CN114908372A - 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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- CN114908372A CN114908372A CN202210333046.XA CN202210333046A CN114908372A CN 114908372 A CN114908372 A CN 114908372A CN 202210333046 A CN202210333046 A CN 202210333046A CN 114908372 A CN114908372 A CN 114908372A
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- zirconium
- phosphotungstic acid
- mesoporous
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- mesoporous carbon
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 93
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 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 92
- 239000003377 acid catalyst Substances 0.000 claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 51
- 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 33
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 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 21
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims abstract description 21
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 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 15
- 230000003100 immobilizing effect Effects 0.000 claims abstract description 13
- 230000000694 effects Effects 0.000 claims abstract description 11
- 238000005470 impregnation Methods 0.000 claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 46
- 239000011259 mixed solution Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 24
- 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 19
- 239000005011 phenolic resin Substances 0.000 claims description 19
- 229920001568 phenolic resin Polymers 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 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
- 238000005530 etching Methods 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- 230000008569 process Effects 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
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000004873 anchoring Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000000047 product 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
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000009471 action Effects 0.000 abstract description 4
- 239000010411 electrocatalyst Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 8
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- 238000010586 diagram Methods 0.000 description 4
- 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
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- 230000002829 reductive effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
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- 238000011056 performance test Methods 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
- 238000012545 processing Methods 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
- 238000012360 testing method Methods 0.000 description 2
- 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 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
- 238000007664 blowing Methods 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
- 239000000969 carrier Substances 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 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
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 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
- 238000013507 mapping Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000037361 pathway Effects 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
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003378 silver Chemical class 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
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 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
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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- 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 coated 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, feeding in batches, and heating and stirring under mild conditions to prepare the zirconium-loaded phosphotungstic acid catalyst; then immobilizing the zirconium-loaded phosphotungstic acid catalyst into the multilevel pore channels of the mesoporous hollow carbon spheres by an impregnation method, and developing the zirconium-loaded phosphotungstic acid electrocatalyst which is wrapped by the mesoporous carbon spheres and has high activity and high stability for the first time; the electrocatalyst prepared by the invention has strong nitrogen activation capacity, can effectively inhibit hydrogen evolution side reaction, has excellent activity and selectivity for synthesizing ammonia by electrocatalysis, and simultaneously shows good chemical structure and performance stability under the action of space confinement.
Description
Technical Field
The invention relates to a preparation method and application of a mesoporous carbon sphere-coated zirconium supported catalyst, belonging to the technical fields of material synthesis, electrocatalysis and fine chemical engineering.
Background
Ammonia is not only one kindThe important chemical raw materials are ideal energy storage and transportation carriers, and have 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 significant role in the strategic layout of agricultural production of fertilizers and new energy sources. Over a century of development, the Haber-Bosch process has been the dominant technique used in the current industrial synthesis of ammonia. However, because the reaction conditions of the process are harsh, 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 accounts for about 1-2% of the global energy consumption, and hundreds of millions of tons of carbon dioxide are discharged, thereby causing serious energy crisis and environmental pollution problems. Therefore, the search for sustainable green ammonia synthesis technology is a worldwide research topic.
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 the air in a normal-temperature normal-pressure aqueous solution system. Because the reaction takes water as a hydrogen source, the reaction device can be modularized and distributed, and has zero CO 2 And (4) discharging, and performing green synthesis on ammonia according to requirements. Therefore, eNRR is considered to be an ideal efficient sustainable ammonia synthesis pathway. However, since the normal-temperature normal-pressure aqueous eNRR is a typical gas-liquid-solid reaction system, there are technical bottlenecks, such as the ultra-high chemical stability of nitrogen molecules and the dominance of hydrogen evolution side reaction, which result in the low activity and selectivity of eNRR for ammonia synthesis. Therefore, the design and synthesis of a novel efficient and stable electrocatalyst have important research significance for improving the performance of the electrocatalytic synthesis of ammonia.
The phosphotungstic acid with a Keggin structure is used as a multifunctional novel green catalyst, has a unique space geometric structure, can accurately anchor modified metal species on a four-fold hollow site formed by rich oxygen coordination sites, and can adjust the electronic structure of the catalyst to enable electrons in polyanion of the phosphotungstic acid to migrate to introduced metal species to form an electron-rich active center so as to improve the adsorption and activation capability 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 the aspects of promoting nitrogen activation and inhibiting hydrogen evolution side reaction. In addition, the d-orbital of the transition metal zirconium species can be combined with nitrogen, so that the N ≡ N bond is effectively weakened, and the zirconium species has weak binding capacity for hydrogen, which is beneficial to improving the selectivity of electrocatalytic nitrogen reduction. Based on the above analysis, zirconium metal species modified phosphotungstic acid has the potential to be developed into a high-efficiency eNRR catalyst.
On the other hand, considering that the phosphotungstic acid based catalyst is very soluble in a polar solvent, and the eNRR system is a typical gas-liquid-solid three-phase interface reaction, the phosphotungstic acid based catalyst is very soluble in an aqueous electrolyte in the eNRR process, and the reaction activity is low, so that the application of the phosphotungstic acid based catalyst in the field of water system electrocatalysis is limited. In order to improve the stability of phosphotungstic acid in a polar solvent, a proper carrier is searched for to fix the phosphotungstic acid based catalyst on the carrier, and the dissolution of the phosphotungstic acid based catalyst is effectively inhibited by enhancing the acting force between the catalyst and the carrier, so that the stability of the catalyst in an aqueous electrolyte is improved.
Because the carbon material has the characteristics of high chemical stability and thermal stability, good conductivity, internal hydrophobicity, easy modification of surface chemistry and the like, the carbon nano material and the composite material thereof attract extensive attention in the fields of biomedicine, catalysis, absorption, energy storage and the like. Compared with microporous or non-porous carbon materials, the mesoporous hollow carbon sphere has 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 sphere becomes a potential excellent carrier. In addition, the mesoporous hollow carbon spheres have strong adsorption force on the phosphotungstic acid based catalyst, and can be used as a protective layer to wrap the phosphotungstic acid based catalyst in the carbon spheres to greatly reduce the dissolution of the catalyst under the action of space confinement. Meanwhile, the carbon sphere surface has the advantage that rich 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 cavity, the pore diameter and the shell thickness of the hollow carbon sphere of the carrier are difficult to accurately regulate and control, so that the phosphotungstic acid based catalyst cannot be effectively immobilized in the carbon sphere, and the performance stability of the electro-catalytic nitrogen reduction synthesis of 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-coated zirconium-supported catalyst, wherein a mesoporous hollow carbon sphere carrier and a zirconium-supported phosphotungstic acid catalyst are sequentially prepared, the zirconium-supported phosphotungstic acid catalyst is immobilized in the mesoporous hollow carbon sphere by an impregnation method, and the high-performance and high-stability zirconium-supported phosphotungstic acid catalyst coated with the mesoporous carbon sphere for electrocatalytic nitrogen fixation is firstly developed by utilizing the space confinement effect.
The technical scheme of the invention is as follows:
the invention discloses a preparation method of a zirconium supported catalyst wrapped by mesoporous carbon spheres, 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 immobilized carrier of the catalyst; then taking phosphotungstic acid and zirconium sulfate as raw materials, feeding in batches, heating and stirring under mild conditions, 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 the multilevel pore channels of the mesoporous hollow carbon sphere carrier by an impregnation method, and preparing the zirconium-loaded phosphotungstic acid catalyst wrapped by the mesoporous carbon spheres by utilizing the space confinement effect.
Further, the preparation method of the mesoporous carbon sphere coated 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, violently stirring for 15-25 min, adding resorcinol and formaldehyde into the mixed solution, performing hydrolytic condensation, centrifuging and washing the mixed solution for multiple times by using the deionized water and the ethanol, and drying the collected precursor to obtain the SiO 2 @SiO 2 A phenolic resin precursor;
(2) SiO obtained in the step (1) 2 @SiO 2 Placing the phenolic resin precursor sample in a porcelain boat, calcining at high temperature for 5-6 h under the condition of argon gas for carbonization, and performing high-temperature carbonization treatment on the sample to obtain SiO 2 @SiO 2 Conversion of phenolic resin precursors to SiO 2 @SiO 2 /C；
(3) Etching SiO with HF solution 2 @SiO 2 Removing SiO from the C sample for 12-48 h 2 Carrying out core washing, namely 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, stirring at room temperature for 2-6 h, and then placing the mixed solution into a magnetic heating stirrer for heat treatment for 4-6 h to obtain a zirconium species supported phosphotungstic acid catalyst;
(5) and (3) dispersing the zirconium species supported phosphotungstic acid catalyst sample obtained in the step (4) in an ethanol solution, then immobilizing the zirconium species supported phosphotungstic acid catalyst in the mesoporous hollow carbon spheres by an impregnation method, ultrasonically dispersing 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 the tetrapropyl orthosilicate to the tetraethyl orthosilicate in the step (1) is 1: 1-3.
Further, the volume ratio of the ethanol to the deionized water to the concentrated ammonia water in the step (1) is 70:30: 3; the mass ratio of the added resorcinol to the volume ratio of the mixed solution is (0.4-1) g:103mL, 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.
Further, in the step (2), the temperature of the carbonization treatment is increased to 700-800 ℃ at the speed of 5-7 ℃/min.
Further, the molar ratio of phosphotungstic acid to zirconium sulfate in the step (4) is 100: 0.5-5; the heat treatment temperature is 60-200 ℃.
Further, the adding mass ratio of the zirconium species supported phosphotungstic acid catalyst to the mesoporous hollow carbon spheres in the step (5) is 1: 9-30.
The invention also discloses a zirconium-loaded phosphotungstic acid catalyst wrapped by the mesoporous carbon spheres prepared by the preparation method.
The invention also discloses application of the mesoporous carbon sphere-coated zirconium supported catalyst in an electrochemical ammonia synthesis reaction.
Further, the zirconium-supported catalyst wrapped by the mesoporous carbon spheres 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 mixed solution is dropwise coated on hydrophilic carbon paper to assemble a working electrode, and a three-electrode system is utilized to carry out electrocatalytic ammonia synthesis reaction.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a mesoporous carbon sphere-coated zirconium supported catalyst and a preparation method thereof, wherein the mesoporous hollow carbon sphere has the advantages of low density, porous shell, accessible internal space, high surface area, large pore volume and the like compared with microporous or non-porous carbon materials, has strong adsorption force on a phosphotungstic acid based catalyst, and simultaneously has the advantage that rich mesopores can fully expose active sites of the catalyst.
(2) The invention can accurately regulate and control the size of the cavity, the aperture and the shell thickness of the hollow carbon sphere of the carrier, wherein the cavity of the hollow mesoporous carbon sphere is made of SiO 2 The SiO can be controlled by nuclear determination and regulation of hydrolysis time 2 The size of the core, the invention controls the stirring time after the tetrapropyl orthosilicate is added into the mixed liquid to control the SiO 2 The size of the core further realizes the accurate regulation and control of the cavity of the hollow carbon ball of the carrier; the invention replaces tetrapropyl orthosilicate with partial tetraethyl orthosilicate, and forms SiO because tetraethyl orthosilicate is hydrolyzed at high speed under the condition of ensuring that the content of silicon is not changed 2 The core size will be larger than that of SiO prepared using pure tetrapropyl orthosilicate 2 The core size is large, and the thickness of the hollow mesoporous carbon spheres can be reduced after the consumption of tetrapropyl orthosilicate is reduced; the shell thickness of the hollow mesoporous carbon sphere is determined by the polymerization degree of the phenolic resin, and the shell thickness of the hollow mesoporous carbon sphere is determined by regulating the application of resorcinol and formaldehydeThe amount is used for controlling the shell thickness size; as the hydrolysis rate of tetrapropyl orthosilicate in water is higher 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 green and 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-loaded phosphotungstic acid catalyst wrapped by the mesoporous carbon spheres prepared by the method has strong stability and reproducibility in an electrocatalytic reaction system, is high in repeated utilization rate, and has high practical value and application prospect.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of a zirconium-supported catalyst coated with mesoporous carbon spheres prepared in example 1 of the present invention;
FIG. 2 is a morphology chart of a mesoporous carbon sphere coated zirconium supported catalyst prepared in example 1 according to the present invention;
FIG. 3 is a schematic structural diagram of a zirconium-supported catalyst coated with mesoporous carbon spheres prepared in example 1 of the present invention;
fig. 4 is a comparison graph of the performance of the zirconium supported catalyst coated with mesoporous carbon spheres and the zirconium supported catalyst without the mesoporous carbon spheres prepared in example 1 of the present invention for synthesizing ammonia by electrocatalytic nitrogen reduction and the performance stability thereof.
Detailed Description
The invention is further described in connection with the preferred embodiments, and the endpoints of the ranges disclosed herein and any values are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values; for ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, which ranges of values 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 procedures in the following examples are conventional unless otherwise specified.
Example 1
A preparation method of a mesoporous carbon sphere coated zirconium supported catalyst is characterized in that tetrapropyl orthosilicate, tetraethyl orthosilicate, resorcinol and formaldehyde are used as raw materials, and a mesoporous hollow carbon sphere carrier is prepared by adopting a template method; then, taking phosphotungstic acid and zirconium sulfate as raw materials, feeding in batches, and heating and stirring under mild conditions to prepare the zirconium-loaded phosphotungstic acid catalyst; then immobilizing the zirconium-loaded phosphotungstic acid catalyst into the multilevel pore channels of the mesoporous hollow carbon spheres by an impregnation method, and preparing the zirconium-loaded phosphotungstic acid catalyst wrapped by the mesoporous carbon spheres by utilizing the space confinement effect, wherein the method specifically comprises the following steps:
(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, violently stirring for 15min, sequentially adding 0.4g of resorcinol and 0.66mL of formaldehyde with the concentration of 37% into the mixed solution, performing hydrolysis condensation for 24h, centrifuging and washing the mixed solution for multiple times by using deionized water and ethanol, and then putting the collected precursor into a 50 ℃ oven for drying to obtain SiO 2 @SiO 2 A phenolic resin precursor;
(2) 2gSiO obtained in the step (1) 2 @SiO 2 Placing the phenolic resin precursor sample in a porcelain boat, heating to 700 deg.C at a rate of 5 deg.C/min under argon gas condition, calcining at high temperature for 5h, carbonizing at high temperature, and processing with SiO 2 @SiO 2 Conversion of phenolic resin precursors to SiO 2 @SiO 2 /C；
(3) Then, etching SiO in the calcined sample by using HF solution with the concentration of 25 percent 2 Etching for 22h, centrifugally washing the mixed solution with deionized water, drying the obtained precipitate to obtain the hollow mesoporous carbonA spherical carrier;
(4) dropwise adding 0.7 mu mol of zirconium sulfate aqueous solution into 100 mu mol of phosphotungstic acid aqueous solution, stirring for 4h at room temperature, and then placing the mixed solution into a magnetic heating stirrer with the temperature of 100 ℃ for heat treatment for 4h to obtain a zirconium species supported phosphotungstic acid catalyst;
(5) and (3) dispersing the 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 using a dipping method, ultrasonically dispersing for 0.5h, stirring the mixed solution for 2h, and finally drying in an oven at 60 ℃ 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 coated zirconium supported catalyst is characterized in that tetrapropyl orthosilicate, tetraethyl orthosilicate, resorcinol and formaldehyde are used as raw materials, and a mesoporous hollow carbon sphere carrier is prepared by adopting a template method; then, taking phosphotungstic acid and zirconium sulfate as raw materials, feeding in batches, and heating and stirring under mild conditions to prepare the zirconium-loaded phosphotungstic acid catalyst; then immobilizing the zirconium-loaded phosphotungstic acid catalyst into the multilevel pore channels of the mesoporous hollow carbon spheres by an impregnation method, and preparing the zirconium-loaded phosphotungstic acid catalyst wrapped by the mesoporous carbon spheres by utilizing the space confinement effect, wherein the method specifically comprises the following steps:
(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 strong ammonia water, violently stirring for 25min, sequentially adding 0.6g of resorcinol and 0.56mL of 37% formaldehyde into the mixed solution, performing hydrolysis condensation for 12h, repeatedly centrifugally washing the mixed solution by using deionized water and ethanol, and then putting the collected precursor into a 50 ℃ oven for drying to obtain SiO 2 @SiO 2 A phenolic resin precursor;
(2) 2gSiO obtained in the step (1) 2 @SiO 2 Placing the phenolic resin precursor sample in a porcelain boat, heating to 800 deg.C at a rate of 7 deg.C/min under argon gas condition, calcining at high temperature for 6h, carbonizing at high temperature, and making into SiO 2 @SiO 2 Conversion of phenolic resin precursors to SiO 2 @SiO 2 /C；
(3) Etching the SiO in the calcined sample by using HF solution with the concentration of 25% 2 The core is etched for 12 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 0.5 mu mol of zirconium sulfate aqueous solution into 100 mu mol of phosphotungstic acid aqueous solution, stirring at room temperature for 2h, and then placing the mixed solution into a heating stirrer with magnetic force of 60 ℃ for heat treatment for 6h to obtain a zirconium species supported phosphotungstic acid catalyst;
(5) and (3) dispersing the 10mg zirconium species supported phosphotungstic acid catalyst sample obtained in the step (4) in 10mL of ethanol solution, immobilizing the zirconium species supported phosphotungstic acid catalyst in 150mg mesoporous hollow carbon spheres by using a dipping 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 coated zirconium supported catalyst is characterized in that tetrapropyl orthosilicate, tetraethyl orthosilicate, resorcinol and formaldehyde are used as raw materials, and a mesoporous hollow carbon sphere carrier is prepared by adopting a template method; then, taking phosphotungstic acid and zirconium sulfate as raw materials, feeding in batches, and heating and stirring under mild conditions to prepare the zirconium-loaded phosphotungstic acid catalyst; then immobilizing the zirconium-loaded phosphotungstic acid catalyst into the multilevel pore channels of the mesoporous hollow carbon spheres by an impregnation method, and preparing the zirconium-loaded phosphotungstic acid catalyst wrapped by the mesoporous carbon spheres by utilizing the space confinement effect, wherein the method specifically comprises the following steps:
(1) adding 6mmol of tetrapropyl orthosilicate and 12mmol of tetraethyl orthosilicate into a mixed solution containing 70mL of ethanol, 10mL of deionized water and 3mL of concentrated ammonia water, vigorously stirring for 20min, sequentially adding 0.8g of resorcinol and 0.36mL of formaldehyde with the concentration of 37% into the mixed solution, performing hydrolysis and condensation for 36h, centrifuging and washing the mixed solution for multiple times by using deionized water and ethanol, and drying the collected precursor in an oven at 50 ℃ to prepare the nano-silver/zinc/To obtain SiO 2 @SiO 2 A phenolic resin precursor;
(2) 2gSiO obtained in the step (1) 2 @SiO 2 Placing the phenolic resin precursor sample in a porcelain boat, heating to 750 deg.C at a rate of 6 deg.C/min under argon gas condition, calcining at high temperature for 5.5h, carbonizing at high temperature, and processing with SiO 2 @SiO 2 Conversion of phenolic resin precursors to SiO 2 @SiO 2 /C；
(3) Etching the SiO in the calcined sample by using HF solution with the concentration of 25% 2 The core is etched for 48 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 2 mu mol of zirconium sulfate aqueous solution into 100 mu mol of phosphotungstic acid aqueous solution, stirring at room temperature for 6h, and then placing the mixed solution into a heating stirrer with magnetic force of 80 ℃ for heat treatment for 5h to obtain a zirconium species supported phosphotungstic acid catalyst;
(5) and (3) dispersing the 10mg zirconium species supported phosphotungstic acid catalyst sample obtained in the step (4) in 10mL of ethanol solution, immobilizing the zirconium species supported phosphotungstic acid catalyst in 200mg mesoporous hollow carbon spheres by using a dipping 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 zirconium supported catalyst wrapped by mesoporous carbon spheres 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, feeding in batches, and heating and stirring under mild conditions to prepare the zirconium-loaded phosphotungstic acid catalyst; then immobilizing the zirconium-loaded phosphotungstic acid catalyst into the multilevel pore channels of the mesoporous hollow carbon spheres by an impregnation method, and preparing the zirconium-loaded phosphotungstic acid catalyst wrapped by the mesoporous carbon spheres by utilizing the space confinement effect, wherein the method specifically comprises the following steps:
(1) 6mmol tetrapropyl orthosilicate and 18mmol tetraethyl orthosilicate were added to a solution containing 70mL ethanol,10mL of deionized water and 3mL of strong ammonia water, vigorously stirring for 22min, sequentially adding 1.0g of resorcinol and 1mL of formaldehyde with the concentration of 37% into the mixed solution, carrying out hydrolysis condensation for 72h, centrifuging and washing the mixed solution for multiple times by using the deionized water and ethanol, and then putting the collected precursor into a 50 ℃ oven for drying to obtain the SiO 2 @SiO 2 A phenolic resin precursor;
(2) 2gSiO obtained in the step (1) 2 @SiO 2 Placing the phenolic resin precursor sample in a porcelain boat, heating to 780 ℃ at the speed of 5 ℃/min under the condition of argon, calcining for 6h at high temperature, carrying out high-temperature carbonization treatment, and then carrying out SiO 2 @SiO 2 Conversion of phenolic resin precursors to SiO 2 @SiO 2 /C；
(3) Etching the SiO in the calcined sample by using HF solution with the concentration of 25% 2 After 30h of etching, 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 at room temperature for 5h, and then placing the mixed solution into a heating stirrer with magnetic force of 200 ℃ for heat treatment for 4h to obtain a zirconium species supported phosphotungstic acid catalyst;
(5) and (4) dispersing the zirconium species-supported phosphotungstic acid catalyst sample of 10mg obtained in the step (3) in 10mL of ethanol solution, immobilizing the zirconium species-supported phosphotungstic acid catalyst in a mesoporous hollow carbon sphere of 300mg by an impregnation method, ultrasonically dispersing for 1h, stirring the mixed solution for 3h, and finally drying in a drying oven at 60 ℃ to obtain the zirconium-supported phosphotungstic acid catalyst wrapped by the mesoporous hollow carbon sphere.
Example 5
The application of mesoporous carbon sphere-coated zirconium supported catalyst in electrochemical ammonia synthesis reaction comprises the steps of dispersing the prepared mesoporous carbon sphere-coated zirconium supported catalyst of 5mg in a mixed solution of 360 mu L ethanol, 120 mu L water and 20 mu L Nafion, carrying out ultrasonic treatment for 1-2 h, then dripping the uniformly dispersed catalyst mixed solution on hydrophilic carbon paper to assemble a working electrode, and carrying out the electrochemical ammonia synthesis reaction by using a three-electrode system.
And (3) performance testing:
the characterization and performance detection of the mesoporous carbon sphere coated zirconium supported catalyst prepared by 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 embodiment 1 of the present invention, and it can be seen from the pattern that a characteristic diffraction peak belonging to zirconium-phosphotungstic acid appears in a diffraction pattern of a mesoporous carbon sphere coated zirconium species supported phosphotungstic acid in addition to a peak belonging to carbon, which indicates that the zirconium-phosphotungstic acid and the mesoporous carbon sphere are 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 embodiment 1 of the present invention, and fig. 2a and 2b are SEM images of the mesoporous carbon sphere, which indicate that the mesoporous carbon sphere is a nanosphere with uniform distribution, and the surface of the mesoporous carbon sphere has a mesoporous shell and an open inlet; the TEM image further presents the hollow morphology and radial pore channels of the mesoporous carbon spheres (as shown in fig. 2 c); the holes on the surface of the mesoporous carbon sphere are disordered through TEM and SEM images, the diameter of the cavity of the carbon sphere is 180nm, and the thickness of the carbon shell is 20 nm; as shown in fig. 2d-f, after zirconium-phosphotungstic acid is filled and immersed into the carbon spheres, obvious sample filling traces exist in surface pore channels of the carbon spheres; further, an element mapping chart of zirconium-loaded phosphotungstic acid wrapped by the mesoporous carbon spheres shows that phosphorus, zirconium and tungsten elements are uniformly dispersed in the hollow carbon elements (as shown in fig. 2g), which shows that the prepared zirconium-phosphotungstic acid electrocatalyst is anchored in the pore channels of the mesoporous carbon spheres in a highly dispersed manner, and is favorable for improving the stability of the catalyst under the action of space confinement;
fig. 3 is a schematic structural diagram of mesoporous carbon sphere-coated zirconium-loaded phosphotungstic acid prepared by the preparation method provided in example 1 of the present invention, and it can be seen from the diagram that the zirconium species-loaded phosphotungstic acid catalyst is highly dispersedly anchored in the pores of the mesoporous carbon sphere;
FIG. 4 shows electrocatalytic nitrogen reduction activities of the mesoporous carbon sphere coated zirconium supported catalyst and the zirconium supported catalyst without mesoporous carbon sphere coating prepared according to the preparation methods provided in example 1 of the present inventionA comparison graph and a performance stability comparison graph thereof; the electrocatalysis nitrogen reduction performance test is carried out in an H-shaped reactor, a three-electrode system is adopted in the electrocatalysis process, a catalyst is assembled into a working electrode through example 1, a platinum sheet is used as a counter electrode, and saturated silver/silver chloride is used as a reference electrode; before performance test, blowing purified nitrogen into electrolyte (lithium sulfate with pH value of 4), and applying different bias voltages to react when the nitrogen in the electrolyte is saturated, wherein all potentials are relative to a standard hydrogen electrode; as can be seen from FIG. 4a, compared with the zirconium-phosphotungstic acid catalyst without mesoporous carbon sphere coating, the mesoporous carbon sphere coated zirconium species supported phosphotungstic acid has more excellent performance for synthesizing ammonia by electrocatalysis, 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 reported numerical values of the current same system work, and in addition, as can be seen from a graph in FIG. 4b, under the action of a space confinement, the electrocatalytic nitrogen reduction performance of the mesoporous carbon sphere coated zirconium species loaded phosphotungstic acid is basically kept unchanged after four-wheel stability experiment tests, and good synthetic ammonia performance stability is demonstrated.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A preparation method of a zirconium supported catalyst wrapped by mesoporous carbon spheres is characterized by comprising the following steps: taking tetrapropyl orthosilicate, tetraethyl orthosilicate, resorcinol and formaldehyde as raw materials, and preparing mesoporous hollow carbon spheres as an immobilized carrier of the catalyst by adopting a template method; then taking phosphotungstic acid and zirconium sulfate as raw materials, feeding in batches, heating and stirring under mild conditions, 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 the multilevel pore channels of the mesoporous hollow carbon sphere carrier by an impregnation method, and preparing the zirconium-loaded phosphotungstic acid catalyst wrapped by the mesoporous carbon spheres by utilizing the space confinement effect.
2. The method for preparing the mesoporous carbon sphere coated zirconium supported catalyst according to claim 1, wherein the method for preparing the mesoporous carbon sphere coated zirconium supported catalyst comprises the following steps:
(1) adding tetrapropyl orthosilicate and tetraethyl orthosilicate into a mixed solution containing ethanol, deionized water and concentrated ammonia water, violently stirring for 15-25 min, adding resorcinol and formaldehyde into the mixed solution, performing hydrolytic condensation, centrifuging and washing the mixed solution for multiple times by using the deionized water and the ethanol, and drying the collected precursor to obtain the SiO 2 @SiO 2 A phenolic resin precursor;
(2) SiO obtained by the step (1) 2 @SiO 2 Placing a phenolic resin precursor sample in a porcelain boat, calcining at high temperature for 5-6 h under the condition of argon gas for carbonization, and performing high-temperature carbonization treatment on the carbonized product to obtain SiO 2 @SiO 2 Conversion of phenolic resin precursors to SiO 2 @SiO 2 /C；
(3) Etching SiO with HF solution 2 @SiO 2 Removing SiO from the/C sample for 12-48 h 2 Carrying out centrifugal washing on 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, stirring at room temperature for 2-6 h, and then placing the mixed solution into a magnetic heating stirrer for heat treatment for 4-6 h to obtain a zirconium species supported phosphotungstic acid catalyst;
(5) and (3) dispersing the zirconium species supported phosphotungstic acid catalyst sample obtained in the step (4) in an ethanol solution, then immobilizing the zirconium species supported phosphotungstic acid catalyst in the mesoporous hollow carbon spheres by an impregnation method, ultrasonically dispersing 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.
3. The preparation method of the mesoporous carbon sphere coated zirconium supported catalyst according to claim 2, characterized by comprising the following steps: the molar ratio of the tetrapropyl orthosilicate to the tetraethyl orthosilicate in the step (1) is 1: 1-3.
4. The preparation method of the mesoporous carbon sphere coated zirconium supported catalyst according to claim 2, characterized by comprising the following steps: the volume ratio of the ethanol to the deionized water to the strong ammonia water in the step (1) is 70:30: 3; the mass ratio of the added resorcinol to the mixed solution is (0.4-1) g:103mL, 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.
5. The preparation method of the mesoporous carbon sphere coated zirconium supported catalyst according to claim 2, characterized by comprising the following steps: in the step (2), the temperature of the carbonization treatment is increased to 700-800 ℃ at the speed of 5-7 ℃/min.
6. The preparation method of the mesoporous carbon sphere coated zirconium supported catalyst according to claim 2, characterized by comprising the following steps: in the step (4), the molar ratio of phosphotungstic acid to zirconium sulfate is 100: 0.5-5; the heat treatment temperature is 60-200 ℃.
7. The preparation method of the mesoporous carbon sphere coated zirconium supported catalyst according to claim 2, characterized by comprising the following steps: in the step (5), the adding mass ratio of the zirconium supported phosphotungstic acid catalyst to the mesoporous hollow carbon spheres is 1: 9-30.
8. The zirconium-loaded phosphotungstic acid catalyst wrapped by the mesoporous carbon spheres prepared by the preparation method of any one of claims 1 to 7.
9. The use of the mesoporous carbon sphere-coated zirconium supported catalyst of claim 8 in an electrochemical ammonia synthesis reaction.
10. The application of the mesoporous carbon sphere coated zirconium supported catalyst in the reaction of electrochemically synthesizing ammonia according to claim 9, wherein the mesoporous carbon sphere coated zirconium supported catalyst comprises: the zirconium-supported catalyst wrapped by the mesoporous carbon spheres is dispersed in a mixed solution of ethanol and water, ultrasonic treatment is carried out for 0.5-1 h, the uniformly dispersed catalyst mixed solution is dropwise coated on hydrophilic carbon paper to assemble a working electrode, and a three-electrode system is utilized to carry out electrocatalytic ammonia synthesis reaction.
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