CN109433202A - A kind of ruthenium-based catalyst being carried on barium tantalate surface and its application in synthesis ammonia - Google Patents
A kind of ruthenium-based catalyst being carried on barium tantalate surface and its application in synthesis ammonia Download PDFInfo
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- CN109433202A CN109433202A CN201811246294.0A CN201811246294A CN109433202A CN 109433202 A CN109433202 A CN 109433202A CN 201811246294 A CN201811246294 A CN 201811246294A CN 109433202 A CN109433202 A CN 109433202A
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6486—Tantalum
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- 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
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The present invention provides a kind of ruthenium-based catalyst for being carried on barium tantalate surface and its application in synthesis ammonia, belongs to catalytic field.Using barium tantalate as carrier, barium tantalate area load active constituent ruthenium, wherein Ru and barium tantalate mass ratio are 0.1~16:100, and the specific surface area of barium tantalate is 10-50m2/g.Preparation method of the present invention is simple, and ammonia synthesis catalyst carrier can be prepared by simple hydro-thermal reaction.The catalyst activity of invention preparation is high, stability is good, security performance is high.
Description
Technical field
The invention belongs to catalytic fields, and in particular to a kind of ruthenium-based catalyst for being carried on barium tantalate surface and its synthesize
Application in ammonia.
Background technique
Ammonia synthesizing industry is one of most important chemical industry, and countries in the world are devoted to the development of ammonia synthesizing industry.It closes
Ammonification is a kind of effective artificial fixed nitrogen means, provides the nitrogen source of 40-60% for human body.Ammonia is easily liquefied (0.86MPa
20 DEG C or -33.4 DEG C at 0.1MPa of at) and it is not carbon containing, so ammonia is counted as a kind of closest practical recyclable fuel,
It is also considered as the important Hydrogen carrier that can coordinate energy and environmental problem.1913, the ammonia synthesis iron of Haber-Bosch
((Oppau) realizes industrialization for the first time, drills the synthetic method of ammonia from cyaniding in German treasured difficult to understand for catalyst and its process flow
The nitrogen and hydrogen mixture synthesis of ammonia is changed to, so that the yield for greatly improving ammonia is known as first generation ammonia synthesis catalyst.Haber-
The service condition of Bosch technique generally under 400-600 DEG C of high temperature and the high pressure of 20-100MPa, greatly consumes energy,
Ammonia synthesizing industry is caused to consume the 1% of whole world energy consumption.At this stage, the feed hydrogen of ammonia synthesizing industry mainly passes through extensive
What high-pressure natural gas modification (methane steam reforming) obtained.Future is used as renewable energy and Hydrogen carrier
Ammonia, raw material will eventually be transitioned into biomass or electrolysis water from unrenewable natural gas (electric energy is originated from renewable energy).
These small-scale, low pressure hydrogen source pairing ammonification catalyst propose new challenge.Therefore develop one kind has in a mild condition
High performance catalyst substitutes traditional iron catalyst, is not only to promote the needs of traditional Haber-Bosch technique, and reply
The needs of the following ammonia new energy challenge.
Its active component of ammonia synthesis catalyst is mostly Fe, Ru, Co, Ni etc. at present, and carrier is mostly MgO, Al2O3、Nb2O5、
TiO2, active carbon, electronics salt etc..Maximum rate-limiting step is the dissociation of nitrogen in ammonia synthesis, and Ru is because of its superior nitrogen dissociation capability
Be widely used in the synthesis of ammonia, 1992, using activated carbon as the ruthenium catalyst of carrier Canadian Ocelot synthesis ammonia plant for the first time
Realize industrialization.But under the conditions of ammonia synthesis reaction, ruthenium metal is easy to make activity carbon carrier that methanation occur, and causes to be catalyzed
The active reduction of agent, limits the large-scale industrial application of ruthenium catalyst.In addition, carbon material also has inflammability, industrially
Using also there is some potential safety problems.Therefore it provides a kind of chemical property it is stable, using safe ruthenium-based catalytic agent carrier still
It is an important topic.Barium tantalate is because having excellent photoelectric properties and non-linear optical property, good optical effect and electricity
It learns performance and is widely used in the fields such as photocatalysis and laser, battery.But the application in terms of synthesizing ammonia is but never reported.
Summary of the invention
To solve the above-mentioned problems, ruthenium is carried on the surface of barium tantalate by the present invention, and it is high, stable to have prepared catalytic activity
Property is good, uses safe synthetic ammonia catalyst.
Technical solution provided by the invention is specific as follows:
A kind of ruthenium-based catalyst being carried on barium tantalate surface, using barium tantalate as carrier, barium tantalate area load activity at
Point ruthenium, wherein Ru and barium tantalate mass ratio are 0.1~16:100, and the specific surface area of barium tantalate is 10-50m2/g。
Preferably, the structure of the barium tantalate is Ba5Ta4O15。
Preferably, the barium tantalate uses following methods to be prepared: by the molar ratio of Ba and Ta for (8~12): 1 Ta
Presoma and the mixing of Ba presoma, in 150-220 DEG C of 140~180h of heating.
Preferably, the Ta presoma is one or more of oxide, hydroxide, salt of Ta, the Ba
Presoma is one or more of oxide, hydroxide, salt of Ba.
, can be different with the presoma of barium according to tantalum in the preparation process of barium tantalate carrier, selection can dissolve or disperse
Solvent such as water, alcohols, the supercritical CO of corresponding presoma2Deng one or more kinds of mixtures；And the synthetic reaction is suitable
Carried out preferably in the closed reaction system (such as potheater), reaction temperature preferably between 150-220 DEG C, more preferably in 180-
Between 200 DEG C.Reaction time is preferably 140~180h, and the preferred reaction time is 150~170h；Reaction time is too short, tantalum and barium
Forerunner's precursor reactant it is insufficient, cannot get ideal carrier；Reaction time is too long, will increase the energy consumption of synthesis process.It reacts
The sample arrived can recycle the catalyst carrier of synthesis by common solid-liquid separation means (such as filter, be centrifuged), then
It is dry by conventional drying means (such as dry, dry, be freeze-dried, be dried in vacuo).
The present invention also provides the preparation method of above-mentioned ruthenium-based catalyst, include the following steps: barium tantalate support dispersion
In ruthenium precursor solution, wherein the quality of Ru and barium tantalate carrier quality ratio are 0.1~16:100 in ruthenium precursor solution,
It is spin-dried for solvent after stirring, gained mixture is placed in quartz ampoule, is warming up to 150-400 DEG C, under atmosphere of inert gases or vacuum
2-20h is handled to get above-mentioned ruthenium-based catalyst is arrived.
The load factor of barium tantalate surface ruthenium is the 0.1%~16% of barium tantalate carrier quality；If load factor is lower than 0.1%,
The catalytic action of catalyst pairing ammonification is unobvious；If the load factor of ruthenium is higher than 16%, it is too big to will lead to ruthenium grain diameter, reduces
The catalytic efficiency of unit ruthenium.
Preferably, the ruthenium presoma is Ru3(CO)12、Ru(CH3COCHCOCH3)3、Ru(CH3COO)3、Ru(NO)
(NO3)3、RuCl3One or more of.
The present invention also provides the ruthenium-based catalysts that another kind is carried on barium tantalate surface, bear on above-mentioned ruthenium-based catalyst
It is loaded with promoter metal compound.
Preferably, on the basis of barium tantalate area load ruthenium, by adding suitable alkali metal, alkaline-earth metal, rare earth
One or more kinds of mixtures of metal improve the catalytic performance of catalyst as auxiliary agent.Alkali metal, alkaline-earth metal and
The broiler diets of rare earth metal auxiliary agent are 0~16 times of the molal quantity relative to the ruthenium for being carried on barium tantalate surface.Addition is few
Amount promoter metal compound is conducive to auxiliary agent and is distributed in around active ruthenium nano-particle, to be effectively facilitated the catalytic of ruthenium
Energy.Additive amount is not more than 16 times, is in order to avoid the ruthenium nano-particle of catalyst surface is completely covered by auxiliary agent, to hinder anti-
Object and ruthenium surface atom is answered to be in contact and reduce its catalytic activity.
Preferably, the alkali metal compound be sodium acetate, potassium acetate, acetic acid rubidium, cesium acetate, sodium nitrate, potassium nitrate,
One or more of rubidium nitrate, cesium nitrate；The alkaline earth metal compound is calcium acetate, barium acetate, strontium acetate, nitric acid
One or more of calcium, barium nitrate, strontium nitrate；The rare earth compound is lanthanum acetate, acetic acid samarium, cerous acetate, nitre
One or more of sour lanthanum, samaric nitrate, cerous nitrate.Can also specifically add NaOH, KOH, RbOH, CsOH, CaO, SrO,
BaO、La2O3、CeO2、Sm2O3Deng as auxiliary agent.
Above-mentioned load has the preparation method of the ruthenium-based catalyst of auxiliary agent metallic compound, comprising the following steps: by above-mentioned ruthenium
Base catalyst is immersed in the solution of the compound containing promoter metal, is dried after removing solvent, and obtaining the load has auxiliary agent
The ruthenium-based catalyst of metallic compound.
The present invention also provides application of the above-mentioned ruthenium-based catalyst in synthesis ammonia field, and the catalyst is for synthesizing ammonia
Reaction condition when catalysis reaction are as follows: 250-500 DEG C of temperature, 0.1~5.1MPa of pressure, air speed 1000~1000000.
The present invention makes N under certain temperature, pressure and air speed using above-mentioned catalyst2And H2It reacts and generates ammonia
Gas.The temperature of ammonia synthesis reaction is preferably arranged within the scope of 250-500 DEG C.Reaction temperature is higher than 250 DEG C, is to guarantee ruthenium
The activating velocity for being catalyzed nitrogen molecule is sufficiently fast.In addition it is ruthenium active component in order to prevent at 500 DEG C or less that reaction temperature, which is arranged,
Deterioration.The pressure of ammonia synthesis reaction is suitable for being arranged in the range of 0.1~5.1MPa.Pressure is higher than 0.1MPa and is conducive to react
Balance the reserve migration generated to ammonia.Pressure is not higher than 5.1MPa, can save because of bring energy consumption of boosting.Ammonia synthesis is anti-
The air speed (GHSV) answered preferably selects within the scope of 1000~1000000.GHSV setting is 1000 or more, it is possible to prevente effectively from raw
At ammonia be broken down into nitrogen and hydrogen again.And GHSV is arranged 1000000 hereinafter, can save for recycling unreacted
Energy consumed by gas.
The principle of the present invention is as follows:
Low price tantalum can activate nitrogen, but tantalum is difficult to shift to low price under the conditions of synthesizing ammonia, and when Ru is supported on surface
But high price tantalum can be shifted to low price, to further increase the activity of synthesis ammonia.The presence of barium tantalate is to ruthenium-based catalyst
Synthesizing ammonia activity has facilitation, Ba5Ta4O15Carrier is in flaky nanometer structure, and Ru is in Ba5Ta4O15Growth on carrier can be sudden and violent
Reveal more active sites so as to obtain higher catalytic activity.The present invention has the following advantages and beneficial effects:
(1) preparation method of the present invention is simple, and ammonia synthesis catalyst carrier can be prepared by simple hydro-thermal reaction.
(2) catalyst activity of invention preparation is high, stability is good, security performance is high.
Detailed description of the invention
Fig. 1 is 1 gained barium tantalate Ba of embodiment5Ta4O15The SEM spectrum of carrier；
Fig. 2 is 1 gained barium tantalate Ba of embodiment5Ta4O15The XRD spectrum of carrier；
Fig. 3 is the catalytic stability test effect figure of catalyst prepared by embodiment 2.
Specific embodiment
The present invention will be described in detail by embodiment below.These embodiments are not to protection model of the invention
It encloses and carries out any restriction, equivalent result or the equivalent process transformation that all contents and thought using description of the invention are done,
Or it is directly or indirectly used in other related fieldss, similarly it is included within protection scope of the present invention.
Embodiment 1:
Ba5Ta4O15The preparation of carrier
(1) 6.3g Ba (OH) is taken2·8H2O and 0.55g Ta2O5It is dissolved in 45mL aqueous solution, stirs 60min.
(2) mixed solution will be obtained in (1) to be transferred in the reaction kettle of 100mL polytetrafluoroethylene (PTFE).Reaction temperature setting exists
200 DEG C, reaction time 168h.
(3) whiteness is centrifuged, washs, dry after reacting, after obtain Ba5Ta4O15Carrier is as shown in Figure 1, obtain
Arrived by nanometer sheet assemble flower-like structure, growth of the Ru on the carrier of laminated structure be easier be in it is flat, compared to circle
Shape, it is flat to expose more active sites so as to obtain higher catalytic activity.Products therefrom is divided using XRD
Analysis illustrates to have obtained structure to be Ba as a result as shown in Fig. 2, according to PDF (72-0115) card comparative analysis5Ta4O15Tantalic acid
Barium carrier.
The preparation of ruthenium-based catalyst
(1) it takes ten dicarbapentaborane of 0.0315g, three ruthenium to be dissolved in 10mL tetrahydrofuran, is added after the dissolution of ten dicarbapentaborane, three ruthenium
Ba obtained by 0.5012g5Ta4O15Carrier, rotary evaporation 3h obtains mixture after stirring 5h.
(2) mixture obtained in the previous step is put into quartz ampoule, is warming up to 200 DEG C with the speed of 5 DEG C/min, argon atmospher
It encloses lower reduction and sloughs carbonyl, the recovery time is 9~11h, obtains ruthenium-based catalyst.
(3) ruthenium-based catalyst is granulated, takes ruthenium-based catalyst 0.1013g of the particle size range at 0.22~0.45 micron, filled
Enter in quartz ampoule, carries out catalytic activity test.
Ruthenium-based catalyst is catalyzed ammonia synthesis
The rate of synthesis ammonia is calculated using the method for sulfuric acid absorption ammonia, sulfuric acid conductivity variations.
By 200mL sulfuric acid solution (c (H2SO4)=0.00108mol/L) it pours into the three-necked flask of 250mL, blender
Speed is adjusted to 30rpm, and bath temperature is adjusted to 30 DEG C.
H is passed through by airflow rate ratio=3:12/N2, H2: 45mL/min, N2: 15mL/min, pressure 0.1MPa.400℃
The catalytic activity of walking program heating curve determination different temperature points after reduction 3h.The temperature spot of each test is reached, 30min is stablized
It is being tested, length of testing speech 30min, test result is as follows shown in table 1.
Ammonia synthesis rate (μm olg of the different test temperature point of table 1-1 cat·h-1), the wherein quality and barium tantalate of Ru
Carrier quality ratio is 1.96:100.
The ammonia synthesis active testing of the ruthenium-based catalyst of different loads rate
Ten dicarbapentaborane of 0.0212g, 0.0315g, 0.0424g, three ruthenium is taken to be dissolved in 10mL tetrahydrofuran respectively, to 12 carbonyls
0.5003g Ba is added after the dissolution of three ruthenium of base5Ta4O15Carrier.Rotary evaporation 3h obtains mixture after stirring 5h.Previous step is obtained
To mixture be put into quartz ampoule, be warming up to 200 DEG C with the speed of 5 DEG C/min, carbonyl is sloughed in reduction under the atmosphere of argon gas, also
The former time is 9~11h, obtains ruthenium-based catalyst.Ruthenium-based catalyst is granulated, ruthenium of the particle size range at 0.22~0.45 micron is taken
Base 0.1001~0.1013g of catalyst, is fitted into quartz ampoule, carries out catalytic activity test.
The rate of synthesis ammonia is calculated using the method for sulfuric acid absorption ammonia, sulfuric acid conductivity variations.
By 200mL sulfuric acid solution (c (H2SO4)=0.00108mol/L) it pours into the three-necked flask of 250mL, blender
Speed is adjusted to 30rpm, and bath temperature is 30 DEG C.
H is passed through by airflow rate ratio=3:12/N2, H2: 45mL/min, N2: 15mL/min, pressure 0.1MPa.400℃
The catalytic activity of walking program heating curve determination different temperature points after reduction 3h.The temperature spot of each test is reached, 30min is stablized
It is tested again, length of testing speech 30min, test result is as follows shown in table 2.
Ammonia synthesis rate (μm ol of the ruthenium-based catalyst of 2 difference Ru of table and barium tantalate carrier quality ratio (1~3:100)
g-1 cat·h-1)
Embodiment 2
Add auxiliary agent CsNO3Ruthenium-based catalyst preparation
Ten dicarbapentaborane of 0.0315g, three ruthenium is dissolved in 10mL tetrahydrofuran, is added after the dissolution of ten dicarbapentaborane, three ruthenium
0.5012g Ba5Ta4O15Carrier, rotary evaporation 3h obtains mixture after stirring 5h.Mixture obtained in the previous step is put into stone
Ying Guanzhong is warming up to 200 DEG C with the speed of 5 DEG C/min, and carbonyl is sloughed in reduction under the atmosphere of argon gas, and the recovery time is 9~11h,
Obtain ruthenium-based catalyst.
CsNO is added with molar ratio Cs:Ru=1:1,2:1,3:1,4:1 respectively3, 10mL distilled water is added, it is molten to cesium nitrate
0.1505g ruthenium-based catalyst is added in Xie Hou, and rotary evaporation obtains mixture after stirring 5h.Product obtained in the previous step is granulated,
It takes particle size range in 0.22~0.45 micron of catalyst 0.1005g, is fitted into quartz ampoule, carry out catalytic activity test.
The rate of synthesis ammonia is calculated using the method for sulfuric acid absorption ammonia, sulfuric acid conductivity variations.
By 200mL sulfuric acid solution (c (H2SO4)=0.00108mol/L) it pours into the three-necked flask of 250mL, blender
Speed is adjusted to 30rpm, and bath temperature is 30 DEG C.H is passed through by airflow rate ratio=3:12/N2, H2: 45mL/min, N2: 15mL/
Min, pressure 0.1MPa.The catalytic activity of walking program heating curve determination different temperature points after 400 DEG C of reduction 3h.It reaches each
The temperature spot of test first waits 30min, then tests 30min, and test result is as follows shown in table 3.
Ammonia synthesis rate (μm olg of the catalyst of the different auxiliary agent load factors of table 3-1 cat·h-1)
Add auxiliary agent CsNO3Catalyst stability test
The catalyst of molar ratio Cs:Ru=3:1 is taken to carry out stability of catalytic activity test, using sulfuric acid absorption ammonia, sulfuric acid
The method of conductivity variations synthesizes the rate of ammonia to calculate.
By 200mL sulfuric acid solution (c (H2SO4)=0.00108mol/L) it pours into the three-necked flask of 250mL, blender
Speed is adjusted to 30rpm, and bath temperature is 30 DEG C.H is passed through by airflow rate=3:12/N2, H2: 45mL/min, N2: 15mL/min,
Pressure is 0.1MPa.It is warming up to 400 DEG C and first restores the stability test for carrying out 72h after 3h at 400 DEG C, every 2h carries out 30min
Ammonia synthesis rate test, stability test result is as shown in Figure 3.
Claims (10)
1. a kind of ruthenium-based catalyst for being carried on barium tantalate surface, which is characterized in that using barium tantalate as carrier, barium tantalate surface is negative
Carry active constituent ruthenium, wherein Ru and barium tantalate mass ratio are (0.1~16): 100, the specific surface area of barium tantalate is 10-50m2/
g。
2. ruthenium-based catalyst according to claim 1, which is characterized in that the structure of the barium tantalate is Ba5Ta4O15。
3. ruthenium-based catalyst according to claim 1, which is characterized in that the barium tantalate is prepared into using following methods
Arrive: be (8~12) by Ba and Ta molar ratio: 1 Ta presoma and Ba presoma mixes, in 150-220 DEG C of 140~180h of heating
?.
4. ruthenium-based catalyst according to claim 3, which is characterized in that the Ta presoma is oxide, the hydrogen of Ta
One or more of oxide, salt, the Ba presoma are one or more of oxide, hydroxide, salt of Ba.
5. the preparation method of any one of Claims 1 to 4 ruthenium-based catalyst, which comprises the steps of: by tantalum
Sour barium support dispersion is in ruthenium precursor solution, wherein the quality of Ru and barium tantalate carrier quality ratio are in ruthenium precursor solution
(0.1~16): 100, it is spin-dried for solvent after stirring, gained mixture is placed in quartz ampoule, is warming up to 150-400 DEG C, indifferent gas
2-20h is handled under body atmosphere or vacuum to get above-mentioned ruthenium-based catalyst is arrived.
6. preparation method according to claim 5, which is characterized in that the ruthenium presoma is Ru3(CO)12、Ru
(CH3COCHCOCH3)3、Ru(CH3COO)3、Ru(NO)(NO3)3、RuCl3One or more of.
7. a kind of ruthenium-based catalyst for being carried on barium tantalate surface, which is characterized in that in any one of Claims 1 to 4 ruthenium
Load has auxiliary agent metallic compound on base catalyst.
8. ruthenium-based catalyst according to claim 7, which is characterized in that the promoter metal compound is alkali metal chemical combination
The molar ratio of the one or more of object, alkaline earth metal compound, rare earth compound, the promoter metal compound and ruthenium is
(0~16): 1.
9. ruthenium-based catalyst according to claim 7, which is characterized in that the alkali metal compound is sodium acetate, vinegar
One or more of sour potassium, acetic acid rubidium, cesium acetate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate；The alkaline-earth metal
Conjunction object is one or more of calcium acetate, barium acetate, strontium acetate, calcium nitrate, barium nitrate, strontium nitrate；The rare earth metal
Compound is one or more of lanthanum acetate, acetic acid samarium, cerous acetate, lanthanum nitrate, samaric nitrate, cerous nitrate.
10. Claims 1 to 4, application of any one of 7~9 ruthenium-based catalysts in synthesis ammonia field, which is characterized in that
Catalytic reaction condition are as follows: 250-500 DEG C of temperature, 0.1~5.1MPa of pressure, air speed 1000~1000000.
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| CN113694922A (en) * | 2021-09-29 | 2021-11-26 | 石河子大学 | Supported catalyst for ammonia decomposition and preparation method thereof |
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| US20170250031A1 (en) * | 2014-11-21 | 2017-08-31 | Mitsubishi Chemical Corporation | Method of producing composite photocatalyst and composite photocatalyst |
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| WO2012159051A2 (en) * | 2011-05-19 | 2012-11-22 | Research Foundation Of The City University Of New York | Chemically modified graphene |
| CN102658135A (en) * | 2012-05-02 | 2012-09-12 | 福州大学 | Ruthenium supported perovskite-type-oxide ammonia synthesis catalyst and preparation method thereof |
| US20170250031A1 (en) * | 2014-11-21 | 2017-08-31 | Mitsubishi Chemical Corporation | Method of producing composite photocatalyst and composite photocatalyst |
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| CN113694922A (en) * | 2021-09-29 | 2021-11-26 | 石河子大学 | Supported catalyst for ammonia decomposition and preparation method thereof |
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