can be hydrogen peroxide by graphite phase carbon nitride.
Graphitic carbon nitride is a kind of no metal-containing polymer n-type semiconductor, has unique electricity, optics, structure and object
Physicochemical property.As a kind of novel no metal-polymer semiconductor, graphite phase carbon nitride has very big with other semiconductors
Difference, it can also be readily formed various highly selective hydridization photochemical catalysts.Therefore, pass through modification appropriate, exploitation
It is meaningful for being suitable for graphite phase carbon nitride based photocatalyst for various purposes out.Graphite phase carbon nitride also has one to be suitble to
In the conduction band positions of various reduction reactions, electronic band structure appropriate is conducive to the formation of graphite phase carbon nitride.Graphite-phase nitrogen
Changing carbon can be easily with low cost preparation.Several low cost nitrogen-rich organic solid precursors, such as urea, thiocarbamide, melamine
Amine, dicyandiamide, cyanamide and guanidine hydrochloride carry out condensation reaction in air or inert atmosphere at 500-600 DEG C can produce nitridation
Carbon.In order to improve the catalytic performance of graphite phase carbon nitride based photocatalyst, all different photocatalysis stages, should consider simultaneously and
Optimize ownership, charge excitation, electric charge transfer, migration and separation and surface charge utilizes.In addition, its conduction band current potential than oxygen/
Hydrogen peroxide reduction potential is more negative.Therefore, graphite phase carbon nitride can be dynamically by oxygen reduction at hydrogen peroxide.However, photoproduction
Electron hole pair low separation efficiency, it is seen that light utilization efficiency is poor, limits its practical application.In order to improve above situation, the application
Using melamine as presoma, ultra-thin graphite phase carbon nitride is constructed by the method for thermal condensation, is re-introduced into Cu-BTC's
Derivative CuO, with g-C3N4Heterojunction structure is formed, charge transport rate is substantially increased, improves the separative efficiency of carrier,
Improve the generation efficiency of hydrogen peroxide.
[summary of the invention]
The technical problem to be solved in the present invention is to provide a kind of copper oxide and the compound heterojunction photocatalyst of carbonitride
Preparation method, high, light induced electron and hole the separation rate with specific surface area of the heterojunction photocatalyst of this method preparation
The advantages that high, forbidden bandwidth is small and visible light illumination utilization rate, is a kind of catalysis material of environment-friendly type, be can be used for can
Photocatalysis under light-exposed prepares hydrogen peroxide.
The present invention is implemented as follows:
A kind of preparation method of copper oxide and the compound heterojunction photocatalyst of carbonitride, the preparation method step is such as
Under:
Cu-BTC is prepared first, then using melamine as presoma, prepare g-C with the method for thermal condensation3N4；Then it uses
Oxygen is to blocky g-C3N4It is removed, obtains the g-C of sheet3N4；Finally by the g-C of Cu-BTC and sheet3N4After mixing, lazy
CuO/g-C is treated thermally to produce under property gas shield3N4Heterojunction composite.
Further, the preparation method step is specific as follows:
Cu-BTC is prepared first, then using melamine as presoma, prepare g-C with the method for thermal condensation3N4, wherein temperature
It is 500-520 DEG C, time 60-180min；Then it is etched with oxygen, it is removed to obtain sheet g-C3N4, wherein temperature
It is 400-520 DEG C, time 60-360min；
By Cu-BTC and sheet g-C3N4It is mixed according to mass ratio 1:100-1:1, under inert gas protection through tube furnace heat
Processing obtains CuO/g-C at 400-520 DEG C3N4Hetero-junctions recovers condensation material.
Further, with CuO/g-C3N4Heterojunction composite makees photochemical catalyst, is placed in water and alcohol mixed solution,
Hydrogen peroxide is prepared under visible light illumination condition.
The present invention has the advantage that
The legal formation bulk g-C of simple pyrocondensation is utilized in the present invention3N4, and pass through secondary heat treatment, it is shelled
From obtaining sheet g-C3N4, finally by the Cu-BTC prepared and sheet g-C3N4It is thermally treated to obtain CuO/g- after mixing
C3N4, on the one hand this structure largely increases the specific surface area of catalyst, increases the active sites of light-catalyzed reaction
Point, another aspect heterojunction structure increases the transmission of electric charge carrier, separative efficiency, for preparing peroxidating under visible light
Hydrogen has very big application value.
Therefore, compared with traditional carbonitride catalysis material, thin slice carbonitride prepared by the present invention has high-ratio surface
Product advantage introduces the CuO nanocrystal after Cu-BTC derives, the separation rate in light induced electron and hole not only can be improved, also subtract
The advantages that small forbidden bandwidth, raising visible light illumination utilization rate, it is a kind of catalysis material of environment-friendly type, can be used in visible light
Under photocatalysis prepare hydrogen peroxide.
[Detailed description of the invention]
The present invention is further illustrated in conjunction with the embodiments with reference to the accompanying drawings.
Fig. 1 is Cu-BTC, g-C prepared by the embodiment of the present invention 13N4And CuO/g-C3N4SEM figure.
Fig. 2 is g-C prepared by the embodiment of the present invention 13N4And CuO/g-C3N4XRD diagram.
[specific embodiment]
Refering to fig. 1-2, the present invention relates to the preparation method of a kind of copper oxide and the compound heterojunction photocatalyst of carbonitride,
Steps are as follows for the preparation method:
Cu-BTC is prepared first, then using melamine as presoma, prepare g-C with the method for thermal condensation3N4；Then it uses
Oxygen is to blocky g-C3N4It is removed, obtains the g-C of sheet3N4；Finally by the g-C of Cu-BTC and sheet3N4After mixing, lazy
CuO/g-C is treated thermally to produce under property gas shield3N4Heterojunction composite.
The preparation method step is specific as follows:
Cu-BTC is prepared first, then using melamine as presoma, prepare g-C with the method for thermal condensation3N4, wherein temperature
It is 500-520 DEG C, time 60-180min；Then it is etched with oxygen, it is removed to obtain sheet g-C3N4, wherein temperature
It is 400-520 DEG C, time 60-360min；
By Cu-BTC and sheet g-C3N4It is mixed according to mass ratio 1:100-1:1, under inert gas protection through tube furnace heat
Processing obtains CuO/g-C at 400-520 DEG C3N4Hetero-junctions recovers condensation material.
With CuO/g-C3N4Heterojunction composite makees photochemical catalyst, is placed in water and alcohol mixed solution, in visible light
Hydrogen peroxide is prepared according under the conditions of, with the content of POD/DPD method test hydrogen peroxide.
The present invention is further described below in conjunction with specific embodiment.
A kind of preparation method of copper oxide and the compound heterojunction photocatalyst of carbonitride, the specific steps are as follows:
Embodiment 1:
1, the preparation of Cu-BTC: weighing 2.72g copper acetate and be dissolved in the mixed solution of 72mL water, ethyl alcohol and DMF, ultrasound point
It dissipates；The trimesic acid of 1.47g is added to again in the mixed solution of 36mL water, ethyl alcohol and DMF；By the mixing of trimesic acid
Solution is slowly dropped in the mixed solution of copper acetate, and reaction for 24 hours, after reaction, uses DMF, water, ethanol washing respectively.
2, sheet g-C3N4Preparation: weigh 2g melamine, 2 DEG C/min is warming up to 500 DEG C, keep the temperature two hours, 2 DEG C/
Min is warming up to 520 DEG C, then keeps the temperature two hours.Grinding is taken out, 2 DEG C/min is warming up to 520 DEG C under conditions of oxygen, keeps the temperature 4h.
3、CuO/g-C3N4The preparation of hetero-junctions recovery condensation material: Cu-BTC and g-C are taken3N4(mass ratio 1:1) is in small porcelain
In boat, 500 DEG C of heat treatment 1h obtain CuO/g-C in the state of argon gas protection3N4Hetero-junctions recovers condensation material.
4、CuO/g-C3N4Hetero-junctions recovery condensation material prepares the performance test of hydrogen peroxide as photochemical catalyst: measuring
0.1g photochemical catalyst, 90mL water, 10mL dehydrated alcohol is carried out in the dark magnetic agitation in photocatalytic reaction device, under the conditions of being protected from light
It carries out sampling 4mL after 30min is secretly adsorbed, the radiation of visible light that visible light carries out 360min to solution is opened after sampling, and in light
Separately sampled 4mL when reaching 1h, 2h, 3h, 4h, 5h, 6h according to the time, all sampling solution is after sampling immediately with filter membrane mistake
Filter is put into shading in 5mL centrifuge tube and seals, and takes 1mL reaction solution to have in plug graded tube before test in 10mL, deionized water 4mL is added
Configured good color developing agent is added afterwards, with the absorbance of ultravioletvisible absorption optical detector measurement hydrogenperoxide steam generator.It is obtained
Hydrogen peroxide concentration 0.62mmol/L.
Fig. 1 is Cu-BTC, g-C prepared by embodiment 13N4And CuO/g-C3N4SEM figure, (a) in Fig. 1 is Cu-BTC
SEM figure, (b) be g-C3N4SEM figure, (c) be CuO/g-C3N4SEM figure；From figure 1 it appears that Cu-BTC is in positive eight
Face body structure, side length are 2.5um or so；G-C of the carbon nitride precursor melamine after two-step thermal processing3N4Totally in the form of sheets
Structure, length and width dimensions are in 0.5-1um, and thickness is about 0.1um, and the g-C after loaded Cu-BTC3N4After heat treatment, whole still to protect
A nanometer plate shape, length and width dimensions size 0.3-0.5um are held, thickness is about 0.05um, and nanometer sheet surface or interlayer appearance are much received
The CuO nano particle that rice grain, as Cu-BTC derive illustrates the CuO nano particle derived through Cu-BTC successfully
It is supported on g-C3N4In nanometer sheet.
Fig. 2 is g-C prepared by embodiment 13N4And CuO/g-C3N4XRD diagram；As shown in Fig. 2, the XRD diffraction of Cu-BTC
It is kissed at 9.4 °, 10.0 °, 11.1 °, 11.7 °, 13.7 °, 17.2 °, 18.6 °, 22.1 ° and 28.6 ° with MOF199 standard x RD at peak
It closes.g-C3N4XRD diffraction maximum at 13.2 ° and 27.6 ° there are two apparent characteristic peak, correspond respectively to (100) and (002)
Two crystal faces, g-C3N4Heat treatment obtains the g-C of area load CuO after composite Cu-MOF3N4, You Tuzhong XRD it is found that in addition to
(100) and (002) two C3N4Outside representative crystal face, there are 35.50 ° and 38.68 ° of two new diffraction maximums, respectively represent CuO
In (002) and (111) crystal face, meet the crystal face in copper oxide (PDF#45-0937) standard card and its position, illustrate Cu-BTC
It has been converted to CuO and and g-C3N4Form heterojunction structure.
Embodiment 2
1, the preparation of Cu-BTC: weighing 2.72g copper acetate and be dissolved in the mixed solution of 72mL water, ethyl alcohol and DMF, ultrasound point
It dissipates；The trimesic acid of 1.47g is added to again in the mixed solution of 36mL water, ethyl alcohol and DMF；By the mixing of trimesic acid
Solution is slowly dropped in the mixed solution of copper acetate, is reacted later for 24 hours, uses DMF, water, ethanol washing after reaction respectively.
2, sheet g-C3N4Preparation: weigh 2g melamine, 2 DEG C/min is warming up to 500 DEG C, keep the temperature two hours, 2 DEG C/
Min is warming up to 520 DEG C, then keeps the temperature two hours.Grinding is taken out, has 2 DEG C/min under conditions of oxygen to be warming up to 520 DEG C, keeps the temperature 6h.
3、CuO/g-C3N4The preparation of hetero-junctions recovery condensation material: Cu-BTC and g-C are taken3N4(mass ratio 1:1) is in small porcelain
In boat, 500 DEG C of calcining 1h obtain CuO/g-C in the state of argon gas protection3N4Hetero-junctions recovers condensation material.
4、CuO/g-C3N4Hetero-junctions recovery condensation material prepares the performance test of hydrogen peroxide as photochemical catalyst: measuring
0.1g photochemical catalyst, 90mL water, 10mL dehydrated alcohol is carried out in the dark magnetic agitation in photocatalytic reaction device, under the conditions of being protected from light
It carries out sampling 4mL after 30min is secretly adsorbed, the radiation of visible light that visible light carries out 360min to solution is opened after sampling, and in light
Separately sampled 4mL when reaching 1h, 2h, 3h, 4h, 5h, 6h according to the time, all sampling solution is after sampling immediately with filter membrane mistake
Filter is put into shading in 5mL centrifuge tube and seals, and takes 1mL reaction solution to have in plug graded tube before test in 10mL, deionized water 4mL is added
Configured good color developing agent is added afterwards, with the absorbance of ultravioletvisible absorption optical detector measurement hydrogenperoxide steam generator.It is obtained
Hydrogen peroxide concentration 0.81mmol/L.
Embodiment 3
1, the preparation of Cu-BTC: weighing 2.72g copper acetate and be dissolved in the mixed solution of 72mL water, ethyl alcohol and DMF, ultrasound point
It dissipates；The trimesic acid of 1.47g is added to again in the mixed solution of 36mL water, ethyl alcohol and DMF；By the mixing of trimesic acid
Solution is slowly dropped in the mixed solution of copper acetate, is reacted later for 24 hours, uses DMF, water, ethanol washing respectively after reaction.
2, sheet g-C3N4Preparation: weigh 2g melamine, 2 DEG C/min is warming up to 500 DEG C, keep the temperature two hours, 2 DEG C/
Min is warming up to 520 DEG C, keeps the temperature two hours.Grinding is taken out, has 2 DEG C/min under conditions of oxygen to be warming up to 520 DEG C, keeps the temperature 4h.
3、CuO/g-C3N4The preparation of hetero-junctions recovery condensation material: Cu-BTC and g-C are taken3N4(mass ratio 1:10) is in small
In porcelain boat, 500 DEG C of calcining 1h obtain CuO/g-C in the state of argon gas protection3N4Hetero-junctions recovers condensation material.
4、CuO/g-C3N4Hetero-junctions recovery condensation material prepares the performance test of hydrogen peroxide as photochemical catalyst: measuring
0.1g photochemical catalyst, 90mL water, 10mL dehydrated alcohol is carried out in the dark magnetic agitation in photocatalytic reaction device, under the conditions of being protected from light
It carries out sampling 4mL after 30min is secretly adsorbed, the radiation of visible light that visible light carries out 360min to solution is opened after sampling, and in light
Separately sampled 4mL when reaching 1h, 2h, 3h, 4h, 5h, 6h according to the time, all sampling solution is after sampling immediately with filter membrane mistake
Filter is put into shading in 5mL centrifuge tube and seals, and takes 1mL reaction solution to have in plug graded tube before test in 10mL, deionized water 4mL is added
Configured good color developing agent is added afterwards, with the absorbance of ultravioletvisible absorption optical detector measurement hydrogenperoxide steam generator.It is obtained
Hydrogen peroxide concentration 1.0mmol/L.
Embodiment 4
1, the preparation of Cu-BTC: weighing 2.72g copper acetate and be dissolved in the mixed solution of 72mL water, ethyl alcohol and DMF, ultrasound point
It dissipates；The trimesic acid of 1.47g is added to again in the mixed solution of 36mL water, ethyl alcohol and DMF；By the mixing of trimesic acid
Solution is slowly dropped in the mixed solution of copper acetate, is reacted later for 24 hours, uses DMF, water, ethanol washing respectively after reaction.
2, sheet g-C3N4Preparation: weigh 2g melamine, 2 DEG C/min is warming up to 500 DEG C, keep the temperature two hours, 2 DEG C/
Min is warming up to 520 DEG C, keeps the temperature two hours.Grinding is taken out, has 2 DEG C/min under conditions of oxygen to be warming up to 520 DEG C, keeps the temperature 6h.
3、CuO/g-C3N4The preparation of hetero-junctions recovery condensation material: Cu-BTC and g-C are taken3N4(mass ratio 1:10) is in small
In porcelain boat, 500 DEG C of calcining 1h obtain CuO/g-C in the state of argon gas protection3N4Hetero-junctions recovers condensation material.
4、CuO/g-C3N4Hetero-junctions recovery condensation material prepares the performance test of hydrogen peroxide as photochemical catalyst: measuring
0.1g photochemical catalyst, 90mL water, 10mL dehydrated alcohol is carried out in the dark magnetic agitation in photocatalytic reaction device, under the conditions of being protected from light
It carries out sampling 4mL after 30min is secretly adsorbed, the radiation of visible light that visible light carries out 360min to solution is opened after sampling, and in light
Separately sampled 4mL when reaching 1h, 2h, 3h, 4h, 5h, 6h according to the time, all sampling solution is after sampling immediately with filter membrane mistake
Filter is put into shading in 5mL centrifuge tube and seals, and takes 1mL reaction solution to have in plug graded tube before test in 10mL, deionized water 4mL is added
Configured good color developing agent is added afterwards, with the absorbance of ultravioletvisible absorption optical detector measurement hydrogenperoxide steam generator.It is obtained
Hydrogen peroxide concentration 1.2mmol/L.
The legal formation bulk g-C of simple pyrocondensation is utilized in the present invention3N4, and pass through secondary heat treatment, it is shelled
From obtaining sheet g-C3N4, finally by the Cu-BTC prepared and sheet g-C3N4It is thermally treated to obtain CuO/g- after mixing
C3N4, on the one hand this structure largely increases the specific surface area of catalyst, increases the active sites of light-catalyzed reaction
Point, another aspect heterojunction structure increase the transmission of electric charge carrier, separative efficiency, improve the production effect of hydrogen peroxide
Rate, and for preparing hydrogen peroxide under visible light with very big application value.
In short, CuO/g-C prepared by the present invention3N4Hetero-junctions composite catalyst can replace existing nitridation carbons light to urge
Change material, not only generates the higher hydrogen peroxide of content, and show preferable photocatalysis performance and stability, preparation process
Simply, belong to a kind of environmentally friendly material.
Although specific embodiments of the present invention have been described above, those familiar with the art should be managed
Solution, we are merely exemplary described specific embodiment, rather than for the restriction to the scope of the present invention, it is familiar with this
The technical staff in field should be covered of the invention according to modification and variation equivalent made by spirit of the invention
In scope of the claimed protection.
Claims (3)
1. the preparation method of a kind of copper oxide and the compound heterojunction photocatalyst of carbonitride, it is characterised in that: the preparation side
Steps are as follows for method:
Cu-BTC is prepared first, then using melamine as presoma, prepare g-C with the method for thermal condensation3N4；Then oxygen is used
To blocky g-C3N4It is removed, obtains the g-C of sheet3N4；Finally by the g-C of Cu-BTC and sheet3N4After mixing, in indifferent gas
CuO/g-C is treated thermally to produce under body protection3N4Heterojunction composite.
2. the preparation method of a kind of copper oxide according to claim 1 and the compound heterojunction photocatalyst of carbonitride,
Be characterized in that: the preparation method step is specific as follows:
Cu-BTC is prepared first, then using melamine as presoma, prepare g-C with the method for thermal condensation3N4, wherein temperature be
500-520 DEG C, time 60-180min；Then it is etched with oxygen, it is removed to obtain sheet g-C3N4, wherein temperature be
400-520 DEG C, time 60-360min；
By Cu-BTC and sheet g-C3N4It mixes according to mass ratio 1:100-1:1, exists under inert gas protection through tube furnace heat
Processing obtains CuO/g-C at 400-520 DEG C3N4Hetero-junctions recovers condensation material.
3. the preparation method of a kind of copper oxide according to claim 1 or 2 and the compound heterojunction photocatalyst of carbonitride,
It is characterized by: with CuO/g-C3N4Heterojunction composite makees photochemical catalyst, is placed in water and alcohol mixed solution, visible
Light prepares hydrogen peroxide under the conditions of shining.
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| CN114377725B (en) * | 2022-01-26 | 2023-11-14 | 福建农林大学 | Nanocellulose composite graphite phase carbon nitride/COF heterojunction photocatalyst and preparation method and application thereof |
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