CN106955699A - A kind of high-efficiency solar fixed nitrogen catalysis material and preparation method thereof - Google Patents
A kind of high-efficiency solar fixed nitrogen catalysis material and preparation method thereof Download PDFInfo
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- CN106955699A CN106955699A CN201610015669.7A CN201610015669A CN106955699A CN 106955699 A CN106955699 A CN 106955699A CN 201610015669 A CN201610015669 A CN 201610015669A CN 106955699 A CN106955699 A CN 106955699A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000000463 material Substances 0.000 title claims abstract description 72
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 54
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims description 19
- 239000000839 emulsion Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- 150000001621 bismuth Chemical class 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 229910001451 bismuth ion Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 22
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- 238000007146 photocatalysis Methods 0.000 abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 abstract description 8
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 abstract description 5
- 229910052797 bismuth Inorganic materials 0.000 abstract description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 108010020943 Nitrogenase Proteins 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 37
- 229910002915 BiVO4 Inorganic materials 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000012620 biological material Substances 0.000 description 3
- 238000004178 biological nitrogen fixation Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 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
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- -1 oleate ions Chemical class 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
Abstract
The present invention relates to a kind of high-efficiency solar fixed nitrogen catalysis material and preparation method thereof, the chemical composition of the catalysis material is Bi2O3-x/nBiaMOb, wherein, x=0~1, n=0~1, a=0~2, b=0~6, M is at least one of V, Mo, W.The catalysis material of the present invention includes bismuth-based oxide Bi2O3-x(x=0~1) or itself and BiaMObThe composite of (M=V, Mo, W) catalysis material, catalysis material of the invention not only has high photocatalysis nitrogenase activity, also with high stability.Bi in the material2O3-x(x=0~1) can be adsorbed and the nitrogen in activating air, promote the key fracture of nitrogen nitrogen three, ammonia is generated in water.
Description
Technical field
The present invention relates to a kind of high-efficiency solar fixed nitrogen catalysis material and preparation method thereof, belong to catalysis material technology neck
Domain.
Background technology
Ammonia provides nitrogen for plant particularly cereal crops, in the widely used of industrial quarters, is sulfuric acid in the world today
The maximum chemical products of outer yield, maximum consumption is chemical fertilizer at present.Traditional fixed nitrogen approach mainly has biological nitrogen fixation, chemistry
Fixed nitrogen.Biological nitrogen fixation can be carried out under the conditions of comparatively gentle, but can only occur in the plant and microorganism of minority, it is difficult to
Carry out large-scale production application.Chemical nitrogen fixation effectively solves the deficiency of biological nitrogen fixation, but whole process energy consumption is big, greatly
The use of amount not only causes soil hardening, and nitrate causes the more serious pollution of environment with water seepage.At present, All Around The World is all
The energy, grain and environmental problem are faced with, the method for new fixed nitrogen production ammonia is probed into the popular problem of scientific circles.
The key of ammonia synthesis reaction is N2Activation.If luminous energy is introduced into this reaction system, it is likely that realize
This reaction.Photocatalysis fixed nitrogen is to utilize response of the semiconductor light-catalyst to light, by the way that nitrogen is converted ammonification, turns luminous energy
A kind of new technology of chemical energy is melted into, the energy, environmental protection is saved because of it and is asked as the important Science and Technology of photocatalysis field
Topic.
The key problem of photocatalysis nitrogen fixation technology is the design of suitable photochemical catalyst, exploitation with developing.Current research is main
Concentrate on the TiO of Fe doping2Base system row photochemical catalyst.But with regard to TiO2For, there are several crucial technical barriers, such as
TiO2Band gap be 3.2eV, be only capable of being excited by ultraviolet light (only account for solar energy 3.8%), in addition TiO2Photo-generated carrier is answered
Conjunction rate is high, and quantum efficiency is low (less than 4%), and the utilization rate of solar energy is low, almost without photoresponse in visible-range；With
When photocatalysis fixed nitrogen, 1-10 μm of ol/L ammonia nitrogen can only be produced.
New and effective catalysis material is researched and developed, is the key that photocatalysis fixed nitrogen is realized using solar energy, is also that photocatalysis enters one
Step moves towards practical inexorable trend and developing direction.The key issue of photocatalysis fixed nitrogen is the activation of the keys of N ≡ N tri-.It is big absolutely
Most catalysis materials are in itself without activation N2Ability, therefore, fundamentally to realize catalysis material solar energy consolidate
Nitrogen, it is necessary to make it with N can be activated2Other materials be combined.This material can be noble metal or the metal rich in electronics
Oxide.In view of the Cost Problems of noble metal, the metal oxide of electron rich turns into the first choice of co-catalyst.Bi elements exist
When forming metal oxide, the lone pair electrons contained on its Bi atom, which are often not involved in into, to be built, and becomes electron rich chemical combination
Thing.It therefore, it can consider to introduce Bi ions in catalysis material preparation process, make it while generating a part of Bi metal
The oxide carried surface in catalysis material, plays activation N2Effect.Prepare this Bi base oxides and catalysis material
Composite, can be greatly improved catalysis material solar energy effect under nitrogen-fixing efficiency, both with higher scientific value
There is the practical significance to alleviating energy crisis, preventing and treating environmental pollution again.
The content of the invention
The above mentioned problem existed for existing photocatalysis nitrogen fixation technology, it is solid it is an object of the invention to provide a kind of high-efficiency solar
Nitrogen catalysis material, while providing a kind of simple, method for preparing the catalysis material that quick, controllability is high.
Here, the present invention provides a kind of high-efficiency solar fixed nitrogen catalysis material, the chemical composition of the catalysis material is
Bi2O3-x/nBiaMOb, wherein, x=0~1, n=0~1, a=0~2, b=0~6, M is at least one in V, Mo, W
Kind.It is preferred that x, n ≠ 0.
The catalysis material of the present invention includes bismuth-based oxide Bi2O3-x(x=0~1) or itself and BiaMOb(M=V, Mo, W) light
The composite of catalysis material, catalysis material of the invention not only has high photocatalysis nitrogenase activity, also with high
Stability.Bi in the material2O3-x(x=0~1) can be adsorbed and the nitrogen in activating air, promote the key fracture of nitrogen nitrogen three, in water
Middle generation ammonia.The material had significant photocatalytic activity to solar energy photocatalytic fixed nitrogen, in simulated solar illumination in 24 hours
Under, 1~10mg/L ammonia nitrogen can be produced in pure water, is photocatalysis in pure water under the conditions of the solar energy reported both at home and abroad at present
The peak efficiency that fixed nitrogen reaches.The TiO of Fe doping under the same conditions20.03mg/L ammonia nitrogen can only be produced.Bi2O3- x(x=0~1) composite photocatalyst material shows the advantage of high-efficiency nitrogen-fixing under field conditions (factors), with application prospect.
In the present invention, Bi in the catalysis material2O3-xA diameter of 1~1000 nanometer of particle, preferably 1~100 receives
Rice, BiaMObA diameter of 1~1000 nanometer of particle, preferably 1~100 nanometer.Particle size is increased to after 100 nanometers
Reduced as specific grain surface is accumulated, catalytic activity is greatly reduced.
The present invention also provides a kind of preparation method of the high-efficiency solar fixed nitrogen catalysis material, the preparation method bag
Include：Bismuth salt is soluble in water with enuatrol, and emulsion form precursor solution A is made in stirring；M salt is dispersed in water, surpassed
Sound obtains solution B；Appropriate solution A is mixed with solution B, synthesized more than 2 hours in 80~180 DEG C, washs, dry
After obtain the high-efficiency solar fixed nitrogen catalysis material." appropriate solution A is mixed with solution B ", " appropriate "
It is the catalysis material Bi for instigating the mixed solution to prepare2O3-x/nBiaMObIn n=0~1.
The present invention is molten by the scattered emulsion form presoma of acquisition in deionized water of bismuth salt by using enuatrol as surfactant
Liquid A, M salt (M=V, Mo, W) is disperseed to obtain solution B in deionized water.When only by precursor solution A in 80~
180 DEG C are synthesized more than 2 hours, and Bi is then can obtain after washing, drying2O3-x(x=0~1) catalysis material, the height now prepared
Imitate solar energy fixed nitrogen catalysis material Bi2O3-x/nBiaMObMiddle n value is 0.When by appropriate solution A and appropriate molten
Liquid B is mixed, and is synthesized more than 2 hours in 80~180 DEG C, and the photocatalysis material of n=0~1 can be then prepared after washing, drying
Expect Bi2O3-x/nBiaMOb.The preparation method of the present invention is without special installation and harsh conditions, and technique is simple, and controllability is strong, holds
Easily accomplish scale production, with practicality.
It is preferred that the bismuth salt is at least one of bismuth salts such as bismuth nitrate, bismuth chloride, bismuth ion complex compound.
It is preferred that Bi molar concentration is 0.001~0.2mol/L in solution A, excessive concentration can make reaction product particle
It is excessive.
It is preferred that the molar concentration of enuatrol is 0.001~1mol/L in solution A, oleic acid concentration is too low to be fully complexed
Bismuth ion, it is too high to make reaction liquid alkalescence and reproducibility increase, it is unfavorable for product generation.
It is preferred that the mixing time that emulsion form precursor solution A is made is 1~3 hour.
It is preferred that the M salt be ammonium metavanadate, ammonium vanadate, vanadic anhydride, sodium tungstate, sodium molybdate, tungsten chloride,
The wherein at least one such as phosphotungstic acid, phosphomolybdic acid.
It is preferred that the molar concentration of M salt is 0.001~0.1mol/L in solution B.
It is preferred that generated time is 2~48 hours.
Brief description of the drawings
Fig. 1 is with BiO and BiVO in embodiment 14Exemplified by the BiO/BiVO that obtains4The XRD of composite photocatalyst material
Diffracting spectrum；
Fig. 2 is embodiment 1 with BiO and BiVO4Exemplified by the BiO/BiVO that obtains4The transmission electron microscope photo of composite photocatalyst material；
Fig. 3 is that embodiment 1 obtains BiO/BiVO4BiO is obtained with embodiment 2 and embodiment 4 obtains BiVO4Mixed Deng material with Fe
Miscellaneous TiO2The comparison diagram of photocatalysis nitrogen-fixing efficiency under simulated solar irradiation；
Fig. 4 is the XRD spectrum of acquisition BiO in embodiment 2；
Fig. 5 is to obtain BiVO in embodiment 44XRD spectrum.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and following embodiments, it should be appreciated that following embodiments are only used for
The bright present invention, is not intended to limit the present invention.
It is an object of the present invention to provide a kind of high-efficiency solar fixed nitrogen catalysis material, while providing one kind prepares the light
The method of catalysis material.The catalysis material chemical composition of the present invention is Bi2O3-x/nBiaMOb, including with Bi2O3-x(x=0~1)
Catalysis material and its and Bi for main catalytic active speciesaMObCompound catalysis material.As n=0, the light is urged
Change material is bismuth-based oxide Bi2O3-x(x=0~1), as n ≠ 0, the catalysis material is Bi2O3-xWith BiaMOb
The composite of (M=V, Mo, W) catalysis material.
The present invention uses liquid phase method, using enuatrol as surfactant, and bismuth salt is disperseed to obtain emulsion in deionized water
Shape precursor solution A, by M salt (M=V, Mo, W) it is soluble in water precursor solution B, heating precursor solution or its with
The mixed solution of M salt, prepares the high-efficiency solar fixed nitrogen catalysis material of the present invention.It is excellent on the preparation of solution A
Choosing will first be dissolved in deionized water as surfactant enuatrol, can so make it that oleic acid molecular fully dissolves to form micella, then
Adding bismuth salt makes it be uniformly dispersed.Bi is can obtain when only heating precursor solution A2O3-x(x=0~1) catalysis material, now
The high-efficiency solar fixed nitrogen catalysis material Bi of preparation2O3-x/nBiaMObMiddle n value is 0.When by appropriate solution A with
Heated after appropriate solution B mixing, n=0~1 can be prepared and the catalysis material Bi of n for 02O3-x/nBiaMOb；
" appropriate " is the catalysis material Bi for instigating the mixed solution to prepare2O3-x/nBiaMObIn n=0~1 and n
It is not 0；Separately, the mol ratio of the mixed liquor on solution A and solution B, wherein bismuth salt and M salt (M=V, Mo, W) is preferred
For 1:1~1:2；When the amount of bismuth salt can cause the Bi without fixed nitrogen catalytic activity too much2O3Generation, point that M salt can be produced very little
Phase.
In the present invention, configuration emulsion form precursor solution includes bismuth salt is soluble in water with enuatrol, stirring, and emulsion is made
The step of shape precursor solution.The bismuth salt includes but is not limited to complex compound of bismuth nitrate, bismuth chloride, bismuth etc..The emulsion form
Molar concentration containing Bi preferably 0.001~0.2mol/L in precursor solution, the molar concentration preferably 0.001 of enuatrol~
1mol/L, more than concentration range, reactant concentration is excessive to occur that product grain is excessive, the problems such as catalytic performance is reduced.Oleic acid
Na concn, which crosses conference, to be caused reaction solution acid-base property and reduces to sexually revise to be unfavorable for product generation.Specifically, being used as an example, example
Such as bismuth nitrate or bismuth chloride are dissolved in deionized water by a certain percentage with enuatrol, stirring makes to form emulsion form for 1~3 hour
Precursor solution.On bismuth salt and the mixed proportion of enuatrol, both mol ratios can be 1:3~1:Between 6, both ensure Bi
Ion is fully complexed, and concentrations of sodium oleate is only high.
In the present invention, M salt (M=V, Mo, W) includes but is not limited to be ammonium metavanadate, ammonium vanadate, vanadic anhydride, tungsten
Sour sodium, sodium molybdate, tungsten chloride, phosphotungstic acid, phosphomolybdic acid etc..M salt is dissolved in after water and stirred 0.5~2 hour, and ultrasound point
Dissipate uniform, M salt is dissolved in molar concentration preferably 0.001~0.1mol/L of water.
The catalysis material that the present invention is synthesized is included with Bi2O3-x(x=0~1) for main catalytic active species catalysis material and
Itself and BiaMObCompound catalysis material.As an example, synthesis step can include：
More than when by emulsion form precursor solution in 80~180 DEG C of oil baths or small Hydrothermal Synthesiss 2, with organic solvent washing, after drying
Obtain Bi2O3-x(x=0~1) catalysis material；
Mixed when by emulsion form precursor solution with M saline solutions, in 80~180 DEG C of oil baths or Hydrothermal Synthesiss more than 2 hours, with having
Machine solvent is washed, and Bi is obtained after drying2O3-xThe composite photocatalyst material of (x=0~1) load；
Described organic solvent is n-hexane, hexamethylene, acetone, alcohol etc..
Compared with prior art, the present invention has the advantages that：
1) Bi obtained by the inventive method2O3-x/nBiaMObCatalysis material, not only with high photocatalysis nitrogenase activity, also has
There is high stability.Material can produce 1~10mg/L ammonia nitrogen in pure water, be under simulated solar illumination in 24 hours
The peak efficiency that photocatalysis fixed nitrogen reaches in pure water under the conditions of the solar energy reported both at home and abroad at present.Fe adulterates under the same conditions
TiO20.03mg/L ammonia nitrogen can only be produced.Bi2O3-x(x=0~1) composite photocatalyst material shows high under field conditions (factors)
The advantage of fixed nitrogen is imitated, with application prospect；
2)Bi2O3-x/nBiaMObThe preparation method of catalysis material is without special installation and harsh conditions, and technique is simple, and controllability is strong,
Easily accomplish scale production, with practicality.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this hair
It is bright to be further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to the present invention's
Some nonessential modifications and adaptations that the above is made belong to protection scope of the present invention.Following specific technique ginsengs of example
Number etc. is also only an example in OK range, i.e. those skilled in the art can be done in suitable scope by this paper explanation
Selection, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
1.2mmoL enuatrols are dissolved in 20mL deionized waters, 0.194g Bi (NO are added after dissolving3)3·5H2O, magnetic agitation
Form emulsion form precursor solution within 1.5 hours；
0.4mmoL ammonium metavanadates are dissolved in 20mL deionized waters, stirs 1 hour and ultrasound makes to be uniformly dispersed；
It is transferred to after two groups of solution are mixed 1 hour in 50mL water heating kettle, it is natural in 105 DEG C of hydro-thermal reactions 16 hours
It is cooled to room temperature；
Obtaining powder using Vacuum Freezing ＆ Drying Technology by solid sample in water heating kettle through n-hexane, after the washing such as ethanol is
BiO/BiVO4Composite.
Fig. 1 is the BiO/BiVO that the present embodiment is obtained4The XRD diffracting spectrums of composite, can through XRD constituent analyses
Know：The composite photocatalyst material obtained is monoclinic phase BiVO4With a small amount of hexagonal phase BiO.
Fig. 2 is the BiO/BiVO that the present embodiment is obtained4The transmission electron microscope photo of composite, as seen from Figure 2：Obtained
Composite in BiVO4The structure being made up of a diameter of 40-50nm or so nanometer rods, BiO is a diameter of 3-4nm
The nanometer rods of left and right, and BiO nanometer rods compact growths are in BiVO4On.
In order to study under the photocatalysis fixed nitrogen performance of prepared sample, design simulation sunshine material in pure aquatic system by sky
N in gas2It is reduced to NH4 +Experiment." Fe doping TiO described in embodiment2" it is reference literature (Appl.Catal.B:
Environ.2014,144,468-477) it is prepared.
NH is measured by salicylic acid AAS (HJ 536-2009) in experiment4 +Concentration.
By the BiO/BiVO of equivalent40.5wt%Fe doping TiO made from composite and hydro-thermal method2Nano material adds respectively
Enter in 200mL pure water, between being 3-4 with watery hydrochloric acid tune pH, be subsequently placed under 500W xenon lamps and irradiate 24 hours, inspection
Survey NH in solution4 +Concentration simultaneously records result.
Testing result shows：Illumination is developed the color for 24 hours, finds BiO/BiVO4Ammonia nitrogen in the suspension of composite
Concentration reaches 3.9mg/L, illustrates obtained BiO/BiVO4Composite has higher photocatalysis nitrogen fixing capacity.
Fig. 3 shows the BiO/BiVO that the present embodiment is obtained4Composite and Fe doping TiO2Nano material is in simulated solar irradiation
Lower photocatalysis fixed nitrogen (N in reducing atmosphere under xenon lamp2) comparison diagram of efficiency.As seen from Figure 3：Obtained
BiO/BiVO4Composite is than Fe doping TiO2Nitrogen-fixing efficiency is substantially improved under similarity condition.
Embodiment 2
2.2mmoL enuatrols are dissolved in 20mL deionized waters, 0.194g Bi (NO are added after dissolving3)3·5H2O, magnetic agitation
Form emulsion form precursor solution within 1.5 hours, precursor solution is added to the hydro-thermal that 50mL is transferred to after 20mL deionized waters
In kettle, in 105 DEG C of hydro-thermal reactions 20 hours, room temperature is naturally cooled to；
It is BiO materials to obtain powder using Vacuum Freezing ＆ Drying Technology after solid sample is washed through ethanol etc..
Learnt (see Fig. 4) through XRD detection and analysis：The material that the present embodiment is obtained is BiO material (quantum sizes
BiO (quantum sized BiO)).
The present embodiment obtains nitrogen production in reducing atmosphere under composite the same terms that BiO materials are obtained than embodiment 1
Raw NH4 +Efficiency it is lower slightly (see Fig. 3).
Embodiment 3
1.2mmoL enuatrols are dissolved in 20mL deionized waters, 0.194g Bi (NO are added after dissolving3)3·5H2O, magnetic agitation
Form emulsion form precursor solution within 1.5 hours；
0.1mmoL sodium tungstate is dissolved in 20mL deionized waters, stirs 1 hour and ultrasound makes to be uniformly dispersed；
It is transferred to after two groups of solution are mixed 1 hour in 50mL water heating kettle, it is natural in 105 DEG C of hydro-thermal reactions 16 hours
It is cooled to room temperature；
By solid sample in water heating kettle through n-hexane, it is BiO to obtain powder using Vacuum Freezing ＆ Drying Technology after the washing such as ethanol,
Bi2O3, Bi2O2.33/Bi2WO6Composite.
The Bi that the present embodiment is obtained2O3-xCompound Bi2WO6Catalysis material is obtained under the conditions of same as Example 1
BiO/BiVO4Material is the 85% of embodiment 1 to photocatalysis nitrogen-fixing efficiency.
Embodiment 4
The present embodiment the difference is that only with embodiment 1：Oleic acid is added without in preparation process to receive；
Remaining content is identical with described in embodiment 1.
The present embodiment product is defined as pure BiVO through XRD constituent analyses4Phase (see Fig. 5), illustrates the presence of oleate ions
It is the necessary condition to form BiO phases.
Product BiVO4The BiO/BiVO obtained with embodiment 14Compare, nitrogen-fixing efficiency only has composite under the same terms
2% (see Fig. 3).
Claims (10)
1. a kind of high-efficiency solar fixed nitrogen catalysis material, it is characterised in that the chemical composition of the catalysis material is Bi2O3-x/nBiaMOb, wherein, x=0~1, n=0~1, a=0~2, b=0~6, M is at least one of V, Mo, W.
2. catalysis material according to claim 1, it is characterised in that Bi in the catalysis material2O3-xA diameter of 1~1000 nanometer of particle, preferably 1~100 nanometer, BiaMObA diameter of 1~1000 nanometer of particle, preferably 1~100 nanometer.
3. the preparation method of the high-efficiency solar fixed nitrogen catalysis material described in a kind of claim 1 or 2, it is characterised in that the preparation method includes：Bismuth salt is soluble in water with enuatrol, and emulsion form precursor solution A is made in stirring；M salt is dispersed in water, ultrasound obtains solution B；Appropriate solution A is mixed with solution B, synthesized more than 2 hours in 80~180 DEG C, the high-efficiency solar fixed nitrogen catalysis material is obtained after washing, drying.
4. preparation method according to claim 3, it is characterised in that the bismuth salt is at least one of bismuth nitrate, bismuth chloride, bismuth ion complex compound.
5. the preparation method according to claim 3 or 4, it is characterised in that Bi molar concentration is 0.001~0.2mol/L in solution A.
6. the preparation method according to any one of claim 3 to 5, it is characterised in that the molar concentration of enuatrol is 0.001~1mol/L in solution A.
7. the preparation method according to any one of claim 3 to 6, it is characterised in that the mixing time that emulsion form precursor solution A is made is 1~3 hour.
8. the preparation method according to any one of claim 3 to 7, it is characterised in that the M salt is at least one of ammonium metavanadate, ammonium vanadate, vanadic anhydride, sodium tungstate, sodium molybdate, tungsten chloride, phosphotungstic acid, phosphomolybdic acid.
9. the preparation method according to any one of claim 3 to 8, it is characterised in that the molar concentration of M salt is 0.001~0.1 mol/L in solution B.
10. the preparation method according to any one of claim 3 to 9, it is characterised in that generated time is 2~48 hours.
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