CN109225222A - A kind of composite photo-catalyst and its application - Google Patents
A kind of composite photo-catalyst and its application Download PDFInfo
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- CN109225222A CN109225222A CN201710562701.8A CN201710562701A CN109225222A CN 109225222 A CN109225222 A CN 109225222A CN 201710562701 A CN201710562701 A CN 201710562701A CN 109225222 A CN109225222 A CN 109225222A
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- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910002451 CoOx Inorganic materials 0.000 claims abstract description 35
- 239000003426 co-catalyst Substances 0.000 claims abstract description 19
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 9
- 229910005855 NiOx Inorganic materials 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 46
- 229910021529 ammonia Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 13
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 23
- 230000015572 biosynthetic process Effects 0.000 abstract description 22
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 238000004176 ammonification Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- -1 quantum rod Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004178 biological nitrogen fixation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of composite photo-catalyst and its application, the composite photo-catalyst includes: N2Active cocatalyst, photohole capture co-catalyst and as carrier and provide the photochemical catalyst of photo-generated carrier；The N2Active cocatalyst is alkaline earth oxide；The photohole capture co-catalyst is CoOxOr NiOx, wherein 1≤x≤1.33；It is described as carrier and provide photo-generated carrier photochemical catalyst be TiO2Or/and g-C3N4.The present invention, which prepares high activity photocatalytic synthesis ammonification material and constructs mild, low energy consumption photocatalytic synthesis, has huge scientific value and realistic meaning at ammono-system.
Description
Technical field
The invention belongs to artificial fixed nitrogen to synthesize ammonia field, be related to a kind of composite photo-catalyst and its application, be suitable for environment,
The fields such as the energy, material.
Background technique
Fixed nitrogen is that the photosynthetic second important chemical process is only second in nature, and people it is expected to obtain as solid always
Chemical nitrogen fixation system as nitrogen enzyme makes nitrogen and water in atmosphere change ammonification at normal temperatures and pressures.Theoretically, synthesis ammonia is anti-
Should be one thermodynamically cannot spontaneous progress reaction, three key bond energy 941KJ mol of nitrogen molecule-1, the first ionization potential
15.58eV has very high stability, thirdly key bond energy is maximum in all homonuclear diatomic molecules, it is difficult to realize such as
Azotase is like that at normal temperatures and pressures by N2And H2O converts ammonification.Ammonia synthesizing industry metaplasia, which produces, at present is still based on high temperature, high pressure
Reaction condition.The ammonia synthesis process industrially applied is Haber-Bosch method (N2+3H2→2NH3), the method use is based on iron
The multiple catalyst of body occurs under the conditions of 500 DEG C or so and 20-50MPa.The biological nitrogen fixation of chemical nitrogen fixation effective solution
Deficiency, but the requirement to equipment and power is harsher, and energy consumption is high for whole process.Especially by the steam reforming of hydrocarbon
During obtaining hydrogen, a large amount of CO2Enter atmosphere as byproduct emission, increases environmental pressure.Secondly, although ruthenium-based catalytic
The research and development of agent are as second generation synthetic ammonia catalyst, but there is still a need for the energy barriers that high temperature (being greater than 300 DEG C) reduces activating nitrogen gas.From conjunction
For proton source chooses angle in ammonification reaction, above-mentioned high temperature catalyst can only be with H2Match.Obviously, H is compared2, H2O makees
It is proton carrier pollution-free, cheap and easy to get more suitable for realizing low energy consumption, ammonia synthesis reaction without secondary pollution.But H2O
The catalysis of molecule dissociates and realizes same N2In conjunction with proton transfer, be still restrict realize this reaction bottleneck.
In recent years, start some reports occur using photocatalytic method synthesis ammonia, but selected catalyst is mostly metal-
Metal oxide or metal oxide supported noble metal, and the yield of ammonia is relatively low, therefore is also not carried out its application.It is insufficient
Be mainly reflected in: 1. need the position of energy band of conductor photocatalysis material, improve utilization rate and photo-generated carrier to light
Transport efficiency, the surface electronic/hole for making to move to surface has stronger oxidation-reduction quality；2. needing to construct photocatalysis material
Expect the N on surface2Site is activated, and guarantees its stability；3.N2The generation of reduzate needs to cooperate H+Turn of ion or proton
It moves, general photocatalytic system then selects organic sacrificial agent to provide H+The donor of ion or proton, however for application angle, it is sacrificial
Domestic animal agent or solvent increase reaction cost and bring the new problems such as " three wastes " discharge and improvement.
Summary of the invention
In view of the above-mentioned problems, the purpose of the present invention is to provide the catalyst and structure of a kind of high activity photocatalytic synthesis ammonification
Build room temperature normal pressure, Driven by Solar Energy photocatalytic synthesis at ammono-system.
On the one hand, the present invention provides a kind of composite photo-catalysts, comprising: N2Active cocatalyst, photohole capture
Co-catalyst and as carrier and provide the photochemical catalyst of photo-generated carrier；
The N2Active cocatalyst is alkaline earth oxide；
The photohole capture co-catalyst is CoOxOr NiOx, wherein 1≤x≤1.33；
It is described as carrier and provide photo-generated carrier photochemical catalyst be TiO2Or/and g-C3N4。
The present invention selects alkaline earth oxide as N2Active cocatalyst, CoOxOr NiOxIt is captured as photohole
Co-catalyst, TiO2Or/and g-C3N4As carrier and provide the photochemical catalyst of photo-generated carrier.The present invention is partly led using inorganic
Body catalyst efficient catalytic restores N2System, which can efficiently activate N under the irradiation of ultraviolet-visible light2And solution
From H2O molecule, finally synthesizes NH3。
Preferably, the alkaline earth oxide is CaO or MgO.
Preferably, the N2The molar ratio of active cocatalyst and photohole capture co-catalyst is (0.1~10): 1.
Preferably, photohole capture co-catalyst and as carrier and the photochemical catalyst that provides photo-generated carrier
Mass ratio is (0.001~0.05): 1.
On the other hand, the present invention also provides a kind of methods for synthesizing ammonia is passed through N under light source irradiation2/H2O gaseous mixture
Body, using above-mentioned composite photo-catalyst, so that the H being passed through2O and N2It reacts to form NH3。
Differential responses course of the present invention for photocatalysis fixed nitrogen synthesis this specific catalytic process of ammonia, comprising: N2Molecule
Activation, the separation of photo-generated carrier, the capture of photohole, the dissociation of hydrone and NH3Generation, design based on compound
Photochemical catalyst and its catalysis and synthesis ammono-system, play the function of each component to the maximum extent and realize the energy of its concerted catalysis
Power, as shown in Figure 4.The present invention regard nanostructure alkaline earth oxide such as MgO etc. as N first2The catalyst of activation utilizes
The delocalized electronics in surface brought by the defect of the material surfaces such as MgO and N2Molecule, which combines, generates N2 -Secondly free radical species will
Alkaline earth metal oxide and photochemical catalyst are compound, further promote N using the light induced electron of photochemical catalyst2Activation, while benefit
Water is decomposed with photohole and obtains proton, realizes N2Hydrogenation synthesis ammonia realizes the tandem reaction of catalysis.
Preferably, the N2/H2The middle N of O mixed gas2/H2The molar ratio of O be (10~100): 1, flow velocity be 60~
100ml/ minutes.Preferably, the irradiation power of the light source is 50~500W.
The present invention has the characteristics that following:
(1) raw material of the present invention are simple, from a wealth of sources, and preparation process is simple and controllable, can realize magnanimity system in a short time
It is standby；
(2) co-catalyst involved in the present invention does not include noble metal, cheap and easy to get；
(3) present invention is with H2O is as N2The proton source of reduction plus hydrogen, avoids using H2Deng causing carrying capacity of environment；
(4) present invention prepares high activity photocatalytic synthesis ammonification material and constructs mild, low energy consumption photocatalytic synthesis and has at ammono-system
There are huge scientific value and realistic meaning.
Detailed description of the invention
Fig. 1 is MgO-CoOx/TiO2X-ray powder diffraction pattern (XRD)；
Fig. 2 is MgO-CoOx/TiO2And TiO2UV-Vis DRS map (DRS)；
Fig. 3 is MgO-CoOx/TiO2Transmission electron microscope picture (TEM)；
Fig. 4 is MgO-CoOx/TiO2Photocatalytic synthesis ammonification schematic diagram；
Fig. 5 is MgO-CoOx/TiO2Synthesize yield-time diagram of ammonia photochemical catalyst；
Fig. 6 is MgO-CoOx/TiO2With MgO/TiO2Photoelectric current comparison diagram；
Fig. 7 is MgO-CoOx/TiO2With MgO/TiO2Photocatalytic synthesis ammonification performance comparison figure；
Fig. 8 is MgO-CoOx/TiO2With CoOx/TiO2Photocatalytic synthesis ammonification performance comparison figure.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The heretofore described composite photocatalyst mixture with high catalytic efficiency, low cost is by activating N2Co-catalysis
Agent, capture photohole co-catalyst and as carrier and provide photo-generated carrier photochemical catalyst three parts composition.
Above-mentioned activation N2Catalyst (N2Active cocatalyst) it can be alkaline earth oxide, preferably MgO or CaO
At least one of.The catalyst (photohole capture co-catalyst) of the capture photohole is in CoOx or NiOx
One kind, preferably CoOx.The CoOxOr NiOxThe value range of middle x is between 1~1.33.Described is used as carrier and mentions
Photochemical catalyst for photo-generated carrier is TiO2Or g-C3N4One of.The N2Active cocatalyst and photohole capture
The molar ratio of co-catalyst can be (0.1~10): 1, preferably (0.6~4): 1.The photohole capture co-catalyst and work
For carrier and the mass ratio that provides the photochemical catalyst of photo-generated carrier can be (0.001~0.05): 1.
Above-mentioned N2Active cocatalyst, photohole capture co-catalyst and as carrier and provide photo-generated carrier
Photochemical catalyst can be the nano composite structure of quantum dot, quantum rod, nano wire, nanometer rods, nanometer sheet or other patterns.And institute's group
At the pattern of the composite photo-catalyst be not limited with synthesis mode: can for quantum dot, quantum rod, nano wire, nanometer rods,
The semiconductor nano material of nanometer sheet or other patterns.Material component of the present invention is simple, cheap and easy to get, light utilization efficiency is high, simultaneously
It is suitble to magnanimity preparation, there is application prospect.
The present invention also provides a kind of methods for catalyzing and synthesizing ammonia using above-mentioned composite photocatalyst mixture comprising: it is compound
Photochemical catalyst, N2, water and illumination.This method can be restored efficiently under the irradiation of full spectrum or visible light and generate corresponding go back
Originate in object.
It is provided by the invention to synthesize ammonia catalyst system using composite photo-catalyst, mainly by composite photo-catalyst in light
H is utilized according under the conditions of2O is by N2It is reduced to NH3.As a photo catalytic reduction N2And generate NH3Operating method example, behaviour
Steps are as follows for work: (1) composite photo-catalyst being added in the reactor, in the reactor by composite photo-catalyst dispersion.(2) to anti-
It answers and is passed through N in device2/H2O mixed gas.(3) with the photochemical catalyst in light source irradiation reactor, occur that it with the gas being passed through
Reaction.(4) product obtained is collected with dilute sulfuric acid aqueous solution, and according to national standard method (Berthelot spectrophotometry) into
The detection of row ammonia density.The quality of the composite photo-catalyst can be 0.1-0.5g.The gas flow rate being passed through in reactor can be
60-100mL/min, the N2/H2The middle N of O mixed gas2/H2The molar ratio of O can be (10~100): 1.In addition, the reactant
System can carry out within the scope of very wide temperature, not make particular/special requirement.As long as the light source is capable of providing excitation composite photocatalyst
Major catalyst in agent generates the light source of photo-generate electron-hole pairs, such as the ultraviolet-visible light, and irradiation power can be 50
~500W.Preferably, the light source is artificial light source or lamp.
The characterization method of the composite photo-catalyst includes: that X powder x ray diffraction (XRD), spectrum, high-resolution electronic are aobvious
Micro mirror (HRTEM) and optical electro-chemistry test etc..
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 1MgO-CoOx/TiO2Synthesize the preparation of ammonia photochemical catalyst
Experimental procedure includes: 1. to weigh 0.5g nano-TiO first2Powder is added in 50ml water, and is kept stirring.2. being added
2mmol magnesium nitrate is warming up to 100 DEG C under continuous agitation, until liquid evaporating completely.3. taking out dry powder to set
In Muffle furnace, 350 DEG C are warming up to, is cooled, to realize that the load 4. of MgO co-catalyst disperses the powder after roasting
It is impregnated 3 hours in the cobalt nitrate aqueous solution of 0.5mmol, then by the way that filter cake is obtained by filtration.5. the powder that will be obtained by filtration, again
It is placed in Muffle furnace, is warming up to 300 DEG C, cools, to realize CoOxThe load of co-catalyst.Gained sample is denoted as MgO-
CoOx/TiO2.Fig. 1 is the X-ray powder diffraction pattern (XRD) of synthetic sample, and as shown in Figure 1, the main phase of synthetic sample is
TiO2, Fig. 3 be synthetic sample transmission electron microscope picture (TEM), MgO is distributed in TiO2The edge of crystal grain, CoOxThen it is grown in TiO2?
Grain surface.By the UV-Vis DRS map (Fig. 2) for analyzing sample, it is known that the load of MgO and CoOx is not significantly changed
TiO2Absorption to light.Fig. 4 is the schematic diagram of synthetic sample photocatalytic synthesis ammonification.
Embodiment 2MgO-CoOx/g-C3N4Synthesize the preparation of ammonia photochemical catalyst
Experimental procedure includes: 1. to weigh 5g melamine and 0.1g magnesium nitrate first, and the two is mixed.2. the mixture that will be obtained
It is placed in Muffle furnace and is heated to 550 DEG C, cool.It is impregnated 3. resulting powder is dispersed in the cobalt nitrate aqueous solution of 1mmol,
Again by the way that filter cake is obtained by filtration.4. the powder that will be obtained by filtration, is again placed in Muffle furnace, kept the temperature at 300 DEG C, to realize
CoOxThe load of co-catalyst.Gained sample is denoted as MgO-CoOx/g-C3N4。
The operating method of 3 composite photo-catalyst of embodiment synthesis ammonia
Experimental procedure includes: 1. by MgO-CoO obtained in embodiment 1x/TiO2Photochemical catalyst is put into reactor, will be compound
Photochemical catalyst disperses in the reactor.2. being passed through N into reactor2/H2O mixed gas.3. irradiating reactor using xenon lamp 500W
In photochemical catalyst, so that it is reacted with gas is passed through.4. using 0.2mmol aqueous sulfuric acid as NH3Absorbing liquid, according to
Berthelot spectrophotometry is to NH3Concentration Testing.Fig. 5 show MgO-CoOx/TiO2Yield-the time diagram for synthesizing ammonia, from figure
The sample known in 5 synthesizes ammonia efficiency in 2 hours and keeps stablizing.
Comparative example 1
This comparative example 1 difference from example 1 is that: removal step 5, i.e., it is unsupported as photohole capture co-catalysis
Agent CoOx, it is denoted as MgO/TiO2, remaining content is identical with described in embodiment 1.It is learnt through photoelectrochemical assay,
Unsupported CoOxSample density of photocurrent be less than MgO-CoOx/TiO2Sample, it follows that CoOxAs photohole
Capture catalyst can promote the separation of photo-generated carrier.In conjunction with optical electro-chemistry as a result, also turning out CoOxIt is able to suppress photoproduction
Electrons and holes it is compound, referring to Fig. 6.
Comparative example 2
This comparative example and embodiment 3 the difference is that: the photochemical catalyst used is MgO/TiO described in comparative example 12,
Remaining content is identical with described in embodiment 3.Through performance test analysis, load has CoOxSample show more
Good photocatalytic synthesis ammonification performance, reaches 340 μm of ol/g, compares MgO/TiO2Sample, MgO-CoOx/TiO2Photocatalytic synthesis ammonification
Performance improves 2 times, referring to Fig. 7.
Comparative example 3
This comparative example 3 difference from example 1 is that: removal step 3, i.e., it is unsupported be used as N2Active cocatalyst MgO,
It is denoted as CoOx/TiO2, remaining content is identical with described in embodiment 1.This comparative example it is different from embodiment 3 it
Being in: the photochemical catalyst used is CoO described in comparative example 3x/TiO2, remaining content is and described in embodiment 3
It is identical.Through performance test analysis, load has the sample of MgO to show better photocatalytic synthesis ammonification performance, reaches 340 μ
Mol/g compares CoOx//TiO2Sample, MgO-CoOx/TiO2Photocatalytic synthesis ammonification performance improves 10 times, referring to Fig. 8.
Claims (7)
1. a kind of composite photo-catalyst characterized by comprising N2Active cocatalyst, photohole capture co-catalyst and
As carrier and provide the photochemical catalyst of photo-generated carrier；
The N2Active cocatalyst is alkaline earth oxide；
The photohole capture co-catalyst is CoOxOr NiOx, wherein 1≤x≤1.33；
It is described as carrier and provide photo-generated carrier photochemical catalyst be TiO2Or/and g-C3N4。
2. composite photo-catalyst according to claim 1, which is characterized in that the alkaline earth oxide be CaO or
MgO。
3. composite photo-catalyst according to claim 1 or 2, which is characterized in that the N2Active cocatalyst and photoproduction are empty
The molar ratio that cave captures co-catalyst is (0.1~10): 1.
4. composite photo-catalyst according to any one of claim 1-3, which is characterized in that the photohole capture helps
Catalyst and as carrier and provide photo-generated carrier photochemical catalyst mass ratio be (0.001~0.05): 1.
5. a kind of method for synthesizing ammonia, which is characterized in that under light source irradiation, be passed through N2/H2O mixed gas, utilizes claim
Composite photo-catalyst described in any one of 1-4, so that the H being passed through2O and N2It reacts to form NH3。
6. according to the method described in claim 5, it is characterized in that, the N2/H2The middle N of O mixed gas2/H2The molar ratio of O is
(10~100): 1, flow velocity is 60~100ml/ minutes.
7. method according to claim 5 or 6, which is characterized in that the irradiation power of the light source is 50~500W.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252376A (en) * | 2019-07-01 | 2019-09-20 | 吉林大学 | A kind of metal-semiconductor composite photo-catalyst, the preparation method and applications of photocatalysis nitrogen and hydrogen synthesis ammonia |
| CN111632566A (en) * | 2020-05-07 | 2020-09-08 | 福州大学 | Catalytic nitrogen fixation device |
| CN111704146A (en) * | 2020-06-09 | 2020-09-25 | 山西大学 | Pickering microbubble system construction method and application for synthesizing ammonia by photocatalytic nitrogen fixation |
| CN113318725A (en) * | 2021-06-22 | 2021-08-31 | 电子科技大学长三角研究院(湖州) | Preparation method and application of alkaline earth metal oxide sub-nanocluster |
| CN115155634A (en) * | 2022-03-29 | 2022-10-11 | 广州大学 | Synthesis and application of alkaline earth metal coordination modified bubbly porous g-C3N4 nanosheet photocatalyst |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04349935A (en) * | 1991-05-29 | 1992-12-04 | Mitsubishi Heavy Ind Ltd | Oxidation catalyst |
| EP0754163A1 (en) * | 1994-04-08 | 1997-01-22 | Kansas State University Research Foundation | Iron oxide/magnesium oxide composites and method for destruction of chlorinated hydrocarbons using such composites |
| CN1290573A (en) * | 2000-10-04 | 2001-04-11 | 中国科学院兰州化学物理研究所 | Light catalyst for purifying air |
| EP1113875A1 (en) * | 1998-08-12 | 2001-07-11 | Kansas State University Research Foundation | Dispersion and stabilization of reactive atoms on the surface of metal oxides |
| EP1513602A1 (en) * | 2002-06-07 | 2005-03-16 | Nanoscale Materials, Inc. | Air-stable metal oxide nanoparticles |
| CN1836772A (en) * | 2005-03-23 | 2006-09-27 | 中国石油化工股份有限公司 | Load type calcium oxide catalyst, its preparation method and uses |
| CN102139890A (en) * | 2010-01-28 | 2011-08-03 | 新疆大学 | Novel method for synthesizing ammonia at low temperature and normal pressure |
| CN102513115A (en) * | 2011-10-28 | 2012-06-27 | 中国科学院过程工程研究所 | Perovskite supported nickel base methanation catalyst and preparation method thereof |
| CN102962068A (en) * | 2012-11-08 | 2013-03-13 | 浙江理工大学 | Nickel titanate catalyst for organic dyestuff degradation by visible light and preparation method thereof |
| CN103977828A (en) * | 2013-12-10 | 2014-08-13 | 中国科学院大连化学物理研究所 | Catalyst for ammonia synthesis and ammonia decomposition |
| CN105800679A (en) * | 2016-03-08 | 2016-07-27 | 南京大学 | Method for preparing TiO2 spherical three-level hierarchical structure |
| CN106082270A (en) * | 2016-06-08 | 2016-11-09 | 南京科技职业学院 | A kind of method of photocatalytic synthesis ammonification |
| CN106163658A (en) * | 2014-02-27 | 2016-11-23 | 国立研究开发法人科学技术振兴机构 | Metal supported catalyst and the ammonia synthesis of this catalyst of use |
| CN106881133A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of catalyst for synthesizing ammonia |
-
2017
- 2017-07-11 CN CN201710562701.8A patent/CN109225222B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04349935A (en) * | 1991-05-29 | 1992-12-04 | Mitsubishi Heavy Ind Ltd | Oxidation catalyst |
| EP0754163A1 (en) * | 1994-04-08 | 1997-01-22 | Kansas State University Research Foundation | Iron oxide/magnesium oxide composites and method for destruction of chlorinated hydrocarbons using such composites |
| EP1113875A1 (en) * | 1998-08-12 | 2001-07-11 | Kansas State University Research Foundation | Dispersion and stabilization of reactive atoms on the surface of metal oxides |
| CN1290573A (en) * | 2000-10-04 | 2001-04-11 | 中国科学院兰州化学物理研究所 | Light catalyst for purifying air |
| EP1513602A1 (en) * | 2002-06-07 | 2005-03-16 | Nanoscale Materials, Inc. | Air-stable metal oxide nanoparticles |
| CN1836772A (en) * | 2005-03-23 | 2006-09-27 | 中国石油化工股份有限公司 | Load type calcium oxide catalyst, its preparation method and uses |
| CN102139890A (en) * | 2010-01-28 | 2011-08-03 | 新疆大学 | Novel method for synthesizing ammonia at low temperature and normal pressure |
| CN102513115A (en) * | 2011-10-28 | 2012-06-27 | 中国科学院过程工程研究所 | Perovskite supported nickel base methanation catalyst and preparation method thereof |
| CN102962068A (en) * | 2012-11-08 | 2013-03-13 | 浙江理工大学 | Nickel titanate catalyst for organic dyestuff degradation by visible light and preparation method thereof |
| CN103977828A (en) * | 2013-12-10 | 2014-08-13 | 中国科学院大连化学物理研究所 | Catalyst for ammonia synthesis and ammonia decomposition |
| CN106163658A (en) * | 2014-02-27 | 2016-11-23 | 国立研究开发法人科学技术振兴机构 | Metal supported catalyst and the ammonia synthesis of this catalyst of use |
| CN106881133A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of catalyst for synthesizing ammonia |
| CN105800679A (en) * | 2016-03-08 | 2016-07-27 | 南京大学 | Method for preparing TiO2 spherical three-level hierarchical structure |
| CN106082270A (en) * | 2016-06-08 | 2016-11-09 | 南京科技职业学院 | A kind of method of photocatalytic synthesis ammonification |
Non-Patent Citations (3)
| Title |
|---|
| JAE-SUK CHOI等: ""Development of nickel catalyst supported on MgO-TiO2 composite oxide for DIR-MCFC"", 《CATALYSIS TODAY》 * |
| LIMIN SONG等: ""Highly active NiO–CaO photocatalyst for degrading organic contaminants under visible-light irradiation"", 《CATALYSIS COMMUNICATIONS》 * |
| 吴玉琪: ""CoOx改性TiO2光催化剂的制备、优化及其光催化分解水析氢性能研究"", 《无机化学学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110252376A (en) * | 2019-07-01 | 2019-09-20 | 吉林大学 | A kind of metal-semiconductor composite photo-catalyst, the preparation method and applications of photocatalysis nitrogen and hydrogen synthesis ammonia |
| CN111632566A (en) * | 2020-05-07 | 2020-09-08 | 福州大学 | Catalytic nitrogen fixation device |
| CN111704146A (en) * | 2020-06-09 | 2020-09-25 | 山西大学 | Pickering microbubble system construction method and application for synthesizing ammonia by photocatalytic nitrogen fixation |
| CN111704146B (en) * | 2020-06-09 | 2021-12-31 | 山西大学 | Pickering microbubble system construction method and application for synthesizing ammonia by photocatalytic nitrogen fixation |
| CN113318725A (en) * | 2021-06-22 | 2021-08-31 | 电子科技大学长三角研究院(湖州) | Preparation method and application of alkaline earth metal oxide sub-nanocluster |
| CN113318725B (en) * | 2021-06-22 | 2022-10-21 | 电子科技大学长三角研究院(湖州) | Preparation method and application of alkaline earth metal oxide sub-nanocluster |
| CN115155634A (en) * | 2022-03-29 | 2022-10-11 | 广州大学 | Synthesis and application of alkaline earth metal coordination modified bubbly porous g-C3N4 nanosheet photocatalyst |
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