CN113318750A - Lithium-doped two-dimensional iron-molybdenum catalyst for synthesizing ammonia gas by thermally catalyzing nitrogen and hydrogen through mobile phase and preparation method thereof - Google Patents
Lithium-doped two-dimensional iron-molybdenum catalyst for synthesizing ammonia gas by thermally catalyzing nitrogen and hydrogen through mobile phase and preparation method thereof Download PDFInfo
- Publication number
- CN113318750A CN113318750A CN202110691226.0A CN202110691226A CN113318750A CN 113318750 A CN113318750 A CN 113318750A CN 202110691226 A CN202110691226 A CN 202110691226A CN 113318750 A CN113318750 A CN 113318750A
- Authority
- CN
- China
- Prior art keywords
- lithium
- iron
- doped
- catalyst
- molybdenum catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000001257 hydrogen Substances 0.000 title claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 title claims abstract 20
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 92
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 80
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 239000010453 quartz Substances 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- 238000010438 heat treatment Methods 0.000 claims description 52
- 239000012018 catalyst precursor Substances 0.000 claims description 28
- 238000007789 sealing Methods 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 239000006004 Quartz sand Substances 0.000 claims description 20
- 239000012495 reaction gas Substances 0.000 claims description 19
- 238000011049 filling Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000007036 catalytic synthesis reaction Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 3
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 2
- 229910021576 Iron(III) bromide Inorganic materials 0.000 claims description 2
- 229910010084 LiAlH4 Inorganic materials 0.000 claims description 2
- 239000012448 Lithium borohydride Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 229910000155 iron(II) phosphate Inorganic materials 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 16
- 239000002253 acid Substances 0.000 abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052744 lithium Inorganic materials 0.000 abstract description 8
- 238000011068 loading method Methods 0.000 abstract description 7
- 230000004913 activation Effects 0.000 abstract description 5
- -1 iron ions Chemical class 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- KWUUWVQMAVOYKS-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe][Mo][Mo] KWUUWVQMAVOYKS-UHFFFAOYSA-N 0.000 description 76
- 238000010521 absorption reaction Methods 0.000 description 39
- 239000007788 liquid Substances 0.000 description 38
- 239000000243 solution Substances 0.000 description 34
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 21
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 18
- 150000002500 ions Chemical class 0.000 description 17
- 239000000395 magnesium oxide Substances 0.000 description 17
- 239000002243 precursor Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004255 ion exchange chromatography Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 229910001309 Ferromolybdenum Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 102000008857 Ferritin Human genes 0.000 description 2
- 108050000784 Ferritin Proteins 0.000 description 2
- 238000008416 Ferritin Methods 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000009623 Bosch process Methods 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L Cs2CO3 Substances [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 229910010951 LiH2 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 241000589180 Rhizobium Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
A lithium-doped two-dimensional iron-molybdenum catalyst for synthesizing ammonia gas by thermally catalyzing nitrogen and hydrogen with a mobile phase and a preparation method thereof belong to the technical field of ammonia synthesis catalysis. The invention uses MoO2Vacuum calcining treatment, and loading iron ions and iron atoms to MoO2Mixing the surface of the substrate with lithium-containing reducing agent uniformly, calcining the mixture at high temperature in vacuum, and washing the calcined product with acid or water to dope lithium into MoO2Thereby peeling the two-dimensional catalyst to obtain the lithium-doped two-dimensional iron-molybdenum catalyst. According to the invention, a large amount of electrons are introduced into the catalyst by doping lithium, the catalyst has iron-molybdenum double activation sites, and can be subjected to mobile phase catalysis in a fixed bed reactor, and the catalyst can be used at high temperatureAnd can catalyze nitrogen and hydrogen to synthesize ammonia for a long time under high pressure. Wherein, the generation amount of ammonia gas of the lithium-doped two-dimensional iron-molybdenum catalyst can reach 3007.11umol g‑1*h‑1The ammonia gas generation amount of the acid-treated lithium-doped two-dimensional iron-molybdenum catalyst can reach 3207.61umol g‑1*h‑1。
Description
Technical Field
The invention belongs to the technical field of synthetic ammonia catalysis, and particularly relates to a lithium-doped two-dimensional iron-molybdenum catalyst for synthesizing ammonia gas by thermally catalyzing nitrogen and hydrogen through a mobile phase and a preparation method thereof.
Background
Ammonia has a very important influence on human sustainable development and is one of important chemical fertilizer raw materials and chemical raw materials in the world. Synthesis of ammonia (N) by the Habor-Bosch Process2+3H2＝2NH3350-500 ℃ and 50-200 bar), but still consumes a lot of energy in the field of ammonia synthesis, and faces a lot of challenges. Although the biocatalysis, the electrocatalysis, the photocatalysis and the thermocatalysis are developed in the field of ammonia synthesis at present, each catalytic direction has room for improvement, for example, an iron-based catalyst is low in price but low in catalytic efficiency, a ruthenium-based catalyst is high in activity but high in price and has a strong inhibition effect on hydrogen, and a thermocatalysis effect is good but high in energy consumption.
At present, ammonia synthesis towers are common in the chemical industry of China, a large amount of solid particle catalysts are stacked together to form a particle bed layer, and gas flow is subjected to gas-solid phase catalysis through the bed layer, so that a fixed bed reactor can effectively perform heterogeneous catalytic reaction.
However, the rotation system of leguminous plants and non-leguminous plants is still maintained in China from ancient times to present, and ancient people record that leguminous plants have the function of 'soil maturity and fertility'. Compared with the industrial nitrogen fixation method, the biological nitrogen preparation can be carried out at normal temperature and normal pressure. Various researches show that two independent enzyme proteins can be separated from the rhizobium azotase of the soybean, wherein one enzyme protein is ferromolybdenum, the other enzyme protein is ferritin, the two enzyme proteins have azotase activity only when being combined together, and the azotase is inactive when being separated. In the synergistic effect of the two, ferritin provides electrons for ferromolybdenum protein, and the ferromolybdenum protein plays a catalytic and complexing role in catalyzing nitrogen (N)2+8e-+8H++16Mg·ATP+16H2O→2NH3 +H2+16 Mg. ADP +16Pi), i.e. electrons and hydrogen in the case of ATP-supplied energyIon transfer to N by nitrogenase2Reducing them to NH3. At present, Michikazu Hara et al published a title "Synthesis of ammonia by Using a Stable Electron Compound as an Electron Donor and a reversible Hydrogen storage", in Nature Chemistry journal (2012, No. 4, pp. 934-940), and prepared a ruthenium-supported Electron Compound activated Nitrogen. Michikazu Hara et al, later, published a title "Synthesis of ammonia at 50 ℃ with solid solution" in Nature Communications journal (20: 15868-15876 of 2020) by introducing F-The electron-pushing capacity of the CaFH solid solution is enhanced, so that ammonia can be synthesized under low-temperature conditions, and the ammonia is compared with an industrial iron-based catalyst in the article. However, the method for preparing the catalyst by Michikazu Hara is harsh and is not suitable for industrial mass production.
Therefore, there is a need to design a catalyst that can have a large number of electrons to maintain the excellent activity of the catalyst and to stabilize the existing catalyst to solve the current problems.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a lithium-doped two-dimensional iron-molybdenum catalyst for synthesizing ammonia gas by thermally catalyzing nitrogen and hydrogen through a mobile phase and a preparation method thereof.
The invention uses MoO2Vacuum calcining treatment, and loading iron ions and iron atoms to MoO2Mixing the surface of the substrate with lithium-containing reducing agent uniformly, calcining the mixture at high temperature in vacuum, and washing the calcined product with acid or water to dope lithium into MoO2Thereby peeling the two-dimensional catalyst to obtain the lithium-doped two-dimensional iron-molybdenum catalyst. According to the invention, a large amount of electrons are introduced into the catalyst through lithium doping, the catalyst has iron-molybdenum double activation sites, and can be subjected to mobile phase catalysis in a fixed bed reactor, and the catalyst can catalyze nitrogen and hydrogen to synthesize ammonia for a long time at high temperature and high pressure. The catalyst utilizes a small amount of iron, and has a simple structure and low price.
The invention relates to a preparation method of a lithium-doped two-dimensional iron-molybdenum catalyst for synthesizing ammonia gas by thermally catalyzing nitrogen and hydrogen with a mobile phase, which comprises the following steps:
(1) iron molybdenum catalyst precursorPreparation of the body: adding 0.4-5 g of MoO2Calcining the ground mixture for 1 to 5 hours at 300 to 800 ℃ in vacuum, and then placing the calcined mixture in 0.1 to 2g/L of organic solvent solution of iron salt in inert atmosphere (N)2Or Ar) stirring and dipping for 3-10 h, and performing rotary evaporation and evaporation to dryness and then vacuum drying to obtain an iron-molybdenum catalyst precursor; the organic solvent solution of ferric salt is FeCl3Ethanol solution of (3), Fe2(SO4)3Ethanol solution of (3), Fe3(CO)12THF solution of (1), Fe2(CO)9THF solution of (1), FeC4H7O5·nH2Ethanol solution of O, FePO4Ethanol solution of (3), Fe2(C2O4)3Ethanol solution of (2), FeSO4Ethanol solution of (3), Fe3(PO4)2·nH2Ethanol solution of O, FeBr3Ethanol solution of (D), FeCl2Ethanol solution of (5) FeBr2One of the ethanol solutions of (a);
(2) preparing a lithium-doped two-dimensional iron-molybdenum catalyst: mixing the iron-molybdenum catalyst precursor obtained in the step (1) with lithium salt in a molar ratio of 1: 5-13, grinding and uniformly mixing, slowly heating to 200-600 ℃ in a vacuum state, keeping for 1-10 h (the heating rate is 0.2-2 ℃/min), cooling to room temperature, and sealing; slowly injecting a little deionized water into the reaction system under the ice-water bath condition to immerse the reaction product, and transferring to 50-1000 mL of concentrated hydrochloric acid (the density is 1.179 g/cm) containing 0-10 mL after the reaction is completed3) Performing ultrasonic treatment for 2-10 min in the deionized water; washing the reaction product with deionized water for 3-5 times, and then drying in vacuum to obtain a lithium-doped two-dimensional iron-molybdenum catalyst; the sample washed without hydrochloric acid was named Li-Fe-MoO2The sample washed with hydrochloric acid was named H+-Li-Fe-MoO2(ii) a The lithium salt is LiH or C4H9Li、LiAlH4、LiBH4One of (1);
(3) thermal catalytic synthesis of ammonia: 0.1-1 g of the lithium-doped two-dimensional iron-molybdenum catalyst prepared in the step (2) is pressed into tablets under 2-30 MPa for 1-30 min, and the pressed tablets are taken out, smashed and sieved; selecting 20-60 mesh catalyst particles, filling the catalyst particles into a quartz reaction tube (inner diameter is 4-8 mm)The filling height of the catalyst is 2-3 times of the inner diameter, and the quartz reaction tube is sealed and then transferred to a fixed bed reactor; or 0.01-1 g of catalyst and 0.4-1.0 g of quartz sand of 20-140 meshes are uniformly mixed in a glove box, filled into a quartz reaction tube and sealed, and then transferred to a fixed bed reactor; the method comprises the following steps of: 3 is N2And H2The mixed gas is reaction gas, the flow rate is 5-100 mL/min, and the pressure is kept at 0.1-4 MPa; after the airflow is stable, the temperature is raised to 50-800 ℃ for catalytic reaction for 1-120 h, and the temperature raising rate is 3-5 ℃/min, so that the thermal catalytic synthesis of ammonia is completed.
MoO used in the invention2LiH, hydrochloric acid, sulfuric acid, quartz sand and other metals are commercially available.
Drawings
FIG. 1: is Li-MoO2、Li-Fe-MoO2And H+-Li-Fe-MoO2(wherein Li-Fe-MoO)2Is a lithium-doped two-dimensional iron-molybdenum catalyst, Li-MoO2Is a lithium-doped molybdenum dioxide catalyst, H+-Li-Fe-MoO2Lithium doped two-dimensional iron molybdenum catalyst washed with hydrochloric acid) and standard MoO2XRD pattern of (a); illustrates the MoO2The molybdenum at the edge of the lithium salt is reduced into molybdenum metal, MoO by the action of the reduced lithium salt LiH2The bulk phase has good crystallinity, the framework is not damaged, and the main diffraction peaks are shifted to small angles to indicate that lithium enters MoO2In the crystal lattice. MoO2After loading with iron, LiH is preferentially attracted by iron, bridging with MoO via iron2Reaction, MoO2The bulk phase crystal lattice is still intact, the edge metal molybdenum exists at the same time, and the main peak shifts; exposing a large amount of edge molybdenum after acid washing;
FIG. 2: (a) is Li-Fe-MoO2A transmission diagram of Li-Fe-MoO2Is a layered two-dimensional material; (b) is Li-Fe-MoO2STEM dark field map of (1); (c) is Li-Fe-MoO2The elemental distribution of O of (1); (d) is Li-Fe-MoO2The elemental distribution of Fe of (1); (e) is Li-Fe-MoO2The element distribution of Mo of (a); (b) the scale bar of the graphs (c), (d) and (e) is 500nm, which shows that Fe, O and Mo are uniformly distributed; corresponding to example 3;
FIG. 3: is Li-Fe-MoO2High resolution transmission diagram ofLi-Fe-MoO2The edge of (a) can see an obvious number of layers, 7-9 molecular layers, corresponding to example 3;
FIG. 4: (a) is H+-Li-Fe-MoO2Transmission diagram of (A), showing H after pickling+-Li-Fe-MoO2Still a layered two-dimensional material; (b) is H+-Li-Fe-MoO2STEM dark field map of (1); (c) is H+-Li-Fe-MoO2The elemental distribution of O of (1); (d) is H+-Li-Fe-MoO2The elemental distribution of Fe of (1); (e) is H+-Li-Fe-MoO2The element distribution of Mo of (a); (b) the scale bars of the graphs (c), (d) and (e) are 500nm, which shows that Fe, O and Mo are uniformly distributed, excessive acid washing cannot wash out all iron, and part of iron and MoO2Newly formed chemical bond stabilized in MoO2Above, corresponding to example 4;
FIG. 5: is Li-MoO2、Li-Fe-MoO2And H+-Li-Fe-MoO2The temperature programmed reaction of hydrogen (H) is shown in the figure+-Li-Fe-MoO2The adsorption capacity to hydrogen is strongest;
FIG. 6: is Li-MoO2、Li-Fe-MoO2And H+-Li-Fe-MoO2The electron spin resonance diagram shows that the three catalysts have a large number of lone-pair electrons which exist independently;
FIG. 7: is Li-MoO2、Li-Fe-MoO2、H+-Li-Fe-MoO2And MoO2FT-IR spectrum of (1), indicating the presence of MoO2And Li-MoO2Comparative Li-Fe-MoO2In addition to the pronounced Mo O, Mo-O-OH vibration, there is also the pronounced Fe O, Fe-O-Mo vibration, while H+-Li-Fe-MoO2Although the material is washed by hydrochloric acid, the obvious vibration of Fe-O, Fe-O-Mo still exists, and the excellent catalytic performance of the lithium-doped two-dimensional iron-molybdenum material is proved to be influenced by the coexistence of iron and molybdenum;
FIG. 8: standard NH determination by ion chromatography4 +Standard curve of concentration, the equation for the curve is Y-629748X-3641.5, Y represents NH measured by ion chromatography4 +Peak area, X represents NH4 +The unit of (1) is mmol/L; the curve passes throughMeasuring eight groups of NH of different concentrations4 +The series of peak areas are measured by ion chromatography, and NH is obtained by using the eight concentration/peak area mapping4 +Standard curve of concentration.
In each embodiment, the exhaust gas flows through the absorption liquid, and the ammonia gas generated by catalysis is dissolved in the absorption liquid to form NH4 +Taking out 1mL of tail gas absorption liquid of each embodiment, pumping into an ion chromatograph, and measuring NH in the tail gas absorption liquid4 +Substituting the peak area into a standard curve equation to obtain the tail gas absorption liquid NH4 +And (4) concentration.
FIG. 9: ammonia gas yield plot for the catalyst prepared in the examples, in umol g-1*h-1Corresponding to examples 1 to 9.
FIG. 10: ammonia gas yield plot for the catalyst prepared in the examples, in umol g-1*h-1Wherein Fe-1 corresponds to example 10, Fe-2 corresponds to example 3, Fe-3 corresponds to example 11, and Fe-4 corresponds to example 12.
FIG. 11: is Li-Fe-MoO2The ammonia yield plot over time, corresponding to example 13, shows Li-Fe-MoO2The catalytic performance of the catalyst is very stable.
FIG. 12: is Li-Fe-MoO2The activation energy graphs of (1) correspond to examples 14-17, and the activation energy can be obtained by taking one thousand times of reciprocal of different temperatures as the abscissa and taking the logarithm of the ammonia gas generation amount as the ordinate and multiplying the slope of the obtained trend line by R (8.314), which shows that the catalyst needs less activation energy and has good catalytic performance.
Detailed Description
The following examples are presented to further illustrate the practice and results of the invention and are not intended to limit the invention thereto.
Example 1
Preparation of iron-molybdenum catalyst precursor (named Fe-MoO)2) And their catalysis of N2、H2Synthesis of NH3。
(1) Preparing an iron-molybdenum catalyst precursor: 1g of MoO was weighed2Grinding, transferring into quartz boat, and placing in vacuumCalcining at 500 deg.C for 2 hr in an empty tube furnace, and placing in 14.48ml FeCl3In 0.5g/L of ethanol under an inert atmosphere (N)2Or Ar) stirring and dipping for 5h, evaporating to dryness by rotary evaporation, and then drying in vacuum to obtain an iron-molybdenum catalyst precursor Fe-MoO2；
(2) 30mg of Fe-MoO2Mixing with 0.5g and 140 mesh quartz sand in glove box, loading into quartz reaction tube (inner diameter of 6mm), sealing, transferring to fixed bed reactor, and adding N at molar ratio of 1:32And H2The mixed gas is used as reaction gas, the flow rate is 60mL/min, and the pressure is kept at 1 Mpa; after the gas flow is stable, heating to 400 ℃ for reaction for 3h (the heating rate is 4 ℃/min), thereby completing the thermocatalytic synthesis of ammonia; the final tail gas is diluted with 0.25mM of H2SO4Absorbing the solution, taking 1mL of tail gas absorption liquid to measure NH in the ion chromatogram4 +The peak area of (A) is substituted into the regression curve equation of FIG. 8 to obtain NH of the tail gas absorption liquid4 +The concentration is calculated, and the generation amount of ammonia gas can reach 95.99umol g-1*h-1。
Example 2
Preparation of lithium-doped molybdenum dioxide catalyst (named Li-MoO)2) And their catalysis of N2、H2Synthesis of NH3。
(1) Preparing a molybdenum dioxide catalyst precursor: 1g of MoO was weighed2Grinding, transferring the mixture into a quartz boat, placing the quartz boat into a vacuum tube furnace, and calcining the quartz boat for 2 hours at 500 ℃ to obtain a molybdenum dioxide catalyst precursor;
(2) grinding and uniformly mixing 0.8g of molybdenum dioxide catalyst and 0.4g of LiH, quickly transferring into a quartz bubble which is easy to seal, slowly heating to 450 ℃ in a vacuum state, keeping for 2h, wherein the heating rate is 1 ℃/min, sealing after cooling to room temperature, slowly injecting 5mL of deionized water into the quartz bubble under the condition of ice-water bath until the reaction is completed, transferring into 300mL of deionized water, and carrying out ultrasonic treatment for 8 min; washing the mixture for three times by using deionized water, and then drying the mixture in vacuum to obtain the lithium-doped two-dimensional molybdenum dioxide catalyst Li-MoO2；
(3) 30mg of Li-MoO20.5g, 140 meshMixing quartz sand in a glove box, loading into a quartz reaction tube (inner diameter of 6mm), sealing, transferring to a fixed bed reactor, and adding N at a molar ratio of 1:32And H2The mixed gas is used as reaction gas, the flow rate is 60mL/min, and the pressure is kept at 1 Mpa; after the gas flow is stable, heating to 400 ℃ for reaction for 3h (the heating rate is 4 ℃/min), thereby completing the thermocatalytic synthesis of ammonia; final tail gas consumption of 0.25mM H2SO4Absorbing the solution, taking 1mL of tail gas absorption liquid to measure NH in the ion chromatogram4 +The peak area of (A) is substituted into the regression curve equation of FIG. 8 to obtain NH of the tail gas absorption liquid4 +The concentration is calculated, and the generation amount of ammonia gas can reach 1191.48umol g-1*h-1。
Example 3
Preparation of lithium-doped two-dimensional iron-molybdenum catalyst (named Li-Fe-MoO)2) And their catalysis of N2、H2Synthesis of NH3。
(1) Preparing an iron-molybdenum catalyst precursor: same as example 1;
(2) preparing a lithium-doped two-dimensional iron-molybdenum catalyst: grinding 0.8g of a precursor of the iron-molybdenum catalyst and 0.4g of LiH to uniformly mix, quickly transferring the mixture into a quartz bubble which is easy to store, slowly heating to 450 ℃ in a vacuum state, keeping the temperature for 2 hours, wherein the heating rate is 1 ℃/min, sealing after cooling to room temperature, slowly injecting 5mL of deionized water into the quartz bubble under the condition of ice-water bath until the reaction is completed, transferring the mixture into 300mL of deionized water, and carrying out ultrasonic treatment for 8 minutes; washing with deionized water for three times, and vacuum drying to obtain Li-Fe-MoO as lithium-doped two-dimensional iron-molybdenum catalyst2；
(3) Mixing 30mg of lithium-doped two-dimensional iron-molybdenum catalyst and 0.5g of quartz sand of 140 meshes uniformly in a glove box, filling the mixture into a quartz reaction tube (the inner diameter is 6mm), sealing, transferring the quartz reaction tube to a fixed bed reactor, and adopting N with the molar ratio of 1:32And H2The mixed gas is used as reaction gas, the flow rate is 60mL/min, and the pressure is kept at 1 Mpa; after the gas flow is stable, heating to 400 ℃ for reaction for 3h (the heating rate is 4 ℃/min), thereby completing the thermocatalytic synthesis of ammonia; final tail gas consumption of 0.25mM H2SO4Absorbing the solution, taking 1mL of tail gas absorption liquid to measure NH in the ion chromatogram4 +The peak area of (A) is substituted into the regression curve equation of FIG. 8 to obtain NH of the tail gas absorption liquid4 +The concentration is calculated, and the generation amount of ammonia gas can reach 3007.11umol g-1*h-1。
Example 4
Preparation of acid-treated lithium-doped two-dimensional iron molybdenum catalyst (designated as H)+-Li-Fe-MoO2) And their catalysis of N2、H2Synthesis of NH3。
(1) Preparing an iron-molybdenum catalyst precursor: same as example 1;
(2) preparation of acid-treated lithium-doped two-dimensional iron-molybdenum catalyst: grinding 0.8g of precursor of the iron-molybdenum catalyst and 0.4g of LiH to uniformly mix, quickly transferring the mixture into a quartz bubble which is easy to store, slowly heating to 450 ℃ in a vacuum state, keeping the temperature for 2 hours, wherein the heating rate is 1 ℃/min, sealing after cooling to room temperature, slowly injecting 5mL of deionized water into the quartz bubble under the condition of ice-water bath until the reaction is completed, and transferring the mixture into concentrated hydrochloric acid containing 6mL (the density is 1.179 g/cm)3) In 300mL of deionized water, and carrying out ultrasonic treatment for 8 min; washing for three times by using deionized water, and then drying in vacuum to obtain the acid-treated lithium-doped two-dimensional iron-molybdenum catalyst H+-Li-Fe-MoO2；
(3) Mixing 30mg of acid-treated lithium-doped two-dimensional iron-molybdenum catalyst and 0.5g of 140-mesh quartz sand uniformly in a glove box, filling the mixture into a quartz reaction tube (the inner diameter is 6mm), sealing, transferring the quartz reaction tube to a fixed bed reactor, and adopting N with the molar ratio of 1:32And H2The mixed gas is used as reaction gas, the flow rate is 60mL/min, and the pressure is kept at 1 Mpa; after the gas flow is stable, heating to 400 ℃ for reaction for 3h (the heating rate is 4 ℃/min), thereby completing the thermocatalytic synthesis of ammonia; final tail gas consumption of 0.25mM H2SO4Absorbing the solution, taking 1mL of tail gas absorption liquid to measure NH in the ion chromatogram4 +The peak area of (A) is substituted into the regression curve equation of FIG. 8 to obtain NH of the tail gas absorption liquid4 +Concentration, and calculating the amount of ammonia gas generated, wherein the amount of ammonia gas generated can be3207.61umol g is achieved-1*h-1。
Example 5
Preparation of molybdenum dioxide catalyst (named MoO)2) And their catalysis of N2、H2Synthesis of NH3。
(1) Preparing a molybdenum dioxide catalyst precursor: the catalyst MoO was obtained in the same manner as in example 22；
(2) Mixing 30mg of molybdenum dioxide catalyst precursor and 0.5g of quartz sand with 140 meshes uniformly in a glove box, filling the mixture into a quartz reaction tube (the inner diameter is 6mm), sealing, transferring the quartz reaction tube to a fixed bed reactor, and adopting N with the molar ratio of 1:32And H2The mixed gas is used as reaction gas, the flow rate is 60mL/min, and the pressure is kept at 1 Mpa; after the gas flow is stable, heating to 400 ℃ for reaction for 3h (the heating rate is 4 ℃/min), thereby completing the thermocatalytic synthesis of ammonia; final tail gas consumption of 0.25mM H2SO4Absorbing the solution, taking 1mL of tail gas absorption liquid to measure NH in the ion chromatogram4 +The peak area of (A) is substituted into the regression curve equation of FIG. 8 to obtain NH of the tail gas absorption liquid4 +The concentration is calculated, and the generation amount of ammonia gas can reach 62.49umol g-1*h-1。
Example 6
Traditional catalyst-ruthenium cesium-loaded modified magnesium oxide (named as Ru-Cs-MgO) and catalytic N thereof2、H2Synthesis of NH3。
(1) Preparation of ruthenium-loaded magnesium oxide precursor: weighing 1.5g MgO, grinding, transferring into quartz boat, placing into vacuum tube furnace, calcining at 500 deg.C for 6 hr, and placing into a furnace containing 0.0314g Ru3(CO)12In tetrahydrofuran solution under an inert atmosphere (N)2Or Ar) stirring and dipping for 5h, evaporating to dryness by rotation, and then drying in vacuum to obtain a precursor Ru3(CO)12-MgO；
(2) 1.0g of Ru3(CO)12Transferring MgO into quartz bulb easy to be sealed, slowly heating to 450 deg.C under vacuum condition for 2 hr at heating rate of 1 deg.C/min, sealing after cooling to room temperature, and filling inert gas (N)2Or Ar) is rapidly transferred to Cs2CO3Evaporating the ethanol solution in a rotary manner to dryness and then drying in vacuum to obtain a catalyst Ru-Cs MgO;
(3) mixing 30mg Ru-Cs-MgO catalyst and 0.5g quartz sand of 140 meshes uniformly in a glove box, loading the mixture into a quartz reaction tube (the inner diameter is 6mm), sealing, transferring the quartz reaction tube to a fixed bed reactor, and adopting N with the molar ratio of 1:32And H2The mixed gas is used as reaction gas, the flow rate is 60mL/min, and the pressure is kept at 1 Mpa; after the gas flow is stable, heating to 400 ℃ for reaction for 3h (the heating rate is 4 ℃/min), thereby completing the thermocatalytic synthesis of ammonia; absorbing the final tail gas with 0.25mM H2SO4 solution, and taking 1mL tail gas absorption solution to measure NH in ion chromatography4 +The peak area of (A) is substituted into the regression curve equation of FIG. 8 to obtain NH of the tail gas absorption liquid4 +The concentration is calculated, and the generation amount of ammonia gas can reach 828.88umol g-1*h-1。
Example 7
Preparation of iron-supported magnesium oxide catalyst (named Li-Fe-MgO) and its catalytic N2、H2Synthesis of NH3。
(1) Preparing an iron-loaded magnesium oxide precursor: weighing 1g of MgO, grinding, transferring into a quartz boat, placing into a vacuum tube furnace, calcining at 500 ℃ for 6h, and placing into 14.48ml of FeCl3In 0.5g/L of ethanol under an inert atmosphere (N)2Or Ar) stirring and dipping for 5h, then carrying out rotary evaporation and evaporation to dryness, and then carrying out vacuum drying to obtain an iron-molybdenum catalyst precursor Fe-MgO; (ii) a
(2) Preparation of iron-supported magnesium oxide catalyst: grinding 0.8g of iron-loaded magnesium oxide precursor and 0.4g of LiH to achieve uniform mixing, quickly transferring into a quartz bubble which is easy to store, slowly heating to 450 ℃ in a vacuum state, keeping for 2h, wherein the heating rate is 1 ℃/min, sealing after cooling to room temperature, slowly injecting 5mL of deionized water into the quartz bubble under the condition of ice water bath until the reaction is completed, transferring into 300mL of deionized water, and carrying out ultrasonic treatment for 8 min; washing with deionized water for three times, and vacuum drying to obtain iron-loaded magnesium oxide catalyst Li-Fe-MgO;
(3) 30mg of iron was loaded with oxygenMixing magnesium oxide catalyst and 0.5g of 140-mesh quartz sand uniformly in a glove box, loading into a quartz reaction tube (the inner diameter is 6mm), sealing, transferring to a fixed bed reactor, and adopting N with the molar ratio of 1:32And H2The mixed gas is used as reaction gas, the flow rate is 60mL/min, and the pressure is kept at 1 Mpa; after the gas flow is stable, heating to 400 ℃ for reaction for 3h (the heating rate is 4 ℃/min), thereby completing the thermocatalytic synthesis of ammonia; final tail gas consumption of 0.25mM H2SO4Absorbing the solution, taking 1mL of tail gas absorption liquid to measure NH in the ion chromatogram4 +The peak area of (A) is substituted into the regression curve equation of FIG. 8 to obtain NH of the tail gas absorption liquid4 +The concentration is calculated, and the generation amount of ammonia gas can reach 26.00umol g-1*h-1。
Example 8
Preparation of calcium-doped two-dimensional iron-molybdenum catalyst (named Ca-Fe-MoO)2) And their catalysis of N2、H2Synthesis of NH3。
(1) Preparing an iron-molybdenum catalyst precursor: same as example 1;
(2) preparing a calcium-doped two-dimensional iron-molybdenum catalyst: 0.8g of precursor of the iron-molybdenum catalyst and 2.1328g of CaH are taken2Grinding to achieve uniform mixing, quickly transferring into a quartz bubble which is easy to store, slowly heating to 450 ℃ in a vacuum state, keeping for 2h, heating at the rate of 1 ℃/min, sealing after cooling to room temperature, slowly injecting 5mL of deionized water into the quartz bubble under the condition of ice-water bath, transferring into 300mL of deionized water after complete reaction, and carrying out ultrasonic treatment for 8 min; washing with deionized water for three times, and vacuum drying to obtain Ca-Fe-MoO as Ca-doped two-dimensional iron-molybdenum catalyst2；
(3) Mixing 30mg of calcium-doped two-dimensional iron-molybdenum catalyst and 0.5g of 140-mesh quartz sand uniformly in a glove box, filling the mixture into a quartz reaction tube (the inner diameter is 6mm), sealing, transferring the quartz reaction tube to a fixed bed reactor, and adopting N with the molar ratio of 1:32And H2The mixed gas is used as reaction gas, the flow rate is 60mL/min, and the pressure is kept at 1 Mpa; after the gas flow is stable, heating to 400 ℃ for reaction for 3h (the heating rate is 4 ℃/min), thereby completing the thermocatalytic synthesis of ammonia; finally, the0.25mM of H for the tail gas2SO4Absorbing the solution, taking 1mL of tail gas absorption liquid to measure NH in the ion chromatogram4 +The peak area of (A) is substituted into the regression curve equation of FIG. 8 to obtain NH of the tail gas absorption liquid4 +The concentration is calculated, and the generation amount of ammonia gas can reach 29.15umol g-1*h-1。
Example 9
Preparation of lithium-doped two-dimensional nickel-molybdenum catalyst (named Li-Ni-MoO)2) And their catalysis of N2、H2Synthesis of NH3。
(1) Preparing a nickel-molybdenum catalyst precursor: 1g of MoO was weighed2Grinding, transferring into quartz boat, calcining in vacuum tube furnace at 500 deg.C for 2 hr, and placing into 0.5g/L NiCl2In an inert atmosphere (N)2Or Ar) stirring and dipping for 5h, evaporating to dryness by rotary evaporation, and then drying in vacuum to obtain the precursor Ni-MoO of the iron-molybdenum catalyst2；
(2) Preparing a lithium-doped two-dimensional nickel-molybdenum catalyst: grinding 0.8g of a precursor of the nickel-molybdenum catalyst and 0.4g of LiH to uniformly mix, quickly transferring the mixture into a quartz bubble which is easy to store, slowly heating to 450 ℃ in a vacuum state, keeping the temperature for 2 hours, wherein the heating rate is 1 ℃/min, sealing after cooling to room temperature, slowly injecting 5mL of deionized water into the quartz bubble under the condition of ice-water bath until the reaction is completed, transferring the mixture into 300mL of deionized water, and carrying out ultrasonic treatment for 8 minutes; washing the mixture for three times by using deionized water, and then drying the mixture in vacuum to obtain the lithium-doped two-dimensional iron-molybdenum catalyst Li-Ni-MoO2；
(3) Mixing 30mg of lithium-doped two-dimensional nickel-molybdenum catalyst and 0.5g of 140-mesh quartz sand uniformly in a glove box, filling the mixture into a quartz reaction tube (the inner diameter is 6mm), sealing, transferring the quartz reaction tube to a fixed bed reactor, and adopting N with the molar ratio of 1:32And H2The mixed gas is used as reaction gas, the flow rate is 60mL/min, and the pressure is kept at 1 Mpa; after the gas flow is stable, heating to 400 ℃ for reaction for 3h (the heating rate is 4 ℃/min), thereby completing the thermocatalytic synthesis of ammonia; final tail gas consumption of 0.25mM H2SO4Absorbing the solution, taking 1mL of tail gas absorption liquid to measure in ion chromatographyNH4 +The peak area of (A) is substituted into the regression curve equation of FIG. 8 to obtain NH of the tail gas absorption liquid4 +The concentration is calculated, and the generation amount of ammonia gas can reach 1549.93umol g-1*h-1。
The above examples illustrate that lithium-doped two-dimensional iron molybdenum catalysts have significant advantages in the effect of ammonia synthesis compared to conventional catalysts and other differently doped or supported metals.
Example 10
Preparation of lithium-doped two-dimensional iron-molybdenum catalyst (named as Fe-0.5) and catalysis of N by using lithium-doped two-dimensional iron-molybdenum catalyst2、H2Synthesis of NH3。
(1) Preparing an iron-molybdenum catalyst precursor: 1g of MoO was weighed2Grinding, transferring into quartz boat, calcining in vacuum tube furnace at 500 deg.C for 2 hr, and placing in 7.24ml FeCl3In 0.5g/L of ethanol under an inert atmosphere (N)2Or Ar) stirring and dipping for 5h, evaporating to dryness by rotary evaporation, and then drying in vacuum to obtain an iron-molybdenum catalyst precursor Fe-MoO2；
(2) Preparing a lithium-doped two-dimensional iron-molybdenum catalyst: same as example 3, record as Fe-0.5;
(3) mixing 30mg of lithium-doped two-dimensional iron-molybdenum catalyst and 0.5g of quartz sand of 140 meshes uniformly in a glove box, filling the mixture into a quartz reaction tube (the inner diameter is 6mm), sealing, transferring the quartz reaction tube to a fixed bed reactor, and adopting N with the molar ratio of 1:32And H2The mixed gas is used as reaction gas, the flow rate is 60mL/min, and the pressure is kept at 1 Mpa; after the gas flow is stable, heating to 400 ℃ for reaction for 3h (the heating rate is 4 ℃/min), thereby completing the thermocatalytic synthesis of ammonia; final tail gas consumption of 0.25mM H2SO4Absorbing the solution, taking 1mL of tail gas absorption liquid to measure NH in the ion chromatogram4 +The peak area of (A) is substituted into the regression curve equation of FIG. 8 to obtain NH of the tail gas absorption liquid4 +The concentration is calculated, and the generation amount of ammonia gas can reach 1083.17umol g-1*h-1。
Example 11
Lithium-doped two-dimensional iron-molybdenum catalystPreparation of the Agents (named Fe-3) and their catalysis of N2、H2Synthesis of NH3。
(1) Preparing an iron-molybdenum catalyst precursor: 1g of MoO was weighed2Grinding, transferring into quartz boat, calcining in vacuum tube furnace at 500 deg.C for 2 hr, and placing into 43.44ml FeCl3In 0.5g/L of ethanol under an inert atmosphere (N)2Or Ar) stirring and dipping for 5h, evaporating to dryness by rotary evaporation, and then drying in vacuum to obtain an iron-molybdenum catalyst precursor Fe-MoO2；
(2) Preparing a lithium-doped two-dimensional iron-molybdenum catalyst: same as example 3, noted as Fe-3;
(3) mixing 30mg of lithium-doped two-dimensional iron-molybdenum catalyst and 0.5g of quartz sand of 140 meshes uniformly in a glove box, filling the mixture into a quartz reaction tube (the inner diameter is 6mm), sealing, transferring the quartz reaction tube to a fixed bed reactor, and adopting N with the molar ratio of 1:32And H2The mixed gas is used as reaction gas, the flow rate is 60mL/min, and the pressure is kept at 1 Mpa; after the gas flow is stable, heating to 400 ℃ for reaction for 3h (the heating rate is 4 ℃/min), thereby completing the thermocatalytic synthesis of ammonia; final tail gas consumption of 0.25mM H2SO4Absorbing the solution, taking 1mL of tail gas absorption liquid to measure NH in the ion chromatogram4 +The peak area of (A) is substituted into the regression curve equation of FIG. 8 to obtain NH of the tail gas absorption liquid4 +The concentration is calculated, and the generation amount of ammonia gas can reach 2140.59umol g-1*h-1。
Example 12
Preparation of lithium-doped two-dimensional iron-molybdenum catalyst (named as Fe-5) and N catalysis thereof2、H2Synthesis of NH3。
(1) Preparing an iron-molybdenum catalyst precursor: 1g of MoO was weighed2Grinding, transferring into quartz boat, calcining in vacuum tube furnace at 500 deg.C for 2 hr, and placing into 72.4ml FeCl3In 0.5g/L of ethanol under an inert atmosphere (N)2Or Ar) stirring and dipping for 5h, evaporating to dryness by rotary evaporation, and then drying in vacuum to obtain an iron-molybdenum catalyst precursor Fe-MoO2；
(2) Preparing a lithium-doped two-dimensional iron-molybdenum catalyst: same as example 3, noted as Fe-5;
(3) mixing 30mg of lithium-doped two-dimensional iron-molybdenum catalyst and 0.5g of quartz sand of 140 meshes uniformly in a glove box, filling the mixture into a quartz reaction tube (the inner diameter is 6mm), sealing, transferring the quartz reaction tube to a fixed bed reactor, and adopting N with the molar ratio of 1:32And H2The mixed gas is used as reaction gas, the flow rate is 60mL/min, and the pressure is kept at 1 Mpa; after the gas flow is stable, heating to 400 ℃ for reaction for 3h (the heating rate is 4 ℃/min), thereby completing the thermocatalytic synthesis of ammonia; final tail gas consumption of 0.25mM H2SO4Absorbing the solution, taking 1mL of tail gas absorption liquid to measure NH in the ion chromatogram4 +The peak area of (A) is substituted into the regression curve equation of FIG. 8 to obtain NH of the tail gas absorption liquid4 +The concentration is calculated, and the generation amount of ammonia gas can reach 1763.99umol g-1*h-1。
Example 13
Preparation of lithium-doped two-dimensional iron-molybdenum catalyst (named Li-Fe-MoO)2) And their catalysis of N2、H2Synthesis of NH3。
(1) Preparing an iron-molybdenum catalyst precursor: same as example 1;
(2) preparing a lithium-doped two-dimensional iron-molybdenum catalyst: same as in example 3;
(3) mixing 30mg of lithium-doped two-dimensional iron-molybdenum catalyst and 0.5g of quartz sand of 140 meshes uniformly in a glove box, filling the mixture into a quartz reaction tube (the inner diameter is 6mm), sealing, transferring the quartz reaction tube to a fixed bed reactor, and adopting N with the molar ratio of 1:32And H2The mixed gas is used as reaction gas, the flow rate is 60mL/min, and the pressure is kept at 1 Mpa; after the gas flow is stable, heating to 400 ℃ for reaction for 1h, 3h, 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h and 50h (the heating rate is 4 ℃/min), thereby completing the thermocatalytic synthesis of ammonia; final tail gas consumption of 0.25mM H2SO4Absorbing the solution, taking 1mL of tail gas absorption liquid to measure NH in the ion chromatogram4 +The peak area of (A) is substituted into the regression curve equation of FIG. 8 to obtain NH of the tail gas absorption liquid4 +Concentration and calculating the amount of ammonia gas producedThe ammonia gas can reach 2723.08umol g-1*h-1，3007.11umol*g-1*h-1， 1951.9umol*g-1*h-1，2486.61umol*g-1*h-1，2465.94umol*g-1*h-1，2475.7umol*g-1*h-1， 2309.37umol*g-1*h-1，2309.3umol*g-1*h-1，2335.08umol*g-1*h-1，2480.92umol*g-1*h-1， 2655.71umol*g-1*h-1，2525.77umol*g-1*h-1。
Example 14
Preparation of lithium-doped two-dimensional iron-molybdenum catalyst (named Li-Fe-MoO)2) And their catalysis of N2、H2Synthesis of NH3。
(1) Preparing an iron-molybdenum catalyst precursor: same as example 1;
(2) preparing a lithium-doped two-dimensional iron-molybdenum catalyst: same as in example 3;
(3) mixing 30mg of lithium-doped two-dimensional iron-molybdenum catalyst and 0.5g of quartz sand of 140 meshes uniformly in a glove box, filling the mixture into a quartz reaction tube (the inner diameter is 6mm), sealing, transferring the quartz reaction tube to a fixed bed reactor, and adopting N with the molar ratio of 1:32And H2The mixed gas is used as reaction gas, the flow rate is 60mL/min, and the pressure is kept at 1 Mpa; after the gas flow is stable, heating to 350 ℃ for reaction for 3h (the heating rate is 4 ℃/min), thereby completing the thermocatalytic synthesis of ammonia; final tail gas consumption of 0.25mM H2SO4Absorbing the solution, taking 1mL of tail gas absorption liquid to measure NH in the ion chromatogram4 +The peak area of (A) is substituted into the regression curve equation of FIG. 8 to obtain NH of the tail gas absorption liquid4 +The concentration is calculated, and the generation amount of ammonia gas can reach 779.06umol g-1*h-1。
Example 15
Preparation of lithium-doped two-dimensional iron-molybdenum catalyst (named Li-Fe-MoO)2) And their catalysis of N2、H2Synthesis of NH3。
(1) Preparing an iron-molybdenum catalyst precursor: same as example 1;
(2) preparing a lithium-doped two-dimensional iron-molybdenum catalyst: same as in example 3;
(3) mixing 30mg of lithium-doped two-dimensional iron-molybdenum catalyst and 0.5g of quartz sand of 140 meshes uniformly in a glove box, filling the mixture into a quartz reaction tube (the inner diameter is 6mm), sealing, transferring the quartz reaction tube to a fixed bed reactor, and adopting N with the molar ratio of 1:32And H2The mixed gas is used as reaction gas, the flow rate is 60mL/min, and the pressure is kept at 1 Mpa; after the gas flow is stable, heating to 375 ℃ and reacting for 3h (the heating rate is 4 ℃/min), thereby completing the thermal catalytic synthesis of ammonia; final tail gas consumption of 0.25mM H2SO4Absorbing the solution, taking 1mL of tail gas absorption liquid to measure NH in the ion chromatogram4 +The peak area of (A) is substituted into the regression curve equation of FIG. 8 to obtain NH of the tail gas absorption liquid4 +The concentration is calculated, and the generation amount of ammonia gas can reach 1603.48umol g-1*h-1。
Example 16
Preparation of lithium-doped two-dimensional iron-molybdenum catalyst (named Li-Fe-MoO)2) And their catalysis of N2、H2Synthesis of NH3。
(1) Preparing an iron-molybdenum catalyst precursor: same as example 1;
(2) preparing a lithium-doped two-dimensional iron-molybdenum catalyst: same as in example 3;
(3) mixing 30mg of lithium-doped two-dimensional iron-molybdenum catalyst and 0.5g of quartz sand of 140 meshes uniformly in a glove box, filling the mixture into a quartz reaction tube (the inner diameter is 6mm), sealing, transferring the quartz reaction tube to a fixed bed reactor, and adopting N with the molar ratio of 1:32And H2The mixed gas is used as reaction gas, the flow rate is 60mL/min, and the pressure is kept at 1 Mpa; after the gas flow is stable, heating to 425 ℃ and reacting for 3h (the heating rate is 4 ℃/min), thereby completing the thermocatalytic synthesis of ammonia; final tail gas consumption of 0.25mM H2SO4Absorbing the solution, taking 1mL of tail gas absorption liquid to measure NH in the ion chromatogram4 +The peak area of (A) is substituted into the regression curve equation of FIG. 8 to obtain NH of the tail gas absorption liquid4 +The concentration is calculated, and the generation amount of ammonia gas can reach 4108.97umol g-1*h-1。
Example 17
Preparation of lithium-doped two-dimensional iron-molybdenum catalyst (named Li-Fe-MoO)2) And their catalysis of N2、H2Synthesis of NH3。
(1) Preparing an iron-molybdenum catalyst precursor: same as example 1;
(2) preparing a lithium-doped two-dimensional iron-molybdenum catalyst: same as in example 3;
(3) mixing 30mg of lithium-doped two-dimensional iron-molybdenum catalyst and 0.5g of quartz sand of 140 meshes uniformly in a glove box, filling the mixture into a quartz reaction tube (the inner diameter is 6mm), sealing, transferring the quartz reaction tube to a fixed bed reactor, and adopting N with the molar ratio of 1:32And H2The mixed gas is used as reaction gas, the flow rate is 60mL/min, and the pressure is kept at 1 Mpa; after the gas flow is stable, heating to 425 ℃ and reacting for 3h (the heating rate is 4 ℃/min), thereby completing the thermocatalytic synthesis of ammonia; final tail gas consumption of 0.25mM H2SO4Absorbing the solution, taking 1mL of tail gas absorption liquid to measure NH in the ion chromatogram4 +The peak area of (A) is substituted into the regression curve equation of FIG. 8 to obtain NH of the tail gas absorption liquid4 +The concentration is calculated, and the generation amount of ammonia gas can reach 6068.27umol g-1*h-1。
Claims (7)
1. A preparation method of a lithium-doped two-dimensional iron-molybdenum catalyst for synthesizing ammonia gas by thermally catalyzing nitrogen and hydrogen with a mobile phase comprises the following steps:
(1) preparing an iron-molybdenum catalyst precursor: adding 0.4-5 g of MoO2Calcining the ground mixture for 1 to 5 hours at 300 to 800 ℃ in vacuum, and then placing the calcined mixture in 0.1 to 2g/L of organic solvent solution of iron salt in inert atmosphere (N)2Or Ar) stirring and dipping for 3-10 h, and performing rotary evaporation and evaporation to dryness and then vacuum drying to obtain an iron-molybdenum catalyst precursor;
(2) preparing a lithium-doped two-dimensional iron-molybdenum catalyst: mixing the iron-molybdenum catalyst precursor obtained in the step (1) with lithium salt in a molar ratio of 1: 5-13, grinding and uniformly mixing, slowly heating to 200-600 ℃ in a vacuum state, keeping for 1-10 h, cooling to room temperature, and sealing; slowly injecting a little deionized water into the reaction system under the ice-water bath condition to immerse the reaction product, transferring the reaction product into 50-1000 mL of deionized water containing 0-10 mL of concentrated hydrochloric acid after the reaction is completed, and carrying out ultrasonic treatment for 2-10 min; and washing the reaction product with deionized water for 3-5 times, and then drying in vacuum to obtain the lithium-doped two-dimensional iron-molybdenum catalyst for synthesizing ammonia gas by using the mobile phase thermal catalysis nitrogen and hydrogen.
2. The preparation method of the lithium-doped two-dimensional iron-molybdenum catalyst for synthesizing ammonia gas by thermally catalyzing nitrogen and hydrogen with the mobile phase according to claim 1, which is characterized by comprising the following steps: in the step (1), the organic solvent solution of ferric salt is FeCl3Ethanol solution of (3), Fe2(SO4)3Ethanol solution of (3), Fe3(CO)12THF solution of (1), Fe2(CO)9THF solution of (1), FeC4H7O5·nH2Ethanol solution of O, FePO4Ethanol solution of (3), Fe2(C2O4)3Ethanol solution of (2), FeSO4Ethanol solution of (3), Fe3(PO4)2·nH2Ethanol solution of O, FeBr3Ethanol solution of (D), FeCl2Ethanol solution of (5) FeBr2And (3) one of the ethanol solutions of (1).
3. The preparation method of the lithium-doped two-dimensional iron-molybdenum catalyst for synthesizing ammonia gas by thermally catalyzing nitrogen and hydrogen with the mobile phase according to claim 1, which is characterized by comprising the following steps: in the step (2), the temperature is slowly raised to 200-600 ℃ in a vacuum state at a heating rate of 0.2-2 ℃/min.
4. The preparation method of the lithium-doped two-dimensional iron-molybdenum catalyst for synthesizing ammonia gas by thermally catalyzing nitrogen and hydrogen with the mobile phase according to claim 1, which is characterized by comprising the following steps: the lithium salt is LiH or C4H9Li、LiAlH4、LiBH4One kind of (1).
5. A lithium-doped two-dimensional iron-molybdenum catalyst for synthesizing ammonia gas by thermally catalyzing nitrogen and hydrogen with a mobile phase is characterized in that: is prepared by the method of any one of claims 1 to 4.
6. The application of the lithium-doped two-dimensional iron-molybdenum catalyst for synthesizing ammonia gas by thermally catalyzing nitrogen and hydrogen with the mobile phase according to claim 5 in the thermal catalysis synthesis of ammonia.
7. The application of the lithium-doped two-dimensional iron-molybdenum catalyst for synthesizing ammonia gas by thermally catalyzing nitrogen and hydrogen with a mobile phase in the thermal catalysis of ammonia synthesis according to claim 6, wherein the lithium-doped two-dimensional iron-molybdenum catalyst comprises the following components in percentage by weight: 0.1-1 g of lithium-doped two-dimensional iron-molybdenum catalyst is pressed into tablets under 2-30 MPa for 1-30 min, and the pressed tablets are taken out, smashed and sieved; selecting 20-60-mesh catalyst particles, filling the catalyst particles into a quartz reaction tube with the inner diameter of 4-8 mm in a glove box, wherein the filling height of the catalyst is 2-3 times of the inner diameter, and transferring the quartz reaction tube to a fixed bed reactor after sealing; or 0.01-1 g of catalyst and 0.4-1.0 g of quartz sand of 20-140 meshes are uniformly mixed in a glove box, filled into a quartz reaction tube and sealed, and then transferred to a fixed bed reactor; the method comprises the following steps of: 3 is N2And H2The mixed gas is reaction gas, the flow rate is 5-100 mL/min, and the pressure is kept at 0.1-4 MPa; after the airflow is stable, the temperature is raised to 50-800 ℃ for catalytic reaction for 1-120 h, and the temperature raising rate is 3-5 ℃/min, so that the thermal catalytic synthesis of ammonia is completed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110691226.0A CN113318750B (en) | 2021-06-22 | 2021-06-22 | Lithium-doped two-dimensional iron-molybdenum catalyst for the synthesis of ammonia from nitrogen and hydrogen in mobile phase thermal catalysis and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110691226.0A CN113318750B (en) | 2021-06-22 | 2021-06-22 | Lithium-doped two-dimensional iron-molybdenum catalyst for the synthesis of ammonia from nitrogen and hydrogen in mobile phase thermal catalysis and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113318750A true CN113318750A (en) | 2021-08-31 |
| CN113318750B CN113318750B (en) | 2022-04-26 |
Family
ID=77424237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110691226.0A Active CN113318750B (en) | 2021-06-22 | 2021-06-22 | Lithium-doped two-dimensional iron-molybdenum catalyst for the synthesis of ammonia from nitrogen and hydrogen in mobile phase thermal catalysis and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113318750B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115821315A (en) * | 2022-10-14 | 2023-03-21 | 哈尔滨理工大学 | A kind of preparation method and application of ternary iron molybdenum oxide synthesis ammonia catalyst |
| CN116020457A (en) * | 2023-01-30 | 2023-04-28 | 上海大学 | A kind of ruthenium-based catalyst and its preparation method and application |
| CN116440911A (en) * | 2022-11-21 | 2023-07-18 | 浙江华源颜料股份有限公司 | Preparation and Application of Fe-doped Molybdenum Oxide Photocatalyst |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103855367A (en) * | 2012-11-28 | 2014-06-11 | 中国科学院大连化学物理研究所 | Nitrogen-doped porous carbon material used for anode of lithium-air cell |
| WO2018215202A1 (en) * | 2017-05-22 | 2018-11-29 | Siemens Aktiengesellschaft | Catalyst for ammonia synthesis |
| CN110115995A (en) * | 2018-02-05 | 2019-08-13 | 天津大学 | A kind of iron sodium/molybdenum composite metal oxide catalyst and its preparation method and application |
| CN110201697A (en) * | 2019-05-29 | 2019-09-06 | 浙江大学 | A kind of three-dimensional N doping transition metal oxide/vulcanization nickel composite catalyst and preparation method and application |
| CN110247063A (en) * | 2019-06-26 | 2019-09-17 | 太原理工大学 | A kind of preparation method and application of nano molybdenum disulfide/nitrogen-doped carbon nanometer pipe array hybridization compounding electrode |
| CN110479244A (en) * | 2019-07-08 | 2019-11-22 | 浙江新和成股份有限公司 | Catalyst with base of molybdenum and its preparation method and application |
-
2021
- 2021-06-22 CN CN202110691226.0A patent/CN113318750B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103855367A (en) * | 2012-11-28 | 2014-06-11 | 中国科学院大连化学物理研究所 | Nitrogen-doped porous carbon material used for anode of lithium-air cell |
| WO2018215202A1 (en) * | 2017-05-22 | 2018-11-29 | Siemens Aktiengesellschaft | Catalyst for ammonia synthesis |
| CN110115995A (en) * | 2018-02-05 | 2019-08-13 | 天津大学 | A kind of iron sodium/molybdenum composite metal oxide catalyst and its preparation method and application |
| CN110201697A (en) * | 2019-05-29 | 2019-09-06 | 浙江大学 | A kind of three-dimensional N doping transition metal oxide/vulcanization nickel composite catalyst and preparation method and application |
| CN110247063A (en) * | 2019-06-26 | 2019-09-17 | 太原理工大学 | A kind of preparation method and application of nano molybdenum disulfide/nitrogen-doped carbon nanometer pipe array hybridization compounding electrode |
| CN110479244A (en) * | 2019-07-08 | 2019-11-22 | 浙江新和成股份有限公司 | Catalyst with base of molybdenum and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| XIA WANG ET AL.: ""Facile fabrication of molybdenum dioxide/nitrogen-doped graphene hybrid as high performance anode material for lithium ion batteries"", 《JOURNAL OF POWER SOURCES》 * |
| YUEYAO DU ET AL.: ""Anionic Biopolymer Assisted Preparation of MoO2@C Heterostructure Nanoparticles with Oxygen Vacancies for Ambient Electrocatalytic Ammonia Synthesis"", 《INORG.CHEM.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115821315A (en) * | 2022-10-14 | 2023-03-21 | 哈尔滨理工大学 | A kind of preparation method and application of ternary iron molybdenum oxide synthesis ammonia catalyst |
| CN116440911A (en) * | 2022-11-21 | 2023-07-18 | 浙江华源颜料股份有限公司 | Preparation and Application of Fe-doped Molybdenum Oxide Photocatalyst |
| CN116440911B (en) * | 2022-11-21 | 2024-10-22 | 浙江华源颜料股份有限公司 | Preparation and application of iron-doped molybdenum oxide photocatalyst |
| CN116020457A (en) * | 2023-01-30 | 2023-04-28 | 上海大学 | A kind of ruthenium-based catalyst and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113318750B (en) | 2022-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113318750A (en) | Lithium-doped two-dimensional iron-molybdenum catalyst for synthesizing ammonia gas by thermally catalyzing nitrogen and hydrogen through mobile phase and preparation method thereof | |
| CN109772355B (en) | Preparation method of amorphous iron oxyhydroxide/bismuth vanadate composite photocatalytic material | |
| JP5820817B2 (en) | Ammonia synthesis catalyst and ammonia synthesis method | |
| CN107252700B (en) | Multi-metal phosphide nanotube catalyst with uniformly distributed catalytic centers and low-temperature preparation method | |
| CN112221528A (en) | A kind of single-atom catalyst and its preparation method and application | |
| Liu et al. | Rational tuning towards B-sites (B= Mn, Co, Al) on CoB2O4 binary oxide for efficient selective catalytic oxidation of ammonia | |
| CN109999837B (en) | Preparation method of metal sulfide catalyst with surface defect state modification | |
| CN112569896A (en) | Calcium oxide-based bimetal composite material, preparation method and application | |
| CN105819418A (en) | Method for loading nanometer metal phosphide on porous carbon | |
| CN106268952A (en) | The preparation method of a kind of load type double-metal organic framework material MIL 100 (Fe Cu) and denitration application | |
| CN113398945B (en) | Spherical C/FeMo nano composite photocatalyst and preparation method thereof | |
| CN111036243A (en) | Oxygen vacancy-containing transition metal doped BiOBr nanosheet photocatalyst, preparation method and application thereof | |
| CN107597106A (en) | A kind of preparation method and applications of hollow nanometer capsule parcel platinum catalyst | |
| CN111036249A (en) | A kind of FexP/Mn0.3Cd0.7S composite photocatalyst and its preparation method and application | |
| CN110404585A (en) | A method for preparing MOF sheets on a substrate by heating in a water bath | |
| CN106694004A (en) | Loaded type transition metal phosphide catalyst and preparation method thereof | |
| Mi et al. | Activation of partial metal sites in high-entropy oxides for enhancing thermal and electrochemical catalysis | |
| CN112371120B (en) | High-dispersion platinum modified metal ion doped semiconductor photocatalyst, preparation method and application thereof | |
| CN112582628B (en) | FeMn bimetallic monatomic oxygen reduction catalyst and preparation method and application thereof | |
| Feng et al. | Self-assembled chromium-based nitrogen carrier for chemical looping ammonia synthesis | |
| CN106391015B (en) | Catalytic material and its preparation method and use | |
| CN1666817A (en) | A kind of preparation method of transition metal phosphide | |
| CN113430556B (en) | Surface-doped metal nano pyrite material and preparation and application thereof | |
| CN112295563B (en) | Co-based catalyst for breaking limitation relation of synthetic ammonia reaction and preparation method and application thereof | |
| CN109364919B (en) | Hydrogenation catalyst based on CNT-aluminum oxide/silica gel composite carrier and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |