CN110152693A - A kind of photo catalytic reduction CO2Catalyst and its preparation method and application - Google Patents
A kind of photo catalytic reduction CO2Catalyst and its preparation method and application Download PDFInfo
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- CN110152693A CN110152693A CN201910542052.4A CN201910542052A CN110152693A CN 110152693 A CN110152693 A CN 110152693A CN 201910542052 A CN201910542052 A CN 201910542052A CN 110152693 A CN110152693 A CN 110152693A
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 25
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000010949 copper Substances 0.000 claims abstract description 29
- 239000006185 dispersion Substances 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 41
- 239000011259 mixed solution Substances 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 24
- 239000004094 surface-active agent Substances 0.000 claims description 19
- 239000000460 chlorine Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 10
- 229930195725 Mannitol Natural products 0.000 claims description 10
- 239000000594 mannitol Substances 0.000 claims description 10
- 235000010355 mannitol Nutrition 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 4
- TXKAQZRUJUNDHI-UHFFFAOYSA-K bismuth tribromide Chemical compound Br[Bi](Br)Br TXKAQZRUJUNDHI-UHFFFAOYSA-K 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 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 239000008236 heating water Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 241000165940 Houjia Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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)
Abstract
The present invention relates to a kind of photo catalytic reduction CO2Catalyst and its preparation method and application, copper source is added by being dispersed in water BiOCl nanometer sheet to form dispersion liquid in the method, and heat treatment is so that Cu in dispersion liquid2+Homogeneous precipitation is deposited in BiOCl nanometer sheet；The granularity of CuO cluster is small on the catalyst that the method for the invention is prepared, and dispersing uniformity is good, to reach under the premise of not influencing absorption of the BiOCl nanometer sheet to light, more active sites are provided for catalyst, so that the activity of catalyst significantly improves.
Description
Technical field
The present invention relates to field of nano material preparation more particularly to a kind of photo catalytic reduction CO2Catalyst and its preparation
Method and purposes.
Background technique
BiOCl is a kind of n-type semiconductor, and forbidden bandwidth is about 3.3eV, due to its stabilization, nontoxic, abundant raw materials, quilt
It is widely used in photocatalysis CO2The fields such as reduction, photocatalysis fixed nitrogen and organic synthesis.BiOCl nanometer sheet due to its mono-crystalline structures,
Strong built in field and high-specific surface area etc. are conducive to the separation and directional transmissions of photo-generated carrier, have obtained extensive research and have answered
With.But since surface-active site is limited, BiOCl cannot efficiently drive photocatalysis CO2Reduction reaction, so that it is wide to limit it
General application.While keeping BiOCl material own advantages, in order to further increase its performance, people sink usually on BiOCl
Other co-catalysts of product, so that light-catalyzed reaction is promoted, especially photocatalysis CO2Reduction reaction performance, such as BiOCl/Au,
BiOCl/BiVO4With BiOCl/CQD etc..
Cu is a kind of transition metal element, and crustal abundance is high, cheap.Its unique d9Electronic structure is expected into it
For the substitute of the classical noble metal catalyst such as Pt, Pd.Have a few thing in recent years to prepare BiOCl/CuO system
And application study.For example, CN107042108A uses low-temperature reduction method, BiOCl/CuO composite catalyzing is prepared in the following order
Agent: precursor salt dispersion → reducing agent low temperature dispersion → direct-reduction prepares BiOCl/CuO composite catalyst, but its preparation section is multiple
Miscellaneous, time-consuming, and product control is difficult.CuO BiOCl nanometers of piece preparation methods of doping in CN108383160A are relatively easy,
The method for directlying adopt ball milling obtains CuO doping BiOCl nanometer sheet from one step of precursor salt, but obtains CuO and adulterate BiOCl nanometers
Piece homogeneity is not good enough, while ball-milling technology energy consumption is higher, and product recycling is difficult.CN108514885A uses photoreduction met hod, presses
Following sequence prepares the BiOCl nanometer sheet of Cu (II) modification: one-step method hydro-thermal+light deposition reduction prepares Cu (II) modification
BiOCl nanometer sheet, but also it is unable to get the good product of homogeneity.
Studies have shown that, by depositing specific cocatalyst materials, can be dropped when preparing semiconductor material photochemical catalyst
Compound, the promotion energy conversion efficiency of low photo-generate electron-hole.Since extra small cluster itself is having the same of good catalytic activity
When, it will not influence absorption of the carrier semiconductor to light.The BiOCl nanometer sheet catalysis of CuO cluster extra small for surface modification at present
The preparation and application study of agent have not been reported.
Summary of the invention
The purpose of the present invention is to provide a kind of photo catalytic reduction CO2Catalyst and its preparation method and application, it is described
Method is added copper source, heats the Cu so that in dispersion liquid by being dispersed in water BiOCl nanometer sheet to form dispersion liquid2+
Homogeneous precipitation is deposited in BiOCl nanometer sheet；The granularity of CuO cluster is small on the catalyst that the method for the invention is prepared,
And dispersing uniformity is good, to reach under the premise of not influencing absorption of the BiOCl nanometer sheet to light, provides more for catalyst
More active site, so that the activity of catalyst significantly improves.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of photo catalytic reduction CO2Catalyst preparation method, the method includes
Following steps:
(1) BiOCl nanometer sheet is prepared；
(2) the BiOCl nanometer sheet that step (1) is prepared is dispersed in water, obtains BiOCl nanometer sheet dispersion liquid, it
Copper source is added in the dispersion liquid afterwards, heats, obtains the catalyst.
The preparation method of catalyst of the present invention in the dispersion liquid of BiOCl nanometer sheet by being added copper source, Zhi Houjia
Heat treatment, so that the Cu in dispersion liquid2+It is converted into CuO cluster by precipitating deposition, is supported in BiOCl nanometer sheet, obtains institute
State catalyst；The granularity for the CuO cluster that the method for the invention is prepared is small and is uniformly dispersed in BiOCl nanometer sheet, from
And under the premise of not influencing absorption of the BiOCl nanometer sheet to light, the quantity of the active site of catalyst surface is increased, so that
Catalyst photo catalytic reduction CO2Performance significantly improved compared to simple BiOCl nanometer sheet.
Preferably, step (1) method for preparing BiOCl nanometer sheet the following steps are included:
(a) bismuth source, surfactant and solvent are mixed, obtains mixed solution A；
(b) chlorine source solution is added in the mixed solution A that step (a) obtains, obtains mixed solution B；
(c) the mixed solution B for obtaining step (b) carries out solvent thermal reaction, obtains the BiOCl nanometer sheet.
Preferably, Bi in step (a) mixed solution A3+Concentration be 0.01-0.08mol/L, such as 0.02mol/L,
0.03mol/L, 0.04mol/L, 0.05mol/L, 0.06mol/L or 0.07mol/L etc..
Preferably, step (a) the bismuth source includes any one in bismuth nitrate, bismuth chloride or bismuth bromide or at least two
Mixture, the mixture illustratively includes the mixture of bismuth nitrate and bismuth chloride, the mixture of bismuth nitrate and bismuth bromide
Or bismuth chloride and the mixture of bismuth bromide etc..
Preferably, step (a) solvent is the mixed liquor of water and ethylene glycol.
In the preparation process of BiOCl nanometer sheet of the present invention, using the mixed liquor of ethylene glycol and water as solvent, and add
Enter surfactant, with the Cl containing saturation-Aqueous solution as chlorine source so that the BiOCl nanometer sheet being prepared is to light
Absorbability enhancing, to further increase the catalytic activity of catalyst.
Preferably, the volume ratio of the water and ethylene glycol is 0.6-1.2, such as 0.7,0.8,0.9,1.0 or 1.1 etc..
In BiOCl nanometer sheet preparation process of the present invention, select the mixed liquor of water and ethylene glycol as solvent, compared to
Simple water and ethylene glycol is more advantageous to the absorbing ability for improving the BiOCl nanometer sheet being prepared, has simultaneously as solvent
Conducive to high degree of dispersion of the CuO cluster in BiOCl nanometer sheet, it is 0.6- that the present invention, which selects the mixing ratio of optimal water and ethylene glycol,
1.2, as mixing ratio < 0.6, it is unfavorable for catalyst stability；As mixing ratio > 1.2, it is unfavorable for the Cluster deposition of CuO.
Preferably, step (a) surfactant is nonionic surface active agent.
Preferably, the nonionic surface active agent includes mannitol and/or polyvinyl pyrrolidone.
Preferably, the molecular weight of the polyvinyl pyrrolidone be 6000-10000, such as 6500,7000,7500,8000,
8500,9000 or 9500 etc..
Preferably, step (a) surfactant is the mixture of mannitol and polyvinyl pyrrolidone.
Preferably, the mass ratio of mannitol and polyvinyl pyrrolidone is 0.5-2, example in step (a) surfactant
Such as 0.6,0.7,0.8,0.9,1.1,1.5 or 1.8.
In the preparation process of BiOCl nanometer sheet of the present invention, mannitol is added and polyvinyl pyrrolidone is conducive to improve
The photo absorption performance for the BiOCl nanometer sheet being prepared, and optimal surfactant is the mixed of mannitol and polyvinyl pyrrolidone
Object is closed, the preferably mass ratio of mannitol and polyvinyl pyrrolidone is 0.5-2.
Preferably, surfactant concentration is 0.01-0.03g/mL in the mixed solution B that step (b) obtains, such as
0.015g/mL, 0.02g/mL or 0.025g/mL etc..
Preferably, step (b) chlorine source solution is the Cl containing saturation-Aqueous solution.
Preferably, step (b) chlorine source solution includes NaCl aqueous solution and/or KCl aqueous solution.
Preferably, the volume ratio of step (b) chlorine source solution and mixed solution A be 0.1-0.4, such as 0.15,0.2,
0.25,0.3 or 0.35 etc..
Preferably, the temperature of step (c) solvent thermal reaction be 150-180 DEG C, such as 155 DEG C, 160 DEG C, 165 DEG C,
170 DEG C or 175 DEG C etc..
Preferably, the time of step (c) solvent thermal reaction be 0.5-6h, such as 1h, 1.5h, 2h, 2.5h, 3h,
3.5h, 4h, 4.5h, 5h or 5.5h etc., preferably 2-4h.
It preferably, further include that reaction product is separated by solid-liquid separation, washed and is done after step (c) solvent thermal reaction
It is dry.
Preferably, the detergent of the washing includes second alcohol and water.
Preferably, the drying includes vacuum drying.
Preferably, step (2) copper source includes any one in copper nitrate, copper chloride or copper sulphate or at least two
Mixture, the mixture illustratively includes the mixture of the mixture of copper nitrate and copper chloride, copper nitrate and copper sulphate
Or copper chloride and the mixture of copper sulphate etc..
Preferably, the additional amount of step (2) copper source makes Cu in dispersion liquid2+Concentration be 0.1-1.5mmol/L, example
As 0.2mmol/L, 0.3mmol/L, 0.4mmol/L, 0.5mmol/L, 0.6mmol/L, 0.7mmol/L, 0.8mmol/L,
0.9mmol/L, 1.0mmol/L, 1.1mmol/L, 1.2mmol/L, 1.3mmol/L or 1.4mmol/L etc..
Preferably, the concentration of BiOCl nanometer sheet is 5-10g/L in step (2) the BiOCl nanometer sheet dispersion liquid, such as
6g/L, 7g/L, 8g/L or 9g/L etc..
Preferably, the temperature of step (2) described heat treatment is 80-100 DEG C, such as 85 DEG C, 90 DEG C or 95 DEG C etc..
The method of the invention passes through Cu in control BiOCl nanometer sheet dispersion liquid2+Concentration and subsequent processing mode make
The CuO cluster that must be prepared is highly dispersed in BiOCl nanometer sheet while keeping compared with small particle, so that in CuO cluster
Absorption of the BiOCl nanometer sheet to light is not influenced after being supported in BiOCl nanometer sheet.
Preferably, the mode of step (2) described heat treatment includes heating water bath.
Preferably, the time of step (2) described heat treatment be 40-90min, such as 45min, 50min, 55min,
60min, 65min, 70min, 75min, 80min or 85min etc..
It preferably, further include that product is washed and dried after step (2) described heat treatment.
As currently preferred technical solution, the photo catalytic reduction CO2The preparation method of catalyst include following
Step:
(1 ') mixes bismuth source, surfactant and solvent, obtains mixed solution A；Bi in the mixed solution A3+It is dense
Degree is 0.01-0.08mol/L, and the surfactant includes mannitol and/or polyvinyl pyrrolidone, and the solvent is water and second
The mixed liquor of glycol；The volume ratio of the water and ethylene glycol is 0.6-1.2；
The Cl containing saturation is added in (2 ') in the mixed solution A that step (1 ') obtains-Aqueous solution, obtain mixed solution B；Institute
State the Cl containing saturation-Aqueous solution and mixed solution A volume ratio be 0.1-0.4；Surfactant is dense in the mixed solution B
Degree is 0.01-0.03g/mL；
The mixed solution B that (3 ') obtains step (2 ') solvent thermal reaction 0.5-6h at 150-180 DEG C, after through solid-liquid
Separation, washing and drying, obtain BiOCl nanometer sheet；
The BiOCl nanometer sheet that step (3 ') obtains is dispersed in water by (4 '), obtains BiOCl nanometer sheet dispersion liquid, later
Copper source is added, heats 40-90min at 80-100 DEG C, obtains the catalyst, the BiOCl nanometer sheet dispersion later
The concentration of BiOCl nanometer sheet is 5-10g/L in liquid, and the additional amount of copper source makes Cu in dispersion liquid2+Concentration be 0.1-
1.5mmol/L。
Second aspect, the present invention provides the photo catalytic reduction CO that method as described in relation to the first aspect is prepared2Catalysis
Agent, the catalyst include BiOCl nanometer sheet and the CuO cluster being dispersed in the BiOCl nanometer sheet.
Preferably, in the catalyst 90% or more CuO cluster partial size be 0.5-2nm, such as 0.6nm, 0.8nm,
1nm, 1.2nm, 1.5nm or 1.8nm etc..
Preferably, the mass ratio of the BiOCl nanometer sheet and CuO cluster is 0.6-2%, for example, 0.7%, 0.8%, 1%,
1.2%, 1.5%, 1.7% or 1.9% etc., preferably 1-1.2%.
The third aspect, the present invention provides the purposes of the catalyst as described in second aspect, the catalyst is urged for light
Change reduction CO2。
Compared with the existing technology, the invention has the following advantages:
(1) granularity of CuO cluster is small on the catalyst that the method for the invention is prepared, and is uniformly dispersed, to reach
To under the premise of not influencing absorption of the BiOCl to light, the active site of catalyst surface is increased, so that catalyst photocatalysis
Restore CO2Activity be obviously improved；
(2) preparation process of the method for the invention is simple, is easy to industrial applications.
Detailed description of the invention
Fig. 1 is photo catalytic reduction CO of the present invention2Catalyst structural schematic diagram；
Fig. 2 is the transmission electron microscope picture for the BiOCl nanometer sheet that the embodiment of the present invention 1 is prepared；
Fig. 3 is the transmission electron microscope picture for the CuO/BiOCl that the embodiment of the present invention 1 is prepared；
Fig. 4 is the EDX distribution diagram of element of the Cu element for the CuO/BiOCl that the embodiment of the present invention 1 is prepared；
Fig. 5 is the EDX distribution diagram of element of the Cl element for the CuO/BiOCl that the embodiment of the present invention 1 is prepared；
Fig. 6 is the EDX distribution diagram of element of the O element for the CuO/BiOCl that the embodiment of the present invention 1 is prepared；
Fig. 7 is the EDX distribution diagram of element of the Bi element for the CuO/BiOCl that the embodiment of the present invention 1 is prepared；
Fig. 8 be the CuO/BiOCl that the embodiment of the present invention 1 is prepared and the BiOCl photocatalysis that comparative example 1 is prepared also
Former CO2Activity curve；
1-BiOCl nanometer sheet, 2-CuO cluster.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
The structural schematic diagram for the catalyst that specific embodiment of the invention part is prepared is as shown in Figure 1, the catalysis
Agent includes BiOCl nanometer sheet 1 and the CuO cluster 2 that is dispersed in the BiOCl nanometer sheet 1.
Embodiment 1
Photo catalytic reduction CO2Catalyst preparation method:
(1) by 1.0g Bi (NO3)3·5H2O (2mmol), 0.9g mannitol (5mmol) and 0.8g polyvinyl pyrrolidone (divide
Son amount~8000) it is dissolved in 50mL solvent, the solvent is the mixed liquor of water and ethylene glycol；The volume of the water and ethylene glycol
Than being 1；After solution clarification；The KCl solution of 10mL saturation is added；
(2) mixed solution that step (1) obtains is transferred in hydrothermal reaction kettle, the solvent thermal reaction 3h at 160 DEG C, to
After reaction kettle natural cooling, product ethyl alcohol and water wash 3 times respectively, and 60 DEG C are dried in vacuum overnight, and obtain BiOCl nanometer sheet；
(3) the BiOCl nanometer sheet that 0.3g step (2) is prepared is dispersed in 40mL water, obtains BiOCl nanometer sheet point
CuCl is added in dispersion liquid later2·2H2O, the CuCl2·2H2The additional amount of O makes Cu in dispersion liquid2+With BiOCl nanometer sheet
Mass ratio is 0.01 (i.e. Cu in dispersion liquid2+Concentration be 1.17mmol/L), water-bath heating stirring handles 60min at 90 DEG C, from
Heart separation, washing, 60 DEG C are dried in vacuum overnight, and obtain the catalyst, are denoted as CuO/BiOCl.
The transmission electron microscope picture for the BiOCl nanometer sheet that the present embodiment step (2) is prepared by figure as shown in Fig. 2, can be seen
Out, BiOCl is flaky nanometer structure, having a size of 200-250nm.
The transmission electron microscope picture of the CuO/BiOCl that the present embodiment is prepared is as shown in figure 3, as seen from the figure, in BiOCl
CuO cluster is distributed in nanometer sheet (as shown in white circle in figure)；The diameter of CuO cluster is about 1nm；
The EDX distribution diagram of element of Cu, Cl, O and Bi element for the CuO/BiOCl that the present embodiment is prepared is respectively such as Fig. 4-
(point dispersed in figure represents corresponding element) shown in 7, Cu, Cl, O and Bi element are all evenly distributed on entirely as seen from the figure
In nanometer sheet, to further illustrate that CuO cluster is evenly distributed in BiOCl nanometer sheet.
Comparative example 1
The BiOCl nanometer sheet that this comparative example is prepared using 1 step of embodiment (2) is denoted as BiOCl as catalyst.
The catalyst photocatalysis CO that embodiment 1 and comparative example 1 are prepared2The quantum of output curve of the CO of reduction process is as schemed
Shown in 8, as seen from the figure, the catalytic performance of the BiOCl nanometer sheet after the CuO cluster modification used in the present invention is substantially better than
Simple BiOCl nanometer sheet, so that the method modifies CuO cluster to explanation in BiOCl nanometer sheet through the invention, it can be effective
The quantity for increasing activity over catalysts site, so that the activity of catalyst significantly improves.
Performance test:
Photo catalytic reduction CO is carried out to the catalyst that embodiment 1 and comparative example 1 are prepared2Performance test, test side
Method is as follows:
It takes 20mg catalyst to be scattered in 100mL pure water, then adds quartz cover to seal reactor.It is being passed through CO2Before,
First the circulatory system is vacuumized, is then slowly filled with Ar gas (> 99.999%), is so repeated three times.Then it takes out again true
Sky is slowly filled with CO2Gas (> 99.999%) so repeats three times, finally by CO2It is filled with system, until system pressure is
25kPa stirs 120min in the dark state to reach catalyst and CO2Suction/desorption equilibrium.Then xenon source is opened, is spaced
Certain time sampling, uses gas chromatograph (Agilent 7890A) on-line checking gaseous product content.Gas chromatograph is equipped with
There are hydrogen flame ionization detector (FID) and thermal conductivity detector (TCD) (TCD), uses He as carrier gas.
Using CO yield as judging catalyst photo catalytic reduction CO2The standard of performance superiority and inferiority, test result such as 1 institute of table
Show:
Table 1
| CO yield, μm ol/g/h | |
| Embodiment 1 | 9.5 |
| Comparative example 1 | 6.4 |
As can be seen from the above table, the catalyst photo catalytic reduction CO that the method for the invention is prepared2Performance it is higher.
To which the method modifies extra small CuO cluster to explanation in BiOCl nanometer sheet through the invention, the CuO cluster not only body
Product is small, and the high degree of dispersion in BiOCl nanometer sheet, thus under the premise of not influencing BiOCl nanometer sheet to light absorption, for catalysis
Agent provides higher surface-active site, so that catalyst photo catalytic reduction CO2Performance significantly improve.
Comparative example 1 and comparative example 1 in BiOCl nanometer sheet as can be seen that modify what CuO cluster to be prepared
The performance of catalyst is obviously improved.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of photo catalytic reduction CO2Catalyst preparation method, which is characterized in that the described method comprises the following steps:
(1) BiOCl nanometer sheet is prepared；
(2) the BiOCl nanometer sheet that step (1) is prepared is dispersed in water, obtains BiOCl nanometer sheet dispersion liquid, Zhi Hou
Copper source is added in the dispersion liquid, heats, obtains the catalyst.
2. the method as described in claim 1, which is characterized in that step (1) method for preparing BiOCl nanometer sheet include with
Lower step:
(a) bismuth source, surfactant and solvent are mixed, obtains mixed solution A；
(b) chlorine source solution is added in the mixed solution A that step (a) obtains, obtains mixed solution B；
(c) the mixed solution B for obtaining step (b) carries out solvent thermal reaction, obtains the BiOCl nanometer sheet.
3. method according to claim 2, which is characterized in that Bi in step (a) mixed solution A3+Concentration be 0.01-
0.08mol/L；
Preferably, step (a) the bismuth source include in bismuth nitrate, bismuth chloride or bismuth bromide any one or at least two it is mixed
Close object；
Preferably, step (a) solvent is the mixed liquor of water and ethylene glycol；
Preferably, the volume ratio of the water and ethylene glycol is 0.6-1.2.
4. method as claimed in claim 2 or claim 3, which is characterized in that step (a) surfactant is non-ionic surface
Activating agent；
Preferably, the nonionic surface active agent includes mannitol and/or polyvinyl pyrrolidone；
Preferably, the molecular weight of the polyvinyl pyrrolidone is 6000-10000；
Preferably, surfactant concentration is 0.01-0.03g/mL in the mixed solution B that step (b) obtains.
5. such as any one of claim 2-4 the method, which is characterized in that step (b) chlorine source solution is the Cl containing saturation-'s
Aqueous solution；
Preferably, step (b) chlorine source solution includes NaCl aqueous solution and/or KCl aqueous solution；
Preferably, the volume ratio of step (b) chlorine source solution and mixed solution A is 0.1-0.4.
6. such as the described in any item methods of claim 2-5, which is characterized in that the temperature of step (c) solvent thermal reaction is
150-180℃；
Preferably, the time of step (c) solvent thermal reaction is 0.5-6h, preferably 2-4h；
It preferably, further include that reaction product is separated by solid-liquid separation, washed and is dried after step (c) solvent thermal reaction；
Preferably, the detergent of the washing includes second alcohol and water；
Preferably, the drying includes vacuum drying.
7. as the method according to claim 1 to 6, which is characterized in that step (2) copper source includes copper nitrate, chlorination
In copper or copper sulphate any one or at least two mixture；
Preferably, the additional amount of step (2) copper source makes Cu in dispersion liquid2+Concentration be 0.1-1.5mmol/L；
Preferably, the concentration of BiOCl nanometer sheet is 5-10g/L in step (2) the BiOCl nanometer sheet dispersion liquid；
Preferably, the temperature of step (2) described heat treatment is 80-100 DEG C；
Preferably, the mode of step (2) described heat treatment includes heating water bath；
Preferably, the time of step (2) described heat treatment is 40-90min；
It preferably, further include that product is washed and dried after step (2) described heat treatment.
8. the method according to claim 1 to 7, which is characterized in that the described method comprises the following steps:
(1 ') mixes bismuth source, surfactant and solvent, obtains mixed solution A；Bi in the mixed solution A3+Concentration be
0.01-0.08mol/L, the surfactant include mannitol and/or polyvinyl pyrrolidone, and the solvent is water and ethylene glycol
Mixed liquor；The volume ratio of the water and ethylene glycol is 0.6-1.2；
The Cl containing saturation is added in (2 ') in the mixed solution A that step (1 ') obtains-Aqueous solution, obtain mixed solution B；It is described to contain
It is saturated Cl-Aqueous solution and the volume ratio of mixed solution A be 0.1-0.4, the concentration of surfactant is in the mixed solution B
0.01-0.03g/mL；
The mixed solution B that (3 ') obtains step (2 ') solvent thermal reaction 0.5-6h at 150-180 DEG C, after through solid-liquid point
From washing and drying obtain BiOCl nanometer sheet；
The BiOCl nanometer sheet that step (3 ') obtains is dispersed in water by (4 '), is obtained BiOCl nanometer sheet dispersion liquid, is added later
Copper source, heats 40-90min at 80-100 DEG C, obtains the catalyst later, in the BiOCl nanometer sheet dispersion liquid
The concentration of BiOCl nanometer sheet is 5-10g/L, and the additional amount of copper source makes Cu in dispersion liquid2+Concentration be 0.1-
1.5mmol/L。
9. the photo catalytic reduction CO being prepared such as any one of claim 1-8 the method2Catalyst, which is characterized in that institute
State the CuO cluster that catalyst includes BiOCl nanometer sheet and is dispersed in the BiOCl nanometer sheet.
10. the purposes of catalyst as claimed in claim 9, which is characterized in that the catalyst is used for photo catalytic reduction CO2。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113546647A (en) * | 2021-07-22 | 2021-10-26 | 海南大学 | Preparation method and application of defect type ultrathin nanosheet self-assembled nanospheres |
| CN114160172A (en) * | 2021-12-16 | 2022-03-11 | 中国船舶重工集团公司第七一九研究所 | For CO2Cu/BiOI catalyst for preparing methanol by catalytic hydrogenation and preparation method thereof |
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| CN113546647A (en) * | 2021-07-22 | 2021-10-26 | 海南大学 | Preparation method and application of defect type ultrathin nanosheet self-assembled nanospheres |
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