CN110560126A - Preparation method, product and application of Zn/carbon nitride heterojunction material rich in low-valence zinc ions - Google Patents
Preparation method, product and application of Zn/carbon nitride heterojunction material rich in low-valence zinc ions Download PDFInfo
- Publication number
- CN110560126A CN110560126A CN201910841627.2A CN201910841627A CN110560126A CN 110560126 A CN110560126 A CN 110560126A CN 201910841627 A CN201910841627 A CN 201910841627A CN 110560126 A CN110560126 A CN 110560126A
- Authority
- CN
- China
- Prior art keywords
- preparation
- heterojunction
- carbon nitride
- ion
- rich
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 72
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011701 zinc Substances 0.000 title claims description 108
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006303 photolysis reaction Methods 0.000 claims abstract description 8
- 230000015843 photosynthesis, light reaction Effects 0.000 claims abstract description 8
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 14
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 11
- 230000005012 migration Effects 0.000 abstract description 6
- 238000013508 migration Methods 0.000 abstract description 6
- 238000005215 recombination Methods 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 5
- 230000005284 excitation Effects 0.000 abstract description 4
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000006694 eating habits Nutrition 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000004355 nitrogen functional group Chemical group 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920001992 poloxamer 407 Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- 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 a Zn rich in low valence state+A preparation method of ionic Zn/carbon nitride heterojunction material, a product and application thereof, in particular to a method for modifying g-C by using metal3N4A method for preparing the material. The process comprises hydrogenating g-C3N4Preparation of material and assembled diffusion of metal ions to hydrogenated g-C by vacuum chemical gas-solid phase reaction3N4In order to obtain Zn rich in low valence state+Zn/C of ion3N4A heterojunction composite material. Zn/C3N4Due to the existence of the heterojunction structure, the migration of photo-generated electrons and holes to the surface can be accelerated, and the recombination of the photo-generated electrons and the holes can be effectively inhibited; meanwhile, a certain amount of high-activity Zn exists in the composite material+The ions generate electron transfer under the excitation of visible light, and the photocatalytic activity is greatly improved. The material was determined to beThe hydrogen production yield can reach 36.98 mmol h−1g−1And the material shows excellent performance of hydrogen production by photolysis of water.
Description
Technical Field
The invention relates to a Zn rich in low valence state+A preparation method, a product and application of an ionic Zn/carbon nitride heterojunction material, in particular to a method for modifying a carbon nitride material by using metal.
Background
Energy is an important material basis for our human survival and development. The exploitation and utilization of energy is so large as to concern the development of a country and even the whole world, and so small as to be closely related to the clothes and eating habits of each individual. The hydrogen has the advantages of high combustion heat value, wide source, no pollution of reaction products, multiple utilization forms, energy storage and the like, and is an ideal and extremely important clean energy carrier in the future. According to the research report on the development of Chinese hydrogen energy and fuel cell industry published by the Chinese hydrogen energy and fuel cell industry peak forum in 2018, China is the first hydrogen producing country in the world at present and has abundant hydrogen energy foundation, and China plans to enable the hydrogen energy to account for 10% in a terminal energy system in China in 2050, so that the hydrogen energy is widely applied to the fields of buildings, traffic, chemical raw materials and industry and becomes an important component of an energy strategy in China.
Much attention has been attracted in recent years to the study and application of carbon nitride (g-C)3N4) The carbon material has the characteristics of large surface area, chemical stability and the like of a common carbon material, and meanwhile, the specific and abundant nitrogen functional groups on the surface of the carbon material can interact with metal, so that metal particles are stably distributed on the surface of the carbon material. In fact, g-C with a band gap of 2.7eV3N4The carbon nitride has certain chemical activity, and shows good activity in the hydrogen production reaction by photolysis of water in the presence of a proper electron donor. The study shows that g-C3N4And the metal nano particles are combined to form a metal semiconductor heterojunction, so that the electron transfer process between the metal and the semiconductor caused by light excitation is enhanced, and the chemical activity can be improved. Therefore, the supported metal catalyst taking carbon nitride as the carrier has important research significance.
At present, there are many modification modes for carbon nitride materials, and after carbon nitride and metal particles form a semiconductor heterojunction, migration of photo-generated electrons and holes to the surface can be accelerated, recombination of the photo-generated electrons and the holes can be effectively inhibited, the photocatalytic activity can be remarkably improved, and an obvious hydrogen production effect can be generated. In addition, the effective separation of electrons and holes can be realized by means of energy level matching,Such as g-C3N4With CdS, SnO2And W2O3The materials are compounded, so that the photo-generated electrons can be transferred from the semiconductor with narrow band gap and lower conduction band to the conduction band in the carbon nitride, the separation of electron holes is realized, the quantum efficiency is improved, and the photocatalytic activity of the material is finally improved. Chinese invention patent 201711264203.1 discloses a CuO/C3N4The invention discloses a preparation method of a composite photocatalyst, and CuO/C is prepared by utilizing Pluronic F127 and phenolic resin3N4The heterojunction material has high activity of hydrogen production catalyzed by visible light.
Lower valence Zn+ The ion is a metal ion with higher activity reported in recent years, has higher photocatalytic activity and can capture oxygen molecules in the air. Chinese invention patent CN201010577730.X provides a Zn-containing fertilizer+Preparation method of ionic molecular sieve composite material, Zn under irradiation of visible light+The ions show the performance of efficiently catalyzing the coupling of methane to prepare ethane.
Although some reference is currently made to g-C3N4And lower valence Zn+ The report of the ion has certain application prospect in the field of photolysis of water; however, currently, there are few reports mentioned in g-C3N4zn can be stably existed in the material+Ions, Zn metal and g-C simultaneously3N4Can be stably associated into Zn/C3N4A heterojunction material. The invention provides a method for forming Zn/C by metal Zn and carbon nitride3N4Method for the production of a heterojunction material by Zn with g-C3N4The surface hydrogen protons of the material directly undergo oxidation-reduction reaction to obtain special low-valence Zn+ Ions. The invention applies to Zn/C by adopting a chemical gas phase reaction method3N4Preparation of a heterojunction composite material, the material obtained storing a certain amount of Zn+ Ions. Guest Zn+Introduction of ions, capable of reacting with Zn/C3N4The heterojunction material generates a catalytic synergistic effect, so that the hydrogen production performance of the heterojunction materialIs far higher than the reported related g-C3N4A catalytic material.
Disclosure of Invention
aiming at the defects of the prior art, the invention aims to provide a Zn rich in low valence state+A preparation method of an ionic Zn/carbon nitride heterojunction material.
Yet another object of the present invention is to: provides a method for preparing Zn rich in low valence state+Zn/C of ion3N4A heterojunction material product.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme: rich in low valence Zn+preparation method of ionic Zn/carbon nitride heterojunction material, wherein molecular formula of carbon nitride is C3N4Modification of g-C with metals3N4The material is prepared by introducing metal ions such as zinc to g-C by vacuum chemical gas-solid phase reaction3N4In the substrate, the rich low valence Zn is prepared+Zn/C of ion3N4A heterojunction material comprising the steps of:
First step, hydrogenation of g-C3N4Preparation of the Material
weighing melamine and ammonium sulfate according to the mass ratio of 1: 1 ~ 5, uniformly grinding, and transferring the obtained white powder into a tubular furnace;
Introducing high-purity Ar gas in advance before using the tubular furnace to exhaust residual air in the tubular furnace; followed by reduction of H2Calcining for 4 hours under the condition of/Ar mixed gas, cooling to room temperature, and grinding to obtain hydrogenated g-C3N4A material;
Second step, containing Zn+Zn/C of ion3N4Preparation of heterojunction composite materials
Will hydrogenate g to C3N4placing the material and metal simple substance Zn particles at the two ends of a reactor according to the molar ratio of (5 ~ 15) to 1, sealing the reactor under the high vacuum condition, placing the reactor in a tubular furnace, and diffusing metal ions to hydrogenated g by utilizing a chemical gas ~ solid phase reaction method-C3N4In the next step, the hydrogenated g-C is removed by means of a temperature difference3N4The redundant simple substance Zn on the surface of the material is finally obtained to be rich in low valence state Zn+Zn/C of ion3N4A heterojunction material.
wherein, the calcining temperature in the first step is 500 ~ 600 ℃.
the reactor in the second step is a hard glass tube or a quartz tube with one closed end and one open end.
On the basis of the scheme, the reactor is sealed and placed in a tubular furnace under the condition that the vacuum degree is higher than 0.02 Pa and high vacuum is achieved.
further, the chemical gas ~ solid phase reaction method is that the temperature of the reactor is raised to 400 ~ 600 ℃ from room temperature at the heating rate of 1 ~ 5 ℃/min, and the temperature is kept for 5 ~ 20 hours.
The invention also provides a Zn rich in low valence state+Zn/C of ion3N4A heterojunction material prepared according to any of the methods described above.
The invention also provides application of the Zn/C3N4 heterojunction material rich in low-valence Zn + ions as visible light catalysis in hydrogen production by photolysis of water.
The reaction efficiency of photocatalytic hydrogen production is calculated by monitoring the amount of generated gas on line by using a gas chromatograph. Monitoring conditions are as follows: GC-2014 for gas chromatography, a TCD detector, a TDX-01 chromatographic column and a column temperature of 70 ℃.
Zn/C3N4Due to the existence of the heterojunction structure, the migration of photo-generated electrons and holes to the surface can be accelerated, and the recombination of the photo-generated electrons and the holes can be effectively inhibited; meanwhile, a certain amount of high-activity Zn exists in the composite material+The ions generate electron transfer under the excitation of visible light, and the photocatalytic activity is greatly improved. The material contains Zn+ions show high-efficiency hydrogen production performance by photolysis of water. Related Zn/C3N4Material ratio, the Zn/C3N4The heterojunction material has high activity, can accelerate the migration of photo-generated electrons and holes to the surface, effectively inhibit the recombination of the photo-generated electrons and holes, and has the hydrogen production yield of 36.98 mmol h−1g−1And the material shows excellent performance of hydrogen production by photolysis of water.
Zn/C prepared by the method3N4The heterojunction composite material retains g-C3N4The complete configuration of the material; simultaneously hydrogenating g-C3N4hydrogen protons on the material undergo an oxidation-reduction reaction with Zn vapour to produce a quantity of lower valence Zn+Ions. Adding Zn to C3N4The heterojunction composite material is placed in a reaction for producing hydrogen by photolysis of water, and the reaction efficiency of the photocatalytic hydrogen production can reach 36.98 mmol h−1g−1The apparent quantum efficiency reaches 25.47% (365 nm), and the reaction activity is very high.
The invention has the following obvious uniqueness:
1) Using ammonium sulfate molecules for g-C3N4The preparation of the material, the amino in the molecular structure of the ammonium sulfate can form hydrogen bond with the melamine, and can inhibit g-C to a certain extent3N4The agglomeration phenomenon in the polymerization process improves the specific surface area of the catalyst and provides more active sites for the photocatalytic reaction.
2) Prepared Zn/C3N4Presence of low valence Zn in heterojunction composites+Ion, the lower valence Zn+The ions have very high activity and can generate strong electron transfer characteristics under the excitation of visible light.
3) Adopts a unique chemical gas-solid reaction method to realize the reaction of the metallic Zn simple substance and the g-C3N4Effectively combining to form a heterojunction material; the heterojunction can accelerate the migration of photo-generated electrons and holes to the surface, effectively inhibit the recombination of the photo-generated electrons and the holes, and remarkably improve the photocatalytic activity.
Drawings
FIG. 1 shows Zn synthesized in example 1 of the present invention+/Zn/C3N4Transmission electron microscopy of the composite.
Detailed Description
the following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
The reaction efficiency of photocatalytic hydrogen production is calculated by monitoring the amount of generated gas on line by using a gas chromatograph. Monitoring conditions are as follows: GC-2014 for gas chromatography, a TCD detector, a TDX-01 chromatographic column and a column temperature of 70 ℃.
Example 1
Zn/carbon nitride heterojunction material rich in low-valence zinc ions, wherein the molecular formula of carbon nitride is C3N4Modification of g-C with metals3N4Material, zinc metal ion is introduced into g-C by vacuum chemical gas-solid phase reaction method3N4In the substrate, the rich low valence Zn is prepared+Zn/C of ion3N4The heterojunction material is prepared by the following steps:
The first step is as follows: weighing 1.2g of melamine and 1.2g of ammonium sulfate, uniformly grinding, and transferring the obtained white powder into a tube furnace; introducing high-purity Ar gas into the tube furnace to exhaust residual air in the tube furnace; then introducing H2Mixed gas of/Ar in reducing H2Calcining at 500 deg.C for 4 hr under the condition of/Ar mixed gas, cooling to room temperature, and grinding to obtain hydrogenated g-C3N4A material;
The second step is that: 0.2g of the thus-prepared hydrogenated g-C was weighed3N4The powder material and 0.1g zinc particle metal simple substance are respectively placed at two ends of a special hard glass reactor. Sealing the glass reactor by using oxygen flame and separating from a vacuum system in a vacuum-pumping state; then the vacuum-tight reactor is placed in a tube furnace and heated at 450 ℃ for 20 hours, and the zinc is assembled into hydrogenated g-C by chemical vapor deposition3N4Obtaining Zn-containing material+ionic Zn/g-C3N4A heterojunction composite material. Zn is added+-Zn/g-C3N4The composite material is used as a catalyst and is placed in a reaction for producing hydrogen by photolyzing water, and tests show that the reaction efficiency of the photocatalytic hydrogen production can reach 36.98 mmol h−1g−1。
FIG. 1 shows Zn contents obtained in example 1+Ionic Zn/g-C3N4Transmission electron microscope picture of composite material, metal Zn particle is precipitated in g-C3N4the surface of the substrate has Zn particles of 3 ~ 10nm in size and g ~ C3N4Tightly combined together to form a heterojunction structure, which is beneficial to the migration of photo-generated electrons and holes to the surface and ensures the high-efficiency proceeding of the photocatalytic hydrogen production reaction.
Example 2
A Zn/carbon nitride heterojunction material rich in low-valence zinc ions is prepared by the following steps:
The first step is as follows: weighing 1.2g of melamine and 5.96g of ammonium sulfate, uniformly grinding, and transferring the obtained white powder into a tube furnace; introducing high-purity Ar gas into the tube furnace to exhaust residual air in the tube furnace; then introducing H2Mixed gas of/Ar in reducing H2Calcining at 550 deg.C for 4 hr under the condition of/Ar mixed gas, cooling to room temperature, and grinding to obtain hydrogenated g-C3N4A material.
The second step is that: 0.4 g of the thus-prepared hydrogenated g-C was weighed3N4The powder material and 0.1g zinc particle metal simple substance are respectively placed at two ends of a special hard glass reactor. Sealing the glass reactor by using oxygen flame and separating from a vacuum system in a vacuum-pumping state; then placing the vacuum sealed reactor into a tube furnace, heating at 500 deg.C for 20 hr, and assembling zinc into hydrogenated g-C by chemical vapor deposition3N4Obtaining Zn-containing material+Ionic Zn/g-C3N4A heterojunction composite material. Zn is added+-Zn/g-C3N4The composite material is used as a catalyst and is placed in a reaction for producing hydrogen by photolyzing water, and tests show that the reaction efficiency of the photocatalytic hydrogen production can reach 35.82 mmol h−1g−1。
Example 3
A Zn/carbon nitride heterojunction material rich in low-valence zinc ions is prepared by the following steps:
First step of: weighing 2.5g of melamine and 5.9 g of ammonium sulfate, uniformly grinding, and transferring the obtained white powder into a tube furnace; introducing high-purity Ar gas into the tube furnace to exhaust residual air in the tube furnace; then introducing H2Mixed gas of/Ar in reducing H2Calcining at 550 deg.C for 4 hr under the condition of/Ar mixed gas, cooling to room temperature, and grinding to obtain hydrogenated g-C3N4A material.
The second step is that: 0.4 g of the thus-prepared hydrogenated g-C was weighed3N4The powder material and 0.1g zinc particle metal simple substance are respectively placed at two ends of a special hard glass reactor. Sealing the glass reactor by using oxygen flame and separating from a vacuum system in a vacuum-pumping state; then placing the vacuum sealed reactor into a tube furnace, heating at 480 ℃ for 20 hours, assembling zinc into hydrogenated g-C by using a chemical vapor deposition method3N4Obtaining Zn-containing material+Ionic Zn/g-C3N4A heterojunction composite material. Zn is added+-Zn/g-C3N4The composite material is used as a catalyst and is placed in a reaction for producing hydrogen by photolyzing water, and tests show that the reaction efficiency of the photocatalytic hydrogen production can reach 32.75 mmol h−1g−1。
Example 4
A Zn/carbon nitride heterojunction material rich in low-valence zinc ions is prepared by the following steps:
The first step is as follows: weighing 2.5g of melamine and 7.5g of ammonium sulfate, uniformly grinding, and transferring the obtained white powder into a tube furnace; introducing high-purity Ar gas into the tube furnace to exhaust residual air in the tube furnace; then introducing H2Mixed gas of/Ar in reducing H2Calcining at 500 deg.C for 8 hr under the condition of/Ar mixed gas, cooling to room temperature, and grinding to obtain hydrogenated g-C3N4A material.
The second step is that: 0.4 g of the thus-prepared hydrogenated g-C was weighed3N4The powder material and 0.1g zinc particle metal simple substance are respectively placed at two ends of a special hard glass reactor. Sealing and removing the glass reactor by oxygen flame under vacuum conditionA vacuum-off system; then placing the vacuum sealed reactor into a tube furnace, heating at 480 ℃ for 20 hours, assembling zinc into hydrogenated g-C by using a chemical vapor deposition method3N4Obtaining Zn-containing material+Ionic Zn/g-C3N4a heterojunction composite material. Zn is added+-Zn/g-C3N4The composite material is used as a catalyst and is placed in a reaction for producing hydrogen by photolyzing water, and tests show that the reaction efficiency of the photocatalytic hydrogen production can reach 31.34 mmol h−1g−1。
Claims (7)
1. Preparation method of Zn/carbon nitride heterojunction material rich in low-valence zinc ions, wherein the molecular formula of carbon nitride is C3N4Characterized in that g-C is modified with a metal3N4Material, zinc metal ion is introduced into g-C by vacuum chemical gas-solid phase reaction method3N4In the substrate, the rich low valence Zn is prepared+Zn/C of ion3N4A heterojunction material comprising the steps of:
First step, hydrogenation of g-C3N4Preparation of the Material
weighing melamine and ammonium sulfate according to the mass ratio of 1: 1 ~ 5, uniformly grinding, and transferring the obtained white powder into a tubular furnace;
Introducing high-purity Ar gas in advance before using the tubular furnace to exhaust residual air in the tubular furnace; followed by reduction of H2Calcining for 4 hours under the condition of/Ar mixed gas, cooling to room temperature, and grinding to obtain hydrogenated g-C3N4A material;
Second step, containing Zn+Zn/C of ion3N4Preparation of heterojunction composite materials
Will hydrogenate g to C3N4placing the material and metal simple substance Zn particles at the two ends of a reactor according to the molar ratio of (5 ~ 15) to 1, sealing the reactor under the high vacuum condition, placing the reactor in a tubular furnace, and diffusing metal ions to hydrogenated g ~ C by utilizing a chemical gas ~ solid phase reaction method3N4In order to obtain Zn rich in low valence state+Zn/C of ion3N4A heterojunction material.
2. Enriched low valence Zn according to claim 1+the preparation method of the ionic Zn/carbon nitride heterojunction material is characterized in that in the first step, the calcination temperature is 500 ~ 600 ℃.
3. Enriched low valence Zn according to claim 1+The preparation method of the ionic Zn/carbon nitride heterojunction material is characterized in that the reactor in the step b is a hard glass tube or a quartz tube with one closed end and one open end.
4. the lower valence Zn-rich composition according to claim 1 or 3+The preparation method of the ionic Zn/carbon nitride heterojunction material is characterized in that a reactor is sealed and placed in a tubular furnace under the high vacuum condition that the vacuum degree is higher than 0.02 Pa.
5. Enriched in lower valence Zn according to claim 1+Zn/C of ion3N4the preparation method of the heterojunction material is characterized in that the chemical gas ~ solid phase reaction method is that a reactor is heated to 400 ~ 600 ℃ from room temperature at a heating rate of 1 ~ 5 ℃/min and is kept warm for 5 ~ 20 hours.
6. Rich in low valence Zn+Zn/C of ion3N4Heterojunction material, characterized in that it is prepared according to the method of any one of claims 1 to 5.
7. The method according to claim 6 for enriching Zn in low valence state+Zn/C of ion3N4The heterojunction material is applied to visible light catalysis in hydrogen production by photolysis of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910841627.2A CN110560126B (en) | 2019-09-06 | 2019-09-06 | Preparation method, product and application of Zn/carbon nitride heterojunction material rich in low-valence zinc ions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910841627.2A CN110560126B (en) | 2019-09-06 | 2019-09-06 | Preparation method, product and application of Zn/carbon nitride heterojunction material rich in low-valence zinc ions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110560126A true CN110560126A (en) | 2019-12-13 |
| CN110560126B CN110560126B (en) | 2022-04-05 |
Family
ID=68778224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910841627.2A Active CN110560126B (en) | 2019-09-06 | 2019-09-06 | Preparation method, product and application of Zn/carbon nitride heterojunction material rich in low-valence zinc ions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110560126B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084228A (en) * | 2014-06-25 | 2014-10-08 | 华南理工大学 | Oxygen-doped carbon nitride/zinc oxide photo-catalyst as well as preparation method and application thereof |
| CN107185580A (en) * | 2017-06-12 | 2017-09-22 | 青岛科技大学 | A kind of g C3N4/ ZnO nano piece multistage heterogeneous structure photochemical catalyst and preparation method thereof |
| CN109465019A (en) * | 2018-09-30 | 2019-03-15 | 江苏理工学院 | A kind of preparation method and application aoxidizing Zinc modified graphite phase carbon nitride visible light catalyst |
-
2019
- 2019-09-06 CN CN201910841627.2A patent/CN110560126B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084228A (en) * | 2014-06-25 | 2014-10-08 | 华南理工大学 | Oxygen-doped carbon nitride/zinc oxide photo-catalyst as well as preparation method and application thereof |
| CN107185580A (en) * | 2017-06-12 | 2017-09-22 | 青岛科技大学 | A kind of g C3N4/ ZnO nano piece multistage heterogeneous structure photochemical catalyst and preparation method thereof |
| CN109465019A (en) * | 2018-09-30 | 2019-03-15 | 江苏理工学院 | A kind of preparation method and application aoxidizing Zinc modified graphite phase carbon nitride visible light catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110560126B (en) | 2022-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Recent advances in surface-modified g-C3N4-based photocatalysts for H2 production and CO2 reduction | |
| Zhang et al. | Black magnetic Cu-g-C3N4 nanosheets towards efficient photocatalytic H2 generation and CO2/benzene conversion | |
| CN105344369A (en) | Cobalt and nitrogen codoped carbon-based oxygen reduction catalyst of three-dimensional hierarchical porous structure and preparation and application thereof | |
| CN108607593B (en) | Cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen-doped graphene composite photocatalyst and application thereof | |
| CN108993574B (en) | Preparation method of high-performance graphite-phase carbon nitride photocatalytic material | |
| CN111774083B (en) | Preparation method of hydrogen evolution catalyst of low-temperature phosphorus-doped carbon nitride-loaded high-dispersion palladium, product and application | |
| CN112076791A (en) | Ni-MOF film photocatalyst growing on surface of foamed nickel in situ, and preparation method and application thereof | |
| CN113289653A (en) | g-C of load metal monoatomic3N4Method for preparing photocatalyst | |
| CN113262809A (en) | Method for preparing CdS @ CoP @ NC heterojunction photocatalyst based on ZIF-67 precursor | |
| CN114177923A (en) | Can be used for CO2UiO-66/MoS for preparing acetic acid2Composite nano material, preparation method and application | |
| CN107335456B (en) | Carbon-doped modified graphite-phase carbon nitride photocatalyst and preparation method thereof | |
| CN111760582A (en) | MOF-based MoP-Cu3P transition metal phosphide heterojunction photocatalyst | |
| CN110560126B (en) | Preparation method, product and application of Zn/carbon nitride heterojunction material rich in low-valence zinc ions | |
| CN110152706B (en) | Method for preparing carbon-rich carbon nitride visible-light-induced photocatalyst from eutectic precursor | |
| CN113617376A (en) | P-doped g-C3N4Catalyst for hydrogen production by water photolysis through MoP and preparation method thereof | |
| CN113522367A (en) | Preparation method and preparation method of nano silver chromate modified MOFs photocatalyst | |
| CN114540840B (en) | FeCo/N-C nano composite material and preparation method and application thereof | |
| CN110947408B (en) | Iron monatomic catalyst and preparation method and application thereof | |
| CN106006740A (en) | Carbon fiber@ tungsten disulfide nanosheet kernel-shell composite structure and preparation method thereof | |
| CN110354885A (en) | A kind of neodymium oxide doping carbon nitride photocatalyst and preparation method thereof | |
| CN115180998B (en) | Method for preparing ethylene and ethane by photocatalytic reduction of carbon dioxide by red phosphorus composite material | |
| CN113755874B (en) | CoNi/C nano composite material, preparation method thereof and application thereof in synthesizing ammonia by electrocatalysis nitrogen fixation | |
| CN113304783B (en) | Tin-based metal-organic framework photocatalytic material and preparation method and application thereof | |
| CN115318307B (en) | Method for designing high-performance hydrogen-producing promoter by introducing electric coupling layer and constructing snowflake CuNi@EDL/CdS catalyst | |
| CN115845893B (en) | Method for in-situ construction of metal-doped two-dimensional carbon nitride nano sheet/carbon nano tube multi-stage structure and product 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 |