CN109675563B - High-efficiency self-loading type iron-based nano composite material used as synthetic ammonia catalyst and preparation method thereof - Google Patents
High-efficiency self-loading type iron-based nano composite material used as synthetic ammonia catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN109675563B CN109675563B CN201811613389.1A CN201811613389A CN109675563B CN 109675563 B CN109675563 B CN 109675563B CN 201811613389 A CN201811613389 A CN 201811613389A CN 109675563 B CN109675563 B CN 109675563B
- Authority
- CN
- China
- Prior art keywords
- iron
- self
- solution
- aluminum
- preparation
- 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.)
- Active
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 82
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 238000011068 loading method Methods 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims description 47
- 239000002184 metal Substances 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000011240 wet gel Substances 0.000 claims description 15
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 14
- 239000013110 organic ligand Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 12
- 150000002505 iron Chemical class 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 11
- 230000001681 protective effect Effects 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000002082 metal nanoparticle Substances 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000013557 residual solvent Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims description 2
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000003837 high-temperature calcination Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000000499 gel Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 7
- 230000003213 activating effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000011943 nanocatalyst Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- -1 bipyridyl dicarboxylic acid Chemical compound 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B01J35/613—
-
- B01J35/615—
-
- 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
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
Abstract
The invention discloses an efficient self-loading iron-based nano composite material and a preparation method thereof. The preparation method has the advantages of simple process, short period, low cost and high yield, and the self-loading iron-based nanocomposite obtained by the preparation method has the advantages of high activity, high thermal stability and the like when used as an ammonia synthesis catalyst, and the performance of the self-loading iron-based nanocomposite is greatly improved compared with that of a molten iron catalyst which is used in the industry at present.
Description
Technical Field
The invention belongs to the technical field of synthetic ammonia, and particularly relates to a high-efficiency self-loading type iron-based nanocomposite used as a synthetic ammonia catalyst and a preparation method thereof.
Background
The synthetic ammonia industry is a large-support industry of chemical industry, and is also an energy consumption type industry with high energy consumption and low output. Although new catalyst formulas are continuously proposed in the last century, the traditional iron melting catalyst is still used in industry in large scale at present, alumina and potassium oxide are taken as promoters, and the harsh requirements on equipment and low conversion rate of the high-temperature and high-pressure reaction environment become important factors for restricting the development of the synthetic ammonia industry and saving energy and reducing emission.
The nano catalyst is known as a fourth-generation catalyst, and the nano-catalysis of the active components of the catalyst realizes milder reaction conditions and higher conversion rate, improves the toxicity resistance and the thermal stability of the material, and can be said to be a necessary development trend in the future of the catalytic industry.
At present, the nano-catalyst has the defects of high requirement on the preparation process, poor thermal stability, more factors influencing performance, poor stability and the like, and the current research mainly focuses on ruthenium-based catalysts, so that the research on iron-based catalysts directly applied in industry is less, the current situation of research and industrialization is disjointed, and the application of the nano-catalyst in the field of ammonia synthesis is limited. The common supported metal nano-catalyst generally relates to independent nano-particle and substrate preparation processes and additional supporting processes, and has the disadvantages of multiple steps, great operation difficulty and difficulty in controlling the dispersion and fixation of the metal nano-particles on the substrate.
Therefore, the development of the novel nano iron-based catalyst which has high activity and high stability, simple preparation process, low cost and easy large-scale production has important significance for the synthetic ammonia industry.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide the high-efficiency self-loading iron-based nanocomposite and the preparation method thereof.
Therefore, the invention provides a self-loading type iron-based nanocomposite material, which comprises a porous substrate, carbon-coated active metal nanoparticles loaded on the porous substrate and a metal oxide auxiliary agent filled in pore channels of the porous substrate; the carbon-coated active metal nanoparticles are active metal nanoparticles, the surfaces of which are coated with protective carbon layers, the active metal nanoparticles are alpha-phase iron nanoparticles or iron alloy nanoparticles, and the porous substrate is amorphous porous carbon, amorphous porous alumina or a composite of the amorphous porous carbon and the amorphous porous alumina.
Preferably, the thickness of the protective carbon layer is 2-20nm, the diameter of the carbon-coated active metal nano-particles is 5-200nm, the mass percent of iron element in the self-loading type iron-based nano composite material is 30-60%, the mass percent of aluminum element in the self-loading type iron-based nano composite material is 0-30%, and the self-loading type iron isThe BET surface area of the base nanocomposite material is 50 to 500m2/g。
Further, the self-supported iron-based nanocomposite material of the present invention is used as a catalyst for ammonia synthesis.
Further, the invention also provides a preparation method of the self-supported iron-based nanocomposite, which comprises the steps of dissolving iron salt in one part of solvent to generate solution A, dissolving oxygen-containing polydentate organic ligand in the other part of solvent to generate solution B, mixing the solution A and the solution B at room temperature, heating and aging, and separating the rest of solvent to obtain iron-containing metal organic wet gel; drying the ferrous metal-containing organic wet gel to obtain a ferrous metal-containing organic xerogel; and calcining the iron-containing metal organic xerogel at high temperature in a protective atmosphere to obtain the self-loading iron-based nanocomposite.
In addition, the invention also provides another preparation method of the self-loading iron-based nanocomposite, which comprises the following steps: dissolving iron salt in one part of solvent to generate solution A, dissolving oxygen-containing polydentate organic ligand in the other part of solvent to generate solution B, mixing the solution A and the solution B at room temperature, heating and aging, and separating the residual solvent to obtain iron-containing metal organic wet gel; drying the ferrous metal-containing organic wet gel to obtain a ferrous metal-containing organic xerogel; adding the iron-containing metal organic xerogel into a soluble inorganic salt solution of an auxiliary element, and impregnating and drying to obtain the iron-containing metal organic xerogel doped with the auxiliary element; and calcining the iron-containing metal organic xerogel doped with the auxiliary element at high temperature in a protective atmosphere to obtain the self-loading iron-based nanocomposite.
In addition, the invention also provides another preparation method of the self-loading iron-based nanocomposite, which comprises the following steps: dissolving iron salt in one part of solvent to generate solution A, dissolving oxygen-containing polydentate organic ligand in the other part of solvent to generate solution B, dissolving aluminum salt in the solution A or the solution B, mixing the solution A and the solution B at room temperature, and separating the rest of solvent after heating and aging to obtain aluminum-doped iron-containing metal organic wet gel; drying the aluminum-doped ferrous metal-containing organic wet gel to obtain a ferrous metal-containing organic xerogel; adding the aluminum-doped iron-containing metal organic xerogel into a soluble inorganic salt solution of an auxiliary element, and impregnating and drying to obtain the aluminum-doped iron-containing metal organic xerogel containing the auxiliary element; and calcining the iron-containing metal organic xerogel containing the auxiliary element and doped with aluminum at high temperature in a protective atmosphere to obtain the self-loading iron-based nanocomposite.
Preferably, in the above method, the iron salt and the aluminum salt are nitrate, sulfate, acetate, chloride, etc., and the iron salt accounts for 50% -100% of the total molar ratio of the iron salt and the aluminum salt; the oxygen-containing polydentate organic ligand is one or more of terephthalic acid, isophthalic acid, trimesic acid, biphenyldicarboxylic acid, biphenyltetracarboxylic acid, bipyridyl dicarboxylic acid and other similar organic polycarboxylic acids containing aromatic rings; the solvent is one or more of water, methanol, ethanol, isopropanol, N, N-dimethylformamide, acetone and ethyl acetate; the heating temperature is 20-150 ℃, the heating time is from no heating to heating for 2 days, and the aging time is from no aging to aging for 7 days.
Preferably, in the method, the iron salt and the aluminum salt are nitrates, the mole ratio of the iron salt to the total of the iron salt and the aluminum salt is 80%, the oxygen-containing polydentate organic ligand is trimesic acid, the solvent is ethanol, the heating temperature is 120 ℃, the heating time is 8 hours, and the aging is avoided.
Preferably, in the above method, the iron salt is a nitrate, no aluminum salt is added, the oxygen-containing polydentate organic ligand is trimesic acid, the solvent is ethanol, the reaction temperature is room temperature, and the aging time is 1 day.
Preferably, the drying method in the above method is room temperature natural air drying, freeze drying, heating and blowing constant temperature drying, supercritical drying, etc.
Preferably, in the above method, the auxiliary element is one or more of Li, Na, K, Mg, Ca, Ba, Co and Ce, the soluble inorganic salt of the auxiliary element is one or more of carbonate, nitrate, sulfate, basic carbonate and oxychloride, and the content of the auxiliary element is 0-50% of the mass of the xerogel calculated by the corresponding oxide.
Preferably, the auxiliary element is K, and the oxysalt is KNO35% (in K) of dry gel2And O is calculated).
Preferably, in the above method, the calcination temperature is 500-1000 ℃, the calcination atmosphere is one or more of helium, nitrogen, argon and hydrogen, and the calcination time is 1-24 hours.
More preferably, the calcination temperature is 600-900 ℃, the calcination atmosphere is helium or argon, and the calcination time is 1-3 hours.
According to the preparation method, firstly, the metal organogel containing iron is prepared, the ratio of the metal salt and the oxygen-containing polydentate organic ligand in the raw materials for preparing the metal organogel determines the gelling condition, the selected ratio is 1: 3-3: 1, and when the content of any one of the metal salt and the oxygen-containing polydentate organic ligand is too low, gelling cannot be effectively achieved (is lower than 1:3 or higher than 3: 1). The excessively high content of the metal salt affects the size and dispersion degree of active nano particles in the finally obtained composite material, and the excessively low content of the metal salt causes low content of active iron in the finally obtained composite material, so that the activity of the finally obtained self-supported iron-based nano composite material when the self-supported iron-based nano composite material is used as a catalyst is affected.
In addition, in the aspect of solvent selection, the alcohol solvent is more favorable for gelling, and ethanol is preferred from the aspects of cost and environmental protection.
Furthermore, the proportion of the iron salt and the aluminum salt determines the content of active iron and the content of a cocatalyst alumina in a final product, the content of the active iron directly determines the catalytic activity of the catalyst, the alumina has important significance for improving the thermal stability of the obtained material, and experiments prove that the sufficient thermal stability can be provided on the premise of not sacrificing the catalytic activity when the molar content of the aluminum reaches 20%.
If a product containing no alumina is prepared, aluminum salt is not added in the raw materials, the gel can be effectively formed at room temperature, heating is not needed, and the obtained gel can be separated and dried after being aged for one night; if aluminum salt is added, because the aluminum salt can not participate in coordination at room temperature, the gel needs to be heated in a closed container to form gel, the minimum heating temperature is 80 ℃, and the mechanical strength of the obtained gel can be improved by properly increasing the heating temperature and the heating time.
In the invention, the obtained wet gel does not need to be washed, and the drying step can be carried out after the residual solvent is simply separated.
Furthermore, the addition of the auxiliary agent element can obviously improve the catalytic activity of the obtained self-supported iron-based nano composite material. Represented by a K cocatalyst commonly used in industry, when pure iron gel is taken as a precursor, the K cocatalyst is added to 1 percent of the mass of the xerogel2Calculated by O), the catalytic activity is highest; when the precursor contains aluminum, part K2O is used for neutralizing the acidity of the alumina, and more K promoter needs to be added at this time, and when the molar ratio of aluminum salt in the raw material to the total metal salt is 20%, the K content is preferably 5%.
In the final calcination process, in order to thermally decompose the metal organogel as the precursor, the minimum temperature required is 500 ℃, and the appropriate increase of the calcination temperature is beneficial to the complete removal of volatile components and the complete reduction of active iron nanoparticles, thereby improving the stability and activity of the product. However, too high calcination temperature can cause excessive loss of substrate carbon, agglomeration of active iron nanoparticles and generation of inactive iron carbide phase, which is not favorable for obtaining good performance of the catalyst; the effect of calcination time is similar to temperature.
The nano particles have high specific surface energy, are easy to agglomerate to cause inactivation, and are often required to be loaded on a stable porous substrate in actual use to obtain the loaded nano material. Since the loading requires a separate process and the substrate used is often purchased as a commercial product or prepared by itself, the process is complicated and the cost is very high. In addition, nanoparticles loaded in a similar manner tend to have a weaker interaction with the substrate and are still inevitably agglomerated and deactivated during use. In contrast, the preparation method of the invention directly obtains the loaded and uniformly dispersed nano-particles from a single precursor through a one-step calcination process, omits a series of complex steps of synthesis-dispersion-loading in the traditional supported nano-material synthesis, and the supported nano-particles and the supported substrate thereof are included, so the supported nano-material is called as a self-supported nano-material.
The preparation method of the invention can be completed by using the metal organic gel as a precursor through a one-step calcining procedure to obtain a final product. The metal organic gel is non-toxic and harmless, is cheap and easy to obtain, and is convenient for large-scale production. In the metal organogel, metal ions and organic ligands are directly combined through coordination bonds and are alternately arranged in an atomic level. In the calcining process, the organic ligand is converted into porous carbon through a series of complex reactions such as decarboxylation, dehydrogenation, condensation and the like, and iron ions are reduced into metallic iron nanoparticles by a carbon substrate and reducing substances such as hydrogen generated in situ. On one hand, metal ions and organic ligands in the metal organic gel are uniformly dispersed in atomic level, and meanwhile, a nano-level pore channel structure can effectively adsorb a solution containing an auxiliary element, so that active iron particles and a cocatalyst in the composite material obtained after calcination realize uniform distribution in nano-scale; on the other hand, the original structure of metal and organic ligand in the metal organogel in atomic-level alternate arrangement is also retained to a certain extent after pyrolysis, and a layer of extremely thin carbon shell is formed on the surface of the active iron nano particle to be tightly combined with the porous substrate, so that the movement and agglomeration of the nano particle are effectively inhibited, and the cycle performance and the thermal stability of the catalyst are improved.
Compared with the prior art, the invention has the following beneficial effects:
the self-supported iron-based nanocomposite material is used as a synthetic ammonia catalyst, has extremely high catalytic activity for synthetic ammonia reaction, and has the advantages of cheap and easily-obtained raw materials, short production period, simple and convenient operation, low equipment requirement, contribution to large-scale industrial production and energy consumption saving.
Detailed Description
The self-loading iron-based nanocomposite and the preparation method thereof according to the present invention will be described with reference to specific embodiments for better understanding of the technical contents, but not for limiting the technical contents, and in fact, the improvement of the self-loading iron-based nanocomposite and the preparation method thereof based on the same or similar principles is within the technical scope of the invention claimed in the present invention.
Example one
Firstly, dissolving ferric nitrate in one part of solvent to generate solution A, dissolving trimesic acid in the other part of solvent to generate solution B, mixing the solution A and the solution B at room temperature, standing and aging to obtain the reddish brown iron-containing metal organic wet gel.
And then, removing the residual solvent from the iron-containing metal organic wet gel by simple decantation, heating and drying to obtain the iron-containing metal organic xerogel, and then calcining under protective atmosphere to obtain the self-loading iron-based nanocomposite material.
The self-supported iron-based nanocomposite material of the embodiment is used as a catalyst for ammonia synthesis to perform an effect test, and the specific test conditions are as follows: 78mg of catalyst, 1:3 of nitrogen: hydrogen with the pressure of 3MPa and the gas flow rate of 30ml/min, activating at 450 ℃ for 4h and activating at 475 ℃ for 1 h; then reacting at a gas flow rate of 45ml/min, specifically, at 300 ℃ at a reaction rate of 5.2mmol NH3·gcat -1·h-1Reaction rate at 400 ℃ of 10.3mmol NH3·gcat -1·h-1(ii) a Then raising the temperature to 475 ℃ and keeping the temperature for 24 hours, then lowering the temperature to 400 ℃ and evaluating the activity again, wherein the reaction rate is 0.9mmol NH3·gcat -1·h-1. Wherein h is an hour.
The above tests show that the self-supported iron-based nanocomposite material of the present example has higher activity than the conventional industrial iron catalyst when used as a catalyst for ammonia synthesis without adding any co-catalyst.
Example two
Firstly, dissolving ferric nitrate in one part of solvent to generate solution A, dissolving trimesic acid in the other part of solvent to generate solution B, mixing the solution A and the solution B at room temperature, standing and aging to obtain the reddish brown iron-containing metal organic wet gel.
And then, removing residual solvent from the iron-containing metal organic wet gel by simple decantation, and heating and drying to obtain the iron-containing metal organic xerogel.
As to the foregoing embodimentImprovement of embodiment, in this embodiment, the aforementioned iron-containing metal organic xerogel is impregnated with KNO3The solution is doped with K promoter and then calcined under protective atmosphere to obtain the self-loading iron-based nanocomposite material.
The self-supported iron-based nanocomposite material of the embodiment is used as a catalyst for ammonia synthesis to perform an effect test, and the specific test conditions are as follows: 78mg of catalyst, 1:3 of nitrogen: hydrogen with the pressure of 3MPa and the gas flow rate of 30ml/min, activating at 450 ℃ for 4h and activating at 475 ℃ for 1 h; followed by a reaction at a gas flow rate of 45ml/min, specifically at 300 ℃ at a reaction rate of 13.1 mmoleNH3·gcat -1·h-1The reaction rate at 400 ℃ was 30.5mmol NH3·gcat -1·h-1Then raising the temperature to 475 ℃ and keeping the temperature for 24 hours, then lowering the temperature to 400 ℃ and evaluating the activity again, wherein the reaction rate is 28.7mmol NH3·gcat -1·h-1. Wherein h is an hour.
The tests show that the addition of the K cocatalyst greatly improves the catalytic activity and the thermal stability of the self-supported iron-based nanocomposite when the self-supported iron-based nanocomposite is used as a synthetic ammonia catalyst.
EXAMPLE III
First, iron nitrate was dissolved in one part of a solvent to produce a solution A, and as a modification of the previous example, aluminum nitrate and trimesic acid were dissolved in the other part of a solvent to produce a solution B, and the solution A and the solution B were mixed at room temperature, followed by heating reaction in a closed vessel to obtain a reddish brown iron-containing metal organic wet gel.
And then, removing the residual solvent from the ferrous metal-containing organic wet gel by simple decantation, and heating and drying to obtain the aluminum-doped ferrous metal organic xerogel.
Next, the aforementioned aluminum-doped iron-containing metal-organic xerogel is impregnated with KNO3The solution is doped with K promoter and then calcined under protective atmosphere to obtain the self-loading iron-based nanocomposite material.
The self-loading iron-based nanocomposite material of the embodiment is used as the ammonia synthesis catalystThe effect test of the reagent is carried out under the specific test conditions that: 78mg of catalyst, 1:3 of nitrogen: hydrogen with the pressure of 3MPa and the gas flow rate of 30ml/min, activating at 450 ℃ for 4h and activating at 475 ℃ for 1 h; then reacting at a gas flow rate of 45ml/min, specifically, at 400 ℃ at a reaction rate of 22.3mmol NH3·gcat -1·h-1(ii) a Then raising the temperature to 475 ℃ and keeping the temperature for 24 hours, then lowering the temperature to 400 ℃ and evaluating the activity again, wherein the reaction rate is 23.2mmol NH3·gcat -1·h-1. Wherein h is an hour.
The tests show that when the self-supported iron-based nanocomposite containing aluminum and K cocatalyst is used as a synthetic ammonia catalyst, the activity of the self-supported iron-based nanocomposite is not reduced after high-temperature reaction, but is slightly improved, and the improved self-supported iron-based nanocomposite is proved to have more excellent thermal stability when used as the synthetic ammonia catalyst.
The above examples are provided only for illustrating the present invention and are not intended to limit the present invention. Since modifications of the process flow described in the present invention can be easily made by a person skilled in the relevant art, any modifications and changes made within the spirit of the present invention and the scope of the appended claims will fall within the scope of the present invention.
Claims (6)
1. A preparation method for preparing a self-loading type iron-based nanocomposite material is characterized in that the self-loading type iron-based nanocomposite material comprises a porous substrate, carbon-coated active metal nanoparticles loaded on the porous substrate and a metal oxide auxiliary agent filled in pore channels of the porous substrate; the carbon-coated active metal nanoparticles are prepared by coating protective carbon layers on the surfaces of active metal nanoparticles, the active metal nanoparticles are alpha-phase iron nanoparticles, and the porous substrate is a composite of amorphous porous carbon and amorphous porous alumina; the preparation method comprises the following steps:
(1) dissolving iron salt in one part of solvent to generate solution A, dissolving oxygen-containing polydentate organic ligand in the other part of solvent to generate solution B, dissolving aluminum salt in the solution A or the solution B, mixing the solution A and the solution B at room temperature, heating and aging in a closed container, and separating the residual solvent to obtain aluminum-doped iron-containing metal organic wet gel; wherein the heating temperature is 80-120 ℃;
(2) drying the aluminum-doped ferrous metal organic wet gel to obtain an aluminum-doped ferrous metal organic xerogel;
(3) adding the aluminum-doped iron-containing metal organic xerogel into a soluble inorganic salt solution of an auxiliary element, and impregnating and drying to obtain the aluminum-doped iron-containing metal organic xerogel containing the auxiliary element;
(4) and calcining the iron-containing metal organic xerogel containing the auxiliary element and doped with aluminum at high temperature in a protective atmosphere to obtain the self-loading iron-based nanocomposite.
2. The production method according to claim 1, wherein in the step (1), the oxygen-containing polydentate organic ligand is one or more of terephthalic acid, isophthalic acid, trimesic acid, biphenyldicarboxylic acid, biphenyltetracarboxylic acid, and bipyridylitic acid.
3. The production method according to claim 1 or 2, wherein in the step (1), the heating time is not more than 48 hours.
4. The preparation method according to claim 1 or 2, wherein in the step (4), the high-temperature calcination is performed at a calcination temperature of 500 to 1000 ℃ for 1 to 2 hours, and the protective atmosphere is one or more of hydrogen, helium, argon and nitrogen.
5. A self-supporting iron-based nanocomposite prepared by the preparation method according to any one of claims 1 to 4.
6. Use of the self-supported iron-based nanocomposite material of claim 5 as a catalyst for ammonia synthesis.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811613389.1A CN109675563B (en) | 2018-12-27 | 2018-12-27 | High-efficiency self-loading type iron-based nano composite material used as synthetic ammonia catalyst and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811613389.1A CN109675563B (en) | 2018-12-27 | 2018-12-27 | High-efficiency self-loading type iron-based nano composite material used as synthetic ammonia catalyst and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109675563A CN109675563A (en) | 2019-04-26 |
CN109675563B true CN109675563B (en) | 2020-11-10 |
Family
ID=66190582
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811613389.1A Active CN109675563B (en) | 2018-12-27 | 2018-12-27 | High-efficiency self-loading type iron-based nano composite material used as synthetic ammonia catalyst and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109675563B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110695366A (en) * | 2019-09-30 | 2020-01-17 | 武汉大学 | Method for rapidly preparing porous carbon-loaded metal or metal carbide nanoparticles |
CN115254118B (en) * | 2022-08-31 | 2023-05-30 | 中国科学院上海硅酸盐研究所 | CO reduction method for photocatalysis 2 Organic xerogel nano material as well as preparation method and application thereof |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101161705A (en) * | 2006-10-13 | 2008-04-16 | 中国科学院化学研究所 | Functional polymer nano composite material and preparation method and uses thereof |
CN102161671A (en) * | 2011-02-23 | 2011-08-24 | 中山大学 | Coordination polymer material with multistage pore passage structure and preparation method thereof |
CN103111262A (en) * | 2013-01-31 | 2013-05-22 | 北京大学 | Porous material of metal-organic framework and preparation method of material |
CN106111198A (en) * | 2016-06-17 | 2016-11-16 | 三峡大学 | A kind of preparation method and applications of the catalyst of metal organic gel materials loaded Ag based on MIL 100 (Al) |
CN106311237A (en) * | 2015-06-18 | 2017-01-11 | 中国石油化工股份有限公司 | Iron carbon-based composite porous material catalyst and preparation method and application thereof |
CN106868332A (en) * | 2017-02-20 | 2017-06-20 | 安徽农业大学 | A kind of methods and applications that transition metal alloy is prepared based on metal organogel |
CN108067231A (en) * | 2016-11-11 | 2018-05-25 | 株式会社模范 | A kind of load-type iron-based fischer-tropsch catalysts and its preparation and application |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6656339B2 (en) * | 2001-08-29 | 2003-12-02 | Motorola, Inc. | Method of forming a nano-supported catalyst on a substrate for nanotube growth |
-
2018
- 2018-12-27 CN CN201811613389.1A patent/CN109675563B/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101161705A (en) * | 2006-10-13 | 2008-04-16 | 中国科学院化学研究所 | Functional polymer nano composite material and preparation method and uses thereof |
CN102161671A (en) * | 2011-02-23 | 2011-08-24 | 中山大学 | Coordination polymer material with multistage pore passage structure and preparation method thereof |
CN103111262A (en) * | 2013-01-31 | 2013-05-22 | 北京大学 | Porous material of metal-organic framework and preparation method of material |
CN106311237A (en) * | 2015-06-18 | 2017-01-11 | 中国石油化工股份有限公司 | Iron carbon-based composite porous material catalyst and preparation method and application thereof |
CN106111198A (en) * | 2016-06-17 | 2016-11-16 | 三峡大学 | A kind of preparation method and applications of the catalyst of metal organic gel materials loaded Ag based on MIL 100 (Al) |
CN108067231A (en) * | 2016-11-11 | 2018-05-25 | 株式会社模范 | A kind of load-type iron-based fischer-tropsch catalysts and its preparation and application |
CN106868332A (en) * | 2017-02-20 | 2017-06-20 | 安徽农业大学 | A kind of methods and applications that transition metal alloy is prepared based on metal organogel |
Non-Patent Citations (1)
Title |
---|
"铈锰/硅基气凝胶载体的制备及其在合成碳酸二苯酯中的应用";洪超 等;《分子催化》;20170831;第31卷(第4期);第348-355页 * |
Also Published As
Publication number | Publication date |
---|---|
CN109675563A (en) | 2019-04-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110534752B (en) | Iron and nitrogen co-doped carbon-oxygen reduction catalyst and preparation method thereof | |
CN108097316B (en) | Preparation method of MOFs nano material loaded with nano metal particles | |
Zhao et al. | Solid-state CTAB-assisted synthesis of mesoporous Fe3O4 and Au@ Fe3O4 by mechanochemistry | |
CN110048128A (en) | A kind of nitrogen-doped carbon nanometer pipe oxygen reduction electro-catalyst and preparation method thereof | |
CN108772067B (en) | Preparation method of loaded double-transition metal monoatomic ACF catalyst for degrading VOCs at normal temperature | |
Gong et al. | Facile synthesis of porous α-Fe2O3 nanostructures from MIL-100 (Fe) via sacrificial templating method, as efficient catalysts for NH3-SCR reaction | |
CN113578359B (en) | Hollow nitrogen-doped nano carbon sphere loaded high-dispersion palladium-based catalyst, preparation method thereof and application thereof in ethylbenzene dehydrogenation | |
CN110721728A (en) | Supported bifunctional catalytic composite material and preparation method thereof | |
CN113422073B (en) | Preparation method of cobalt-modified carbon-supported superfine platinum nano alloy catalyst | |
CN112916009A (en) | Preparation method of biomass-derived porous carbon-limited-domain monoatomic metal composite material | |
CN110075831B (en) | Iridium supported catalyst for catalytic combustion of low-concentration methane and preparation method thereof | |
CN106391037B (en) | One kind decomposing N for high-temperature catalytic2The preparation process of the catalyst of O | |
CN109675563B (en) | High-efficiency self-loading type iron-based nano composite material used as synthetic ammonia catalyst and preparation method thereof | |
CN111672529A (en) | Nano-carbon-loaded cobalt nitrogen carbon catalytic material and preparation method and application thereof | |
CN114797912A (en) | Dehydrogenation catalyst and preparation method thereof | |
CN111359672B (en) | UiO-67 loaded Rh-based catalyst, and preparation method and application thereof | |
CN104959150B (en) | Preferential oxidation CO Au/CuO/CeO2‑TiO2Catalyst and preparation method | |
Zhe-qin et al. | A high-performance nitrogen-rich ZIF-8-derived Fe-NC electrocatalyst for the oxygen reduction reaction | |
CN108948366B (en) | Preparation of Fe-MOF catalyst with rich Lewis acid sites and desulfurization application thereof | |
Sun et al. | AgPd nanoparticles anchored on TiO2 derived from a titanium metal–organic framework for efficient dehydrogenation of formic acid | |
Wang et al. | Metal-organic frameworks-derived manganese trioxide with uniformly loaded ultrasmall platinum nanoparticles boosting benzene combustion | |
CN112246273B (en) | Catalyst for preparing low-carbon alcohol through carbon dioxide conversion, preparation method and application | |
CN113546687A (en) | Preparation method and application of visible light catalyst of ultrathin titanium-based MOFs nanosheets | |
CN106475128B (en) | A kind of preparation method of industrial waste gas purifying catalyst | |
CN110038591B (en) | Copper-iridium composite oxide catalyst for preparing methanol by methane oxidation |
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 |