CN114950561A - CO (carbon monoxide) 2 Preparation method of photoreduction catalyst - Google Patents

CO (carbon monoxide) 2 Preparation method of photoreduction catalyst Download PDF

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CN114950561A
CN114950561A CN202210371728.XA CN202210371728A CN114950561A CN 114950561 A CN114950561 A CN 114950561A CN 202210371728 A CN202210371728 A CN 202210371728A CN 114950561 A CN114950561 A CN 114950561A
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drying
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aqueous solution
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CN114950561B (en
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苏晓文
吴珊
龙晓星
高雪
苏继新
曹晓晴
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Shandong University
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • 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
    • B01J23/80—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 zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
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    • 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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    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
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    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
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Abstract

CO (carbon monoxide) 2 The preparation method of the photoreduction catalyst comprises the following steps: (1) preparing an aqueous solution, wherein each 100ml of the aqueous solution contains 1-5g of zinc acetate dihydrate: 0-92.5mg powder GO: 5-10ml of triethanolamine, and all the components are stirred and mixed together; (2) centrifuging the aqueous solution, washing the separated precipitate and drying; (3) mixing the obtained sample with deionized water, simultaneously adding sulfonated cobalt phthalocyanine, stirring and mixing uniformly, reacting the mixed solution at 120 ℃ for 12 hours, then centrifugally separating out mother liquor, ultrasonically washing the precipitate with purified water and centrifugally separating until the washing water is checked with barium chlorideNo sulfonic group, finally washing with absolute ethyl alcohol by ultrasonic wave, obtaining a sample after centrifugal separation, (4) baking after drying, and obtaining CO 2 A photoreduction catalyst. The invention adopts a gas-solid two-phase reaction process, has small diffusion resistance and prepares CO 2 The photoreduction catalyst has the function of converting CO 2 Excellent performance and high selectivity for catalytic reduction to CO.

Description

CO (carbon monoxide) 2 Preparation method of photoreduction catalyst
Technical Field
The invention relates to CO 2 A preparation method of a photoreduction catalyst belongs to the technical field of photoreduction catalyst preparation.
Background
The main approach to prevent climate change is based on broader renewable energy utilization and CO 2 And (5) emission reduction. In the process of exchanging energy and materials of the biosphere, the rock ring, the water ring and the atmospheric ring of the earth, the carbon cycle is one of the most important processes, and CO 2 Is a key element of carbon cycle, the relative stability of which has been subject to industrial revolution for billions of years, CO 2 The significant impact of large intensity, cumulative emissions, corresponds to significant changes in global climate.
The earth biological activity is always the main mode for converting sunlight into storable products and energy in a large scale, and the conversion of sunlight into carbon-containing materials by utilizing the principle that semiconductor photocatalytic materials simulate plant photosynthesis is an effective way for realizing the aim of carbon neutralization.
At present, CO 2 The research of the photo-reduction catalytic material has made a certain progress, for example, Chinese patent document CN114146715A discloses a heterojunction composite material and its preparation method and application, the method prepares CeO 2 /MoSe 2 Composite material, successfully CO 2 Conversion to CO, CH 4 Hollow CeO rich in oxygen vacancies 2 And MoSe 2 Forming a heterojunction, hollow CeO rich in oxygen vacancies 2 The hollow structure is uniform, the specific surface area of the heterojunction composite material is improved, the adsorption capacity to carbon dioxide is strong, and the unique hollow structure can enable visible light to be in CeO 2 The hollow cavity is internally reflected for multiple times, so that the utilization efficiency of visible light is improved; the introduction of oxygen vacancy is beneficial to the capture of electrons by carbon dioxideThereby promoting the photocatalytic reduction process of the heterojunction composite material on the carbon dioxide. Introduced narrow bandgap semiconductor MoSe 2 With CeO 2 The heterojunction is formed, the absorption range of visible light and the separation efficiency of photon-generated carriers are increased, and the catalytic activity of the heterojunction composite material on reduction of carbon dioxide is improved.
Photocatalytic reduction of CO 2 In an attempt to introduce CO into a continuous production plant for the photocatalytic synthesis of methanol from carbon dioxide and water, as disclosed in CN113877496A 2 Directly converting into chemical products such as methanol and the like; the device comprises a tank body, wherein a methanol synthesis reaction chamber is arranged at the middle lower part in the tank body, a separation part made of a light source and activated carbon is arranged in the methanol synthesis reaction chamber, the separation part divides the methanol synthesis reaction chamber into a filter chamber and a methanol synthesis chamber, the filter chamber is connected with the gas outlet of a carbon dioxide gas input pipe and the water outlet of a water input pipe, a water outlet is arranged on the wall of the lower part chamber of the methanol synthesis chamber, a gasified methanol recovery device is arranged at the top end in the tank body, a compression chamber is arranged in the tank body above the methanol synthesis reaction chamber, and a gasification separation chamber is arranged in the tank body above the compression chamber. Also, the metal organic compound is compounded with other materials to obtain the compound with CO 2 A technical scheme of a photoreduction active catalytic material. CN113083367A discloses a single-atom catalytic material NiPc-MPOP for efficient photocatalytic carbon dioxide reduction and a preparation method thereof, and a series of porous organic polymers NiPc-MPOP containing M-N4 and M-N2O2 single-atom sites at the same time are prepared. The polymer not only can synergistically improve the catalytic efficiency, but also provides a more direct opportunity to recognize the activity of the metal center. CO2 2 The results of the photo-reduction show that the introduction of a Ni-N2O2 catalytic center into the original phthalocyanine-based Ni-N4 framework can realize excellent CO generation capability (7.77 mmoleg) -1 ) Relative to H 2 The selectivity of (A) is up to 96%. Combining control experiments and theoretical studies, the Ni-N2O2 moiety proved to be a site of higher CO2RR activity compared to the conventional Ni-N4 moiety. CN112791747A discloses a preparation method and application of an ultrathin two-dimensional phosphoric acid regulated metal phthalocyanine/perylene imide composite photocatalyst, and the ultrathin two-dimensional phosphoric acid regulated metal phthalocyanine/perylene imide composite photocatalyst can be obtainedA photocatalyst. CN112473747A discloses a preparation method and application of a gold nanoparticle regulated ultrathin two-dimensional metal phthalocyanine/bismuth vanadate heterojunction photocatalyst, which solves the problems of low separation efficiency of a photo-generated carrier and lack of a catalytic active center in the preparation of a bismuth vanadate-based heterojunction composite system in the prior art. The method comprises the following steps: 1. preparing bismuth vanadate nanosheets; 2. dispersing bismuth vanadate nanosheets in a precursor solution of gold; 3. separating, washing and drying; 4. dispersing the complex in an alcohol solution of metal phthalocyanine; 5. evaporating the solution to dryness in water bath; 6. and drying the reaction product IV to obtain the ultrathin two-dimensional metal phthalocyanine/gold-bismuth vanadate heterojunction photocatalyst.
In addition, there is a prior art that attempts are made to obtain a photocatalytic material having higher efficiency by compounding a carbon material such as g — C3N4 or GO (graphene oxide), a semiconductor, and a transition metal. For example, CN107649159A discloses an organic dye modified carbon nitride graphene composite material, which is prepared by the following method: mixing the g-C3N4 alcohol solution with the graphene alcohol solution, ultrasonically mixing uniformly, keeping the temperature at 100-240 ℃ for 8-24 hours, centrifuging to remove ethanol, and vacuum-drying the precipitate to obtain a g-C3N 4/r-graphene compound; mixing the g-C3N 4/r-graphene composite with organic dye and organic alcohol C, ultrasonically mixing uniformly, centrifuging, washing the precipitate with the organic alcohol C, and drying in the dark to obtain the organic dye modified carbon nitride graphene composite material. CN113957458A discloses a preparation method and application of a g-C3N 4/two-dimensional porphyrin MOF material, wherein when a g-C3N 4/two-dimensional porphyrin MOF composite material is synthesized, g-C3N4 with different amounts is synthesized to form a stable g-C3N 4/two-dimensional porphyrin MOF material; g-C3N 4/two-dimensional porphyrin MOF material semiconductor electrocatalyst. CN108070874A discloses an atom-dispersed water oxidation catalyst, a preparation method and an application thereof, the method can prepare a catalyst containing metal ions such as vanadium, chromium, manganese, iron, cobalt, nickel, copper, ruthenium, palladium, silver, cadmium, iridium and lead with dispersed atoms, the metal ions in the material synthesized by the method are mainly embedded in the framework of a carbon-based carrier in a single-atom mode, and the metal loading capacity can be up to more than 1.5 wt.%. CN113600221A discloses an Au/g-C 3 N 4 Monoatomic photocatalyst based on Au chelate as precursor, and its preparing process and applicationThe Au/g-C is prepared by simply utilizing a method of continuous stirring and one-step calcination 3 N 4 A monatomic photocatalyst. CN113680361A discloses a cobalt-ruthenium bimetallic monatomic photocatalyst and a preparation method thereof, wherein the photocatalyst is a two-dimensional porous reticular structure, and the pore diameter is 2-10 nm; the carbon-nitrogen polymer composite material consists of a carbon-nitrogen polymer carrier and cobalt-ruthenium bimetallic single atoms anchored on the carbon-nitrogen polymer carrier, wherein the chemical formula of the carbon-nitrogen polymer is g-C4N3, and the mass ratio of the carbon-nitrogen polymer to cobalt to ruthenium is (100-150): (2-3): 1; the preparation method is that solid precursor cobalt salt and ruthenium salt are subjected to in-situ self-growth to form metal monoatomic atoms in the process of forming g-C4N3 by dehydrating and condensing formamide through a solvothermal method.
The method and the prepared product thereof have CO 2 The catalytic material with the photo-reduction activity is mostly applied to gas-solid-liquid three-phase photo-catalytic reaction, and has the problems of large mass transfer resistance caused by multi-stage diffusion between gas and a catalytic center, difficulty in considering both the selectivity and the activity of the catalytic material and the like.
Disclosure of Invention
The present invention is directed to existing CO 2 The defects of the preparation technology of the photoreduction catalyst are that the preparation technology of the photoreduction catalyst provides a method for preparing the catalyst by using CO 2 Highly active and highly selective CO for catalytic reduction to CO 2 A method for preparing a photoreduction catalyst.
CO of the invention 2 The preparation method of the photoreduction catalyst comprises the following steps:
(1) preparing aqueous solution containing 1-5g zinc acetate dihydrate (C) per 100ml 4 H 10 O 6 Zn): 0-92.5mg powder GO: 5-10ml of triethanolamine, and all the components are stirred and mixed together;
the stirring and mixing are carried out by ultrasonic stirring for 1 hour at the temperature of 20 ℃, then the mixture is transferred to mechanical stirring, the mechanical stirring is carried out for 2 hours at the temperature of 50 ℃, and then the temperature is raised to 90 ℃ and the mechanical stirring is carried out for 6 to 10 hours.
(2) Centrifugally separating the aqueous solution obtained in the step (1), washing and drying separated precipitates to obtain a sample;
the washing is ultrasonic washing and centrifugal separation with deionized water for 5 times (each ultrasonic washing is followed by centrifugal separation), ultrasonic washing and centrifugal separation with ethanol for 2 times.
The drying is carried out in a vacuum drying oven at 60 ℃ for 12 hours.
(3) Mixing the sample obtained in the step (2) with 50ml of deionized water per 100ml of aqueous solution (single batch), adding 37-185mg of sulfonated cobalt phthalocyanine at the same time, stirring and mixing uniformly, reacting the mixed solution at 120 ℃ for 12 hours (in a hydrothermal high-pressure kettle), then centrifugally separating out mother liquor, ultrasonically washing and centrifugally separating precipitates with purified water until no sulfonic group exists in the washing water detected by barium chloride, finally ultrasonically washing with anhydrous ethanol, and centrifugally separating to obtain the sample.
(4) Drying and roasting the sample obtained in the step (3) to obtain CO 2 A photoreduction catalyst.
The drying is carried out in an oven at 105 ℃ for 6 hours.
The roasting is carried out in a muffle furnace N 2 Roasting for 6 hours at 550 ℃ under the atmosphere.
The obtained CO was subjected to the following procedure 2 Carrying out gas-solid phase reaction evaluation on the photoreduction catalyst;
the specific process is as follows: introducing CO 2 The photoreactor is arranged on a tray in a photoreactor (closed glass reactor), the photoreactor is provided with a jacket with constant temperature water bath circulation (the temperature in the reactor is prevented from changing due to illumination, the constant temperature water bath is about 8 ℃), and high-purity CO is arranged in the photoreactor 2 (99.99% (v/v)) and deionized water, the deionized water is added into the space under the tray in the reactor, a xenon lamp simulating sunlight is used for irradiation, a gas sample can be taken every hour after the irradiation, and a gas chromatographic analyzer is used for analyzing the gas composition in the optical reactor, so that the yield and the selectivity of the CO are obtained.
The invention adopts the combination of ZnO base, cobalt phthalocyanine and rGO (reduced graphene oxide) to prepare CO 2 A photoreduction catalyst having the function of converting CO 2 Excellent performance and high selectivity for catalytic reduction to CO. It features that it adopts gas-solid two-phase reaction process, its diffusion resistance is small, and the new catalytic material can utilize natural light to make CO produce reaction with high activity and high selectivity 2 Catalytic reduction to CO.
Drawings
FIG. 1 is the CO of sample 1, sample 2 and sample 3 synthesized separately in three examples 2 The results of the yield and selectivity of photocatalytic reduction of CO are shown.
Fig. 2 is an SEM micrograph of sample 1 synthesized in example 1.
FIG. 3 is an SEM micrograph of sample 3 synthesized in example 3.
Detailed Description
The invention aims to provide CO 2 A method for preparing a photoreduction catalyst for the reduction of CO 2 The method for catalytically reducing the CO specifically comprises the following steps.
1. Preparing aqueous solution
Adding 1-5g zinc acetate dihydrate (C) into 100ml water solution 4 H 10 O 6 Zn), 0-92.5mg of powder GO and 5-10ml of triethanolamine. Mixing the components together, and ultrasonically stirring at 20 ℃ for 1 h. Transferring to mechanical stirring, mechanically stirring for 2h at 50 ℃, heating to 90 ℃ again, and stirring for 6-10 h.
2. Washing, separating and drying
Centrifuging the aqueous solution, ultrasonically washing the precipitate with deionized water, centrifuging, ultrasonically washing and centrifuging for 5 times, ultrasonically washing with ethanol, and centrifuging for 2 times.
And drying the washed precipitate in a vacuum drying oven at 60 ℃ for 12 h.
3. Mixing a sample (single batch) obtained in each 100ml of aqueous solution with 50ml of deionized water, simultaneously adding 37-185mg of sulfonated cobalt phthalocyanine, stirring and uniformly mixing, transferring the mixed solution into a hydrothermal autoclave, reacting at 120 ℃ for 12 hours, centrifugally separating out mother liquor, ultrasonically washing precipitates by 25ml of purified water, centrifugally separating for five times, and then checking that no sulfonic group exists in washing water by barium chloride. If the unwashed state is complete, the number of times of ultrasonic washing and centrifugal separation should be increased. Finally, 10ml of absolute ethyl alcohol is used for ultrasonic washing and centrifugal separation, and a sample is obtained.
4. After drying the sample obtained in step 3 in an oven at 105 ℃ for 6h, the sample was transferred to a tubular muffle furnace, N 2 Baking at 550 ℃ under atmosphereFiring for 6h to obtain the final catalyst material, namely CO 2 A photoreduction catalyst.
Specific examples are given below.
Example 1
(1) 1g of zinc acetate dihydrate (C) 4 H 10 O 6 Zn), 0mg of powder GO and 5ml of triethanolamine are added into water, stirred and mixed to prepare 100ml of aqueous solution. The stirring and mixing process is ultrasonic stirring at 20 deg.c for 1 hr, mechanical stirring at 50 deg.c for 2 hr, and mechanical stirring at 90 deg.c for 6 hr.
(2) Centrifuging the aqueous solution, washing and centrifuging the separated precipitate with deionized water for 5 times (each ultrasonic washing followed by centrifuging), further washing with ethanol and centrifuging for 2 times. The washed precipitate was dried in a vacuum oven at 60 ℃ for 12 hours to obtain a single batch of samples.
(3) Mixing the obtained sample with 50ml of deionized water, simultaneously adding 37mg of sulfonated cobalt phthalocyanine, stirring and mixing uniformly, transferring the mixed solution into a hydrothermal autoclave, reacting at 120 ℃ for 12 hours, centrifugally separating out mother liquor, ultrasonically washing precipitates by 25ml of purified water, centrifugally separating for five times, and then detecting the absence of sulfonic acid groups in the washing water by barium chloride. If the unwashed state is complete, the number of times of ultrasonic washing and centrifugal separation should be increased. Finally, 10ml of absolute ethyl alcohol is used for ultrasonic washing and centrifugal separation, and a sample is obtained.
(4) After drying the sample in an oven at 105 ℃ for 6h, the sample was transferred to a tubular muffle furnace, N 2 Roasting at 550 ℃ for 6h under the atmosphere to obtain CO 2 Sample 1 of the photo-reduction catalyst.
(5) For CO prepared in example 1 2 The photoreduction catalyst sample 1 was evaluated to yield CO yield and selectivity:
20mg of CO 2 Sample 1 of the photo-reduction catalyst was placed on a circular tray having a capacity of 180ml in a closed glass reactor and subjected to gas-solid phase reaction evaluation, the tray having a diameter of 50 mm. The reactor jacket adopts constant temperature water bath circulating water for constant temperature, so as to prevent the fluctuation and the change of the temperature in the reactor under illumination, and the inside of the reactor is99.99% (v/v) purity CO 2 And 3ml of deionized water, wherein the deionized water is added into a space below a tray in the reactor, a sealed cover plate of the reactor is a polished quartz cover plate, the Xe lamp of 300W simulated sunlight is used for irradiation, and the distance between a xenon lamp light source and the tray is 4 cm. After the light irradiation, a gas sample was taken every hour and the gas composition in the reactor was analyzed by a gas chromatograph to obtain the yield and selectivity of CO.
CO of sample 1 2 The yield and selectivity results of photocatalytic reduction of CO are shown in fig. 1. FIG. 2 shows SEM micrographs of sample 1 synthesized in this example.
Example 2
(1) 3g of zinc acetate dihydrate (C) 4 H 10 O 6 Zn), 55.5mg of powder GO and 7ml of triethanolamine are added into water, stirred and mixed to prepare 100ml of aqueous solution. The stirring and mixing process is ultrasonic stirring at 20 deg.c for 1 hr, mechanical stirring at 50 deg.c for 2 hr, and mechanical stirring at 90 deg.c for 10 hr.
(2) The aqueous solution was centrifuged according to the procedure of step (2) of example 1, and the precipitate was washed and dried to obtain a single batch of samples.
(3) Mixing the obtained sample with 50ml of deionized water, adding 115mg of sulfonated cobalt phthalocyanine at the same time, stirring and mixing uniformly, reacting the mixed solution in a hydrothermal autoclave at 120 ℃ for 12 hours, then centrifugally separating out a mother solution, and washing and separating precipitates according to the process of example 1 to obtain the sample.
(4) The obtained sample was calcined by the procedure of step (4) of example 1 to obtain CO 2 Sample 2 of the photo-reduction catalyst.
(5) The CO prepared in this example was treated in the same manner as in example 1 2 Sample 2 of the photoreduction catalyst was evaluated to yield the yield and selectivity of CO.
CO of sample 2 2 The yield and selectivity results of photocatalytic reduction of CO are shown in fig. 1.
Example 3
(1) 1g of zinc acetate dihydrate (C) 4 H 10 O 6 Zn), 11.1mg of powder GO and 10ml of triethanolamine are added into water, stirred and mixed to prepare 100ml of water-soluble solutionAnd (4) liquid. The stirring and mixing process is ultrasonic stirring at 20 deg.c for 1 hr, mechanical stirring at 50 deg.c for 2 hr, and mechanical stirring at 90 deg.c for 8 hr.
(2) The aqueous solution was centrifuged according to the procedure of step (2) of example 1, and the precipitate was washed and dried to obtain a single batch of samples.
(3) Mixing the obtained sample with 50ml of deionized water, adding 37mg of sulfonated cobalt phthalocyanine at the same time, stirring and mixing uniformly, reacting the mixed solution in a hydrothermal autoclave at 120 ℃ for 12 hours, then centrifugally separating out mother liquor, and washing and separating precipitates according to the process of example 1 to obtain the sample.
(4) The obtained sample was calcined by the procedure of step (4) of example 1 to obtain CO 2 Sample 3 of the photo-reduction catalyst.
(5) The CO prepared in this example was treated in the same manner as in example 1 2 Sample 3 of the photoreduction catalyst was evaluated to yield and selectivity to CO.
CO of sample 3 2 The yield and selectivity results of photocatalytic reduction of CO are shown in fig. 1. FIG. 3 shows SEM micrographs of sample 3 synthesized in example 3.
Example 4
(1) 5g of zinc acetate dihydrate (C) 4 H 10 O 6 Zn), 92.5mg of powder GO and 10ml of triethanolamine are added into water, stirred and mixed to prepare 100ml of aqueous solution. The stirring and mixing process is ultrasonic stirring at 20 deg.c for 1 hr, mechanical stirring at 50 deg.c for 2 hr, and mechanical stirring at 90 deg.c for 6 hr.
(2) The aqueous solution was centrifuged according to the procedure of step (2) of example 1, and the precipitate was washed and dried to obtain a single batch of samples.
(3) Mixing the obtained sample with 50ml of deionized water, adding 185mg of sulfonated cobalt phthalocyanine at the same time, stirring and mixing uniformly, reacting the mixed solution in a hydrothermal autoclave at 120 ℃ for 12 hours, then centrifugally separating out mother liquor, and washing and separating precipitates according to the process of example 1 to obtain the sample.
(4) The obtained sample was calcined by the procedure of step (4) of example 1 to obtain CO 2 Photo reductionCatalyst sample 4.
(5) The CO prepared in this example was treated in the same manner as in example 1 2 Sample 2 of the photoreduction catalyst was evaluated to yield the yield and selectivity of CO.

Claims (6)

1. CO (carbon monoxide) 2 The preparation method of the photoreduction catalyst is characterized by comprising the following steps:
(1) preparing aqueous solution, wherein each 100ml of aqueous solution contains 1-5g of zinc acetate dihydrate, 0-92.5mg of powder GO and 5-10ml of triethanolamine, and all the components are stirred and mixed together;
(2) centrifugally separating the aqueous solution obtained in the step (1), washing and drying separated precipitates to obtain a sample;
(3) mixing the sample obtained from each 100ml of the aqueous solution in the step (2) with 50ml of deionized water, simultaneously adding 37-185mg of sulfonated cobalt phthalocyanine, stirring and mixing uniformly, reacting the mixed solution at 120 ℃ for 12 hours, then centrifugally separating out mother liquor, ultrasonically washing and centrifugally separating precipitates by using purified water until no sulfonic group exists in the washing water by using barium chloride, finally ultrasonically washing by using absolute ethyl alcohol, and centrifugally separating to obtain the sample.
(4) Drying and roasting the sample obtained in the step (3) to obtain CO 2 A photoreduction catalyst.
2. CO according to claim 1 2 The preparation method of the photoreduction catalyst is characterized in that the stirring and mixing in the step (1) are ultrasonic stirring for 1 hour at the temperature of 20 ℃, then mechanical stirring is carried out, mechanical stirring is carried out for 2 hours at the temperature of 50 ℃, and then the temperature is raised to 90 ℃ and mechanical stirring is carried out for 6-10 hours.
3. CO according to claim 1 2 The preparation method of the photo-reduction catalyst is characterized in that in the step (2), washing is carried out for 5 times by using deionized water for ultrasonic washing and centrifugal separation, and then ultrasonic washing and centrifugal separation are carried out by using ethanol for 2 times.
4. The method of claim 1CO of (2) 2 The preparation method of the photo-reduction catalyst is characterized in that the drying in the step (2) is drying for 12 hours in a vacuum drying oven at 60 ℃.
5. CO according to claim 1 2 The preparation method of the photo-reduction catalyst is characterized in that the drying in the step (4) is drying for 6 hours in an oven at 105 ℃.
6. CO according to claim 1 2 The preparation method of the photoreduction catalyst is characterized in that in the step (4), the calcination is carried out in a muffle furnace N 2 Roasting for 6 hours at 550 ℃ under the atmosphere.
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