CN108671955B - Composite catalyst for photolysis of aquatic hydrogen and preparation method thereof - Google Patents
Composite catalyst for photolysis of aquatic hydrogen and preparation method thereof Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 55
- 239000001257 hydrogen Substances 0.000 title claims abstract description 55
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006303 photolysis reaction Methods 0.000 title claims description 16
- 230000015843 photosynthesis, light reaction Effects 0.000 title claims description 16
- 238000005984 hydrogenation reaction Methods 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 58
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 claims abstract description 31
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical group S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002135 nanosheet Substances 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000011259 mixed solution Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000011941 photocatalyst Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 15
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 229940011182 cobalt acetate Drugs 0.000 claims description 8
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 235000015393 sodium molybdate Nutrition 0.000 claims description 6
- 239000011684 sodium molybdate Substances 0.000 claims description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 15
- 239000000178 monomer Substances 0.000 abstract description 6
- 238000006068 polycondensation reaction Methods 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000005215 recombination Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 6
- 230000006798 recombination Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
-
- 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 provides a composite catalyst for producing hydrogen by photolyzing water and a preparation method thereof, wherein the composite catalyst is MoS2/Co‑g‑C3N4Is in g-C3N4Middle doped Co and MoS2Wherein Co is doped in g-C3N4In-bulk, strip-shaped nanosheet MoS2Supports by g-C3N4A surface. The photocatalytic hydrogen production performance of the composite catalyst is tested, and the composite catalyst MoS is found2/Co‑g‑C3N4Has excellent performance and good stability, and the hydrogen yield is monomer g-C3N44.36 times of. The invention prepares the composite catalyst MoS by a simple thermal polycondensation method and an ultrasonic impregnation method2/Co‑g‑C3N4The experimental process is simple and easy to operate.
Description
Technical Field
The invention belongs to the technical field of photocatalytic hydrogen production catalysts, and particularly relates to a photocatalytic hydrogen production composite catalyst and a preparation method thereof.
Background
The direct conversion of solar energy into hydrogen is the most ideal way of energy conversion and storage. At the end of the 60 s of the 20 th century, the japanese scholars Fujishima and Honda discovered an illuminated n-type semiconducting titanium dioxide TiO2The electrode can lead water to be decomposed, so that the hydrogen production by decomposing water by using solar energy gradually becomes one of research hotspots in the energy field. The researchers gradually found that except for using titanium dioxide (TiO)2) In addition, zinc oxide (ZnO), tin oxide (SnO)2) Zirconium dioxide (ZrO)2) And a plurality of oxide sulfide semiconductors such as cadmium sulfide (CdS) and the like can also produce hydrogen by photolysis of water. Among them, cadmium sulfide (CdS) and zinc oxide (ZnO) are chemically unstable, and undergo photo-dissolution during photocatalysis, thereby dissolving out harmful metal ions. TiO 22The photocatalyst has the characteristics of low price, no toxicity, strong oxidation capacity, good stability and the like, and becomes one of the most researched and widely applied semiconductor photocatalysts at present. However, due to the large forbidden band width (3.0-3.2 eV), the photocatalytic reaction can only be effectively carried out under the drive of ultraviolet light, and the ultraviolet light only accounts for about 4% of the total solar energy, so that the TiO is limited2The large-scale utilization of solar energy in practical application. Therefore, the design and development of new, efficient and visible light responsive photocatalytic semiconductor materials is an important research direction.
Recent studies have found that graphite-phase carbon nitride (g-C)3N4) Is a novel visible light responding nonmetal photocatalyst. g-C3N4Is a stable carbon-nitrogen nonpolar covalent compound with a laminated structure, g-C3N4In which C, N atom is sp2The substance has good chemical and thermodynamic stability, proper forbidden bandwidth, simple preparation method and low cost, but g-C3N4Insufficient absorption of visible light, resulting in a single phase g-C3N4The photocatalytic activity is low and the application is limited.
Elemental doping and semiconductor composite construction g-C3N4Can improve g-C3N4The photocatalytic performance of the catalyst is improved, and the photocatalytic reaction efficiency is improved. To date, various metal dopings and semiconductors have been used with g-C3N4Recombination is a heterojunction catalyst, facilitating the separation of photogenerated electrons from photogenerated holes by charge transfer between the semiconductors. The best promoter at present is noble metal Pt, etc., but noble goldThe high cost limits the application. Therefore, it is necessary to find a band structure and g-C with low cost and good stability3N4Matched non-noble metal promoters address this problem.
Disclosure of Invention
The invention provides a composite catalyst for producing hydrogen by photolyzing water and a preparation method thereof, which uses MoS2Composite Co-doped g-C3N4To solve g-C3N4Insufficient absorption capacity for visible light and low photocatalytic activity.
In order to achieve the purpose, the invention is realized by the following technical scheme:
composite catalyst MoS for photolysis of aquatic hydrogen2/Co-g-C3N4The composite catalyst is in g-C3N4Middle doped Co and MoS2Wherein Co is doped in g-C3N4In-bulk, strip-shaped nanosheet MoS2Supports by g-C3N4A surface.
MoS in the composite catalyst is calculated by mass fraction2：Co：g-C3N4The ratio of (1-8) to (1-10) to 100.
Composite catalyst MoS for photolysis of aquatic hydrogen2/Co-g-C3N4The preparation method comprises the following operations:
1) dissolving dicyanodiamine and a cobalt source compound in deionized water to obtain a raw material solution, wherein the ratio of Co: the mass ratio of dicyanodiamine is 1-8: 100, respectively; heating and stirring the raw material liquid, and fully mixing; drying to obtain a precursor;
heating the precursor to 400-600 ℃ at a heating rate of 2-4 ℃/min in an air atmosphere, and continuously calcining for 2-4 h to obtain Co-doped Co-g-C3N4；
2) Mixing Co-g-C3N4And MoS2The nano-sheet is dissolved in a mixed solution of distilled water and ethanol, wherein MoS2：g-C3N4The mass ratio of (A) to (B) is 1-10: 100; then carrying out ultrasonic treatment and centrifugal washing to obtain a solid product;
mixing the obtained solidDrying the product in vacuum; heating the mixture from room temperature to 200-600 ℃ at a heating rate of 2-4 ℃/min in an inert atmosphere, and calcining the mixture for 2-4 hours to obtain MoS2/Co-g-C3N4And (3) compounding a catalyst.
Dissolving dicyanodiamine and cobalt acetate in a mixed solution of deionized water and ethanol, wherein the volume ratio of the deionized water to the ethanol in the mixed solution is 30: 70-70: 30; the mass ratio of dicyanodiamine to cobalt acetate is 100: 3-100: 24.
And drying the mixed solution in an oven at 80-100 ℃ for 12-24 h to obtain a precursor.
The ultrasonic treatment comprises the following steps: doping Co with g-C3N4And ultrasonically dispersing the photocatalyst and MoS2 for 5-10 hours under the conditions of frequency of 40-60 KHz and power of 150-200W.
The MoS2The preparation of the nano-sheet comprises the following steps:
dissolving sodium molybdate and thiourea in distilled water to obtain a mixed solution; adding hydrochloric acid into the obtained mixed solution to enable the pH value to be 0.1-1, and stirring;
transferring the solution into a reaction kettle, and continuously reacting for 12-36 h at 150-250 ℃; washing after the reaction is finished; drying the mixture for 10 to 20 hours at the temperature of between 60 and 80 ℃ in a vacuum environment, and grinding the dried mixture to obtain MoS2Nanosheets.
Sequentially dissolving 0.2-0.8 g of sodium molybdate and 0.6-2.4 g of thiourea in 50mL of distilled water according to the following proportion to obtain a mixed solution;
and respectively centrifugally cleaning the mixed solution after the reaction for three to five times by using deionized water and ethanol, wherein the centrifugal speed is 3000-10000 rpm, and the centrifugal time is 30-60 min.
The MoS2Nanosheets and Co-g-C3N4The mass ratio of (2-8) to (100); in the mixed solution of the deionized water and the ethanol, the ratio of the deionized water to the ethanol is 30:70 to 70: 30;
the composite catalyst MoS for photolysis of water to produce hydrogen2/Co-g-C3N4The application in hydrogen production by photolysis of water.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention provides a composite photocatalyst MoS2/Co-g-C3N4The composite catalyst is in g-C3N4Middle doped Co and MoS2To solve g-C3N4The defects of insufficient absorption capacity to visible light and low photocatalytic activity; doping a small amount of Co metal ions to g-C3N4In the structural unit, the structure can be used as a shallow trapping trap of a photogenerated electron-hole pair, and the recombination time of electrons and holes is prolonged; mixing MoS2And g-C3N4The recombination constitutes a heterojunction, g-C due to the difference in the positions of the conduction band and the valence band3N4Electrons or holes generated by light excitation are transferred to a conduction band or a valence band of the compound, the electrons and the holes are separated, the recombination rate is reduced, and therefore active particles generated by light excitation can be more effectively utilized, and g-C is improved3N4Photocatalytic performance. The method has no special requirements on the specific process of preparing hydrogen by photocatalytic water decomposition by the composite photocatalyst, and can be carried out according to the operation mode of preparing hydrogen by photocatalytic water decomposition well known by the technical personnel in the field.
The invention dopes Co element and MoS2The MoS is prepared in a composite mode2/Co-g-C3N4As a result, it was found that the catalyst MoS after the recombination2/Co-g-C3N4The efficiency of photolysis of water is monomer g-C3N44.3 times of; illustrating the Co doping and MoS2Strategy pair g-C for compositely constructing heterojunction3N4The catalytic activity plays a good role in improving, and the separation efficiency of photo-generated electrons and holes of the composite catalyst is greatly improved by combining with the characteristics of XRD and the like, so that the capability of photolyzing water to produce hydrogen is effectively improved.
Drawings
FIG. 1 is a schematic diagram of the synthetic route of the present invention;
FIG. 2 shows X-ray diffraction patterns of photocatalysts obtained in comparative examples 1-2 and 1-2, wherein (a) is comparative example 1, (b) is comparative example 2, (c) is example 1, and (d) is example 2.
FIG. 3 shows Fourier infrared spectra of photocatalysts obtained in comparative examples 1-2 and examples 1-2, wherein (a) is comparative example 1, (b) is comparative example 2, (c) is example 1, and (d) is example 2.
FIG. 4 is an SEM photograph and a TEM photograph of the photocatalyst obtained in example 2-3, wherein (A) is the SEM photograph of example 1, (B) is the SEM photograph of example 2, (C) is the TEM photograph of example 1, and (d) is the TEM photograph of example 2.
FIG. 5 is an XPS plot of the photocatalyst obtained in example 1: (a) XPS survey scan in example 1, (b) XPS fine scan of C element in example 1, (C) XPS fine scan of N element in example 1, (d) XPS fine scan of O element in example 1, (e) XPS fine scan of Co element in example 1, (f) XPS fine scan of S element in example 1, and (g) XPS fine scan of Mo element in example 1.
Fig. 6 is a graph for evaluating hydrogen production efficiency of photocatalysts obtained in comparative examples 1 and 2 and example 1, with the abscissa representing reaction time(s) and the ordinate representing hydrogen production efficiency (μmol): (a) comparative example 1, (b) comparative example 2, and (c) example 1.
Fig. 7 is a corresponding histogram of fig. 6.
Detailed Description
The composite photocatalyst and the preparation method thereof provided by the present invention are described in detail below with reference to the following examples, which are intended to illustrate, but not limit the present invention.
The invention provides a composite photocatalyst MoS2/Co-g-C3N4The composite catalyst is in g-C3N4Middle doped Co and MoS2To solve g-C3N4Insufficient absorption capacity for visible light and low photocatalytic activity.
Doping a small amount of Co metal ions to g-C3N4In the structural unit, the structure can be used as a shallow trapping trap of a photogenerated electron-hole pair, and the recombination time of electrons and holes is prolonged; mixing MoS2And g-C3N4The recombination constitutes a heterojunction, g-C due to the difference in the positions of the conduction band and the valence band3N4The electrons or holes generated by light excitation are transferred to the conduction band or valence band of the compound, the electrons and the holes are separated, the recombination rate is reduced, and therefore the light excitation generation can be more effectively utilizedThereby increasing g-C3N4Photocatalytic performance.
Wherein Co is doped in g-C3N4In-bulk, strip-shaped nanosheet MoS2Supports by g-C3N4A surface.
Example 1
Referring to FIG. 1, the composite photocatalyst MoS2/Co-g-C3N4The preparation method comprises the following operations:
Co-g-C by thermal polycondensation3N4The preparation of (1): 4.0g of dicyanodiamide and 0.3g of cobalt acetate were dissolved in 50mL of deionized water, stirred vigorously for 80min, and the resulting solution was placed in an oven at 60 ℃ for 24 h.
Heating the obtained sample to 550 ℃ at the heating rate of 2 ℃/min in the air atmosphere, and continuously calcining the sample at 550 ℃ for 2h to obtain Co-g-C3N4。
MoS2The preparation of (1): 0.6g of sodium molybdate and 1.8g of thiourea are dissolved in distilled water, hydrochloric acid is added to make the sodium molybdate-thiourea solution in a strong acid environment with the pH value of 0.5, the solution is stirred for 1h, and then the solution is transferred to a 100mL hydrothermal reaction kettle and is continuously reacted for 36h at the temperature of 200 ℃. After the reaction is finished, taking out the mixed solution, respectively centrifugally cleaning the mixed solution for three times by using deionized water and ethanol, drying the obtained solid for 12 hours in a vacuum drying oven at the temperature of 60 ℃, and grinding to obtain MoS2Nanosheets.
MoS2/Co-g-C3N4Preparing a composite material: weighing the prepared Co-g-C3N40.2g and 0.006g MoS2Dissolving the solid powder in 100mL of solvent composed of distilled water and ethanol (the volume ratio at room temperature is 30: 70); carrying out ultrasonic treatment for 8h under the conditions of 40KHz frequency and 150W power; the resulting suspension was centrifuged at 8000rpm for 30min and washed three times. Drying the obtained solid in a vacuum drying oven at 60 ℃ for 15 h; in Ar inert atmosphere, heating from room temperature to 300 ℃ at the heating rate of 4 ℃/min and calcining for 3h to obtain MoS2/Co-g-C3N4And (3) compounding a catalyst.
In the XRD spectrum, two distinct diffraction peaks appear at 27.8 ° 2 θ and 13.2 ° 2 θ, which are indicative of the diffraction peaksIs g-C3N4Characteristic peak of (a); in IR spectrum, 850cm-1、1210cm-1-1640cm-1And 3000cm-1–3300cm-1Is g-C3N4The characteristic functional group vibrates, and the prepared sample is graphite phase carbon nitride (g-C) according to XRD and IR spectrums3N4). From the XPS spectrum, all the elements of C, N, O, Co, Mo and S are monitored, and the MoS is proved2/Co-g-C3N4Successful synthesis of novel catalysts. From SEM and TEM spectra, the prepared samples g-C3N4The structure is a layered structure, and obvious strip-shaped MoS can be observed at the same time2Nanosheets (having a typical MoS2Lattice fringes).
The method has no special requirements on the specific process of preparing hydrogen by photocatalytic water decomposition by the composite photocatalyst, and can be carried out according to the operation mode of preparing hydrogen by photocatalytic water decomposition well known by the technical personnel in the field.
The hydrogen production experiment by photolysis is carried out in a 100mL quartz reactor, the test amount of a catalyst is 10-50 mg, 5-10% of triethanolamine is added as a sacrificial agent in the experiment process, a 300W xenon lamp (filtering out ultraviolet light) is used as a light source, and the hydrogen production amount is recorded every half hour in the experiment process.
Testing the hydrogen production capacity of photocatalytic water decomposition: a30 mg sample of the catalyst was weighed and dispersed in a mixed solution of 5mL of triethanolamine and 45mL of distilled water, and the air of the hydrogen production system was removed before the reaction. The reactor was charged with circulating condensed water at a temperature of 6 ℃. The light source used was a 300W xenon lamp (uv filtered). In the experimental process, a magnetic stirrer is used for keeping the solution in a stirring state; the content of hydrogen is recorded by gas chromatography every half an hour, and the hydrogen production efficiency is 14.17umol/h after calculation.
Example 2
Referring to FIG. 1, the composite photocatalyst MoS2/Co-g-C3N4The preparation method comprises the following operations:
Co-g-C3N4the preparation of (1): 4.0g of dicyanodiamide and 0.2g of cobalt acetate were dissolved in 50mL of deionized water, stirred vigorously for 60min, and the resulting solution was placed in an oven at 60 ℃ for 24 h.Heating the obtained sample to 550 ℃ at the heating rate of 4 ℃/min in the air atmosphere, and continuously calcining the sample at 550 ℃ for 4h to obtain Co-g-C3N4。
MoS2The preparation of (1): 0.6g of sodium molybdate and 1.8g of thiourea are dissolved in distilled water, hydrochloric acid is added to make the sodium molybdate-thiourea solution in a strong acid environment with the pH value of 0.1, the solution is stirred for 1 hour, and then the solution is transferred to a 100mL hydrothermal reaction kettle and is continuously reacted for 24 hours at the temperature of 200 ℃. After the reaction is finished, taking out the mixed solution, respectively centrifugally cleaning the mixed solution for three times by using deionized water and ethanol, drying the obtained solid for 12 hours in a vacuum drying oven at the temperature of 60 ℃, and grinding to obtain MoS2Nanosheets.
MoS2/Co-g-C3N4Preparing a composite material: weighing the prepared Co-g-C3N40.2g and 0.004g of MoS2Dissolving the solid powder in 100mL of solvent composed of distilled water and ethanol (the volume ratio at room temperature is 30: 70); carrying out ultrasonic treatment for 10h under the conditions of 50KHz frequency and 180W power; the resulting suspension was centrifuged at 5000rpm for 30min and washed three times. The resulting solid was dried in a vacuum oven at 60 ℃ for 12 h. Obtaining MoS2/Co-g-C3N4And (3) compounding a catalyst.
Testing the hydrogen production capacity of photocatalytic water decomposition: a30 mg sample of the catalyst was weighed and dispersed in a mixed solution of 5mL of triethanolamine and 45mL of distilled water, and the air of the hydrogen production system was removed before the reaction. The reactor was charged with circulating condensed water at a temperature of 6 ℃. The light source used was a 300W xenon lamp (uv filtered). In the experimental process, a magnetic stirrer is used for keeping the solution in a stirring state; the content of hydrogen is recorded by gas chromatography every half an hour, and the hydrogen production efficiency is calculated to be 12.82 umol/h.
Example 3
Composite photocatalyst MoS2/Co-g-C3N4The preparation method comprises the following operations:
Co-g-C3N4the preparation of (1): 4.0g of dicyanodiamide and 0.1g of cobalt acetate were dissolved in 30mL of deionized water, stirred vigorously for 60min, and the resulting solution was placed in an oven at 60 ℃ for 12 h. Adding the obtained sample at 2 ℃/min in air atmosphereHeating to 450 ℃ at a heat rate, and continuously calcining for 2h at 450 ℃ to obtain Co-g-C3N4。
MoS2The preparation of (1): 0.2g of sodium molybdate and 0.6g of thiourea were dissolved in distilled water, hydrochloric acid was added to make the sodium molybdate-thiourea solution in a strong acid environment with a pH of 1, the solution was stirred for 0.5h, and then the solution was transferred to a 100mL hydrothermal reaction kettle and reacted at 200 ℃ for 12 h. After the reaction is finished, taking out the mixed solution, respectively centrifugally cleaning the mixed solution for three times by using deionized water and ethanol, drying the obtained solid for 12 hours in a vacuum drying oven at the temperature of 60 ℃, and grinding to obtain MoS2Nanosheets.
MoS2/Co-g-C3N4Preparing a composite material: weighing the prepared Co-g-C3N40.2g and 0.002g of MoS2The solid powder was dissolved in 100mL of a solvent composed of distilled water and ethanol (volume ratio 50: 50 at room temperature), sonicated for 15h at a frequency of 60KHz and a power of 200W, and the resulting suspension was centrifuged at 3000rpm for 10min and washed three times. The resulting solid was dried in a vacuum oven at 60 ℃ for 12 h. Obtaining MoS2/Co-g-C3N4And (3) compounding a catalyst.
Testing the hydrogen production capacity of photocatalytic water decomposition: a30 mg sample of the catalyst was weighed and dispersed in a mixed solution of 5mL of triethanolamine and 45mL of distilled water, and the air of the hydrogen production system was removed before the reaction. The reactor was charged with circulating condensed water at a temperature of 6 ℃. The light source used was a 300W xenon lamp (uv filtered). In the experimental process, a magnetic stirrer is used for keeping the solution in a stirring state; and recording the content of hydrogen once every half hour by using a gas chromatography, and calculating to obtain the hydrogen production efficiency of 5.15 umol/h.
Comparative example 1
g-C3N4The preparation of (1): 4.0g of dicyanodiamine was dissolved in 50mL of deionized water, stirred vigorously for 80min, and the resulting solution was placed in an oven at 60 ℃ for 24 h. The obtained sample is continuously calcined for 2h at 550 ℃ at the heating rate of 4 ℃/min to obtain the monomer g-C3N4A catalyst.
Testing the hydrogen production capacity of photocatalytic water decomposition: a30 mg sample of the catalyst was weighed and dispersed in a mixed solution of 5mL of triethanolamine and 45mL of distilled water, and the air of the hydrogen production system was removed before the reaction. The reactor was charged with circulating condensed water at a temperature of 6 ℃. The light source used was a 300W xenon lamp (uv filtered). In the experimental process, a magnetic stirrer is used for keeping the solution in a stirring state; and recording the content of hydrogen once every half hour by using a gas chromatography, and calculating to obtain the hydrogen production efficiency of 3.25 umol/h.
Comparative example 2
Co-g-C3N4The preparation of (1): 4.0g of dicyanodiamide and 0.3g of cobalt acetate were dissolved in 50mL of deionized water, stirred vigorously for 80min, and the resulting solution was placed in an oven at 60 ℃ for 24 h. The obtained sample is continuously calcined for 2h at the temperature of 550 ℃ at the heating rate of 4 ℃/min to obtain 3-Co-g-C3N4A catalyst.
Testing the hydrogen production capacity of photocatalytic water decomposition: a30 mg sample of the catalyst was weighed and dispersed in a mixed solution of 5mL of triethanolamine and 45mL of distilled water, and the air of the hydrogen production system was removed before the reaction. The reactor was charged with circulating condensed water at a temperature of 6 ℃. The light source used was a 300W xenon lamp (uv filtered). In the experimental process, a magnetic stirrer is used for keeping the solution in a stirring state; the content of hydrogen is recorded by gas chromatography every half an hour, and the hydrogen production efficiency is calculated to be 9.42 umol/h.
Fig. 6 and 7 show the photocatalytic water hydrogen production activity test results. As can be seen from the figure, monomers g to C3N4The hydrogen production amount of (2) is 3.25. mu. mol. h-1，Co-g-C3N4The hydrogen production amount of (b) is 9.42. mu. mol. h-1，MoS2/Co-g-C3N4The hydrogen production amount of (b) is 14.17. mu. mol. h-1. Co-g-C after doping with Co element3N4The amount of hydrogen produced is monomer g-C3N42.89 times of that of the product, and further compounding MoS2Then, MoS2/Co-g-C3N4The amount of hydrogen produced is monomer g-C3N44.36 times of. This illustrates the Co-doped and composite MoS of the present invention2Can greatly improve g-C3N4Photocatalytic hydrogen production activity.
From the above embodiments, the invention provides a composite photocatalyst MoS2/Co-g-C3N4Co doping in g-C3N4In the bulk phase, MoS2Supports by g-C3N4Surface, MoS2Is in a strip-shaped nanosheet structure. The composite photocatalyst provided by the invention is Co and MoS2As cocatalyst with g-C3N4Composite to form a heterojunction for solving g-C3N4Insufficient absorption capacity to visible light, low photocatalytic activity and the like. The present invention is to mix MoS by a thermal polycondensation method, a hydrothermal method, or the like2Nanosheets and Co-g-C3N4The preparation method is simple and easy to operate.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. The composite catalyst for photolyzing water to produce hydrogen is characterized in that the composite catalyst is MoS2/Co-g-C3N4Is in g-C3N4Middle doped Co and MoS2Wherein Co is doped in g-C3N4In-bulk, strip-shaped nanosheet MoS2Supports by g-C3N4Surface, in mass fraction, MoS in the composite catalyst2：Co：g-C3N4The ratio of (1-8) to (1-10) to 100, the MoS2The preparation of the nano-sheet comprises the following steps:
sequentially dissolving 0.2-0.8 g of sodium molybdate and 0.6-2.4 g of thiourea in 50mL of distilled water according to the following proportion to obtain a mixed solution;
respectively centrifugally cleaning the mixed solution after the reaction for three to five times by using deionized water and ethanol, wherein the centrifugal speed is 3000-10000 rpm, and the centrifugal time is 30-60 min;
adding hydrochloric acid into the obtained mixed solution to enable the pH value to be 0.1-1, and stirring;
transferring the solution into a reaction kettle, and continuously reacting for 12-36 h at 150-250 ℃; washing after the reaction is finished; then in a vacuum environmentDrying at 60-80 ℃ for 10-20 h, and grinding to obtain MoS2Nanosheets.
2. Composite catalyst MoS for photolysis of aquatic hydrogen2/Co-g-C3N4The preparation method is characterized by comprising the following operations:
1) dissolving dicyanodiamine and a cobalt source compound in a mixed solution of deionized water and ethanol to obtain a raw material solution, wherein the ratio of Co: the mass ratio of dicyanodiamine is 1-8: 100, respectively; heating and stirring the raw material liquid, and fully mixing; drying to obtain a precursor;
heating the precursor to 400-600 ℃ at a heating rate of 2-4 ℃/min in an air atmosphere, and continuously calcining for 2-4 h to obtain Co-doped Co-g-C3N4；
2) Mixing Co-g-C3N4And MoS2Dissolving the nano-sheet in a mixed solution of deionized water and ethanol, wherein MoS2：g-C3N4The mass ratio of (A) to (B) is 1-10: 100; then carrying out ultrasonic treatment and centrifugal washing to obtain a solid product;
drying the obtained solid product in vacuum; heating the mixture from room temperature to 200-600 ℃ at a heating rate of 2-4 ℃/min in an inert atmosphere, and calcining the mixture for 2-4 hours to obtain MoS2/Co-g-C3N4And (3) compounding a catalyst.
3. The composite catalyst MoS for photolysis of water to produce hydrogen according to claim 22/Co-g-C3N4The preparation method is characterized in that dicyanodiamine and cobalt acetate are dissolved in a mixed solution of deionized water and ethanol, and the volume ratio of the deionized water to the ethanol in the mixed solution is 30: 70-70: 30; the mass ratio of dicyanodiamine to cobalt acetate is 100: 3-100: 24.
4. The composite catalyst MoS for photolysis of water to produce hydrogen according to claim 22/Co-g-C3N4The preparation method is characterized in that the mixed solution is dried in an oven at 80-100 ℃ for 12-24 hours to obtain the precursor.
5. The composite catalyst MoS for photolysis of water to produce hydrogen according to claim 22/Co-g-C3N4The preparation method is characterized in that the ultrasonic treatment comprises the following steps: doping Co with g-C3N4Photocatalyst and MoS2And ultrasonically dispersing for 5-10 h under the conditions of 40-60 KHz frequency and 150-200W power.
6. The composite catalyst MoS for photolysis of water to produce hydrogen according to claim 22/Co-g-C3N4Characterized in that said MoS2Nanosheets and Co-g-C3N4The mass ratio of (2-8) to (100); the ratio of the deionized water to the ethanol in the mixed solution of the deionized water and the ethanol is 30:70 to 70: 30.
7. The composite catalyst MoS for hydrogen production by photolysis of water as claimed in claim 12/Co-g-C3N4The application in hydrogen production by photolysis of water.
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