CN117019195A - g-C 3 N 4 /NiS/TiO 2 Preparation method of ternary composite photocatalytic material - Google Patents
g-C 3 N 4 /NiS/TiO 2 Preparation method of ternary composite photocatalytic material Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 59
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011206 ternary composite Substances 0.000 title claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
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- 239000002243 precursor Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
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- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 26
- 239000001257 hydrogen Substances 0.000 abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 24
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 3
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
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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
- B01J27/24—Nitrogen compounds
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J27/043—Sulfides with iron group metals or platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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Abstract
The invention discloses g-C 3 N 4 /NiS/TiO 2 The invention relates to a preparation method of a ternary composite photocatalytic material, belonging to the technical field of photocatalytic material preparation. The invention solves the problems of TiO 2 The light utilization rate is low, the photo-generated carrier recombination rate is high, and the technical problem of poor photo-catalytic hydrogen production performance is caused. The invention prepares the g-C by the synthesis of a calcination method, a sol-gel method and an alcohol thermal method 3 N 4 /NiS/TiO 2 The ternary photocatalytic material has the structure of uniformly distributed spherical TiO on carbon nitride nanometer sheet as base 2 In TiO 2 And NiS nano particles are attached on the surface. Selecting g-C 3 N 4 As a substrate, the specific surface area can be increased and the active sites can be increased. The direct coupling is subject to light absorptionInsufficient yield, slow oxidation-reduction reaction rate and the like. By constructing an indirect Z-shaped heterostructure, the charge transfer capability can be improved through a cocatalyst NiS, and the catalyst has longer service life of charge carriers and better photocatalytic activity. The method is to load the cocatalyst on the semiconductor, so that the active site can be enhanced, and simultaneously, the activation energy is reduced, the charge carriers are captured, and the recombination of photo-generated electrons and holes is inhibited to promote the oxidation-reduction reaction. NiS is a transition metal oxide and can replace expensive noble metal cocatalysts. At the same time, niS can also reduce g-C 3 N 4 And the charge recombination rate of the catalyst is improved. The photocatalytic material prepared by the invention has uniform microstructure, good photocatalytic hydrogen production activity, the hydrogen production amount for 4 hours is 45.49mmoL/g, and the hydrogen production rate is 11.37mmoL/g/h.
Description
Technical Field
The invention belongs to the field of photocatalytic material preparation, and in particular relates to g-C 3 N 4 /NiS/TiO 2 Preparation of ternary composite photocatalytic material and test of photocatalytic hydrogen production performance.
Background
The life and development of the modern society are not separated from the use of energy, and the excessive consumption of fossil energy such as coal, petroleum, natural gas and the like causes ever-increasing global energy crisis and ecological destruction, so that the requirement of environmental protection cannot be ignored. The key to solving these two problems is to explore new "green" energy sources to replace traditional fossil energy sources. Hydrogen (H) 2 ) As a clean energy source with high combustion value, high energy density and no byproducts, attention has recently been paid. It is expected that H will be in the near future 2 Will be a good substitute for fossil fuels. Among the numerous hydrogen production methods, the photocatalysis technology becomes a very promising hydrogen production method at present by virtue of energy conservation and environmental protection, and is considered as an effective strategy for solving the global energy problem. The influence of the semiconductor photocatalyst on the hydrogen production efficiency in the process of decomposing water into hydrogen by photocatalysis is important. The photocatalytic reaction process is mainly dependent on the following aspects: the absorption and utilization rate of sunlight, the separation and transfer efficiency of photo-generated carriers on the surface of the catalyst and the number of reactive sites on the surface of the catalyst. Large-scale production of H 2 Excellent photocatalyst is needed, and the photocatalyst meets the requirements of low cost, environmental protection, high efficiency and stability.
TiO 2 Photocatalysts are suitable for H due to low cost, light corrosion resistance + The advantages of strong reduction potential, strong oxidation-reduction capability, environmental friendliness, good chemical stability and the like are widely studied in the two fields of decomposing water to produce hydrogen and degrading pollutants, and play an important role in various photocatalysis and photoelectrocatalysis processes. TiO is well known 2 Mainly comprises three crystal forms of rutile, anatase and brookite. Different crystalline phases have different properties, anatase TiO 2 The average effective mass of the photogenerated carriers is lowest. Thus, anatase type TiO 2 The carrier in the catalyst has the fastest migration rate from the inside to the surface, the recombination rate is lower, and the service life of the carrier is obviously longer than that of rutile TiO 2 . Moreover, nano-scale anatase TiO 2 With the smallest surface energy, exhibiting the most stable state. However, anatase TiO 2 The utilization rate of sunlight and hydrogen production efficiency are greatly limited by the inherent defects of the solar energy, including wide forbidden band (3.2 eV), high recombination efficiency of photo-generated electron-hole pairs and slow surface hydrogen evolution reaction kinetics.
g-C 3 N 4 Is a metal-free semiconductor which is chemically stable and has a higher chemical property than TiO 2 Can ensure that electrons can go from g-C 3 N 4 To which the conduction band of (c) migrates. Second, carbon nitride exhibits a high reduction potential and titanium dioxide exhibits a high oxidation potential. Therefore, the photo-generated electrons having more aerobic ability remain on the conduction band of titanium oxide, and the photo-generated holes having more reducing ability remain on the valence band of carbon nitride, and do not migrate to other semiconductors. And both of these semiconductors have excellent photo-reduction resistance and photo-oxidation resistance. Thereby ensuring long-term stability.
g-C 3 N 4 The solar energy water heater has the most negative conduction band position and a medium band gap, can absorb sunlight with the wavelength less than 475nm, can decompose water in a photocatalytic manner under the irradiation of visible light, and is matched with an energy band structure required by water separation and hydrogen production. And g-C 3 N 4 Has good chemical stability, thermal stability and easy modification. Selecting g-C 3 N 4 As a substrate, the specific surface area and the active sites can be increasedAnd (5) a dot. However, direct coupling suffers from insufficient light absorption, slow redox reaction rate, and the like. Instead of direct coupling of the binary photocatalyst, an indirect Z-type heterostructure is chosen, which acts to increase the charge transfer capacity, and has a longer charge carrier lifetime and better photocatalytic activity, by means of promoters (e.g. platinum, silver, palladium, graphene, etc.). The method is to load the cocatalyst on the semiconductor, so that the active site can be enhanced, and simultaneously, the activation energy is reduced, the charge carriers are captured, and the recombination of photo-generated electrons and holes is inhibited to promote the oxidation-reduction reaction. NiS is a transition metal oxide and can replace expensive noble metal cocatalysts. At the same time, niS can also reduce g-C 3 N 4 And the charge recombination rate of the catalyst is improved.
Disclosure of Invention
The invention mainly solves the problem of TiO under the prior art condition 2 The method has the advantages of low sunlight utilization rate and high photo-generated carrier recombination rate. g-C is produced by three calcination of melamine powder 3 N 4 Two-dimensional material, and TiO is produced by gel-sol method with titanium isopropoxide as precursor 2 Further by TiO 2 The nickel nitrate and thiourea with proper proportion are used as raw materials to generate NiS/TiO by a one-step alcohol heating method 2 Composite material, finally g-C 3 N 4 And NiS/TiO 2 Fully grinding and calcining to generate g-C 3 N 4 /NiS/TiO 2 Photocatalytic material. The ternary material forms a Z-shaped heterostructure, which is beneficial to improving the photocatalytic performance.
g-C 3 N 4 /NiS/TiO 2 The preparation method of the ternary composite photocatalytic material comprises the following steps:
1. g-C 3 N 4 Is prepared from the following steps:
5g of melamine is weighed and placed in a covered crucible, then the crucible is placed in a box-type muffle furnace for calcination, and the temperature is raised to 500-550 ℃ at a heating rate of 5 ℃/min, and the temperature is kept for 240 minutes. The product was then cooled to room temperature, collected and triturated, denoted as CN.
Then, the pale yellow powder containing 500mg of CN was calcined at 520℃for 240 to 300 minutes at a rate of 5℃per minute, and was designated as TCN.
Finally, 500mg of TCN was calcined in a tube furnace at 5℃per minute at 460℃for 60 minutes, and the resulting powder was designated TCN-460.
2. TiO (titanium dioxide) 2 Is prepared from the following steps:
in-situ generation of TiO by taking titanium isopropoxide as precursor 2 Mixing 10mL of titanium isopropoxide with 10-30 mL of absolute ethyl alcohol, marking the obtained solution as A solution, marking 3mL of deionized water and 10mL of absolute ethyl alcohol as B solution, separately stirring for 25-35 min, dropwise adding 2mL of glacial acetic acid into the A solution to promote gel formation, continuously stirring, gradually dropwise adding the B solution into the A solution, slowly changing the solution into white turbid colloid from transparent clarification, enabling the pH of the mixed sol solution to be about 6.5 and weak acidity, completely coagulating the sol within 5min after the dropwise addition, and aging the gel for 6h at room temperature. Taking 40g of aged gel, filling the gel into a 100ml reaction kettle, reacting for 20-24 hours at the temperature of 100-140 ℃, naturally cooling a sample, washing for multiple times, vacuum drying, and grinding into powder by an agate mortar to obtain TiO 2 Sample powder.
3. NiS/TiO 2 Preparation of the composite material:
TiO prepared as described above 2 Nickel nitrate and thiourea are used as precursors, and a one-step alcohol heating method is adopted to prepare the TiO modified by nickel sulfide 2 Is a photocatalytic material of (a): will be 1.5g TiO 2 Dispersed in a solution containing 70ml of ethylene glycol, 0.58g of nickel nitrate and 0.3g of thiourea (Ni/s=1:2 molar ratio). Stirring at room temperature for 30min, transferring to a 100ml hydrothermal reaction kettle, heating with 160-200deg.C alcohol for 12-16 hr, cooling, filtering, washing, vacuum drying at 60deg.C for 12 hr to obtain powder which is NiS/TiO 2 Photocatalytic material.
4. g-C 3 N 4 /NiS/TiO 2 Preparation of the photocatalytic material:
50mg of TCN-460 prepared as described above and 50mg of NiS/TiO prepared as described above were weighed out 2 Grinding and mixing the materials in an agate mortar, then placing the materials in a covered crucible, calcining the materials at the temperature of 500 ℃ for 2 to 4 hours at the speed of 5 ℃ per minute to obtain powder, namely g-C 3 N 4 /NiS/TiO 2 Photocatalytic material.
The heat preservation temperature of the CN two-dimensional material prepared in the first step is 500-550 ℃.
The heat preservation temperature of the TCN two-dimensional material prepared in the first step is 500-550 ℃.
Preparing TiO in the second step 2 The added absolute ethyl alcohol is 10-30 mL.
Preparing TiO in the second step 2 The heat preservation temperature of the steel is 100-140 ℃.
Preparing TiO in the second step 2 The heat preservation time of the steel is 20-24 h.
Preparation of NiS/TiO in step three 2 The heat preservation temperature of the composite material is 160-200 ℃.
Preparation of NiS/TiO in step three 2 The heat preservation time of the composite material is 20-24 h.
Preparing g-C in the fourth step 3 N 4 /NiS/TiO 2 The calcination time of the composite material is 2-4 h.
The beneficial effects of the invention are as follows:
the invention synthesizes and prepares the g-C through a calcination method, a sol-gel method and an alcohol thermal method for the first time 3 N 4 /NiS/TiO 2 The ternary photocatalytic material has the structure of uniformly distributed spherical TiO on carbon nitride nanometer sheet as base 2 In TiO 2 And NiS nano particles are attached on the surface. Selecting g-C 3 N 4 As a substrate, the specific surface area can be increased and the active sites can be increased. Direct coupling suffers from insufficient light absorption, slow redox reaction rates, etc. By constructing an indirect Z-shaped heterostructure, the charge transfer capability can be improved through a cocatalyst NiS, and the catalyst has longer service life of charge carriers and better photocatalytic activity. The method is to load the cocatalyst on the semiconductor, so that the active site can be enhanced, and simultaneously, the activation energy is reduced, the charge carriers are captured, and the recombination of photo-generated electrons and holes is inhibited to promote the oxidation-reduction reaction. NiS is a transition metal oxide and can replace expensive noble metal cocatalysts. At the same time, niS can also reduce g-C 3 N 4 And the charge recombination rate of the catalyst is improved.
g-C prepared by the invention 3 N 4 /NiS/TiO 2 The photocatalytic material has higher photocatalytic hydrogen production performance. The light source was a 300W xenon lamp and 10mg of catalyst was suspended in aqueous lactic acid (50 mL,20 vol%) for hydrogen generation (H) 2 ) Gas, 3% H was added to the reactant solution 2 PtCl 6 And (3) irradiating the aqueous solution for 30min under a xenon lamp to enable platinum to be deposited on the surface of the catalyst, carrying out hydrogen production experiments on the catalyst in a photocatalysis hydrogen production system, acquiring data once every 1 hour, wherein the photocatalysis hydrogen production amount for 4h is 45.49mmoL/h, and the hydrogen production rate can reach 11.37mmoL/h/g. Thus g-C prepared according to the invention 3 N 4 /NiS/TiO 2 The ternary composite photocatalytic material has higher hydrogen production performance.
The photocatalytic material prepared by the invention has uniform microstructure, good photocatalytic hydrogen production activity, the hydrogen production amount for 4 hours is 45.49mmoL/g, and the hydrogen production rate is 11.37mmoL/g/h.
Description of the drawings:
FIG. 1 is an XRD pattern of the photocatalytic material synthesized in the examples;
FIG. 2 is an ultraviolet-visible absorption spectrum of the photocatalytic material synthesized in the examples;
FIG. 3 is a band diagram of the photocatalytic material synthesized in the example;
FIG. 4 is a photo-catalytic hydrogen production diagram of the photo-catalytic material synthesized in the example;
fig. 5 is an SEM image of the photocatalytic material synthesized in the example.
Detailed Description
The invention will be described in further detail with reference to specific examples.
This example is g-C 3 N 4 /NiS/TiO 2 The preparation method of the ternary composite photocatalytic material comprises the following steps:
the preparation method of the invention is as follows;
1. g-C 3 N 4 Is prepared from the following steps:
5g of melamine is weighed, placed in a capped crucible, then placed in a box-type muffle furnace for calcination, and heated to 550 ℃ at a heating rate of 5 ℃/min for 240 minutes. The product was then cooled to room temperature, collected and triturated, denoted as CN.
Then, a pale yellow powder containing 500mg of CN was calcined at 520℃for 270 minutes at a rate of 5℃per minute, and the resultant powder was designated as TCN.
Finally, 500mg of TCN was calcined in a tube furnace at 5℃per minute at 460℃for 60 minutes, and the resulting powder was designated TCN-460.
2. TiO (titanium dioxide) 2 Is prepared from the following steps:
in-situ generation of TiO by taking titanium isopropoxide as precursor 2 Mixing 10mL of titanium isopropoxide with 20mL of absolute ethyl alcohol, marking the obtained solution as solution A, marking the mixed solution of 3mL of deionized water and 10mL of absolute ethyl alcohol as solution B, separately stirring for 30min, dropwise adding 2mL of glacial acetic acid into the solution A to promote gel formation, continuously stirring, slowly dropwise adding the solution B into the solution A, slowly changing the solution from transparent clear to white turbid colloid, mixing the sol solution with pH of about 6.5 to be weak acidity, completely coagulating the sol within 5min after the dropwise adding, and aging the gel for 6h at room temperature. Taking 40g of aged gel, placing the gel into a 100ml reaction kettle, reacting for 18 hours at 120 ℃, naturally cooling a sample, washing for multiple times, vacuum drying, and grinding into powder by an agate mortar to obtain TiO 2 Sample powder.
3. NiS/TiO 2 Preparation of the composite material:
TiO prepared as described above 2 Nickel nitrate and thiourea are used as precursors, and a one-step alcohol heating method is adopted to prepare the TiO modified by nickel sulfide 2 Is a photocatalytic material of (a): will be 1.5g TiO 2 Dispersed in a solution containing 70ml of ethylene glycol, 0.58g of nickel nitrate and 0.3g of thiourea (Ni/s=1:2 molar ratio). Stirring at room temperature for 30min, transferring into 100ml hydrothermal reaction kettle, heating with 180 deg.C alcohol for 12 hr, cooling, filtering, washing, vacuum drying at 60deg.C for 12 hr to obtain powder which is NiS/TiO 2 Photocatalytic material.
4. g-C 3 N 4 /NiS/TiO 2 Preparation of the photocatalytic material:
50mg of TCN-460 prepared as described above and 50mg of NiS/TiO prepared as described above were weighed out 2 Put into agateGrinding and mixing thoroughly in a mortar, then placing in a covered crucible, calcining at 500 ℃ at 5 ℃/min for 2 hours to obtain powder which is g-C 3 N 4 /NiS/TiO 2 Photocatalytic material.
Claims (9)
1. g-C 3 N 4 /NiS/TiO 2 The preparation method of the ternary composite photocatalytic material is characterized by comprising the following specific steps of:
1. g-C 3 N 4 Photocatalytic material:
5g of melamine is weighed, placed in a capped crucible, then placed in a box-type muffle furnace for calcination, and heated to 550 ℃ at a heating rate of 5 ℃/min for 240 minutes. The product was then cooled to room temperature, collected and triturated, denoted as CN.
Then, a pale yellow powder containing 500mg of CN was calcined at 520℃for 270 minutes at a rate of 5℃per minute, and the resultant powder was designated as TCN.
Finally, 500mg of TCN was calcined in a tube furnace at 5℃per minute at 460℃for 60 minutes, and the resulting powder was designated TCN-460.
2. TiO (titanium dioxide) 2 Photocatalytic material:
in-situ generation of TiO by taking titanium isopropoxide as precursor 2 Mixing 10mL of titanium isopropoxide with 20mL of absolute ethyl alcohol, marking the obtained solution as solution A, marking the mixed solution of 3mL of deionized water and 10mL of absolute ethyl alcohol as solution B, separately stirring for 30min, dropwise adding 2mL of glacial acetic acid into the solution A to promote gel formation, continuously stirring, slowly dropwise adding the solution B into the solution A, slowly changing the solution from transparent clear to white turbid colloid, mixing the sol solution with pH of about 6.5 to be weak acidity, completely coagulating the sol within 5min after the dropwise adding, and aging the gel for 6h at room temperature. Taking 40g of aged gel, placing the gel into a 100ml reaction kettle, reacting for 18 hours at 120 ℃, naturally cooling a sample, washing for multiple times, vacuum drying, and grinding into powder by an agate mortar to obtain TiO 2 Sample powder.
3. NiS/TiO 2 Photocatalytic material:
TiO prepared as described above 2 Nickel nitrate and thiourea as precursorsThe TiO modified by nickel sulfide is prepared by adopting a one-step alcohol heating method 2 Is a photocatalytic material of (a): will be 1.5g TiO 2 Dispersed in a solution containing 70ml of ethylene glycol, 0.58g of nickel nitrate and 0.3g of thiourea (Ni/s=1:2 molar ratio). Stirring at room temperature for 30min, transferring into 100ml hydrothermal reaction kettle, heating with 180 deg.C alcohol for 12 hr, cooling, filtering, washing, vacuum drying at 60deg.C for 12 hr to obtain powder which is NiS/TiO 2 Photocatalytic material.
4. g-C 3 N 4 /NiS/TiO 2 Is prepared from the following steps:
50mg of TCN-460 prepared as described above and 50mg of NiS/TiO prepared as described above were weighed out 2 Grinding and mixing in agate mortar, and calcining at 500 deg.C for 2 hr at 5 deg.C/min to obtain powder g-C 3 N 4 /NiS/TiO 2 Photocatalytic material. The method comprises the steps of carrying out a first treatment on the surface of the
2. g-C according to claim 1 3 N 4 /NiS/TiO 2 The preparation method of the ternary composite photocatalytic material is characterized in that the heat preservation temperature of the CN two-dimensional material prepared in the first step is 500-550 ℃.
3. g-C according to claim 1 3 N 4 /NiS/TiO 2 The preparation method of the ternary composite photocatalytic material is characterized in that the heat preservation temperature of the TCN two-dimensional material prepared in the first step is 500-550 ℃.
4. The g-C of claim 1 3 N 4 /NiS/TiO 2 The preparation method of the ternary composite photocatalytic material is characterized by preparing TiO in the second step 2 The added absolute ethyl alcohol is 10-30 mL.
5. g-C according to claim 1 3 N 4 /NiS/TiO 2 The preparation method of the ternary composite photocatalytic material is characterized by preparing TiO in the second step 2 The heat preservation temperature of the steel is 100-140 ℃.
6. g-C according to claim 1 3 N 4 /NiS/TiO 2 The preparation method of the ternary composite photocatalytic material is characterized by preparing TiO in the second step 2 The heat preservation time of the steel is 20-24 h.
7. g-C according to claim 1 3 N 4 /NiS/TiO 2 The preparation method of the ternary composite photocatalytic material is characterized by preparing NiS/TiO in the third step 2 The heat preservation temperature of the composite material is 160-200 ℃.
8. g-C according to claim 1 3 N 4 /NiS/TiO 2 The preparation method of the ternary composite photocatalytic material is characterized by preparing NiS/TiO in the third step 2 The heat preservation time of the composite material is 20-24 h.
9. g-C according to claim 1 3 N 4 /NiS/TiO 2 The preparation method of the ternary composite photocatalytic material is characterized by preparing g-C in the fourth step 3 N 4 /NiS/TiO 2 The calcination time of the composite material is 2-4 h.
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