CN116273059A - Photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide as well as preparation method and application thereof - Google Patents
Photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide as well as preparation method and application thereof Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 125
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 70
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 62
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 61
- 238000007540 photo-reduction reaction Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000010931 gold Substances 0.000 claims abstract description 38
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052737 gold Inorganic materials 0.000 claims abstract description 34
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 18
- 239000011593 sulfur Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000012876 carrier material Substances 0.000 claims abstract description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 12
- 239000011592 zinc chloride Substances 0.000 claims abstract description 12
- 239000002135 nanosheet Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims abstract description 7
- 239000003446 ligand Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims abstract description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 17
- 230000009467 reduction Effects 0.000 claims description 14
- 238000006722 reduction reaction Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000003464 sulfur compounds Chemical class 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- UDWJTDBVEGNWAB-UHFFFAOYSA-N zinc indium(3+) sulfide Chemical compound [S-2].[Zn+2].[In+3] UDWJTDBVEGNWAB-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002343 gold Chemical class 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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Abstract
The invention discloses a photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide, and a preparation method and application thereof, and the photocatalytic material comprises the following steps: zinc chloride, indium chloride and thioacetamide powder are dissolved in ethanol and water mixed solution according to a proportion, the hydrothermal reaction temperature is 80-160 ℃, and the reaction time is 6-24 hours, so that the ultrathin sulfur indium zinc (sulfur indium zinc) nanosheet carrier material is obtained; slowly adding excessive sulfur-containing compound aqueous solution into chloroauric acid aqueous solution to form a sulfur coordinated gold complex precursor; the sulfur-containing compound is selected from thiosulfate, thiourea, thiocyanate and sulfite; mixing the gold complex precursor solution coordinated with sulfur and the suspension of the sulfur indium zinc nanosheet carrier material, heating, stirring and impregnating to enable the ligand of the gold complex to exchange with sulfur atoms on the surface of the sulfur indium zinc material, so as to obtain the photocatalytic material for preparing methane by high-selectivity photo-reduced carbon dioxide.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and relates to a photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide, and a preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
Significant carbon dioxide emissions and serious energy crisis are created by the continued and excessive burning of fossil fuels. The catalyst is directly driven by sunlight to reduce carbon dioxide into hydrocarbon fuels with high added value, such as formic acid, methanol, methane and the like, so that a cheap and environment-friendly way is provided for realizing carbon neutralization society. However, the existing photocatalyst for synthesizing hydrocarbon fuel by photocatalytic carbon dioxide reduction still has the problems of poor selectivity, low activity and the like of products.
Due to the excellent catalytic properties, monoatomic catalysts have been widely reported in the field of photocatalytic carbon dioxide reduction. However, the product distribution of Shan Yuanzi photocatalyst to carbon dioxide reduction is still dominated by carbon monoxide rather than related hydrocarbon fuels such as methane, limited by carrier separation efficiency, proton mobility and adsorption strength of individual metal atoms to the carbon dioxide reduction intermediates.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a photocatalytic material for preparing methane by reducing carbon dioxide with high selectivity, and a preparation method and application thereof.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the invention provides a method for preparing a photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide, comprising the following steps: zinc chloride, indium chloride and thioacetamide powder are dissolved in a mixed solution of ethanol and water according to a proportion, and hydrothermal reaction is carried out, wherein the reaction temperature is 80-160 ℃, and the reaction time is 6-24 hours, so that the ultrathin sulfur indium zinc (sulfur indium zinc) nanosheet carrier material is obtained;
slowly adding excessive sulfur-containing compound aqueous solution into chloroauric acid aqueous solution to form a sulfur coordinated gold complex precursor; the sulfur-containing compound is selected from thiosulfate, thiourea, thiocyanate and sulfite;
mixing the gold complex precursor solution coordinated with sulfur and the suspension of the sulfur indium zinc nanosheet carrier material, heating, stirring and impregnating to enable the ligand of the gold complex to exchange with sulfur atoms on the surface of the sulfur indium zinc material, so as to obtain the photocatalytic material for preparing methane by high-selectivity photo-reduced carbon dioxide.
In a second aspect, the invention provides a photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide, which is obtained by the preparation method.
In a third aspect, the present invention provides an application of the photocatalytic material for methane production by high-selectivity photo-reduction of carbon dioxide in photocatalytic carbon dioxide reduction.
The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:
the sulfur indium zinc carrier material with the optimal energy band structure and shape and size can be obtained by regulating and controlling the mole ratio of zinc chloride and indium chloride in the carrier synthesis process. Meanwhile, taking a gold complex coordinated by sulfur as a precursor, adding the gold complex into the sulfur indium zinc suspension according to a certain amount, and heating and stirring. In the heating process, the gold complex containing the sulfur ligand can exchange ligand with sulfur atoms on the surface of the carrier material, so that gold single atoms in the prepared photocatalytic material for preparing methane by high-selectivity photo-reduction carbon dioxide have the characteristic of low coordination structure. The abundant low-coordination gold monoatoms are beneficial to promoting the separation of photogenerated carriers and the adsorption and activation of carbon dioxide molecules. In addition, the low coordinated gold monoatoms serve as catalytic sites to more easily inhibit desorption of the CO intermediates, so that the CO intermediates can be further protonated to form methane, and the energy barrier of carbon dioxide reduction can be obviously reduced.
The photocatalytic material for preparing methane by high-selectivity photo-reduction carbon dioxide can realize 12.4 mu mol g in a system for photo-catalytic carbon dioxide reduction at a gas-solid interface in the presence of water vapor and saturated carbon dioxide gas under illumination - 1 h -1 The high methane generation rate and the high selectivity of 86 percent, and can keep stable yield increase within 6 hours, which indicates that the photocatalytic material for preparing methane by high-selectivity photo-reduction carbon dioxide has high photocatalytic methanogenesis activity and selectivity.
The photocatalytic material obtained by the invention has simple preparation, is easy to expand the scale and has wide prospect in the aspect of practical application.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is an XRD of the photocatalytic material for methane production by high-selectivity photo-reduction of carbon dioxide prepared in example 1, the photocatalytic material for indium zinc sulfide prepared in comparative example 1, the photocatalytic material for supported gold monoatoms and gold clusters mixed prepared in comparative example 2, and the photocatalytic material for supported gold nanoparticles prepared in comparative example 3;
FIG. 2 is a TEM of the photocatalytic material for methane production by high-selectivity photo-reduction of carbon dioxide prepared in example 1, the S-in-Zn photocatalytic material prepared in comparative example 1, the supported gold monoatoms and gold clusters mixed photocatalytic material prepared in comparative example 2, and the supported gold nanoparticle photocatalytic material prepared in comparative example 3;
FIG. 3 is a steady state fluorescence spectrum and a transient state fluorescence spectrum of the photocatalytic material for methane production by high-selectivity photo-reduction of carbon dioxide prepared in example 1, the S-in-Zn photocatalytic material prepared in comparative example 1 and the supported gold nanoparticle photocatalytic material prepared in comparative example 3;
FIG. 4 is a graph showing the methane yield and selectivity of the photocatalytic material for methane production by high-selectivity photo-reduction of carbon dioxide prepared in example 1, the zinc indium sulfide photocatalytic material prepared in comparative example 1, the supported gold nanoparticle photocatalytic material prepared in comparative example 3, and the photocatalytic material prepared in comparative example 4;
fig. 5 is a graph of methane yield measured over time for photocatalytic carbon dioxide reduction of the photocatalytic material for methane production by high selectivity photocatalytic carbon dioxide prepared in example 1.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. 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.
As described in the background art, the problems of poor selectivity, low activity and the like exist in the prior art, and in order to solve the technical problems, the invention provides a photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide, and a preparation method and application thereof.
In a first aspect, the invention provides a method for preparing a photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide, comprising the following steps: zinc chloride, indium chloride and thioacetamide powder are dissolved in a mixed solution of ethanol and water according to a proportion, and hydrothermal reaction is carried out, wherein the reaction temperature is 80-160 ℃, and the reaction time is 6-24 hours, so that the ultrathin sulfur indium zinc (sulfur indium zinc) nanosheet carrier material is obtained;
slowly adding excessive sulfur-containing compound aqueous solution into chloroauric acid aqueous solution to form a sulfur coordinated gold complex precursor; the sulfur-containing compound is selected from thiosulfate, thiourea, thiocyanate and sulfite;
mixing the gold complex precursor solution coordinated with sulfur and the suspension of the sulfur indium zinc nanosheet carrier material, heating, stirring and impregnating to enable the ligand of the gold complex to exchange with sulfur atoms on the surface of the sulfur indium zinc material, so as to obtain the photocatalytic material for preparing methane by high-selectivity photo-reduced carbon dioxide.
In some embodiments, the molar ratio of zinc chloride, indium chloride, and thioacetamide is 1:1-2:4-12. For example, it may be 1:1:4,1:1:6,1:1:9,1:2:4,1:2:6,1:2:9.
Preferably, the molar ratio of zinc chloride, indium chloride and thioacetamide is 1:1:6-9.
In some embodiments, the hydrothermal reaction temperature is 80-160 ℃ and the reaction time is 6-24 hours.
By adjusting the reaction temperature and the reaction time, the sulfur indium zinc nano sheet carrier materials with different thickness and crystallinity can be obtained, thereby influencing the dispersity of gold monoatoms and the reduction activity of photocatalytic carbon dioxide. When the hydrothermal reaction temperature is about 120 ℃ and the reaction time is about 12 hours, the prepared photocatalytic material for preparing methane by photo-reducing carbon dioxide with high selectivity has the highest yield and selectivity for generating methane by reducing carbon dioxide.
In some embodiments, the volume fraction of ethanol in the mixed solution of ethanol and water is 20% -50%.
In some embodiments, the mass ratio of chloroauric acid to sulfur compounds is 1:6 to 1:10.
In some embodiments, the gold atoms in the gold complex comprise 0.1 to 3wt% of the mass of the indium zinc sulfide support material, and more preferably 0.5wt%.
In some embodiments, the temperature of the heated, stirred, and impregnated is 60 to 95 ℃ for a period of 2 to 10 hours.
In a second aspect, the invention provides a photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide, which is obtained by the preparation method.
In a third aspect, the present invention provides an application of the photocatalytic material for methane production by high-selectivity photo-reduction of carbon dioxide in photocatalytic carbon dioxide reduction.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Example 1
A preparation method of a photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide comprises the following steps:
(1) Dissolving 0.6mmol of zinc chloride, 1.2mmol of indium chloride and 3.6mmol of thioacetamide powder in a mixed solution containing 15mL of ethanol and 15mL of water, and carrying out hydrothermal reaction for 12h at 120 ℃ by using a 50mL reaction kettle to obtain an ultrathin sulfur indium zinc (sulfur indium zinc) nanosheet carrier material;
(2) To 10mL of aqueous chloroauric acid solution, 40mL of aqueous thiourea solution was slowly added, wherein the concentration of gold in the aqueous chloroauric acid solution was 1mg mL -1 The concentration of thiourea in the sodium thiosulfate aqueous solution was 2mg mL -1 Finally, the gold concentration is 0.2mg mL -1 Is a sulfur-coordinated gold complex precursor aqueous solution;
(3) 2.5mL of the gold complex precursor aqueous solution was slowly added to 35mL of the suspension containing the S-in-Zn carrier, which contained 100mg of S-in-Zn carrier. Then stirring for 6h at 70 ℃ to obtain the photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide, which is named as Au 1 /ZIS。
Example 2
Unlike example 1, zinc chloride, indium chloride and thioacetamide in step (1) were added in amounts of 0.6mmol,1.2mmol and 7.2mmol, respectively, to obtain products.
Example 3
Unlike example 1, 20mL of the gold complex precursor aqueous solution was added in step (3), and the product was obtained.
Example 4
Unlike example 1, the following is: the thiourea of example 1 was replaced with 30mL of an aqueous sodium thiosulfate solution having a concentration of 1mg mL -1 . The other components are the same as in example 1.
Example 5
Unlike example 1, the following is: the sodium thiocyanate in example 1 was replaced with 50mL of an aqueous solution of sodium thiocyanate having a concentration of 1mg mL -1 . The other components are the same as in example 1.
Example 6
Unlike example 1, the following is: in the step (3), the process of stirring for 6 hours at 70 ℃ to obtain the photocatalytic material for preparing methane by high-selectivity photo-reduction carbon dioxide is replaced by the process of stirring for 2 hours at 95 ℃ to obtain the photocatalytic material for preparing methane by high-selectivity photo-reduction carbon dioxide. The other components are the same as in example 1.
Example 7
Unlike example 1, the following is: in the step (3), the process of stirring for 6 hours at 70 ℃ to obtain the photocatalytic material for preparing methane by high-selectivity photo-reduction carbon dioxide is replaced by the process of stirring for 10 hours at 60 ℃ to obtain the photocatalytic material for preparing methane by high-selectivity photo-reduction carbon dioxide. The other components are the same as in example 1.
Example 8
The difference from example 1 is that: the procedure of example 1 was repeated except that the "mixed solution of 15mL of ethanol and 15mL of water" was replaced with the "mixed solution of 12mL of ethanol and 15mL of water".
Comparative example 1
Unlike example 1, which is only step (1), the obtained sample is denoted as ZIS.
Comparative example 2
In contrast to example 1, in step (2), no sulfur compound was added, and the obtained sample was designated as Au 1+NPs /ZIS。
Comparative example 3
Unlike example 1, after step (1), 100mg of the indium zinc sulfide support material was dispersed in 50mL of an aqueous solution containing 10v% methanol, and 5mL of an aqueous chloroauric acid solution was added, in which the concentration of gold was 0.1mg mL -1 . And stirred under 300W xenon lamp illumination for 30min, the obtained sample was designated as Au NPs /ZIS。
Comparative example 4
In step (1), 0.6mmol of zinc chloride, 1.2mmol of indium chloride and 3 were mixed, unlike in example 1.6mmol thioacetamide powder was dissolved in a mixed solution containing 7mL of glycerol and 28mL of water, and a 50mL flask was used for water bath at 80℃for 2 hours to obtain an ultrathin nano-sheet carrier material of indium zinc sulfide (indium zinc sulfide), and the obtained sample was designated as Au 1 /def-ZIS。
For example 1, comparative examples 1-4, the experiments for photocatalytic carbon dioxide reduction were performed under the following experimental conditions:
to a 50mL self-made quartz reactor, 100. Mu.L of pure water was charged, and carbon dioxide gas of 1 atmosphere was introduced thereinto, and comparative examples 1 to 4 were put into the solution for testing.
Photocatalytic carbon dioxide reduction test
1. The test method comprises the following steps:
the photocatalytic carbon dioxide reduction experiments were performed in a closed, self-made quartz reactor. 10mg of the catalyst was ultrasonically dispersed in 1mL of pure water, and after that, the suspension was applied dropwise to a quartz glass plate and dried, which was put into the bottom of the reactor, and 100. Mu.L of pure water was added around the inside of the reactor. A 300W xenon lamp was used as a light source. Before the photocatalytic test, the reactor was evacuated, and then carbon dioxide gas at 1 atmosphere was introduced into the reactor. Every 1 hour of reaction, a certain amount of gas was taken and the reaction product was measured by Gas Chromatography (GC).
2. Test results:
XRD of the catalysts prepared in comparative examples 1-3 under the different experimental conditions for example 1 is shown in FIG. 1. It can be seen that the products obtained in example 1 and comparative examples 1-3 all maintained a basic hexagonal indium zinc sulfide phase structure.
For example 1, transmission Electron Microscopy (TEM) of the catalysts prepared in comparative examples 1-3 under different experimental conditions is shown in FIG. 2. It can be seen that example 1, comparative examples 1-3, in which the catalysts exhibit morphology of flexible ultrathin nanoplatelets under different experimental conditions, and example 1, comparative example 1, in which gold nanoparticles were absent, and comparative examples 2,3, in which nanoparticles of different sizes were seen.
For example 1, the steady state fluorescence (PL) spectrum and time resolved transient fluorescence (TRPL) spectrum of the catalyst at different experimental conditions for the catalyst prepared in comparative example 3 are shown in fig. 3. It can be seen that the catalyst prepared in example 1 has the lowest fluorescence intensity and the shortest fluorescence lifetime, indicating the highest photogenerated carrier separation efficiency.
The methane yields and selectivities for the photocatalytic carbon dioxide reduction of the catalysts prepared in comparative examples 1,3 and 4 under different experimental conditions are shown in figure 4 for example 1. It can be seen that the catalyst prepared in example 1 has the highest methane yield (12.4. Mu. Mol g) -1 h -1 ) And methane selectivity (86%).
It can be seen from fig. 5 that the catalyst prepared in example 1 maintained a steady increase in methane yield over a long period of 6 hours of testing, indicating that the catalyst had better long term stability.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide is characterized by comprising the following steps of: the method comprises the following steps: zinc chloride, indium chloride and thioacetamide powder are dissolved in a mixed solution of ethanol and water according to a proportion, and hydrothermal reaction is carried out, wherein the reaction temperature is 80-160 ℃, and the reaction time is 6-24 hours, so that the ultrathin sulfur indium zinc nanosheet carrier material is obtained;
slowly adding excessive sulfur-containing compound aqueous solution into chloroauric acid aqueous solution to form a sulfur coordinated gold complex precursor; the sulfur-containing compound is selected from thiosulfate, thiourea, thiocyanate and sulfite;
mixing the gold complex precursor solution coordinated with sulfur and the suspension of the sulfur indium zinc nanosheet carrier material, heating, stirring and impregnating to enable the ligand of the gold complex to exchange with sulfur atoms on the surface of the sulfur indium zinc material, so as to obtain the photocatalytic material for preparing methane by high-selectivity photo-reduced carbon dioxide.
2. The method for preparing the photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide according to claim 1, characterized in that: the method comprises the following steps: the mol ratio of zinc chloride, indium chloride and thioacetamide is 1:1-2:4-12.
3. The method for preparing the photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide according to claim 1, characterized in that: the mol ratio of zinc chloride, indium chloride and thioacetamide is 1:1:6-9.
4. The method for preparing the photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide according to claim 1, characterized in that: the hydrothermal reaction temperature is 80-160 ℃, and the reaction time is 6-24 h.
5. The method for preparing the photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide according to claim 1, characterized in that: in the mixed solution of the ethanol and the water, the volume fraction of the ethanol is 20-50%.
6. The method for preparing the photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide according to claim 1, characterized in that: the mass ratio of chloroauric acid to sulfur compound is 1:6-1:10.
7. The method for preparing the photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide according to claim 1, characterized in that: the gold atoms in the gold complex account for 0.1 to 3 weight percent of the sulfur indium zinc carrier material.
8. The method for preparing the photocatalytic material for preparing methane by high-selectivity photo-reduction of carbon dioxide according to claim 1, characterized in that: the temperature of heating, stirring and soaking is 60-95 ℃ and the time is 2-10 h.
9. A high-selectivity photocatalytic material for preparing methane by photo-reducing carbon dioxide is characterized in that: obtained by the preparation process according to any one of claims 1 to 8.
10. Use of the photocatalytic material for the production of methane by the high-selectivity photo-reduction of carbon dioxide according to claim 9 for the reduction of photo-catalytic carbon dioxide.
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