CN111871442B - Niobium-tantalum sulfide/carbon nitride nanosheet photocatalytic material, and preparation method and application thereof - Google Patents
Niobium-tantalum sulfide/carbon nitride nanosheet photocatalytic material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN111871442B CN111871442B CN202010758890.8A CN202010758890A CN111871442B CN 111871442 B CN111871442 B CN 111871442B CN 202010758890 A CN202010758890 A CN 202010758890A CN 111871442 B CN111871442 B CN 111871442B
- Authority
- CN
- China
- Prior art keywords
- carbon nitride
- heating
- niobium
- 60min
- tantalum sulfide
- 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
Links
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002135 nanosheet Substances 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 38
- MLMJNGDMHZFDJJ-UHFFFAOYSA-N [S-2].[Ta+5].[Nb+5].[S-2].[S-2].[S-2].[S-2] Chemical compound [S-2].[Ta+5].[Nb+5].[S-2].[S-2].[S-2].[S-2] MLMJNGDMHZFDJJ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010955 niobium Substances 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims description 53
- 239000000843 powder Substances 0.000 claims description 26
- 239000011521 glass Substances 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 229910000510 noble metal Inorganic materials 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 2
- 230000007480 spreading Effects 0.000 claims description 2
- 238000003892 spreading Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 23
- 239000001257 hydrogen Substances 0.000 abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 22
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 239000002131 composite material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000006303 photolysis reaction Methods 0.000 abstract description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract description 2
- 238000003746 solid phase reaction Methods 0.000 abstract description 2
- 238000010671 solid-state reaction Methods 0.000 abstract description 2
- 238000012719 thermal polymerization Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 1
- FAWYJKSBSAKOFP-UHFFFAOYSA-N tantalum(iv) sulfide Chemical compound S=[Ta]=S FAWYJKSBSAKOFP-UHFFFAOYSA-N 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NYPFJVOIAWPAAV-UHFFFAOYSA-N sulfanylideneniobium Chemical compound [Nb]=S NYPFJVOIAWPAAV-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010893 electron trap Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- -1 transition metal sulfide Chemical class 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- C01B2203/1094—Promotors or activators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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 relates to a photocatalytic material, in particular to a niobium tantalum sulfide/carbon nitride nanosheet photocatalytic material, a preparation method and application thereof, and belongs to the technical field of nanomaterials and photolysis of hydrogen. The invention firstly adopts high-temperature solid-state reaction to synthesize Nb 0.9 Ta 0.1 S 2 The material is prepared into 2D g-C by thermal polymerization and thermal stripping 3 N 4 Finally, the solvent thermal method is used for preparing Nb 0.9 Ta 0.1 S 2 /2D g‑C 3 N 4 A composite material. On the basis, novel Nb is synthesized 0.9 Ta 0.1 S 2 /2D g‑C 3 N 4 A composite material. The hydrogen production performance is obviously improved compared with the hydrogen production activity of single two-dimensional carbon nitride.
Description
Technical Field
The invention relates to a photocatalytic material, in particular to a niobium tantalum sulfide/carbon nitride nanosheet photocatalytic material, a preparation method and application thereof, and belongs to the technical field of nanomaterials and photolysis of hydrogen.
Background
With the progress of scientific technology and the advance of industrialization process, the quality of life standard of people is obviously improved, but the problems of energy crisis and environmental pollution become a difficult problem in the development of the current society. Therefore, how to reasonably and efficiently solve the problems becomes a focus of competitive attention of researchers for environmental governance and energy development of all countries in the world. Hydrogen energy is regarded as the most promising clean energy source in the 21 st century, and human interest in hydrogen energy application has been generated since 200 years ago, and hydrogen energy research has been widely conducted in many countries and regions in the world since the 70 th century. The solar hydrogen production is a green and environment-friendly technology, and infinite solar energy is continuously converted into hydrogen energy for human use. Up to now, direct conversion of solar energy into energy fuels and chemical energy has been considered as one of green sustainable approaches to solve future energy and environmental crisis.
In addition to sunlight as a driving force, photocatalysis requires an appropriate semiconductor to perform many catalytic reactions, and at present, when a visible light-active and responsive semiconductor photocatalyst is studied, a graphitic carbonitride (g-C) as a polymer semiconductor 3 N 4 ) Has attracted people's extensive attention in the research field of new generation photocatalyst, because it is easy to synthesize, excellent semiconductor property as pi-pi conjugated material, response to visible light and carrier transmissionStrong transportation capability, rapid separation and migration of photo-generated electrons and holes, high physical and chemical stability and rich surface content, thereby being widely applied to the research in the fields of photocatalytic hydrogen production, pollutant degradation, organic reaction and the like. However, due to g-C 3 N 4 High recombination rate of medium charge carriers, low quantum efficiency, small specific surface area, poor conductivity, insufficient absorption performance above 460nm and the like, so that the g-C 3 N 4 There are still obstacles in practical applications. To increase g-C 3 N 4 The photocatalytic efficiency of (2) is often a metal such as platinum as a promoter for improving the photocatalytic effect, however, platinum is a noble metal, and the high cost of platinum limits the application range of platinum, so that it is promising and meaningful to develop a non-noble metal promoter having a high photocatalytic effect to replace the noble metal platinum.
The two-dimensional transition metal sulfide has unique electrical, optical and thermal properties due to the layered structure, is widely applied to the fields of photocatalytic hydrogen production and pollutant degradation, and can be captured from 2D g-C as an electron trap due to excellent conductivity of niobium and tantalum sulfide 3 N 4 The generated electrons, niobium-tantalum sulfide as a relative cheap cocatalyst remarkably improve g-C 3 N 4 The photocatalytic hydrogen production performance.
The preparation method of the porous carbon nitride photocatalyst is applied before the subject group, however, 2D-C still exists 3 N 4 Poor conductivity, high recombination rate of photon-generated carriers and the like, so that the crystal can be captured from 2D g-C by introducing niobium tantalum sulfide which has excellent conductivity and is used as an electron trap as an auxiliary catalyst 3 N 4 For the purpose of generating electrons, ultimately improving 2D-C 3 N 4 The photocatalytic hydrogen production performance.
Disclosure of Invention
The invention aims to provide an efficient, stable and relatively cheap niobium tantalum sulfide/carbon nitride nanosheet photocatalytic material and a preparation method thereof, and aims to provide possibility for research and development of a promoter replacing platinum by using niobium tantalum sulfide, and effectively promote the performance of a two-dimensional carbon nitride semiconductor for catalyzing water decomposition to prepare hydrogen under visible light irradiation by using the promoter.
One of the objectives of the present invention is to provide a niobium tantalum sulfide/carbon nitride nanosheet material, which is prepared by synthesizing Nb through high temperature solid state reaction 0.9 Ta 0.1 S 2 The material is prepared into 2D g-C by thermal polymerization and thermal stripping 3 N 4 Finally, nb is prepared by solvothermal method 0.9 Ta 0.1 S 2 /2D g-C 3 N 4 The composite material comprises niobium and tantalum sulfide and carbon nitride, wherein the mass ratio of niobium and tantalum sulfide to carbon nitride is 5:100 to 20:100, and the optimal ratio is 5:100, respectively; the niobium sulfide and tantalum sulfide are nanoparticles, the carbon nitride is a two-dimensional nanosheet, and the niobium sulfide and tantalum sulfide are loaded on the surface of the carbon nitride which is the two-dimensional nanosheet as the nanoparticles. The work is expected to realize the g-C with high efficiency and low cost by taking transition metal sulfide as a non-noble metal cocatalyst 3 N 4 Provides a new idea for hydrogen production by base photocatalysis and provides possibility for research and development of a cocatalyst for replacing platinum. Therefore, ternary transition metal sulfide materials are promising promoters to replace noble metals such as platinum.
The second purpose of the invention is to provide a preparation method of the niobium tantalum sulfide/carbon nitride nanosheet photocatalytic material, which comprises the following specific preparation steps:
(1) Calcining melamine serving as a precursor in a muffle furnace to obtain the two-dimensional carbon nitride nanosheet, and specifically comprising the following steps: putting 2g of melamine into a crucible with a cover, heating to 550 ℃ at the heating rate of 2 ℃/min in a muffle furnace, keeping the temperature at 550 ℃ for 250min to obtain blocky carbon nitride, grinding the blocky carbon nitride into powder by grinding, weighing 400mg of ground blocky carbon nitride powder, placing the blocky carbon nitride powder in a ceramic square cup, uniformly paving the blocky carbon nitride powder, placing the blocky carbon nitride powder in the muffle furnace, heating to 550 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 90min to obtain the ultrathin two-dimensional carbon nitride nanosheet material.
(2)Nb 0.9 Ta 0.1 S 2 The preparation of (1): 354mg of niobium metal powder, 76mg of tantalum metal powder and 68.1mg of sulfur powder were put into a glass tube and vacuum-sealed. Firing the sealed glass tube in a high-temperature tube furnace in a staged heating mode,the obtained black sample is Nb 0.9 Ta 0.1 S 2 。
(3) Respectively taking a certain amount of ultrathin two-dimensional carbon nitride nanosheets and Nb 0.9 Ta 0.1 S 2 The powder was dispersed in 20mL of benzyl alcohol while ultrasonically dissolved, and then stirred for a while.
(4) Taking Nb 0.9 Ta 0.1 S 2 And mixing the solution with the ultrathin two-dimensional carbon nitride nanosheet solution, then putting the mixture into a reaction kettle for hydrothermal reaction, after the reaction is finished, centrifugally washing the solid product, and drying the solid product in vacuum to obtain the niobium tantalum sulfide/carbon nitride nanosheet photocatalytic material.
In the step (2), the stepwise temperature rise mode is as follows: the first heating stage heats the temperature from 50 ℃ to 150 ℃ within 60min and keeps the temperature for 24h, the second heating stage heats the temperature from 150 ℃ to 200 ℃ within 60min and keeps the temperature for 24h, the third heating stage heats the temperature from 200 ℃ to 250 ℃ within 60min and keeps the temperature for 24h, the fourth heating stage heats the temperature from 250 ℃ to 300 ℃ within 60min and keeps the temperature for 24h, the fifth heating stage heats the temperature from 300 ℃ to 350 ℃ within 60min and keeps the temperature for 24h, the sixth heating stage heats the temperature from 350 ℃ to 400 ℃ within 60min and keeps the temperature for 24h, the seventh heating stage heats the temperature from 400 ℃ to 450 ℃ within 60min and keeps the temperature for 24h, the eighth heating stage heats the temperature from 450 ℃ to 500 ℃ within 60min and keeps the temperature for 24h, and so on, the ninth heating stage heats the temperature from 500 ℃ to 550 ℃ within 60min and keeps the temperature for 24h, the tenth heating stage heats the temperature from 550 min to 600 ℃ within 60min and keeps the temperature for 600 h, the eleventh heating stage heats the temperature from 650 ℃ to 600 h and keeps the temperature for 650 h, and the reaction for obtaining the bulk 0.9 Ta 0.1 S 2 A material.
In the step (3), the ultrasonic time is 15-30min, and the stirring time is 15-30min.
In the step (3), 5-20mg of Nb are measured 0.9 Ta 0.1 S 2 The powder is dispersed in 20mL of benzyl alcohol, preferably 5mg of Nb 0.9 Ta 0.1 S 2 (ii) a Weighing 100mg of 2D g-C 3 N 4 The powder was dispersed in 20mL of benzyl alcohol.
In the step (4), the mixed solution is put into a reaction kettle for hydrothermal reaction, and the hydrothermal reaction is carried out by heating at 140 ℃ for 240 min.
Compared with the prior material preparation technology, the invention has the advantages that: by solvothermal method of melting Nb 0.9 Ta 0.1 S 2 Loaded at 2D g-C 3 N 4 In addition, the two-dimensional ultrathin structure and the excellent conductivity of the niobium tantalum sulfide are fully utilized to be used as electron traps to capture the secondary 2D-C 3 N 4 The advantage of the electrons generated. The composite photocatalyst shows good photocatalytic performance in the hydrogen production process, and the preparation process is controllable, the raw materials are relatively cheap and easily available, and the composite photocatalyst has certain market application prospect.
Drawings
FIG. 1 is an X-ray diffraction pattern and an infrared spectrum of the prepared niobium tantalum sulfide/carbon nitride nanosheet photocatalytic material.
FIG. 2 is the scanning lens and transmission electron microscope images of the prepared niobium tantalum sulfide/carbon nitride nanosheet photocatalytic material. (a) Monomers 2D g-C 3 N 4 A TEM image of (a); (b-c) Nb 0.9 Ta 0.1 S 2 /2D g-C 3 N 4 A TEM image of (a); (d) Bulk Nb 0.9 Ta 0.1 S 2 SEM image of (d).
Fig. 3 shows hydrogen activity of the prepared niobium tantalum sulfide/carbon nitride nanosheet photocatalytic material in decomposing water under irradiation of visible light, wherein a is a graph of average hydrogen production rate per hour of different catalysts, and b is a graph of hydrogen production amount per 5 hours of different catalysts.
Detailed Description
The invention is explained in further detail below with reference to the drawings.
Example (b): the preparation method of the niobium tantalum sulfide/carbon nitride nanosheet photocatalytic material comprises the following steps:
(1) Placing 2g of melamine in a ceramic crucible with a cover, heating to 550 ℃ at the speed of 2 ℃/min in a muffle furnace, calcining for 250min to obtain a yellow substance, grinding the yellow substance into powder, spreading 400mg of the yellow powder in a canoe without the cover, placing the canoe in the muffle furnace, heating to 550 ℃ at the speed of 10 ℃/min, and calcining for 90min to obtain a white powdery material, namely the two-dimensional carbon nitride nanosheet.
(2) 354mg of niobium metal powder, 76mg of tantalum metal powder and 68.1mg of sulfur powder were put into a glass tube and vacuum-sealed. Firing the sealed glass tube in a high-temperature tube furnace by adopting a staged heating manner, wherein the staged heating time is that the first heating stage heats the glass tube from 50 ℃ to 150 ℃ within 60min and keeps the glass tube for 24h, the second heating stage heats the glass tube from 150 ℃ to 200 ℃ within 60min and keeps the glass tube for 24h, the third heating stage heats the glass tube from 200 ℃ to 250 ℃ within 60min and keeps the glass tube for 24h, the fourth heating stage heats the glass tube from 250 ℃ to 300 ℃ within 60min and keeps the glass tube for 24h, the fifth heating stage heats the glass tube from 300 ℃ to 350 ℃ within 60min and keeps the glass tube for 24h, the sixth heating stage heats the glass tube from 350 ℃ to 400 ℃ within 60min and keeps the glass tube for 24h, the seventh heating stage heats the glass tube from 400 ℃ to 450 ℃ within 60min and keeps the glass tube for 24h, the eighth heating stage heats the glass tube from 450 ℃ to 500 ℃ within 60min and keeps the glass tube for 24h, the ninth heating stage heats the glass tube from 500 ℃ to 500 min and keeps the sample black within 60min, the eleventh heating stage heats the sample from 550 ℃ to 600 h, and keeps the sample from 650 ℃ within 60 h, and the eleventh heating stage to the sample for 600 h, and keeps the sample from the sample for 600 h 0.9 Ta 0.1 S 2 。
(3) Weighing 5, 10, 15 and 20mg Nb 0.9 Ta 0.1 S 2 The powders were dispersed in 20mL of benzyl alcohol, and 100mg of 2D g-C was measured 3 N 4 Dispersing the powder into 20mL of benzyl alcohol, and simultaneously dissolving by ultrasonic for 15-30min, and then stirring for 15-30min;
(4) Taking Nb 0.9 Ta 0.1 S 2 And mixing the solution with the ultrathin two-dimensional carbon nitride nanosheet solution, then putting the mixture into a reaction kettle, heating the mixture for 240min at the temperature of 140 ℃ for hydrothermal reaction, after the reaction is finished, centrifugally washing the solid product, and drying the solid product in vacuum to obtain the sample.
FIG. 1 shows XRD and FT-IR spectra of niobium tantalum sulfide/carbon nitride nanosheets, and the obtained sample showsThe peak spectrum similar to that of single carbon nitride is shown, which indicates that the chemical structure of the carbon nitride is not changed after loading niobium tantalum sulfide, and the peak spectrum can also determine Nb 0.9 Ta 0.1 S 2 /2D g-C 3 N 4 Successful formation of nano-heterojunctions.
FIG. 2 is the scanning lens and transmission electron microscope images of the prepared niobium tantalum sulfide/carbon nitride nanosheet photocatalytic material. Fully proves Nb 0.9 Ta 0.1 S 2 With 2D g-C 3 N 4 With intimate interfacial contact therebetween.
Fig. 3 shows hydrogen decomposition performance of the prepared niobium tantalum sulfide/carbon nitride nanosheet material under visible light irradiation. Under the condition of visible light, niobium-tantalum sulfide is used as a promoter, and the volume ratio of the niobium-tantalum sulfide to the promoter is 1:9, the weight of the catalyst is 10mg, and the volume of the solution is 100mL (the mixed solution of 10mL triethanolamine and 90mL distilled water), so that the hydrogen production by water decomposition can be effectively realized. The hydrogen production performance of the niobium sulfide/carbon nitride nanosheet material synthesized by loading niobium sulfide and tantalum sulfide can be obviously improved compared with the hydrogen production activity of single two-dimensional carbon nitride, wherein the activity of a sample with 5% loading capacity reaches 1961.6 mu mol g -1 h -1 。
Claims (8)
1. The niobium-tantalum sulfide/carbon nitride nanosheet photocatalytic material is characterized in that niobium-tantalum sulfide is a nanoparticle, carbon nitride is a two-dimensional nanosheet, the niobium-tantalum sulfide nanoparticle is loaded on the surface of the two-dimensional carbon nitride nanosheet, and the mass ratio of niobium-tantalum sulfide to carbon nitride is 5:100 to 20:100, the preparation method of the niobium tantalum sulfide/carbon nitride nanosheet photocatalytic material comprises the following specific steps:
(1) Calcining melamine serving as a precursor in a muffle furnace to obtain the two-dimensional carbon nitride nanosheet, and specifically comprising the following steps: putting 2g of melamine into a crucible with a cover, heating to 550 ℃ at a heating rate of 2 ℃/min in a muffle furnace, keeping at 550 ℃ for 250min to obtain blocky carbon nitride, grinding the blocky carbon nitride into powder by grinding, weighing 400mg of ground blocky carbon nitride powder, placing the blocky carbon nitride powder in a ceramic square cup, uniformly spreading the blocky carbon nitride powder, placing the ceramic square cup in the muffle furnace, heating to 550 ℃ at a heating rate of 10 ℃/min, and keeping for 90min to obtain an ultrathin two-dimensional carbon nitride nanosheet material;
(2) Preparation of Nb 0.9 Ta 0.1 S 2 ；
(3) Respectively taking ultrathin two-dimensional carbon nitride nanosheets and Nb 0.9 Ta 0.1 S 2 Dispersing the powder into benzyl alcohol, dissolving with ultrasound, and stirring for a period of time;
(4) Taking Nb 0.9 Ta 0.1 S 2 And mixing the solution with the ultrathin two-dimensional carbon nitride nanosheet solution, then putting the mixture into a reaction kettle for hydrothermal reaction, after the reaction is finished, centrifugally washing the solid product, and then drying the solid product in vacuum to obtain the niobium-tantalum sulfide/carbon nitride nanosheet photocatalytic material.
2. The niobium tantalum sulfide/carbon nitride nanosheet photocatalytic material of claim 1, wherein the mass ratio of niobium tantalum sulfide to carbon nitride is 5:100.
3. the niobium tantalum sulfide/carbon nitride nanosheet photocatalytic material of claim 1, wherein in step (2), nb is prepared 0.9 Ta 0.1 S 2 Comprises the following steps: putting 354mg of niobium metal powder, 76mg of tantalum metal powder and 68.1mg of sulfur powder into a glass tube, sealing the glass tube in vacuum, and firing the sealed glass tube in a high-temperature tube furnace in a step-wise heating manner to obtain a black sample, namely Nb 0.9 Ta 0.1 S 2 。
4. The niobium tantalum sulfide/carbon nitride nanosheet photocatalytic material of claim 3, wherein the stepwise temperature increase is by: the first heating stage is to heat from 50 deg.C to 150 deg.C within 60min and maintain for 24h, the second heating stage is to heat from 150 deg.C to 200 deg.C within 60min and maintain for 24h, the third heating stage is to heat from 200 deg.C to 250 deg.C within 60min and maintain for 24h, the fourth heating stage is to heat from 250 deg.C to 300 deg.C within 60min and maintain for 24h, the fifth heating stage is to heat from 250 deg.C to 300 deg.C within 60min and maintain for 24hHeating to 350 deg.C within 60min, maintaining for 24h, heating to 350 deg.C within 60min for the sixth time, heating to 400 deg.C within 60min for 24h, heating to 450 deg.C within 60min for the seventh time, heating to 500 deg.C within 60min for 24h, heating to 450 deg.C within 60min for 500 h, and so on, heating to 550 deg.C within 60min for the ninth time, maintaining for 24h, heating to 550 deg.C within 60min for the tenth time, heating to 600 deg.C within 60min for 24h, heating to 600 deg.C within 60min for the eleventh time, maintaining for 264h, and obtaining block Nb 0.9 Ta 0.1 S 2 A material.
5. The niobium tantalum sulfide/carbon nitride nanosheet photocatalytic material of claim 1, wherein in step (3), 5-20mg of Nb is measured 0.9 Ta 0.1 S 2 Dispersing the powder into 20mL of benzyl alcohol, and weighing 100mg of 2D g-C 3 N 4 The powder was dispersed in 20mL of benzyl alcohol.
6. The niobium tantalum sulfide/carbon nitride nanosheet photocatalytic material of claim 5, wherein in step (3), 5mgNb is measured in an amount of 5mgNb 0.9 Ta 0.1 S 2 The powder was dispersed in 20mL of benzyl alcohol.
7. The niobium tantalum sulfide/carbon nitride nanosheet photocatalytic material of claim 1, wherein in step (4), the mixed solution is placed in a reaction vessel for hydrothermal reaction by heating at 140 ℃ for 240 min.
8. The use of the niobium tantalum sulfide/carbon nitride nanosheet photocatalytic material as claimed in claim 1, wherein the photocatalytic material is produced by decomposing water as a catalyst under visible light irradiation without adding noble metal platinum as a promoter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010758890.8A CN111871442B (en) | 2020-07-31 | 2020-07-31 | Niobium-tantalum sulfide/carbon nitride nanosheet photocatalytic material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010758890.8A CN111871442B (en) | 2020-07-31 | 2020-07-31 | Niobium-tantalum sulfide/carbon nitride nanosheet photocatalytic material, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111871442A CN111871442A (en) | 2020-11-03 |
| CN111871442B true CN111871442B (en) | 2023-04-11 |
Family
ID=73204876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010758890.8A Active CN111871442B (en) | 2020-07-31 | 2020-07-31 | Niobium-tantalum sulfide/carbon nitride nanosheet photocatalytic material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111871442B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108187718A (en) * | 2017-12-28 | 2018-06-22 | 江苏大学 | A kind of Preparation method and use of carbonitride/tantalic acid calcium potassium nanosheet composite material |
| CN108380230A (en) * | 2018-01-24 | 2018-08-10 | 江苏大学 | The preparation method and application of ultra-thin graphite phase carbon nitride |
-
2020
- 2020-07-31 CN CN202010758890.8A patent/CN111871442B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108187718A (en) * | 2017-12-28 | 2018-06-22 | 江苏大学 | A kind of Preparation method and use of carbonitride/tantalic acid calcium potassium nanosheet composite material |
| CN108380230A (en) * | 2018-01-24 | 2018-08-10 | 江苏大学 | The preparation method and application of ultra-thin graphite phase carbon nitride |
Non-Patent Citations (2)
| Title |
|---|
| "Large second harmonic generation in alloyed TMDs and boron nitride nanostructures";Michael C. Lucking et al.;《Scientific Reports》;20180730;第8卷;第1-13页 * |
| "Oxygenated monolayer carbon nitride for excellent photocatalytic hydrogen evolution and external quantum efficiency";Xiaojie She et al.;《Nano Energy》;20160623;第27卷;第138-146页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111871442A (en) | 2020-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gong et al. | Noble-metal-free heterostructure for efficient hydrogen evolution in visible region: molybdenum nitride/ultrathin graphitic carbon nitride | |
| Ai et al. | Rational modulation of pn homojunction in P-doped g-C3N4 decorated with Ti3C2 for photocatalytic overall water splitting | |
| CN110624550B (en) | In-situ carbon-coated copper-nickel alloy nanoparticle photocatalyst and preparation method and application thereof | |
| Li et al. | The facile synthesis of graphitic carbon nitride from amino acid and urea for photocatalytic H 2 production | |
| CN110743596A (en) | Ruthenium nanoparticle/three-dimensional porous carbon nitride composite material, and preparation method and application thereof | |
| Sun et al. | Task-specific synthesis of 3D porous carbon nitrides from the cycloaddition reaction and sequential self-assembly strategy toward photocatalytic hydrogen evolution | |
| CN105709793A (en) | Cadmium sulfide nanoparticle modified niobium pentoxide nanorod/nitrogen doped graphene composite photocatalyst and preparation method and application thereof | |
| CN111790432A (en) | Nickel carbide/carbon nitride nanosheet photocatalytic material and preparation method and application thereof | |
| CN113952986A (en) | WO (WO)3TpPa-1-COF composite material and preparation method and application thereof | |
| CN109225298A (en) | A kind of MnISCN nanocomposite and its preparation method and application with high visible-light activity | |
| CN108823601A (en) | A kind of preparation method of metal oxide/graphene composite film | |
| CN108461725A (en) | Vanadium trioxide hollow microsphere of carbon confinement and its preparation method and application | |
| CN106299392A (en) | A kind of nanometer Mn with manganese defect3o4and preparation method thereof and application in electrocatalytic oxidation reduction reaction | |
| CN112495411B (en) | Carbon nitride nanosheet loaded indium vanadate quantum dot photocatalyst and preparation and application thereof | |
| CN106384832A (en) | ZnO-CuO/rGO (reduced graphene oxide) composite material with efficient electrocatalytic oxygen reduction performance | |
| CN113617376A (en) | P-doped g-C3N4Catalyst for hydrogen production by water photolysis through MoP and preparation method thereof | |
| CN113385210A (en) | Photocatalytic hydrogen production catalyst and preparation method and application thereof | |
| CN111871442B (en) | Niobium-tantalum sulfide/carbon nitride nanosheet photocatalytic material, and preparation method and application thereof | |
| CN112958096A (en) | Preparation method and application of flower-ball-shaped nickel-aluminum hydrotalcite/titanium dioxide in-situ growth flaky titanium tricarboxide composite photocatalyst | |
| CN115090318B (en) | Preparation method and application of high specific surface area intermolecular heterojunction carbon nitride photocatalyst | |
| CN114210315B (en) | Preparation and application of rare earth erbium modified pollen carbon composite photocatalyst | |
| Yang et al. | Rational Construction of Electrostatic Self‐Assembly of Metallike MoP and ZnIn2S4 Based on Density Functional Theory to Form Schottky Junction for Photocatalytic Hydrogen Production | |
| CN114517303A (en) | Honeycomb electrolyzed water catalyst and preparation method and application thereof | |
| CN113522298A (en) | Perovskite oxide/Ti3C2MXene/foamed nickel composite material and preparation method and application thereof | |
| CN111715257A (en) | CO2Cycloaddition reaction catalyst, 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 | ||
| CB03 | Change of inventor or designer information |
Inventor after: Xu Hui Inventor after: Chen Hanxiang Inventor before: Xu Hui Inventor before: Chen Hanxiang |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |