CN110404556A - A kind of preparation method of the photochemical catalyst of compound core-shell structure liquid metal - Google Patents
A kind of preparation method of the photochemical catalyst of compound core-shell structure liquid metal Download PDFInfo
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- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 79
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000011258 core-shell material Substances 0.000 title claims abstract description 31
- 150000001875 compounds Chemical group 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 239000002923 metal particle Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000008187 granular material Substances 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 239000006070 nanosuspension Substances 0.000 claims abstract description 12
- -1 gallium metal oxide Chemical class 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 239000012498 ultrapure water Substances 0.000 claims description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052738 indium Inorganic materials 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 229910000846 In alloy Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000004033 diameter control Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 23
- 230000015556 catabolic process Effects 0.000 abstract description 21
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 abstract description 18
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 16
- 238000002835 absorbance Methods 0.000 abstract description 16
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 16
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 11
- 229910052724 xenon Inorganic materials 0.000 abstract description 9
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002905 metal composite material Substances 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 239000011941 photocatalyst Substances 0.000 description 11
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000013528 metallic particle Substances 0.000 description 7
- 239000000975 dye Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000003863 metallic catalyst Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910000807 Ga alloy Inorganic materials 0.000 description 2
- 241001247821 Ziziphus Species 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 229910001751 gemstone Inorganic materials 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing 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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
A kind of preparation method of compound core-shell structure photochemical catalyst be using the micro-nano suspension of liquid metal, metal powder, gallium metal oxide as raw material, respectively by nano-metal particle and the preparation of liquid metal micro-nano granules, the preparation of the spherical liquid metal catalyst of loaded metal particle, core-shell structure multifunctional sphere composite catalyst preparation and etc. be made.Degradation of methylene blue effect of the present invention is good, the initial absorbance of methylene blue solution is 1.5, it degrades 120 minutes under xenon lamp by composite catalyst, absorbance is only capable of reaching 0.24, and the Congo red effect of present invention degradation is good, Congo red initial absorbance is 0.58, after the liquid metal composite catalyst containing W is degraded 18 hours under xenon lamp, absorbance is only capable of reaching 0.15, shows good photocatalysis performance, preparation method simple possible of the present invention is worth marketing application.
Description
Technical field
The present invention relates to a kind of preparation methods of compound core-shell structure photochemical catalyst, and in particular to a kind of α/β/γ-Ga2O3
Modify the preparation method based on the micro-nano core-shell structure novel composite catalyst of liquid metal/metal oxide.
Background technique
Global environmental pollution and ecological disruption make people give great pass to completely new free of contamination clean manufacturing
Note.Environmental pollution is the major issue that human kind sustainable development is faced, and the development and application of Photocatalyst,
New approach is provided to solve this problem.Photocatalysis possesses feature high-efficient, that reaction condition is mild, opens in new energy
Hair becomes a glittering jewel in terms of environmental improvement, has played important function, such as at aspect of curbing environmental pollution, can
Utilize the degradation of solar energy photocatalytic organic pollutant；In terms of energy development, using photocatalytic hydrogen production by water decomposition, photo-reduction
CO2Deng, it is effective that the mankind is assisted to face various challenges, it is concerned in recent years.
It is small by organic pollutant degradation using a kind of photocatalyst for degrading organic pollutant in terms of photocatalytic degradation
Molecular organic acids and other innocuous substances improve soil to play the role of protection water source, from current field dynamic,
There is more universal TiO2Nano-photocatalyst.
Micro-nano liquid metal significantly changes and improves the specific physical and chemical performance of macroscopical liquid metal, shows macro
See liquid metal performance beyond one's ability.In metallic composite field, nanometer liquid metal watch reveals higher particle fusion
Potential barrier, improve the degree of scatter and controllability of product significantly.Liquid metal just mentions in the recent period as the report of photochemical catalyst
Out, the state of comprehensive current photocatalysis field, currently, modifying liquid metal micro-nano based on a kind of α/β/γ-Ga2O3 not yet
Core-shell structure prepares the appearance of novel composite catalyst, and the composite catalyst is not applied to photocatalytic hydrogen production by water decomposition and light yet
Catalysis reduction CO2Aspect.
Therefore, the problem of developing novel photocatalyst, being those skilled in the art's rhymed formula solve, but in actual fabrication process, general
When the micro-nano suspension of nano metal powder, liquid metal mixes, it is easy to appear metallic particles and mixes unevenness with liquid metal, from
And cause the various metal powder accounting differences born in subsequent loaded catalyst obtained that catalytic effect is caused to decline.This
When outside, using the spherical liquid metal catalyst of gallium metal modified oxide loaded metal particle, if all kinds of technological parameter controls
It is improper to make, and required product can not be made by eventually leading to.
Summary of the invention
The main purpose of the present invention is to provide a kind of preparation methods of compound core-shell structure photochemical catalyst.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of compound core-shell structure photochemical catalyst, which is characterized in that it be with the micro-nano suspension of liquid metal,
Metal powder, gallium metal oxide are raw material, prepare respectively by nano-metal particle and liquid metal micro-nano granules, is negative
Carry the steps such as the preparation of the spherical liquid metal catalyst of metallic particles, the preparation of multifunctional sphere composite catalyst of core-shell structure
It is rapid to be made.
Further, the micro-nano suspension of the liquid metal is to mix liquid metal, be placed in magnetic stirring apparatus with 55 ~
It 65 DEG C, persistently stirs 30 ~ 40 minutes, obtains liquid alloy, be subsequently placed in appropriate vessel, a small amount of ultrapure water is added, then sets
In ultrasonic cleaning instrument, setting temperature is 20 ~ 40 DEG C, and 60 ~ 70min of ultrasound is to get the micro-nano suspension of liquid metal；The liquid
State metal is two or more in gallium, indium, tin, bismuth, zinc and lead；The mass ratio of the liquid metal alloy and ultrapure water be 1:5 ~
8。
Further, the liquid metal is preferably gallium-indium alloy or gallium-indium-tin alloy, gallium and indium matter in the gallium-indium alloy
Amount is made for magnetic agitation 30 minutes at a temperature of 60 ~ 65 DEG C than being 3:1；The mass ratio of gallium, indium and tin in the gallium-indium-tin alloy
It is made within magnetic agitation 30 minutes under 60 DEG C of heating water baths for 67:20.5:12.5.
Further, the metal powder is one of silver, copper, palladium, copper, tungsten, molybdenum, nickel or a variety of.
Further, the gallium metal oxide is preferably α-Ga2O3, β-Ga2O3,γ-Ga2O3One of or it is a variety of.
Further, the preparation of the nano-metal particle and liquid metal micro-nano granules is to take metal powder, liquid gold
Belong to micro-nano suspension while being placed in micro runner device, channel diameter is controlled in 300 ~ 400nm, utilizes the hole of fluid channel
Metallic particles and liquid metal micro-nano granules having a size of Nano grade are squeezed out, the nano-metal particle additive amount is nanometer
1 ~ 20wt% of metallic particles and liquid metal micro-nano granules.Liquid metal micro-nano granules are according to liquid metal " packet gulp down effect
Answer ", it is welcome to be coated with nano-metal particle, it can also preferably be merged between different liquid metal droplets, allow nanogold
Category powder is uniform, completely incorporates liquid metal, makes the nanometer that a variety of materials accounting 7% or 10% is born inside liquid metal nucleome
Metallic particles forms the interior loaded catalyst like " jujube cake model ".
Further, the preparation of the spherical liquid metal catalyst of the loaded metal particle is by nanogold obtained above
Metal particles and liquid metal micro-nano granules are mixed with ultrapure water 1:5 ~ 8 in mass ratio, are subsequently placed in ultrasonic cleaning instrument, ultrasound
Time is 25 ~ 35 minutes, it is made to generate the spherical liquid metal catalyst of nanoscale loaded metal particle.
Further, the preparation of the multifunctional sphere composite catalyst of the core-shell structure is in carried metal obtained above
1 ~ 5wt% nanoscale gallium metal oxide is added in the spherical liquid metal catalyst of particle, it is straight in ultrapure water using ultrasonic method
Connect ultrasound 25 ~ 35 minutes, contain ultrapure water in the spherical liquid metal catalyst of loaded metal particle, with liquid metal particle with
Oxygen in water occurs oxidation reaction and generates miniature oxide layer, which has extraordinary adhesion strength and adsorption capacity, can
It is easy to obtain adherency α-Ga2O3,β-Ga2O3,γ-Ga2O3Equal gallium oxides nano particle, then be made the multi-function ball of core-shell structure
Shape composite catalyst.
Further, the nano-metal particle is preferably copper, tungsten, silver, molybdenum four kinds of metals composition, mass ratio 1:1:1:
1, the additive amount is preferably the 7% or 15% of nano-metal particle and liquid metal micro-nano granules.
A kind of compound core-shell structure photochemical catalyst can be used for photocatalysis Decomposition, photocatalytic degradation, photo catalytic reduction, photocatalysis
One or more of hydrogen manufacturing, hydrogen production by water decomposition, photocatalytic cleavage methane, photochemical catalyst restore CO under the conditions of preferred illumination2Deng.
A kind of compound core-shell structure photochemical catalyst can be used for photocatalytically degradating organic dye methylene blue, methyl
One or more of organic pollutants dyestuff such as orange, Congo red etc., which can be used one of ultraviolet light, xenon lamp
Or it is several；
The invention has the following advantages:
The present invention proposes a kind of feasible α/β/γ-Ga2O3Modify liquid metal micro-nano core-shell structure novel composite catalyst
Preparation method, and a series of relevant practical applications are designed on this basis, to enhance its practical application value.Present invention drop
It is good to solve methylene blue effect, the initial absorbance of methylene blue solution is 1.5, degrades 120 under xenon lamp by composite catalyst
Minute, absorbance is only capable of reaching 0.24, and the present invention degrades, and Congo red effect is good, and Congo red initial absorbance is 0.58, passes through
After liquid metal composite catalyst containing W is degraded 18 hours under xenon lamp, absorbance is only capable of reaching 0.15, shows good
Photocatalysis performance, preparation method simple possible of the present invention are worth marketing application.
Detailed description of the invention
Fig. 1 is the Technology Roadmap of compound core-shell structure photochemical catalyst being synthetically prepared.
Fig. 2 is each element in compound core-shell structure photochemical catalyst electron microscope, and doping Ag liquid metal composite catalyst
The energy spectrum diagram of content.
Fig. 3 is compound core-shell structure photocatalyst applications in the real effect picture of methylene blue pollutant photocatalytic degradation.
Fig. 4 is compound core-shell structure photocatalyst applications in the example effect diagram of Congo red pollutant photocatalytic degradation.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used
In invention is further explained, it should not be understood as limiting the scope of the invention, person skilled in art can
To make some nonessential modifications and adaptations to the present invention according to aforementioned present invention content.
Embodiment 1:
A kind of compound core-shell structure photochemical catalyst, is made as follows:
1. the preparation of the micro-nano raw material of liquid metal
Ga and In is blended in magnetic stirring apparatus according to mass ratio 3:1 with 60 DEG C, is persistently stirred 30 minutes, pure function liquid is made
State metal indium gallium alloy (EGa-In), its fusing point are 15.5 DEG C, can also keep liquid at room temperature.Then 4.99g is made
Liquid metal indium gallium alloy (EGa-In) in reagent bottle, a small amount of ultrapure water is added, be placed in ultrasonic cleaning instrument in 20 ~ 40 DEG C
The raw material of the micro-nano suspension of liquid metal are made in ultrasound 65 minutes.
2. the preparation of liquid metal catalyst
0.88g nanometers of Cu, W, Ag, Mo metal powders will respectively be taken by dividing, and contain the micro-nano suspension raw material of 4.99g liquid metal
Be placed in micro runner device simultaneously, using the hole of fluid channel squeeze out having a size of μm/metallic particles of mm rank and liquid gold
Belong to micro-nano granules, according to liquid metal " packet gulp down effect ", it is welcome to merge and coat with nano metals such as W, Cu, difference
Can preferably be merged between liquid metal and other molten drops, allow nano metal powder uniformly, completely incorporate liquid metal, make
The nano-metal particle of a variety of materials accounting 15% is born inside liquid metal nucleome, forms the interior support type like " jujube cake model "
Catalyst；Then the liquid metal miniature droplets of four kinds of loaded metal particles are added in 100ml ultrapure water, are placed in ultrasonic cleaning
It in instrument, sonic wave amplitude is emitted it using ultrasound further shakes and become smaller, ultrasonic time is 30 minutes, its is made to generate nanoscale
The spherical liquid metal catalyst of loaded metal particle；3wt% nanometer alpha-Ga is further added in ultrapure water2O3, utilize liquid
Oxygen in state metallic particles and water occurs oxidation reaction and generates miniature oxide layer, which has extraordinary adhesion strength
With adsorption capacity, adherency α-Ga can be easy to obtain2O3The multifunctional sphere composite catalyst of core-shell structure is then made in nano particle.
Embodiment 2: composite photo-catalyst electron microscope
Liquid metal catalyst made from Example 1 is placed on sample preparation platform, and guarantees the cleaning of sample surfaces, is placed in 60 DEG C of perseverances
Warm drying box) in dry 2 hours, it is ensured that characterized after liquid is dry using SEM.Fig. 2 is system provided in an embodiment of the present invention
The novel nano liquid metal that Preparation Method is prepared/appearance structure of the metal oxide composite catalyst under SEM scanning electron microscope
And energy spectrum analysis.See that spheroidal, table is presented in this composite micro/nano liquid metal/metal oxide composite catalyst in Fig. 2
The rough little particle object in face is α-Ga2O3, and the size of the spherical shape can by fluid channel duct size in preparation process into
Row is adjusted.
The energy spectrum analysis figure is to adulterate the liquid metal composite catalyst of Ag, and each element Ga, In, Ag contains as can be seen from Figure
Amount is evenly distributed.
Embodiment 3: catalytic degradation methylene blue pollutant solution
1. precise methylene blue powder 0.1g, completely dissolves in water, it is molten to be configured to the methylene blue that concentration is 20mg/L
Liquid.
2. in the present embodiment 1, the degradation process of organic dyestuff methylene blue is as follows: using composite photocatalyst made from embodiment 1
Agent carries out the degradation of organic dyestuff, and process object is the methylene blue solution 20ml of 20mg/L, and mixing for 2g is added into reactor
The liquid metal composite catalyst of miscellaneous Ni, stirs 30min under conditions of unglazed, and catalyst surface is made to reach suction-desorption equilibrium,
With xenon lamp (simulated solar irradiation) for light source, reactor illumination 18 hours, is tested away from light source 5cm with ultraviolet-uisible spectrophotometer
In the absorbance value of maximum wavelength, composite photo-catalyst is calculated to the catalytic degradation of methylene blue by the variation of absorbance value
Rate.
Experimental result is as shown in figure 3, by as can be seen from Fig., cladding liquid metal/metal oxide of Ni nanoparticle
Composite catalyst has extraordinary effect to the catalytic degradation of the contaminant material.The initial absorbance of the methylene blue solution is
1.5, after composite catalyst is degraded 18 hours under xenon lamp, absorbance is only capable of reaching 0.24, shows good light and urges
Change performance.According to formula degradation rate=Shu (A0-A) /A0Shu × 100% can obtain: degradation rate=Shu (1.5-0.24)/1.5 Shu × 100%=
84%.As seen from the figure, wherein (1) is the original liquid uv-vis spectra of methylene blue；(2) any catalysis is added without for methylene blue
Uv-vis spectra and (1) figure contrast difference are little after agent photocatalytic degradation；(3) liquid metal catalyst for Ni nanoparticle is added
Methylene blue uv-vis spectra after degradation, is obviously degraded as seen from the figure.
Embodiment 4: the Congo red solution of catalytic degradation
1. the Congo red powder 0.1g of precise, completely dissolves in water, it is configured to the Congo red solution that concentration is 20mg/L.
2. in the present embodiment 1, the Congo red degradation process of organic dyestuff is as follows: using composite photo-catalyst made from embodiment 1
The degradation of organic dyestuff is carried out, process object is the Congo red solution 20ml of 20mg/L, and the doping Ni/ of 2g is added into reactor
W/Ga2O3Liquid metal composite catalyst, 30min is stirred under conditions of unglazed, so that catalyst surface is reached suction-desorption flat
Weighing apparatus, with xenon lamp (simulated solar irradiation) for light source, reactor illumination 3 ~ 18 hours, uses ultraviolet-uisible spectrophotometer away from light source 5cm
The absorbance value in maximum wavelength is tested, composite photo-catalyst is calculated by the variation of absorbance value, Congo red catalysis is dropped
Solution rate.
Experimental result is as shown in figure 4, by figure 4, it is seen that cladding Ni nanoparticle/W/Ga2O3Liquid metal/
Metal oxide composite catalyst has extraordinary effect to the catalytic degradation of the contaminant material.At the beginning of the Congo red solution
Beginning absorbance is 0.58, and after the liquid metal composite catalyst containing W is degraded 18 hours under xenon lamp, absorbance is only capable of reaching
To 0.15, good photocatalysis performance is shown.According to formula degradation rate=Shu (A0-A) /A0Shu × 100% can obtain: degradation rate=Shu
(0.58-0.15)/0.58 Shu × 100%=74%.As seen from the figure, wherein (1) is Congo red original liquid uv-vis spectra；(2) it is
Congo red uv-vis spectra after being added without any catalyst photocatalytic degradation, it is little with (1) figure contrast difference；It (3) is addition
Congo red uv-vis spectra after the composite liquefied metallic catalyst degradation of nanometer W, shows that partially catalyzed degradation has occurred；
It (4) is addition nanometer Ga2O3The degradation of composite liquefied metallic catalyst after Congo red uv-vis spectra, show that portion has occurred
Divide catalytic degradation；(5) for uv-vis spectra Congo red after the composite liquefied metallic catalyst of Ni nanoparticle is degraded is added, show to urge
It is very good to change degradation effect.
Claims (9)
1. a kind of preparation method of compound core-shell structure photochemical catalyst, which is characterized in that it is with the micro-nano suspension of liquid metal
Liquid, metal powder, gallium metal oxide are raw material, pass through nano-metal particle and liquid metal micro-nano granules system respectively
The preparation of standby, loaded metal particle spherical liquid metal catalyst, the multifunctional sphere composite catalyst of core-shell structure system
It is standby and etc. to be made.
2. a kind of preparation method of compound core-shell structure photochemical catalyst as described in claim 1, which is characterized in that the liquid gold
Belonging to micro-nano suspension is to mix liquid metal, is placed in magnetic stirring apparatus with 55 ~ 65 DEG C, persistently stirs 30 ~ 40 minutes, obtains
It to liquid alloy, is subsequently placed in appropriate vessel, a small amount of ultrapure water is added, be subsequently placed in ultrasonic cleaning instrument, setting temperature is
20 ~ 40 DEG C, 60 ~ 70min of ultrasound is to get the micro-nano suspension of liquid metal；The liquid metal be gallium, indium, tin, bismuth, zinc and
Two or more in lead；The mass ratio of the liquid metal alloy and ultrapure water is 1:5 ~ 8.
3. a kind of preparation method of compound core-shell structure photochemical catalyst as claimed in claim 2, which is characterized in that the liquid gold
Belonging to is preferably gallium-indium alloy or gallium-indium-tin alloy, and gallium and indium mass ratio are 3:1 in the gallium-indium alloy, at a temperature of 60 ~ 65 DEG C
It is made within magnetic agitation 30 minutes；The mass ratio of gallium, indium and tin is 67:20.5:12.5 in the gallium-indium-tin alloy, in 60 DEG C of water-baths
Under heating, it is made within magnetic agitation 30 minutes.
4. a kind of preparation method of compound core-shell structure photochemical catalyst as claimed in claim 3, which is characterized in that the metal powder
End is one of silver, copper, palladium, copper, tungsten, molybdenum, nickel or a variety of.
5. a kind of preparation method of compound core-shell structure photochemical catalyst as claimed in claim 4, which is characterized in that the gallium metal
Oxide is preferably α-Ga2O3, β-Ga2O3,γ-Ga2O3One of or it is a variety of.
6. a kind of preparation method of compound core-shell structure photochemical catalyst as claimed in claim 5, which is characterized in that the nanogold
The preparation of metal particles and liquid metal micro-nano granules is to take the micro-nano suspension of metal powder, liquid metal while being placed in micro-
In flow passage device, channel diameter control squeezes out the metal having a size of Nano grade in 300 ~ 400nm, using the hole of fluid channel
Grain and liquid metal micro-nano granules, the nano-metal particle additive amount are nano-metal particle and liquid metal micro-nano
1 ~ 20wt% of grain.
7. a kind of preparation method of compound core-shell structure photochemical catalyst as claimed in claim 6, which is characterized in that the gold-supported
The preparation of the spherical liquid metal catalyst of metal particles is by nano-metal particle obtained above and liquid metal micro-nano
Grain is mixed with ultrapure water 1:5 ~ 8 in mass ratio, is subsequently placed in ultrasonic cleaning instrument, and ultrasonic time is 25 ~ 35 minutes, makes its generation
The spherical liquid metal catalyst of nanoscale loaded metal particle.
8. a kind of preparation method of compound core-shell structure photochemical catalyst as claimed in claim 7, which is characterized in that the shell core knot
The preparation of the multifunctional sphere composite catalyst of structure is the spherical liquid metal catalyst in loaded metal particle obtained above
Middle addition 1 ~ 5wt% nanoscale gallium metal oxide, using ultrasonic method directly ultrasound 25 ~ 35 minutes in ultrapure water.
9. a kind of preparation method of compound core-shell structure photochemical catalyst as claimed in claim 8, which is characterized in that the nanogold
Metal particles are preferably four kinds of copper, tungsten, silver, molybdenum metal compositions, and mass ratio 1:1:1:1, the additive amount is preferably nanogold
The 7% or 15% of metal particles and liquid metal micro-nano granules.
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| CN112678768A (en) * | 2021-01-04 | 2021-04-20 | 重庆文理学院 | Method for preparing hydrogen by photocatalytic decomposition of water by using liquid metal |
| CN113584723A (en) * | 2021-08-02 | 2021-11-02 | 岭南师范学院 | Liquid metal nanoparticle composite nanofiber membrane and preparation method and application thereof |
| CN113603177A (en) * | 2021-02-07 | 2021-11-05 | 北京航空航天大学 | Reconfigurable and regenerative azo dye adsorption method and application thereof |
| CN114276600A (en) * | 2021-12-23 | 2022-04-05 | 南通宝加利新材料有限公司 | Preparation method of degradable PE film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112678768A (en) * | 2021-01-04 | 2021-04-20 | 重庆文理学院 | Method for preparing hydrogen by photocatalytic decomposition of water by using liquid metal |
| CN113603177A (en) * | 2021-02-07 | 2021-11-05 | 北京航空航天大学 | Reconfigurable and regenerative azo dye adsorption method and application thereof |
| CN113584723A (en) * | 2021-08-02 | 2021-11-02 | 岭南师范学院 | Liquid metal nanoparticle composite nanofiber membrane and preparation method and application thereof |
| CN114276600A (en) * | 2021-12-23 | 2022-04-05 | 南通宝加利新材料有限公司 | Preparation method of degradable PE film |
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