CN111569920A - Tungsten carbide/cadmium zinc sulfide composite photocatalyst and preparation method and application thereof - Google Patents
Tungsten carbide/cadmium zinc sulfide composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 52
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011701 zinc Substances 0.000 claims abstract description 67
- 239000000725 suspension Substances 0.000 claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 23
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 150000001661 cadmium Chemical class 0.000 claims abstract description 19
- 150000003751 zinc Chemical class 0.000 claims abstract description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 18
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical group [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 239000000243 solution Substances 0.000 description 39
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- -1 transition metal sulfides Chemical class 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CEKJAYFBQARQNG-UHFFFAOYSA-N cadmium zinc Chemical compound [Zn].[Cd] CEKJAYFBQARQNG-UHFFFAOYSA-N 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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- B01J35/39—
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1094—Promotors or activators
-
- 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
Abstract
The invention relates to a tungsten carbide/cadmium zinc sulfide composite photocatalyst and a preparation method and application thereof. The method comprises the following steps: s1, dispersing tungsten carbide in water to obtain a suspension; s2, adding soluble cadmium salt and soluble zinc salt into the suspension according to the molar mass ratio of cadmium to zinc of 1: 10-10: 1, then adjusting the pH value to 4-10, and stirring uniformly; s3, adding the sodium sulfide solution or the potassium sulfide solution into the suspension according to the molar mass ratio of the total molar mass of cadmium in the soluble cadmium salt and zinc in the soluble zinc salt to the molar mass of sulfur in the sodium sulfide solution and/or the potassium sulfide solution being 1:1-2, and continuously stirring to obtain the tungsten carbide/cadmium zinc sulfide composite photocatalyst. The tungsten carbide/cadmium zinc sulfide composite photocatalyst has excellent photocatalytic hydrogen production performance. The invention also comprises the application of the composite photocatalyst in the aspect of preparing hydrogen by decomposing water.
Description
Technical Field
The invention relates to the field of photocatalytic materials, in particular to a tungsten carbide/cadmium zinc sulfide composite photocatalyst and a preparation method and application thereof.
Background
With the emergence of global energy shortage and environmental pollution, the development and utilization of new energy sources become the subject of much attention in the modern times. Solar energy is inexhaustible, clean, pollution-free, renewable and the like, so that the semiconductor photocatalyst is used for converting light energy into chemical energy, and has potential economic benefits.
ZnxCd1－xThe S nano material is a very typical II-VI group ternary metal sulfide and is mainly based on Zn formed by ZnS with a lattice structure similar to that of CdS and the same coordination modexCd1－xAnd (3) S solid solution. The positions of the valence band and the conduction band can be accurately regulated and controlled by changing the molar ratio of zinc to cadmium, and the photoproduction electrons and holes can move in the continuous valence band and conduction band instead of moving in discrete donor impurity energy level or acceptor impurity energy level, so that ZnxCd1－xThe S solid solution has great potential in the aspects of degrading pollutants in water, cracking water to produce hydrogen and the like. However, due to the fact that separation speed of electrons and holes generated by self light excitation is low, carrier recombination is serious, hydrogen over-potential is high, quantum efficiency is low, and wide practical application of the quantum is severely limited.
For ZnxCd1－xThe above-mentioned disadvantages of S have been a lot of work and it has been found that Zn can be effectively improved by the loading of the cocatalystxCd1－xAnd S is separated from carriers in the photocatalysis process, so that the overpotential of surface hydrogen evolution is reduced, and the photocatalysis performance of the material is greatly improved. At present, the commonly used promoters mainly include noble metals, metal oxides, transition metal sulfides, transition metal hydroxides, and the like. The noble metal promoter has obvious enhancement effect on the hydrogen production performance of the photocatalyst, but the noble metal promoter is expensive and limits the application and popularization of the noble metal promoter. Thus, cheaper promoters and Zn were developedxCd1－xS is compounded, which is an effective way to obtain cheap and high-efficiency photocatalyst. And some research results also show that the transition metal carbide also really shows better prospect in the field of photocatalysis. However, so far, we have dealt with how to combine WyCzWith ZnxCd1－xS is compounded to prepare WyCz/ZnxCd1-xThe S composite photocatalyst and the application thereof in the aspect of hydrogen production by photocatalytic water decomposition are not reported.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: pure ZnxCd1-xS has lower photocatalytic activity due to serious carrier recombination and higher hydrogen evolution overpotential in the photocatalytic process. For single ZnxCd1-xThe problems of low separation efficiency of carrier fluid space in S and high overpotential of hydrogen production,
in order to solve the technical problems, the invention provides a tungsten carbide/cadmium zinc sulfide composite photocatalyst and a preparation method and application thereof.
A preparation method of a tungsten carbide/cadmium zinc sulfide composite photocatalyst comprises the following steps:
s1, dispersing tungsten carbide in water to obtain a suspension;
s2, adding soluble cadmium salt and soluble zinc salt into the suspension according to the molar mass ratio of cadmium to zinc of 1: 10-10: 1, then adjusting the pH value to 4-10, and stirring uniformly;
s3, adding the sodium sulfide solution and/or the potassium sulfide solution into the suspension according to the molar mass ratio of the total molar mass of cadmium in the soluble cadmium salt and zinc in the soluble zinc salt to sulfur in the sodium sulfide solution and/or the potassium sulfide solution being 1:1-2, and continuously stirring to obtain the tungsten carbide/cadmium zinc sulfide composite photocatalyst.
Further, in step S2, the soluble cadmium salt is cadmium acetate; and/or the soluble zinc salt is zinc acetate.
Further, in step S3, adding the sodium sulfide solution and/or the potassium sulfide solution into the suspension, and continuously stirring at a temperature of 0-80 ℃ to obtain the tungsten carbide/cadmium zinc sulfide composite photocatalyst.
Further, in step S3, stirring is continued for 5-30 hours at the temperature of 0-80 ℃ to obtain the tungsten carbide/cadmium zinc sulfide composite photocatalyst.
Further, in step S2, the sodium sulfide solution and/or the potassium sulfide solution is added to the suspension at a rate of 2-4mL/min according to a molar mass ratio of the total of the cadmium in the soluble cadmium salt and the zinc in the soluble zinc salt to the sulfur in the sodium sulfide solution and/or the potassium sulfide solution of 1: 1-2.
Further, in step S3, the concentration of the sodium sulfide solution and/or the potassium sulfide solution is 0.01 mol. L-1～1mol·L-1。
Further, in step S3, the tungsten carbide/cadmium zinc sulfide composite photocatalyst W is obtainedyCzWith ZnxCd1-xAnd adding the sodium sulfide solution and/or the potassium sulfide solution into the suspension in a theoretical mass ratio of 1: 500-1: 2 of S.
Further, in step S3, the concentration of the sodium sulfide solution and/or the potassium sulfide solution is 0.01 mol. L-1～1mol·L-1。
Further, in step S2, soluble cadmium salt and soluble zinc salt are added to the suspension according to the molar mass ratio of cadmium to zinc of 1: 10-10: 1, and then the concentration is added to the suspension to be 0.0001 mol.L-1～10mol·L-1And/or the concentration of sodium hydroxide is 0.0001 mol.L-1～10mol·L-1And adjusting the pH value to 4-10 by using potassium hydroxide.
The invention also discloses the tungsten carbide/cadmium zinc sulfide composite photocatalyst prepared by the preparation method.
In addition, the invention also comprises the application of the tungsten carbide/cadmium zinc sulfide composite photocatalyst in the aspect of preparing hydrogen by decomposing water.
Compared with the prior art, the invention has the advantages that: dispersing tungsten carbide in water to obtain a turbid liquid, then adding soluble cadmium salt and soluble zinc salt into the turbid liquid according to the molar mass ratio of cadmium to zinc of 1: 10-10: 1, dissolving the soluble cadmium salt and the soluble zinc salt in water, wherein cadmium and zinc exist in the form of ions, then adjusting the pH value to 4-10, and adding a sodium sulfide solution and/or a potassium sulfide solution to form cadmium sulfideThe method comprises the steps of providing a proper environment with zinc, avoiding the situation that cadmium zinc sulfide cannot be dissolved under an acidic condition due to the fact that the pH value is too low to obtain a target product, forming hydroxide by cadmium zinc ions to influence the formation of the target product, adding the sodium sulfide solution and/or the potassium sulfide solution into the suspension according to the molar ratio of 1:1-2 between the total molar mass of cadmium in the soluble cadmium salt and zinc in the soluble zinc salt and the molar mass of sulfur in the sodium sulfide solution and/or the potassium sulfide solution, combining the sulfur ions with cadmium ions and zinc ions in the solution to form cadmium zinc sulfide, and combining with tungsten carbide under the stirring action to form the tungsten carbide/cadmium zinc sulfide composite photocatalystyCzW in an amount of 8 wt%yCz/ZnxCd1-xThe hydrogen production rate of the S composite photocatalyst reaches 17805 mu mol.h-1·g-1Is about pure ZnxCd1-xThe hydrogen production rate of S is 5.24 times.
The invention adopts a cheap cocatalyst WyCzWith ZnxCd1-xS composite strategy to construct a structure WyCz/ZnxCd1-xAnd (S) a composite photocatalyst. In the composite photocatalyst, tungsten carbide can efficiently receive electrons in cadmium zinc sulfide on one hand, the space separation efficiency of current carriers is effectively improved, and on the other hand, more efficient hydrogen evolution active sites can be provided, so that the composite photocatalyst has excellent photocatalytic hydrogen production performance.
Drawings
The features and advantages of the present invention will be more clearly understood by reference to the accompanying drawings, which are illustrative and not to be construed as limiting the invention in any way, and in which:
FIG. 1 is pure Zn prepared in comparative example 1xCd1-xScanning electron micrograph (SEM picture) of S.
FIG. 2 is W prepared in example 3yCzW in an amount of 4 wt%yCz/ZnxCd1-xAnd SEM image of the S composite photocatalyst.
FIG. 3 is a drawing obtained in example 3Raw material WyCzXRD pattern of (a).
FIG. 4 is W prepared in example 3yCzW in an amount of 4 wt%yCz/ZnxCd1-xS composite photocatalyst and Zn prepared in comparative example 1xCd1-xXRD pattern of S.
FIG. 5 shows W in examples 1 to 4 of the present inventionyCzW in amounts of 1 wt%, 2 wt%, 4 wt% and 8 wt%yCz/ZnxCd1-xS and pure Zn prepared in comparative example 1xCd1-xAnd (S) decomposing water under visible light in the presence of a sacrificial agent to obtain a hydrogen rate histogram.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The specific embodiment provides a preparation method of a tungsten carbide/cadmium zinc sulfide composite photocatalyst, which comprises the following steps:
s1, dispersing tungsten carbide in water to obtain a suspension;
s2, adding soluble cadmium salt and soluble zinc salt into the suspension according to the molar mass ratio of cadmium to zinc of 1: 10-10: 1, and then adding the suspension with the concentration of 0.0001 mol.L-1～10mol·L-1Sodium hydroxide and/or concentration of 0.0001 mol.L-1～10mol·L-1Adjusting the pH value to 4-10 by potassium hydroxide, and uniformly stirring; the soluble cadmium salt is cadmium acetate; and/or, the soluble zinc salt is zinc acetate;
s3, obtaining the total molar mass of cadmium in the soluble cadmium salt and zinc in the soluble zinc salt and the molar mass ratio of sulfur in the sodium sulfide solution and/or the potassium sulfide solution, wherein the total molar mass of cadmium in the soluble cadmium salt and zinc in the soluble zinc salt is 1:1-2W in the tungsten carbide/cadmium zinc sulfide composite photocatalystyCzWith ZnxCd1-xAdding the sodium sulfide solution or the potassium sulfide solution into the suspension at a speed of 2-4mL/min according to a theoretical mass ratio of 1: 500-1: 2 of S, and continuously stirring for 5-30 h at a temperature of 0-80 ℃ to obtain the tungsten carbide/cadmium zinc sulfide composite photocatalyst (namely WyCz/ZnxCd1-xS composite photocatalyst, wherein, 0<x<1，1<y:z<2) (ii) a Wherein the concentration of the sodium sulfide solution and/or the potassium sulfide solution is 0.01 mol.L-1～1mol·L-1。
The specific embodiment also comprises the tungsten carbide/cadmium zinc sulfide composite photocatalyst prepared by the preparation method.
The specific embodiment also comprises the application of the tungsten carbide/cadmium zinc sulfide composite photocatalyst in the aspect of preparing hydrogen by decomposing water.
The following examples are provided to further illustrate the preparation process of this embodiment.
Example 1
A preparation method of a tungsten carbide/cadmium zinc sulfide composite photocatalyst comprises the following steps:
s1, weighing 7.250mg of tungsten carbide, and ultrasonically dispersing the tungsten carbide in 100mL of deionized water to obtain a tungsten carbide suspension;
s2, 0.7996g of cadmium acetate and 0.6585g of zinc acetate are added into the suspension, the mixture is stirred uniformly, and the obtained suspension is treated with NaOH solution (0.2 mol. L)-1) Adjusting the pH to 7; stirring for half an hour until the mixture is uniform;
s3, dropwise adding 12mLNa2S solution (0.5 mol. L)-1) Stirring for 18h at 30 ℃, collecting the obtained precipitate, washing the precipitate for multiple times by using absolute ethyl alcohol and deionized water, and drying to obtain WyCzW in an amount of 1 wt%yCz/ZnxCd1-xAnd (S) a composite photocatalyst.
Example 2
A preparation method of a tungsten carbide/cadmium zinc sulfide composite photocatalyst comprises the following steps:
s1, weighing 14.5mg of tungsten carbide, and ultrasonically dispersing the tungsten carbide in 100mL of deionized water to obtain a tungsten carbide suspension;
s2, 0.7996g of cadmium acetate and 0.6585g of zinc acetate are added into the suspension, the mixture is stirred uniformly, and the obtained suspension is treated with NaOH solution (0.2 mol. L)-1) The pH was adjusted to 7. Stirring for half an hour until the mixture is uniform;
s3, dropwise adding 12mLNa2S solution (0.5 mol. L)-1). Stirring at 30 deg.C for 18h, collecting the obtained precipitate, washing the precipitate with anhydrous ethanol and deionized water for several times, and drying to obtain WyCzW in an amount of 2 wt%yCz/ZnxCd1-xAnd (S) a composite photocatalyst.
Example 3
A preparation method of a tungsten carbide/cadmium zinc sulfide composite photocatalyst comprises the following steps:
s1, weighing 29mg of tungsten carbide, and ultrasonically dispersing the tungsten carbide in 100mL of deionized water to obtain a tungsten carbide suspension;
s2, 0.7996g of cadmium acetate and 0.6585g of zinc acetate are added into the suspension, the mixture is stirred uniformly, and the obtained suspension is treated with NaOH solution (0.2 mol. L)-1) Adjusting the pH value to 7, and stirring for half an hour until the mixture is uniform;
s3, dropwise adding 12mLNa2S solution (0.5 mol. L)-1) Stirring for 18h at 30 ℃, collecting the obtained precipitate, washing the precipitate for multiple times by using absolute ethyl alcohol and deionized water, and drying to obtain WyCzW in an amount of 4 wt%yCz/ZnxCd1-xAnd (S) a composite photocatalyst. The scanning electron micrograph is shown in FIG. 2, in which tungsten carbide has a lamellar structure, ZnxCd1-xS is in the form of nanoparticles, WyCz/ZnxCd1-xS is formed by nano-particles ZnxCd1-xS is attached to the tungsten carbide nano-sheet to form a blocky aggregate, which indicates that the compound is WyCz/ZnxCd1-xAnd (S) a composite photocatalyst. The preparation of W is further illustrated from XRD patterns in conjunction with FIGS. 3-4yCz/ZnxCd1-xS composite photocatalyst, WyCz/ZnxCd1-xIn XRD pattern of S composite photocatalyst, W isyCzIn ZnxCd1-xS is uniformly dispersed on the surface and has a low content, so WyCzThe peak of (a) is not significant.
Example 4
A preparation method of a tungsten carbide/cadmium zinc sulfide composite photocatalyst comprises the following steps:
s1, weighing 58mg of ultrasonic wave, and dispersing the ultrasonic wave in 100mL of deionized water to obtain a tungsten carbide suspension;
s2, 0.7996g of cadmium acetate and 0.6585g of zinc acetate are added into the suspension, the mixture is stirred uniformly, and the obtained suspension is treated with NaOH solution (0.2 mol. L)-1) Adjusting the pH value to 7, and stirring for half an hour until the mixture is uniform;
s3, dropwise adding 12mLNa2S solution (0.5 mol. L)-1) Stirring at 30 deg.C for 18h, collecting the obtained precipitate, washing with anhydrous ethanol and deionized water for several times, and drying to obtain WyCzW in an amount of 8 wt%yCz/ZnxCd1-xAnd (S) a composite photocatalyst.
Comparative example 1
0.7996g of cadmium acetate and 0.6585g of zinc acetate are weighed and dissolved in 100mL of deionized water, and the uniformly mixed solution is dissolved in sodium hydroxide solution (0.2 mol. L)-1) The pH is adjusted to 7, the mixture is stirred for half an hour until homogeneous, and then 12mL of Na are added2S solution (0.5 mol. L)-1). Continuously stirring the mixed solution at 30 ℃ for 18h, collecting the obtained precipitate, washing with anhydrous ethanol and deionized water for multiple times, and drying to obtain ZnxCd1-xAnd S. The scanning electron micrograph is shown in FIG. 1, ZnxCd1-xS is nano-particles, and certain agglomeration phenomenon exists among the particles, and the particles are stacked into irregular agglomerates, which further illustrates that Zn is attached to the tungsten carbide nano-sheets in example 3xCd1-xS。
Application example 1
Composite photocatalyst WyCz/ZnxCd1-xS and ZnxCd1-xAnd (4) comparing the photocatalytic hydrogen production performance of S under visible light.
W obtained in examples 1 to 4yCzW in amounts of 1 wt%, 2 wt%, 4 wt% and 8 wt%yCz/ZnxCd1-xS and pure Zn obtained in comparative example 1xCd1-xAnd S is used for decomposing water to produce hydrogen under visible light, 30mg of sample is weighed and added into 100mL of aqueous solution containing 10mL of lactic acid sacrificial agent, after the photocatalytic hydrogen production system is vacuumized, the light source is turned on to carry out photocatalytic hydrogen production. The amount of photocatalytic hydrogen generation was detected by chromatography. Invention WyCz/ZnxCd1-xS composite photocatalyst and control group ZnxCd1-xThe comparative situation of the photocatalytic hydrogen generation performance of S under visible light is shown in FIG. 5. As can be seen from the figure, WyCz/ZnxCd1-xThe hydrogen production rate of the S composite sample is obviously higher than that of pure ZnxCd1-xS, wherein WyCzW in an amount of 8 wt%yCz/ZnxCd1-xThe hydrogen production rate of the S composite photocatalyst reaches 17805 mu mol.h-1·g-1Is about pure ZnxCd1-xThe hydrogen production rate of S is 5.24 times, and W of the invention is shownyCz/ZnxCd1-xThe S composite photocatalyst has high-efficiency photocatalytic hydrogen production activity.
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. The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
Claims (10)
1. A preparation method of a tungsten carbide/cadmium zinc sulfide composite photocatalyst is characterized by comprising the following steps:
s1, dispersing tungsten carbide in water to obtain a suspension;
s2, adding soluble cadmium salt and soluble zinc salt into the suspension according to the molar mass ratio of cadmium to zinc of 1: 10-10: 1, then adjusting the pH value to 4-10, and stirring uniformly;
s3, adding the sodium sulfide solution and/or the potassium sulfide solution into the suspension according to the molar mass ratio of the total molar mass of cadmium in the soluble cadmium salt and zinc in the soluble zinc salt to sulfur in the sodium sulfide solution and/or the potassium sulfide solution being 1:1-2, and continuously stirring to obtain the tungsten carbide/cadmium zinc sulfide composite photocatalyst.
2. The method of claim 1, wherein in step S2, the soluble cadmium salt is cadmium acetate; and/or the soluble zinc salt is zinc acetate.
3. The preparation method of claim 1, wherein in step S3, the sodium sulfide solution and/or the potassium sulfide solution is added to the suspension, and stirring is continued at a temperature of 0-80 ℃ to obtain the tungsten carbide/cadmium zinc sulfide composite photocatalyst.
4. The preparation method of claim 3, wherein in step S3, the tungsten carbide/cadmium zinc sulfide composite photocatalyst is obtained by continuing to stir at 0-80 ℃ for 5-30 hours.
5. The method according to claim 1, wherein in step S2, the sodium sulfide solution and/or the potassium sulfide solution is added to the suspension at a rate of 2 to 4mL/min in accordance with a molar mass ratio of the total of the cadmium in the soluble cadmium salt and the zinc in the soluble zinc salt to the sulfur in the sodium sulfide solution and/or the potassium sulfide solution of 1:1 to 2.
6. The production method according to claim 1, wherein in step S3, the concentration of the sodium sulfide solution and/or the potassium sulfide solution is 0.01 mol-L-1～1mol·L-1。
7. The method for preparing a tungsten carbide/cadmium zinc sulfide composite photocatalyst according to claim 1, wherein in step S3, W is added to the tungsten carbide/cadmium zinc sulfide composite photocatalystyCzWith ZnxCd1-xAnd adding the sodium sulfide solution and/or the potassium sulfide solution into the suspension in a theoretical mass ratio of 1: 500-1: 2 of S.
8. The method according to claim 1, wherein in step S2, a soluble cadmium salt and a soluble zinc salt are added to the suspension in a molar mass ratio of cadmium to zinc of 1:10 to 10:1, and then the concentration is 0.0001 mol.L-1～10mol·L-1And/or the concentration of sodium hydroxide is 0.0001 mol.L-1～10mol·L-1And adjusting the pH value to 4-10 by using potassium hydroxide.
9. A tungsten carbide/cadmium zinc sulfide composite photocatalyst prepared by the preparation method according to any one of claims 1 to 8.
10. The use of the tungsten carbide/cadmium zinc sulfide composite photocatalyst described in claim 9 for preparing hydrogen by decomposing water.
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| CN114275737A (en) * | 2021-12-29 | 2022-04-05 | 长沙学院 | Method for preparing hydrogen by performing piezoelectric catalytic cracking on water through Zn and N co-doped graphene nano foam |
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| CN114275737A (en) * | 2021-12-29 | 2022-04-05 | 长沙学院 | Method for preparing hydrogen by performing piezoelectric catalytic cracking on water through Zn and N co-doped graphene nano foam |
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Application publication date: 20200825 |