CN110327962B - Nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material, and preparation method and application thereof - Google Patents
Nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material, and preparation method and application thereof Download PDFInfo
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- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 110
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- 238000000034 method Methods 0.000 claims abstract description 14
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- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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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Abstract
The invention provides a preparation method of a nickel-cobalt double-metal oxide @ nitrogen-oxygen Co-doped carbon material/CdS photocatalytic material, the composite photocatalytic material is formed by compounding a transition metal compound cocatalyst which is derived from a metal organic framework and is coated by a nitrogen-oxygen Co-doped carbon material and CdS, Co-MOF is formed by mixing cobalt nitrate and 2-methylimidazole, then the Co-MOF is mixed with nickel nitrate to form NiCo-LDH double-metal hydroxide, the layered NiCo-LDH double-metal hydroxide is used for pyrolysis to derive the nickel-cobalt double-metal oxide coated by the nitrogen-oxygen Co-doped carbon material, and then the nickel-cobalt double-metal oxide @ nitrogen-oxygen Co-doped carbon material/CdS photocatalytic material is formed by adopting an ethanol heating reflux method and CdS compounding. The composite photocatalytic material is applied to photocatalytic hydrogen evolution reaction, the photocatalytic hydrogen production activity and stability are obviously improved, the hydrogen production rate is greatly improved, and the synthesis process is simple and easy to operate.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material, and a preparation method and application thereof.
Background
The massive combustion of fossil fuels brings global energy crisis and environmental pollution problems, and the search for clean and sustainable alternative energy is a hot spot of current research and a demand for rapid development of the current society. Obtaining hydrogen energy by utilizing a semiconductor photocatalysis technology is an effective way for developing and seeking new energy, wherein in the technical field of photocatalytic hydrogen production, a catalyst CdS is a key semiconductor material which is widely researched due to proper band gap and conduction band position. Although cadmium sulfide is a photocatalytic semiconductor material with excellent performance, photoproduction electrons and holes are easy to combine, corrosion is caused by illumination, the stability needs to be improved, and in order to improve the efficiency of photocatalytic hydrogen production by cadmium sulfide, noble metals and transition metal promoters are generally loaded on the surface of the cadmium sulfide.
Due to the scarcity and high cost of noble metals, promoters are currently mostly transition metal compounds of some non-noble metals. The synthesis and structure of transition metal compounds affect the efficiency of the whole photocatalytic hydrogen production system, but the transition metal compounds often have the problems of conductivity and unsuitable hydrogen evolution active sites.
Aiming at the problem, the invention mainly adopts the in-situ coating of the active carbon material on the surface of the transition metal compound, realizes the synergistic cocatalyst effect by improving the electrical conductivity and more active sites, and effectively improves the efficiency of the photocatalytic hydrogen production of the cadmium sulfide.
Disclosure of Invention
The invention aims to provide a preparation method of a nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of a nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material comprises the following steps:
(1) stirring cobalt salt and 2-methylimidazole in an aqueous phase system, standing and aging to obtain Co-MOF;
(2) mixing the Co-MOF obtained in the step (1) with nickel salt to obtain a mixed solution, and performing ultrasonic dispersion on the mixed solution to obtain NiCo-LDH double metal hydroxide;
(3) putting the NiCo-LDH double-metal hydroxide obtained in the step (2) into a tubular furnace for high-temperature pyrolysis to obtain a nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material;
(4) heating and refluxing cadmium acetate and thiourea in a diethylenetriamine system to obtain a CdS nanorod;
(5) heating and refluxing the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material obtained in the step (3) and the CdS nanorods in the step (4) in a solvent to obtain a precipitate;
(6) and (4) centrifugally washing the precipitate obtained in the step (5), and drying to obtain the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material.
In the preparation method of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material, preferably, the cobalt salt is cobalt nitrate.
In the preparation method of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material, preferably, the mass ratio of the cobalt salt to the 2-methylimidazole is 1: (5-20).
In the preparation method of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen Co-doped carbon material/CdS photocatalytic material, preferably, the nickel salt is nickel nitrate, and the mass ratio of the Co-MOF to the nickel salt is 1: (2-10).
In the preparation method of the nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material, preferably, in the step (3), the NiCo-LDH double-metal hydroxide is placed in an inert atmosphere tube furnace for high-temperature pyrolysis;
preferably, the inert atmosphere in the tube furnace is argon.
In the preparation method of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material, the temperature for performing high-temperature pyrolysis in the inert atmosphere tubular furnace is preferably 300-500 ℃.
In the preparation method of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material, preferably, the solvent heated and refluxed in the solvent in the step (5) is ethanol, and the heating and refluxing temperature is 60-80 ℃.
In the preparation method of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material, preferably, the mass ratio of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material to the CdS nanorods in (5) is (0.01-0.1): 1.
A preparation method of a nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material is provided.
The nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material is applied to photocatalytic hydrogen evolution.
Compared with the closest prior art, the technical scheme provided by the invention has the following excellent effects:
the composite photocatalytic material is composed of a transition metal compound cocatalyst which is derived from a metal organic framework and coated by a nitrogen-oxygen co-doped carbon material and a CdS semiconductor, wherein a layered NiCo-LDH double-metal hydroxide is used for pyrolyzing at high temperature to derive a nickel-cobalt double-metal transition metal oxide coated by the nitrogen-oxygen co-doped carbon material, and the nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material is compounded with CdS by adopting a heating reflux method. According to the preparation process, raw materials such as a cobalt source, an organic ligand 2-methylimidazole and nickel nitrate participate in a reaction according to a certain molar ratio, and are compounded with CdS under the heating reflux condition by using the solvent action of ethanol, so that the uniformly dispersed nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material is finally obtained.
The nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material prepared by the method is an ultrathin two-dimensional nanosheet, and the amorphous carbon occupies a main component; after being loaded on the surface of cadmium sulfide, the hydrogen production rate is 1.7 mmoleg under the visible light illumination-1h-1Increased to 56 mmoleg-1h-1The method improves the hydrogen production by 32 times, has obvious improvement effect on photocatalytic hydrogen production, and has simple synthesis method and easy operation.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 is an XRD pattern of ZIF-67 of example 1 of the present invention;
FIG. 2 is an XRD pattern of a nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material in example 1 of the present invention;
FIG. 3 is a Raman diagram of a nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material in example 1 of the present invention;
FIG. 4 is an SEM image of CdS nanorods of example 1;
FIG. 5 is a TEM image of Ni-Co bimetallic oxide @ NI-O co-doped carbon/CdS of example 1 of the present invention;
fig. 6 is a hydrogen production performance curve of photolytic hydrogen production under visible light irradiation of the nickel-cobalt double metal oxide @ nitrogen-oxygen co-doped carbon/CdS in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention provides a nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS composite photocatalytic material, which is composed of a transition metal compound cocatalyst and a CdS semiconductor, wherein the transition metal compound cocatalyst is derived from a metal organic framework and coated by a doped carbon material, and the preparation method of the composite photocatalytic material mainly comprises the following steps: firstly, synthesizing ZIF-67 (Co-MOF) by a room temperature precipitation method, and then synthesizing Layered NiCo-LDH Double metal Hydroxide (Layered Double Hydroxide abbreviated as LDH) by ultrasonic and nickel nitrate etching; the nickel cobalt bimetal oxide @ nitrogen and oxygen codoped carbon material is synthesized by high-temperature pyrolysis under the protection of a tubular furnace inert atmosphere, a CdS nanorod is synthesized by heating reflux, and finally the nickel cobalt bimetal oxide @ nitrogen and oxygen codoped carbon material and CdS are heated and refluxed in an ethanol solvent system to obtain the nickel cobalt bimetal oxide @ nitrogen and oxygen codoped carbon material/CdS composite photocatalytic material.
The invention provides a nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS composite photocatalytic material, which comprises the following steps of:
(1) stirring cobalt salt and 2-methylimidazole in an aqueous phase system, standing and aging to obtain purple Co-MOF, namely ZIF-67;
in a specific embodiment of the invention, the cobalt salt is cobalt nitrate.
In a specific embodiment of the invention, the mass ratio of cobalt salt to 2-methylimidazole is 1: (5-20) (e.g., 1:5, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1: 20); preferably, the mass ratio of the cobalt salt to the 2-methylimidazole is 1: 10.
(2) mixing the ZIF-67 obtained in the step (1) with nickel salt to obtain a mixed solution, and performing ultrasonic treatment on the mixed solution to obtain a green NiCo-LDH double-metal hydroxide with the surface containing excessive organic ligands under the action of ultrasonic dispersion and nickel salt etching;
in a specific embodiment of the invention, the nickel salt is nickel nitrate; the nitrate has no influence on nitrogen and oxygen co-doped carbon materials formed by subsequent high-temperature pyrolysis, and impurity ions cannot be introduced.
In a specific embodiment of the invention, the mass ratio of ZIF-67 to nickel salt is 1: (2-10) (e.g., 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1: 10); preferably, the mass ratio of the ZIF-67 to the nickel salt is 1: 5.
(3) putting the NiCo-LDH double-metal hydroxide obtained in the step (2) into a tubular furnace for high-temperature pyrolysis to obtain a black nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material;
in a specific embodiment of the invention, NiCo-LDH double metal hydroxide is subjected to pyrolysis in an inert atmosphere tube furnace; preferably, the inert atmosphere in the tube furnace is high purity argon.
In an embodiment of the present invention, the pyrolysis in the atmospheric tube furnace is performed at a temperature of 300 to 500 ℃ (e.g., 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃).
(4) Heating and refluxing cadmium acetate and thiourea in a diethylenetriamine system to obtain a CdS nanorod;
in the specific embodiment of the invention, cadmium acetate and thiourea are heated and refluxed at 110 ℃ in a diethylenetriamine system to obtain the CdS nanorod.
(5) Heating and refluxing the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material obtained in the step (3) and the CdS nanorods in the step (4) in a solvent to obtain a precipitate;
in the specific embodiment of the present invention, the solvent in the step (5) is ethanol, and the heating reflux temperature is 60 to 80 ℃ (for example, 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 77 ℃, 78 ℃, 80 ℃).
In the specific embodiment of the invention, the mass ratio of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material to the CdS nanorod in the step (5) is (0.01-0.1): 1 (such as 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1 and 0.09: 1).
Preferably, the mass ratio of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material to the CdS nanorods in the step (5) is 0.05: 1.
(6) And (4) centrifugally washing the precipitate obtained in the step (5), and drying the precipitate in a vacuum drying oven to obtain the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material.
The invention also provides an application of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material prepared by the preparation method of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material, and the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material is applied to the field of photocatalytic hydrogen evolution.
Example 1
The embodiment of the invention provides a preparation method of a nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material, which comprises the following steps:
(1) 0.1g of cobalt nitrate cobalt salt and 1g of 2-methylimidazole organic ligand are stirred at room temperature in an aqueous phase system, and the mixture is kept stand and aged to obtain purple Co-MOF, namely ZIF-67.
(2) 0.1g of ZIF67 and 0.5g of nickel nitrate are mixed to obtain a mixed solution, and the mixed solution is subjected to ultrasonic etching to obtain green NiCo-LDH double-metal hydroxide with the surface containing excessive organic ligands.
(3) And (3) putting the NiCo-LDH double-metal hydroxide prepared in the step (2) into an argon atmosphere tubular furnace for pyrolysis at the temperature of 350 ℃ to obtain a black cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material, wherein the purity of the high-purity argon is 98%.
(4) Cadmium acetate and thiourea are heated and refluxed at 110 ℃ in a diethylenetriamine system to obtain the CdS nanorod.
(5) Weighing 0.05g of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material obtained in the step (3) and 1g of the CdS nanorod prepared in the step (4), heating in an ethanol solvent at 60 ℃, and refluxing to obtain a dark yellow nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS composite photocatalytic material precipitate.
(6) And (3) centrifuging and washing the dark yellow nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS composite photocatalytic material precipitate in the step (5), and drying in a vacuum drying oven at 60 ℃ to obtain the nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material.
XRD diffraction analysis is carried out on the ZIF-67 and the nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material prepared in the embodiment, and the results are shown in figures 1 and 2;
the X-ray powder diffraction in fig. 1 shows that the ZIF-67 prepared in this example has no impurity peak, indicating that the product purity is high.
X-ray powder diffraction in figure 2 shows that the crystal diffraction peak of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material corresponds to Ni3CoO4The crystal form of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material is not changed after the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material is coated, and the nickel-cobalt bimetallic oxide Ni is kept3CoO4A crystalline form of (a). The diffraction peak does not show a carbon peak because the surface of the material is relatively low in carbon content and the crystallinity is reduced due to nitrogen and oxygen co-doping.
As shown in fig. 3, a Raman spectrum of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material prepared in the embodiment of the invention shows that the nickel-cobalt bimetallic oxide Ni3CoO4Surface in-situ formed nitrogen-oxygen co-doped carbon, Ni3CoO4The peak occupies a dominant position, and the G peak corresponding to a small amount of carbon on the surface is weaker, which indicates that the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material is a composite material with a small amount of carbon loaded on the surface of the bimetallic transition metal oxide nanosheet in situ. FIG. 4 shows an SEM image of CdS nanorods of the embodiment of the invention.
As shown in fig. 5, a TEM spectrogram of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material in the embodiment of the present invention shows that the product presents a ultrathin two-dimensional nanosheet and a CdS nanorod, and the ultrathin two-dimensional nanosheet and the CdS nanorod are tightly combined to form the composite photocatalytic material.
As shown in fig. 6, it is a performance curve of hydrogen produced by photolysis of a nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon/CdS photocatalytic material under visible light irradiation according to an embodiment of the present invention.
The nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material prepared by the embodiment is used as a hydrogen promoter for photolysis of water, and the photocatalytic performance of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon/CdS is tested by the following specific method: weighing 50mg of nickel-cobalt double metal oxide @ nitrogen-oxygen co-doped carbon/CdS powder, ultrasonically dispersing the powder in 200mL of aqueous solution, adding 20mL of lactic acid sacrificial agent solution after uniform dispersion, putting the solution into a photochemical reactor, introducing Ar to purge for 20min under dark state stirring to remove air in the reactor, opening a circulating cooling water pump to keep the reaction temperature of the system at about 20 ℃, and starting a light source 300W xenon lamp (added with a 420nm cut-off filter) to perform a visible light photocatalysis experiment under stirring. At intervals during the photocatalytic reaction, 1mL of gas was withdrawn from the photocatalytic reactor by a syringe and analyzed for the content of hydrogen produced by gas chromatography.
Analysis of the chromatographic model of the gaseous product: the natural beauty GC7900 is used for preparing a natural beauty food,
molecular sieve, TCD, Ar are carrier gases.
In the experimental process, data are prepared into a performance curve, as shown in fig. 6, a photolysis water hydrogen production performance curve under 5h is obtained, and the graph shows that the composite photocatalytic material has excellent hydrogen production activity; it can be seen from the figure that the composite photocatalyst prepared in this exampleThe hydrogen yield of the chemical material reaches 277.7 mmoleg after 5 hours of illumination-1The average hydrogen production rate reaches 56 mmoleg-1h-1。
Example 2
The embodiment of the invention provides a preparation method of a nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material, which comprises the following steps:
(1) 0.1g of cobalt nitrate cobalt salt and 0.5g of 2-methylimidazole organic ligand are stirred at room temperature in an aqueous phase system, and the mixture is stood still and aged to obtain purple Co-MOF, namely ZIF-67.
(2) 0.1g of ZIF67 and 0.5g of nickel nitrate are mixed to obtain a mixed solution, and the mixed solution is subjected to ultrasonic etching to obtain green NiCo-LDH double-metal hydroxide with the surface containing excessive organic ligands.
(3) And (3) putting the NiCo-LDH double-metal hydroxide prepared in the step (2) into an argon atmosphere tubular furnace for pyrolysis at the temperature of 350 ℃ to obtain a black cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material, wherein the purity of the high-purity argon is 98%.
(4) Cadmium acetate and thiourea are heated and refluxed at 110 ℃ in a diethylenetriamine system to obtain the CdS nanorod.
(5) Weighing 0.05g of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material obtained in the step (3) and 1g of the CdS nanorod prepared in the step (4), heating in an ethanol solvent at 70 ℃, and refluxing to obtain a dark yellow nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS composite photocatalytic material precipitate.
(6) And (3) centrifuging and washing the dark yellow nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS composite photocatalytic material precipitate in the step (5), and drying in a vacuum drying oven at 60 ℃ to obtain the nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material.
The nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material prepared in this example was subjected to a photocatalytic hydrogen production performance test under 5h illumination as in example 1, and the specific hydrogen evolution amount is shown in table 1 below.
Example 3
The embodiment of the invention provides a preparation method of a nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material, which comprises the following steps:
(1) 0.1g of cobalt nitrate cobalt salt and 2g of 2-methylimidazole organic ligand are stirred at room temperature in an aqueous phase system, and the mixture is kept stand and aged to obtain purple Co-MOF, namely ZIF-67.
(2) 0.1g of ZIF67 and 1g of nickel nitrate are mixed to obtain a mixed solution, and the mixed solution is subjected to ultrasonic etching to obtain green NiCo-LDH double-metal hydroxide with the surface containing excessive organic ligands.
(3) And (3) putting the NiCo-LDH double-metal hydroxide prepared in the step (2) into an argon atmosphere tubular furnace for pyrolysis at the high temperature of 300 ℃ to obtain a black cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material, wherein the purity of the high-purity argon is 98%.
(4) Cadmium acetate and thiourea are heated and refluxed at 110 ℃ in a diethylenetriamine system to obtain the CdS nanorod.
(5) Weighing 0.1g of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material obtained in the step (3) and 1g of the CdS nanorod prepared in the step (4), heating in an ethanol solvent at 80 ℃, and refluxing to obtain a dark yellow nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS composite photocatalytic material precipitate.
(6) And (3) centrifuging and washing the dark yellow nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS composite photocatalytic material precipitate in the step (5), and drying in a vacuum drying oven at 60 ℃ to obtain the nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material.
The nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material prepared in this example was subjected to a photocatalytic hydrogen production performance test under 5h illumination as in example 1, and the specific hydrogen evolution amount is shown in table 1 below.
Example 4
The embodiment of the invention provides a preparation method of a nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material, which comprises the following steps:
(1) 0.1g of cobalt nitrate cobalt salt and 1g of 2-methylimidazole organic ligand are stirred at room temperature in an aqueous phase system, and the mixture is kept stand and aged to obtain purple Co-MOF, namely ZIF-67.
(2) 0.1g of ZIF67 and 0.2g of nickel nitrate are mixed to obtain a mixed solution, and the mixed solution is subjected to ultrasonic etching to obtain green NiCo-LDH double-metal hydroxide with the surface containing excessive organic ligands.
(3) And (3) putting the NiCo-LDH double-metal hydroxide prepared in the step (2) into an argon atmosphere tube furnace for high-temperature pyrolysis at the temperature of 400 ℃ to obtain a black cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material, wherein the purity of the high-purity argon is 98%.
(4) Cadmium acetate and thiourea are heated and refluxed at 110 ℃ in a diethylenetriamine system to obtain the CdS nanorod.
(5) Weighing 0.06g of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material obtained in the step (3) and 1g of the CdS nanorod prepared in the step (4), heating in an ethanol solvent at 70 ℃, and refluxing to obtain a dark yellow nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS composite photocatalytic material precipitate.
(6) And (3) centrifuging and washing the dark yellow nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS composite photocatalytic material precipitate in the step (5), and drying in a vacuum drying oven at 60 ℃ to obtain the nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material.
The nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material prepared in this example was subjected to a photocatalytic hydrogen production performance test under 5h illumination as in example 1, and the specific hydrogen evolution amount is shown in table 1 below.
Example 5
The embodiment of the invention provides a preparation method of a nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material, which comprises the following steps:
(1) 0.1g of cobalt nitrate cobalt salt and 1.5g of 2-methylimidazole organic ligand are stirred at room temperature in an aqueous phase system, and the mixture is stood still and aged to obtain purple Co-MOF, namely ZIF-67.
(2) 0.1g of ZIF67 and 1g of nickel nitrate are mixed to obtain a mixed solution, and the mixed solution is subjected to ultrasonic etching to obtain green NiCo-LDH double-metal hydroxide with the surface containing excessive organic ligands.
(3) And (3) putting the NiCo-LDH double-metal hydroxide prepared in the step (2) into an argon atmosphere tubular furnace for high-temperature pyrolysis at the temperature of 500 ℃ to obtain a black cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material, wherein the purity of the high-purity argon is 98%.
(4) Cadmium acetate and thiourea are heated and refluxed at 110 ℃ in a diethylenetriamine system to obtain the CdS nanorod.
(5) Weighing 0.07g of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material obtained in the step (3) and 1g of the CdS nanorod prepared in the step (4), heating in an ethanol solvent at 75 ℃, and refluxing to obtain a dark yellow nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS composite photocatalytic material precipitate.
(6) And (3) centrifuging and washing the dark yellow nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS composite photocatalytic material precipitate in the step (5), and drying in a vacuum drying oven at 60 ℃ to obtain the nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material.
The nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material prepared in this example was subjected to a photocatalytic hydrogen production performance test under 5h illumination as in example 1, and the specific hydrogen evolution amount is shown in table 1 below.
Comparative example 1
The difference between the comparative example and the example 1 is that the photocatalytic performance is tested by only using the CdS nanorods prepared in the step (4) as the promoter for photolyzing water to produce hydrogen, and the steps of the photocatalytic method are the same as those of the example 1.
The specific hydrogen evolution amount of the photocatalytic hydrogen production performance test under 5h illumination in the comparative example is shown in the following table 1.
Comparative example 2
The comparative example is different from example 1 in that 0.1g of cobalt nitrate cobalt salt and 0.1g of 2-methylimidazole organic ligand in step (1) are stirred at room temperature in an aqueous phase system, and are kept stand and aged to obtain purple ZIF-67, and other steps are the same as example 1 and are not repeated.
The nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material prepared in the comparative example was subjected to a photocatalytic hydrogen production performance test under 5h illumination as in example 1, and the specific hydrogen evolution amount is shown in table 1 below.
Comparative example 3
The comparison example is different from the example 1 in that 0.1g of ZIF67 and 0.1g of nickel nitrate in the step (2) are mixed, and other steps are the same as the example 1 and are not repeated.
The nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material prepared in the comparative example was subjected to a photocatalytic hydrogen production performance test under 5h illumination as in example 1, and the specific hydrogen evolution amount is shown in table 1 below.
Comparative example 4
The difference between the comparative example and the example 1 is that 0.05g of nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material and 10g of CdS nanorod are weighed in the step (5) and mixed, and other steps are the same as the example 1 and are not repeated herein.
The nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material prepared in the comparative example was subjected to a photocatalytic hydrogen production performance test under 5h illumination as in example 1, and the specific hydrogen evolution amount is shown in table 1 below.
Comparative example 5
The difference between the comparative example and example 1 is that the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material in step (5) and the CdS nanorod prepared in step (4) are heated in an ethanol solvent to 40 ℃ and then refluxed to obtain a dark yellow nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS composite photocatalytic material precipitate, and other steps are the same as those in example 1 and are not repeated here.
The nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material prepared in the comparative example was subjected to a photocatalytic hydrogen production performance test under 5h illumination as in example 1, and the specific hydrogen evolution amount is shown in table 1 below.
The following table 1 shows the hydrogen evolution data of photocatalytic water hydrogen production under 5h illumination in different examples and comparative examples.
In summary, the following steps: as can be seen from the data in Table 1, the Ni-Co-Bi prepared by the present invention in example 1 is compared to the control 1, which uses CdS nanorods singly as the promoter for photolyzing water to produce hydrogenThe hydrogen production rate of the metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material within 5h is 1.7mmol g-1h-1Increased to 56 mmoleg-1h-1The method improves the hydrogen production rate by 32 times, greatly improves the photocatalytic hydrogen production rate and has obvious improvement effect.
According to the invention, a layered NiCo-LDH double-metal hydroxide is generated by reacting cobalt salt, an organic ligand and nickel salt in a certain mass ratio, then the NiCo-LDH double-metal hydroxide is pyrolyzed at high temperature to generate a nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material, and finally the obtained nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material is compounded with a CdS nanorod to generate the nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS composite photocatalytic material.
The composite photocatalytic material is composed of a nitrogen-oxygen co-doped carbon material derived from a metal organic framework and coated with a cocatalyst of a transition metal oxide and a CdS semiconductor, and the nitrogen-oxygen co-doped carbon material coated nickel-cobalt bimetallic oxide and CdS are compounded to form the photocatalytic material, so that the defect of singly using the cocatalyst of cadmium sulfide is overcome, and the problems of conductivity and few hydrogen evolution active sites are caused after the cocatalyst of a transition metal compound is added; according to the invention, the nitrogen-oxygen co-doped active carbon material is coated on the surface of the transition metal compound nickel-cobalt bimetallic compound in situ, and the synergistic cocatalyst effect is realized by improving the conductivity and more active sites of the transition metal compound nickel-cobalt bimetallic compound, so that the efficiency of photocatalytic hydrogen production of cadmium sulfide is effectively improved, and meanwhile, the synthesis method is simple and easy to operate.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of a nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material is characterized by comprising the following steps of:
(1) stirring cobalt salt and 2-methylimidazole in an aqueous phase system, standing and aging to obtain Co-MOF;
(2) mixing the Co-MOF obtained in the step (1) with nickel salt to obtain a mixed solution, and performing ultrasonic dispersion on the mixed solution to obtain NiCo-LDH double metal hydroxide;
(3) placing the NiCo-LDH double-metal hydroxide obtained in the step (2) in an inert atmosphere tube furnace for high-temperature pyrolysis to obtain a nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material;
(4) heating and refluxing cadmium acetate and thiourea in a diethylenetriamine system to obtain a CdS nanorod;
(5) heating and refluxing the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material obtained in the step (3) and the CdS nanorods in the step (4) in a solvent to obtain a precipitate;
(6) centrifugally washing the precipitate obtained in the step (5), and drying to obtain a nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material;
in the step (5), the mass ratio of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material to the CdS nanorods is (0.01-0.1): 1;
the mass ratio of the cobalt salt to the 2-methylimidazole is 1: (5-20);
the mass ratio of the Co-MOF to the nickel salt is 1: (2-10);
in the step (5), the heating reflux temperature is 60-80 ℃;
and the temperature for carrying out high-temperature pyrolysis in the inert atmosphere tube furnace is 300-500 ℃.
2. The method for preparing the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material as defined in claim 1, wherein the cobalt salt is cobalt nitrate.
3. The method for preparing the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material as defined in claim 1, wherein the nickel salt is nickel nitrate.
4. The method for preparing the nickel-cobalt double-metal oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material as defined in claim 1, wherein the inert atmosphere in the tubular furnace is argon.
5. The method for preparing the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material as defined in claim 1, wherein the solvent in the step (5) is ethanol.
6. The nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material prepared by the preparation method of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material as claimed in any one of claims 1 to 5.
7. The application of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material prepared by the preparation method of the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material as claimed in any one of claims 1 to 5, wherein the nickel-cobalt bimetallic oxide @ nitrogen-oxygen co-doped carbon material/CdS photocatalytic material is used for photocatalytic hydrogen evolution.
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