CN107029775A - A kind of nitrogen oxygen zirconium cerium solid solution and its preparation method and application - Google Patents
A kind of nitrogen oxygen zirconium cerium solid solution and its preparation method and application Download PDFInfo
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- CN107029775A CN107029775A CN201710229881.8A CN201710229881A CN107029775A CN 107029775 A CN107029775 A CN 107029775A CN 201710229881 A CN201710229881 A CN 201710229881A CN 107029775 A CN107029775 A CN 107029775A
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- nitrogen oxygen
- cerium
- oxygen zirconium
- solid solution
- zirconium cerium
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- NUYWKZCDZBRUMP-UHFFFAOYSA-N [Ce].[N].[O].[Zr] Chemical compound [Ce].[N].[O].[Zr] NUYWKZCDZBRUMP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000006104 solid solution Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 13
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000007146 photocatalysis Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- UMPMZCPVCSZTJA-UHFFFAOYSA-N cerium nitrous acid Chemical compound [Ce].N(=O)O UMPMZCPVCSZTJA-UHFFFAOYSA-N 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 235000013339 cereals Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 5
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 5
- ANMIZSGJINIIAN-UHFFFAOYSA-N [N].[O].[Zr] Chemical compound [N].[O].[Zr] ANMIZSGJINIIAN-UHFFFAOYSA-N 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 229940119177 germanium dioxide Drugs 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- GJFXIYGDVYZDRX-UHFFFAOYSA-N cerium;oxozirconium Chemical compound [Ce].[Zr]=O GJFXIYGDVYZDRX-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 239000003643 water by type Substances 0.000 claims 1
- 229910052684 Cerium Inorganic materials 0.000 abstract 1
- 206010037660 Pyrexia Diseases 0.000 abstract 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 229910052726 zirconium Inorganic materials 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 230000007547 defect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012512 characterization method Methods 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
- 238000006303 photolysis reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910002937 BaTaO2N Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910003071 TaON Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a kind of new material nitrogen oxygen zirconium cerium and its preparation method and application.The present invention uses hydro-thermal method synthetic intermediate germanic acid cerium and germanic acid zirconium first, then obtains the nano-scale nitrogen oxygen zirconium cerium Ce that final product is sub-stoichiometric ratio by hightemperature gas-phase reduction method0.3Zr0.7O1.88N0.12.This method is easy to operate, and process equipment is simple, and raw material is easy to get, and preparation cost is relatively low, and reaction time is short, and repeatability is high.This materials application shows excellent H2-producing capacity in Photocatalyzed Hydrogen Production reaction, and can simultaneously serve as Z systems production hydrogen end material and realize visible photocatalysis pure water.This new solid-solution material nitrogen oxygen zirconium cerium has very important purposes in environmental science and field of solar energy conversion.
Description
Technical field
The invention belongs to a kind of nitrogen oxygen zirconium cerium Ce with sub-stoichiometric ratio0.3Zr0.7O1.88N0.12Nano material, it is by 5
~30 nanometers of little particles are agglomerated into spherical macro, possess excellent properties in terms of Photocatalyzed Hydrogen Production, in other energy developments and
Field of environment protection also possesses potential application performance.
Background technology
Suitable semi-conducting material is found as stability and high efficiency and visible light-responded photochemical catalyst turns into the focus of research.
For universal, the photochemical catalyst studied at present all contains d0Electron configuration is (for example：Ti4+,Nb5+And Ta5+) or d10Electronics structure
Type is (for example：In3+,Ga3+And Ge4+) transition metal ions.These contain d0Or d10The valence band of the metal oxide of metal ion
Top is typically to be made up of O 2p tracks, therefore these metal oxides have wider energy gap so that visible
Do not possess photocatalysis performance under light.Because N 2p states are more positive in electricity compared with O 2p states, these oxide photocatalysis
It can be improved at the top of the valence band of agent by introducing N element.Therefore, people have studied many nitrogen oxides as visible ray
The photochemical catalyst of response, for example：TaON,BaTaO2N,SrNbO2N,TiO2N, etc..But these nitrogen oxides are more unstable
It is fixed, it may be possible to due to causing the appearance of a large amount of bodies and surface defect while introducing N element, so as to cause more slow
Separation of charge efficiency and quick electric charge echo efficiency.But also have such report：Body defects can be used as light induced electron
Center is echoed in hole, however the oxygen defect of surface and sub-surface can as light-catalyzed reaction reaction active site or favourable
In separation of charge.In addition, these surface defects can as photo-generate electron-hole trap center so that play promotion electronics turn
Move and suppress the effect that electric charge is echoed.It should be noted that the concentration of these System of Detecting Surface Defects For Material in theory can be by adjusting
Save the geometry and electronic structure of material and be adjusted.However, by adjusting the concentration of surface defect so that nitrogen oxides is made
A challenge is still for the photochemical catalyst of stability and high efficiency.
We devise a kind of novel C e with appropriate surfaces defect density in the present invention0.3Zr0.7O1.88N0.12Solid solution
Material is used as stability and high efficiency and visible light-responded production hydrogen photochemical catalyst.Moreover, this material is constructed Z bodies as production hydrogen end
System, it is possible to achieve visible photocatalysis pure water.Integrated structure is characterized and the calculated results, and we are Ce0.3Zr0.7O1.88N0.12Gu
Solution material has outstanding photocatalytic activity and stability is attributed to surface and sub-surface oxygen vacancies improves photo-generated carrier
Separation rate.
The content of the invention
In view of the foregoing, it is an object to provide a kind of nanometer nitrogen oxygen zirconium cerium and its preparation method and application, make
Preparation Method is simple, and cost is low.Prepared nano material has excellent Photocatalyzed Hydrogen Production performance.It need not be answered in building-up process
It is miscellaneous instrument, simple to operate, be conducive to large-scale production.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of nitrogen oxygen zirconium cerium solid solution, the molecular formula of the solid solution is Ce0.3Zr0.7O1.88N0.12, size is 5~30 to receive
Rice, small nanoparticle agglomerates globulate bulky grain, crystalline form are Emission in Cubic.
A kind of preparation method of oxygen zirconium cerium solid solution, comprises the following steps：
(1) nitrous acid cerium (0.1~0.9 mM), zirconium nitrate (0.9 are added in the water heating kettle of polytetrafluoroethyllining lining
~0.1 mM), germanium dioxide (0.1~1.0 mM), citric acid (0.1~1.0 mM) and 30~50 milliliters are gone
Deionized water solution, takes out after 150~250 DEG C of 12~48 hours of reaction；
(2) product for taking 50~200 milligrams of steps (1) to obtain is placed in the quartzy Noah's ark in tube furnace, with 0.02~
0.08L/min is passed through abundant ammonia, reacts 6~30 hours, obtains solid solution Ce0.3Zr0.7O1.88N0.12, size is 5~30 to receive
Rice, small nanoparticle agglomerates globulate bulky grain, crystalline form are Emission in Cubic.
The application of above-mentioned nanometer nitrogen oxygen zirconium cerium, for photocatalytic hydrogen production by water decomposition.
Above-mentioned application process is as follows：30~200 milligrams of nitrogen oxygen zirconium ceriums are added to 0.1~0.35 mol/L Na2S and 0.1~
0.25 mol/L Na2SO3In solution, it is seen that light or all band the light irradiation hydrogen output of 24 hours be respectively 10~25 micromoles and
80~120 micromoles；30~200 milligrams of 2%RuO2What the nitrogen oxygen zirconium cerium solid solution of load and 30~200 milligrams of 1%Pt were loaded
Tungstic acid is added in 1 mM/l of IodineSodium Solution, it is seen that the production hydrogen oxygen-producing amount irradiated 24 hours under light is 1.1 respectively
~3.3 micromoles and 0.6~1.7 micromole, all band light irradiation production hydrogen oxygen-producing amount of 24 hours are 6.2~10.8 micro- to rub respectively
You and 3.1~5.4 micromoles.
The beneficial effects of the present invention are：
(1) using simple two-step method synthesis nano-scale nitrogen oxygen zirconium cerium solid solution material C e0.3Zr0.7O1.88N0.12, synthesis
Method is simple, easy to operate, mild condition, and target product purity is high, and safety non-toxic can be synthesized in high volume；
(2) by nano-scale nitrogen oxygen zirconium cerium solid solution Ce0.3Zr0.7O1.88N0.12As production hydrogen photochemical catalyst, as a result show it
With preferable Photocatalyzed Hydrogen Production performance and preferable stability.Visible ray or all band the light irradiation hydrogen output of 24 hours are distinguished
It is 19 micromoles and 102 micromoles, stability 24 days；
(3) in preparation process, all reagents are commercial product, it is not necessary to further processing；
(4) synthetic method is simple, and obtained material is easy to application, is conducive to the popularization and application in industrialized production, is used for
Liberation of hydrogen material in chlorine industry, photodissociation hydraulic art, solar photolysis water hydrogen and Z systems.
Brief description of the drawings
Fig. 1 is the electronic photo of the nitrogen oxygen zirconium cerium prepared by embodiment 1；
Fig. 2 is performance map of the nitrogen oxygen zirconium cerium prepared by embodiment 1 as production hydrogen photochemical catalyst；
Fig. 3 is photocatalysis Decomposition pure water figure of the nitrogen oxygen zirconium cerium prepared by embodiment 1 as Z systems production hydrogen end；
Fig. 4 is the X ray diffracting spectrum of the nitrogen oxygen zirconium cerium prepared by embodiment 1；
Fig. 5 is the transmission electron microscope picture of the nitrogen oxygen zirconium cerium prepared by embodiment 1；
Fig. 6 is the scanning electron microscopic picture of the nitrogen oxygen zirconium cerium prepared by embodiment 1.
Embodiment
Below, in conjunction with the accompanying drawings and embodiments, specific embodiments of the present invention are further described in detail, but should not
Limited the scope of the invention with this.
" scope " disclosed herein is in the form of lower and upper limit.Can be respectively one or more lower limits, and one
Or multiple upper limits.Given range is defined by selecting a lower limit and a upper limit.Selected lower and upper limit limit
The border of special scope is determined.All scopes that can be defined by this way are included and can be combined, i.e., any lower limit
It can combine to form a scope with any upper limit.For example, listing 60-120 and 80-110 scope for special parameter, manage
The scope solved as 60-110 and 80-120 is also what is expected.If in addition, the minimum zone value 1 and 2 listed, and if listed
Maximum magnitude 3,4 and 5, then following scope can all expect：1-2,1-4,1-5,2-3,2-4 and 2-5.
In the present invention, unless otherwise indicated, number range " a-b " represents the breviary of any real combinings between a to b
Represent, wherein a and b are real numbers.Such as number range " 0-5 " represents all to have listed herein complete between " 0-5 "
Portion's real number, " 0-5 " is that the breviary of these combinations of values is represented.
In the present invention, if without particularly illustrating, all embodiments mentioned in this article and the side of being preferable to carry out
Formula can be combined with each other to form new technical scheme.
In the present invention, if without particularly illustrating, all technical characteristics and preferred feature mentioned in this article can
New technical scheme is formed to be combined with each other.
The present invention is specifically described below in conjunction with specific embodiment is preferable to carry out method, but it is to be understood that ability
Field technique personnel can reasonably be become on the premise of the scope limited without departing substantially from claims to these embodiments
Change, improve and be mutually combined, so as to obtain new specific implementation method, these are by changing, improveing and be mutually combined acquisition
New embodiment is also included within protection scope of the present invention.
Embodiment 1
Step 1: the preparation of nitrogen oxygen zirconium cerium solid solution
The addition nitrous acid cerium (0.3 mM) in the water heating kettle of polytetrafluoroethyllining lining, zirconium nitrate (0.7 mM),
Germanium dioxide (0.5 mM), citric acid (0.5 mM) and 30 ml deionized water solution, 200 DEG C of 24 hours of reaction
After take out；The product for taking 50~200 milligrams of steps (1) to obtain is placed in the quartzy Noah's ark in tube furnace, is passed through with 0.04L/min
Abundant ammonia, reacts 10 hours, obtains solid solution Ce0.3Zr0.7O1.88N0.12, size is 5~30 nanometers, small nanoparticle agglomerates
Globulate bulky grain, crystalline form are Emission in Cubic.
Step 2: performance characterization is tested
50 milligrams of nitrogen oxygen zirconium ceriums are added to 0.35 mol/L Na2S and 0.25 mol/L Na2SO3In solution, it is seen that light or
All band light irradiation 24 hours, then vacuumizes and more than repetition operates, coreaction 24 days；50 milligrams of 2%RuO2The nitrogen oxygen of load
Zirconium cerium solid solution and the tungstic acid of 50 milligrams of 1%Pt loads are added in 1 mM/l of IodineSodium Solution, it is seen that light is complete
Wave band light irradiation 24 hours, then vacuumizes and more than repetition operates, coreaction 72 hours.
Fig. 1 is the electronic photo of product, it can be seen that prepared nitrogen oxygen zirconium cerium is yellow greenish powder.
Fig. 2 is performance map of the nitrogen oxygen zirconium cerium prepared by embodiment 1 as production hydrogen photochemical catalyst.Wherein：Curve 1 is with reality
50 milligrams of nitrogen oxygen zirconium cerium prepared by example 1 is applied as production hydrogen photochemical catalyst, all band light irradiation, 50 milliliter of 0.35 mol/L
Na2S and 0.25 mol/L Na2SO3Production hydrogen curve under the test condition of solution.Curve 2 is that the production hydrogen under radiation of visible light is bent
Line.As can be seen from Figure 2, nitrogen oxygen zirconium cerium is distinguished as production hydrogen photochemical catalyst in visible ray or all band the light irradiation hydrogen output of 24 hours
It is 19 micromoles and 102 micromoles.Meanwhile, reaction the 24th day hydrogen output do not decline still explanation nitrogen oxygen zirconium cerium have it is extraordinary
Stability.
Fig. 3 is photocatalysis Decomposition pure water figure of the nitrogen oxygen zirconium cerium prepared by embodiment 1 as Z systems production hydrogen end.Wherein：It is bent
Line H2And O2It is with 50 milligrams of 2%RuO2The nitrogen oxygen zirconium cerium solid solution of load and the tungstic acid of 50 milligrams of 1%Pt loads add 1
MM/l IodineSodium Solution in, the production hydrogen oxygen-producing amount of 24 hours is irradiated under all band light.Curve H2' and O2' it is visible ray
Production hydrogen production oxygen curve under irradiation.It is that 2.28 micromoles and 1.11 micro- are rubbed respectively that the production hydrogen oxygen-producing amount of 24 hours is irradiated under visible ray
You, all band light irradiation production hydrogen oxygen-producing amount of 24 hours is 8.63 micromoles and 4.11 micromoles respectively.
Fig. 4 is the X ray diffracting spectrum of product, is identified as Ce0.3Zr0.7O1.88N0.12.Curve is prepared nitrogen oxygen zirconium
Cerium particle is 3 °/min in sweep speed, and scanning range is 10 ° -80 ° of X ray diffracting spectrum.
Fig. 5 is the transmission electron microscope picture of embodiment 1, and the lattice line and Ce of sample are found by observing sample0.3Zr0.7O1.88N0.12
The spacing of lattice of crystal formation matches, it was demonstrated that the particle of synthesis is Ce0.3Zr0.7O1.88N0.12。
Fig. 6 is the scanning electron microscope (SEM) photograph of embodiment 1, by observing sample topography, and it is 5~30 nanometers of little particle reunion balling-up
Shape bulky grain.
Embodiment 2
Step 1: CexZr1-xO1.88N0.12The preparation of (x=0.1~0.9) solid solution
Nitrous acid cerium (x mMs), zirconium nitrate (1-x mMs), two are added in the water heating kettle of polytetrafluoroethyllining lining
Germanium oxide (0.5 mM), citric acid (0.5 mM) and 30 ml deionized water solution, after 200 DEG C of 24 hours of reaction
Take out；The product for taking 50~200 milligrams of steps (1) to obtain is placed in the quartzy Noah's ark in tube furnace, is passed through and filled with 0.04L/min
Divide ammonia, react 10 hours, obtain solid solution CexZr1-xO1.88N0.12。
Step 2: performance characterization is tested
50 milligrams of nitrogen oxygen zirconium ceriums are added in 10% methanol solution, it is seen that light or all band light irradiation 24 hours, are then taken out
Vacuum is operated more than repeating；50 milligrams of 2%RuO2The nitrogen oxygen zirconium cerium solid solution of load and the tungstic acid of 50 milligrams of 1%Pt loads
Add in 1 mM/l of IodineSodium Solution, it is seen that light or all band light irradiation 24 hours, then vacuumize and more than repetition grasp
Make.
Embodiment 3
Step 1: Pt/Ce0.3Zr0.7O1.88N0.12The preparation of photochemical catalyst
The addition nitrous acid cerium (0.3 mM) in the water heating kettle of polytetrafluoroethyllining lining, zirconium nitrate (0.7 mM),
Germanium dioxide (0.5 mM), citric acid (0.5 mM) and 30 ml deionized water solution, 200 DEG C of 24 hours of reaction
After take out；The product for taking 50~200 milligrams of steps (1) to obtain is placed in the quartzy Noah's ark in tube furnace, is passed through with 0.04L/min
Abundant ammonia, reacts 10 hours, obtains solid solution Ce0.3Zr0.7O1.88N0.12.To obtain 100 milligrams of nitrogen oxygen zirconium cerium solid solution and
2.1~10.5 milligrams of chloroplatinic acids (Pt and Ce0.3Zr0.7O1.88N0.12Mass ratio 1~5%) sintered 3 hours in air at 400 DEG C
After take out.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, should all belong to the covering scope of the present invention.
Claims (6)
1. a kind of nitrogen oxygen zirconium cerium solid solution, it is characterised in that the molecular formula of the nitrogen oxygen zirconium cerium solid solution is
Ce0.3Zr0.7O1.88N0.12, size is 5~30 nanometers, and small nanoparticle agglomerates globulate bulky grain, crystalline form are Emission in Cubic.
2. a kind of preparation method of oxygen zirconium cerium solid solution, it is characterised in that comprise the following steps：
(1) nitrous acid cerium (0.1~0.9 mM), zirconium nitrate (0.9~0.1 are added in the water heating kettle of polytetrafluoroethyllining lining
MM), germanium dioxide (0.1~1.0 mM), citric acid (0.1~1.0 mM) and 30~50 ml deionized waters
Solution, takes out after 150~250 DEG C of 12~48 hours of reaction；
(2) product for taking 50~200 milligrams of steps (1) to obtain is placed in the quartzy Noah's ark in tube furnace, with 0.02~0.08L/
Min is passed through abundant ammonia, reacts 6~30 hours, obtains solid solution Ce0.3Zr0.7O1.88N0.12, size is 5~30 nanometers, small to receive
Rice grain is agglomerated into spherical macro, crystalline form for Emission in Cubic.
3. the application of nitrogen oxygen zirconium cerium solid solution according to claim 1, it is characterised in that the nitrogen oxygen zirconium cerium is used for photocatalysis
Hydrogen production by water decomposition.
4. the application of nitrogen oxygen zirconium cerium solid solution according to claim 1, it is characterised in that the nitrogen oxygen zirconium cerium is used as Z systems
Hydrogen end material is produced, visible photocatalysis pure water is realized.
5. application according to claim 3, it is characterised in that application process is as follows：30~200 milligrams of nitrogen oxygen zirconium ceriums are added
To 0.1~0.35 mol/L Na2S and 0.1~0.25 mol/L Na2SO3In solution, it is seen that light or all band light irradiation 24 are small
When hydrogen output be 10~25 micromoles and 80~120 micromoles respectively；30~200 milligrams of 2%RuO2The nitrogen oxygen zirconium cerium of load
Solid solution and the tungstic acid of 30~200 milligrams of 1%Pt loads are added in 1 mM/l of IodineSodium Solution, it is seen that shone under light
The production hydrogen oxygen-producing amount penetrated 24 hours is 1.1~3.3 micromoles and 0.6~1.7 micromole respectively, all band light irradiation 24 hours
It is 6.2~10.8 micromoles and 3.1~5.4 micromoles respectively to produce hydrogen oxygen-producing amount.
6. method according to claim 2, adds the nitrous acid cerium (0.1~0.9 mM) of water heating kettle, zirconium nitrate (0.9
~0.1 mM), it is characterised in that wherein nitrous acid cerium and zirconium nitrate mole and for 1.
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