CN109589985B - Preparation method of doped nano zinc germanate and catalytic reduction of carbon dioxide by using doped nano zinc germanate - Google Patents
Preparation method of doped nano zinc germanate and catalytic reduction of carbon dioxide by using doped nano zinc germanate Download PDFInfo
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- 239000011701 zinc Substances 0.000 title claims abstract description 66
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 63
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 26
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000010531 catalytic reduction reaction Methods 0.000 title claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 24
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000003860 storage Methods 0.000 claims abstract description 22
- 239000004246 zinc acetate Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 16
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940080264 sodium dodecylbenzenesulfonate Drugs 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 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 18
- 239000000498 cooling water Substances 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims 2
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 abstract description 2
- FNIHDXPFFIOGKL-UHFFFAOYSA-N disodium;dioxido(oxo)germane Chemical compound [Na+].[Na+].[O-][Ge]([O-])=O FNIHDXPFFIOGKL-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 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
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 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
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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
- B01J23/76—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
-
- B01J35/39—
-
- 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
Abstract
The invention discloses a preparation method of doped nano zinc germanate and a catalytic reduction method of carbon dioxide, and the method comprises the following steps: (1) preparation of a solution I: mixing zinc acetate, copper acetate and germanium oxide according to a molar ratio, and placing the mixture into a raw material storage tank; (2) preparation of a solution II: dissolving sodium dodecyl benzene sulfonate in a certain amount of water, and uniformly stirring and mixing in a storage tank; (3) preparing doped nano zinc germanate: conveying the solution I prepared in the step 1) and the solution II prepared in the step 2) into a reaction kettle according to a molar ratio, and adding a sodium hydroxide solution to adjust the pH value; reacting under the reaction condition, and washing the product to be neutral. The invention does not need to synthesize the sodium germanate at high temperature, thereby reducing the energy consumption; the temperature is low in the process of synthesizing the doped zinc copper germanate, only 100-180 ℃ is needed, the time is short for 4-10 hours, and the energy consumption is further reduced.
Description
Technical Field
The invention relates to the technical field of doping nano zinc germanate, in particular to a novel method for doping by simple hydrothermal synthesis and further carrying out photocatalytic reduction on carbon dioxide by doping zinc germanate.
Background
In the modern society, the rapid development of industry brings serious problems of environmental pollution and energy shortage, and how to effectively solve the problems of energy and environment becomes a worldwide problem. Excessive use of fossil fuels releases large amounts of CO2Resulting in the formation of CO in the atmosphere2The concentration of the dominant greenhouse gases is continuously increased, which greatly hinders the sustainable development of human society. However, CO2Is also a potential carbon resource, and therefore how to effectively utilize CO2Become a global hotspot because of the introduction of CO2The conversion into clean energy can contribute to solving the problems of energy shortage and environmental deterioration at the same time. In which CO is photocatalytically reduced2Is considered to be a potential solution, because the light energy is inexhaustible clean energy and is enough to meet the global demand; in addition, photocatalytic reduction of CO is achieved compared to other processes2The method is generally carried out at normal temperature and normal pressure, solar energy is directly utilized without consuming other auxiliary energy, and the cyclic utilization of the carbon material can be really realized.To date, a number of photocatalytic materials have been applied to the photocatalytic reduction of CO2However, the extremely low conversion efficiency seriously hinders its practical application. Therefore, the search for efficient, stable, and inexpensive photocatalysts has attracted a great deal of attention.
In the past decades, titanium dioxide has been attracting attention due to its chemical stability, non-toxicity, and other advantages. However, titanium dioxide has high band gap energy and high photoelectron and hole recombination rate after excitation, so that the photocatalytic activity of titanium dioxide is restricted. Therefore, in order to improve the utilization of solar energy, a non-titanium type high-efficiency catalyst has been sought while modifying titanium dioxide. Zinc germanate, as a wide bandgap semiconductor material, is a wide bandgap semiconductor material similar to TiO 2. The zinc germanate has important research value for solving the problems of energy crisis and water pollution due to conduction band dispersion, high photoproduction electron mobility and good light stability, and is considered to be a semiconductor photocatalytic material with application prospect. Zinc germanate belongs to n-type metal oxide semiconductor materials, shows good visible light response and excellent photocatalytic activity, and has proper conduction band potential which is enough to reduce water or carbon dioxide and degrade organic pollutants in water in general. To date, zinc germanate semiconductor materials have been shown to be capable of photocatalytic reduction of CO2However, the defects of few active sites, weak intrinsic activity and the like of the common bulk zinc germanate material seriously affect the photocatalytic reduction of CO2Activity of (2). The preparation of the nano zinc germanate material is helpful for solving the problems. Because the band gap of zinc germanate is wide (4.5eV), light absorption is in the ultraviolet light range, but the ultraviolet light in the natural world only accounts for 4% of the sunlight, so that the band gap width is reduced, and the expansion of the light absorption to the visible light range is important for the development of zinc germanate in the aspect of photocatalysis. The invention utilizes a hydrothermal method to synthesize doped nano zinc germanate to adjust the energy band structure of the doped nano zinc germanate, reduce the band gap width of the doped nano zinc germanate and use the prepared doped nano zinc germanate for photocatalytic reduction of CO2The application of (A) has not been reported yet.
Disclosure of Invention
Based on the technical problems existing in the background technology, one of the purposes of the invention is to provide a process method for preparing a doped nano zinc germanate material and regulating and controlling the concentration of doped copper in the zinc germanate; the second purpose of the invention is to realize the performance of high-efficiency photocatalytic reduction of carbon dioxide by using the prepared material at normal temperature and normal pressure on the basis of the performance.
A preparation method of doped nano zinc germanate is characterized by comprising the following steps:
1) preparation of a solution I: mixing zinc acetate, copper acetate and germanium oxide according to a molar ratio, and placing the mixture into a raw material storage tank;
2) preparation of a solution II: dissolving sodium dodecyl benzene sulfonate and zinc acetate in a certain amount of water according to the molar ratio, and uniformly stirring and mixing the sodium dodecyl benzene sulfonate and the zinc acetate in a storage tank;
3) preparing doped nano zinc germanate: conveying the solution I prepared in the step 1) and the solution II prepared in the step 2) into a reaction kettle according to a molar ratio, and adding a sodium hydroxide solution to adjust the pH value; reacting under the reaction condition, and washing the product to be neutral.
The molar ratio of zinc acetate, copper acetate and germanium oxide in the step 1) is 1:0-0.09: 0.90-1.10.
The molar ratio of the sodium dodecyl benzene sulfonate to the zinc acetate in the step 2) is 1: 0.8-1.5.
The pH value of the step 2) is 9.0-11.0.
The reaction condition of the step 2) is that the temperature is 100-180 ℃ for 4-10 hours.
The prepared doped nano zinc germanate.
The doped nano zinc germanate is applied to catalytic reduction of carbon dioxide.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) the process does not need high-temperature synthesis of sodium germanate, so that energy consumption is reduced;
(2) the temperature in the process of synthesizing the doped zinc copper germanate in the technical process is low, only 100-180 ℃ is needed, the time is short for 4-10 hours, and the energy consumption is further reduced;
(3) the process is simple, low in cost, capable of realizing continuous production and easy for industrial production;
(4) the product doped with copper nano zinc germanate produced by the process has small size and large specific surface area;
(5) compared with zinc germanate, the product doped with nano zinc germanate expands the light absorption to the visible light range, and the light in the whole spectrum range can be utilized in the process of photocatalytic reduction of carbon dioxide;
(6) the product is doped with nano zinc germanate, so that more oxygen vacancies are generated in the zinc germanate, and the oxygen vacancies reduce the recombination of photo-generated electrons and holes;
(7) the copper-doped nano zinc germanate belongs to an n-type metal oxide semiconductor material, when light with energy larger than or equal to the forbidden bandwidth Eg irradiates the copper-doped nano zinc germanate, valence band electrons are excited to a conduction band to generate high-activity photo-generated electrons (e-), and positive photo-generated holes (h +) are left in the valence band. The carbon dioxide adsorbed on the surface of the copper-doped nano zinc germanate is easy to accept photoproduction electrons to generate photocatalytic reduction because electron clouds are concentrated on oxygen atoms on two sides and a carbon atom in the middle has stronger electrophilicity.
Drawings
FIG. 1 is a process flow diagram for synthesizing doped nano zinc germanate according to the present invention;
fig. 2 is XRD diffraction pattern diagrams of prepared nano zinc germanate (a), nano zinc germanate doped with 2% copper (b) and nano zinc germanate doped with 4% copper (c) according to the present invention;
FIG. 3 is a Transmission Electron Microscope (TEM) image of the prepared nano zinc germanate provided by the invention
FIG. 4 is a Transmission Electron Microscope (TEM) image of the prepared 2% doped nano-zinc copper germanate provided by the invention
FIG. 5 is a Transmission Electron Microscope (TEM) image of the prepared 4% doped nano zinc germanate
FIG. 6 shows XRD diffraction pattern of nano zinc germanate doped with 15% copper prepared by the present invention
Fig. 7 is a carbon dioxide physical absorption diagram of the prepared nano zinc germanate (a), nano zinc germanate (b) doped with 2% copper and nano zinc germanate (c) doped with 4% copper.
Fig. 8 is a graph showing the yields of carbon monoxide from the photocatalytic reduction of carbon dioxide by the prepared nano zinc germanate (a), the nano zinc germanate (b) doped with 2% copper, and the nano zinc germanate (c) doped with 4% copper.
In the figure: v1-Zn(CH3COO)2Storage tank, V2-Cu(CH3COO)2Storage tank, V3-GeO2A storage tank, a D0101-dryer, an E0101-heat exchanger A, E0102-heat exchanger B, F0101-filter, an M0101-mixing tank, a P0101-material pump A, P0102-material pump B, R0101-reaction kettle, a V0101-wastewater recovery tank and a W0101-washing tank.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Referring to FIG. 1, Zn (CH)3COO)2、Cu(CH3COO)2And GeO2Respectively entering a mixing tank from a storage tank for uniform mixing, then conveying to a reaction kettle, completely dissolving the sodium dodecyl benzene sulfonate in water in the storage tank, then cooling the mixture by a heat exchanger A in the conveying process, finally feeding the cooled mixture into a reaction kettle, adding the sodium dodecyl benzene sulfonate and the zinc acetate in the reaction kettle according to a certain molar ratio, adding NaOH into the reaction kettle, adjusting the pH value of the reaction, then high-pressure steam is continuously input in the reaction process, the solution after the reaction is conveyed to a washing tank through a material pump A, before entering the washing tank, the materials are cooled by a heat exchanger B, washed in the washing tank until the product is neutral, and then the materials are conveyed to a filter through a material pump B, a plurality of materials are filtered, the filtered solids enter a dryer for drying, and the filtered liquid enters a backwater recovery tank for unified treatment.
The cooling water of heat exchanger A and heat exchanger B is imported through recirculated cooling water inlet pipe way, then discharges through recirculated cooling water return water pipeline, and unnecessary steam is discharged from reation kettle's steam escape pipe way in the reation kettle, then discharges from steam condensate water pipeline after the water cooling on the recirculated cooling water, and the filter upper end still is equipped with technology water input pipeline, mainly washes the solid after the filtration.
Example 1
Mixing zinc acetate, copper acetate and germanium oxide at a molar ratio of 1:0.03:0.97, placing into a raw material storage tank, and mixing uniformly. Dissolving sodium dodecyl benzene sulfonate with the molar ratio of 1:1 to zinc acetate in a certain amount of water, and stirring and mixing uniformly in a storage tank. Conveying water dissolved with sodium dodecyl benzene sulfonate into a reaction kettle by a material pump, conveying the uniformly mixed zinc acetate, copper acetate and germanium oxide into the reaction kettle, stirring for 30 minutes, and adding a sodium hydroxide solution to adjust the pH value to 11.0. The reaction is carried out for 10 hours at the temperature of 100 ℃, and the product is washed to be neutral by water. Vacuum drying is carried out.
Example 2
Mixing zinc acetate, copper acetate and germanium oxide at a molar ratio of 1:0.06:0.93, placing into a raw material storage tank, and mixing uniformly. Dissolving sodium dodecyl benzene sulfonate with the molar ratio of 1:1.2 to zinc acetate in a certain amount of water, and stirring and mixing uniformly in a storage tank. Conveying water dissolved with sodium dodecyl benzene sulfonate into a reaction kettle by a material pump, conveying the uniformly mixed zinc acetate, copper acetate and germanium oxide into the reaction kettle, stirring for 30 minutes, and adding a sodium hydroxide solution to adjust the pH value to 9.0. Reacting for 4 hours at the temperature of 180 ℃, and washing the product to be neutral. Vacuum drying is carried out.
Example 3
Mixing zinc acetate, copper acetate and germanium oxide at a molar ratio of 1:0.06:0.93, placing into a raw material storage tank, and mixing uniformly. Dissolving sodium dodecyl benzene sulfonate with the molar ratio of 1:1.4 to zinc acetate in a certain amount of water, and stirring and mixing uniformly in a storage tank. Conveying water dissolved with sodium dodecyl benzene sulfonate into a reaction kettle by a pump, conveying the uniformly mixed zinc acetate, copper acetate and germanium oxide into the reaction kettle, stirring for 30 minutes, and adding a sodium hydroxide solution to adjust the pH value to 10.5. The reaction is carried out for 3.5 hours at the temperature of 120 ℃, and the product is washed to be neutral by water. Vacuum drying is carried out.
Comparative example 1
Mixing zinc acetate and germanium oxide at a molar ratio of 1:1, placing into a raw material storage tank, and mixing uniformly. Dissolving sodium dodecyl benzene sulfonate with the molar ratio of 1:1 to zinc acetate in a certain amount of water, and stirring and mixing uniformly in a storage tank. Conveying water dissolved with sodium dodecyl benzene sulfonate into a reaction kettle by a pump, conveying the uniformly mixed zinc acetate and germanium oxide into the reaction kettle, stirring for 30 minutes, and adding a sodium hydroxide solution to adjust the pH value to 9.0-11.0. Reacting for 4-10 hours at the temperature of 100-180 ℃, and washing the product to be neutral. Vacuum drying is carried out.
Application example 1: the prepared nano zinc germanate, 2% copper-doped nano zinc germanate and 4% copper-doped nano zinc germanate are used for measuring carbon dioxide physical adsorption and photocatalytic reduction CO2To produce CO
100mg of the zinc germanate products doped with different copper contents obtained in this comparative example 1, example 1 and example 2 were uniformly dispersed in a photocatalytic reactor containing 100ml of water, respectively, and high purity CO was introduced2Gas for half an hour to make the water solution be CO2Saturation, reactor connected to gas chromatography (Techcomp GC7900) (Lab Solar-III AG, PerfectLightLimited, Beijing) and charged with high purity CO2The air inside the glass instrument was replaced, and the operation was repeated 3 times so that the glass instrument was sealed at a pressure of about ambient pressure. And then, using a 300W xenon lamp to simulate sunlight as a light source for reaction, realizing continuous sunlight irradiation, and measuring the amount of generated CO after reaction for 1h, 3h, 6h, 9h, 12h and 15 h.
Fig. 8 is a graph showing the yield of carbon monoxide obtained by photocatalytic reduction of carbon dioxide using nano zinc germanate (a) prepared according to comparative example 1, nano zinc germanate (b) doped with 2% copper in example 1, and nano zinc germanate (c) doped with 4% copper in example 2. As can be seen from FIG. 8, the 4% copper doped nano zinc germanate obtained by the invention realizes high-efficiency photocatalytic reduction of carbon dioxide at normal temperature and normal pressure by using water as a reducing agent, and compared with the 2% copper doped nano zinc germanate, the 4% copper doped nano zinc germanate obtained by the invention is prepared by CO under the irradiation of sunlight2The rate or yield of CO production is about 2-fold or greater.
Claims (4)
1. A preparation method of doped nano zinc germanate is characterized by comprising the following steps:
1) preparation of a solution I: mixing zinc acetate, copper acetate and germanium oxide according to a molar ratio, and placing the mixture into a raw material storage tank;
2) preparation of a solution II: dissolving sodium dodecyl benzene sulfonate in a certain amount of water, and uniformly stirring and mixing in a storage tank;
3) preparing doped nano zinc germanate: conveying the solution I prepared in the step 1) and the solution II prepared in the step 2) into a reaction kettle according to a molar ratio, and adding a sodium hydroxide solution to adjust the pH value; reacting under the reaction condition, and washing the product to be neutral;
the reaction condition of the step 3) is that the reaction is carried out for 4 to 10 hours at the temperature of 100-180 ℃;
the molar ratio of zinc acetate, copper acetate and germanium oxide in the step 1) is 1:0-0.09:0.90-1.10, wherein the molar ratio of copper acetate is not 0;
the molar ratio of the zinc acetate to the sodium dodecyl benzene sulfonate in the step 2) is 1: 0.8-1.5;
the equipment for producing the doped nano zinc germanate comprises Zn (CH) connected with a mixing tank3COO)2Storage tank, Cu (CH)3COO)2Storage tank, GeO2The system comprises a mixing tank, a reaction kettle, a storage tank, a heat exchanger A, a high-pressure steam pipe, a washing tank, a material pump, a filter, a return water recovery tank and a return water recovery tank, wherein an outlet of the mixing tank is connected with an inlet of the reaction kettle through a pipeline; cooling water of the heat exchanger A and the heat exchanger B is input through a circulating cooling water upper water pipeline and then is discharged through a circulating cooling water return pipeline, and redundant steam in the reaction kettle is discharged from a steam discharge pipe of the reaction kettleAnd discharging the water from the pipeline, cooling the water by circulating cooling water, and discharging the water from a steam condensate pipeline, wherein a process water input pipeline is further arranged at the upper end of the filter and used for washing the filtered solid.
2. The method for preparing doped nano zinc germanate according to claim 1, wherein the pH value in the step 3) is 9.0-11.0.
3. The doped nano zinc germanate prepared by the preparation method of claim 1.
4. The application of the doped nano zinc germanate prepared by the preparation method of claim 1 in catalytic reduction of carbon dioxide.
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| 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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| CN106186049A (en) * | 2016-07-14 | 2016-12-07 | 南京大学 | A kind of hydrothermal preparing process of the bar-shaped zinc germanate of size adjustable |
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| "Cobalt-doped Zn2GeO4 nanorods assembled into hollow spheres as high-performance anode materials for lithium-ion batteries";Jiaxue Lu等;《J. Mater. Chem. A》;20180224;第6卷;实验部分 * |
| "Growth of Zn2GeO4 and Cu-Doped Zn2GeO4 Nanowires by Thermal Evaporation";Chih-Cheng Hung等;《Journal of The Electrochemical Society》;20100225;第157卷(第4期);摘要 * |
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