CN108187718A - A kind of Preparation method and use of carbonitride/tantalic acid calcium potassium nanosheet composite material - Google Patents
A kind of Preparation method and use of carbonitride/tantalic acid calcium potassium nanosheet composite material Download PDFInfo
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- CN108187718A CN108187718A CN201711455164.3A CN201711455164A CN108187718A CN 108187718 A CN108187718 A CN 108187718A CN 201711455164 A CN201711455164 A CN 201711455164A CN 108187718 A CN108187718 A CN 108187718A
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- acid calcium
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- carbonitride
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- 239000002131 composite material Substances 0.000 title claims abstract description 43
- NYRAVIYBIHCEGB-UHFFFAOYSA-N [K].[Ca] Chemical compound [K].[Ca] NYRAVIYBIHCEGB-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000002253 acid Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002135 nanosheet Substances 0.000 title description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 230000001699 photocatalysis Effects 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000007146 photocatalysis Methods 0.000 claims abstract description 7
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 34
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 6
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000005588 protonation Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- NWEKXBVHVALDOL-UHFFFAOYSA-N butylazanium;hydroxide Chemical compound [OH-].CCCC[NH3+] NWEKXBVHVALDOL-UHFFFAOYSA-N 0.000 claims 1
- 238000003801 milling Methods 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 6
- 239000011941 photocatalyst Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/23—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- 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
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
- C01G35/006—Compounds containing, besides tantalum, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to nano materials and photocatalysis technology field, and in particular to a kind of Preparation method and use of carbonitride/tantalic acid calcium potassium composite nano materials.The invention aims to solve the problems, such as the carbon nitride photocatalyst of prior art preparation, there are visible light utilization efficiency is low, hole and electronics are easily compound.The present invention prepares carbonitride/tantalic acid calcium potassium composite semiconductor material using hydro-thermal method, have many advantages, such as that of low cost, preparation process is simple, reaction condition is mild, high catalytic efficiency, prepared composite photo-catalyst has preferable hydrogen production by water decomposition effect under visible light exposure, has larger potentiality in terms of hydrogen energy source preparation.
Description
Technical field
The invention belongs to field of nanometer material technology, are related to a kind of system of carbonitride/tantalic acid calcium potassium nanometer sheet composite nano materials
Preparation Method, carbonitride/tantalic acid calcium potassium nanosheet composite material of specifically a kind of perovskite structure and preparation method thereof with
On the way.
Technical background
Graphite phase carbon nitride (graphitic carbon nitride, g-C3N4), as a kind of novel metalloid polymer
Semi-conducting material has the characteristics such as band gap (2.7eV) is narrow, nontoxic, at low cost, thermal stability is good, causes the extensive pass of people
Note.However, simple g-C in practical applications3N4Photo-generate electron-hole to easily it is compound, cause photocatalytic activity relatively low.Therefore
Researchers wish to improve the photocatalytic activity of carbonitride by constructing composite photocatalyst material.Tantalic acid calcium potassium KCa2Ta3O10
(being abbreviated as KCTO) as a kind of perovskite of two-dimentional (2D) layer structure, has low cost, nontoxic, and chemical property is stablized etc.
Feature, but such perovskite type metal oxide nanometer causes photocatalytic activity poor because of the wide grade (about 3.5eV) of itself band gap.
Researchers have found that, with 0D-2D, 1D-2D composite materials are compared, and 2D-2D materials have larger contact area, are conducive to light
The migration of raw charge is so as to enhance its photocatalysis performance.Therefore carbonitride/tantalic acid calcium potassium 2D-2D nano-heterogeneous structures are constructed to answer
Closing light catalysis material helps to improve the photocatalytic activity of tantalic acid calcium potassium.
Up to the present, it is not yet found that preparing carbonitride/tantalic acid calcium potassium nitridation carbon composite nano-material and its photocatalysis
The documents and materials report of application.Gained composite material has good Photocatalyzed Hydrogen Production performance under solar irradiation, and prepares
Journey is environmentally protective, gathers around and has broad application prospects in the preparation of hydrogen energy source.
Invention content
The problem of visible light catalytic efficiency of the invention for graphite phase carbon nitride composite nano materials is low, provides one kind
Simple carbonitride/tantalic acid calcium potassium composite nano materials catalysis material preparation method.The preparation method is with simple and practicable water
Hot method synthesizes carbonitride/tantalic acid calcium potassium composite material, and the photochemical catalyst being prepared has preferable sunlight photocatalysis hydrogen manufacturing
Efficiency.
Technical solution of the present invention is as follows：
(1) graphite phase carbon nitride (g-C is prepared3N4) powder：
A certain amount of melamine is weighed in semi-enclosed crucible, is first placed in 80 DEG C of drying boxes 48h by raw material stoving,
Crucible is transferred in temperature programming tube furnace；With the heating rate of 3~5 DEG C/min be warming up to 400~600 DEG C calcining 2~
6h；After room temperature, take out, Yong Yan be ground to it is powdered after, use 0.05-0.2molL-1Dust technology cleans
For several times, removal residual basic species, then product is cleaned with distilled water and absolute ethyl alcohol, it centrifuges, it is dry, it is ground to powder with is ground
It is spare after shape, obtain g-C3N4Sample.
(2) tantalic acid calcium potassium KCa is prepared2Ta3O10Bulk powder：
Weigh potassium carbonate and grind 3~5min, according still further to ratio weigh calcium carbonate powder and potassium carbonate powder co-ground 5~
10min finally proportionally weighs tantalum pentoxide, is placed in mortar and is ground 5~10min, by the powder of gained mixture
End is transferred in corundum crucible, is placed in tube furnace and is calcined, and after room temperature, is taken out, and obtains tantalic acid calcium potassium bulk
Powder；The molar ratio of the raw material potassium carbonate, calcium carbonate and tantalum pentoxide is 1.1：2：3.
The calcining manners are：After being warming up to 600~800 DEG C first with the heating rate of 3~6 DEG C/min, then with 1~3
DEG C/heating rate of min is warming up to 1000~1400 DEG C, calcine 12-16h.Cooling rate is 4~6 DEG C/min, is cooled to 400
Room temperature cools down after~600 DEG C.
(3) tantalic acid calcium potassium (KCTO) flakelike powder is prepared：
The blocky powder obtained by step (2) is weighed in beaker, is immersed in salpeter solution and is sufficiently stirred to obtain H+
Ca2Ta3O10, centrifuge washing alcohol and wash for several times, drying weighs H+Ca2Ta3O10Powder is transferred to addition tetrabutyl hydrogen-oxygen in beaker
Change ammonium salt solution and deionized water, continual stirring ultrasound obtains H+Ca2Ta3O10Colloid, then by H+Ca2Ta3O10Colloid drops
It is added in Klorvess Liquid, stirs, static, centrifugation, washing alcohol is washed, and is dried, and grinding obtains KCTO flakelike powders；The nitric acid
Solution concentration is 3~6M, and mixing time is 48~72h.
H+Ca2Ta3O10, tetrabutylammonium hydroxide solution, deionized water, the usage ratio of Klorvess Liquid be 1g：0.5~
3ml：100~300ml：100~300ml；
Wherein, a concentration of the 10% of tetrabutylammonium hydroxide solution；A concentration of 1~3M of Klorvess Liquid；
(4) g-C is prepared3N4/KCa2Ta3O10Composite material：
a:Weigh the tantalic acid calcium potassium piece powder obtained by step (3) be added to ground several minutes in mortar after be proportionally added into step
Suddenly the nitridation carbon dust that prepared by (1) will be transferred to the deionized water that is added in beaker after several minutes of two kinds of material co-grounds,
Ultrasonic disperse, and be transferred in the hydrothermal reaction kettle of polytetrafluoroethyllining lining after stirring evenly, it is placed in baking oven and calcines, carry out
Hydro-thermal reaction, centrifuge washing are dry.
In step a, the KCa2Ta3O10With g-C3N4Ratio be 1g:0.42~0.67g.
The temperature of the hydro-thermal reaction is 120~160 DEG C, and the reaction time is 10~14h；
The temperature of the drying is 60 DEG C, drying time 12h.
The power of ultrasonic machine used is 250W, ultrasonic time 0.5-1h in the ultrasonic reaction.
A kind of tantalic acid calcium potassium/nitridation carbon composite of the present invention is used for the purposes of photocatalytic hydrogen production by water decomposition.
Using X-ray diffractometer (XRD), transmission electron microscope (TEM), micromorphology analysis is carried out to product, with first
Alcohol carries out photocatalysis hydrogen production experiment as solution, simulated visible light.
The features of the present invention：
The present invention is successfully prepared efficient g-C using calcination method and hydro-thermal method3N4/KCa2Ta3O10Nanometer sheet complex light is urged
Agent, preparation process have it is simple for process, of low cost, the period is short, advantages of environment protection.Prepared binary g-C3N4/
KCa2Ta3O10Catalysis material effectively improves the separative efficiency of photo-generate electron-hole pair, and then improves photocatalysis hydrogen production
Performance, and the recyclable stability of composite photo-catalyst is good, has potential application prospect in catalyzing manufacturing of hydrogen field.
Description of the drawings
Fig. 1 is prepared simple g-C3N4、KCa2Ta3O10、g-C3N4/KCa2Ta3O10The XRD diffraction spectras of composite photo-catalyst
Figure.
Fig. 2 a, b, c are respectively prepared simple g-C3N4, simple KCa2Ta3O10Sample, KCa2Ta3O10/g-C3N4Composite wood
The transmission electron microscope photo of material；D is g-C3N4/KCa2Ta3O10The high-resolution-ration transmission electric-lens photo of composite catalyst.
Fig. 3 is prepared simple g-C3N4, simple KCa2Ta3O10Sample, g-C3N4/KCa2Ta3O10Composite material is visible
Light H2-producing capacity figure.
Specific embodiment
Embodiment 1
(1) graphite-phase nitrogen carbide (g-C3N4) preparation：
g-C3N4Preparation using thermal polymerization melamine method；The melamine of 10g is weighed in semi-enclosed earthenware
In crucible, 48h is first placed in 80 DEG C of drying boxes by raw material stoving, then crucible is transferred in temperature programming tube furnace.With 3 DEG C/
The heating rate of min is heated to 500 DEG C of calcining 3h.After room temperature, take out, with mortar grinder to after powdered,
With a concentration of 50mL 0.01molL-1Dilute HNO3Cleaning 3 times, removal residual basic specie, then with deionized water and anhydrous
Ethyl alcohol is respectively washed 3 times.Most after 12h dry in 80 DEG C of baking ovens.
(2) tantalic acid calcium potassium (KCa2Ta3O10) preparation：
0.0860 g potassium carbonate powders are weighed first, are ground 5 minutes, and proportionally weigh the Paris white of 0.2265g
End, the powder co-ground ground with potassium carbonate proportionally weigh the tantalum pentoxide powder of 0.7500g after five minutes, with
Ground potassium carbonate, calcium carbonate mixed-powder are ground 10 minutes jointly.Mixed powder is transferred in crucible, is placed in
It runs affairs after being warming up to 600~800 DEG C with the heating rate of 5 DEG C/min in stove, then be warming up to the heating rate of 3 DEG C/min
1200 DEG C, calcine 14h.Cooling rate is 4 DEG C/min, and room temperature cools down after being cooled to 600 DEG C.Recovery product obtains tantalum after grinding
Sour calcium potassium bulk powder.Blocky powder 2g is weighed in beaker, 5M salpeter solutions 200ml stirring 72h is added in, makes its protonation
Obtain H+Ca2Ta3O10, after obtained material centrifugation drying, weigh 0.1 and powder be transferred in beaker, add in 100ml deionizations
Water, 0.05ml tetrabutylammonium hydroxide solution uninterruptedly stir ultrasound 15 days, obtain H+Ca2Ta3O10Colloid, then by H+
Ca2Ta3O10Colloid is added drop-wise in the Klorvess Liquid of 2M and stirs, static, is centrifuged out solid, and washing alcohol is washed for several times, and drying takes
Go out, with grind be ground to it is powdered after spare obtain KCa2Ta3O10Flakelike powder.
(3) 30%-g-C3N4/KCa2Ta3O10The preparation of composite material：
Weigh 1g KCa2Ta3O10It is added in mortar and grinds, then add in the g-C that 0.42g is prepared3N4Co-ground again
5 minutes, ground mixture is transferred in 100ml beakers, and adds in 50ml deionized waters, stirred, in the ultrasound of 250W
Ultrasound 1h under machine, the ground mixture that will be uniformly dispersed are transferred in the water heating kettle of 50ml polytetrafluoroethyllining linings, hydro-thermal at 160 DEG C
14h is reacted, is collected by centrifugation, washing alcohol is washed respectively three times, dry 12h at 60 DEG C.
Embodiment 2：40%-g-C3N4/KCa2Ta3O10The preparation of composite material：
Step (1) and step (2) are the same as embodiment 1；
(3) 40%-g-C3N4/KCa2Ta3O10The preparation of composite material：
Weigh 1g KCa2Ta3O10It is added in mortar and grinds, then add in the g-C that 0.67g is prepared3N4Co-ground again
5 minutes, ground mixture is transferred in 100ml beakers, and adds in 50ml deionized waters, stirred, in the ultrasound of 250W
Ultrasound 1h under machine, the ground mixture that will be uniformly dispersed are transferred in the water heating kettle of 50ml polytetrafluoroethyllining linings, hydro-thermal at 160 DEG C
14h is reacted, is collected by centrifugation, washing alcohol is washed respectively three times, dry 12h at 60 DEG C.
Embodiment 3：g-C3N4/KCa2Ta3O10Composite material photocatalytic hydrogen production activity is tested
Before Photocatalyzed Hydrogen Production experiment, 1wt%Pt loads first are carried out to catalyst.It is as follows：Take 50mg complex lights
Catalyst adds in suitable chloroplatinic acid in the Photoreactor of water containing 50mL and 10mL methanol solutions, the lower 300W of lasting stirring
Xenon light shining 1h obtains the photochemical catalyst of supporting Pt.It turns on light before reaction, by the suspension of catalyst ultrasonic wave decentralized processing
10min, then the nitrogen led into reactor and ensure that the reaction is under anaerobic to remove the oxygen dissolved in solution completely
It carries out.During reaction, it should be ensured that reaction solution, which is in, continues stirring to keep light in the entire experiment process
The suspended state of catalyst.It is intermittently sampled by diaphragm, every time extraction 0.4mL gases, last nitrogen buffer gas,
The hydrogen that light-catalyzed reaction generates is passed through into gas chromatographic analysis.
Fig. 1 is prepared simple g-C3N4、KCa2Ta3O10、g-C3N4/KCa2Ta3O10The XRD diffraction spectras of composite photo-catalyst
Figure.As can be seen from Figure 1 g-C3N4/KCa2Ta3O10XRD spectrum in without find g-C3N4Diffraction maximum, it may be possible to g-C3N4
Diffraction maximum (27.4 °) and KCa2Ta3O10Diffraction maximum compared to peak intensity it is too weak the reason of.In KCa2Ta3O10、 g-C3N4/
KCa2Ta3O10XRD spectra in can see apparent KCa2Ta3O10Diffraction maximum, and the two to be said there is no significantly distinguishing
Bright KCa2Ta3O10Preferable crystal form is still kept in composite catalyst.
Fig. 2 a, b, c are respectively prepared simple g-C3N4, simple KCa2Ta3O10Sample, KCa2Ta3O10/g-C3N4Composite wood
The transmission electron microscope photo of material.From Fig. 2 (a) it can be seen that simple g-C3N4Sheet class graphene-structured is presented；Scheming can be in (b)
Find out simple KCa2Ta3O10Rectangular pieces for rule；That figure (c) shows is g-C3N4With KCa2Ta3O10It is combined with each other, structure
G-C is built3N4/KCa2Ta3O10Composite catalyst；That figure (d) shows is g-C3N4/KCa2Ta3O10The high-resolution of composite catalyst
Transmission electron microscope photo, as we can clearly see from the figure g-C3N4With KCa2Ta3O10It is combined with each other well.
Fig. 3 is prepared simple g-C3N4, simple KCa2Ta3O10Sample, g-C3N4/KCa2Ta3O10Composite material is visible
Light H2-producing capacity figure.G-C can be analyzed from Fig. 33N4/KCa2Ta3O10Composite material has excellent photocatalytic activity, phase
Monolithic catalyst hydrogen manufacturing effect is compared to be obviously improved.
Claims (10)
1. the preparation method of a kind of carbonitride/tantalic acid calcium potassium composite material, which is characterized in that include the following steps：
(1) graphite phase carbon nitride g-C is prepared3N4Powder, it is spare；
(2) tantalic acid calcium potassium KCa is prepared2Ta3O10Bulk powder, it is spare；
a：A certain amount of potassium carbonate powder is weighed, is ground several minutes；
b：A certain amount of calcium carbonate powder is weighed in proportion, with several minutes of co-ground again of ground potassium carbonate powder；
c：A certain amount of tantalum pentoxide powder is weighed in proportion, and with ground potassium carbonate, calcium carbonate mixed-powder is ground jointly
Several minutes of mill；
d：Mixed powder is transferred in crucible, is placed in calcining in tube furnace, after room temperature is naturally cooled to, take out
To tantalic acid calcium potassium bulk powder；
(3) tantalic acid calcium potassium flakelike powder is prepared：
The blocky powder obtained by step (2) is weighed in beaker, being immersed in salpeter solution and being sufficiently stirred makes its protonation obtain H+
Ca2Ta3O10, obtained material centrifugation washing alcohol wash for several times, drying, powder is transferred in beaker, add in tetrabutylammonium hydroxide
Solution and deionized water, continual stirring ultrasound, obtain H+Ca2Ta3O10Colloid, then by H+Ca2Ta3O10Colloid is added drop-wise to
In Klorvess Liquid, stirring is static, centrifugation, and washing alcohol is washed for several times, is dried, and grinding obtains KCa2Ta3O10Flakelike powder；
(4) carbonitride/tantalic acid calcium potassium composite material is prepared：
Weigh in proportion step (3) preparation tantalic acid calcium potassium piece powder be placed in mortar grind several minutes after be proportionally added into step
(1) g-C prepared3N4Powder remixes and ultrasonic disperse in deionized water is shifted after grinding several minutes, stirs evenly, by acquisition
Solution is transferred in the hydrothermal reaction kettle of polytetrafluoroethyllining lining, is placed in baking oven and is calcined, progress hydro-thermal reaction, centrifuge washing,
It is dry.
2. a kind of preparation method of carbonitride/tantalic acid calcium potassium composite material as described in claim 1, it is characterised in that：Step
(1) in, graphite phase carbon nitride g-C is prepared3N4The step of powder is：
It weighs a certain amount of melamine to be positioned in semi-enclosed crucible, is first placed in 80 DEG C of drying boxes 48h by raw material stoving,
Crucible is transferred in the tube furnace of auto-programming heating, 400~600 DEG C of calcinings are warming up to the heating rate of 3~5 DEG C/min
2~6h；After room temperature, take out, Yong Yan be fully ground to after powdered, use 0.05-0.2molL-1It is dilute
HNO3It cleans for several times, removal residual basic species, then product is cleaned with distilled water and absolute ethyl alcohol, centrifuge, it is dry, it is ground with is ground
It is extremely powdered rear spare, obtain g-C3N4Sample.
3. a kind of preparation method of carbonitride/tantalic acid calcium potassium composite material as described in claim 1, it is characterised in that：Step
(2) in, the potassium carbonate, the molar ratio of calcium carbonate and tantalum pentoxide is 1.1：2：3.
4. a kind of preparation method of carbonitride/tantalic acid calcium potassium composite material as described in claim 1, it is characterised in that：Step
(2) in a, the milling time of the potassium carbonate is 3~5min.
5. a kind of preparation method of carbonitride/tantalic acid calcium potassium composite material as described in claim 1, it is characterised in that：Step
(2) in b, the time of potassium carbonate and calcium carbonate co-ground is 5~10min.
6. a kind of preparation method of carbonitride/tantalic acid calcium potassium composite material as described in claim 1, it is characterised in that：Step
(2) in c, the time of the potassium carbonate, calcium carbonate and tantalum pentoxide co-ground is 5~10min.
7. a kind of preparation method of carbonitride/tantalic acid calcium potassium composite material as described in claim 1, it is characterised in that：Step
(2) in d, the calcining manners are：
After being warming up to 600~800 DEG C first with the heating rate of 3~6 DEG C/min, then the heating rate heating with 1~3 DEG C/min
To 1000~1400 DEG C, 12-16h is calcined；Cooling rate is 4~6 DEG C/min, and room temperature cools down after being cooled to 400~600 DEG C.
8. a kind of preparation method of carbonitride/tantalic acid calcium potassium composite material as described in claim 1, it is characterised in that：Step
(3) in, a concentration of 3~6M of salpeter solution, volume is 200~500ml, and mixing time is 48~72h；H+Ca2Ta3O10, four
Butyl ammonium hydroxide solution, deionized water, the usage ratio of Klorvess Liquid are 1g：0.5~3ml：100~300ml：100~
300ml；
Wherein, the mass percentage concentration of tetrabutylammonium hydroxide solution is 10%；A concentration of 1~3M of Klorvess Liquid.
9. a kind of preparation method of carbonitride/tantalic acid calcium potassium composite material as described in claim 1, it is characterised in that：Step
(4) in, the amount ratio of the tantalic acid calcium potassium piece powder and graphite phase carbon nitride is 1g：Ultrasonic disperse institute described in 0.42~0.67g
Be 250W with the power of ultrasonic machine, ultrasonic time 0.5-1h, the hydro-thermal reaction time is 10~14h, reaction temperature for 120~
160 DEG C, the temperature of the drying is 60 DEG C, drying time 12h.
10. a kind of carbonitride made from the preparation method as described in claim 1~9/tantalic acid calcium potassium composite material is used for photocatalysis
The purposes of hydrogen production by water decomposition.
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| CN113304765A (en) * | 2020-02-26 | 2021-08-27 | 南京理工大学 | Antimony nanosheet and graphite-like phase carbon nitride nanosheet composite material and preparation method thereof |
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| CN111871442B (en) * | 2020-07-31 | 2023-04-11 | 江苏大学 | Niobium-tantalum sulfide/carbon nitride nanosheet photocatalytic material, and preparation method and application thereof |
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