CN109908959B - Core-shell ZnO/precious metal @ ZIF-8 photocatalytic material and preparation method and application thereof - Google Patents
Core-shell ZnO/precious metal @ ZIF-8 photocatalytic material and preparation method and application thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Abstract
The invention discloses a core-shell ZnO/precious metal @ ZIF-8 photocatalytic material and a preparation method and application thereof, wherein a ZnO nanorod is taken as a core, a ZIF-8 layer is taken as a shell, and reduced precious metal nanoparticles are loaded between the ZnO nanorod and the ZIF-8 layer, wherein the loading capacity of the reduced precious metal nanoparticles is 0.1-10% of the mass of the ZnO nanorod. The preparation method comprises the steps of firstly preparing ZnO nano-rods; then carrying out thermal reduction compounding on the ZnO nano-rod and a soluble precious metal precursor solvent to obtain a ZnO/precious metal nano-rod; and finally, mixing the ZnO/noble metal nanorod with a mixed solvent of 2-methylimidazole, N-dimethylformamide and water, and carrying out hydrothermal reaction to obtain the ZnO/noble metal nanorod. The invention can realize the carrier separation efficiency and CO simultaneously under the condition of not weakening the light absorption capacity2The capture capability is synergistically enhanced, the excellent photocatalytic activity is shown, and the greenhouse gas CO can be efficiently captured2Selective reduction to CH3The solar energy fuels such as OH and the like have wide application prospect in solving the problems of greenhouse effect, energy shortage and the like.
Description
Technical Field
The invention belongs to the field of photocatalytic materials, and particularly relates to a core-shell ZnO/noble metal @ ZIF-8 photocatalytic material and a preparation method and application thereof.
Background
Over-use of fossil fuels has not only exacerbated the global energy crisis but also emitted CO for decades2Isothermal chamber gases make the greenhouse effect increasingly severe, and therefore CO2Have received worldwide attention for capture, storage and utilization. CO conversion by photocatalytic technology2Conversion into solar fuel not only contributes to CO reduction2Relieving greenhouse effect and realizing CO2And the solar energy is converted into storable and transportable chemical energy for recycling, so that the problem of energy crisis is effectively solved.
Multiple semiconductor photocatalysts such as TiO2、ZnO、CdS、g-C3N4、ZnGe2O4Etc. are widely used in photocatalysis2In the field, among others, ZnO is receiving attention due to its advantages of low cost, non-toxicity, good crystal structure anisotropy, direct band gap, high electron mobility, etc., and in particular, a one-dimensional (1D) ZnO structure, including nanorods or nanotubes, has a high surface-to-volume ratio, a short lateral charge transport length, and a low light reflectanceOf photocatalytic CO2The reduction efficiency is higher than that of the block structure. However, CO of existing ZnO-based photocatalysts2The reduction performance is still influenced by CO2A limitation of low adsorption capacity. Therefore, the transparent conductive adsorption layer is optimally designed, and the CO of the ZnO-based photocatalyst is improved2The adsorption activation capability and the photoproduction electron hole separation capability are used for improving the photocatalysis CO2The key breakthrough of the reduction conversion performance.
The metal organic framework material ZIF-8 has good light transmission in the ultraviolet visible spectrum range so as not to lose the light capturing capability of a ZnO substrate, and has the chemical functional groups such as porosity, high specific surface area and abundant surface amino groups so as to obtain CO2The adsorption capacity is high, and the interface compatibility is good, so that a film can be uniformly formed on the surfaces of various materials, and the method is an excellent choice for constructing a surface adsorption layer. In addition, ZIF-8 has adsorption selectivity, and the ZIF-8 modified photocatalytic system can effectively adsorb reactant CO2But has no affinity for the reduction product, and favors CO by inhibiting the oxidation side reactions of the hydrocarbon product2And (4) carrying out a reduction reaction process. And the ZIF-8 layer has a passivation effect on the surface of ZnO, so that the surface defect concentration is reduced, and the reduction potential is improved. However, the weak conductivity of ZIF-8 is detrimental to charge transport in the ZIF-8 based adsorption layer. Therefore, the limitation of ZIF-8 alone as an adsorption layer is that it is relatively weak in electrical conductivity.
At present, the problems of weak conductivity and low charge separation efficiency can be improved by the prior art methods of noble metal nanoparticle surface modification, non-metal doping, proper semiconductor coupling and the like. Among them, noble metal modification on the surface of semiconductor photocatalyst will construct schottky junction, and has promoter effect, can improve charge separation efficiency, and is the most widely used preferred method. However, due to the lower fermi level of the noble metal, the photogenerated electrons on ZnO are transferred to the surface of the noble metal and their CO2The reduction potential is reduced. The enrichment of electrons on the noble metal nanoparticles is beneficial to CH3Formation of OH, but reduction of the reduction potential of ZnO/noble Metal composite systems photocatalytic CO2The reduction efficiency is unfavorable. How to fully exert the coordination of the ZIF-8 surface layer and the Pt nano particle modificationWith the effect, establish novel transparent conductive surface adsorbed layer, be full of the challenge, nevertheless have important scientific meaning and practical value.
Disclosure of Invention
In order to solve the technical problems, the primary object of the present invention is to provide a core-shell ZnO/noble metal @ ZIF-8 photocatalytic material, which can not only reduce the recombination efficiency of photon-generated carriers but also improve CO without reducing the light absorption capacity2Adsorption performance and photocatalytic reduction efficiency.
The invention further aims to provide a preparation method of the core-shell ZnO/noble metal @ ZIF-8 photocatalytic material.
The invention further aims to provide the core-shell ZnO/noble metal @ ZIF-8 photocatalytic material for capturing and catalytically converting greenhouse gas CO2The use of (1).
The invention is realized by the following technical scheme:
the core-shell ZnO/noble metal @ ZIF-8 photocatalytic material takes ZnO nanorods as a core, a ZIF-8 layer as a shell, and reduced noble metal nanoparticles are loaded between the ZnO nanorods and the ZIF-8 layer, wherein the loading capacity of the reduced noble metal nanoparticles is 0.1-10% of the mass of the ZnO nanorods, and is preferably 0.5-3%.
The principle of the invention is as follows: firstly modifying a certain amount of reduced noble metal nano-particles on a ZnO nano-rod by adopting a synergistic surface modification method to generate a Schottky junction so as to improve the charge separation efficiency, and then synthesizing a ZIF-8 layer on the surface of the ZnO nano-rod modified by the reduced noble metal nano-particles so as to improve CO2Trapping ability, passivating surface defects, increasing conduction band potential, while not diminishing light absorption ability. The core-shell ZnO/noble metal @ ZIF-8 photocatalytic material obtained by the method not only can reduce the recombination efficiency of photon-generated carriers, but also can enhance CO2Capture effect and photocatalytic reduction efficiency.
The reduced noble metal nanoparticles are selected from one of Pt nanoparticles, Au nanoparticles and Ag nanoparticles, and are preferably Pt nanoparticles.
In the core-shell structure of the photocatalytic material, part of reduced noble metal nano particles are protruded on the ZIF-8 layer, so that the structure is favorable for outward charge transport, and the defect of poor electronic conductivity of the surface ZIF-8 layer is overcome. Preferably, the particle size of the reduced noble metal nanoparticles is 1 to 10 nm.
The adopted zeolite imidazole framework material (ZIF-8) layer not only has high porosity and remarkable thermal/chemical stability, but also has good transparency of the ZIF-8 in an ultraviolet-visible light wave band, so that the introduction of the ZIF-8 adsorption layer can not generate obvious negative influence on the light absorption capacity of a bottom semiconductor. In addition, ZIF-8 has adsorption selectivity, and the ZIF-8 modified photocatalytic system can effectively adsorb reactant CO2But has no affinity for the reduction product, and is beneficial to CO by inhibiting the adverse reaction of hydrocarbon products2And (4) carrying out a reduction reaction process. Preferably, the ZIF-8 layer has a pore size of 0.8 to 5nm and a thickness of 1 to 30nm, preferably 5 to 15 nm.
The invention also provides a preparation method of the core-shell ZnO/noble metal @ ZIF-8 photocatalytic material, which comprises the following steps:
(1) preparing a ZnO nanorod by adopting a PVP (polyvinyl pyrrolidone) assisted hydrothermal method, and calcining at high temperature to remove surface impurities;
(2) using ethylene glycol as a solvent, and carrying out thermal reduction compounding on the ZnO nanorod and a soluble precious metal precursor to obtain a ZnO/precious metal nanorod;
(3) and mixing the ZnO/noble metal nanorod with a mixed solvent of 2-methylimidazole, N-dimethylformamide and water, and carrying out hydrothermal reaction to obtain the ZnO/noble metal @ ZIF-8 photocatalytic material with the core-shell structure.
The ZnO nanorod can be prepared by adopting a conventional method in the field, for example, PVP (polyvinyl pyrrolidone) is adopted for assisting a hydrothermal reaction, a zinc salt aqueous solution and a NaOH aqueous solution are sequentially dripped into the PVP aqueous solution, water is added for mixing, and the ZnO nanorod is obtained by the hydrothermal reaction. The zinc salt can be zinc nitrate, zinc acetate, zinc chloride or the like; the high-temperature calcination temperature is 500-550 ℃ and the time is 2-5 hours.
Preferably, in step (2), the soluble noble metal precursor solvent is a noble metal salt soluble in ethylene glycol, including but not limited to a noble metal chloride salt, chlorate or nitrate; the heating temperature is 110-150 ℃ and the time is 10-24 hours.
Preferably, in the step (3), the volume ratio of the N, N-dimethylformamide to the water is 1-5: 1; the dosage of the 2-methylimidazole is 0.5-5 mmol.
Preferably, in the step (3), the temperature of the hydrothermal reaction is 60-90 ℃. The thickness of the ZIF-8 layer can be adjusted by controlling the hydrothermal time, preferably, the time is more than 0.5h, preferably 1-3 h.
The invention also provides the core-shell ZnO/noble metal @ ZIF-8 photocatalytic material for capturing and catalytically converting greenhouse gas CO2The use of (1).
The ZnO/noble metal @ ZIF-8 photocatalytic material prepared by the invention can be used for photocatalytic CO2The possible reaction paths for the reduction are as follows:
from the above reaction route, chemisorbed CO2Molecules are evolved into surface bond-CO through a two-electron and two-proton reaction path, part of the surface bond-CO is released into CO, and the other part of the surface bond-CO can be further hydrogenated, namely a rate determining step, to generate HCHO and methoxyl (CH)3O) intermediate, methoxy forms CH by a one-electron, one-proton reaction path3OH or CH4。
Compared with the prior art, the invention has the following beneficial effects:
the core-shell ZnO/noble metal @ ZIF-8 photocatalytic material prepared by the invention utilizes the synergistic modification effect of the noble metal modification on the surface of the preformed ZnO nanorod and the wrapping of the ZIF-8 porous adsorption layer, introduces the noble metal/ZIF-8 transparent conductive adsorption layer, constructs a novel efficient multi-element composite system, and effectively overcomes the defects of low charge separation efficiency, poor adsorption performance and the like of the existing photocatalyst. The invention can realize the carrier separation efficiency and CO simultaneously under the condition of not weakening the light absorption capacity2The capture capability is enhanced synergistically, and the excellent photocatalytic activity is shownCan efficiently remove greenhouse gas CO2Selective reduction to CH3OH and the like.
The preparation method has the characteristics of few raw materials, simple process, relatively mild conditions and the like, can realize industrial application, and has wide application prospect in the aspects of solving the problems of greenhouse effect, energy shortage and the like.
Drawings
FIG. 1 is a flow chart of a process for preparing a material prepared in accordance with an embodiment of the present invention;
FIG. 2 is an XRD pattern of the ZnO/Pt @ ZIF-8 material prepared in example 1 of the present invention;
FIG. 3 is an SEM and TEM image of a ZnO/Pt @ ZIF-8 material prepared in example 1 of the present invention;
FIG. 4 is a UV-vis plot of a ZnO/Pt @ ZIF-8 material prepared in example 1 of the present invention;
FIG. 5 is a CO of the ZnO/Pt @ ZIF-8 material prepared in example 1 of the present invention2An adsorption performance graph;
FIG. 6 is a CO of the ZnO/Pt @ ZIF-8 material prepared in example 1 of the present invention2Reduction cycle activity diagram.
Detailed Description
The present invention is further illustrated by the following specific examples, which are, however, not intended to limit the scope of the invention.
The raw materials used in the examples and comparative examples of the present invention were all commercially available.
Example 1: preparation of ZnO/Pt @ ZIF-8
(1) Adding 11.25 ml of 0.3 mol/L Zn (NO)3)2·6H2The O water solution and 11.25 mL of 5 mol/L NaOH water solution are sequentially dropped into 11.25 mL of 5mmol/LPVP water solution under the condition of violent stirring; then, 67.5mL of deionized water was added to the above mixed solution; after ultrasonic treatment, putting the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 180 ℃ for 12 hours, washing the obtained product with deionized water for several times, drying at 80 ℃ for 12 hours and calcining at 500 ℃ in air for 2 hours to obtain ZnO nanorods;
(2) 50ml of ethylene glycol and 0.5g of the ZnO nanorods obtained in step (1) were placed in a round-bottomed flask, stirred at 130 ℃ and then, 0.5ml of 1g/L H was added2PtCl6Heating the solution at 130 ℃ for 24 h, washing the final product with ethanol, and drying at 60 ℃ for 12h to obtain ZnO/Pt nanorods;
(3) putting the ZnO/Pt nano rod obtained in the step (2) into a stainless steel autoclave with a polytetrafluoroethylene lining, and mixing 2 mmol of 2-methylimidazole with 96 mL of DMF/H2Dissolving the mixed solvent of O (3:1 of v/v), heating to 70 ℃ after mixing, reacting for 1h, washing the obtained product with ethanol for several times, and drying at 60 ℃ for 12h to obtain the ZnO/Pt @ ZIF-8 photocatalytic material.
FIG. 1 shows a schematic diagram of a preparation process flow of the ZnO/Pt @ ZIF-8 photocatalytic material, which comprises the steps of firstly preparing a ZnO nanorod, then uniformly depositing Pt nanoparticles on the ZnO nanorod, and then wrapping a ZIF-8 layer on the surface of the ZnO nanorod modified by the Pt nanoparticles.
FIG. 2 is an X-ray diffraction pattern (XRD) of the ZnO/Pt @ ZIF-8 material prepared by the present invention, and it can be seen that the X-ray diffraction peak of the prepared material belongs to typical hexagonal phase wurtzite type ZnO. In addition, a characteristic X-ray diffraction peak of ZIF-8 was also observed.
FIG. 3 (a) is a Scanning Electron Microscope (SEM) image of the ZnO/Pt @ ZIF-8 photocatalytic material obtained in example 1, from which it can be seen that the prepared material has a uniform rod-like morphology, and the ZnO nanorods have an average diameter of 220 nm. FIG. 3 (b-c) is a transmission electron microscope photograph of the ZnO/Pt @ ZIF-8 photocatalytic material obtained in example 1, from which the surface microstructure of the prepared material can be seen. The lattice spacing of the modified platinum nanoparticles was 0.23 nm (corresponding to the (111) crystal plane of platinum). These Pt nanoparticles had an average particle size of about 5 nm. The ZIF-8 cover layer was about 9nm thick. The modified Pt nanoparticles were seen to be located at the interface of ZnO and ZIF-8. It is worth noting that part of Pt nano particles protrude from the surface ZIF-8 layer, so that outward charge transport is facilitated, and poor electronic conductivity of the surface ZIF-8 layer is overcome. FIG. 3 (d-g) is an EDS element mapping chart of the ZnO/Pt @ ZIF-8 photocatalytic material obtained in example 1, and it can be seen that the distribution profiles of Zn, O, Pt and N are identical to the contour of the nanorod, which illustrates that the modified Pt nanoparticles and the coated ZIF-8 layer are uniformly distributed on the outer surface of the ZnO nanorod.
FIG. 4 is an ultraviolet diffuse reflectance (UV-vis) plot of the ZnO/Pt @ ZIF-8 material prepared in accordance with the present invention, with the absorption edges of the samples ZnO, ZnO @ ZIF-8, ZnO/Pt, and ZnO/Pt @ ZIF-8 being the same, about 386 nm, corresponding to the same band gap of 3.21 eV. The Pt modification and ZIF-8 coating are shown to have no obvious influence on the light absorption capability of the current mixed photocatalyst system.
Example 2: preparation of ZnO/Pt @ ZIF-8
In step (3), the mixture was heated to 70 ℃ after mixing and reacted for 0.5h, as in example 1.
Example 3: preparation of ZnO/Pt @ ZIF-8
In step (3), the mixture was heated to 70 ℃ after mixing and reacted for 3 hours, as in example 1.
Example 4: preparation of ZnO/Pt @ ZIF-8
(1) Adding 11.25 ml of 0.3 mol/L Zn (NO)3)2·6H2The O water solution and 11.25 mL of 5 mol/L NaOH water solution are sequentially dropped into 11.25 mL of 5mmol/LPVP water solution under the condition of violent stirring; then, 67.5mL of deionized water was added to the above mixed solution; after ultrasonic treatment, putting the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 180 ℃ for 12 hours, washing the obtained product with deionized water for several times, drying at 80 ℃ for 12 hours and calcining at 550 ℃ in air for 2 hours to obtain ZnO nanorods;
(2) 50ml of ethylene glycol and 0.5g of the ZnO nanorods obtained in step (1) were placed in a round-bottomed flask, stirred at 150 ℃ and then, 0.5ml of 0.5g/L H was added2PtCl6Heating the solution at 150 ℃ for 20 h, washing the final product with ethanol and drying at 80 ℃ for 10h to obtain ZnO/Pt nanorods;
(3) putting the ZnO/Pt nano rod obtained in the step (2) into a stainless steel autoclave with a polytetrafluoroethylene lining, and mixing 2 mmol of 2-methylimidazole with 96 mL of DMF/H2Dissolving O (4:1 of v/v) in mixed solvent, mixing, heating to 90 deg.C for 1h, washing with ethanol several times, and standing at 60 deg.CDrying for 12h at the temperature of DEG C to obtain the ZnO/Pt @ ZIF-8 photocatalytic material.
Example 5: preparation of ZnO/Pt @ ZIF-8
(1) Adding 11.25 ml of 0.3 mol/L Zn (NO)3)2·6H2The O water solution and 11.25 mL of 5 mol/L NaOH water solution are sequentially dropped into 11.25 mL of 5mmol/LPVP water solution under the condition of violent stirring; then, 67.5mL of deionized water was added to the above mixed solution; after ultrasonic treatment, putting the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 180 ℃ for 12 hours, washing the obtained product with deionized water for several times, drying at 80 ℃ for 12 hours and calcining at 500 ℃ in air for 3 hours to obtain ZnO nanorods;
(2) 50ml of ethylene glycol and 0.5g of the ZnO nanorods obtained in step (1) were placed in a round-bottomed flask, stirred at 140 ℃ and then, 0.5ml of 1.5g/L H was added2PtCl6Heating the solution at 140 ℃ for 22 h, washing the final product with ethanol and drying at 70 ℃ for 11h to obtain ZnO/Pt nanorods;
(3) putting the ZnO/Pt nano rod obtained in the step (2) into a stainless steel autoclave with a polytetrafluoroethylene lining, and mixing 2 mmol of 2-methylimidazole with 96 mL of DMF/H2Dissolving the mixed solvent of O (5:1 of v/v), heating to 2 hours at 60 ℃, washing the obtained product with ethanol for several times, and drying at 60 ℃ for 12 hours to obtain the ZnO/Pt @ ZIF-8 photocatalytic material.
Example 6: preparation of ZnO/Ag @ ZIF-8
In the step (2), H is added2PtCl6The solution is replaced by silver nitrate solution, and the ZnO/Ag @ ZIF-8 photocatalytic material is prepared by the same method as the example 1.
Example 7: preparation of ZnO/Au @ ZIF-8
In the step (2), H is added2PtCl6Replacement of solution by H2AuCl6The solution was prepared as in example 1 except that the ZnO/Au @ ZIF-8 photocatalytic material was prepared.
Comparative example 1: preparation of ZnO/Pt
(1) Adding 11.25 ml of 0.3 mol/L Zn (NO)3)2·6H2Aqueous O solution and 11.25 mL of 5 mol/L aqueous NaOH solution in a vigorous atmosphereStirring and dropping into 11.25 mL of 5mmol/LPVP aqueous solution in turn; then, 67.5mL of deionized water was added to the above mixed solution; after ultrasonic treatment, putting the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 180 ℃ for 12 hours, washing the obtained product with deionized water for several times, drying at 80 ℃ for 12 hours and calcining at 500 ℃ in air for 2 hours to obtain ZnO nanorods;
(2) 50ml of ethylene glycol and 0.5g of the ZnO nanorods obtained in step (1) were placed in a round-bottomed flask, stirred at 130 ℃ and then, 0.5ml of 1g/L H was added2PtCl6The solution was heated at 130 ℃ for 24 h, and the final product was washed with ethanol and dried at 60 ℃ for 12h to give ZnO/Pt.
Comparative example 2: preparation of ZnO @ ZIF-8
(1) Adding 11.25 ml of 0.3 mol/L Zn (NO)3)2·6H2The O water solution and 11.25 mL of 5 mol/L NaOH water solution are sequentially dropped into 11.25 mL of 5mmol/LPVP water solution under the condition of violent stirring; then, 67.5mL of deionized water was added to the above mixed solution; after ultrasonic treatment, putting the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 180 ℃ for 12 hours, washing the obtained product with deionized water for several times, drying at 80 ℃ for 12 hours and calcining at 500 ℃ in air for 2 hours to obtain ZnO nanorods;
(2) putting the ZnO nano-rod obtained in the step (1) into a stainless steel autoclave with a polytetrafluoroethylene lining, and mixing 2 mmol of 2-methylimidazole with 96 mL of DMF/H2Dissolving the mixed solvent of O (3:1 of v/v), heating to 70 ℃ for 1h after mixing, washing the obtained product with ethanol for several times, and drying at 60 ℃ for 12h to obtain the ZnO @ ZIF-8 material.
Application example 1: CO 22Reduction experiment
At ambient temperature and atmospheric pressure in a 200 ml homemade two-neck top irradiation reactor. The two necks of the reactor were sealed with silicone rubber septa to form a closed system. A300 w Xe arc lamp (Perfect light, PLS-SXE300, China) was used as the light source, placed about 10cm above the photocatalytic reactor. In a typical photocatalytic experiment, 100 mg of photocatalyst was uniformly deposited on the substrateThe bottom of the reactor. Before light irradiation, the reactor was sealed and nitrogen was introduced for 30 minutes to ensure that the reaction system was in an anaerobic state. In one bottleneck of the reactor, through specially designed NaHCO in groove3Powder and H2SO4Reaction of aqueous solution to generate CO in situ2And H2And O steam. 0.084 g of NaHCO was added before sealing3The powder was placed in a recess and 0.3 mL of 2mol/L H was injected with a syringe before irradiation2SO4An aqueous solution is injected into the recess. After 1h of light irradiation, the gaseous products extracted from the reactor were analyzed by gas chromatography (GC-7890B, Agilent).
Photocatalytic reduction of CO for examples 1-3 and comparative examples 1-2 were tested with reference to the above method2The activity, results are given in the following table:
as can be seen from the above table in example 1 and comparative examples 1-2, the ZnO/Pt @ ZIF-8 material obtained after Pt modification and ZIF-8 layer coating according to the present invention photocatalyzes CO, relative to ZnO/Pt and ZnO @ ZIF-82The reduction activity is obviously increased, which shows that the Pt modification and the ZIF-8 coating are used for improving the photocatalytic CO2The material shows remarkable synergistic effect in the aspect of reduction performance, and particularly, the material with 1h of ZIF-8 layer wrapping is used for catalyzing CO2The reduction activity is strongest.
The ZnO/Pt @ ZIF-8 material prepared by the invention is used for treating CO2The main product of the reduction is methanol (CH)3OH), is one of the most promising solar fuels.
Application example 2: CO 22Adsorption experiments
CO2The adsorption-desorption experiment is to measure CO by using a gas adsorption apparatus (Kubo X1000, China)2Adsorption profile, before experimental analysis, the sample needs to be pre-treated with vacuum at 100 ℃, the specific surface area (BET) of the sample is given by the linear part of the BET curve (P/P0=0.1-0.25), and the pore size distribution curve is given by BJH (Barret-Joyner-Halenda) model.
Example 1, comparative examples 1-2, Z were tested according to the methods described aboveCO of nO, ZIF-82The adsorption performance, results are shown in the following table and fig. 5:
the CO of the material produced can be seen in FIG. 52Adsorption Curve, CO over the entire P/P0 range2The adsorption capacity of (A) is almost linear with respect to the relative pressure, which indicates that CO is present2There was a dominant physical interaction with each sample. ZnO/Pt @ ZIF-8 prepared by the invention is used for treating CO2The adsorption capacity of the catalyst is obviously higher than that of ZnO/Pt and ZnO @ ZIF-8 to CO2The adsorption capacity of (1).
Application example 3: circulation experiment of photocatalyst
0.05g of the material prepared in example 1 was weighed into a 200 ml self-made two-neck top irradiation reactor, which was sealed and purged with nitrogen for 30 minutes before light irradiation. In one neck of the reactor, 0.084 g NaHCO was added before sealing3The powder was placed in a recess and 0.3 mL of 2mol/L H was injected with a syringe before irradiation2SO4An aqueous solution is injected into the recess. After 1h of light irradiation, the gaseous products extracted from the reactor were analyzed by gas chromatography (GC-7890B, Agilent). Sample recovery continues for the next CO2Reduction experiment, circulating for 3 times, making material to reduce CO2The results are shown in FIG. 6: from FIG. 6, it can be seen that the ZnO/Pt @ ZIF-8 material prepared by the present invention photocatalyzes CH after 3 consecutive cycles (3 hours per cycle)3The yield of OH is basically kept unchanged, and the ZnO/Pt @ ZIF-8 has good stability.
Claims (10)
1. The core-shell ZnO/precious metal @ ZIF-8 photocatalytic material is characterized in that a ZnO nanorod is used as a core, a ZIF-8 layer is used as a shell, and reduced precious metal nanoparticles are loaded between the ZnO nanorod and the ZIF-8 layer, wherein part of the reduced precious metal nanoparticles protrude out of the ZIF-8 layer, the particle size of the reduced precious metal nanoparticles is 1-10nm, the loading amount of the reduced precious metal nanoparticles is 0.1-10% of the mass of the ZnO nanorod, and the reduced precious metal nanoparticles are Pt nanoparticles; the aperture of the ZIF-8 layer is 0.8-5nm, and the thickness of the ZIF-8 layer is 1-30 nm.
2. The core-shell ZnO/noble metal @ ZIF-8 photocatalytic material as claimed in claim 1, wherein the loading amount of the reduced noble metal nanoparticles is 0.5-3% of the mass of the ZnO nanorods.
3. The core-shell ZnO/noble metal @ ZIF-8 photocatalytic material of claim 1, wherein the thickness of the ZIF-8 layer is 5-15 nm.
4. The method for preparing the core-shell ZnO/noble metal @ ZIF-8 photocatalytic material as recited in any one of claims 1 to 3, comprising the steps of:
(1) preparing a ZnO nanorod by adopting a PVP (polyvinyl pyrrolidone) assisted hydrothermal method, and calcining at high temperature to remove surface impurities;
(2) using ethylene glycol as a solvent, and carrying out thermal reduction compounding on the ZnO nanorod and a soluble precious metal precursor to obtain a ZnO/precious metal nanorod;
(3) and mixing the ZnO/noble metal nanorod with a mixed solvent of 2-methylimidazole, N-dimethylformamide and water, and carrying out hydrothermal reaction to obtain the ZnO/noble metal @ ZIF-8 photocatalytic material with the core-shell structure.
5. The method for preparing the core-shell ZnO/noble metal @ ZIF-8 photocatalytic material as claimed in claim 4, wherein in the step (2), the soluble noble metal precursor solvent is a noble metal salt soluble in ethylene glycol, including a chloride, nitrate or chlorate of the noble metal; the heating temperature is 110-150 ℃ and the time is 10-24 hours.
6. The method for preparing the core-shell ZnO/noble metal @ ZIF-8 photocatalytic material as claimed in claim 4, wherein in the step (3), the volume ratio of the N, N-dimethylformamide to water is 1-5: 1; the dosage of the 2-methylimidazole is 0.5-5 mmol.
7. The method for preparing the core-shell ZnO/noble metal @ ZIF-8 photocatalytic material as claimed in claim 4, wherein the temperature of the hydrothermal reaction in the step (3) is 60-90 ℃.
8. The method for preparing the core-shell ZnO/noble metal @ ZIF-8 photocatalytic material as claimed in claim 4, wherein the hydrothermal reaction time in step (3) is 0.5h or more.
9. The method for preparing the core-shell ZnO/noble metal @ ZIF-8 photocatalytic material as claimed in claim 8, wherein the hydrothermal reaction time in step (3) is 1-3 h.
10. The core-shell ZnO/noble metal @ ZIF-8 photocatalytic material as claimed in any one of claims 1 to 3 for capturing and catalytically converting greenhouse gas CO2The use of (1).
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