CN115709090A - CuSCN/CoS 2 Composite photocatalytic material, preparation method and application - Google Patents
CuSCN/CoS 2 Composite photocatalytic material, preparation method and application 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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Abstract
The invention provides a CuSCN/CoS 2 The composite photocatalytic material, the preparation method and the application thereof, wherein the method comprises the following steps: weighing Co (NO) 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and KSCN are mixed and ground to obtain Cu (SCN) 2 And Co (SCN) 2 A mixture of (a); the resulting mixture was transferred to an alumina crucible under an atmosphere without inert gas, with excess KSCN is used as a molten salt medium and is roasted for a first time at a first temperature; after naturally cooling to room temperature, washing with deionized water, and drying in a vacuum drying oven at a second temperature for a second time to obtain CuSCN/CoS 2 A composite photocatalytic material. The invention is prepared by mixing CuSCN and CoS 2 The light utilization rate and the separation and transfer capacity of the photo-generated carriers are enhanced by compounding, and the visible light catalysis CO is improved 2 Reduction to CO activity.
Description
Technical Field
The invention relates to the technical field of preparation of photocatalytic materials, in particular to CuSCN/CoS 2 A composite photocatalytic material, a preparation method and application.
Background
During the course of industrial development, the consumption of fossil fuels, an essential energy source for the development of the industry, increases year by year, leading to degradation of the natural carbon cycle and atmospheric CO 2 The concentration is increased sharply. Particularly over the last decades, due to the rapid increase in population and the rapid development of industry, human respiration and the combustion of fossil fuels produce CO 2 Yields have far exceeded historical levels. In addition, the ecological damage caused by human development also weakens the absorption of CO in the nature 2 Of the carbon dioxide, resulting in atmospheric CO 2 The increase in concentration.
At present, in respect of CO 2 The studies of fixation and transformation became increasingly popular. In particular for reducing CO in the atmosphere 2 Methods of concentration include capture, storage, conversion, and reuse. By using CO 2 This potential carbon resource is reduced to CO 2 In the direction of very promising approaches. In this context, various CO are involved 2 Methods of reductive transformation are gradually being developed. Common reduction pathways include: electrochemical reduction, photochemical reduction and biotransformation. Among the most promising ones, the photochemical reduction is used to convert CO 2 The method of (4). Converts nearly infinite natural solar energy into usable chemical energy, and realizes CO 2 Transformation and utilization of (2).
CO 2 The photocatalytic reduction is a surface/interface reaction and is used for the photocatalytic reduction of CO by semiconductors 2 The catalyst of (2) comprises a metal oxide (e.g. In) 2 O 3 ，WO 3 ，TiO 2 ) Metal sulfides (e.g. CoS) 2 ，MoS 2 ，SnS 2 ) Nitride (g-C) 3 N 4 ) Bismuth oxyhalides (BiOCl, biOBr) and double metal hydroxides (NiAl-LDH). Although the above-mentioned photocatalysts have proven capable of photocatalytic reduction of CO 2 But still have some disadvantages. For example, although the bismuth oxyhalide compound has strong oxidizing power, the bottom position of the conduction band is not negative enough, and the reduction performance is not good; in addition, the chemical properties of some photocatalysts are easy to change, the structure can be damaged in the process of illumination, and even substances with changed properties are not environment-friendly and cause harm.
CoS 2 The photocatalytic material has wide photoresponse range, and can efficiently utilize sunlight due to narrow band gap. Meanwhile, the narrow band gap causes the electrons and the holes to be quickly recombined after being excited by the energy of light, which is not beneficial to the photocatalytic reduction of CO 2 . Also, a narrow band gap indicates that its conduction band position is not sufficiently negative or its valence band position is not sufficiently positive. Namely: coS 2 The oxidation or reduction capability of the charges generated by light excitation is weak, which is not beneficial to the photocatalytic reduction of CO 2 . However, the band gap (not less than 3.5 eV) of CuSCN is wide, the oxidation or reduction capability of charges generated by light excitation is strong, but the photoresponse range is narrow, and the sunlight utilization rate is low.
Based on this, it is necessary to provide a method capable of combining CuSCN and CoS 2 A composite photocatalyst is prepared to realize good CO 2 The photocatalytic reduction effect of (1).
Disclosure of Invention
Based on the above, the invention aims to provide CuSCN/CoS 2 Composite photocatalytic material prepared by CuSCN and CoS 2 Constructing a composite photocatalyst, thereby adjusting the energy band structure to obtain a proper potential,improving visible light reduction of CO 2 Activity of (2).
Specifically, the invention provides CuSCN/CoS 2 The preparation method of the composite photocatalytic material comprises the following steps:
step one, weighing Co (NO) with a preset mass ratio of A to B to C 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and KSCN are mixed and ground to obtain Cu (SCN) 2 And Co (SCN) 2 A mixture of (a);
step two, transferring the obtained mixture into an alumina crucible, roasting the mixture at a first temperature for a first time by using excessive KSCN as a molten salt medium under the atmosphere without inert gas protection, wherein the first temperature is Cu (SCN) 2 Self-oxidation-reduction to CuSCN and (SCN) 2 ，Co(SCN) 2 Is oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying in a vacuum drying oven for a second time at a second temperature to obtain CuSCN/CoS 2 A composite photocatalytic material.
The invention provides a CuSCN/CoS 2 The preparation method of the composite photocatalytic material comprises the step of weighing Co (NO) with the preset mass ratio of A to B to C 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O was mixed and ground with KSCN to give Cu (SCN) 2 And Co (SCN) 2 A mixture of (a); the resulting mixture is then transferred to an alumina crucible and calcined at a first temperature for a first time, cu (SCN), in an atmosphere without inert gas shielding with an excess of KSCN as the molten salt medium 2 Self-oxidation-reduction to CuSCN and (SCN) 2 ，Co(SCN) 2 Is oxidized to CoS 2 (ii) a Naturally cooling to room temperature, washing with deionized water, and drying in a vacuum drying oven at a second temperature for a second time to obtain CuSCN/CoS 2 A composite photocatalytic material. The invention provides CuSCN/CoS 2 The preparation method of the composite photocatalytic material comprises the steps of mixing CuSCN and CoS 2 For recombination, enhancing the utilization of light and combining photogenerated carriersSeparating and transferring capability, and improving visible light catalytic CO 2 Reduction to CO.
The CuSCN/CoS 2 In the step one, the value of A is 0.01-0.11g, the value of B is 1.31-1.51g, and the value of C is 10g.
The CuSCN/CoS 2 The preparation method of the composite photocatalytic material comprises the steps of setting the first temperature at 300 ℃, setting the first time at 2h, setting the second temperature at 60 ℃ and setting the second time at 8h.
The CuSCN/CoS 2 The preparation method of the composite photocatalytic material, wherein in the step one, cu (SCN) 2 And Co (SCN) 2 In the mixture of (1), co (SCN) 2 Is dark blue, cu (SCN) 2 Is black;
in the third step, cuSCN/CoS 2 The color of the composite photocatalytic material is black.
The CuSCN/CoS 2 The preparation method of the composite photocatalytic material comprises the following steps:
step one, weighing 0.01g of Co (NO) 3 ) 2 ·6H 2 O, 1.51g of Cu (NO) 3 ) 2 ·3H 2 O and 10g of KSCN were put in a mortar and sufficiently ground to obtain Cu (SCN) 2 And Co (SCN) 2 A mixture of (a);
step two, transferring the obtained mixture into an alumina crucible, roasting the mixture at the temperature of 300 ℃ for 2h by using excess KSCN as a molten salt medium under the atmosphere without inert gas protection, wherein the temperature of the molten salt medium is lower than that of the molten salt medium, and roasting the mixture for 2h 2 Self-oxidation-reduction to CuSCN and (SCN) 2 ，Co(SCN) 2 Is oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying for 8 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain CuSCN/CoS 2 A composite photocatalytic material.
The CuSCN/CoS 2 A preparation method of the composite photocatalytic material, wherein the methodThe method comprises the following steps:
step one, weighing 0.05g of Co (NO) 3 ) 2 ·6H 2 O, 1.46g of Cu (NO) 3 ) 2 ·3H 2 O and 10g of KSCN were put in a mortar and sufficiently ground to obtain Cu (SCN) 2 And Co (SCN) 2 A mixture of (a);
step two, transferring the obtained mixture into an alumina crucible, roasting the mixture at the temperature of 300 ℃ for 2h by using excess KSCN as a molten salt medium under the atmosphere without inert gas protection, wherein the temperature of the molten salt medium is lower than that of the molten salt medium, and roasting the mixture for 2h 2 Self-oxidation-reduction to CuSCN and (SCN) 2 ，Co(SCN) 2 Is oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying for 8 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain CuSCN/CoS 2 A composite photocatalytic material.
The CuSCN/CoS 2 The preparation method of the composite photocatalytic material comprises the following steps:
step one, weighing 0.11g of Co (NO) 3 ) 2 ·6H 2 O, 1.31g of Cu (NO) 3 ) 2 ·3H 2 O and 10g of KSCN were put in a mortar and sufficiently ground to obtain Cu (SCN) 2 And Co (SCN) 2 A mixture of (a);
step two, transferring the obtained mixture into an alumina crucible, roasting the mixture at the temperature of 300 ℃ for 2h by using excess KSCN as a molten salt medium under the atmosphere without inert gas protection, wherein the temperature of the molten salt medium is lower than that of the molten salt medium, and roasting the mixture for 2h 2 Self-oxidation-reduction to CuSCN and (SCN) 2 ，Co(SCN) 2 Is oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying for 8 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain CuSCN/CoS 2 A composite photocatalytic material.
The invention also provides CuSCN/CoS 2 The composite photocatalytic material is CuSCN/CoS 2 The composite photocatalytic material is prepared by the method.
The invention also provides CuSCN/CoS 2 Application of composite photocatalytic material, wherein CuSCN/CoS prepared by using method as described above 2 Composite photocatalytic material for CO 2 The method for carrying out photocatalytic reduction comprises the following steps:
weighing 30mg of CuSCN/CoS in a 50ml closed quartz reactor by adopting a xenon lamp with a light source of 300W 2 Measuring 3ml acetonitrile, 2ml deionized water and 1ml triethanolamine with a composite photocatalytic material and 5mg tris (2, 2' -bipyridyl) ruthenium (II) chloride hexahydrate, and carrying out ultrasonic treatment for 2min to make the mixture uniform;
introducing high-purity CO with the pressure of 1atm at a position without illumination under the condition of magnetic stirring 2 Gas is discharged for 0.5h to exhaust the air in the reactor and make the reaction system reach CO 2 A state of adsorption saturation;
sealing the reactor after the ventilation is finished, then illuminating for reaction for 2H, cooling after the reaction is finished, taking 1ml of gas by using a sample injection needle, introducing the gas into a gas chromatograph, detecting products CO and H obtained after the reaction 2 、CH 4 。
Additional features and advantages of the disclosure will be set forth in the description which follows, or in part may be learned by the practice of the above-described techniques of the disclosure, or may be learned by practice of the disclosure.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
FIG. 1 is SEM, TEM and HRTEM images of each sample in the present invention;
FIG. 2 is a graph of CO yield and selectivity under visible light illumination for various samples of the present invention;
FIG. 3 is a graph showing the CO yield and selectivity of sample 1-Cu/Co under different conditions according to the present invention;
FIG. 4 is an XRD pattern of various samples of the invention;
FIG. 5 is a UV-vis-DRS profile of various samples according to the invention;
FIG. 6 is a graph of photocurrent response of various samples of the invention;
FIG. 7 is an impedance plot of various samples of the present invention;
FIG. 8 is a photoluminescence spectrum of various samples of the invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully hereinafter with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a CuSCN/CoS 2 The preparation method of the composite photocatalytic material comprises the following steps:
step one, weighing Co (NO) with a preset mass ratio of A to B to C 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and KSCN are mixed and ground to obtain Cu (SCN) 2 And Co (SCN) 2 A mixture of (a).
In the first step, A takes a value of 0.01-0.11g, B takes a value of 1.31-1.51g, and C takes a value of 10g. In addition, in Cu (SCN) 2 And Co (SCN) 2 In the mixture of (1), co (SCN) 2 Is dark blue, cu (SCN) 2 Is black.
Step two, transferring the obtained mixture into an alumina crucible, and roasting the mixture at a first temperature for a first time by using excessive KSCN as a molten salt medium under the atmosphere without inert gas protection, wherein the first temperature is Cu (S)CN) 2 Self-redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Is oxidized to CoS 2 。
In this step, the first temperature is 300 ℃ and the first time is 2 hours.
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying in a vacuum drying oven for a second time at a second temperature to obtain CuSCN/CoS 2 A composite photocatalytic material.
In this step, the second temperature was 60 ℃ and the second time was 8 hours. Furthermore, in this step, cuSCN/CoS 2 The color of the composite photocatalytic material is black.
The invention provides a CuSCN/CoS 2 The preparation method of the composite photocatalytic material comprises the steps of weighing Co (NO) with the preset mass ratio of A to B to C 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and KSCN are mixed and ground to obtain Cu (SCN) 2 And Co (SCN) 2 A mixture of (a); the resulting mixture is then transferred to an alumina crucible and calcined at a first temperature for a first time, cu (SCN), in an atmosphere without inert gas shielding with an excess of KSCN as the molten salt medium 2 Self-redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Is oxidized to CoS 2 (ii) a Naturally cooling to room temperature, washing with deionized water, and drying in a vacuum drying oven at a second temperature for a second time to obtain CuSCN/CoS 2 A composite photocatalytic material. The invention provides CuSCN/CoS 2 The preparation method of the composite photocatalytic material comprises the steps of mixing CuSCN and CoS 2 The light utilization rate and the separation and transfer capacity of the photo-generated carriers are enhanced by compounding, and the visible light catalysis CO is improved 2 Reduction to CO activity.
The following examples are provided to illustrate CuSCN/CoS of the present invention 2 The preparation method of the composite photocatalytic material is described in detail.
The first embodiment is as follows:
the CuSCN/CoS provided by the first embodiment of the invention 2 Preparation method of composite photocatalytic materialThe method specifically comprises the following steps:
step one, weighing 0.01g of Co (NO) 3 ) 2 ·6H 2 O, 1.51g of Cu (NO) 3 ) 2 ·3H 2 O and 10g of KSCN were put in a mortar and sufficiently ground to obtain Cu (SCN) 2 And Co (SCN) 2 A mixture of (a);
step two, transferring the obtained mixture into an alumina crucible, roasting the mixture at the temperature of 300 ℃ for 2h by using excess KSCN as a molten salt medium under the atmosphere without inert gas protection, wherein the temperature of the molten salt medium is lower than that of the molten salt medium, and roasting the mixture for 2h 2 Self-oxidation-reduction to CuSCN and (SCN) 2 ，Co(SCN) 2 Is oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying for 8 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain CuSCN/CoS 2 Composite photocatalytic material (noted as 1-Cu/Co).
The second embodiment:
the CuSCN/CoS provided by the second embodiment of the invention 2 The preparation method of the composite photocatalytic material specifically comprises the following steps:
step one, weighing 0.05g of Co (NO) 3 ) 2 ·6H 2 O, 1.46g of Cu (NO) 3 ) 2 ·3H 2 O and 10g of KSCN were put in a mortar and sufficiently ground to obtain Cu (SCN) 2 And Co (SCN) 2 A mixture of (a);
step two, transferring the obtained mixture into an alumina crucible, roasting the mixture at the temperature of 300 ℃ for 2h by using excess KSCN as a molten salt medium under the atmosphere without inert gas protection, wherein the temperature of the molten salt medium is lower than that of the molten salt medium, and roasting the mixture for 2h 2 Self-oxidation-reduction to CuSCN and (SCN) 2 ，Co(SCN) 2 Is oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying for 8 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain CuSCN/CoS 2 The composite photocatalytic material (marked as 5-Cu/Co).
Example three:
the third embodiment of the present invention proposesCuSCN/CoS of 2 The preparation method of the composite photocatalytic material specifically comprises the following steps:
step one, weighing 0.11g of Co (NO) 3 ) 2 ·6H 2 O, 1.31g of Cu (NO) 3 ) 2 ·3H 2 O and 10g of KSCN were put in a mortar and sufficiently ground to obtain Cu (SCN) 2 And Co (SCN) 2 A mixture of (a);
step two, transferring the obtained mixture into an alumina crucible, roasting the mixture for 2h at the temperature of 300 ℃ by using excess KSCN as a molten salt medium under the atmosphere without inert gas protection, and then roasting the mixture for Cu (SCN) 2 Self-oxidation-reduction to CuSCN and (SCN) 2 ，Co(SCN) 2 Is oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying for 8 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain CuSCN/CoS 2 Composite photocatalytic material (10-Cu/Co).
The invention provides a CuSCN/CoS 2 The preparation method of the composite photocatalytic material comprises the steps of weighing Co (NO) with the preset mass ratio of A to B to C 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and KSCN are mixed and ground to obtain Cu (SCN) 2 And Co (SCN) 2 A mixture of (a); the resulting mixture is then transferred to an alumina crucible and calcined at a first temperature for a first time, cu (SCN), in an atmosphere without inert gas shielding with an excess of KSCN as the molten salt medium 2 Self-redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Is oxidized to CoS 2 (ii) a After naturally cooling to room temperature, washing with deionized water, and finally drying in a vacuum drying oven at a second temperature for a second time to obtain CuSCN/CoS 2 A composite photocatalytic material. The invention provides CuSCN/CoS 2 The preparation method of the composite photocatalytic material comprises the steps of mixing CuSCN and CoS 2 The light utilization rate and the separation and transfer capacity of the photo-generated carriers are enhanced by compounding, and the visible light catalysis CO is improved 2 Reduction to CO.
For the CuSCN/CoS prepared in the above examples one to three 2 The composite photocatalytic material is characterized in that the product in the first embodiment is marked as 1-Cu/Co, the product in the second embodiment is marked as 5-Cu/Co, and the product in the third embodiment is marked as 10-Cu/Co. For the prepared CuSCN/CoS 2 The composite photocatalytic material is subjected to chemical characterization, and the corresponding chemical characterization results are analyzed as follows.
FIG. 1 is SEM, TEM and HRTEM images of each sample in the present invention. In FIG. 1, part (a) is CoS 2 As shown in part (a) of fig. 1: coS 2 Is composed of aggregated nanoparticles. Part (b) in fig. 1 is an SEM image of CuSCN, as shown in part (b) in fig. 1: cuSCN is composed of nanorods and some agglomeration occurs.
The SEM image of 1-Cu/Co in part (c) of FIG. 1, as shown in part (c) of FIG. 1: in CuSCN/CoS 2 In the SEM image of the composite photocatalytic material (1-Cu/Co), it can be found that: attachment of CuSCN to CoS 2 On top of the nanoparticles, successful preparation of 1-Cu/Co composite samples was demonstrated.
Further, a TEM image of 1-Cu/Co is shown in part (d) of FIG. 1, as shown in part (d) of FIG. 1: from the TEM image of 1-Cu/Co, two kinds of substances, i.e., granular and rod-like substances, were observed, and from the foregoing SEM image structure, it was judged that the granular substances were CoS 2 The smaller rod is CuSCN. Likewise, it can be seen that CuSCN adheres to CoS 2 On the nanoparticles, which is consistent with the SEM results, again demonstrating CoS 2 And CuSCN successfully complexed.
In addition, FIG. 1 shows HRTEM image of 1-Cu/Co in part (e). As shown in part (e) of fig. 1: from the HRTEM image of 1-Cu/Co, it can be observed that the lattice spacing of d =0.226nm corresponds to CoS 2 And a lattice spacing of d =0.293nm corresponds to the (112) plane of CuSCN, further indicating CuSCN/CoS 2 Successfully preparing the composite photocatalyst.
As shown in FIG. 2, under light, one-component CuSCN and CoS 2 Photo-reduction of CO 2 The activity is very low, and the effect is obviously improved after the composition. As the amount of CuSCN added increases, the rate of CO generation decreases. This can be doneThe reason is that the added amount of CuSCN is increased, the separation efficiency of photo-generated charges of the sample is reduced, and the photocatalytic activity of the sample is influenced.
Further, ru-free, catalyst-free, and N were each performed 2 Substitute for CO 2 Control activity experiments without light and without TEOA (triethanolamine) conditions. As shown in FIG. 3, there was almost no CO formation in the control experiment, indicating that the CO in the product was derived from CO 2 Rather than decomposition of the catalyst or other materials, also demonstrates that each of the experimental conditions described above plays an important role in the reaction. When using N 2 Replacement of CO 2 In time, more H is generated 2 Note that when 1-Cu/Co is catalyzed, the presence of reduced CO 2 And reduction of H originally functioning to donate protons 2 Competing reactions of O, only in CO 2 Under the atmosphere, 1-Cu/Co can preferentially reduce CO 2 The excellent selectivity of the composite photocatalytic material is proved.
Figure 4 is an XRD pattern of different samples of the invention. As shown in FIG. 4, coS for a single component 2 And CuSCN both correspond well to standard cubic CoS 2 (JCPDS PDF # 89-1492) and orthorhombic phase alpha-CuSCN (JCPDS PDF # 29-0582), while for the composite material, there is no distinct CuSCN characteristic peak on the XRD spectrum, probably due to CuSCN/CoS 2 The composite photocatalyst has very low content of CuSCN.
FIG. 5 is a UV-vis-DRS profile of various samples of the invention. As can be seen from fig. 5: single-component CoS 2 The absorption intensity of the composite material is obviously higher than that of CuSCN, which indicates that the sample basically keeps CoS 2 Absorption characteristics to light, cuSCN and CoS 2 The composite material is basically not affected by the problem of insufficient optical absorption of CuSCN in the visible light range, and the composite material can well utilize visible light.
Fig. 6 is a graph of photocurrent response for different samples of the invention. The photocurrent density-time curve indicates the generation of photo-generated charge by the semiconductor photocatalyst, while a lower photocurrent density indicates a greater probability of recombination of photo-generated electrons and holes. As shown in fig. 6: the photocurrent response of the sample 1-Cu/Co is stronger, so that the 1-Cu/Co can generate more photon-generated carriers and can separate and transfer photon-generated electrons/holes more effectively.
FIG. 7 is a graph of the impedance of various samples of the present invention. The electrochemical alternating-current impedance spectrum further researches the charge transfer efficiency of the prepared sample, and the curvature radius of the curve in the electrochemical alternating-current impedance spectrum can directly reflect the resistance of charge transfer. As shown in FIG. 7, coS with a Single component 2 Compared with CuSCN, the curvature radius of the curve in the electrochemical alternating-current impedance spectrum of the 1-Cu/Co composite material is minimum, which shows that the charge transfer resistance is minimum, the charge separation efficiency is highest, and the result is consistent with the photocurrent test result.
FIG. 8 is a photoluminescence spectrum of different samples according to the invention. The recombination of the photo-generated electrons and holes will dissipate energy in the form of light and heat, creating a fluorescence phenomenon, so for photocatalysis, a good catalytic effect corresponds to a high separation efficiency of photo-generated charges, i.e. a low photoluminescence intensity. As shown in FIG. 8, the sample has an emission peak at 682nm under the excitation wavelength of 340nm, and the fluorescence intensity of the composite sample 1-Cu/Co is higher than that of the two pure samples CuSCN and CoS 2 Low, which indicates that the separation capability of the photogenerated carrier of the 1-Cu/Co sample is stronger, and proves that CuSCN and CoS 2 The separation of photo-generated charges can be enhanced by the recombination, and the photocatalytic activity of the photo-generated charges is further improved.
Example four:
the fourth embodiment of the invention provides a CuSCN/CoS 2 Application of the composite photocatalytic material, wherein the CuSCN/CoS prepared in the first to third embodiments is applied 2 Composite photocatalytic material for CO 2 The method for carrying out photocatalytic reduction comprises the following steps:
weighing 30mg of CuSCN/CoS in a 50ml closed quartz reactor by adopting a xenon lamp with a light source of 300W 2 Measuring 3ml acetonitrile, 2ml deionized water and 1ml triethanolamine with a composite photocatalytic material and 5mg tris (2, 2' -bipyridyl) ruthenium (II) chloride hexahydrate, and carrying out ultrasonic treatment for 2min to make the mixture uniform;
in a non-illuminated position, while stirring magnetically, introducing a gas under a pressure of 1atmHigh purity CO 2 Gas is discharged for 0.5h to exhaust the air in the reactor and make the reaction system reach CO 2 A state of adsorption saturation;
sealing the reactor after the ventilation is finished, then illuminating for reaction for 2H, cooling after the reaction is finished, taking 1ml of gas by using a sample injection needle, introducing the gas into a gas chromatograph, detecting products CO and H obtained after the reaction 2 、CH 4 。
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that the following descriptions are only illustrative and not restrictive, and that the scope of the present invention is not limited to the above embodiments: those skilled in the art can still make modifications or changes to the embodiments described in the foregoing embodiments, or make equivalent substitutions for some features, within the scope of the disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the embodiments of the present invention, and they should be construed as being included therein. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. CuSCN/CoS 2 The preparation method of the composite photocatalytic material is characterized by comprising the following steps of:
step one, weighing Co (NO) with a preset mass ratio of A to B to C 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O was mixed and ground with KSCN to give Cu (SCN) 2 And Co (SCN) 2 A mixture of (a);
step two, transferring the obtained mixture into an alumina crucible, roasting the mixture at a first temperature for a first time by using excessive KSCN as a molten salt medium under the atmosphere without inert gas protection, wherein the first temperature is Cu (SCN) 2 Self-oxidation-reduction to CuSCN and (SCN) 2 ，Co(SCN) 2 Is oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying in a vacuum drying oven for a second time at a second temperature to obtain CuSCN/CoS 2 A composite photocatalytic material.
2. CuSCN/CoS according to claim 1 2 The preparation method of the composite photocatalytic material is characterized in that in the step one, the value of A is 0.01-0.11g, the value of B is 1.31-1.51g, and the value of C is 10g.
3. CuSCN/CoS according to claim 2 2 The preparation method of the composite photocatalytic material is characterized in that the first temperature is 300 ℃, the first time is 2 hours, the second temperature is 60 ℃, and the second time is 8 hours.
4. CuSCN/CoS according to claim 3 2 The preparation method of the composite photocatalytic material is characterized in that in the step one, cu (SCN) 2 And Co (SCN) 2 In the mixture of (1), co (SCN) 2 Is dark blue, cu (SCN) 2 Is black;
in the third step, cuSCN/CoS 2 The color of the composite photocatalytic material is black.
5. CuSCN/CoS according to claim 4 2 The preparation method of the composite photocatalytic material is characterized by comprising the following steps of:
step one, weighing 0.01g of Co (NO) 3 ) 2 ·6H 2 O, 1.51g of Cu (NO) 3 ) 2 ·3H 2 O and 10g of KSCN were put in a mortar and sufficiently ground to obtain Cu (SCN) 2 And Co (SCN) 2 A mixture of (a);
step two, transferring the obtained mixture into an alumina crucible, roasting the mixture at the temperature of 300 ℃ for 2h by using excess KSCN as a molten salt medium under the atmosphere without inert gas protection, wherein the temperature of the molten salt medium is lower than that of the molten salt medium, and roasting the mixture for 2h 2 Self-bodyRedox to CuSCN and (SCN) 2 ，Co(SCN) 2 Is oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying for 8 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain CuSCN/CoS 2 A composite photocatalytic material.
6. The CuSCN/CoS of claim 4 2 The preparation method of the composite photocatalytic material is characterized by comprising the following steps of:
step one, weighing 0.015g of Co (NO) 3 ) 2 ·6H 2 O, 1.46g of Cu (NO) 3 ) 2 ·3H 2 O and 10g of KSCN were put in a mortar and sufficiently ground to obtain Cu (SCN) 2 And Co (SCN) 2 A mixture of (a);
step two, transferring the obtained mixture into an alumina crucible, roasting the mixture for 2h at the temperature of 300 ℃ by using excess KSCN as a molten salt medium under the atmosphere without inert gas protection, and then roasting the mixture for Cu (SCN) 2 Self-redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Is oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying for 8 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain CuSCN/CoS 2 A composite photocatalytic material.
7. CuSCN/CoS according to claim 4 2 The preparation method of the composite photocatalytic material is characterized by comprising the following steps of:
step one, weighing 0.11g of Co (NO) 3 ) 2 ·6H 2 O, 1.31g of Cu (NO) 3 ) 2 ·3H 2 O and 10g of KSCN were put in a mortar and sufficiently ground to obtain Cu (SCN) 2 And Co (SCN) 2 A mixture of (a);
step two, transferring the obtained mixture into an alumina crucible, and taking excessive KSCN as the raw material under the atmosphere without inert gas protectionMelting salt medium, roasting at 300 deg.C for 2h, cu (SCN) 2 Self-oxidation-reduction to CuSCN and (SCN) 2 ，Co(SCN) 2 Is oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying for 8 hours in a vacuum drying oven at the temperature of 60 ℃ to obtain CuSCN/CoS 2 A composite photocatalytic material.
8. CuSCN/CoS 2 The composite photocatalytic material is characterized in that the CuSCN/CoS 2 A composite photocatalytic material prepared by the method as claimed in any one of claims 1 to 7.
9. CuSCN/CoS 2 Use of a composite photocatalytic material, characterized in that the CuSCN/CoS prepared by the method according to any one of claims 1 to 7 is used 2 Composite photocatalytic material for CO 2 The method for carrying out photocatalytic reduction comprises the following steps:
weighing 30mg of CuSCN/CoS in a 50ml closed quartz reactor by adopting a 300W xenon lamp as a light source 2 Measuring 3ml acetonitrile, 2ml deionized water and 1ml triethanolamine with a composite photocatalytic material and 5mg tris (2, 2' -bipyridyl) ruthenium (II) chloride hexahydrate, and carrying out ultrasonic treatment for 2min to make the mixture uniform;
introducing high-purity CO with the pressure of 1atm at a position without illumination under the condition of magnetic stirring 2 Gas is discharged for 0.5h to exhaust the air in the reactor and make the reaction system reach CO 2 A state of adsorption saturation;
sealing the reactor after the ventilation is finished, then illuminating for reaction for 2H, cooling after the reaction is finished, taking 1ml of gas by using a sample injection needle, introducing the gas into a gas chromatograph, detecting products CO and H obtained after the reaction 2 、CH 4 。
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