CN107790142B - A kind of cobalt hydroxide/niobic acid tin composite material and its preparation method and application - Google Patents
A kind of cobalt hydroxide/niobic acid tin composite material and its preparation method and application Download PDFInfo
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- CN107790142B CN107790142B CN201711052930.1A CN201711052930A CN107790142B CN 107790142 B CN107790142 B CN 107790142B CN 201711052930 A CN201711052930 A CN 201711052930A CN 107790142 B CN107790142 B CN 107790142B
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- niobic acid
- acid tin
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- cobalt hydroxide
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- 239000002253 acid Substances 0.000 title claims abstract description 81
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 title claims abstract description 26
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 claims abstract description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 15
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 10
- 238000006722 reduction reaction Methods 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 8
- 238000007146 photocatalysis Methods 0.000 claims abstract description 7
- 238000001338 self-assembly Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 7
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- 240000007594 Oryza sativa Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000004817 gas chromatography Methods 0.000 claims description 3
- 238000007689 inspection Methods 0.000 claims description 3
- 239000002135 nanosheet Substances 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 241000446313 Lamella Species 0.000 claims description 2
- 230000008901 benefit Effects 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims 2
- 239000010955 niobium Substances 0.000 claims 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229910000428 cobalt oxide Inorganic materials 0.000 claims 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims 1
- 238000002242 deionisation method Methods 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 38
- 239000003054 catalyst Substances 0.000 abstract description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 1
- 239000012429 reaction media Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 abstract 1
- 239000002356 single layer Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001994 activation Methods 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- -1 ZnGe2O4 Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 229910003378 NaNbO3 Inorganic materials 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910007486 ZnGa2O4 Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- MUPJWXCPTRQOKY-UHFFFAOYSA-N sodium;niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Na+].[Nb+5] MUPJWXCPTRQOKY-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8474—Niobium
-
- 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
-
- B01J35/39—
Abstract
The invention discloses a kind of Co (OH)2/SnNb2O6The novel processing step and its photo catalytic reduction CO of composite material2System probe, belong to material preparation and Utilization of Carbon Dioxide technical field.The cobalt hydroxide load niobic acid tin composite material is using niobic acid tin as carrier, using cobalt nitrate and sodium hydroxide as reactant, by complex coordination-Electrostatic Absorption-self assembly strategy, self assembly is the Co (OH) of few layer after the niobic acid tin surfaces one-step method in-situ preparation cobalt hydroxide of single layer2/SnNb2O6The preparation process of composite material, the material is simple and convenient, at low cost.Meanwhile the present invention discloses out one kind and carries out high efficiency photocatalysis reduction CO based on the catalytic composite materials2System, with Co (OH)2/SnNb2O6Composite material is as photochemical catalyst, and by introducing the addition of specific reaction medium, acquisition can efficiently restore CO2For the light-catalyzed reaction system of CO.
Description
Technical field
The invention belongs to material preparation and Utilization of Carbon Dioxide fields, and in particular to a kind of cobalt hydroxide/niobic acid tin
Composite material and preparation method and application.
Background technique
How greenhouse effects control effectively to it and solve by complete as one of current most important environmental problem
The extensive concern of ball.Largely studies have shown that greenhouse gases CO may be implemented using photocatalysis technology2Effective conversion, pass through
It is driving force using solar energy, by CO2It is converted to CH3OH、CH4And the fuel and other chemicals of the high added values such as CO.But
CO2Condition needed for the activation process of molecule is harsh, therefore photocatalysis CO2Reduction is most challenging forward position research direction.
In recent years, many inorganic matter semiconductor materials (such as: NaNbO3, ZnGe2O4, ZnGa2O4And TiO2) applied
In photo catalytic reduction CO2In the process.Likewise, part researcher also explore organic semiconducting materials (such as: g-C3N4,
MOFs) and layered double hydroxide (LDHs) etc. is in photo catalytic reduction CO2The application of aspect.In addition to this, dye sensitization,
The means such as noble metal decorated and co-catalyst load are also commonly used for improving the reduction activation of catalyst.However, constructing realization
Visible light photocatalysis restores CO2Reaction system be still a stern challenge.Reason is most inorganic semiconductor
Material is only capable of using ultraviolet light, and organic semiconductor photochemical catalyst is there are photo-generated carrier recombination rate is high, and stability is low to lead
The problems such as activation is not high.Importantly, most of photochemical catalyst and CO2Interaction between molecule is weaker, Wu Fashi
Existing CO2The efficient absorption and activating catalytic of molecule.
Niobic acid tin has good photocatalytic activity and structural specificity as a kind of typical layered semiconductor material.
Its photo catalytic reduction CO2Activity was also once explored and studied.Up to now, to niobic acid tin material in photo catalytic reduction CO2Aspect
Research it is still seldom, and most of activity is not high.The major reason of this result is caused to may is that higher internal electricity
Lotus density and too small interlamellar spacing make niobic acid tin for CO2The adsorption capacity of molecule is weaker, limits CO2Molecule is in reaction system
In activating catalytic process.Other than photochemical catalyst, photo catalytic reduction CO2Reaction system construct be also influence reaction live
An important factor for property.Effective reaction system is constructed, and the migration of carrier can be promoted, and improves solar energy utilization ratio, enhancing
Interaction between catalyst reaction molecule is to sufficiently improve system photo catalytic reduction CO2Activity.With regard to current research
As a result from the point of view of, the photo catalytic reduction CO that is explored out2Reaction system have that reactivity is low, and selectivity of product is low and urges
Change the problems such as mechanism is still not clear.
Summary of the invention
The purpose of the present invention is to provide a kind of Co (OH)2/SnNb2O6The novel processing step of composite material simultaneously constructs one
A efficient realization CO2Photo catalytic reduction reaction system.The catalyst and constructing for reaction system solve traditional niobic acid tin
The problem that reactivity is low and quantum efficiency is low, and substantially increase CO2The selectivity of reduzate and photocatalytic process it is anti-
Answer activity.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of cobalt hydroxide load niobic acid tin composite material is cobalt nitrate and sodium hydroxide conduct using niobic acid tin as carrier
The Co (OH) of few layer is prepared by hydro-thermal method-ligand complex method-self-assembly method for reactant2/SnNb2O6Composite material.And
The material is applied to a kind of novel photo catalytic reduction CO2Reaction system realizes CO2Efficient reduction.Specifically include following step
It is rapid:
1) preparation of niobic acid tin: weighing 3g niobic acid and stannic chloride mixing sample (molar ratio 1:1) is added to 70 mL and goes
Ionized water, in 150-220o48 h of hydro-thermal reaction under the conditions of C, after be centrifuged, wash, it is dry, obtain stratiform niobic acid tin.Institute
Obtained stratiform niobic acid tin sample takes 2 g in the mixed solution of 100 mL water and 1 g methyl pyrrolidone after 6 h of ultrasound,
Centrifugation obtains the finely dispersed suspension of monolithic layer niobic acid tin after removing unstripped stratiform niobic acid tin under 4000 rmp/min.
2) Co (OH)2/SnNb2O6The preparation of composite material: the suspension containing 1 g monolithic layer niobic acid tin is placed in a beaker,
0-0.5 g polyvinylpyrrolidone and 0-0.5 g methyl pyrrolidone is first added, after being uniformly mixed, adds 200-500
Sodium hydroxide solution is added dropwise thereto, is again sealed off stirring, by the solution after 1 h is stirred in sealing for the cobalt nitrate solution of μ L
It is transferred in the ptfe autoclave of 100 mL, in 100-200o5-12 h is reacted under conditions of C, to its natural cooling
Sample is taken out afterwards, it is sufficiently dry after centrifuge washing, it can be obtained the modification of in-situ preparation cobalt hydroxide in few layer niobic acid sijna rice
Piece composite material.
3) photo catalytic reduction CO2System construction method: 10 mg Co (OH) are added in the reactor2/SnNb2O6Composite wood
Material, the mixed solution (volume ratio 1: 2: 3) of 0.5-10 mL triethanolamine, water and acetonitrile, 0.5-5 mg dichloro join pyrrole
Pyridine ruthenium ([Ru (bpy)3]Cl2•6H2O), it is passed through CO2Other gases in solution are removed, and keep CO in reactor2Partial pressure is 1
Then bar carries out photo catalytic reduction CO2Reaction, products therefrom carry out offline inspection using gas-chromatography.
Remarkable advantage of the invention is:
1) preparation condition of the present invention is low, easy to operate, through the invention preparation method Co (OH)2It can uniformly modify
SnNb2O6On each lamella, so as to sufficiently improve niobic acid tin in photo catalytic reduction CO2The reactivity of aspect.Effectively overcome
Previous SnNb2O6Equal photochemical catalysts exist in modification co-catalyst disperses non-uniform problem.
2) composite material being prepared through the invention, because its surface introduces basic specie, to CO2Molecule have compared with
Strong adsorption capacity, therefore it has stronger CO compared to traditional niobic acid tin material2Absorption and activation capacity.
3) using the composite material as photochemical catalyst, a novel photo catalytic reduction CO is constructed2Reaction system, the body
System is for CO2Molecule has efficient adsorption activation and catalyzed conversion ability, can realize CO under visible light2Efficient reduction.
Meanwhile the stability and high recycling rate of the catalysis material, practical application value with higher.
Detailed description of the invention
Fig. 1 is the X-ray powder diffraction figure of embodiment 1, comparative example and the niobic acid tin photochemical catalyst being prepared.
Fig. 2 is the cobalt hydroxide/niobic acid tin composite material photochemical catalyst for the few layer that embodiment 1 and comparative example are prepared
Transmission electron microscope picture.
Fig. 3 be embodiment 1, comparative example and pure phase niobic acid tin under constructed system photo catalytic reduction CO2Activity comparison
Figure.
Fig. 4 is the photo catalytic reduction CO in different reaction systems of embodiment 12Active comparison diagram.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
Comparative example
It weighs 3g niobic acid and stannic chloride mixing sample (molar ratio 1:1) is added to 70 mL deionized waters, 200oC
Under the conditions of 48 h of hydro-thermal reaction, after be centrifuged, wash, it is dry, obtain stratiform niobic acid tin.100 mg stratiform niobic acid tin are placed in
In beaker, the cobalt nitrate solution of 300 μ L is added thereto, 500 μ L hydroxides are added dropwise thereto after 1 h is stirred in sealing
Sodium solution is again sealed off stirring, finally obtained sample is carried out centrifuge washing, and sufficiently dry.
Embodiment 1
It weighs 3g niobic acid and stannic chloride mixing sample (molar ratio 1:1) is added to 70 mL deionized waters, 220oC
Under the conditions of 48 h of hydro-thermal reaction, after be centrifuged, wash, it is dry, obtain stratiform niobic acid tin.Obtained stratiform niobic acid tin sample
It takes 2 g in the mixed solution of 100 mL water and 1 g methyl pyrrolidone after 6 h of ultrasound, removal is centrifuged under 4000 rmp/min
The finely dispersed suspension of monolithic layer niobic acid tin is obtained after unstripped stratiform niobic acid tin.Tin containing 1 g monolithic layer niobic acid is hanged
Turbid is placed in a beaker, and 0.5 g polyvinylpyrrolidone is first added, and after being uniformly mixed, adds the cobalt nitrate of 200 μ L
Sodium hydroxide solution is added dropwise thereto, is again sealed off stirring, which is transferred to 100 after 1 h is stirred in sealing for solution
In the ptfe autoclave of mL, 100o5 h are reacted under conditions of C, take out sample after its natural cooling, are centrifuged
It is sufficiently dry after washing, it can be obtained the modification of in-situ preparation cobalt hydroxide in few layer niobic acid tin nanosheet composite material.
Embodiment 2
It weighs 3g niobic acid and stannic chloride mixing sample (molar ratio 1:1) is added to 70 mL deionized waters, 150oC
Under the conditions of 48 h of hydro-thermal reaction, after be centrifuged, wash, it is dry, obtain stratiform niobic acid tin.Obtained stratiform niobic acid tin sample
It takes 2 g in the mixed solution of 100 mL water and 1 g methyl pyrrolidone after 6 h of ultrasound, removal is centrifuged under 4000 rmp/min
The finely dispersed suspension of monolithic layer niobic acid tin is obtained after unstripped stratiform niobic acid tin.It will be outstanding containing 1 g monolithic layer niobic acid tin
Turbid is placed in a beaker, and 0.5 g methyl pyrrolidone is first added, and after being uniformly mixed, the cobalt nitrate for adding 500 μ L is molten
Sodium hydroxide solution is added dropwise thereto, is again sealed off stirring, which is transferred to 100 mL after 1 h is stirred in sealing for liquid
Ptfe autoclave in, 200o12 h are reacted under conditions of C, are taken out sample after its natural cooling, centrifugation is washed
It is sufficiently dry after washing, it can be obtained the modification of in-situ preparation cobalt hydroxide in few layer niobic acid tin nanosheet composite material.
Embodiment 3
It weighs 3g niobic acid and stannic chloride mixing sample (molar ratio 1:1) is added to 70 mL deionized waters, 180oC
Under the conditions of 48 h of hydro-thermal reaction, after be centrifuged, wash, it is dry, obtain stratiform niobic acid tin.Obtained stratiform niobic acid tin sample
It takes 2 g in the mixed solution of 100 mL water and 1 g methyl pyrrolidone after 6 h of ultrasound, removal is centrifuged under 4000 rmp/min
The finely dispersed suspension of monolithic layer niobic acid tin is obtained after unstripped stratiform niobic acid tin.It will be outstanding containing 1 g monolithic layer niobic acid tin
Turbid is placed in a beaker, and 0.2 g polyvinylpyrrolidone and 0.3 g methyl pyrrolidone is first added, after being uniformly mixed, then
The cobalt nitrate solution of 300 μ L is added sodium hydroxide solution is added dropwise thereto, is again sealed off stirring after 1 h is stirred in sealing,
The solution is transferred in the ptfe autoclave of 100 mL, 160o8 h are reacted under conditions of C, to its natural cooling
Sample is taken out afterwards, it is sufficiently dry after centrifuge washing, it can be obtained the modification of in-situ preparation cobalt hydroxide in few layer niobic acid sijna rice
Piece composite material.
Embodiment 4
It weighs 3g niobic acid and stannic chloride mixing sample (molar ratio 1:1) is added to 70 mL deionized waters, 160oC
Under the conditions of 48 h of hydro-thermal reaction, after be centrifuged, wash, it is dry, obtain stratiform niobic acid tin.Obtained stratiform niobic acid tin sample
It takes 2 g in the mixed solution of 100 mL water and 1 g methyl pyrrolidone after 6 h of ultrasound, removal is centrifuged under 4000 rmp/min
The finely dispersed suspension of monolithic layer niobic acid tin is obtained after unstripped stratiform niobic acid tin.It will be outstanding containing 1 g monolithic layer niobic acid tin
Turbid is placed in a beaker, and 0.2 g polyvinylpyrrolidone and 0.5 g methyl pyrrolidone is first added, after being uniformly mixed, then
The cobalt nitrate solution of 400 μ L is added sodium hydroxide solution is added dropwise thereto, is again sealed off stirring after 1 h is stirred in sealing,
The solution is transferred in the ptfe autoclave of 100 mL, 160o6 h are reacted under conditions of C, to its natural cooling
Sample is taken out afterwards, it is sufficiently dry after centrifuge washing, it can be obtained the modification of in-situ preparation cobalt hydroxide in few layer niobic acid sijna rice
Piece composite material.
Embodiment 5
It is added in 10 mg embodiments 1 in the reactor and obtains Co (OH)2/SnNb2O6Composite material, 2 mL triethanolamines,
The mixed solution (volume ratio 1: 2: 3) of water and acetonitrile, 2 mg dichloro bipyridyl ruthenium ([Ru (bpy)3]Cl2•6H2O), lead to
Enter CO2Other gases in solution are removed, and keep CO in reactor2Partial pressure is 1 bar, then carries out photo catalytic reduction CO2Instead
It answers, products therefrom carries out offline inspection using gas-chromatography.
Fig. 1 is the XRD spectrum of the pure phase niobic acid tin, comparative example and the embodiment 1 that are prepared, the niobic acid tin card of contrast standard
Piece knows that niobic acid tin material (PDF# 84-1810) is successfully prepared.After the modification of cobalt hydroxide, the diffraction maximum of sample
There is no significantly changing, this illustrates that modification does not destroy the structure of niobic acid tin.Spreading out for cobalt hydroxide is not observed
Penetrate peak, it may be possible to due to load capacity it is less caused by.
Fig. 2 is the cobalt hydroxide/niobic acid tin composite material photochemical catalyst for the few layer that embodiment 1 and comparative example are prepared
Transmission electron microscope picture.It can be seen that obtained niobic acid tin is few layer material in embodiment 1, cobalt hydroxide can uniform, high dispersive
On the niobic acid tin nanometer sheet surface for being carried on few layer of property.And the obvious lamellar spacing of niobic acid tin sample that comparative example obtains is bigger,
The load factor and uniformity of cobalt hydroxide are worse.
Fig. 3 is the niobic acid that the preparation-obtained cobalt hydroxide of embodiment 1 loads niobic acid tin composite material, comparative example and pure phase
Tin material photo catalytic reduction CO in the system described in embodiment 52For the reactivity result of CO.Compare the reaction result of three
It is found that the amount for the CO that embodiment 1 obtains be it is highest, reached 23.62 μm of ol h-1 g-1, and the niobic acid tin of pure phase is anti-at this
It answers in system substantially without CO2Reduction activation, this illustrates that composite material prepared by the present invention and the reaction system constructed can
Realize efficiently reduction CO2For CO.The Activity Results of comparative example 1 and comparative example are it is found that Co (OH) prepared by the present invention2/
SnNb2O6The reactivity of composite material is conventional method preparation Co (OH)2/SnNb2O610 times or so of composite material.
Fig. 4 is the resulting composite material of embodiment 1 photo catalytic reduction CO in different reaction systems2It is right for the activity of CO
Than figure.R-CO is denoted as with the result that reaction system constructed by the present invention obtains2.Only water is used to be denoted as solvent in the reactor
R-H2O.In R-CO2N is used in reaction system2Instead of CO2Reaction system full of reactor is denoted as R-N2.In R-CO2Reaction system
In the reaction system of dichloro bipyridyl ruthenium be not added be denoted as Without-Ru.As a result as shown in figure 3, using N in reactor2Instead of CO2It is several
It is generated without CO, this illustrates that system is strictly photo catalytic reduction CO2.Comparison system is developed without the performance specification present invention substantially
Reaction system in each element be it is essential, also further demonstrate that the system is high efficiency photocatalysis reduction CO2's
System.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (4)
1. a kind of cobalt hydroxide/niobic acid tin composite material preparation method, it is characterised in that: utilize complex coordination-Electrostatic Absorption-
Self assembly strategy, using cobalt nitrate as presoma, under alkaline condition, in-situ preparation cobalt hydroxide is modified in few layer niobic acid sijna
On rice piece composite material；
Specifically includes the following steps:
1) preparation of niobic acid tin: the niobic acid and stannic chloride mixing sample 3g that molar ratio is 1:1 are weighed, 70 mL deionizations are added to
Water, in 150-220o48 h of hydro-thermal reaction under the conditions of C, after be centrifuged, wash, it is dry, obtain stratiform niobic acid tin；It is acquired
Stratiform niobic acid tin sample take 2 g in the mixed solution of 100 mL water and 1 g methyl pyrrolidone after 6 h of ultrasound, 4000
Centrifugation obtains the finely dispersed suspension of monolithic layer niobic acid tin after removing unstripped stratiform niobic acid tin under rmp/min；
2) preparation of composite material: the suspension containing 1 g monolithic layer niobic acid tin is placed in a beaker, and the poly- second of 0-0.5 g is first added
Alkene pyrrolidone and 0-0.5 g methyl pyrrolidone, after being uniformly mixed, add the cobalt nitrate solution of 200-500 μ L,
After 1 h of sealing stirring, sodium hydroxide solution is added dropwise thereto, is again sealed off stirring, which is transferred to 100 mL's
In ptfe autoclave, in 100-200o5-12 h is reacted under conditions of C, takes out sample after its natural cooling, from
It is sufficiently dry after heart washing, it can be obtained the modification of in-situ preparation cobalt hydroxide in few layer niobic acid tin nanosheet composite material.
2. cobalt hydroxide made from preparation method according to claim 1/niobic acid tin composite material, it is characterised in that: hydrogen
For the particle size of cobalt oxide in 0.5-5 nm, niobic acid tin is few layer nanometer sheet material structure, and cobalt hydroxide is dispersed in niobium
On each lamella of sour tin.
3. the application of cobalt hydroxide according to claim 2/niobic acid tin composite material, it is characterised in that: cobalt hydroxide/niobium
Sour tin composite material can high efficiency photocatalysis reduction CO for constructing2Catalyzed conversion system.
4. application according to claim 3, it is characterised in that: can high efficiency photocatalysis reduction CO2Catalyzed conversion system structure
Building includes: that 10 mg cobalt hydroxides/niobic acid tin composite material is added in the reactor, and 0.5-10 mL volume ratio is 1: 2: 3
Triethanolamine, water and acetonitrile mixed solution, 0.5-5 mg dichloro bipyridyl ruthenium is passed through CO2Remove other gas in solution
Body, and keep CO in reactor2Partial pressure is 1 bar, then carries out photo catalytic reduction CO using visible light2Reaction, products therefrom benefit
Offline inspection is carried out with gas-chromatography.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20160076159A1 (en) * | 2013-05-31 | 2016-03-17 | Kabushiki Kaisha Toshiba | Photochemical reaction device and thin film |
| CN106799222A (en) * | 2017-02-09 | 2017-06-06 | 江苏大学 | A kind of preparation method of titanium dioxide/niobium acid tin composite nano materials |
| CN106881079A (en) * | 2017-02-09 | 2017-06-23 | 江苏大学 | A kind of preparation method of two dimensional oxidation tungsten/niobic acid tin nanometer sheet piece composite |
| CN107224986A (en) * | 2017-07-21 | 2017-10-03 | 江苏大学 | A kind of molybdenum disulfide/niobic acid tin composite nano materials and purposes |
-
2017
- 2017-11-01 CN CN201711052930.1A patent/CN107790142B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160076159A1 (en) * | 2013-05-31 | 2016-03-17 | Kabushiki Kaisha Toshiba | Photochemical reaction device and thin film |
| CN106799222A (en) * | 2017-02-09 | 2017-06-06 | 江苏大学 | A kind of preparation method of titanium dioxide/niobium acid tin composite nano materials |
| CN106881079A (en) * | 2017-02-09 | 2017-06-23 | 江苏大学 | A kind of preparation method of two dimensional oxidation tungsten/niobic acid tin nanometer sheet piece composite |
| CN107224986A (en) * | 2017-07-21 | 2017-10-03 | 江苏大学 | A kind of molybdenum disulfide/niobic acid tin composite nano materials and purposes |
Non-Patent Citations (1)
| Title |
|---|
| A CoOx-modified SnNb2O6 photoelectrode for highly efficient oxygen evolution from water;Ryo Niishiro,et.al.;《ChemComm》;20161212;第53卷;第629-632页 * |
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