CN109589985A - The preparation method and its catalysis reduction carbon dioxide of dopen Nano zinc germanate - Google Patents
The preparation method and its catalysis reduction carbon dioxide of dopen Nano zinc germanate Download PDFInfo
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- 239000011701 zinc Substances 0.000 title claims abstract description 71
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 69
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000009467 reduction Effects 0.000 title claims abstract description 12
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000004246 zinc acetate Substances 0.000 claims abstract description 16
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims abstract description 13
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000003860 storage Methods 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims 1
- 239000010949 copper Substances 0.000 abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000002829 reductive effect Effects 0.000 abstract description 3
- FNIHDXPFFIOGKL-UHFFFAOYSA-N disodium;dioxido(oxo)germane Chemical compound [Na+].[Na+].[O-][Ge]([O-])=O FNIHDXPFFIOGKL-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229910000906 Bronze Inorganic materials 0.000 description 16
- 239000010974 bronze Substances 0.000 description 16
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 16
- 230000001699 photocatalysis Effects 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000010531 catalytic reduction reaction Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- 229910002090 carbon oxide Inorganic materials 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000003911 water pollution Methods 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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- 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
-
- 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 invention discloses the preparation method of dopen Nano zinc germanate and its catalysis reduction carbon dioxide, method and step are as follows: (1) prepared by solution one: the ratio of the foundation mole of zinc acetate, copper acetate and germanium oxide being mixed and is placed in raw material storage tank；(2) prepared by solution two: neopelex being dissolved in a certain amount of water, is uniformly mixed in stock chest；(3) preparation of dopen Nano zinc germanate: by the solution one of step 1) preparation and the solution two of rapid 2) preparation according to mole ratio be conveyed into reaction kettle, while sodium hydroxide solution price adjustment pH value is added；It is reacted under reaction condition, product is washed to neutrality.The present invention does not need first high―temperature nuclei sodium germanate, reduces energy consumption；Temperature is low during synthesizing copper doped zinc germanate, only needs 100 DEG C -180 DEG C, the time is 4-10 hours short, is further reduced energy consumption.
Description
Technical field
The present invention relates to dopen Nano zinc germanate technical fields, are doped especially with simple hydrothermal synthesis, Jin Erli
With the new method of doping zinc germanate photocatalytic reduction of carbon oxide.
Background technique
How effectively today's society, industrial fast development bring serious environmental pollution and energy shortage problem,
Solving energy and environmental problem becomes a global project.The excessive use of fossil fuel releases a large amount of CO2, lead
It has caused in atmosphere with CO2Based on the concentration of greenhouse gases continue to increase, greatly hinder the sustainable development of human society.
But CO2It is also a kind of potential carbon resource, therefore how effectively utilizes CO2The hot spot for becoming the whole world, because by CO2Turn
Being melted into the clean energy can aid in while solving the problems, such as energy shortages and environmental degradation.Wherein photo catalytic reduction CO2Quilt
It is considered a kind of scheme of great potential, because luminous energy is inexhaustible, nexhaustible clear energy sources, meets the whole world enough
Demand；In addition, compared with other methods, photo catalytic reduction CO2Usually carried out under room temperature, normal pressure, directly using solar energy and
Without expending other supplementary energies, recycling for carbon material can be really realized.So far, many catalysis materials have been
Applied to photo catalytic reduction CO2In, however extremely low transformation efficiency seriously hinders its practical application.Therefore, it finds efficiently, surely
Fixed, cheap photochemical catalyst causes the extensive concern of people.
In the past few decades, titanium dioxide with the advantages such as chemical stability, nontoxic due to being concerned.But two
Titanium oxide is since band-gap energy is big, photoelectron and hole-recombination rate is higher constrains its photocatalytic activity after excitation.Therefore, in order to
The utilization to solar energy is improved, on the one hand titanium dioxide is modified, on the other hand finds non-titanium-type effective catalyst.Germanic acid
Zinc is a kind of semiconductor material with wide forbidden band similar to TiO2 as a kind of wide bandgap semiconductor materials.Zinc germanate is due to conduction band
Disperse, light induced electron mobility height and good light stability have very important research to energy crisis and water pollution problems is solved
A kind of value, it is considered to be conductor photocatalysis material with application prospect.Zinc germanate belongs to n-type metal oxide semiconductor
Material shows good visible light-responded and excellent photocatalytic activity, it is generally the case that its suitable conduction band current potential is enough
Reductive water or carbon dioxide, degradation organic pollutants.So far, zinc germanate semiconductor material has been shown to realize light
Catalysis reduction CO2, but the disadvantages of common block zinc germanate material activity site is few, latent active is weak, has seriously affected its light and has urged
Change reduction CO2Activity.And nanometer germanic acid Zinc material is prepared, help to solve problem above.Due to zinc germanate greater band gap
(4.5eV), light absorption is in ultraviolet light range, but the ultraviolet light of nature only accounts for the 4% of sunlight, therefore reduces band gap width,
It is most important for development of the zinc germanate in terms of photocatalysis to visible-range to expand light absorption.The present invention is closed using hydro-thermal method
Its band structure is adjusted at dopen Nano zinc germanate, reduces its band gap width, will be prepared dopen Nano zinc germanate and is used for light
Catalysis reduction CO2Application there is not been reported.
Summary of the invention
Technical problems based on background technology, one of the object of the invention propose a kind of to prepare dopen Nano zinc germanate material
Expect and regulate and control the process of the concentration of copper doped in zinc germanate；Second purpose of the invention, on this basis, in room temperature, normal pressure
The lower material using preparation realizes the performance of efficient photocatalytic reduction of carbon oxide.
A kind of preparation method of dopen Nano zinc germanate, which is characterized in that method and step is as follows:
1) prepared by solution one: the ratio of the foundation mole of zinc acetate, copper acetate and germanium oxide being mixed and is placed in raw material storage tank
In；
2) prepared by solution two: the ratio of neopelex and zinc acetate foundation mole is dissolved in a certain amount of water
In, and it is uniformly mixed in stock chest；
3) preparation of dopen Nano zinc germanate: by two foundation of solution of the solution one of step 1) preparation and the rapid 2) preparation
Mole ratio be conveyed into reaction kettle, while be added sodium hydroxide solution price adjustment pH value；It is reacted under reaction condition, product water
It is washed till neutrality.
The molar ratio of sour zinc, copper acetate and germanium oxide in the step 1) is 1:0-0.09:0.90-1.10.
The molar ratio of neopelex and zinc acetate in the step 2) is 1:0.8-1.5.
The pH value of the step 2) is 9.0-11.0.
Step 2) the reaction condition is to react 4-10 hours under the conditions of temperature is 100-180 DEG C.
The dopen Nano zinc germanate of preparation.
Application of the dopen Nano zinc germanate in catalysis reduction carbon dioxide.
Compared with prior art, the advantageous effects that the present invention has are:
(1) this technique does not need first high―temperature nuclei sodium germanate, reduces energy consumption；
(2) temperature is low during this technical process synthesis copper doped zinc germanate, only needs 100 DEG C -180 DEG C, time short 4-10
Hour, it is further reduced energy consumption；
(3) this technical process it is simple, it is at low cost, can continuous production it is easy to industrialized production；
(4) the product copper doped nanometer zinc germanate size of this technical process production is small, large specific surface area；
(5) product dopen Nano zinc germanate expands light absorption to visible-range, photo catalytic reduction compared with zinc germanate
Carbon dioxide process can use the light in whole spectral regions；
(6) product dopen Nano zinc germanate makes to produce more Lacking oxygens in zinc germanate, and Lacking oxygen reduces photoproduction electricity
Son is compound with hole；
(7) the nanometer zinc germanate of copper doped belongs to n-type metal oxide semiconductor material, when energy is more than or equal to it
When the illumination of forbidden bandwidth Eg is mapped in the nanometer zinc germanate of copper doped, valence-band electrons can be excited on conduction band, be generated high living
The light induced electron (e-) of property, and valence band leaves positively charged photohole (h+).It is adsorbed in the nanometer germanic acid zinc surface of copper doped
Carbon dioxide, all concentrated on due to electron cloud on the oxygen atom on both sides, intermediate carbon atom have stronger electrophilicity, be easy to
Receive light induced electron, photo catalytic reduction occurs.
Detailed description of the invention
Fig. 1 is synthesis dopen Nano zinc germanate process flow chart proposed by the present invention；
Fig. 2 is prepared nanometer zinc germanate (a) proposed by the present invention, adulterates the nanometer zinc germanate (b) and doping of 2% bronze medal
The XRD diffraction pattern figure of the nanometer zinc germanate (c) of 4% bronze medal；
Fig. 3 is the transmission electron microscope picture (TEM) of prepared nanometer zinc germanate proposed by the present invention
Fig. 4 is the transmission electron microscope picture (TEM) of prepared 2% bronze medal nanometer zinc germanate of doping proposed by the present invention
Fig. 5 is the transmission electron microscope picture (TEM) of prepared 4% bronze medal nanometer zinc germanate of doping proposed by the present invention
Fig. 6 is the XRD diffraction pattern of the nanometer zinc germanate of prepared 15% bronze medal of doping proposed by the present invention
Fig. 7 is prepared nanometer zinc germanate (a) proposed by the present invention, the nanometer zinc germanate (b) for adulterating 2% bronze medal, adulterates
The carbon dioxide physical absorption figure of the nanometer zinc germanate (c) of 4% bronze medal.
Fig. 8 is prepared nanometer zinc germanate (a) proposed by the present invention, adulterates the nanometer zinc germanate (b) and doping of 2% bronze medal
The carbon monoxide yields figure that nanometer zinc germanate (c) photocatalytic reduction of carbon oxide of 4% bronze medal obtains.
In figure: V1-Zn(CH3COO)2Storagetank, V2-Cu(CH3COO)2Storagetank, V3-GeO2Storagetank, D0101- are dry
Device, E0101- heat exchanger A, E0102- heat exchanger B, F0101- filter, M0101- puddle slot, P0101- product pump A, P0102-
Product pump B, R0101- reaction kettle, V0101- Sewage treatment tank, W0101- sink.
Specific embodiment
Combined with specific embodiments below the present invention is made further to explain.
With reference to Fig. 1, Zn (CH3COO)2、Cu(CH3COO)2And GeO2Enter to puddle from storagetank respectively and carries out mixing in slot
After even, it is delivered to reaction kettle, neopelex is first completely soluble by its in hopper, then during transportation
It first passes through heat exchanger A to be cooled down, finally enter in reaction kettle, the additive amount and acetic acid of neopelex in reaction kettle
The additive amount of zinc is added by certain molar ratio, and NaOH is added into reaction kettle, adjusts the pH of reaction, then reaction process again
In persistently input high steam, the solution after reaction is delivered to sink through product pump A, enter sink before, first pass through
Heat exchanger B cools down material, is washed material to product in sink and is in neutrality, then defeated by product pump B
It send to filter, more materials are filtered processing, and filtered solid, which enters in drier, to be dried, filtered liquid
Body, which enters in return water recycling can, to be uniformly processed.
The cooling water of heat exchanger A and heat exchanger B are inputted through recirculated cooling water water supply pipeline, then through cooling water return
Pipeline is discharged, and extra steam is discharged from the steam vent tube of reaction kettle in reaction kettle, then through circulating cooling water cooling waterborne
But be discharged after from steam condensate (SC) pipeline, filter upper end is additionally provided with process water input channel, mainly to filtered solid into
Row rinses.
Embodiment 1
The ratio that the molar ratio of zinc acetate, copper acetate and germanium oxide is 1:0.03:0.97 is mixed and is placed in raw material storage tank
It is uniformly mixed.It will be dissolved in a certain amount of water with the molar ratio of zinc acetate for the neopelex of 1:1, in stock chest
It is uniformly mixed.It will be delivered in reaction kettle, retell uniformly mixed dissolved with the water of neopelex by product pump
Zinc acetate, copper acetate and germanium oxide are delivered in reaction kettle, and after stirring 30 minutes, sodium hydroxide solution price adjustment pH value, which is added, is
11.0.It is reacted 10 hours under the conditions of being 100 DEG C in temperature, product is washed to neutrality.It is dried in vacuo.
Embodiment 2
The ratio that the molar ratio of zinc acetate, copper acetate and germanium oxide is 1:0.06:0.93 is mixed and is placed in raw material storage tank
It is uniformly mixed.It will be dissolved in a certain amount of water with the molar ratio of zinc acetate for the neopelex of 1:1.2, in stock chest
In be uniformly mixed.It will be delivered in reaction kettle, retell uniformly mixed dissolved with the water of neopelex by product pump
Zinc acetate, copper acetate and germanium oxide be delivered in reaction kettle, stirring 30 minutes after, be added sodium hydroxide solution price adjustment pH value be
9.0.It is reacted 4 hours under the conditions of being 180 DEG C in temperature, product is washed to neutrality.It is dried in vacuo.
Embodiment 3
The ratio that the molar ratio of zinc acetate, copper acetate and germanium oxide is 1:0.06:0.93 is mixed and is placed in raw material storage tank
It is uniformly mixed.It will be dissolved in a certain amount of water with the molar ratio of zinc acetate for the neopelex of 1:1.4, in stock chest
In be uniformly mixed.It will be delivered in reaction kettle dissolved with the water of neopelex by pumping, retell uniformly mixed vinegar
Sour zinc, copper acetate and germanium oxide are delivered in reaction kettle, and after stirring 30 minutes, sodium hydroxide solution price adjustment pH value, which is added, is
10.5.It is reacted 3.5 hours under the conditions of being 120 DEG C in temperature, product is washed to neutrality.It is dried in vacuo.
Comparative example 1
The ratio that the molar ratio of zinc acetate and germanium oxide is 1:1 is mixed to be placed in raw material storage tank and is uniformly mixed.It will be with vinegar
The molar ratio of sour zinc is that the neopelex of 1:1 is dissolved in a certain amount of water, is uniformly mixed in stock chest.By
Pump will be delivered in reaction kettle dissolved with the water of neopelex, is retell uniformly mixed zinc acetate and germanium oxide and is delivered to
In reaction kettle, after stirring 30 minutes, it is 9.0-11.0 that sodium hydroxide solution price adjustment pH value, which is added,.In temperature be 100-180 DEG C of item
It is reacted 4-10 hours under part, product is washed to neutrality.It is dried in vacuo.
Application examples 1: the nanometer zinc germanate of prepared nanometer zinc germanate, 2% bronze medal of doping, the nanometer germanic acid for adulterating 4% bronze medal
Zinc is for measuring carbon dioxide physical absorption and photo catalytic reduction CO2To generate CO
Respectively by the germanic acid for the doping different Cu content of 100mg obtained by the comparative example 1, embodiment 1 and embodiment 2
Zinc product is dispersed in the photo catalysis reactor of the water containing 100ml, is passed through high-purity CO2Gas half an hour, so that aqueous solution quilt
CO2Saturation, connects gas-chromatography (Techcomp GC7900) (Lab Solar- III AG, Perfectlight for reactor
Limited, Beijing), and it is filled with high-purity CO2The air in it is replaced, is operated 3 times repeatedly, the pressure in it is about
The glass apparatus is sealed for environmental pressure.Later, using the xenon lamp simulated solar irradiation of 300W as the light source of reaction, sunlight is realized
Prolonged exposure measures the amount of the CO of generation after reacting 1h, 3h, 6h, 9h, 12h, 15h.
Fig. 8 shows nanometer zinc germanate (a) prepared by comparative example 1 according to the present invention, embodiment 1 adulterates receiving for 2% bronze medal
Rice zinc germanate (b) and embodiment 2 adulterate the carbon monoxide that nanometer zinc germanate (c) photocatalytic reduction of carbon oxide of 4% bronze medal obtains
Yield mapping.From figure 8, it is seen that the nanometer zinc germanate of 4% bronze medal of doping obtained using the present invention, is reducing agent normal using water
It realizes that high efficiency photocatalysis restores carbon dioxide under temperature, normal pressure, and compared to the nanometer zinc germanate of 2% bronze medal of doping, utilizes this hair
The nanometer zinc germanate of 4% bronze medal of doping of bright acquisition sunlight irradiation under by CO2Generate CO rate or yield be about 2 times or
It is higher.
Claims (7)
1. a kind of preparation method of dopen Nano zinc germanate, which is characterized in that method and step is as follows:
1) prepared by solution one: the ratio of the foundation mole of zinc acetate, copper acetate and germanium oxide being mixed and is placed in raw material storage tank；
2) prepared by solution two: neopelex being dissolved in a certain amount of water, is uniformly mixed in stock chest；
3) preparation of dopen Nano zinc germanate: by step 1) preparation solution one and it is described it is rapid 2) preparation solution two according to mole
Ratio be conveyed into reaction kettle, while be added sodium hydroxide solution price adjustment pH value；It is reacted under reaction condition, product is washed to
It is neutral.
2. a kind of preparation method of dopen Nano zinc germanate according to claim 1, which is characterized in that in the step 1)
Sour zinc, copper acetate and germanium oxide molar ratio be 1:0-0.09:0.90-1.10.
3. a kind of preparation method of dopen Nano zinc germanate according to claim 1, which is characterized in that in the step 2)
Zinc acetate and neopelex molar ratio be 1:0.8-1.5.
4. a kind of preparation method of dopen Nano zinc germanate according to claim 1, which is characterized in that the step 2)
PH value is 9.0-11.0.
5. a kind of preparation method of dopen Nano zinc germanate according to claim 1, which is characterized in that the step 2) is anti-
Answering condition is to react 4-10 hours under the conditions of temperature is 100-180 DEG C.
6. the dopen Nano zinc germanate of claim 1 step method preparation.
7. application of the dopen Nano zinc germanate of claim 1 step method preparation in catalysis reduction carbon dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811555938.4A CN109589985B (en) | 2018-12-19 | 2018-12-19 | Preparation method of doped nano zinc germanate and catalytic reduction of carbon dioxide by using doped nano zinc germanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811555938.4A CN109589985B (en) | 2018-12-19 | 2018-12-19 | Preparation method of doped nano zinc germanate and catalytic reduction of carbon dioxide by using doped nano zinc germanate |
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| Publication Number | Publication Date |
|---|---|
| CN109589985A true CN109589985A (en) | 2019-04-09 |
| CN109589985B CN109589985B (en) | 2020-05-01 |
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| CN112537794A (en) * | 2020-11-17 | 2021-03-23 | 欣旺达电动汽车电池有限公司 | Zinc germanate nano material, preparation method thereof and lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111229205A (en) * | 2020-01-22 | 2020-06-05 | 青岛科技大学 | WO3/Zn2GeO4Non-noble metal bimetal oxide photocatalyst and preparation method and application thereof |
| CN111229239A (en) * | 2020-01-22 | 2020-06-05 | 青岛科技大学 | Zinc oxide/zinc germanate-copper zinc based metal oxide nano photocatalyst and preparation method and application thereof |
| CN111229205B (en) * | 2020-01-22 | 2021-09-21 | 青岛科技大学 | WO3/Zn2GeO4Non-noble metal bimetal oxide photocatalyst and preparation method and application thereof |
| CN111229239B (en) * | 2020-01-22 | 2021-11-05 | 青岛科技大学 | Zinc oxide/zinc germanate-copper nano composite material photocatalyst and preparation method and application thereof |
| CN112537794A (en) * | 2020-11-17 | 2021-03-23 | 欣旺达电动汽车电池有限公司 | Zinc germanate nano material, preparation method thereof and lithium ion battery |
| CN112537794B (en) * | 2020-11-17 | 2023-04-07 | 欣旺达电动汽车电池有限公司 | Zinc germanate nano material, preparation method thereof and lithium ion battery |
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