CN115709090B - 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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- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 title claims abstract description 98
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- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 50
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims abstract description 32
- 238000001816 cooling Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004570 mortar (masonry) Substances 0.000 claims description 9
- 238000005286 illumination Methods 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- WHELTKFSBJNBMQ-UHFFFAOYSA-L dichlororuthenium;2-pyridin-2-ylpyridine;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ru+2].N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 WHELTKFSBJNBMQ-UHFFFAOYSA-L 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
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- 238000003760 magnetic stirring Methods 0.000 claims description 3
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- 229910052724 xenon Inorganic materials 0.000 claims description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
Abstract
The invention provides a CuSCN/CoS 2 The preparation method and application of the composite photocatalytic material comprise the following steps: weighing Co (NO) 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and KSCN to obtain Cu (SCN) 2 And Co (SCN) 2 Is a mixture of (a) and (b); transferring the obtained mixture into an alumina crucible, and roasting at a first temperature for a first time under the atmosphere without inert gas protection by taking excessive KSCN as a salt melting medium; washing with deionized water after naturally cooling to room temperature, 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 realized by combining CuSCN and CoS 2 Compounding, enhancing the light utilization rate, separating and transferring the photo-generated carriers, and improving the visible light catalytic CO 2 Activity to reduce to CO.
Description
Technical Field
The invention relates to the technical field of preparation of photocatalytic materials, in particular to a CuSCN/CoS 2 Composite photocatalytic material, preparation method and application thereof.
Background
In the course of industrial development, fossil as an essential energy source for industrial developmentThe consumption of fuel increases year by year, leading to degradation of natural carbon cycle and atmospheric CO 2 The concentration increases sharply. In particular, for decades, due to the rapid increase in population and the rapid development of industry, human respiration and the CO produced by fossil fuel combustion 2 Yield has far exceeded historical levels. In addition, ecological damage caused by human development also weakens the absorption of CO in nature 2 Is capable of generating CO in the atmosphere 2 Rise in concentration.
Currently, CO is concerned with 2 The studies of immobilization and transformation are becoming increasingly popular. In particular for reducing CO in the atmosphere 2 Methods of concentration include capture, storage, conversion, reuse, and the like. By CO 2 This potential carbon resource becomes a CO reduction 2 Is a very promising direction. In this context, various CO-related species 2 The method of reductive transformation has been gradually developed. Common reduction pathways include: electrochemical reduction, photochemical reduction and bioconversion. Of which the most promising is the conversion of CO by photochemical reduction 2 Is a method of study. Converting almost infinite solar energy into usable chemical energy, realizing CO 2 Is transformed and utilized.
CO 2 Is a surface/interface reaction for the photocatalytic reduction of CO in semiconductors 2 The catalyst of (a) 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 oxyhalide (BiOCl, biOBr), and double metal hydroxide (NiAl-LDH). Although the above mentioned photocatalysts have been shown to be capable of photocatalytic reduction of CO 2 But still have some drawbacks. For example, bismuth oxyhalide compounds, although having a strong oxidizing ability, have a conduction band with a bottom position that is not sufficiently negative, and have poor reducing performance; in addition, some photocatalysts are easy to change in chemical properties, the structure can be damaged in the process of illumination, and even substances with changed properties are harmful to the environment.
CoS 2 Has wide application in hydrogen production by photolysis of waterThe material is a good photocatalysis material, has a wide light response range, and can efficiently utilize sunlight due to a narrow band gap. At the same time, the narrow band gap causes the electrons and holes to be more quickly recombined after being excited by the energy of light, which is unfavorable for the photocatalytic reduction of CO 2 . But a narrow band gap also indicates that its conduction band is not sufficiently negative in position, or that its valence band is not sufficiently positive in position. Namely: coS (CoS) 2 The charge generated by photoexcitation has relatively weak oxidation or reduction power, which is disadvantageous for photocatalytic reduction of CO 2 . However, cuSCN has a wide band gap (. Gtoreq.3.5 eV), and has a strong oxidation or reduction capability of charges generated by photoexcitation, but has a narrow photoresponse range and a low solar light utilization rate.
Based on this, it is necessary to propose a method capable of combining CuSCN and CoS 2 Preparing a composite photocatalyst to realize good CO 2 Is used for the photocatalytic reduction effect of (a).
Disclosure of Invention
Based on this, the object of the present invention is to provide a CuSCN/CoS 2 Composite photocatalytic material is prepared from CuSCN and CoS 2 Constructing a composite photocatalyst, thereby adjusting the energy band structure to obtain proper potential and improving the reduction of CO by visible light 2 Is a compound of formula (I).
Specifically, the invention provides a CuSCN/CoS 2 The preparation method of the composite photocatalytic material comprises the following steps:
step one, co (NO) with the preset mass ratio of A to B to C is weighed 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and KSCN to obtain Cu (SCN) 2 And Co (SCN) 2 Is a mixture of (a) and (b);
transferring the obtained mixture into an alumina crucible, and roasting Cu (SCN) at a first temperature for a first time by taking excessive KSCN as a salt melting medium in an atmosphere without inert gas protection 2 Self redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Oxidized to CoS 2 ；
Step three, after naturally cooling to room temperature, the product is usedWashing with ionized water, and drying at a second temperature in a vacuum drying oven for a second time to obtain CuSCN/CoS 2 A composite photocatalytic material.
The invention provides a CuSCN/CoS 2 Preparation method of composite photocatalytic material comprises weighing Co (NO) with preset mass ratio of A:B:C 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and KSCN to obtain Cu (SCN) 2 And Co (SCN) 2 Is a mixture of (a) and (b); transferring the obtained mixture into an alumina crucible, calcining Cu (SCN) at a first temperature for a first time under the atmosphere without inert gas protection by taking excessive KSCN as a salt melting medium 2 Self redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Oxidized to CoS 2 The method comprises the steps of carrying out a first treatment on the surface of the Washing with deionized water after naturally cooling to room temperature, 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 CuSCN/CoS provided by the invention 2 Preparation method of composite photocatalytic material comprises mixing CuSCN with CoS 2 Compounding, enhancing the light utilization rate, separating and transferring the photo-generated carriers, and improving the visible light catalytic CO 2 Activity to reduce to CO.
The CuSCN/CoS 2 In the first step, the value of A is 0.01-0.11 g, the value of B is 1.31-1.51 g, and the value of C is 10g.
The CuSCN/CoS 2 The preparation method of the composite photocatalytic material comprises the steps of enabling the first temperature to be 300 ℃, enabling the first time to be 2h, enabling the second temperature to be 60 ℃ and enabling the second time to be 8h.
The CuSCN/CoS 2 Method for preparing a composite photocatalytic material, wherein in said step one, in Cu (SCN) 2 And Co (SCN) 2 Co (SCN) 2 Is dark blue in color, cu (SCN) 2 Is black in color;
in the third step, cuSCN/CoS 2 Composite photocatalytic materialThe color of the material is black.
The CuSCN/CoS 2 The preparation method of the composite photocatalytic material comprises the following steps:
step one, 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 added to a mortar and sufficiently ground to obtain Cu (SCN) 2 And Co (SCN) 2 Is a mixture of (a) and (b);
transferring the obtained mixture into an alumina crucible, and roasting the mixture at 300 ℃ for 2 hours and Cu (SCN) in an atmosphere without inert gas protection by taking excessive KSCN as a salt melting medium 2 Self redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying in a vacuum drying oven at 60 ℃ for 8 hours 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, 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 added to a mortar and sufficiently ground to obtain Cu (SCN) 2 And Co (SCN) 2 Is a mixture of (a) and (b);
transferring the obtained mixture into an alumina crucible, and roasting the mixture at 300 ℃ for 2 hours and Cu (SCN) in an atmosphere without inert gas protection by taking excessive KSCN as a salt melting medium 2 Self redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying in a vacuum drying oven at 60 ℃ for 8 hours 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, 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 added to a mortar and sufficiently ground to obtain Cu (SCN) 2 And Co (SCN) 2 Is a mixture of (a) and (b);
transferring the obtained mixture into an alumina crucible, and roasting the mixture at 300 ℃ for 2 hours and Cu (SCN) in an atmosphere without inert gas protection by taking excessive KSCN as a salt melting medium 2 Self redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying in a vacuum drying oven at 60 ℃ for 8 hours to obtain CuSCN/CoS 2 A composite photocatalytic material.
The invention also provides a CuSCN/CoS 2 A composite photocatalytic material, wherein the CuSCN/CoS 2 The composite photocatalytic material is prepared by the method.
The invention also provides a CuSCN/CoS 2 Application of composite photocatalytic material, wherein CuSCN/CoS prepared by the method is applied 2 Composite photocatalytic material pair CO 2 The method for carrying out the photocatalytic reduction comprises the following steps:
30mg CuSCN/CoS was weighed into a 50ml sealed quartz reactor using a 300W xenon lamp as the light source 2 The preparation method comprises the steps of (1) measuring 3ml of acetonitrile, 2ml of deionized water and 1ml of triethanolamine from a composite photocatalytic material and 5mg of tris (2, 2' -bipyridine) ruthenium (II) chloride hexahydrate, and carrying out ultrasonic treatment for 2min to ensure that the mixture is uniform;
at the position without illumination, under the magnetic stirring, high-purity CO with the pressure of 1atm is simultaneously introduced 2 The gas is discharged for 0.5h to exhaust the air in the reactor and lead the reaction system to reach CO 2 Adsorption saturation state;
after aeration, the reactor was sealed and then light was appliedCarrying out reaction for 2H, cooling after the reaction is finished, taking 1ml of gas by a sample injection needle, introducing the gas into a gas chromatograph, and 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 will be obvious from the description, or may be learned by practice of the techniques of the disclosure.
In order to make the above objects, features and advantages of the present invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
FIG. 1 is an SEM, TEM, and HRTEM image of samples according to the invention;
FIG. 2 is a graph showing CO yield versus selectivity for different samples of the present invention under irradiation from a visible light source;
FIG. 3 is a graph showing the CO yield and selectivity of sample 1-Cu/Co of the present invention under various conditions;
FIG. 4 is an XRD pattern for different samples according to the invention;
FIG. 5 is a graph of UV-vis-DRS profile of different samples according to the invention;
FIG. 6 is a graph showing photocurrent response of different samples according to the present invention;
FIG. 7 is a graph of impedance of different samples according to the present invention;
FIG. 8 is a photoluminescence spectrum of different samples according to the invention.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended 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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein 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, co (NO) with the preset mass ratio of A to B to C is weighed 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and KSCN to obtain Cu (SCN) 2 And Co (SCN) 2 Is a mixture of (a) and (b).
In the first step, the value of A is 0.01-0.11 g, the value of B is 1.31-1.51 g, and the value of C is 10g. In addition, in Cu (SCN) 2 And Co (SCN) 2 Co (SCN) 2 Is dark blue in color, cu (SCN) 2 Is black in color.
Transferring the obtained mixture into an alumina crucible, and roasting Cu (SCN) at a first temperature for a first time by taking excessive KSCN as a salt melting medium in an atmosphere without inert gas protection 2 Self redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Oxidized to CoS 2 。
In this step, the first temperature was 300℃and the first time was 2h.
Step three, washing the mixture by deionized water after naturally cooling the mixture to room temperature, and finally drying the mixture in a vacuum drying oven at a second temperature for a second time 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 Preparation method of composite photocatalytic material comprises weighing Co (NO) with preset mass ratio of A:B:C 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and KSCN to obtain Cu (SC)N) 2 And Co (SCN) 2 Is a mixture of (a) and (b); transferring the obtained mixture into an alumina crucible, calcining Cu (SCN) at a first temperature for a first time under the atmosphere without inert gas protection by taking excessive KSCN as a salt melting medium 2 Self redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Oxidized to CoS 2 The method comprises the steps of carrying out a first treatment on the surface of the Washing with deionized water after naturally cooling to room temperature, 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 CuSCN/CoS provided by the invention 2 Preparation method of composite photocatalytic material comprises mixing CuSCN with CoS 2 Compounding, enhancing the light utilization rate, separating and transferring the photo-generated carriers, and improving the visible light catalytic CO 2 Activity to reduce to CO.
The CuSCN/CoS proposed by the present invention is described in several specific examples 2 The preparation method of the composite photocatalytic material is described in detail.
Embodiment one:
the CuSCN/CoS proposed by the first embodiment of the invention 2 The preparation method of the composite photocatalytic material specifically comprises the following steps:
step one, 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 added to a mortar and sufficiently ground to obtain Cu (SCN) 2 And Co (SCN) 2 Is a mixture of (a) and (b);
transferring the obtained mixture into an alumina crucible, and roasting the mixture at 300 ℃ for 2 hours and Cu (SCN) in an atmosphere without inert gas protection by taking excessive KSCN as a salt melting medium 2 Self redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying in a vacuum drying oven at 60 ℃ for 8 hours to obtain CuSCN/CoS 2 Composite photocatalytic material (noted 1-Cu/Co).
Embodiment two:
the CuSCN/CoS proposed by the second embodiment of the invention 2 The preparation method of the composite photocatalytic material specifically comprises the following steps:
step one, 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 added to a mortar and sufficiently ground to obtain Cu (SCN) 2 And Co (SCN) 2 Is a mixture of (a) and (b);
transferring the obtained mixture into an alumina crucible, and roasting the mixture at 300 ℃ for 2 hours and Cu (SCN) in an atmosphere without inert gas protection by taking excessive KSCN as a salt melting medium 2 Self redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying in a vacuum drying oven at 60 ℃ for 8 hours to obtain CuSCN/CoS 2 Composite photocatalytic material (noted 5-Cu/Co).
Embodiment III:
the third embodiment of the invention provides CuSCN/CoS 2 The preparation method of the composite photocatalytic material specifically comprises the following steps:
step one, 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 added to a mortar and sufficiently ground to obtain Cu (SCN) 2 And Co (SCN) 2 Is a mixture of (a) and (b);
transferring the obtained mixture into an alumina crucible, and roasting the mixture at 300 ℃ for 2 hours and Cu (SCN) in an atmosphere without inert gas protection by taking excessive KSCN as a salt melting medium 2 Self redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying in a vacuum drying oven at 60 ℃ for 8 hours to obtain CuSCN/CoS 2 Composite photocatalytic material(noted as 10-Cu/Co).
The invention provides a CuSCN/CoS 2 Preparation method of composite photocatalytic material comprises weighing Co (NO) with preset mass ratio of A:B:C 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and KSCN to obtain Cu (SCN) 2 And Co (SCN) 2 Is a mixture of (a) and (b); transferring the obtained mixture into an alumina crucible, calcining Cu (SCN) at a first temperature for a first time under the atmosphere without inert gas protection by taking excessive KSCN as a salt melting medium 2 Self redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Oxidized to CoS 2 The method comprises the steps of carrying out a first treatment on the surface of the Washing with deionized water after naturally cooling to room temperature, 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 CuSCN/CoS provided by the invention 2 Preparation method of composite photocatalytic material comprises mixing CuSCN with CoS 2 Compounding, enhancing the light utilization rate, separating and transferring the photo-generated carriers, and improving the visible light catalytic CO 2 Activity to reduce to CO.
For the CuSCN/CoS prepared in the above examples one to three 2 The composite photocatalytic material, wherein the product in example one is denoted as 1-Cu/Co, the product in example two is denoted as 5-Cu/Co, and the product in example three is denoted as 10-Cu/Co. For the prepared CuSCN/CoS 2 The composite photocatalytic material is subjected to chemical characterization, and the corresponding chemical characterization result is analyzed as follows.
Fig. 1 is SEM, TEM, and HRTEM images of samples according to the present invention. In FIG. 1, part (a) is a CoS 2 As shown in part (a) of fig. 1: coS (CoS) 2 Is composed of aggregated nanoparticles. Part (b) of fig. 1 is an SEM image of CuSCN, as shown in part (b) of fig. 1: cuSCN is composed of nanorods and has some agglomeration phenomenon.
SEM of part (c) of FIG. 1 for 1-Cu/Co, as shown in part (c) of FIG. 1: at CuSCN/CoS 2 The SEM image of the composite photocatalytic material (1-Cu/Co) can be found: cuSCN attached to CoS 2 The nanoparticle top indicates successful preparation of 1-Cu/Co composite samples.
In addition, the TEM image of the portion (d) in FIG. 1 is 1-Cu/Co, as shown in the portion (d) in FIG. 1: from the TEM image of 1-Cu/Co, it can be seen that the two substances in the form of particles and rods are present, and the particles are judged to be CoS based on the structure of the previous SEM image 2 The smaller rod is CuSCN. Likewise, cuSCN can be found attached to CoS 2 Above the nanoparticles, which is consistent with the results of SEM, again demonstrating CoS 2 And CuSCN.
In addition, in FIG. 1, part (e) is a HRTEM diagram of 1-Cu/Co. As shown in part (e) of fig. 1: from the HRTEM images of 1-Cu/Co, it can be observed that the lattice spacing of d=0.226 nm corresponds to CoS 2 D=0.293 nm, corresponds to the (112) crystal plane of CuSCN, further indicating CuSCN/CoS 2 Successful preparation of the composite photocatalyst.
As shown in FIG. 2, under illumination, the one-component CuSCN and CoS 2 CO is reduced by light of (a) 2 The activity is very low, and the effect is obviously improved after the composition is compounded. As the amount of CuSCN added increases, the rate of CO formation decreases. This is probably due to the fact that the increase of the amount of CuSCN added reduces the separation efficiency of photo-generated charges of the sample, and affects the photo-catalytic activity of the sample.
In addition, ru-free, catalyst-free, N-free, respectively 2 Instead of CO 2 Control activity experiments without light and without TEOA (triethanolamine) conditions. As shown in FIG. 3, the control experiment showed almost no CO formation, indicating that the CO in the product was derived from CO 2 Not the decomposition of the catalyst or other material, also demonstrates that each of the above experimental conditions plays an important role in the reaction. When using N 2 Replacement of CO 2 In this case, a large amount of H is generated 2 Illustrating the presence of reduced CO when the 1-Cu/Co is subjected to catalytic reaction 2 And reducing H which otherwise plays a role in providing protons 2 O competition reaction, only in CO 2 Under the atmosphere, 1-Cu/Co can reduce CO preferentially 2 The superior selectivity of the composite photocatalytic material is demonstrated.
Figure 4 is an XRD pattern for different samples according to the invention. As shown in FIG. 4, for a single component CoS 2 CoS which corresponds well to standard cubic phases with CuSCN 2 (JCPDS PDF#89-1492) and standard orthorhombic phase alpha-CuSCN (JCPDS PDF#29-0582), whereas for composites there is no distinct CuSCN characteristic peak on XRD spectra, probably due to CuSCN/CoS 2 The content of CuSCN in the composite photocatalyst is very small.
FIG. 5 is a UV-vis-DRS profile of various samples according to the invention. As can be seen from fig. 5: single component CoS 2 The absorbance intensity with other composites was significantly higher than that of CuSCN, indicating that the sample maintained CoS substantially 2 Absorption characteristics of light, cuSCN and CoS 2 The composite material is not affected by insufficient optical absorption of CuSCN in the visible light range after being compounded, and can well utilize visible light.
FIG. 6 is a graph showing photocurrent response of different samples according to the present invention. The photocurrent density versus time curve indicates the generation of photo-generated charge by the semiconductor photocatalyst, while a smaller photocurrent density indicates a greater probability of recombination of photo-generated electrons and holes. As shown in fig. 6: the photocurrent response of sample 1-Cu/Co was stronger, thus indicating that 1-Cu/Co can generate more photogenerated carriers and can more effectively separate and transfer photogenerated electrons/holes.
FIG. 7 is an impedance plot 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, with a single component CoS 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 and the charge separation efficiency is highest, and the curvature radius is consistent with the photocurrent test result.
FIG. 8 is a photoluminescence spectrum of different samples according to the invention. The photo-generated electrons and holes combine to emit energy in the form of light and heat to generate fluorescence, so that the good catalysis effect corresponds to high separation efficiency of photo-generated charges, namely low photoluminescence intensity for photocatalysis. As shown in FIG. 8, at 340nm excitation wavelength, the sample showed emission peak at 682nm, and the fluorescence intensity of composite sample 1-Cu/Co was higher than that of the two pure samples CuSCN and CoS 2 Low, showing that the 1-Cu/Co sample has strong separation capability of photon-generated carriers, proving that CuSCN and CoS are used for 2 The separation of photo-generated charges can be enhanced by compounding, so that the improvement of the photo-catalytic activity of the photo-generated charges is promoted.
Embodiment four:
a fourth embodiment of the present invention provides a CuSCN/CoS 2 The application of the composite photocatalytic material comprises the steps of applying the CuSCN/CoS prepared in the first to third embodiments 2 Composite photocatalytic material for CO 2 The method for carrying out the photocatalytic reduction comprises the following steps:
30mg CuSCN/CoS was weighed into a 50ml sealed quartz reactor using a 300W xenon lamp as the light source 2 The preparation method comprises the steps of (1) measuring 3ml of acetonitrile, 2ml of deionized water and 1ml of triethanolamine from a composite photocatalytic material and 5mg of tris (2, 2' -bipyridine) ruthenium (II) chloride hexahydrate, and carrying out ultrasonic treatment for 2min to ensure that the mixture is uniform;
at the position without illumination, under the magnetic stirring, high-purity CO with the pressure of 1atm is simultaneously introduced 2 The gas is discharged for 0.5h to exhaust the air in the reactor and lead the reaction system to reach CO 2 Adsorption saturation state;
sealing the reactor after ventilation, carrying out the reaction for 2 hours by illumination, cooling after the reaction is finished, taking 1ml of gas by a sample injection needle, and introducing the gas chromatograph to detect products CO and H obtained after the reaction 2 、CH 4 。
Finally, it should be noted that: the above examples are only specific embodiments of the present invention, and are not intended to limit the scope of the present invention, but it should be understood by those skilled in the art that the present invention is not limited thereto, and that the present invention is described in detail with reference to the foregoing examples: any person skilled in the art may modify or easily conceive of the technical solution described in the foregoing embodiments, or perform equivalent substitution of some of the technical features, while remaining within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention, and are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. CuSCN/CoS 2 The preparation method of the composite photocatalytic material is characterized by comprising the following steps:
step one, co (NO) with the preset mass ratio of A to B to C is weighed 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and KSCN to obtain Cu (SCN) 2 And Co (SCN) 2 Is a mixture of (a) and (b);
transferring the obtained mixture into an alumina crucible, and roasting Cu (SCN) at a first temperature for a first time by taking excessive KSCN as a salt melting medium in an atmosphere without inert gas protection 2 Self redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Oxidized to CoS 2 ；
Step three, washing the mixture by deionized water after naturally cooling the mixture to room temperature, and finally drying the mixture in a vacuum drying oven at a second temperature for a second time to obtain CuSCN/CoS 2 A composite photocatalytic material.
2. A CuSCN/CoS according to claim 1 2 The preparation method of the composite photocatalytic material is characterized in that in the first step, the value of A is 0.01-0.11 g, the value of B is 1.31-1.51 g, and the value of C is 10g.
3. A CuSCN/CoS as claimed in 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. According to claim 3Said CuSCN/CoS 2 A method for producing a composite photocatalytic material, characterized in that in the first step, cu (SCN) 2 And Co (SCN) 2 Co (SCN) 2 Is dark blue in color, cu (SCN) 2 Is black in color;
in the third step, cuSCN/CoS 2 The color of the composite photocatalytic material is black.
5. A CuSCN/CoS as claimed in claim 4 2 The preparation method of the composite photocatalytic material is characterized by comprising the following steps:
step one, 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 added to a mortar and sufficiently ground to obtain Cu (SCN) 2 And Co (SCN) 2 Is a mixture of (a) and (b);
transferring the obtained mixture into an alumina crucible, and roasting the mixture at 300 ℃ for 2 hours and Cu (SCN) in an atmosphere without inert gas protection by taking excessive KSCN as a salt melting medium 2 Self redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying in a vacuum drying oven at 60 ℃ for 8 hours to obtain CuSCN/CoS 2 A composite photocatalytic material.
6. A CuSCN/CoS as claimed in claim 4 2 The preparation method of the composite photocatalytic material is characterized by comprising the following steps:
step one, 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 added to a mortar and sufficiently ground to obtain Cu (SCN) 2 And Co (SCN) 2 Is a mixture of (a) and (b);
step two, transferring the obtained mixture into an alumina crucibleRoasting in a crucible under inert gas-free atmosphere at 300 ℃ for 2h with excessive KSCN as a salt-melting medium, and Cu (SCN) 2 Self redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying in a vacuum drying oven at 60 ℃ for 8 hours to obtain CuSCN/CoS 2 A composite photocatalytic material.
7. A CuSCN/CoS as claimed in claim 4 2 The preparation method of the composite photocatalytic material is characterized by comprising the following steps:
step one, 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 added to a mortar and sufficiently ground to obtain Cu (SCN) 2 And Co (SCN) 2 Is a mixture of (a) and (b);
transferring the obtained mixture into an alumina crucible, and roasting the mixture at 300 ℃ for 2 hours and Cu (SCN) in an atmosphere without inert gas protection by taking excessive KSCN as a salt melting medium 2 Self redox to CuSCN and (SCN) 2 ，Co(SCN) 2 Oxidized to CoS 2 ；
Step three, washing with deionized water after naturally cooling to room temperature, and finally drying in a vacuum drying oven at 60 ℃ for 8 hours to obtain CuSCN/CoS 2 A composite photocatalytic material.
8. CuSCN/CoS 2 The composite photocatalytic material is characterized in that 2 The composite photocatalytic material is prepared by the method according to any one of the claims 1 to 7.
9. CuSCN/CoS 2 The use of a composite photocatalytic material, characterized in that it is prepared by a process according to any one of the preceding claims 1 to 7, cuSCN/CoS 2 Composite photocatalytic material pair CO 2 The method for carrying out the photocatalytic reduction comprises the following steps:
30mg CuSCN/CoS was weighed into a 50ml sealed quartz reactor using a 300W xenon lamp as the light source 2 The preparation method comprises the steps of (1) measuring 3ml of acetonitrile, 2ml of deionized water and 1ml of triethanolamine from a composite photocatalytic material and 5mg of tris (2, 2' -bipyridine) ruthenium (II) chloride hexahydrate, and carrying out ultrasonic treatment for 2min to ensure that the mixture is uniform;
at the position without illumination, under the magnetic stirring, high-purity CO with the pressure of 1atm is simultaneously introduced 2 The gas is discharged for 0.5h to exhaust the air in the reactor and lead the reaction system to reach CO 2 Adsorption saturation state;
sealing the reactor after ventilation, carrying out the reaction for 2 hours by illumination, cooling after the reaction is finished, taking 1ml of gas by a sample injection needle, and introducing the gas chromatograph to detect products CO and H obtained after the reaction 2 、CH 4 。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011139046A (en) * | 2009-11-30 | 2011-07-14 | Aisin Seiki Co Ltd | Inorganic photovoltaic cell |
| CN108855228A (en) * | 2018-05-21 | 2018-11-23 | 西北师范大学 | The preparation of CS-Cu/ titanic oxide nano compound material and its application of photocatalytic reduction of carbon oxide |
| CN110473927A (en) * | 2019-05-23 | 2019-11-19 | 中国计量大学 | A kind of cuprous oxide/cuprous sulfocyanide heterojunction photovoltaic film and preparation method thereof |
| CN110911509A (en) * | 2019-12-10 | 2020-03-24 | 中国计量大学 | Copper sulfide quantum dot/cuprous thiocyanate heterojunction photoelectric film and preparation method thereof |
| CN113952963A (en) * | 2021-09-22 | 2022-01-21 | 江苏大学 | CuInS based on Co modification2Preparation method and application of photocatalyst |
| CN114316955A (en) * | 2021-12-29 | 2022-04-12 | 安徽科技学院 | Preparation method of porous silicon and cuprous thiocyanate compounded optical material |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011139046A (en) * | 2009-11-30 | 2011-07-14 | Aisin Seiki Co Ltd | Inorganic photovoltaic cell |
| CN108855228A (en) * | 2018-05-21 | 2018-11-23 | 西北师范大学 | The preparation of CS-Cu/ titanic oxide nano compound material and its application of photocatalytic reduction of carbon oxide |
| CN110473927A (en) * | 2019-05-23 | 2019-11-19 | 中国计量大学 | A kind of cuprous oxide/cuprous sulfocyanide heterojunction photovoltaic film and preparation method thereof |
| CN110911509A (en) * | 2019-12-10 | 2020-03-24 | 中国计量大学 | Copper sulfide quantum dot/cuprous thiocyanate heterojunction photoelectric film and preparation method thereof |
| CN113952963A (en) * | 2021-09-22 | 2022-01-21 | 江苏大学 | CuInS based on Co modification2Preparation method and application of photocatalyst |
| CN114316955A (en) * | 2021-12-29 | 2022-04-12 | 安徽科技学院 | Preparation method of porous silicon and cuprous thiocyanate compounded optical material |
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