CN111036249A - FexP/Mn0.3Cd0.7S composite photocatalyst and preparation method and application thereof - Google Patents
FexP/Mn0.3Cd0.7S composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 47
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- 238000010438 heat treatment Methods 0.000 claims description 12
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- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- B01J35/39—
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- 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—
-
- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1088—Non-supported catalysts
-
- 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 discloses FexP/Mn0.3Cd0.7A preparation method and application of the S composite photocatalyst. The method comprises the following steps: adding Mn0.3Cd0.7S, adding the mixture into ethanolamine, and uniformly dispersing to obtain a suspension; FeCl is added3·6H2Adding O and red phosphorus subjected to grinding pretreatment into the suspension, carrying out solvothermal reaction, filtering, and drying to obtain FexP/Mn0.3Cd0.7And (S) a composite photocatalyst. The composite photocatalyst provided by the invention is of a rod-shaped structure, has a larger length-diameter ratio, and is beneficial to transfer and separation of photon-generated carriers; amorphous FexP on Mn0.3Cd0.7On the S nanorod, the short-range ordered structure and the defect sites can provide more reactive active sites, and Fe-S bonds are formed between the S nanorod and the defect sites, so that the migration rate of a photon-generated carrier can be accelerated, the photocatalytic hydrogen production activity is higher, and the problem of poor stability of a sulfide catalyst is obviously solved.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to FexP/Mn0.3Cd0.7S composite photocatalyst and its preparation method and application.
Background
Solar energy with abundant resources can be converted into clean and efficient hydrogen energy by decomposing water through solar photocatalysis, the method is considered to be one of effective technologies for solving energy and environmental problems, and the key point is to find a stable and efficient photocatalyst. Sulfide solid solution photocatalysts gradually become hot spots in the research field due to the advantages of adjustable positions of a conduction band and a valence band, large visible light response range and the like. However, when the sulfide photocatalyst is used for photocatalytic water decomposition reaction, the hydrogen production rate is low and the stability is poor due to the problems that a photogenerated carrier is easy to recombine, the photo-corrosion phenomenon is serious and the like. At present, the hydrogen production activity and stability are improved by means of loading a cocatalyst, coupling a semiconductor, depositing a noble metal and the like.
Han et al (Catalysis Science)&Technology,2019,9(6):1427-xCd1-xS nanocomposite, Mn when x is 0.30.3Cd0.7S is of a nanorod structure and has the highest hydrogen production activity. But the stability is poor, and after four cycles, the 1mol percent CuS/Mn0.3Cd0.7The S hydrogen production activity is only 61.08 percent of that of the primary circulation; preparation of MoS by Zhai et al (Applied Surface Science,2018,430:515-2/Mn0.5Cd0.5S,CuxS/Mn0.5Cd0.5S(1≤x≤2),PdS/Mn0.5Cd0.5S composite photocatalyst with hydrogen production activity higher than that of Mn0.5Cd0.5S is improved to different degrees, PdS/Mn0.5Cd0.5The hydrogen production activity of S after 12 hours of photocatalytic reaction is only 70.59 percent of the initial hydrogen production activity, MoS2/Mn0.5Cd0.5S，CuxS/Mn0.5Cd0.5The photocatalytic activity of S is also reduced to various degrees. At present, MnxCd1-xPoor stability of S-based photocatalysts is one of the bottlenecks impeding their development.
The transition metal phosphide has rich active sites and unique physical and chemical properties, and can be used as a cocatalyst to remarkably reduce hydrogen over-potential, accelerate the transfer rate of photon-generated carriers and improve the photocatalytic hydrogen production activity and stability. Lu et al successfully constructed 0D/2D Ni2P QDs modified ultrathin g-C3N4Nanosheets, XPS result shows that Ni2P QDs and g-C3N4N-Ni bonds are formed between the nanosheets (Applied Catalysis B: Environmental,2018,237: 919-926.). Sun et al successfully synthesized Fe by hydrothermal-calcination auxiliary method2The hydrogen production rate of the CdS nano-rod loaded with P is improved by 30 times (catalysis science)&Technology,2015,5(11): 4964-. Thus, the transition metal phosphide is supported as MnxCd1-xThe improvement of the activity and the stability of the S-based photocatalyst provides a reference technical scheme. However, most of the existing phosphide preparation processes use toxic raw materials such as yellow phosphorus, or harmful gases such as phosphine are released in the preparation process, which easily causes environmental pollution.
Disclosure of Invention
Aiming at the existing MnxCd1-xThe invention aims to provide the environment-friendly, nontoxic, stable and efficient Fe, and solves the problems of serious photo-corrosion phenomenon, poor stability, high toxicity in the preparation process of phosphide and the like of an S catalystxP/Mn0.3Cd0.7S composite photocatalyst and its preparation method and application.
The invention provides FexP/Mn0.3Cd0.7The S composite photocatalyst is stable and efficient MnxCd1-xS-based photocatalyst (Fe)xP/Mn0.3Cd0.7S). Red phosphorus and FeCl as non-toxic phosphorus source3·6H2O is used as a reaction raw material, and Fe is subjected to a hydrothermal methodxP in situ Supported on Mn0.3Cd0.7S surface, amorphous FexP has a short-range ordered structure and a defect site, and can provide more active sites. FexP and Mn0.3Cd0.7The Fe-S bond formed between S is not only beneficial to photo-generated electrons from Mn0.3Cd0.7S transfer to FexP, and can suppress Mn to some extent0.3Cd0.7S photo-corrosion phenomenon occurs, thereby making Fe preparedxP/Mn0.3Cd0.7The S composite photocatalyst has excellent photocatalytic hydrogen production activity and stability.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides FexP/Mn0.3Cd0.7S composite photocatalyst of Mn0.3Cd0.7S is a main catalyst, FexP is a cocatalyst, FexThe amount of P supported is 5 to 40 mol%.
The invention adopts red phosphorus with rich content, low toxicity and relative stability as phosphorus source, and adopts solvothermal method to successfully prepare Fe with amorphous structurexP。
The invention provides FexP/Mn0.3Cd0.7The preparation method of the S composite photocatalyst comprises the following steps:
(1) adding Mn0.3Cd0.7Adding S catalyst into organic solvent, stirring, and ultrasonic treating to obtain Mn0.3Cd0.7S, uniformly dispersing the catalyst to obtain a suspension;
(2) FeCl is stirred3·6H2And (3) adding the O and the pretreated red phosphorus into the suspension liquid in the step (1), uniformly stirring, and performing ultrasonic treatment to form uniformly dispersed suspension liquid. Then transferring and sealing the mixture in a reaction kettle with a polytetrafluoroethylene inner container, heating the mixture to perform solvothermal reaction, cooling the mixture to room temperature, filtering the mixture to obtain precipitate, washing the precipitate, and drying the precipitate to obtain the FexP/Mn0.3Cd0.7And (S) a composite photocatalyst.
Further, the organic solvent in the step (1) is ethanolamine or ethylenediamine.
Preferably, the organic solvent in step (1) is ethanolamine.
Further, the organic solvent of the step (1) is mixed with Mn0.3Cd0.7The volume mass ratio of the S catalyst is 40-60: 500 mL/mg.
Preferably, the organic of step (1)Solvent and Mn0.3Cd0.7The volume mass ratio of the S catalyst is 50: 500 mL/mg.
Mn described in step (1)0.3Cd0.7The S catalyst can be prepared by a solvothermal method; the Mn is0.3Cd0.7The raw material of the S catalyst comprises Mn (OAc)2·4H2O、Cd(OAc)2·2H2O and thioacetamide. The Mn is0.3Cd0.7S catalyst preparation reference (Catalysis Science)&Technology,2019,9(6):1427-1436.)。
Further, the red phosphorus after pretreatment in the step (2) is red phosphorus after pretreatment such as grinding, and the particle size of the red phosphorus after pretreatment is 1-3 μm.
Further, the preparation of the pretreated red phosphorus in the step (2) comprises the following steps:
uniformly mixing red phosphorus and an organic solvent, adding the mixture into an agate tank, sealing, vacuumizing, grinding for 12-36h under a protective atmosphere, washing, and drying in an argon atmosphere to obtain the pretreated red phosphorus.
Further, in the preparation process of the pretreated red phosphorus, the used organic solvent is one of ethylene glycol and isopropanol, and the mass volume ratio of the red phosphorus to the organic solvent is (4-8): (12-18) g/mL; the protective atmosphere is argon atmosphere.
Further, the FeCl in the step (2)3·6H2The molar ratio of O to the pretreated red phosphorus is (0.5-1.5) to (3-5); FeCl described in step (2)3·6H2The mass-volume ratio of O to the organic solvent in the step (1) is (0.05-0.50): (40-60) g/mL.
Preferably, the FeCl of step (2)3·6H2The molar ratio of O to the pretreated red phosphorus is 1: 4.
Further, the temperature of the solvothermal reaction in the step (2) is 170-190 ℃, and the time of the solvothermal reaction is 8-16 h.
Preferably, the temperature of the solvothermal reaction in step (2) is 180 ℃.
Preferably, the solvothermal reaction time of the step (2) is 12 h.
Further, the washing of step (2) comprises: washing with deionized water and ethanol alternately.
Further, the FeCl in the step (2)3·6H2The mass-volume ratio of O to the organic solvent in the step (1) is (0.05-0.50): (40-60) g/mL.
The invention provides FexP/Mn0.3Cd0.7The S composite photocatalyst can be applied to the reaction of decomposing water into hydrogen by photocatalysis, has excellent hydrogen production stability, and has the advantages that the catalytic hydrogen production rate is almost unchanged and can still reach 31.37mmol g after 15-24h of catalytic hydrogen production-1h-1Above, the hydrogen production rate is above 97.09% of the highest rate.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) fe prepared by the inventionxP/Mn0.3Cd0.7The S composite photocatalyst is a rod-shaped structure, has larger length-diameter ratio, is beneficial to transfer and separation of photon-generated carriers, and is amorphous FexP has a short-range ordered structure, a defect site, and FexP and Mn0.3Cd0.7The Fe-S bond formed between S is not only beneficial to photo-generated electrons from Mn0.3Cd0.7S transfer to FexP, and can suppress Mn to some extent0.3Cd0.7S photo-corrosion phenomenon occurs, thereby making Fe preparedxP/Mn0.3Cd0.7The S composite photocatalyst has excellent photocatalytic hydrogen production activity and stability, and the catalytic hydrogen production rate is almost unchanged and still can reach 31.37mmol g after 24 hours of catalytic hydrogen production-1h-1The hydrogen production rate is above 97.09% of the highest rate;
(2) the preparation method provided by the invention has the advantages of simple operation, easy realization and the like, the used raw materials are environment-friendly and nontoxic, and the prepared FexP/Mn0.3Cd0.7The S composite photocatalyst can be applied to a hydrogen production system by photocatalytic water decomposition.
Drawings
FIG. 1 is a graph showing hydrogen production rates by photocatalytic decomposition of catalysts prepared in examples and comparative examples;
FIG. 2 is an XRD pattern of catalysts prepared in examples and comparative examples;
FIG. 3 shows Mn obtained in comparative example 20.3Cd0.7SEM picture of S catalyst;
FIG. 4 shows Fe obtained in example 3xP/Mn0.3Cd0.7An SEM image of the S composite photocatalyst;
FIG. 5 shows Fe obtained in example 3xP/Mn0.3Cd0.7HRTEM image of the S composite photocatalyst;
FIG. 6 is a graph showing the hydrogen production stability of the catalysts prepared in comparative example 2 and example 3;
fig. 7 is a graph of the S2p spectra in XPS scans of the catalysts prepared in comparative example 2 and example 3.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
The following examples and comparative examples use red phosphorus as red phosphorus after a milling pretreatment, the pretreatment process including: uniformly mixing 5g of commercial red phosphorus with 15mL of organic solvent (ethylene glycol is selected), adding the mixture into an agate tank, sealing, vacuumizing, grinding for 24h under a protective atmosphere (argon atmosphere), washing, and drying for 10h under the conditions of argon atmosphere and 100 ℃ to obtain pretreated red phosphorus, wherein the particle size of the pretreated red phosphorus is 1-3 mu m;
mn used in the following examples and comparative examples0.3Cd0.7An S catalyst, the preparation of which comprises: taking 6mmol Mn (OAc)2·4H2O,14mmol Cd(OAc)2·2H2O dissolved in 30mL H2Mixing O and 30mL of anhydrous Ethylenediamine (EDA), stirring, adding 25mmol of thioacetamide, stirring to disperse uniformly, transferring into a polytetrafluoroethylene liner, and sealing in a stainless steel containerHeating steel shell at 200 deg.C for 24 hr, cooling to room temperature, filtering to obtain precipitate, washing, and drying to obtain yellow powder, i.e. Mn0.3Cd0.7S catalyst (see Catalysis Science for preparation process)&Technology,2019,9(6):1427-1436.)。
The hydrogen production performance test of the following examples and comparative examples was conducted in a photocatalytic hydrogen production system using a 300W Xe lamp (. lamda. gtoreq.420 nm) as a light source. The test comprises the following steps: taking 10mg of the prepared catalyst, loading the catalyst into a reactor, adding 100mL of 20 vol% lactic acid aqueous solution, stirring for 5min, carrying out ultrasonic treatment for 10min, vacuumizing for 15min, controlling the reaction temperature at 15 ℃, then starting a light source to carry out photocatalytic reaction, and carrying out online detection by adopting gas chromatography and calculating the hydrogen production.
Example 1
FexP/Mn0.3Cd0.7The preparation method of the S composite photocatalyst comprises the following steps:
(1) 500mg of Mn0.3Cd0.7Adding the S catalyst into 50mL of ethanolamine solvent, uniformly stirring, and then uniformly dispersing by ultrasonic to obtain a suspension;
(2) 54mg of FeCl were added under stirring3·6H2Adding O and 25mg of pretreated red phosphorus into the suspension liquid obtained in the step (1), uniformly stirring, and uniformly ultrasonically dispersing to form uniformly dispersed suspension liquid; then transferring and sealing the mixture in a reaction kettle provided with a polytetrafluoroethylene inner container, heating to 180 ℃ for solvothermal reaction for 12 hours, cooling to room temperature, filtering to obtain precipitate, washing and drying to obtain FexP and Mn0.3Cd0.7Fe with a S molar ratio of 5 mol%xP/Mn0.3Cd0.7S composite photocatalyst, marked as 5 mol% FexP/Mn0.3Cd0.7S。
And (3) performance testing: fe obtained in example 1 under irradiation of 300W Xe lamp at a reaction temperature of 15 ℃xP/Mn0.3Cd0.7The hydrogen production rate of the S composite photocatalyst is 11.85mmol g-1h-1As shown in fig. 1.
Example 2
FexP/Mn0.3Cd0.7The preparation method of the S composite photocatalyst comprises the following steps:
(1) 500mg of Mn0.3Cd0.7Adding the S catalyst into 50mL of ethanolamine solvent, uniformly stirring, and then uniformly dispersing by ultrasonic to obtain a suspension;
(2) 107mg of FeCl were added under stirring3·6H2And (2) adding the O and 49mg of pretreated red phosphorus into the suspension liquid in the step (1), uniformly stirring, and uniformly dispersing by ultrasonic to form uniformly dispersed suspension liquid. Then transferring and sealing the mixture in a reaction kettle provided with a polytetrafluoroethylene inner container, heating to 180 ℃ for solvothermal reaction for 12 hours, cooling to room temperature, filtering to obtain precipitate, washing and drying to obtain FexP and Mn0.3Cd0.7Fe with a S molar ratio of 10 mol%xP/Mn0.3Cd0.7S composite photocatalyst marked as 10 mol% FexP/Mn0.3Cd0.7S。
And (3) performance testing: fe obtained in example 2 under irradiation of 300W Xe lamp at a reaction temperature of 15 ℃xP/Mn0.3Cd0.7The hydrogen production rate of the S composite photocatalyst is 20.90mmol g-1h-1As shown in fig. 1.
Example 3
FexP/Mn0.3Cd0.7The preparation method of the S composite photocatalyst comprises the following steps:
(1) 500mg of Mn0.3Cd0.7Adding the S catalyst into 50mL of ethanolamine solvent, uniformly stirring, and then uniformly dispersing by ultrasonic to obtain a suspension;
(2) 213mg of FeCl were added under stirring3·6H2Adding O and 98mg of pretreated red phosphorus into the suspension liquid obtained in the step (1), uniformly stirring, and uniformly dispersing by ultrasonic waves to form uniformly dispersed suspension liquid; transferring and sealing in a reaction kettle equipped with a polytetrafluoroethylene inner container, heating to 180 ℃ for solvothermal reaction for 12h, cooling to room temperature, filtering to obtain precipitate, washing, and drying to obtain the final productFexP and Mn0.3Cd0.7Fe with a molar ratio of S of 20 mol%xP/Mn0.3Cd0.7S composite photocatalyst, marked as 20 mol% FexP/Mn0.3Cd0.7S。
And (3) performance testing: fe obtained in example 3 under irradiation of 300W Xe lamp at a reaction temperature of 15 ℃xP/Mn0.3Cd0.7The hydrogen production rate of the S composite photocatalyst is 31.42mmol g-1h-1As shown in fig. 1.
Example 4
FexP/Mn0.3Cd0.7The preparation method of the S composite photocatalyst comprises the following steps:
(1) 500mg of Mn0.3Cd0.7Adding the S catalyst into 50mL of ethanolamine solvent, uniformly stirring, and then uniformly dispersing by ultrasonic to obtain a suspension;
(2) 319mg of FeCl were added under stirring3·6H2Adding O and 147mg of pretreated red phosphorus into the suspension liquid obtained in the step (1), uniformly stirring, and uniformly ultrasonically dispersing to form uniformly dispersed suspension liquid; then transferring and sealing the mixture in a reaction kettle provided with a polytetrafluoroethylene inner container, heating to 180 ℃ for solvothermal reaction for 12 hours, cooling to room temperature, filtering to obtain precipitate, washing and drying to obtain FexP and Mn0.3Cd0.7Fe with a molar ratio of S of 30 mol%xP/Mn0.3Cd0.7S composite photocatalyst marked as 30 mol% FexP/Mn0.3Cd0.7S。
And (3) performance testing: fe obtained in example 4 under irradiation of 300W Xe lamp at a reaction temperature of 15 ℃xP/Mn0.3Cd0.7The hydrogen production rate of the S composite photocatalyst is 23.44mmol g-1h-1As shown in fig. 1.
Example 5
FexP/Mn0.3Cd0.7The preparation method of the S composite photocatalyst comprises the following steps:
(1) 500mg of Mn0.3Cd0.7S catalystAdding the mixture into 50mL of ethanolamine solvent, uniformly stirring, and then uniformly dispersing by ultrasonic to obtain a suspension;
(2) 425mg of FeCl are added under stirring3·6H2Adding O and 195mg of pretreated red phosphorus into the suspension liquid in the step (1), uniformly stirring, and uniformly dispersing by ultrasonic to form uniformly dispersed suspension liquid; then transferring and sealing the mixture in a reaction kettle provided with a polytetrafluoroethylene inner container, heating to 180 ℃ for solvothermal reaction for 12 hours, cooling to room temperature, filtering to obtain precipitate, washing and drying to obtain FexP and Mn0.3Cd0.7Fe with a S molar ratio of 40 mol%xP/Mn0.3Cd0.7S composite photocatalyst, marked as 40 mol% FexP/Mn0.3Cd0.7S。
And (3) performance testing: fe obtained in example 5 under irradiation of 300W Xe lamp at a reaction temperature of 15 ℃xP/Mn0.3Cd0.7The hydrogen production rate of the S composite photocatalyst is 21.79mmol g-1h-1As shown in fig. 1.
Example 6
FexP/Mn0.3Cd0.7The preparation method of the S composite photocatalyst comprises the following steps:
(1) 500mg of Mn0.3Cd0.7Adding the S catalyst into 40mL of ethanolamine solvent, uniformly stirring, and then uniformly dispersing by ultrasonic to obtain a suspension;
(2) 213mg of FeCl were added under stirring3·6H2Adding O and 98mg of pretreated red phosphorus into the suspension liquid obtained in the step (1), uniformly stirring, and uniformly ultrasonically dispersing to form uniformly dispersed suspension liquid; then transferring and sealing the mixture in a reaction kettle with a polytetrafluoroethylene inner container, heating to 170 ℃ for solvothermal reaction for 8 hours, cooling to room temperature, filtering to obtain precipitate, washing and drying to obtain the FexP/Mn0.3Cd0.7And (S) a composite photocatalyst. Fe obtained in example 6xP/Mn0.3Cd0.7In the S composite photocatalyst, Fe and Mn0.3Cd0.7The molar ratio of S was 20 mol%.
And (3) performance testing: fe obtained in example 6 under irradiation of 300W Xe lamp at a reaction temperature of 15 ℃xP/Mn0.3Cd0.7The S composite photocatalyst also shows a good hydrogen production rate, and can be seen in figure 1.
Example 7
FexP/Mn0.3Cd0.7The preparation method of the S composite photocatalyst comprises the following steps:
(1) 500mg of Mn0.3Cd0.7Adding the S catalyst into 60mL of ethanolamine solvent, uniformly stirring, and then uniformly dispersing by ultrasonic to obtain a suspension;
(2) 213mg of FeCl were added under stirring3·6H2Adding O and 98mg of pretreated red phosphorus into the suspension liquid obtained in the step (1), uniformly stirring, and uniformly ultrasonically dispersing to form uniformly dispersed suspension liquid; then transferring and sealing the mixture in a reaction kettle with a polytetrafluoroethylene inner container, heating to 190 ℃ for solvothermal reaction for 16 hours, cooling to room temperature, filtering to obtain precipitate, washing and drying to obtain the FexP/Mn0.3Cd0.7And (S) a composite photocatalyst. Fe obtained in example 7xP/Mn0.3Cd0.7In the S composite photocatalyst, Fe and Mn0.3Cd0.7The molar ratio of S was 20 mol%.
And (3) performance testing: fe obtained in example 7 under irradiation of 300W Xe lamp at a reaction temperature of 15 ℃xP/Mn0.3Cd0.7The S composite photocatalyst also shows a good hydrogen production rate, and can be seen in figure 1.
Comparative example 1
Cocatalyst FexThe preparation of P comprises the following steps:
550mg of FeCl is taken3·6H2O, placing 250mg of pretreated red phosphorus in an inner container of a reaction kettle, adding 50mL of ethanolamine, uniformly stirring, and uniformly dispersing by ultrasonic to form uniformly dispersed suspension. Transferring and sealing in a reaction kettle with a polytetrafluoroethylene inner container, heating to 180 deg.C for solvent-thermal reaction for 12 hr, and coolingCooling to room temperature, washing and drying to obtain the catalyst promoter FexP。
And (3) performance testing: the cocatalyst Fe prepared in comparative example 1 is irradiated by a 300W Xe lamp at a reaction temperature of 15 DEG CxThe hydrogen production rate of P is 0mmol g-1h-1As shown in fig. 1.
Comparative example 2
Mn0.3Cd0.7The preparation of the S catalyst comprises the following steps:
taking 6mmol Mn (OAc)2·4H2O,14mmol Cd(OAc)2·2H2O dissolved in 30mL H2And (3) mixing O and 30mL of anhydrous Ethylenediamine (EDA) solution, uniformly stirring, and uniformly dispersing by ultrasonic to form uniformly dispersed suspension. Transferring and sealing in a reaction kettle equipped with a polytetrafluoroethylene inner container, heating at 200 deg.C for 24h, cooling to room temperature, filtering to obtain precipitate, washing, and drying to obtain yellow powder, i.e. Mn0.3Cd0.7And (4) an S catalyst.
And (3) performance testing: mn from comparative example 2 under irradiation of 300W Xe lamp at a reaction temperature of 15 ℃0.3Cd0.7The hydrogen production rate of the S catalyst is 0.041mmol g-1h-1As shown in fig. 1.
Comparative example 3
1wt％Pt/Mn0.3Cd0.7The preparation method of the S composite photocatalyst comprises the following steps:
taking 10mg of Mn0.3Cd0.7S is added to the reactor, 100mL of aqueous lactic acid (20 vol% concentration) is added, and 0.13mL of H is added2PtCl66H2O solution (concentration 2g L)-1) Stirring uniformly, and irradiating by ultraviolet light to obtain the 1 wt% Pt/Mn0.3Cd0.7And (S) suspension of the composite photocatalyst.
And (3) performance testing: the 1 wt% Pt/Mn obtained in comparative example 3 was reacted at a reaction temperature of 15 ℃ under irradiation of a 300W Xe lamp0.3Cd0.7The hydrogen production rate of the S composite photocatalyst is 9.62mmol g-1h-1As shown in fig. 1.
Comparative example 4
FexP/Mn0.3Cd0.7The preparation method of the S-M composite photocatalyst comprises the following steps:
(1) cocatalyst FexPreparation of P: 550mg of FeCl is taken3·6H2O, placing 250mg of pretreated red phosphorus in an inner container of a reaction kettle, adding 50mL of ethanolamine, uniformly stirring, and uniformly dispersing by ultrasonic to form uniformly dispersed suspension. Then transferring and sealing the mixture in a reaction kettle provided with a polytetrafluoroethylene inner container, heating to 180 ℃ for solvothermal reaction for 12 hours, cooling to room temperature, washing and drying to obtain the cocatalyst FexP。
(2) Taking 200mg of the Mn0.3Cd0.7S catalyst, 45mg of cocatalyst Fe prepared in step (1)xP is mixed and grinded to be mixed evenly to obtain FexP and Mn0.3Cd0.7Mechanical mixture of S, labelled FexP/Mn0.3Cd0.7S-M, wherein FexThe loading of P was 20 mol%.
And (3) performance testing: fe obtained in comparative example 4 under irradiation of 300W Xe lamp at a reaction temperature of 15 ℃xP/Mn0.3Cd0.7The hydrogen production rate of the S-M composite photocatalyst is 18.36mmol g-1h-1As shown in fig. 1.
FIG. 1 is a graph showing the rate of hydrogen production by photocatalytic decomposition of the catalysts prepared in examples and comparative examples. As can be seen from FIG. 1, Fe was supportedxP is then Mn0.3Cd0.7The hydrogen production rate of S is obviously improved.
Fig. 2 is an XRD pattern of the catalysts prepared in examples and comparative examples. 5 mol% Fe in FIG. 2xP/Mn0.3Cd0.7S represents Fe obtained in example 1xP/Mn0.3Cd0.7S composite photocatalyst, 10 mol% FexP/Mn0.3Cd0.7S represents Fe obtained in example 2xP/Mn0.3Cd0.7S composite photocatalyst, 20 mol% FexP/Mn0.3Cd0.7S represents Fe obtained in example 3xP/Mn0.3Cd0.7S composite photocatalyst, 30 mol% FexP/Mn0.3Cd0.7S represents Fe obtained in example 4xP/Mn0.3Cd0.7S composite photocatalyst, 40 mol% FexP/Mn0.3Cd0.7S represents Fe obtained in example 5xP/Mn0.3Cd0.7S composite photocatalyst, Mn0.3Cd0.7S represents Mn as obtained in comparative example 20.3Cd0.7And (4) an S catalyst. As can be seen from FIG. 2, FexThe loading of P did not change Mn0.3Cd0.7And the crystal phase structure of S. Furthermore pure FexNo characteristic peak appears in XRD pattern of P, which indicates that synthesized FexP is an amorphous structure.
FIG. 3 shows Mn obtained in comparative example 20.3Cd0.7SEM image of S catalyst. As can be seen from FIG. 3, Mn0.3Cd0.7S shows a good rod-like structure and is uniform in appearance. FIG. 4 shows Fe obtained in example 3xP/Mn0.3Cd0.7S composite photocatalyst (20 mol% Fe)xP/Mn0.3Cd0.7S) TEM images. As can be seen from FIG. 4, FexP/Mn0.3Cd0.7The S composite photocatalyst consists of nano rods and nano particles, and the nano particles are dispersed around the rod-shaped structure to represent FexP is loaded on Mn0.3Cd0.7On the S catalyst. Fe obtained in other examplesxP/Mn0.3Cd0.7The S composite photocatalyst also consists of nano rods and nano particles, and FexP is loaded on Mn0.3Cd0.7On the S catalyst, see FIG. 3.
FIG. 5 shows Fe obtained in example 3xP/Mn0.3Cd0.7S composite photocatalyst (20 mol% Fe)xP/Mn0.3Cd0.7S) HRTEM image. As can be observed from FIG. 5, 0.32nm corresponds to Mn0.3Cd0.7The (011) crystal plane of S. Fe is not found in the figurexThe characteristic interplanar spacing of P can be seen from the figure: mn0.3Cd0.7The surface of the S nano rod is covered by some substances in an amorphous state, so that Fe can be judged by combining an XRD patternxP is an amorphous structure.
FIG. 6 is a graph showing the hydrogen production stability of the catalysts prepared in comparative example 2 and example 3. It can be seen from the figure that: after three cycles, Mn0.3Cd0.7The hydrogen production rate of S is gradually reduced and is only 35.27% of the initial circulation; for 20 mol% FexP/Mn0.3Cd0.7S, after 24 hours, the hydrogen production rate is almost unchanged and still can reach 31.37mmol g-1h-1The hydrogen production rate is 97.09% of the highest rate, which indicates that the Fe is loadedxP is then Mn0.3Cd0.7The hydrogen production activity and stability of S are rapidly improved.
FIG. 7 is a spectrum of S2p in XPS scans of catalysts prepared in comparative example 2 and example 3; with Mn0.3Cd0.7S2p spectrum of S, 20 mol% FexP/Mn0.3Cd0.7A new characteristic peak at 161.7eV appears in S2p of S (catalyst prepared in example 3), due to the interaction of part of S with Fe, forming an Fe-S bond.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. FexP/Mn0.3Cd0.7The preparation method of the S composite photocatalyst is characterized by comprising the following steps:
(1) adding Mn0.3Cd0.7Adding the S catalyst into an organic solvent, uniformly stirring, and uniformly dispersing by ultrasonic to obtain a suspension;
(2) FeCl is stirred3·6H2Adding O and the pretreated red phosphorus into the suspension liquid obtained in the step (1), uniformly stirring, uniformly dispersing by ultrasonic waves, heating to perform solvothermal reaction, filtering to obtain a precipitate, washing, and drying to obtain the FexP/Mn0.3Cd0.7And (S) a composite photocatalyst.
2. According toFe as claimed in claim 1xP/Mn0.3Cd0.7The preparation method of the S composite photocatalyst is characterized in that the organic solvent in the step (1) is one of ethanolamine and ethylenediamine.
3. Fe of claim 1xP/Mn0.3Cd0.7The preparation method of the S composite photocatalyst is characterized in that the organic solvent and Mn in the step (1)0.3Cd0.7The volume mass ratio of the S catalyst is 40-60: 500 mL/mg.
4. Fe of claim 1xP/Mn0.3Cd0.7The preparation method of the S composite photocatalyst is characterized in that the red phosphorus pretreated in the step (2) is ground and pretreated, and the particle size of the pretreated red phosphorus is 1-3 mu m.
5. Fe of claim 1xP/Mn0.3Cd0.7The preparation method of the S composite photocatalyst is characterized in that FeCl in the step (2)3·6H2The molar ratio of O to the pretreated red phosphorus is (0.5-1.5) to (3-5).
6. Fe of claim 1xP/Mn0.3Cd0.7The preparation method of the S composite photocatalyst is characterized in that the temperature of the solvothermal reaction in the step (2) is 170-190 ℃.
7. Fe of claim 1xP/Mn0.3Cd0.7The preparation method of the S composite photocatalyst is characterized in that the solvothermal reaction time in the step (2) is 8-16 h.
8. Fe of claim 1xP/Mn0.3Cd0.7The preparation method of the S composite photocatalyst is characterized in that FeCl in the step (2)3·6H2The mass-volume ratio of O to the organic solvent in the step (1) is (0.05-0).50):(40-60)g/mL。
9. Fe produced by the production method according to any one of claims 1 to 8xP/Mn0.3Cd0.7The S composite photocatalyst is characterized by containing Mn0.3Cd0.7S is a main catalyst, FexP is a cocatalyst, FexThe amount of P supported is 5 to 40 mol%.
10. Fe of claim 9xP/Mn0.3Cd0.7The S composite photocatalyst is applied to the reaction of decomposing water into hydrogen by photocatalysis.
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