CN106955699B - 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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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 77
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 58
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 15
- 239000000839 emulsion Substances 0.000 claims description 13
- 150000001621 bismuth Chemical class 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 7
- 239000002245 particle Substances 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 group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 229910001451 bismuth ion Inorganic materials 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
- 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
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 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 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 20
- 230000001699 photocatalysis Effects 0.000 abstract description 19
- 238000007146 photocatalysis Methods 0.000 abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052721 tungsten Inorganic materials 0.000 abstract description 7
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 abstract description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 108010020943 Nitrogenase Proteins 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 39
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 229910002915 BiVO4 Inorganic materials 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 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
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000010438 heat treatment Methods 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
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000004458 analytical method Methods 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
- 239000006185 dispersion Substances 0.000 description 3
- 238000004090 dissolution 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
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 230000008901 benefit Effects 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
- 238000002474 experimental method Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 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
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- 206010054949 Metaplasia Diseases 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
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 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
- 230000009286 beneficial effect 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
- 230000000536 complexating effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000003760 hair shine 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
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 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
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 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
- 239000002689 soil Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 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 at least one of x=0~1, n=0~1, a=0~2, b=0~6, M V, Mo, W.Catalysis material of the invention includes bismuth-based oxide Bi2O3‑x(x=0~1) or itself and BiaMObThe composite material of (M=V, Mo, W) catalysis material, catalysis material of the invention not only have high photocatalysis nitrogenase activity, also have high stability.Bi in the material2O3‑x(x=0~1) can adsorb and the nitrogen in activating air, promotes the fracture of three key of nitrogen nitrogen, generates ammonia in water.
Description
Technical field
The present invention relates to a kind of high-efficiency solar fixed nitrogen catalysis materials and preparation method thereof, belong to catalysis material technology
Field.
Background technique
Ammonia provides nitrogen for plant especially cereal crops, is sulphur removal in the world today in the widely used of industry
The outer maximum chemical products of yield of acid, current maximum dosage are chemical fertilizer.Traditional fixed nitrogen approach mainly has biological nitrogen fixation, changes
Learn fixed nitrogen.Biological nitrogen fixation can carry out under the conditions of comparatively gentle, but can only occur in a small number of plant and microorganism, difficult
To carry out large-scale production application.The chemical nitrogen fixation effective solution deficiency of biological nitrogen fixation, but energy consumption is high whole process,
A large amount of use not only causes soil hardening, and nitrate is leaked with water, causes the more serious pollution of environment.Currently, All Around The World
The energy, grain and environmental problem are all suffered from, the popular problem that the method that new fixed nitrogen produces ammonia has become scientific circles is probed into.
The key of ammonia synthesis reaction is N2Activation.If luminous energy is introduced into this reaction system, it is likely that real
This existing reaction.Photocatalysis fixed nitrogen is using response of the semiconductor light-catalyst to light, by the way that nitrogen is converted ammonification, by luminous energy
It is converted to a kind of new technology of chemical energy, photocatalysis field important science and skill are had become because its is energy saving, environmentally protective
Art problem.
The key problem of photocatalysis nitrogen fixation technology is the design, exploitation and development of suitable photochemical catalyst.Current research master
Concentrate on the TiO of Fe doping2Base system column photochemical catalyst.But with regard to TiO2For, there are the technical problem of several keys, such as TiO2
Band gap be 3.2eV, be only capable of being excited by ultraviolet light (only account for solar energy 3.8%), furthermore TiO2The recombination rate of photo-generated carrier
Height, quantum efficiency is low (less than 4%), and the utilization rate of solar energy is low, almost without photoresponse in visible-range；It is urged for light
When changing fixed nitrogen, the ammonia nitrogen of 1-10 μm of ol/L can only be generated.
Research and develop new and effective catalysis material, be the key that be able to achieve using the sun photocatalysis fixed nitrogen and photocatalysis into
One step moves towards practical inexorable trend and developing direction.The critical issue of photocatalysis fixed nitrogen is the activation of tri- key of N ≡ N.Absolutely
Most of catalysis materials itself do not have activation N2Ability therefore fundamentally to realize the solar energy of catalysis material
Fixed nitrogen, it is necessary to make it and N can be activated2Other materials it is compound.This material can be noble metal or the gold rich in electronics
Belong to oxide.In view of the cost problem of noble metal, the metal oxide of electron rich becomes the first choice of co-catalyst.Bi element exists
When forming metal oxide, the lone pair electrons contained on Bi atom, which are often not involved in into, to be built, and becomes electron rich compound.
Therefore, it may be considered that introduce Bi ion in catalysis material preparation process, make it while generating the metal oxidation of a part of Bi
Object is supported on the surface of catalysis material, plays activation N2Effect.Prepare answering for this Bi base oxide and catalysis material
Condensation material, can be greatly improved catalysis material solar energy effect under nitrogen-fixing efficiency, not only scientific value with higher but also
With the practical significance to alleviating energy crisis, prevention and treatment environmental pollution.
Summary of the invention
For the above problem existing for existing photocatalysis nitrogen fixation technology, the object of the present invention is to provide a kind of high-efficiency solars
Fixed nitrogen catalysis material, while a kind of simple, quick, controllability is high method for preparing the catalysis material being provided.
Here, the present invention provides a kind of high-efficiency solar fixed nitrogen catalysis material, the chemical composition of the catalysis material
For Bi2O3-x/nBiaMOb, wherein at least one of x=0~1, n=0~1, a=0~2, b=0~6, M V, Mo, W.It is preferred that
x、n≠0。
Catalysis material of the invention includes bismuth-based oxide Bi2O3-x(x=0~1) or itself and BiaMOb(M=V, Mo, W)
The composite material of catalysis material, catalysis material of the invention not only have high photocatalysis nitrogenase activity, also have pole
High stability.Bi in the material2O3-x(x=0~1) can adsorb and the nitrogen in activating air, promotes three key of nitrogen nitrogen disconnected
It splits, generates ammonia in water.The material had significant photocatalytic activity to solar energy photocatalytic fixed nitrogen, in 24 hours simulated solars
Under illumination, the ammonia nitrogen of 1~10mg/L can produce in pure water, be that light is urged in pure water under the conditions of the solar energy reported both at home and abroad at present
Change the peak efficiency that fixed nitrogen reaches.The TiO of Fe doping under the same conditions2The ammonia nitrogen of 0.03mg/L can only be generated.Bi2O3-x(x=
0~1) composite photocatalyst material shows the advantage of high-efficiency nitrogen-fixing under field conditions (factors), has application prospect.
In the present invention, Bi in the catalysis material2O3-xThe diameter of particle is 1~1000 nanometer, and preferably 1~100 receives
Rice, BiaMObThe diameter of particle is 1~1000 nanometer, preferably 1~100 nanometer.Particle size increase to after 100 nanometers with
Specific grain surface product reduces, and catalytic activity is greatly reduced.
The present invention also provides a kind of preparation method of high-efficiency solar fixed nitrogen catalysis material, the preparation method packets
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, ultrasound obtains
Solution B；Suitable solution A is mixed with solution B, synthesized 2 hours in 80~180 DEG C or more, the height is obtained after washing, drying
Imitate solar energy fixed nitrogen catalysis material." suitable solution A is mixed with solution B ", it is described it is " appropriate " be after instigating the mixing
Solution preparation catalysis material Bi2O3-x/nBiaMObIn n=0~1.
The present invention by obtaining emulsion form forerunner for bismuth salt dispersion using enuatrol as surfactant in deionized water
M salt (M=V, Mo, W) dispersion is obtained solution B by liquid solution A in deionized water.When only by precursor solution A in 80~180
DEG C synthesis 2 hours or more, washing, it is dry after Bi then can be obtained2O3-x(x=0~1) catalysis material, prepare at this time efficiently too
Positive energy fixed nitrogen catalysis material Bi2O3-x/nBiaMObThe value of middle n is 0.When suitable solution A is mixed with suitable solution B,
Synthesized 2 hours in 80~180 DEG C or more, the catalysis material Bi of n=0~1 can then be prepared after washing, drying2O3-x/
nBiaMOb.Preparation method of the invention is not necessarily to special installation and harsh conditions, and simple process, controllability is strong, scale easy to accomplish
Metaplasia produces, and has practicability.
Preferably, the bismuth salt is at least one of bismuth salts such as bismuth nitrate, bismuth chloride, bismuth ion complex compound.
Preferably, the molar concentration of Bi is 0.001~0.2mol/L in solution A, excessive concentration can make reaction product particle
It is excessive.
Preferably, the molar concentration of enuatrol is 0.001~1mol/L in solution A, oleic acid concentration is too low cannot abundant network
Bismuth ion is closed, it is excessively high that reaction liquid alkalinity and reproducibility can be made to increase, it is unfavorable for product generation.
Preferably, the mixing time that emulsion form precursor solution A is made is 1~3 hour.
Preferably, the M salt is ammonium metavanadate, ammonium vanadate, vanadic anhydride, sodium tungstate, sodium molybdate, tungsten chloride, phosphorus tungsten
The wherein at least one such as acid, phosphomolybdic acid.
Preferably, the molar concentration of M salt is 0.001~0.1mol/L in solution B.
Preferably, generated time is 2~48 hours.
Detailed description of the invention
Fig. 1 is in embodiment 1 with BiO and BiVO4For the BiO/BiVO that obtains4The XRD diffraction pattern of composite photocatalyst material
Spectrum；
Fig. 2 is embodiment 1 with BiO and BiVO4For the BiO/BiVO that obtains4The transmission electron microscope of composite photocatalyst material shines
Piece；
Fig. 3 is that embodiment 1 obtains BiO/BiVO4BiO is obtained with embodiment 2 and embodiment 4 obtains BiVO4Equal materials and Fe
Adulterate TiO2The comparison diagram of photocatalysis nitrogen-fixing efficiency under simulated solar irradiation；
Fig. 4 is the XRD spectrum that BiO is obtained in embodiment 2；
Fig. 5 is to obtain BiVO in embodiment 44XRD spectrum.
Specific embodiment
The present invention is further illustrated below in conjunction with attached drawing and following embodiments, it should be appreciated that following embodiments are only used for
Illustrate the 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 materials, while providing described in a kind of prepare
The method of catalysis material.Catalysis material chemical composition of the invention is Bi2O3-x/nBiaMOb, including with Bi2O3-x(x=0
It~1) is the catalysis material and its and Bi of main catalytic active speciesaMObCompound catalysis material.As n=0, the light
Catalysis material is bismuth-based oxide Bi2O3-x(x=0~1), as n ≠ 0, the catalysis material is Bi2O3-xWith BiaMOb(M
=V, Mo, W) catalysis material composite material.
The present invention uses liquid phase method, and using enuatrol as surfactant, bismuth salt dispersion is obtained cream in deionized water
Liquid precursor solution A, by M salt (M=V, Mo, W) it is soluble in water precursor solution B, heat precursor solution or itself and M salt
Mixed solution, high-efficiency solar fixed nitrogen catalysis material of the invention is prepared.About the preparation of solution A, preferably first will
It is dissolved in deionized water as surfactant enuatrol, oleic acid molecular can be made sufficiently to dissolve in this way and form micella, added
Bismuth salt makes it be uniformly dispersed.Bi can be obtained when only heating precursor solution A2O3-x(x=0~1) catalysis material, makes at this time
Standby high-efficiency solar fixed nitrogen catalysis material Bi2O3-x/nBiaMObThe value of middle n is 0.When by suitable solution A with it is suitable
It is heated after solution B mixing, n=0~1 can be prepared and n is not 0 catalysis material Bi2O3-x/nBiaMOb；It is described " suitable
Amount " is to instigate the catalysis material Bi of the mixed solution preparation2O3-x/nBiaMObIn n=0~1 and n be not 0；In addition,
About the mixed liquor of solution A and solution B, wherein bismuth salt and the molar ratio of M salt (M=V, Mo, W) are preferably 1:1~1:2；Work as bismuth
The amount of salt will lead to the Bi of no fixed nitrogen catalytic activity too much2O3Generation, the split-phase that M salt can be generated very little.
In the present invention, configuration emulsion form precursor solution include bismuth salt is soluble in water with enuatrol, stir, lotion is made
The step of shape precursor solution.The bismuth salt includes but is not limited to the complex compound etc. of bismuth nitrate, bismuth chloride, bismuth.The emulsion form
Molar concentration preferably 0.001~0.2mol/L in precursor solution containing Bi, the molar concentration of enuatrol preferably 0.001~
The problems such as 1mol/L is more than concentration range, and the excessive product grain that will appear of reactant concentration is excessive, and catalytic performance reduces.Oleic acid
Na concn is excessive to will lead to reaction solution acid-base property and reduction sexually revises and is unfavorable for product generation.Specifically, as an example, example
Such as bismuth nitrate or bismuth chloride and enuatrol are dissolved in deionized water by a certain percentage, stirring makes to form emulsion form for 1~3 hour
Precursor solution.About the mixed proportion of bismuth salt and enuatrol, the two molar ratio can between 1:3~1:6, both guaranteed Bi from
Sub sufficiently complexing, concentrations of sodium oleate are only high.
In the present invention, M salt (M=V, Mo, W) includes but is not limited to for ammonium metavanadate, ammonium vanadate, vanadic anhydride, wolframic acid
Sodium, sodium molybdate, tungsten chloride, phosphotungstic acid, phosphomolybdic acid etc..It is stirred 0.5~2 hour after M salt is dissolved in water, and ultrasonic disperse is uniform, M
Salt is dissolved in molar concentration preferably 0.001~0.1mol/L of water.
The catalysis material that the present invention synthesizes includes with Bi2O3-x(x=0~1) is the photocatalysis of main catalytic active species
Material and its and BiaMObCompound catalysis material.As an example, synthesis step may include:
More than when by emulsion form precursor solution in 80~180 DEG C of oil baths or small hydrothermal synthesis 2, washed with organic solvent
It washs, obtains Bi after dry2O3-x(x=0~1) catalysis material；
When emulsion form precursor solution is mixed with M saline solution, in 80~180 DEG C of oil baths or hydrothermal synthesis 2 hours with
On, with organic solvent washing, Bi is obtained after dry2O3-xThe composite photocatalyst material of (x=0~1) load；
The organic solvent is n-hexane, hexamethylene, acetone, alcohol etc..
Compared with prior art, the invention has the following beneficial effects:
1) Bi obtained by the method for the present invention2O3-x/nBiaMObCatalysis material not only has high photocatalysis fixed nitrogen
Activity also has high stability.Material can produce 1~10mg/L's under simulated solar illumination in 24 hours in pure water
Ammonia nitrogen is 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.In the same terms
The TiO of lower Fe doping2The ammonia nitrogen of 0.03mg/L can only be generated.Bi2O3-x(x=0~1) composite photocatalyst material is shown in nature
Under the conditions of high-efficiency nitrogen-fixing advantage, have application prospect；
2)Bi2O3-x/nBiaMObThe preparation method of catalysis material is not necessarily to special installation and harsh conditions, and simple process can
Strong, the large-scale production easy to accomplish of control property, has practicability.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1
1.2mmoL enuatrol is dissolved in 20mL deionized water, 0.194g Bi (NO is added after dissolution3)3·5H2O, magnetic force
Stir 1.5 hours formation emulsion form precursor solutions；
0.4mmoL ammonium metavanadate is dissolved in 20mL deionized water, stirs 1 hour and ultrasound makes to be uniformly dispersed；
Be transferred in the water heating kettle of 50mL after two groups of solution are mixed 1 hour, 105 DEG C hydro-thermal reaction 16 hours,
Cooled to room temperature；
By solid sample in water heating kettle through n-hexane, obtaining powder using Vacuum Freezing & Drying Technology after the washing such as ethyl alcohol is
For BiO/BiVO4Composite material.
Fig. 1 is the BiO/BiVO that the present embodiment obtains4The XRD diffracting spectrum of composite material, through known to XRD constituent analysis:
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 obtains4The transmission electron microscope photo of composite material, as seen from Figure 2: obtained
BiVO in composite material4The structure being made of the nanometer rods that diameter is 40-50nm or so, BiO are that diameter is 3-4nm or so
Nanometer rods, and BiO nanometer rods compact growth is in BiVO4On.
In order to study the photocatalysis fixed nitrogen performance of prepared sample, material will in pure aquatic system under design simulation sunlight
N in air2It is reduced to NH4 +Experiment.It is as described in the examples that " Fe adulterates TiO2" be reference literature (Appl.Catal.B:
Environ.2014,144,468-477) it is prepared.
NH is measured by salicylic acid spectrophotometry (HJ 536-2009) in experiment4 +Concentration.
By the BiO/BiVO of equivalent40.5wt%Fe made from composite material and hydro-thermal method adulterates TiO2Nano material adds respectively
Enter in 200mL pure water, be to be subsequently placed under 500W xenon lamp and irradiate 24 hours between 3-4 with dilute hydrochloric acid tune pH, detects in solution
NH4 +Concentration simultaneously records result.
Testing result shows: developing the color within illumination 24 hours, finds BiO/BiVO4Ammonia nitrogen in the suspension of composite material
Concentration reaches 3.9mg/L, illustrates BiO/BiVO obtained4Composite material photocatalysis nitrogen fixing capacity with higher.
Fig. 3 shows the BiO/BiVO of the present embodiment acquisition4Composite material and Fe adulterate 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: BiO/BiVO obtained4It is compound
Material ratio Fe adulterates TiO2Nitrogen-fixing efficiency is substantially improved under similarity condition.
Embodiment 2
2.2mmoL enuatrol is dissolved in 20mL deionized water, 0.194g Bi (NO is added after dissolution3)3·5H2O, magnetic force
1.5 hours formation emulsion form precursor solutions are stirred, precursor solution is added after 20mL deionized water to the water for being transferred to 50mL
In hot kettle, 105 DEG C hydro-thermal reaction 20 hours, cooled to room temperature；
It is BiO material that solid sample, which is obtained powder using Vacuum Freezing & Drying Technology after the washing such as ethyl alcohol,.
Through XRD detection and analysis learn (see Fig. 4): the present embodiment material obtained be BiO material (quantum size
BiO(quantum sized BiO))。
Nitrogen in reducing atmosphere under composite material the same terms that the obtained BiO material of the present embodiment is obtained than embodiment 1
Generate NH4 +Efficiency it is slightly lower (see Fig. 3).
Embodiment 3
1.2mmoL enuatrol is dissolved in 20mL deionized water, 0.194g Bi (NO is added after dissolution3)3·5H2O, magnetic force
Stir 1.5 hours formation emulsion form precursor solutions；
The sodium tungstate of 0.1mmoL is dissolved in 20mL deionized water, stirs 1 hour and ultrasound makes to be uniformly dispersed；
Be transferred in the water heating kettle of 50mL after two groups of solution are mixed 1 hour, 105 DEG C hydro-thermal reaction 16 hours,
Cooled to room temperature；
By solid sample in water heating kettle through n-hexane, obtaining powder using Vacuum Freezing & Drying Technology after the washing such as ethyl alcohol is
For BiO, Bi2O3, Bi2O2.33/Bi2WO6Composite material.
The present embodiment Bi obtained2O3-xCompound Bi2WO6Catalysis material obtains under the conditions of same as Example 1
BiO/BiVO4Material is to 85% that photocatalysis nitrogen-fixing efficiency is embodiment 1.
Embodiment 4
The present embodiment, which is different from that of the embodiment 1 only in the following aspects: in preparation process, to be added without oleic acid and receives；
Remaining content is identical with described in embodiment 1.
The present embodiment product is determined as pure BiVO through XRD constituent analysis4Phase (see Fig. 5), illustrates the presence of oleate ions
It is the necessary condition to form BiO phase.
Product BiVO4The BiO/BiVO obtained with embodiment 14It compares, nitrogen-fixing efficiency only has composite material under the same terms
2% (see Fig. 3).
Claims (11)
1. a kind of high-efficiency solar fixed nitrogen catalysis material, which is characterized in that the chemical composition of the catalysis material is BiO/
nBiaMOb, wherein n=0~1 and n are not 0, a=0~2 and a is not 0, b=0~6 and b is not 0, M V, at least one in Mo, W
Kind, the diameter of BiO is 3-4 nanometers in the catalysis material.
2. catalysis material according to claim 1, which is characterized in that Bi in the catalysis materialaMObParticle it is straight
Diameter is 1~1000 nanometer.
3. catalysis material according to claim 2, which is characterized in that Bi in the catalysis materialaMObParticle it is straight
Diameter is 1~100 nanometer.
4. the preparation method of high-efficiency solar fixed nitrogen catalysis material, feature described in a kind of any one of claims 1 to 3
Be, the preparation method include: bismuth salt is soluble in water with enuatrol, stirring, emulsion form precursor solution A is made；By M salt
It is dispersed in water, ultrasound obtains solution B；Suitable solution A is mixed with solution B, synthesized 2 hours in 80~180 DEG C or more, it washes
Wash, dry after obtain the high-efficiency solar fixed nitrogen catalysis material.
5. the preparation method according to claim 4, which is characterized in that the bismuth salt is bismuth nitrate, bismuth chloride, bismuth ion network
Close at least one of object.
6. the preparation method according to claim 4, which is characterized in that in solution A the molar concentration of Bi be 0.001~
0.2mol/L。
7. the preparation method according to claim 4, which is characterized in that in solution A the molar concentration of enuatrol be 0.001~
1mol/L。
8. the preparation method according to claim 4, which is characterized in that the mixing time of emulsion form precursor solution A is made
It is 1~3 hour.
9. the preparation method according to claim 4, which is characterized in that the M salt is ammonium metavanadate, ammonium vanadate, five oxidations
At least one of two vanadium, sodium tungstate, sodium molybdate, tungsten chloride, phosphotungstic acid, phosphomolybdic acid.
10. the preparation method according to claim 4, which is characterized in that in solution B the molar concentration of M salt be 0.001~
0.1 mol/L。
11. the preparation method according to any one of claim 4 to 10, which is characterized in that generated time is 2~48 small
When.
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