CN114908372B - Preparation method and application of mesoporous carbon sphere coated zirconium supported catalyst - Google Patents
Preparation method and application of mesoporous carbon sphere coated zirconium supported catalyst Download PDFInfo
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- CN114908372B CN114908372B CN202210333046.XA CN202210333046A CN114908372B CN 114908372 B CN114908372 B CN 114908372B CN 202210333046 A CN202210333046 A CN 202210333046A CN 114908372 B CN114908372 B CN 114908372B
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- zirconium
- phosphotungstic acid
- carbon sphere
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 70
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000003377 acid catalyst Substances 0.000 claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 50
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 45
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 35
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 21
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 claims abstract description 20
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims abstract description 14
- 238000005470 impregnation Methods 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- 239000011259 mixed solution Substances 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 18
- 239000005011 phenolic resin Substances 0.000 claims description 18
- 229920001568 phenolic resin Polymers 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 230000003100 immobilizing effect Effects 0.000 claims description 11
- 238000005530 etching Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 16
- 229910052681 coesite Inorganic materials 0.000 claims 10
- 229910052906 cristobalite Inorganic materials 0.000 claims 10
- 229910052682 stishovite Inorganic materials 0.000 claims 10
- 229910052905 tridymite Inorganic materials 0.000 claims 10
- 239000000377 silicon dioxide Substances 0.000 claims 5
- 235000012239 silicon dioxide Nutrition 0.000 claims 5
- 239000005539 carbonized material Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 16
- 239000011148 porous material Substances 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 4
- 239000010411 electrocatalyst Substances 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 8
- 230000000670 limiting effect Effects 0.000 description 7
- 230000009467 reduction Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/27—Ammonia
-
- 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
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
-
- 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 a preparation method of a mesoporous carbon sphere-wrapped zirconium supported catalyst, which takes tetrapropyl orthosilicate, tetraethyl orthosilicate, resorcinol and formaldehyde as raw materials and adopts a template method to prepare a mesoporous hollow carbon sphere carrier; then taking phosphotungstic acid and zirconium sulfate as raw materials, and heating and stirring under mild conditions to prepare a zirconium-loaded phosphotungstic acid catalyst by batch feeding; the zirconium-loaded phosphotungstic acid catalyst is immobilized into a multistage pore canal of a mesoporous hollow carbon sphere by an impregnation method, so that the zirconium-loaded phosphotungstic acid electrocatalyst wrapped by the mesoporous carbon sphere with high activity and high stability is developed for the first time; the electrocatalyst prepared by the invention has strong nitrogen activating capability, can effectively inhibit hydrogen evolution side reaction, has excellent electrocatalytic ammonia synthesis activity and selectivity, and simultaneously shows good chemical structure and performance stability under the action of space limitation.
Description
Technical Field
The invention relates to a preparation method and application of a mesoporous carbon sphere wrapped zirconium supported catalyst, and belongs to the technical fields of material synthesis, electrocatalysis and fine chemical engineering.
Background
Ammonia is not only an important chemical raw material, but also an ideal energy storage and transportation carrier, and has high hydrogen content (17.7 wt%) and high energy density (3 kW.h) -1 ) And easy compression and transportation (boiling point-33.5 ℃), and the like, and plays a role in the strategic layout of agricultural production fertilizers and emerging energy sources. Through more than a century of development, the technology of industrial synthesis of ammonia currently mainly adopts the Haber-Bosch process. However, the reaction condition of the process is harsh, and the process needs to be carried out under the conditions of high temperature and high pressure (17.5-20 MPa, 400-500 ℃), so that the reaction energy consumption is about 1-2% of the global energy consumption, and simultaneously, the emission of hundreds of millions of tons of carbon dioxide is caused, thereby causing serious energy crisis and environmental pollution problems. Therefore, the search for sustainable green ammonia synthesis technology has become a worldwide topic of research.
The electrocatalytic nitrogen reduction reaction (eNRR) is driven by renewable energy sources, and ammonia is generated by the reduction reaction of water and nitrogen in air in a normal temperature and normal pressure water solution system. Because the reaction takes water as a hydrogen source, the reaction device can be modularized, distributed and has zero CO 2 And the emission can be carried out according to the requirement to synthesize ammonia in a green way. Thus, eNRR is considered to be an ideal efficient sustainable ammonia synthesis pathway. However, since normal temperature and pressure water system eNRR is a typical gas-liquid-solid reaction system, there are various technical bottlenecks, such as the problems of ultrahigh chemical stability of nitrogen molecules, dominant hydrogen evolution side reaction and the like, so that activity and selectivity of eNRR synthetic ammonia are very low. Therefore, the design of the novel high-efficiency and stable electrocatalyst has important research significance for improving the performance of electrocatalytic synthesis of ammonia.
The phosphotungstic acid with Keggin structure is used as a multifunctional novel green catalyst, has a unique space geometry structure, can accurately anchor modified metal species on four-fold hollow sites formed by rich oxygen coordination sites, and adjusts the electronic structure of the catalyst, so that electrons in polyanion of the phosphotungstic acid migrate to the introduced metal species to form electron-rich active centers, thereby improving the adsorption and activation capacity of nitrogen. Meanwhile, the hydrogen reduction performance of the phosphotungstic acid is poor, the combination of hydrogen and modified metal species can be weakened, and the hydrogen evolution competition reaction rate is reduced. Therefore, the metal species modified phosphotungstic acid catalyst has excellent characteristics in promoting nitrogen activation and suppressing hydrogen evolution side reactions. In addition, the d orbitals of the transition metal zirconium species can be combined with nitrogen, so that N (identical to N) bonds are effectively weakened, the combination capacity of the zirconium species to hydrogen is weak, and the improvement of the selectivity of electrocatalytic nitrogen reduction is facilitated. Based on the above analysis, zirconium metal species modified phosphotungstic acid has the potential to develop into a highly efficient eNRR catalyst.
On the other hand, considering that the phosphotungstic acid-based catalyst is very soluble in polar solvents, and the eNRR system is a typical gas-liquid-solid three-phase interfacial reaction, the phosphotungstic acid-based catalyst is very soluble in aqueous electrolyte in the eNRR process, the reactivity is low, and the like, the application of the phosphotungstic acid-based catalyst in the field of water-based electrocatalysis limited. In order to improve the stability of the phosphotungstic acid in a polar solvent, a proper carrier is searched for to fix the phosphotungstic acid-based catalyst on the carrier, the acting force between the catalyst and the carrier is enhanced to effectively inhibit the dissolution of the phosphotungstic acid-based catalyst, and the stability of the catalyst in an aqueous electrolyte is improved.
Carbon nano materials and composite materials thereof have attracted wide attention in the fields of biomedicine, catalysis, absorption, energy storage and the like because of the characteristics of high chemical stability and thermal stability, good conductivity, inherent hydrophobicity, easy surface chemistry modification and the like of the carbon materials. Compared with microporous or nonporous carbon materials, the mesoporous hollow carbon spheres have the advantages of low density, porous shell, accessible internal space, high surface area, large pore volume and the like, so that the mesoporous hollow carbon spheres become a potential excellent carrier. In addition, in view of the strong adsorption force of the mesoporous hollow carbon spheres on the phosphotungstic acid-based catalyst, the phosphotungstic acid-based catalyst can be wrapped in the carbon spheres as a protective layer under the action of space limitation, so that the dissolution of the catalyst is greatly reduced. Meanwhile, the surface of the carbon sphere has the advantage that abundant mesopores can fully expose the active sites of the catalyst, so that the introduction of the mesoporous hollow carbon sphere as a carrier in the zirconium metal species modified phosphotungstic acid catalyst has wide application prospect. However, at present, the sizes of the cavity, the aperture and the shell thickness of the hollow carbon sphere of the carrier are difficult to accurately regulate, so that the phosphotungstic acid-based catalyst cannot be effectively immobilized in the carbon sphere, and the performance stability of the electrocatalytic nitrogen reduction synthesis ammonia is greatly influenced.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method and application of a mesoporous carbon sphere wrapped zirconium supported catalyst, which sequentially prepare a mesoporous hollow carbon sphere carrier and a zirconium supported phosphotungstic acid catalyst, then the zirconium supported phosphotungstic acid catalyst is fixedly supported in the mesoporous hollow carbon sphere by an impregnation method, and the zirconium supported phosphotungstic acid catalyst wrapped by the mesoporous carbon sphere for electrocatalytic nitrogen fixation with high performance and high stability is developed for the first time by utilizing the space limiting effect.
The technical scheme of the invention is as follows:
the invention discloses a preparation method of a mesoporous carbon sphere-wrapped zirconium supported catalyst, which takes tetrapropyl orthosilicate, tetraethyl orthosilicate, resorcinol and formaldehyde as raw materials, and adopts a template method to prepare mesoporous hollow carbon spheres as an immobilization carrier of the catalyst; then taking phosphotungstic acid and zirconium sulfate as raw materials, heating and stirring under mild conditions by batch feeding, and accurately anchoring zirconium species in an oxygen coordination structure of the phosphotungstic acid to prepare a zirconium-loaded phosphotungstic acid catalyst; and then immobilizing the zirconium-loaded phosphotungstic acid catalyst into a multi-stage pore canal of the mesoporous hollow carbon sphere carrier by an impregnation method, and preparing the zirconium-loaded phosphotungstic acid catalyst wrapped by the mesoporous carbon sphere by utilizing a space limiting function.
Further, the preparation method of the mesoporous carbon sphere wrapped zirconium supported catalyst specifically comprises the following steps:
(1) Adding tetrapropyl orthosilicate and tetraethyl orthosilicate into a mixed solution containing ethanol, deionized water and concentrated ammonia water, vigorously stirring for 15-25 min, adding resorcinol and formaldehyde into the mixed solution, performing hydrolytic condensation, centrifugally washing the mixed solution with deionized water and ethanol for multiple times, and drying the collected precursor to obtain SiO 2 @SiO 2 A phenolic resin precursor;
(2) SiO obtained in the step (1) is treated 2 @SiO 2 Placing a phenolic resin precursor sample in a porcelain boat, and calcining at high temperature for 5-6 h under argon condition to perform carbonAfter high temperature carbonization treatment, siO 2 @SiO 2 Conversion of phenolic resin precursor to SiO 2 @SiO 2 /C；
(3) Etching SiO with HF solution 2 @SiO 2 The SiO is removed after 12 to 48 hours of the sample/C 2 The core is centrifugally washed by deionized water, and the obtained precipitate is dried to obtain the mesoporous carbon hollow sphere carrier;
(4) Dropwise adding a zirconium sulfate aqueous solution into a phosphotungstic acid aqueous solution, stirring for 2-6 hours at room temperature, and placing the mixed solution into a magnetic heating stirrer for heat treatment for 4-6 hours to obtain a zirconium species supported phosphotungstic acid catalyst;
(5) Dispersing the zirconium-species-supported phosphotungstic acid catalyst sample obtained in the step (4) in an ethanol solution, immobilizing the zirconium-species-supported phosphotungstic acid catalyst in mesoporous hollow carbon spheres by an impregnation method, performing ultrasonic dispersion for 0.5-1 h, stirring the mixed solution for 2-6 h, and finally drying to obtain the zirconium-supported phosphotungstic acid catalyst wrapped by the mesoporous hollow carbon spheres.
Further, the molar ratio of tetrapropyl orthosilicate to tetraethyl orthosilicate in the step (1) is 1:1-3.
Further, in the step (1), the volume ratio of the ethanol to the deionized water to the concentrated ammonia water is 70:30:3; the volume ratio of the added resorcinol to the mixed solution is (0.4-1) g to 103mL, and the volume ratio of the added formaldehyde to the mixed solution is (0.36-1) 103; the stirring time in the hydrolytic condensation process is 12-72 h.
Further, in the step (2), the carbonization treatment is heated to 700-800 ℃ at a speed of 5-7 ℃/min.
Further, in the step (4), the molar ratio of the phosphotungstic acid to the zirconium sulfate is 100:0.5-5; the heat treatment temperature is 60-200 ℃.
Further, in the step (5), the adding mass ratio of the zirconium-species-supported phosphotungstic acid catalyst to the mesoporous hollow carbon sphere is 1:9-30.
The invention also discloses a zirconium-loaded phosphotungstic acid catalyst wrapped by the mesoporous carbon sphere prepared by the preparation method.
The invention also discloses application of the mesoporous carbon sphere coated zirconium supported catalyst in electrochemical ammonia synthesis reaction.
Further, the zirconium-supported catalyst wrapped by the mesoporous carbon sphere is dispersed in a mixed solution of ethanol and water, after ultrasonic treatment is carried out for 0.5-1 h, the uniformly dispersed catalyst mixture is dripped on hydrophilic carbon paper to assemble a working electrode, and an electrocatalytic ammonia synthesis reaction is carried out by using a three-electrode system.
Compared with the prior art, the invention has the beneficial effects that:
(1) Compared with microporous or nonporous carbon materials, the mesoporous hollow carbon sphere has the advantages of low density, porous shell, accessible inner space, high surface area, large pore volume and the like, has strong adsorption capacity on a phosphotungstic acid-based catalyst, and meanwhile, the surface of the carbon sphere has the advantage that abundant mesopores can fully expose active sites of the catalyst.
(2) The invention can accurately regulate and control the cavity, aperture and shell thickness of the hollow carbon sphere of the carrier, wherein the cavity of the hollow mesoporous carbon sphere is formed by SiO 2 Nuclear determination, controlling hydrolysis time can control SiO 2 The invention controls SiO by controlling the stirring time after tetrapropyl orthosilicate is added into the mixed solution 2 The size of the core is further used for realizing the precise regulation and control of the hollow cavity of the carrier hollow carbon sphere; the invention replaces tetrapropyl orthosilicate with part of tetraethyl orthosilicate, and under the condition of ensuring the unchanged silicon content, the hydrolysis speed of the tetraethyl orthosilicate is high, so that the formed SiO 2 The core size will be larger than that of SiO made with pure tetrapropyl orthosilicate 2 The core size is large, and after the using amount of the tetrapropyl orthosilicate is reduced, the thickness of the hollow mesoporous carbon sphere is reduced; the shell thickness of the hollow mesoporous carbon sphere is determined by the polymerization degree of phenolic resinThe invention controls the thickness of the shell by adjusting the dosage of resorcinol and formaldehyde; because the hydrolysis rate of tetrapropyl orthosilicate in water is faster than that of tetrapropyl orthosilicate in ethanol, the pore diameter of the hollow mesoporous carbon sphere is regulated and controlled by regulating the volume ratio of water to ethanol.
(3) The preparation method provided by the invention is simple and easy to control, the production process is environment-friendly, the energy consumption is low, the yield is high, the cost is low, the actual production needs are met, and the large-scale popularization is facilitated.
(4) The zirconium-supported phosphotungstic acid catalyst wrapped by the mesoporous carbon sphere prepared by the invention has strong stability and regeneration capability in an electrocatalytic reaction system, high recycling rate and high practical value and application prospect.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of a mesoporous carbon sphere-coated zirconium supported catalyst prepared in accordance with example 1 of the present invention;
FIG. 2 is a morphology diagram of a mesoporous carbon sphere-wrapped zirconium supported catalyst prepared according to example 1 of the present invention;
FIG. 3 is a schematic structural view of a mesoporous carbon sphere-coated zirconium supported catalyst prepared in example 1 according to the present invention;
FIG. 4 is a graph showing the comparison of the performance and the performance stability of electrocatalytic nitrogen reduction ammonia synthesis of mesoporous carbon sphere coated zirconium supported catalyst and non-mesoporous carbon sphere coated zirconium supported catalyst prepared in example 1 according to the present invention.
Detailed Description
The invention is further described below in connection with the preferred embodiments, and neither the endpoints of the ranges disclosed in the invention nor any of the values are limited to the precise range or value, and such range or value should be understood to include values near the range or value; for a range of values, one or more new ranges of values can be obtained in combination with each other between the endpoints of each range, between the endpoints of each range and the individual point values, and between the individual point values, and are to be considered as specifically disclosed herein;
materials, reagents and the like used in the following examples are commercially available unless otherwise specified;
the experimental methods in the following examples are conventional methods unless otherwise specified.
Example 1
A preparation method of a mesoporous carbon sphere-wrapped zirconium supported catalyst uses tetrapropyl orthosilicate, tetraethyl orthosilicate, resorcinol and formaldehyde as raw materials, and adopts a template method to prepare a mesoporous hollow carbon sphere carrier; then taking phosphotungstic acid and zirconium sulfate as raw materials, and heating and stirring under mild conditions to prepare a zirconium-loaded phosphotungstic acid catalyst by batch feeding; and then immobilizing the zirconium-loaded phosphotungstic acid catalyst into a multi-stage pore canal of the mesoporous hollow carbon sphere by an impregnation method, and preparing the zirconium-loaded phosphotungstic acid catalyst wrapped by the mesoporous carbon sphere by utilizing the space limiting effect, wherein the method specifically comprises the following steps of:
(1) Adding 6mmol of tetrapropyl orthosilicate and 6mmol of tetraethyl orthosilicate into a mixed solution containing 70mL of ethanol, 10mL of deionized water and 3mL of concentrated ammonia water, vigorously stirring for 15min, sequentially adding 0.4g of resorcinol and 0.66mL of formaldehyde with concentration of 37% into the mixed solution, performing hydrolysis condensation for 24h, centrifugally washing the mixed solution with deionized water and ethanol for multiple times, and drying the collected precursor in a 50 ℃ oven to obtain SiO 2 @SiO 2 A phenolic resin precursor;
(2) 2g of SiO obtained in the step (1) is reacted 2 @SiO 2 Placing a phenolic resin precursor sample in a porcelain boat, heating to 700 ℃ at a speed of 5 ℃/min under argon condition, calcining for 5 hours at high temperature, and carbonizing at high temperature to obtain SiO 2 @SiO 2 Conversion of phenolic resin precursor to SiO 2 @SiO 2 /C；
(3) Etching SiO in the calcined sample by using HF solution with concentration of 25% 2 After 22h of etching, the mixed solution is centrifugally washed by deionized water to obtain precipitateDrying the material to obtain the mesoporous carbon hollow sphere carrier;
(4) Dropwise adding 0.7 mu mol of zirconium sulfate aqueous solution into 100 mu mol of phosphotungstic acid aqueous solution, stirring for 4 hours at room temperature, and placing the mixed solution in a heating stirrer with magnetic force of 100 ℃ for heat treatment for 4 hours to obtain a zirconium species supported phosphotungstic acid catalyst;
(5) Dispersing a 10mg zirconium-species-supported phosphotungstic acid catalyst sample obtained in the step (4) in 10mL ethanol solution, immobilizing the zirconium-species-supported phosphotungstic acid catalyst in 90mg mesoporous hollow carbon spheres by an impregnation method, ultrasonically dispersing for 0.5h, stirring the mixed solution for 2h, and finally drying in a 60 ℃ oven to obtain the zirconium-supported phosphotungstic acid catalyst wrapped by the mesoporous hollow carbon spheres.
Example 2
A preparation method of a mesoporous carbon sphere-wrapped zirconium supported catalyst uses tetrapropyl orthosilicate, tetraethyl orthosilicate, resorcinol and formaldehyde as raw materials, and adopts a template method to prepare a mesoporous hollow carbon sphere carrier; then taking phosphotungstic acid and zirconium sulfate as raw materials, and heating and stirring under mild conditions to prepare a zirconium-loaded phosphotungstic acid catalyst by batch feeding; and then immobilizing the zirconium-loaded phosphotungstic acid catalyst into a multi-stage pore canal of the mesoporous hollow carbon sphere by an impregnation method, and preparing the zirconium-loaded phosphotungstic acid catalyst wrapped by the mesoporous carbon sphere by utilizing the space limiting effect, wherein the method specifically comprises the following steps of:
(1) Adding 6mmol of tetrapropyl orthosilicate and 8mmol of tetraethyl orthosilicate into a mixed solution containing 70mL of ethanol, 10mL of deionized water and 3mL of concentrated ammonia water, vigorously stirring for 25min, sequentially adding 0.6g of resorcinol and 0.56mL of formaldehyde with concentration of 37% into the mixed solution, performing hydrolysis condensation for 12h, centrifugally washing the mixed solution with deionized water and ethanol for multiple times, and drying the collected precursor in a 50 ℃ oven to obtain SiO 2 @SiO 2 A phenolic resin precursor;
(2) 2g of SiO obtained in the step (1) is reacted 2 @SiO 2 Placing a phenolic resin precursor sample in a porcelain boat, heating to 800 ℃ at a speed of 7 ℃/min under argon gas condition, calcining for 6 hours at high temperature, and passing through the high temperatureAfter the warm carbonization treatment, siO 2 @SiO 2 Conversion of phenolic resin precursor to SiO 2 @SiO 2 /C；
(3) Etching SiO in the calcined sample by using HF solution with concentration of 25% 2 After 12 hours of etching, centrifugally washing the mixed solution with deionized water, and drying the obtained precipitate to obtain the mesoporous carbon hollow sphere carrier;
(4) Dropwise adding 0.5 mu mol of zirconium sulfate aqueous solution into 100 mu mol of phosphotungstic acid aqueous solution, stirring for 2 hours at room temperature, and placing the mixed solution in a heating stirrer with magnetic force of 60 ℃ for heat treatment for 6 hours to obtain a zirconium species supported phosphotungstic acid catalyst;
(5) Dispersing a 10mg zirconium-species-supported phosphotungstic acid catalyst sample obtained in the step (4) in 10mL ethanol solution, immobilizing the zirconium-species-supported phosphotungstic acid catalyst in 150mg mesoporous hollow carbon spheres by an impregnation method, ultrasonically dispersing for 1h, stirring the mixed solution for 4h, and finally drying in an oven at 80 ℃ to obtain the zirconium-supported phosphotungstic acid catalyst wrapped by the mesoporous hollow carbon spheres.
Example 3
A preparation method of a mesoporous carbon sphere-wrapped zirconium supported catalyst uses tetrapropyl orthosilicate, tetraethyl orthosilicate, resorcinol and formaldehyde as raw materials, and adopts a template method to prepare a mesoporous hollow carbon sphere carrier; then taking phosphotungstic acid and zirconium sulfate as raw materials, and heating and stirring under mild conditions to prepare a zirconium-loaded phosphotungstic acid catalyst by batch feeding; and then immobilizing the zirconium-loaded phosphotungstic acid catalyst into a multi-stage pore canal of the mesoporous hollow carbon sphere by an impregnation method, and preparing the zirconium-loaded phosphotungstic acid catalyst wrapped by the mesoporous carbon sphere by utilizing the space limiting effect, wherein the method specifically comprises the following steps of:
(1) 6mmol of tetrapropyl orthosilicate and 12mmol of tetraethyl orthosilicate are added into a mixed solution containing 70mL of ethanol, 10mL of deionized water and 3mL of concentrated ammonia water, after being vigorously stirred for 20min, 0.8g of resorcinol and 0.36mL of formaldehyde with concentration of 37% are sequentially added into the mixed solution, after a hydrolytic condensation process for 36h, the mixed solution is centrifugally washed with deionized water and ethanol for a plurality of times, and then the collected former is collectedThe body is put into a baking oven at 50 ℃ for drying, and the SiO can be prepared 2 @SiO 2 A phenolic resin precursor;
(2) 2g of SiO obtained in the step (1) is reacted 2 @SiO 2 Placing a phenolic resin precursor sample in a porcelain boat, heating to 750 ℃ at a speed of 6 ℃/min under argon condition, calcining at high temperature for 5.5h, and carbonizing at high temperature to obtain SiO 2 @SiO 2 Conversion of phenolic resin precursor to SiO 2 @SiO 2 /C；
(3) Etching SiO in the calcined sample by using HF solution with concentration of 25% 2 After 48 hours of etching, centrifugally washing the mixed solution with deionized water, and drying the obtained precipitate to obtain the mesoporous carbon hollow sphere carrier;
(4) Dropwise adding 2 mu mol of zirconium sulfate aqueous solution into 100 mu mol of phosphotungstic acid aqueous solution, stirring for 6 hours at room temperature, and placing the mixed solution in a heating stirrer with magnetic force of 80 ℃ for heat treatment for 5 hours to obtain a zirconium species supported phosphotungstic acid catalyst;
(5) Dispersing a 10mg zirconium-species-supported phosphotungstic acid catalyst sample obtained in the step (4) in 10mL ethanol solution, immobilizing the zirconium-species-supported phosphotungstic acid catalyst in 200mg mesoporous hollow carbon spheres by an impregnation method, ultrasonically dispersing for 0.5h, stirring the mixed solution for 6h, and finally drying in an oven at 80 ℃ to obtain the zirconium-supported phosphotungstic acid catalyst wrapped by the mesoporous hollow carbon spheres.
Example 4
A preparation method of a mesoporous carbon sphere-wrapped zirconium supported catalyst uses tetrapropyl orthosilicate, tetraethyl orthosilicate, resorcinol and formaldehyde as raw materials, and adopts a template method to prepare a mesoporous hollow carbon sphere carrier; then taking phosphotungstic acid and zirconium sulfate as raw materials, and heating and stirring under mild conditions to prepare a zirconium-loaded phosphotungstic acid catalyst by batch feeding; and then immobilizing the zirconium-loaded phosphotungstic acid catalyst into a multi-stage pore canal of the mesoporous hollow carbon sphere by an impregnation method, and preparing the zirconium-loaded phosphotungstic acid catalyst wrapped by the mesoporous carbon sphere by utilizing the space limiting effect, wherein the method specifically comprises the following steps of:
(1) 6mmol of tetrapropyl orthosilicate and 18mmol of crude siliconAdding tetraethyl acetate into a mixed solution containing 70mL of ethanol, 10mL of deionized water and 3mL of concentrated ammonia water, vigorously stirring for 22min, sequentially adding 1.0g of resorcinol and 1mL of formaldehyde with concentration of 37% into the mixed solution, performing hydrolysis condensation for 72h, centrifugally washing the mixed solution with deionized water and ethanol for multiple times, and then drying the collected precursor in a 50 ℃ oven to obtain SiO 2 @SiO 2 A phenolic resin precursor;
(2) 2g of SiO obtained in the step (1) is reacted 2 @SiO 2 Placing a phenolic resin precursor sample in a porcelain boat, heating to 780 ℃ under the argon condition at the speed of 5 ℃/min, calcining for 6 hours at high temperature, and carbonizing at high temperature to obtain SiO 2 @SiO 2 Conversion of phenolic resin precursor to SiO 2 @SiO 2 /C；
(3) Etching SiO in the calcined sample by using HF solution with concentration of 25% 2 After the core is etched for 30 hours, the mixed solution is centrifugally washed by deionized water, and the obtained precipitate is dried to obtain the mesoporous carbon hollow sphere carrier;
(4) Dropwise adding 5 mu mol of zirconium sulfate aqueous solution into 100 mu mol of phosphotungstic acid aqueous solution, stirring for 5 hours at room temperature, and placing the mixed solution in a heating stirrer with a magnetic force of 200 ℃ for heat treatment for 4 hours to obtain a zirconium species supported phosphotungstic acid catalyst;
(5) Dispersing a 10mg zirconium-species-supported phosphotungstic acid catalyst sample obtained in the step (3) in 10mL ethanol solution, immobilizing the zirconium-species-supported phosphotungstic acid catalyst in 300mg mesoporous hollow carbon spheres by an impregnation method, ultrasonically dispersing for 1h, stirring the mixed solution for 3h, and finally drying in a 60 ℃ oven to obtain the zirconium-supported phosphotungstic acid catalyst wrapped by the mesoporous hollow carbon spheres.
Example 5
The application of a mesoporous carbon sphere coated zirconium supported catalyst in electrochemical ammonia synthesis reaction is that 5mg of the prepared mesoporous carbon sphere coated zirconium supported catalyst is dispersed in a mixed solution comprising 360 mu L of ethanol, 120 mu L of water and 20 mu L of Nafion, after ultrasonic treatment is carried out for 1-2 hours, the uniformly dispersed catalyst mixed solution is dripped on hydrophilic carbon paper to be assembled into a working electrode, and the three-electrode system is utilized for carrying out the electrocatalytic ammonia synthesis reaction.
Performance test:
the characterization and performance detection of the mesoporous carbon sphere coated zirconium supported catalyst prepared according to the preparation method provided by the embodiment 1 of the invention are as follows:
FIG. 1 is an X-ray powder diffraction pattern of a mesoporous carbon sphere-coated zirconium supported catalyst prepared according to the preparation method provided in example 1 of the present invention, from which it can be seen that, in addition to having peaks attributed to carbon, characteristic diffraction peaks attributed to zirconium-phosphotungstic acid appear in the diffraction pattern of a mesoporous carbon sphere-coated zirconium species-supported phosphotungstic acid, which indicates that both zirconium-phosphotungstic acid and mesoporous carbon spheres were successfully compounded;
fig. 2 is a morphology diagram of a mesoporous carbon sphere-coated zirconium supported catalyst prepared according to the preparation method provided in example 1 of the present invention, and fig. 2a and 2b are SEM images of mesoporous carbon spheres, showing that the mesoporous carbon spheres are uniformly distributed nanospheres, and the surface of the mesoporous carbon spheres is provided with a mesoporous shell and an open inlet; the TEM image further presents the hollow morphology and radial channels of mesoporous carbon spheres (as in fig. 2 c); the TEM and SEM images show that the pores on the surface of the mesoporous carbon sphere are disordered, the diameter size of the cavity of the carbon sphere is 180nm, and the thickness of the carbon shell is 20nm; as shown in fig. 2d-f, after zirconium-phosphotungstic acid is filled and immersed into the carbon sphere, obvious sample filling marks are formed in the pore channels on the surface of the carbon sphere; further, the element map of the mesoporous carbon sphere coated zirconium supported phosphotungstic acid shows that the elements of phosphorus, zirconium and tungsten are uniformly dispersed in the hollow carbon element (as shown in figure 2 g), which shows that the prepared zirconium-phosphotungstic acid electrocatalyst is anchored in the pore canal of the mesoporous carbon sphere in a highly dispersed manner, and the stability of the catalyst is improved under the action of a space limiting domain;
fig. 3 is a schematic structural diagram of a mesoporous carbon sphere coated zirconium supported phosphotungstic acid prepared according to the preparation method provided in embodiment 1 of the present invention, from which it can be seen that a zirconium species supported phosphotungstic acid catalyst is anchored in the pores of the mesoporous carbon sphere in a highly dispersed manner;
FIG. 4 shows a mesoporous carbon sphere-coated zirconium supported catalyst and a mesoporous carbon sphere-free zirconium supported catalyst prepared according to the preparation method of example 1 of the present inventionElectrocatalytic nitrogen reduction activity comparison chart and performance stability comparison chart of the catalyst; the electrocatalytic nitrogen reduction performance test was performed in an H-type reactor, the electrocatalytic process using a three electrode system, the catalyst was assembled into a working electrode by example 1, a platinum sheet as a counter electrode, and saturated silver/silver chloride as a reference electrode; before performance test, purified nitrogen is blown into electrolyte (lithium sulfate with pH value of 4), when the nitrogen in the electrolyte reaches saturation, different bias voltages can be applied to react, and all potentials are relative to a standard hydrogen electrode; as can be seen from FIG. 4a, compared with the zirconium-phosphotungstic acid catalyst without the mesoporous carbon sphere coating, the zirconium supported phosphotungstic acid with the mesoporous carbon sphere coating has more excellent electrocatalytic ammonia synthesis performance, and the ammonia synthesis yield can reach 106+/-3 mu g h -1 mg cat. -1 The faraday efficiency reaches 81.8+/-3%, the faraday efficiency value has obvious advantages in the values reported in the same system work at present, and as can be seen from fig. 4b, under the effect of space limitation, after four-wheel stability experiment test, the electrocatalytic nitrogen reduction performance of the mesoporous carbon sphere-coated zirconium species-loaded phosphotungstic acid is basically unchanged, and good ammonia synthesis performance stability is shown.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related arts are included in the scope of the present invention.
Claims (7)
1. The preparation method of the mesoporous carbon sphere-wrapped zirconium supported catalyst is characterized by comprising the following steps of:
(1) Adding tetrapropyl orthosilicate and tetraethyl orthosilicate into a mixed solution containing ethanol, deionized water and concentrated ammonia water, stirring vigorously for 15-25 min, adding resorcinol and formaldehyde into the mixed solution, centrifugally washing the mixed solution with deionized water and ethanol for multiple times after a hydrolytic condensation process, and drying the collected precursor to obtain SiO2@SiO2/phenolic resin precursor;
(2) Placing the SiO2@SiO2/phenolic resin precursor sample obtained in the step (1) in a porcelain boat, calcining at high temperature for 5-6 hours under the condition of argon for carbonization, and converting the SiO2@SiO2/phenolic resin precursor into SiO2@SiO2/C after high-temperature carbonization treatment;
(3) Etching SiO2@SiO2/C samples for 12-48 hours by using an HF solution, removing SiO2 cores, centrifugally washing the mixed solution by using deionized water, and drying the obtained precipitate to obtain the mesoporous carbon hollow sphere carrier;
(4) Dropwise adding a zirconium sulfate aqueous solution into a phosphotungstic acid aqueous solution, wherein the molar ratio of phosphotungstic acid to zirconium sulfate is 100:0.5-5, stirring for 2-6 hours at room temperature, placing the mixed solution into a magnetic heating stirrer, performing heat treatment for 4-6 hours, and obtaining a zirconium species supported phosphotungstic acid catalyst at a heat treatment temperature of 60-200 ℃;
(5) Dispersing the zirconium-species-supported phosphotungstic acid catalyst sample obtained in the step (4) in an ethanol solution, and then immobilizing the zirconium-species-supported phosphotungstic acid catalyst in the mesoporous hollow carbon sphere by an impregnation method, wherein the adding mass ratio of the zirconium-species-supported phosphotungstic acid catalyst to the mesoporous hollow carbon sphere is 1:9-30; and after ultrasonic dispersion for 0.5-1 h, stirring the mixed solution for 2-6 h, and finally drying to obtain the zirconium-loaded phosphotungstic acid catalyst wrapped by the mesoporous hollow carbon sphere.
2. The method for preparing the mesoporous carbon sphere coated zirconium supported catalyst according to claim 1, which is characterized in that: the molar ratio of the tetrapropyl orthosilicate to the tetraethyl orthosilicate in the step (1) is 1:1-3.
3. The method for preparing the mesoporous carbon sphere coated zirconium supported catalyst according to claim 1, which is characterized in that: the volume ratio of the ethanol to the deionized water to the concentrated ammonia water in the step (1) is 70:30:3; the volume ratio of the added resorcinol to the mixed solution is 0.4-1 g/103 mL, and the volume ratio of the added formaldehyde to the mixed solution is 0.36-1:103; the stirring time in the hydrolysis condensation process is 12-72 h.
4. The method for preparing the mesoporous carbon sphere coated zirconium supported catalyst according to claim 1, which is characterized in that: and (3) heating the carbonized material to 700-800 ℃ at a speed of 5-7 ℃/min in the step (2).
5. The mesoporous carbon sphere-coated zirconium supported phosphotungstic acid catalyst prepared according to any one of the preparation methods of claims 1 to 4.
6. The use of a mesoporous carbon sphere coated zirconium supported catalyst according to claim 5 in an electrochemical ammonia synthesis reaction.
7. The use of a mesoporous carbon sphere coated zirconium supported catalyst according to claim 6 in an electrochemical ammonia synthesis reaction, wherein: and dispersing the zirconium-supported catalyst wrapped by the mesoporous carbon spheres in a mixed solution of ethanol and water, carrying out ultrasonic treatment for 0.5-1 h, then, dripping the uniformly dispersed catalyst mixture on hydrophilic carbon paper to assemble a working electrode, and carrying out electrocatalytic ammonia synthesis reaction by using a three-electrode system.
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