CN105381811A - In-situ growth preparation method for mesoporous composite semiconductor material with high stability - Google Patents
In-situ growth preparation method for mesoporous composite semiconductor material with high stability Download PDFInfo
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- CN105381811A CN105381811A CN201510671661.1A CN201510671661A CN105381811A CN 105381811 A CN105381811 A CN 105381811A CN 201510671661 A CN201510671661 A CN 201510671661A CN 105381811 A CN105381811 A CN 105381811A
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 239000004065 semiconductor Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 15
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- BNWPUUZJGBXAFM-UHFFFAOYSA-N azane oxalonitrile Chemical compound N.N#CC#N BNWPUUZJGBXAFM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- CYRONKIISXPXER-UHFFFAOYSA-N 2,4-dibromoquinoline Chemical class C1=CC=CC2=NC(Br)=CC(Br)=C21 CYRONKIISXPXER-UHFFFAOYSA-N 0.000 claims description 3
- ZHXUWDPHUQHFOV-UHFFFAOYSA-N 2,5-dibromopyridine Chemical class BrC1=CC=C(Br)N=C1 ZHXUWDPHUQHFOV-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229940125717 barbiturate Drugs 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- -1 thio ammonium molybdate Chemical compound 0.000 claims description 2
- 150000003053 piperidines Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052961 molybdenite Inorganic materials 0.000 abstract 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 abstract 3
- 239000002243 precursor Substances 0.000 abstract 3
- 238000001035 drying Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 238000001239 high-resolution electron microscopy Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- HLCPWBZNUKCSBN-UHFFFAOYSA-N 2-aminobenzonitrile Chemical compound NC1=CC=CC=C1C#N HLCPWBZNUKCSBN-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 208000012826 adjustment disease Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- YECIFGHRMFEPJK-UHFFFAOYSA-N lidocaine hydrochloride monohydrate Chemical compound O.[Cl-].CC[NH+](CC)CC(=O)NC1=C(C)C=CC=C1C YECIFGHRMFEPJK-UHFFFAOYSA-N 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B01J35/19—
-
- 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
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
-
- 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
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/635—
-
- B01J35/638—
-
- B01J35/647—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
The present invention relates to an in-situ growth preparation method for a mesoporous composite semiconductor material with high stability. The method comprises the following steps: (1) mixing a hexatomic ring solid organic compound with a g-C3N4 precursor in a ratio of 1-50 mg: 1-20 g and grinding; (2) insulating the ground mixture for 2-12 hours at the temperature of 500-750 DEG C, and calcining to obtain a modified graphite-like carbon nitride material; (3) dispersing the modified graphite-like carbon nitride material in a solvent, and adding an MoS2 precursor, and dispersing in an ultrasonic manner, wherein the ratio of the modified graphite-like carbon nitride material, the MoS2 precursor and the solvent is of 0.1-0.5 g: 10-100 mg: 10-50 ml; and (4) transferring the obtained solution into a hydrothermal reactor, reacting for 8-24 hours at the temperature of 120-200 DEG C, cooling, centrifuging and drying to obtain an MoS2/mg-C3N4 composite semiconductor material.
Description
Technical field
The invention provides the composite mesoporous semi-conducting material (MoS that the preparation of a kind of Hydrothermal Synthesis in situ synthesis has high catalytic stability
2/ mg-C
3n
4) method, material prepared by the method not only has higher photocatalytic activity, and has higher catalytic stability, and this composite semiconductor material can realize H under radiation of visible light effect
2o decomposes H processed
2.Belong to catalysis material and technical field of nano material, relate to the preparation method based on the composite mesoporous semi-conducting material of class graphitic nitralloy carbon.
Background technology
Transient metal sulfide has 2D laminated structure, with MoS
2for example, because it has the features such as coefficient of friction is little, diamagnetism, avtive spot are many, be widely used in kollag, photoconductor and field of catalytic chemistry.But as a kind of metal sulfide, easily there is photoetch phenomenon when catalytic applications and make catalysqt deactivation.And mesoporous material has high specific area, large pore volume, the advantages such as regulatable mesoscopic structure and aperture size.Find in this research process: by MoS
2be dispersed in and there is high specific surface area and comparatively in high electron density material, its catalytic stability can be improved.
2009, the people such as Wang Xinchen reported that synthesis has the carbon nitride material of graphite-like structure and uses it in the H-H reaction of light decomposition aquatic products.This 2D material is owing to having high nitrogen content, superior chemistry and thermal stability, special electronic structure, cost low (forming primarily of nitrogen, carbon), prepare the feature such as simple and causing the extensive concern of people.In the last few years, g-C
3n
4extensively studied in fields such as organic matter light degradation, oxygen reduction reactions.But the g-C that dinectly bruning prepares
3n
4the specific area of material is lower, and photo-generate electron-hole easily compound occurs and makes its photocatalysis efficiency step-down.2012, the people such as Wang Xinchen added 2-aminobenzonitrile in cyanamide, calcined the modification class graphitic nitralloy material with carbon element obtained and had higher catalytic activity.
The environmental problem such as energy shortage and greenhouse effects is two large problems that people face at present, in existing solution, by the method for photocatalytic conversion, by CO under room temperature
2be converted into the compound that HC etc. has higher chemical energy, solar energy can be realized to chemical transformation of energy.But the catalyst reported still exists the problems such as catalytic activity is lower before, therefore, the new catalyst system of exploitation is needed badly.
The present invention explores the composite semiconductor material that the preparation of simple hydro-thermal method has meso-hole structure, MoS
2at the class graphitic nitralloy material with carbon element g-C of modification
3n
4upper growth in situ prepares MoS
2/ mg-C
3n
4composite semiconductor material, mg-C
3n
4as composite semiconductor important component and MoS
2carrier, can be MoS
2abundant electronics is provided.The composite semiconductor material prepared has higher catalytic activity and cyclical stability, by the mass ratio between modulation two kinds of compositions, can realize the optimization of the photocatalysis performance of composite semiconductor material.
Summary of the invention
Order of the present invention for providing a kind of growth in situ preparation method with the composite mesoporous semi-conducting material of greater catalytic stability, and uses it for light at room temperature degraded H
2o prepares H
2light-catalyzed reaction.This composite semiconductor material overcomes the weakness that photoetch easily occurs common metal sulfide, has stronger catalytic stability.
At this, the invention provides a kind of growth in situ preparation method with the composite mesoporous semi-conducting material of greater catalytic stability, comprise the following steps: (1) is by hexatomic ring solid organic and g-C
3n
4presoma mixes according to the ratio of 1 ~ 50mg:1 ~ 20g, grinding; (2) mixture after step (1) being ground was 500 ~ 750 DEG C of insulations 2 ~ 12 hours, and calcining obtains the class graphitic nitralloy material with carbon element of modification; (3) the class graphitic nitralloy material with carbon element dispersion of modification step (2) obtained in a solvent, adds MoS
2presoma, ultrasonic disperse, wherein, the class graphitic nitralloy material with carbon element of described modification, described MoS
2the ratio of presoma, described solvent is 0.1 ~ 0.5g:10 ~ 100mg:10 ~ 50ml; (4) solution that step (3) obtains is transferred in water heating kettle, at 120 ~ 200 DEG C react 8 ~ 24 hours, cooling, centrifugal, dry, obtain MoS
2/ mg-C
3n
4composite semiconductor material.
The method is with g-C
3n
4be raw material with hexatomic ring solid organic matters, high-temperature calcination prepares the class graphitic nitralloy material with carbon element mg-C of modification
3n
4.Adopt hydrothermal synthesis method afterwards, prepare MoS by growth in situ
2/ mg-C
3n
4composite semiconductor material.By the catalyst prepared, there is higher specific area.By regulating presoma type, the ratio of reactant, calcining heat, heating rate, and the temperature of hydro-thermal reaction and reaction time, realize the optimal design of catalyst.The composite semiconductor catalyst of the method synthesis can realize H under room temperature
2o decomposes preparation H
2, there is higher stability.Of the present invention preparation is simple, and method is novel, and cost is low, and efficiency is high, in light decomposing H
2o H
2wide application prospect is demonstrated etc. fields such as photocatalytic conversion.
In the present invention, g-C described in step (1)
3n
4presoma is at least one in urea, single cyanogen ammonia and dicyandiamide.
Again, hexatomic ring solid organic described in step (1) is barbiturates, 2,5-dibromo pyridines, 2,4-bis-bromoquinolines, at least one such as 2,5-bis-bromo pyrimi piperidine.
Preferably, the heating rate that step (2) is calcined is 2 ~ 10K/ minute.
In the present invention, MoS in step (3)
2presoma is ammonium molybdate and thiocarbamide, sodium molybdate and thiocarbamide, in four thio ammonium molybdate at least one group.
Preferably, described in step (3), the time of ultrasonic disperse is 5 ~ 60 minutes.
Preferably, described in step (3), solvent is water, DMF, absolute ethyl alcohol or acetone.
In the present invention, the MoS prepared
2/ mg-C
3n
4in composite semiconductor material, MoS
2there is weak crystallization structure.
Again, the MoS prepared
2/ mg-C
3n
4in composite semiconductor material, MoS
2for nano flower-like nano material.
The MoS that the present invention prepares
2/ mg-C
3n
4composite semiconductor material is 2D structural material, and specific area is 50 ~ 300m
2g
-1, pore volume is 0.5 ~ 2cm
3g
-1, aperture is 4 ~ 12nm.
Accompanying drawing explanation
Fig. 1 a and Fig. 1 b is the MoS of embodiment 1 gained
2, MoS
2/ mg-C
3n
4sEM (SEM) photo of composite semiconductor material;
Fig. 2 a is the MoS of embodiment 1 gained
2/ mg-C
3n
4transmission electron microscope (TEM) photo of composite semiconductor material;
Fig. 2 b is the MoS of embodiment 1 gained
2/ mg-C
3n
4high resolution electron microscopy (HRTEM) photo of composite semiconductor material;
Fig. 3 a is the MoS of embodiment 1 gained
2/ g-C
3n
4and MoS
2/ mg-C
3n
4two kinds of composite semiconductor materials hydrogen output under visible light illumination and contrast;
Fig. 3 b is the MoS of embodiment 1 gained
2/ mg-C
3n
4the photochemical catalyzing of composite semiconductor material prepares H
2cyclical stability test result.
Detailed description of the invention
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that following embodiment is only for illustration of the present invention, and unrestricted the present invention.
The invention provides a kind of growth in situ preparation method with the composite mesoporous semi-conducting material of greater catalytic stability.
Preparation method of the present invention comprises: (1) select one have six-membered ring structure, fusing point lower can with class graphitic nitralloy carbon (g-C
3n
4) there is the organic matter of polycondensation reaction, such as barbiturates, 2,5-dibromo pyridines, 2,4-bis-bromoquinoline, 2,5-bis-bromo pyrimi piperidine etc., with g-C
3n
4presoma (urea, single cyanogen ammonia, dicyandiamide) mix according to a certain percentage, grinding, under room temperature, milling time is 10 ~ 60 minutes;
(2) mixture after grinding is shone certain heating rate, such as 4K/min is warming up to reaction temperature, and calcining obtains the class graphitic nitralloy carbon (mg-C of modification
3n
4) material, collect for subsequent use;
(3) mg-C calcining and obtain is taken respectively
3n
4powder and MoS
2presoma, ultrasonic process, disperses in a solvent, the common solvents such as such as water, DMF (DMF), absolute ethyl alcohol, acetone;
(4) above-mentioned solution is transferred in water heating kettle, reaction time and the reaction temperature of baking oven are set;
(5) room temperature is down to by question response still, centrifugal, dry.
In the present invention, MoS
2at the class graphitic nitralloy material with carbon element g-C of modification
3n
4upper growth in situ prepares MoS
2/ mg-C
3n
4composite semiconductor material, mg-C
3n
4as composite semiconductor important component and MoS
2carrier, can be MoS
2abundant electronics is provided.The composite semiconductor material prepared has higher catalytic activity and cyclical stability, by the mass ratio between modulation two kinds of compositions, can realize the optimization of the photocatalysis performance of composite semiconductor material.
As a kind of preferred version, g-C described in step (1)
3n
4the quality of presoma is 1 ~ 20g.
As a kind of preferred version, the quality of step (1) hexatomic ring solid is 1 ~ 50mg.
As a kind of preferred version, in step (2), calcining heat is 500 ~ 750 DEG C.
As a kind of preferred version, calcining heating rate described in step (2) is 2 ~ 10K/min.
As a kind of preferred version, the sintering soak time described in step (2) is 2 ~ 12h.
As a kind of preferred version, mg-C in step (3)
3n
4quality be 0.1 ~ 0.5g.
As a kind of preferred version, MoS in step (3)
2the quality of presoma is 10 ~ 100mg.
As a kind of preferred version, in step (3), the consumption of solvent is 10 ~ 50ml.
As a kind of preferred version, described in step (4), oven temperature is 120 ~ 200 DEG C.
As a kind of preferred version, the time of baking oven described in step (4) is 8 ~ 24h.
As a kind of preferred version, described composite semiconductor material 2D structural material, specific area is 50 ~ 300m
2g
- 1.
Feature of the present invention is: synthetic method of the present invention is simple, and method is novel, and cost is low, and efficiency is high.This composite semiconductor material overcomes the weakness that photoetch easily occurs common metal sulfide, has stronger catalytic stability.Described composite semiconductor material has the even pore distribution of two dimension (2D) material structure characteristic sum, and material has high specific area, homogeneous pore-size distribution, is very beneficial for diffusion and the absorption of reactant and product molecule, such as H
2, H
2o and oil catalytic pyrolysis product etc., be with a wide range of applications in biological, absorption, catalysis and the field such as to be separated.The technological parameters such as adjustment reaction temperature, reaction time, ultrasonic time all can prepare this composite semiconductor material.
Exemplify embodiment below further to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The technological parameter etc. that following example is concrete is also only an example in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Embodiment 1
Take the mono-cyanogen ammonia of 3g, add 10mg2,5-dibromo pyridine, grind 30 minutes under room temperature, collect in mortar, be warming up to 650 DEG C with the heating rate of 10K/min, insulation 3h.Obtain the class graphitic nitralloy material with carbon element mg-C of modification
3n
4.The amount of substance of ammonium molybdate and thiocarbamide controls, for 1:1, to take the thiocarbamide of 20mg ammonium molybdate and correspondence; Weighing m g-C
3n
4material 0.15g, is dispersed in 50mL water, ultrasonic process 10min.Solution is transferred in water heating kettle, at 120 DEG C, reaction 12h.Product is centrifugal, washing, freeze drying, obtain end product.
Fig. 1 a and Fig. 1 b is the MoS of embodiment 1 gained
2, MoS
2/ mg-C
3n
4sEM (SEM) photo of composite semiconductor material.As can be seen from photo: prepared MoS
2material is nano flower-like material.
Fig. 2 a and Fig. 2 b is respectively the MoS of embodiment 1 gained
2/ mg-C
3n
4transmission electron microscope (TEM) photo of composite semiconductor material and high resolution electron microscopy (HRTEM) photo.As can be seen from the figure obtained nano flower-like MoS
2particle size is about 20nm.
Fig. 3 a is the MoS of embodiment 1 gained
2/ g-C
3n
4and MoS
2/ mg-C
3n
4two kinds of composite semiconductor materials hydrogen output under visible light illumination and contrast; Fig. 3 b is the MoS of embodiment 1 gained
2/ mg-C
3n
4the photochemical catalyzing of composite semiconductor material prepares H
2cyclical stability test result.Composition graphs 3a and Fig. 3 b can illustrate that prepared composite semiconductor material has higher photocatalytic activity and stablizes.
Industrial applicability: of the present invention preparation is simple, method is novel, and cost is low, and efficiency is high, in light decomposing H
2o H
2wide application prospect is demonstrated etc. fields such as photocatalytic conversion.
Claims (10)
1. there is a growth in situ preparation method for the composite mesoporous semi-conducting material of greater catalytic stability, it is characterized in that, comprise the following steps:
(1) by hexatomic ring solid organic and g-C
3n
4presoma mixes according to the ratio of 1 ~ 50mg:1 ~ 20g, grinding;
(2) mixture after step (1) being ground was 500 ~ 750 DEG C of insulations 2 ~ 12 hours, and calcining obtains the class graphitic nitralloy material with carbon element of modification;
(3) the class graphitic nitralloy material with carbon element dispersion of modification step (2) obtained in a solvent, adds MoS
2presoma, ultrasonic disperse, wherein, the class graphitic nitralloy material with carbon element of described modification, described MoS
2the ratio of presoma, described solvent is 0.1 ~ 0.5g:10 ~ 100mg:10 ~ 50ml;
(4) solution that step (3) obtains is transferred in water heating kettle, at 120 ~ 200 DEG C react 8 ~ 24 hours, cooling, centrifugal, dry, obtain MoS
2/ mg-C
3n
4composite semiconductor material.
2. preparation method according to claim 1, is characterized in that, g-C described in step (1)
3n
4presoma is at least one in urea, single cyanogen ammonia and dicyandiamide.
3. preparation method according to claim 1 and 2, is characterized in that, hexatomic ring solid organic described in step (1) is at least one in barbiturates, 2,5-dibromo pyridines, 2,4-bis-bromoquinolines, 2,5-bis-bromo pyrimi piperidines.
4. the preparation method according to any one of claims 1 to 3, is characterized in that, the heating rate that step (2) is calcined is 2 ~ 10K/ minute.
5. the preparation method according to any one of Claims 1 to 4, is characterized in that, MoS in step (3)
2presoma is ammonium molybdate and thiocarbamide, sodium molybdate and thiocarbamide, in four thio ammonium molybdate at least one group.
6. the preparation method according to any one of Claims 1 to 5, is characterized in that, the time of ultrasonic disperse described in step (3) is 5 ~ 60 minutes.
7. the preparation method according to any one of claim 1 ~ 6, is characterized in that, described in step (3), solvent is water, DMF, absolute ethyl alcohol or acetone.
8. the preparation method according to any one of claim 1 ~ 7, is characterized in that, the MoS prepared
2/ mg-C
3n
4in composite semiconductor material, MoS
2there is weak crystallization structure.
9. the preparation method according to any one of claim 1 ~ 8, is characterized in that, the MoS prepared
2/ mg-C
3n
4in composite semiconductor material, MoS
2for nano flower-like nano material.
10. the preparation method according to any one of claim 1 ~ 9, is characterized in that, the MoS prepared
2/ mg-C
3n
4composite semiconductor material is 2D structural material, and specific area is 50 ~ 300m
2g
-1, pore volume is 0.5 ~ 2cm
3g
-1, aperture is 4 ~ 12nm.
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| CN108786894B (en) * | 2018-07-02 | 2020-11-03 | 广东石油化工学院 | Graphite-phase carbon nitride/rare earth sodium molybdate heterojunction photocatalyst and preparation method and application thereof |
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