[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

CN118454695B - Heterojunction composite material for catalyzing hydrogen evolution and preparation method and application thereof - Google Patents

Heterojunction composite material for catalyzing hydrogen evolution and preparation method and application thereof Download PDF

Info

Publication number
CN118454695B
CN118454695B CN202410920975.XA CN202410920975A CN118454695B CN 118454695 B CN118454695 B CN 118454695B CN 202410920975 A CN202410920975 A CN 202410920975A CN 118454695 B CN118454695 B CN 118454695B
Authority
CN
China
Prior art keywords
hydrogen evolution
heterojunction composite
stirring
hydrothermal reaction
comoo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202410920975.XA
Other languages
Chinese (zh)
Other versions
CN118454695A (en
Inventor
艾伟
薛丹
段旭
雷楷
师旭军
周晓斌
祁学玲
宋海东
李有凡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CSCEC Aecom Consultant Co Ltd
Original Assignee
CSCEC Aecom Consultant Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CSCEC Aecom Consultant Co Ltd filed Critical CSCEC Aecom Consultant Co Ltd
Priority to CN202410920975.XA priority Critical patent/CN118454695B/en
Publication of CN118454695A publication Critical patent/CN118454695A/en
Application granted granted Critical
Publication of CN118454695B publication Critical patent/CN118454695B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/54—Bars or plates
    • 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
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a heterojunction composite material for catalyzing hydrogen evolution, and a preparation method and application thereof, and belongs to the field of photocatalysts. The preparation method comprises the following steps: dissolving Bi (NO 3)3·5H2 O and thiourea in ultrapure water, adding lithium hydroxide monohydrate, stirring, blackening the solution, performing hydrothermal reaction, cooling to room temperature after the reaction is finished, washing and drying to obtain Bi 2O2 S, respectively dissolving cobalt nitrate hexahydrate and sodium molybdate dihydrate in deionized water, mixing the two solutions after stirring, adding Bi 2O2 S into the mixed solution, stirring again, performing hydrothermal reaction on the stirred mixed solution, cooling the reactant, filtering, washing and drying to obtain the product Bi 2O2 S/CoMoO.

Description

Heterojunction composite material for catalyzing hydrogen evolution and preparation method and application thereof
Technical Field
The invention belongs to the field of photocatalysts, and particularly relates to a heterojunction composite material for catalyzing hydrogen evolution, and a preparation method and application thereof.
Background
With the rapid development of global science and technology, many industries have a close and indiscriminate relationship with the energy industry. In recent years, traditional energy sources such as coal, petroleum and the like, along with over-exploitation, undoubtedly lead to energy crisis and greenhouse effect. In order to effectively solve the problems of environmental pollution and energy exhaustion, it is urgent to explore new energy sources to replace the traditional energy sources. The new energy includes wind energy, biomass energy, geothermal energy and hydrogen energy. Hydrogen energy stands out from a plurality of new energy sources because of the advantages of cleanness, low pollution and the like.
The use of photocatalytic technology to convert solar energy into hydrogen energy is an ideal way to address non-renewable energy sources. However, the photocatalytic efficiency of single-phase photocatalysts remains undesirable, mainly due to slow photo-induced charge separation and migration kinetics. In order to promote the photoactivity of a single photocatalyst, many modification strategies, such as the construction of heterojunctions, defect engineering, energy band modulation, and promoter modification, have been extensively studied. Among them, the construction of heterojunction has proven to be a promising approach, which not only captures electrons from the semiconductor to suppress charge recombination, but also provides sufficient active sites for accelerating the catalytic reaction rate.
Bismuth oxide catalysts have been widely studied in terms of solving energy and environmental problems. Bismuth oxysulfide (Bi 2O2 S), which has a crystal structure similar to bismuth oxyhalide, is a typical layered semiconductor containing [ Bi 2O2]2+ ]. Typically, the Bi 2O2 S crystal structure consists of two [ Bi 2O2]2+ layers, with a row of S 2- in between, which can narrow the bandgap (eg=1.5 eV), maintaining the excellent stability of Bi 2O2 S. In addition, bi 2O2 S has the advantages of fast photoelectric response speed and high charge transfer efficiency under the irradiation of visible light, so that it is commonly used as a solar cell material. However, rapid recombination of the photo-carriers limits the photocatalytic performance of Bi 2O2 S.
The high quality and low cost are another important factor in consideration of the photocatalytic material. The content of Co element on the earth is very rich, and CoMoO 4 is hopeful to become a catalyst for replacing noble metals.
Disclosure of Invention
The invention aims to provide a preparation method of a heterojunction composite material for catalyzing hydrogen evolution, so as to obtain a visible light catalytic nano material which has the advantages of simple preparation method, higher visible light utilization rate and charge separation efficiency, better stability, reusability and capability of realizing photocatalytic reduction hydrogen production.
It is another object of the present invention to provide a heterojunction composite for catalyzing hydrogen evolution.
A third object of the present invention is to provide the use of a heterojunction composite for the catalytic hydrogen evolution.
The technical scheme of the invention is as follows:
(one)
The preparation method of the heterojunction composite material for catalyzing hydrogen evolution comprises the following steps:
A. firstly, dissolving Bi (NO 3)3·5H2 O and thiourea into ultrapure water, then adding a proper amount of lithium hydroxide monohydrate, vigorously stirring to turn the color of the solution black, then transferring the solution into a polytetrafluoroethylene lining hydrothermal reaction kettle for hydrothermal reaction, cooling to room temperature after the reaction is finished, washing with deionized water, and drying to obtain Bi 2O2 S;
B. Respectively dissolving cobalt nitrate hexahydrate and sodium molybdate dihydrate in deionized water, stirring, mixing the two solutions, adding a proper amount of Bi 2O2 S into the mixed solution, stirring vigorously, slowly transferring the stirred mixed solution into a polytetrafluoroethylene lining hydrothermal reaction kettle for hydrothermal reaction, cooling reactants, filtering, washing with deionized water and absolute ethyl alcohol, and drying to obtain a product Bi 2O2S/CoMoO4, namely the heterojunction composite material for catalyzing hydrogen evolution.
As a further improvement of the invention, in step A, bi (NO 3)3·5H2 O, thiourea, lithium hydroxide monohydrate in a molar ratio of 4:3:250-300.
As a further improvement of the invention, in the step A, the stirring speed is 600-800 r/min, and the stirring time is 30-60 min; in the step B, the stirring speed is 600-800 r/min, and the stirring time is 30-60 min.
As a further improvement of the invention, in step A, the temperature of the hydrothermal reaction is 180-220 ℃ and the time of the hydrothermal reaction is 48-72 h.
As a further improvement of the invention, in the step A, the drying temperature is 60-80 ℃ and the drying time is 12-24 h.
As a further improvement of the invention, in the step B, the mass ratio of the cobalt nitrate hexahydrate, the sodium molybdate dihydrate and the Bi 2O2 S is 1:0.8-1.0:1.0-1.2.
As a further improvement of the invention, in step B, the temperature of the hydrothermal reaction is 160-200 ℃ and the time of the hydrothermal reaction is 10-14 h.
As a further improvement of the invention, in the step B, the drying temperature is 60-80 ℃ and the drying time is 8-12h.
(II)
A heterojunction composite material for catalyzing hydrogen evolution is prepared by the preparation method of the heterojunction composite material for catalyzing hydrogen evolution.
(III)
The heterojunction composite material for catalyzing hydrogen evolution is used for photolysis of water to hydrogen.
The beneficial effects of the invention are as follows: according to the invention, bi 2O2 S and CoMoO 4 are compounded by constructing a heterojunction, so that a photocatalysis nano composite material which has stronger carrier separation capability, a light absorption range covers the full visible spectrum and has higher hydrogen production activity, namely Bi 2O2S/CoMoO4.CoMoO4 is a typical photocatalysis candidate material, but in the visible light range, the light absorption range of 400-480 nm and 650-800 nm wave bands is narrow, and the energy conversion efficiency is low; bi 2O2 S is a photocatalytic material that responds in the near infrared region, but the single material has low charge separation efficiency. Bi 2O2 S and CoMoO 4 are compounded, the separation of photo-generated electron-hole pairs of the Bi 2O2S/CoMoO4 composite photocatalytic nanomaterial at a heterogeneous interface is successfully realized, the problem of electron-hole recombination in a band gap of the single CoMoO 4 catalytic nanomaterial is avoided, and the light absorption complementation is formed between Bi 2O2 S and a visible light region of the CoMoO 4. The heterojunction is constructed to more effectively enhance the heterojunction interface charge separation and electron transfer, and the photocatalysis hydrogen evolution efficiency is greatly improved. Finally, the Bi 2O2S/CoMoO4 photocatalytic system realizes considerable hydrogen production rate under the anoxic condition, and has the characteristics of good stability and reusability.
Drawings
FIG. 1 is a scanning electron microscope image of Bi 2O2S/CoMoO4 prepared in example 1 of the present invention;
FIG. 2 is a graph showing the diffuse ultraviolet reflectance spectrum of Bi 2O2S、CoMoO4、Bi2O2S/CoMoO4 prepared in example 1 and comparative examples 1 and 2;
FIG. 3 is a Fourier diffuse reflection infrared spectrum of Bi 2O2S,CoMoO4,Bi2O2S/CoMoO4 prepared in example 1 and comparative examples 1 and 2 of the present invention;
FIG. 4 is a graph showing the comparison of the performance of the Bi 2O2S,CoMoO4,Bi2O2S/CoMoO4 prepared in example 1 and comparative examples 1 and 2 in the visible light catalytic decomposition of hydrogen production;
Fig. 5 is a graph showing the reusability of Bi 2O2S/CoMoO4 prepared in example 1 in the visible light catalytic decomposition of hydrogen produced in water.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and the accompanying drawings.
Example 1,
The preparation method of the heterojunction composite material for catalyzing hydrogen evolution comprises the following steps:
A. 4mmol Bi (NO 3)3·5H2 O and 3mmol thiourea are dissolved in ultrapure water, then 12g lithium hydroxide monohydrate is added, 600 r/min is vigorously stirred for 30 min until the color of the solution turns black, then the solution is transferred into a polytetrafluoroethylene lining hydrothermal reaction kettle for hydrothermal reaction, heating is carried out at 220 ℃ for 48 hours, after the reaction is finished, cooling to room temperature, washing is carried out by deionized water, and drying is carried out at 60 ℃ in an oven for 24h to obtain Bi 2O2 S.
B. respectively dissolving 0.873 g cobalt nitrate hexahydrate and 0.725 g sodium molybdate dihydrate in 30 mL deionized water, carrying out ultrasonic treatment on the solution for 5min, stirring the solution for 5min, and mixing the two solutions to form light red; meanwhile, 0.873 g Bi 2O2 S is added into the mixed solution, and then 600 r/min is vigorously stirred for 30 min; then slowly transferring the stirred mixed solution into a polytetrafluoroethylene lining hydrothermal reaction kettle for hydrothermal reaction, wherein the reaction time is 12 hours, and the reaction temperature is set to 180 ℃; and (3) filtering after the reactant is cooled, washing 3 times by deionized water, washing 6 times by absolute ethyl alcohol, then placing the sample into an oven, setting the temperature to 80 ℃ and the time to 8 hours, and drying to obtain a product Bi 2O2S/CoMoO4, namely the heterojunction composite material for catalyzing and separating hydrogen.
Fig. 1 is a scanning electron microscope image of Bi 2O2S/CoMoO4 prepared in this example. As shown in fig. 1, the Bi 2O2S/CoMoO4 composite photocatalytic nanomaterial is a heterogeneous nanosheet and nanorod composite structure.
EXAMPLE 2,
The preparation method of the heterojunction composite material for catalyzing hydrogen evolution comprises the following steps:
A. 4 mmol Bi (NO 3)3·5H2 O and 3 mmol thiourea are dissolved in ultrapure water, then 12.5 g lithium hydroxide monohydrate is added, the solution is vigorously stirred for 30 min at 800 r/min until the color of the solution turns black, then the solution is transferred into a polytetrafluoroethylene lining hydrothermal reaction kettle for hydrothermal reaction, heating is carried out at 180 ℃ for 72 hours, cooling to room temperature after the reaction is finished, washing by deionized water, and drying 12 h in an oven at 80 ℃ to obtain Bi 2O2 S.
B. Respectively dissolving 1.0 g cobalt nitrate hexahydrate and 0.8 g sodium molybdate dihydrate in 30 mL deionized water, carrying out ultrasonic treatment on the mixture for 5min, stirring the mixture for 5min, and mixing the two solutions to form light red; meanwhile, adding 1.0 g Bi 2O2 S into the mixed solution, and then vigorously stirring for 30min at 800 r/min; then slowly transferring the stirred mixed solution into a polytetrafluoroethylene lining hydrothermal reaction kettle for hydrothermal reaction, wherein the reaction time is 14 hours, and the reaction temperature is set to 160 ℃; and (3) filtering after the reactant is cooled, washing for 6 times by using deionized water, washing for 3 times by using absolute ethyl alcohol, then placing the sample into an oven, setting the temperature to 80 ℃ and the time to 8 hours, and drying to obtain a product Bi 2O2S/CoMoO4, namely the heterojunction composite material for catalyzing and separating hydrogen.
EXAMPLE 3,
The preparation method of the heterojunction composite material for catalyzing hydrogen evolution comprises the following steps:
A. 4mmol Bi (NO 3)3·5H2 O and 3mmol thiourea are dissolved in ultrapure water, then 10.5g of lithium hydroxide monohydrate is added, and the mixture is vigorously stirred for 60 min at 600 r/min until the color of the solution turns black, then the mixture is transferred into a polytetrafluoroethylene lining hydrothermal reaction kettle for hydrothermal reaction, heated at 200 ℃ for 48 hours, cooled to room temperature after the reaction is finished, washed by deionized water, and dried for 24 h at 60 ℃ in an oven to obtain Bi 2O2 S.
B. Respectively dissolving 1.0 g cobalt nitrate hexahydrate and 1.0 g sodium molybdate dihydrate in 30 mL deionized water, carrying out ultrasonic treatment on the mixture for 10min, stirring the mixture for 10min, and mixing the two solutions to form light red; meanwhile, 1.2 g Bi 2O2 S is added into the mixed solution, and then 600 r/min is vigorously stirred for 60 min; then slowly transferring the stirred mixed solution into a polytetrafluoroethylene lining hydrothermal reaction kettle for hydrothermal reaction, wherein the reaction time is 14 hours, and the reaction temperature is set to 160 ℃; and (3) filtering after the reactant is cooled, washing for 6 times by using deionized water, washing for 6 times by using absolute ethyl alcohol, then placing a sample into an oven, setting the temperature to 60 ℃ and the time to 12 hours, and drying to obtain a product Bi 2O2S/CoMoO4, namely the heterojunction composite material for catalyzing and separating hydrogen.
Comparative example 1,
Preparation of Bi 2O2 S: 4mmol Bi (NO 3)3·5H2 O and 3mmol thiourea are dissolved in ultrapure water, then 11 g lithium hydroxide monohydrate is added, and 800 r/min is vigorously stirred for 30 min until the color of the solution turns black, then the solution is transferred into a polytetrafluoroethylene lining hydrothermal reaction kettle for hydrothermal reaction, heating is carried out at 200 ℃ for 72 hours, after the reaction is finished, cooling to room temperature, washing is carried out by deionized water, and 12 h is dried in an oven at 80 ℃ to obtain Bi 2O2 S.
Comparative example 2,
Preparation of CoMoO 4: respectively dissolving 1.0 g cobalt nitrate hexahydrate and 0.8 g sodium molybdate dihydrate in 30 mL deionized water, carrying out ultrasonic treatment on the mixture for 5min, stirring the mixture for 5min, and mixing the two solutions to form light red; slowly transferring the mixed solution into a polytetrafluoroethylene lining hydrothermal reaction kettle for hydrothermal reaction, wherein the reaction time is 12 hours, and the reaction temperature is set to 180 ℃; after the reactants are cooled, filtering, washing with deionized water for 3 times, washing with absolute ethyl alcohol for 3 times, then placing the sample into an oven, setting the temperature to 80 ℃ and the time to 8 hours, and drying to obtain the product CoMoO 4.
Evaluation of Hydrogen production Performance by photocatalysis
The photocatalytic hydrogen production performance was evaluated for example 1 and comparative examples 1 and 2 as follows:
The photocatalytic hydrogen production experiments were performed in a 400 ml double-wall sealed quartz beaker (PQ 256, beijing pofiy technologies, china) at room temperature and atmospheric pressure. The light source was a 300W xenon lamp (lambda > 420 nm) with an average light intensity of 200 mW/cm 2. In each test, 50 mg photocatalyst was dispersed in 100mL aqueous solution containing 10 mL Triethanolamine (TEOA) sacrificial agent. By in situ photo-deposition of chloroplatinic acid (H 2PtCl6), 3% by weight of platinum was deposited on the catalyst surface. TEOA acts as a hole sacrificial agent, alleviating the recombination of photogenerated electron-hole pairs, while deposited Pt acts as a promoter, promoting interfacial electron transfer. Before irradiation, N 2 was blown into the suspension for 0.5 hours to vent the air from the suspension and ensure the anaerobic state of the reactor. In the photocatalytic hydrogen production process, 1.0 mL gas was intermittently sampled with a sampling needle and detected by gas chromatography (Agilent 6890n, ar as carrier gas, TCD detector).
FIG. 2 is a graph showing the diffuse ultraviolet reflectance spectrum of Bi 2O2S、CoMoO4、Bi2O2S/CoMoO4 prepared in example 1 and comparative examples 1 and 2 of the present invention. It can be seen that the light absorption of both single Bi 2O2 S and CoMoO 4 cover the full visible absorption spectrum, but that the light absorption of CoMoO 4 material is significantly reduced in the 400-500 nm and 650-800 nm bands, meaning that the single CoMoO 4 material is not effective in absorbing visible light. After the two materials are compounded, the light absorption of the Bi 2O2S/CoMoO4 material covers the whole full visible spectrum, which indicates that the light trapping efficiency is improved.
Fig. 3 is a fourier diffuse reflection infrared spectrum of Bi 2O2S,CoMoO4,Bi2O2S/CoMoO4 prepared in example 1 and comparative examples 1 and 2 of the present invention. To study the composition and structure of the synthesized samples FTIR analysis was used, as shown in fig. 3. For Bi 2O2 S, the specific fingerprint at wavenumber 1053 cm -1 corresponds to Bi-S stretching vibrations, symmetrical stretching and asymmetrical stretching of the S-O double bond were observed at 1164 and 1357 cm -1, respectively, and the bands at 3466 and 3676 cm -1 are due to stretching vibrations of the structural and free hydroxyl groups. The occurrence of the peak for CoMoO 4,945 cm-1 indicates the presence of a limited mo=o double bond in the Co-Mo bond, and the band at 665 cm -1 shows the extensional vibration mode of the Mo-O single bond. It is worth mentioning that the main typical absorption peaks of original Bi 2O2 S and CoMoO 4 are both present in Bi 2O2S/CoMoO4 samples, which further indicate successful synthesis of Bi 2O2S/CoMoO4 composite heterojunction photocatalysts.
FIG. 4 is a graph showing the comparison of the performance of the Bi 2O2S,CoMoO4,Bi2O2S/CoMoO4 prepared in example 1 and comparative examples 1 and 2 in the visible light catalytic decomposition of hydrogen by water. As shown in fig. 4, the hydrogen generating activity of Bi 2O2 S alone was 37.79 μmol/g/h and the photolytic water hydrogen generating activity of CoMoO 4 alone was 212.53 μmol/g/h, which suggests that Bi 2O2 S alone does not possess significant photocatalytic hydrogen generating activity, whereas CoMoO 4 alone does not possess significant photocatalytic hydrogen generating activity due to rapid carrier in situ recombination even with the proper energy level position. Finally, the hydrogen production rate of the constructed Bi 2O2S/CoMoO4 heterojunction composite material reaches 718.2 mu mol/g/h.
(II) continuous Hydrogen production experiment
After the first hydrogen production reaction of Bi 2O2S/CoMoO4 prepared in example 1 is completed, centrifugally washing the reacted solution, drying the recovered catalyst in a freeze dryer by 48: 48 h, and then putting the catalyst in a reactor again to perform the next hydrogen production experiment, wherein the rest reaction conditions are consistent with the first photocatalytic hydrogen production performance evaluation experiment setting program except materials; repeating the steps after the second reaction is finished, and carrying out three photolysis aquatic hydrogen experiments.
Fig. 5 is a graph showing the reusability of Bi 2O2S/CoMoO4 prepared in example 1 in the visible light catalytic decomposition of hydrogen produced in water. The hydrogen production activity in three continuous degradation experiments is above 600 mu mol/g/h, which shows that the hydrogen production activity of the Bi 2O2S/CoMoO4 photocatalytic nanomaterial is still good after three cycles.
The Bi 2O2S/CoMoO4 photocatalysis composite nano material with a certain hydrogen production activity is successfully prepared by compounding single Bi 2O2 S and CoMoO 4 through a synchronous hydrothermal method. The simple preparation method and excellent photocatalytic performance make the catalyst a potential material for hydrogen production. The prepared material has good stability, can be recycled, and has potential application value in the field of energy utilization.

Claims (10)

1. The preparation method of the heterojunction composite material for catalyzing hydrogen evolution is characterized by comprising the following steps of:
A. Firstly, dissolving Bi (NO 3)3·5H2 O and thiourea into ultrapure water, then adding lithium hydroxide monohydrate, stirring, blackening the color of the solution, then carrying out hydrothermal reaction, cooling to room temperature after the reaction is finished, and washing and drying to obtain Bi 2O2 S;
B. Respectively dissolving cobalt nitrate hexahydrate and sodium molybdate dihydrate in deionized water, stirring, mixing the two solutions, adding Bi 2O2 S into the mixed solution, stirring, carrying out hydrothermal reaction on the stirred mixed solution, cooling reactants, filtering, washing and drying to obtain a product Bi 2O2S/CoMoO4, namely the heterojunction composite material for catalyzing hydrogen evolution.
2. The method for preparing a heterojunction composite for catalyzing hydrogen evolution as claimed in claim 1, wherein: in step A, bi (NO 3)3·5H2 O, thiourea and lithium hydroxide monohydrate in a molar ratio of 4:3:250-300.
3. The method for preparing a heterojunction composite for catalyzing hydrogen evolution as claimed in claim 1, wherein: in the step A, the stirring speed is 600-800 r/min, and the stirring time is 30-60 min; in the step B, the stirring speed is 600-800 r/min, and the stirring time is 30-60 min.
4. The method for preparing a heterojunction composite for catalyzing hydrogen evolution as claimed in claim 1, wherein: in the step A, the temperature of the hydrothermal reaction is 180-220 ℃, and the time of the hydrothermal reaction is 48-72 h.
5. The method for preparing a heterojunction composite for catalyzing hydrogen evolution as claimed in claim 1, wherein: in the step A, the drying temperature is 60-80 ℃, and the drying time is 12-24 h.
6. The method for preparing a heterojunction composite for catalyzing hydrogen evolution as claimed in claim 1, wherein: in the step B, the mass ratio of the cobalt nitrate hexahydrate to the sodium molybdate dihydrate to the Bi 2O2 S is 1:0.8-1.0:1.0-1.2.
7. The method for preparing a heterojunction composite for catalyzing hydrogen evolution as claimed in claim 1, wherein: in the step B, the temperature of the hydrothermal reaction is 160-200 ℃, and the time of the hydrothermal reaction is 10-14 h.
8. The method for preparing a heterojunction composite for catalyzing hydrogen evolution as claimed in claim 1, wherein: in the step B, the drying temperature is 60-80 ℃ and the drying time is 8-12h.
9. A heterojunction composite for catalytic hydrogen evolution, prepared by a method of preparing a heterojunction composite for catalytic hydrogen evolution as claimed in any one of claims 1 to 8.
10. Use of a heterojunction composite for the catalytic hydrogen evolution as claimed in claim 9 for the photolytic hydrogen evolution.
CN202410920975.XA 2024-07-10 2024-07-10 Heterojunction composite material for catalyzing hydrogen evolution and preparation method and application thereof Active CN118454695B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202410920975.XA CN118454695B (en) 2024-07-10 2024-07-10 Heterojunction composite material for catalyzing hydrogen evolution and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202410920975.XA CN118454695B (en) 2024-07-10 2024-07-10 Heterojunction composite material for catalyzing hydrogen evolution and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN118454695A CN118454695A (en) 2024-08-09
CN118454695B true CN118454695B (en) 2024-09-03

Family

ID=92162284

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202410920975.XA Active CN118454695B (en) 2024-07-10 2024-07-10 Heterojunction composite material for catalyzing hydrogen evolution and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN118454695B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114147221A (en) * 2021-12-03 2022-03-08 中北大学 Preparation method of Ag @ CoMoO4 oxygen evolution electrocatalyst
LU503124B1 (en) * 2022-12-01 2023-06-05 Univ Yantai Preparation method and application of bismuth oxysulfide photocatalyst modified by surface iodination

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114147221A (en) * 2021-12-03 2022-03-08 中北大学 Preparation method of Ag @ CoMoO4 oxygen evolution electrocatalyst
LU503124B1 (en) * 2022-12-01 2023-06-05 Univ Yantai Preparation method and application of bismuth oxysulfide photocatalyst modified by surface iodination

Also Published As

Publication number Publication date
CN118454695A (en) 2024-08-09

Similar Documents

Publication Publication Date Title
CN111389442B (en) P-N heterojunction composite material loaded on surface of foamed nickel and preparation method and application thereof
CN110841622B (en) Controllable In preparation based on MOF template2O3Method for preparing @ ZnO nano heterojunction photocatalytic material
CN108067281B (en) Porous g-C3N4Photocatalyst and preparation method and application thereof
CN110624550B (en) In-situ carbon-coated copper-nickel alloy nanoparticle photocatalyst and preparation method and application thereof
CN114377708B (en) Bismuth oxide carbonate nano-sheet containing oxygen vacancy and preparation method and application thereof
CN108671955B (en) Composite catalyst for photolysis of aquatic hydrogen and preparation method thereof
CN113171780B (en) Molybdenum selenide/defect-rich sulfur-indium-zinc/cadmium selenide double-Z-shaped catalyst for photocatalytic water splitting hydrogen production
CN105709793A (en) Cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen doped graphene composite photocatalyst and preparation method and application thereof
CN113019459B (en) Titanium dioxide porphyrin-based covalent organic framework composite material and preparation method and application thereof
CN115069262B (en) Oxygen vacancy modified MoO 3-x /Fe-W 18 O 49 Photocatalyst, preparation thereof and application thereof in nitrogen fixation
CN111203231A (en) Indium zinc sulfide/bismuth vanadate composite material and preparation method and application thereof
CN116139867B (en) MOFs derived ZnO@CDs@Co 3 O 4 Composite photocatalyst, preparation method and application thereof
CN109046391A (en) A kind of composite material and preparation method and the application in visible photocatalysis aquatic products hydrogen
CN118454695B (en) Heterojunction composite material for catalyzing hydrogen evolution and preparation method and application thereof
CN111330566A (en) One-step method for preparing visible light response TiO2@BiVO4Core-shell structure mesoporous nanofiber photocatalytic material
CN116173987A (en) CdIn 2 S 4 /CeO 2 Heterojunction photocatalyst, preparation method and application thereof
CN113101946B (en) NiMoO4Base Z-type heterojunction photocatalyst and preparation and application thereof
CN115090318A (en) Preparation method and application of intermolecular heterojunction carbon nitride photocatalyst with high specific surface area
CN114618526A (en) Cadmium sulfide/platinum/sodium tantalate nanocube composite photocatalyst and preparation method and application thereof
CN112657516A (en) Direct Z-type photocatalyst and preparation method and application thereof
CN111530502A (en) Preparation method of ZnTe-Mo/Mg-MOF photocathode material
CN112958124B (en) Indium-doped molybdenum carbide nanoflower core-shell structure photocatalyst and preparation and application thereof
CN115920945B (en) Hydroxylated graphite phase carbon nitride photocatalyst and preparation method and application thereof
CN114618534B (en) Visible light responsive sulfur-doped bismuth telluride nanowire photocatalytic material and preparation method thereof
CN118268044B (en) Core-shell Cu grown on redox graphene in situ2O/Cu-MOF photo-thermal catalyst and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant