CN116764665B - Composite nitrogen-doped carbon catalyst and preparation method and application thereof - Google Patents
Composite nitrogen-doped carbon catalyst and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 108
- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- 239000002131 composite material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 49
- 239000003513 alkali Substances 0.000 claims abstract description 48
- 238000011282 treatment Methods 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000004933 hydrothermal crystal growth Methods 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 14
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 67
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- 150000002148 esters Chemical class 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- -1 hydroxide ions Chemical class 0.000 claims description 16
- 239000011268 mixed slurry Substances 0.000 claims description 15
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 13
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 11
- 150000000703 Cerium Chemical class 0.000 claims description 10
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 10
- 150000002009 diols Chemical group 0.000 claims description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000007853 buffer solution Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000011258 core-shell material Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 4
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 239000000872 buffer Substances 0.000 claims description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000007036 catalytic synthesis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 75
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 18
- 230000002194 synthesizing effect Effects 0.000 description 17
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 14
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229960004063 propylene glycol Drugs 0.000 description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 229940083957 1,2-butanediol Drugs 0.000 description 8
- 239000007983 Tris buffer Substances 0.000 description 8
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 8
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 7
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229940032296 ferric chloride Drugs 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 150000002118 epoxides Chemical group 0.000 description 2
- 229940093476 ethylene glycol Drugs 0.000 description 2
- 229960005150 glycerol Drugs 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920001690 polydopamine Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- ZXVOCOLRQJZVBW-UHFFFAOYSA-N azane;ethanol Chemical compound N.CCO ZXVOCOLRQJZVBW-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IJWQEEONDXVIGH-UHFFFAOYSA-N but-2-enyl hydrogen carbonate Chemical compound CC=CCOC(O)=O IJWQEEONDXVIGH-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
Abstract
The invention provides a composite nitrogen-doped carbon catalyst, and a preparation method and application thereof, belonging to the field of heterogeneous catalytic synthesis, wherein the preparation method comprises the following steps: mixing an iron source, alkali liquor, a template agent and a solvent, performing hydrothermal crystal growth treatment, and drying to obtain a template product; mixing the template product with a nitrogen-containing carbon source, performing polymerization reaction, and roasting for the first time to obtain a roasting product; and mixing the roasting product, a cerium source, alkali liquor and a solvent, performing hydrothermal crystallization growth treatment, and roasting for the second time to obtain the composite nitrogen-doped carbon catalyst. The invention provides a preparation method with simple process and low cost, and the preparation method is based on the preparation method to obtain the composite nitrogen-doped carbon catalyst which does not need a solvent or a carrier and has the advantages of high activity, high stability, high selectivity, strong recycling property and the like.
Description
Technical Field
The invention belongs to the field of heterogeneous catalytic synthesis, and particularly relates to a composite nitrogen-doped carbon catalyst, and a preparation method and application thereof.
Background
Cyclic carbonates have the characteristics of high boiling point, low odor, low toxicity, biodegradability and the like, and are important chemicals and organic intermediates. Among them, 1, 2-butenyl carbonate has important commercial value, and is mainly used for producing plasticizers, surfactants and reactive intermediate materials of polymers, and can also be used as degreasing solvents, paint removers, wood binder resins, foundry sand binders, and the like, and can also be used for battery electrolytes in lithium batteries, and the like. The synthesis of cyclic carbonates by transesterification of vicinal diols with linear carbonates is a green and high-value synthetic conversion route.
At present, the synthesis method of the cyclic carbonate mainly comprises a carbon dioxide and epoxide ring addition method, a direct coupling method of carbon dioxide and glycol, a urea alcoholysis method, an ester exchange method and the like. The ring addition method meets the requirements of green chemistry, but needs to react under the severe conditions of high temperature and high pressure, has potential safety hazards, and is not beneficial to industrial production because the sources of raw materials are easy to cause environmental pollution; the coupling method has higher yield, but needs higher reaction pressure, easy reaction explosion, harsh operation condition and lower safety coefficient; the catalyst in the urea alcoholysis method is easy to dissolve in an organic solvent, so that the purity of the product is reduced, and the subsequent separation is difficult. The transesterification method utilizes heterogeneous catalyst, utilizes glycol and carbonic ester to synthesize cyclic carbonic ester, and has simple and mild reaction conditions, easily obtained raw materials, easily separated products and low requirements on equipment, so the method is the most commonly used synthesis method at present.
The raw materials of the o-diol for synthesizing the cyclic carbonate by the transesterification method mainly comprise ethylene glycol, glycerol, 1, 2-butanediol, 1, 2-propanediol and the like, and the o-diol has a plurality of important application values, such as the manufacture of explosives, plastics, paint and the like. The catalysts commonly used in the transesterification method at present mainly comprise acid-base homogeneous catalysts (mainly acid alkali metal salts, ionic liquids and the like), heterogeneous acid-base catalysts (solid catalysts prepared from molecular sieves, modified alkali metal oxides, alkaline earth metal oxides and the like) and other lipase catalysts. For example, CN101108843B discloses a method for synthesizing cyclic carbonate in aqueous system, which uses epoxy compound and carbon dioxide as raw materials, and uses bidentate ionic liquid as catalyst and alkali metal salt as promoter in the reaction process. The synthesis method has the advantages of low cost, mild reaction conditions, high thermal stability, high selectivity and the like, and has strong industrial application potential. However, imidazole ring with methyl has low catalytic efficiency, needs to add a cocatalyst and has a complex catalytic system. CN105153104a discloses a method of using CO 2 The method for synthesizing propylene carbonate by using epoxide as a raw material comprises the steps of loading ionic liquid on bentonite as a catalyst, and synthesizing the propylene carbonate in a high-pressure reaction kettle. The catalyst provided by the method has high activity and strong selectivity, but needs to be loaded by a carrier, and is applied in actual application To a certain extent.
Therefore, the search for a heterogeneous transesterification catalyst with high activity and selectivity without solvent and carrier has great value and significance for producing high-quality cyclic carbonates.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a composite nitrogen-doped carbon catalyst, and a preparation method and application thereof. The invention provides a preparation method with simple process and low production cost, and the preparation method is based on the preparation method to obtain the composite nitrogen-doped carbon catalyst which does not need a solvent or a carrier and has the advantages of high activity, high stability, high selectivity, strong recycling property and the like.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a composite nitrogen-doped carbon catalyst, the method comprising the steps of:
(1) Mixing an iron source, alkali liquor, a template agent and a solvent, performing hydrothermal crystal growth treatment, and drying to obtain a template product;
(2) Mixing the template product with a nitrogen-containing carbon source, performing polymerization reaction, and roasting for the first time to obtain a roasting product;
(3) And mixing the roasting product, a cerium source, alkali liquor and a solvent, performing hydrothermal crystallization growth treatment, and roasting for the second time to obtain the composite nitrogen-doped carbon catalyst.
The invention provides a preparation method with simple process and low production cost, and the preparation method is based on the preparation method to obtain the composite nitrogen-doped carbon catalyst which does not need a solvent or a carrier and has the advantages of high activity, high stability, high selectivity, strong recycling property and the like.
In the present invention, the purpose of step (2) is to grow a nitrogen-containing catalyst on the surface of the template product. Thereby preparing the nitrogen-doped carbon catalyst with specific morphology and rich acid-base sites.
It should be noted that the present invention can obtain the composite nitrogen-doped carbon catalyst without removing the template, so that the problem of incomplete columnar structure due to the damage of a small part of features caused in the process of removing the template by acid treatment can be avoided.
As a preferable technical scheme of the invention, the iron source in the step (1) is soluble ferric salt.
Preferably, the soluble iron salt comprises any one or a combination of at least two of ferric nitrate, ferric chloride, ferric carbonate or ferric sulfate. Illustrative, typical, but non-limiting examples of combinations may be combinations of ferric nitrate and ferric chloride, ferric chloride and ferric carbonate, or ferric carbonate and ferric sulfate, etc., the ferric chloride may be ferric chloride hexahydrate or ferric nitrate nonahydrate, etc.
Preferably, the solute in the lye of step (1) comprises NaOH, KOH, naHCO 3 、Na 2 CO 3 Or any one or a combination of at least two of ammonia. Exemplary, but non-limiting, examples of combinations can be a combination of NaOH and KOH, KOH and NaHCO 3 Or NaHCO (combination of (C)) 3 And ammonia water, etc.
Preferably, the solvent of step (1) comprises deionized water.
Preferably, the concentration of hydroxide ions in the alkaline solution in the step (1) is 2 to 10mol/L, and for example, it may be 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L or 10mol/L, etc., but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the template agent in the step (1) comprises any one or a combination of at least two of sodium sulfate, sodium bisulfate or sodium dodecyl sulfate. Illustrative, typical, but non-limiting examples of combinations may be a combination of sodium sulfate and sodium bisulfate, a combination of sodium bisulfate and sodium dodecyl sulfate, or a combination of sodium sulfate and sodium dodecyl sulfate, and the like.
Preferably, the molar ratio of the iron source to the lye in step (1) is (0.25-0.5): 1, which may be, for example, 0.25:1, 0.3:1, 0.35:1, 0.4:1, 0.45:1 or 0.5:1, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the molar ratio of the iron source and the template agent in step (1) is 1 (0.025-0.05), and may be, for example, 1:0.025, 1:0.03, 1:0.035, 1:0.04, 1:0.045, or 1:0.05, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In a preferred embodiment of the present invention, the temperature of the mixing in the step (1) is 60 to 100. DegreeC, for example, 60. DegreeC, 70. DegreeC, 80. DegreeC, 90. DegreeC, 100. DegreeC, etc., but the present invention is not limited to the above-mentioned values, and other values not shown in the numerical range are applicable.
Preferably, the mixing in step (1) includes: stirring and mixing an iron source and a solvent to obtain an iron source solution, sequentially adding an alkali liquor and a template agent into the iron source solution, and continuously stirring and mixing to obtain mixed slurry.
Preferably, the means of addition comprises dropwise addition.
Preferably, the dropping rate is 60-150 drops/min, for example, 60 drops/min, 80 drops/min, 100 drops/min, 120 drops/min or 150 drops/min, etc., but the dropping rate is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the stirring and mixing are continued for 10-30min, for example, 10min, 15min, 20min, 25min or 30min, etc., but the stirring and mixing are not limited to the listed values, and other non-listed values in the numerical range are equally applicable.
The temperature of the hydrothermal crystal growth treatment in the step (1) is preferably 80 to 160 ℃, and may be, for example, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, or the like, but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the time of the hydrothermal crystal growth treatment in the step (1) is 60-120h, for example, 60h, 70h, 80h, 90h, 100h, 110h or 120h, etc., but the method is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, after the hydrothermal crystal growth treatment in step (1), a washing treatment is performed before drying.
Preferably, the drying temperature in the step (1) is 60 to 120 ℃, for example, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ or the like, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the drying time in step (1) is 8-24h, for example, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h, etc., but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
As a preferable technical scheme of the invention, the nitrogen-containing carbon source in the step (2) comprises dopamine hydrochloride.
Preferably, a buffer is also added during the mixing in step (2).
In the invention, the buffer solution is added to stabilize the pH of the solution, thereby being beneficial to the growth of polydopamine.
Preferably, the kind of the buffer solution includes any one of Tris-buffer solution, tris-HCl or ethanol-ammonia solution.
Preferably, the molar ratio of the template product and the nitrogen-containing carbon source in step (2) is 1 (1-4), and may be, for example, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, or 1:4, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the invention, if the molar ratio of the template product to the nitrogen-containing carbon source is too small, partial nitrogen-doped carbon structure is left, a spherical structure is spontaneously formed, and a columnar structure grown on the surface of a uniform template cannot be obtained; excessive molar ratios of template product to nitrogen-containing carbon source can result in incomplete coverage of a portion of the template surface and even no nitrogen-doped carbon growth.
Preferably, the molar ratio of the template product and the buffer in step (2) is 1 (2-4), and may be, for example, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8, 1:3, 1:3.2, 1:3.4, 1:3.6, 1:3.8, or 1:4, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the present invention, the polymerization reaction in the step (2) is carried out at a temperature of 20 to 50℃and may be carried out at 20℃30℃35℃40℃45℃50℃or the like.
Preferably, the polymerization reaction time in step (2) is 6-24h, for example, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h, etc., but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the temperature of the primary baking in the step (2) is 300 to 600 ℃, for example, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ or the like, but the method is not limited to the listed values, and other non-listed values in the numerical range are applicable.
Preferably, the time of the primary baking in the step (2) is 1-8h, for example, 1h, 2h, 3h, 4h, 5h, 6h, 7h or 8h, etc., but the present invention is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, after the polymerization reaction in the step (2) is completed, washing and drying are performed first, and then calcination is performed again.
As a preferred embodiment of the present invention, the cerium source in the step (3) is a soluble cerium salt.
Preferably, the soluble cerium salt includes any one or a combination of at least two of cerium nitrate, cerium chloride, cerium sulfate, or cerium acetate. Illustrative, typical, but non-limiting examples of the combination may be a combination of cerium nitrate and cerium chloride, a combination of cerium chloride and cerium sulfate, or a combination of cerium sulfate and cerium acetate, etc., and the cerium nitrate may be cerium nitrate hexahydrate, etc.
Preferably, the alkaline solution in step (3) comprises any one or a combination of at least two of sodium hydroxide solution, potassium hydroxide solution, urea solution or ammonia solution.
Preferably, the hydroxide ion concentration of the alkaline solution in the step (3) is 2-10mol/L, and may be, for example, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, or 10mol/L, etc., but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the molar ratio of the cerium source and the solute in the lye in step (3) is 1 (60-150), and may be, for example, 1:60, 1:70, 1:80, 1:9110, 1:100, 1:110, 1:120, 1:130, 1:140, or 1:150, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the molar ratio of the calcination product and cerium source in step (3) is (2-8): 1, and may be, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, or 8:1, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the invention, if the molar ratio of the roasting product to the cerium source is too small, the cerium oxide spontaneously grows into a rod-shaped structure; if the molar ratio of the calcined product to the cerium source is too large, the cerium source is insufficient, and a part of the surface of the calcined product cannot be uniformly coated with ceria.
Preferably, the temperature of the hydrothermal crystal growth treatment in the step (3) is 80 to 160 ℃, for example, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 600 ℃, or the like, but the method is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the time of the hydrothermal crystal growth treatment in the step (3) is 12-36h, for example, 12h, 16h, 20h, 24h, 28h, 32h or 36h, etc., but the method is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the temperature of the secondary baking in the step (3) is 300 to 600 ℃, for example, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ or the like, but the method is not limited to the listed values, and other non-listed values in the numerical range are applicable.
Preferably, the time of the secondary roasting in the step (3) is 2-8h, for example, 2h, 3h, 4h, 5h, 6h, 7h or 8h, etc., but the method is not limited to the listed values, and other non-listed values in the range of values are equally applicable.
Preferably, after the hydrothermal crystal growth treatment in the step (3), washing and drying are performed first, and then secondary roasting is performed.
As a preferred technical scheme of the invention, the primary roasting product in the step (3) is mixed with cerium source, alkali liquor and solvent, and the roasting product is subjected to the following steps:
and mixing the roasting product with an acid solution, and performing heat treatment.
According to the invention, the roasting product is subjected to acid etching by adopting an acid solution, so that the nitrogen-doped carbon catalyst with a hollow structure can be obtained.
Preferably, the solute in the acid solution comprises any one or a combination of at least two of hydrochloric acid, nitric acid, sulfuric acid or hydrofluoric acid, and exemplary, but non-limiting examples of the combination may be a combination of hydrochloric acid and nitric acid, a combination of nitric acid and sulfuric acid, or a combination of sulfuric acid and hydrofluoric acid, etc.
The hydrogen ion concentration of the acid solution is preferably 1 to 10mol/L, and may be, for example, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, or 10mol/L, etc., but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The temperature of the heat treatment is preferably 150 to 200 ℃, and may be 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, or the like, for example, but not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
Preferably, the heat treatment is performed for a period of time ranging from 12h to 36h, for example, 12h, 16h, 20h, 24h, 28h, 32h, or 36h, etc., but the heat treatment is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
stirring and mixing soluble ferric salt and deionized water at 60-100 ℃ for 2-30min to obtain an iron source solution, then sequentially dripping alkali liquor and a template agent into the iron source solution, and continuously stirring and mixing for 10-30min to obtain mixed slurry;
wherein, the mol ratio of the soluble ferric salt to the alkali solution is (0.25-0.5) 1, the mol ratio of the soluble ferric salt to the template agent is (0.025-0.05), the concentration of hydroxide ions of the alkali solution is 2-10mol/L, and the dropping rate is 60-150 drops/min;
(II) carrying out hydrothermal crystallization growth treatment on the mixed slurry for 80-110h at 80-120 ℃, then carrying out solid-liquid separation, washing the obtained solid to be neutral, and drying at 60-120 ℃ for 8-24h to obtain a template product;
(III) stirring and mixing the template product, the buffer solution and the nitrogen-containing carbon source, carrying out polymerization reaction at 25-50 ℃ for 6-24 hours, washing and drying after the reaction is finished, and then roasting at 300-600 ℃ for 1-8 hours to obtain a roasting product;
wherein, the molar ratio of the template product to the nitrogen-containing carbon source is 1 (1-4), the molar ratio of the template product to the buffer solution is 1 (2-4), the drying temperature is 50-100 ℃, and the drying time is 8-18h;
(IV) stirring and mixing the roasting product and the acid solution, and performing heat treatment at 160-200 ℃ for 12-36h;
wherein the concentration of hydrogen ions in the acid solution is 1-10mol/L;
(V) stirring and mixing the heat-treated product with soluble cerium salt, alkali liquor and solvent for 0.5-2h, performing hydrothermal crystal growth treatment, washing and drying, and performing secondary roasting at 300-600 ℃ for 2-8h to obtain the composite nitrogen-doped carbon catalyst;
wherein the mole ratio of the product after heat treatment to the soluble cerium salt is (2-8): 1, the mole ratio of the soluble cerium salt to the solute in the alkali solution is (60-150), the hydroxide ion concentration of the alkali solution is 2-10mol/L, the temperature of the hydrothermal crystal growth treatment is 80-160 ℃, the time of the hydrothermal crystal growth treatment is 12-36h, the drying temperature is 60-120 ℃, and the drying time is 8-18h.
In the step (III) of the present invention, the drying temperature is 50 to 100℃and may be, for example, 50℃60℃70℃80℃90℃100℃110℃or the like, but not limited to the values recited, and other values not recited in the numerical range are applicable as well.
In step (III) of the present invention, the drying time is 8 to 18 hours, for example, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours or 18 hours, etc., but not limited to the values recited, and other values not recited in the numerical range are equally applicable.
In the step (V) of the present invention, the stirring and mixing time is 0.5 to 2 hours, and for example, 0.5 hours, 0.8 hours, 1 hours, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours or 2 hours may be used, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the numerical range are applicable.
In the step (V) of the present invention, the drying temperature is 60 to 120℃and may be, for example, 60℃70℃80℃90℃100℃110℃120℃or the like, but not limited to the values recited, and other values not recited in the numerical range are applicable as well.
In step (V) of the present invention, the drying time is 8 to 18 hours, for example, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours or 18 hours, etc., but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
In a second aspect, the present invention provides a composite nitrogen-doped carbon catalyst prepared by the preparation method according to the first aspect;
the composite nitrogen-doped carbon catalyst has a core-shell structure, the inner core of the composite nitrogen-doped carbon catalyst is a nitrogen-doped carbon catalyst with a columnar structure, and the outer shell of the composite nitrogen-doped carbon catalyst is cerium dioxide.
The nitrogen-doped carbon catalyst with the columnar structure is a columnar structure, and can be hollow or solid. If the catalyst is hollow, the ferric oxide template in the nitrogen-doped carbon catalyst is removed, and if the catalyst is solid, the ferric oxide template in the nitrogen-doped carbon catalyst does not need to be removed.
In the invention, the solid nitrogen-doped carbon catalyst is taken as the inner core, which is favorable for forming a stable columnar nitrogen-doped carbon cladding structure, promoting the uniform growth of cerium oxide on the surface of the catalyst and forming strong interaction; the hollow nitrogen-doped carbon catalyst is used as the inner core, which is beneficial to increasing the specific surface area of the nitrogen-doped carbon, increasing the surface active sites and the defect number and the like. However, compared to hollow nitrogen-doped carbon catalysts, solid nitrogen-doped carbon catalysts can avoid the problem of incomplete morphology during template removal.
In a third aspect, the present invention provides the use of a composite nitrogen-doped carbon catalyst as described in the second aspect, for the synthesis of a cyclic carbonate.
Preferably, the specific steps of synthesizing the cyclic carbonate include:
mixing linear carbonic ester, o-diol and the composite nitrogen-doped carbon catalyst, and performing heating treatment to obtain the cyclic carbonic ester.
The invention takes the composite nitrogen-doped carbon catalyst as the catalyst, has mild synthesis condition and simple process, does not need organic solvent, high temperature, high pressure and other harsh conditions, and can prepare the cyclic carbonate with high selectivity, high yield and easy separation of products by using the carbonate and the vicinal diol.
Preferably, the vicinal diols include any one or a combination of at least two of ethylene glycol, glycerol, 1, 2-butanediol, or 1, 2-propanediol.
Preferably, the molar ratio of linear carbonate to vicinal diol is (1-10): 1, which may be, for example, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1, etc., but is not limited to the recited values, as other non-recited values within the range of values are equally applicable.
Preferably, the mass ratio of the composite nitrogen-doped carbon catalyst to the vicinal diol is (0.001-0.2): 1, for example, may be 0.001:1, 0.005:1, 0.01:1, 0.02:1, 0.04:1, 0.06:1, 0.08:1, 0.1:1, 0.12:1, 0.14:1, 0.16:1, 0.18:1, or 0.2:1, etc., but not limited to the recited values, other non-recited values within the numerical range are equally applicable.
The temperature of the heat treatment is preferably 80 to 200 ℃, and may be, for example, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, or the like, but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
Preferably, the heating treatment is performed for 20-300min, for example, 20min, 50min, 80min, 110min, 130min, 160min, 190min, 220min, 250min or 300min, etc., but the heating treatment is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
The numerical ranges recited herein include not only the above-listed point values, but also any point values between the above-listed numerical ranges that are not listed, and are limited in space and for the sake of brevity, the present invention is not intended to be exhaustive of the specific point values that the stated ranges include.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a preparation method with simple process and low production cost, and the composite nitrogen-doped carbon catalyst which does not need a solvent or a carrier, has the advantages of high activity, high stability, high selectivity, strong recycling property and the like can be prepared based on the preparation method.
(2) Compared with other synthetic routes, the catalyst prepared by the invention has the advantages of simple process, mild experimental conditions, no need of solvents, high temperature, high pressure and other harsh conditions, shorter reaction time, easy separation of the catalyst and the product, high o-glycol conversion rate of more than 99 percent and high yield of more than 99 percent.
Drawings
Fig. 1 is an SEM image of a composite nitrogen-doped carbon catalyst prepared in example 1 of the present invention.
Fig. 2 is an SEM image of the composite nitrogen-doped carbon catalyst prepared in example 10 of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method of a composite nitrogen-doped carbon catalyst, which comprises the following steps:
(1) 13.52g of FeCl 3 ·6H 2 O and 30mL of deionized water are stirred and mixed for 5min at 70 ℃ to obtain FeCl 3 Solution, 5.4g NaOH and 30mL deionized water were mixed for 20min,0.213g Na 2 SO 4 Mixing with 5mL deionized water for 10min to obtain alkali solution and template solution, respectively, and sequentially dripping the alkali solution and template solution into FeCl 3 Stirring and mixing the solution for 30min to obtain mixed slurry;
wherein FeCl 3 ·6H 2 The molar ratio of O to NaOH is 0.37:1, feCl 3 ·6H 2 O and Na 2 SO 4 The molar ratio of the alkali solution to the solution is 1:0.03, the hydroxide ion concentration of the alkali solution is 6mol/L, and the dripping rate is 100 drops/min;
(2) Transferring the mixed slurry into a 100mL hydrothermal kettle with a polytetrafluoroethylene lining, performing hydrothermal crystal growth treatment on the mixed slurry at 100 ℃ for 100 hours, performing solid-liquid separation after the reaction is finished, washing the obtained solid to be neutral by using water and ethanol, and drying at 80 ℃ for 12 hours to obtain a template product, namely ferric oxide particles;
(3) Adding the template product into a Tris-buffer solution with the concentration of 10mmol/L, then adding dopamine hydrochloride with the concentration of 2.5mmol, performing polymerization reaction at the temperature of 30 ℃ for 10 hours, washing the template product with ethanol and water after the reaction is finished, drying the template product at the temperature of 80 ℃ for 12 hours, and then roasting the template product at the temperature of 450 ℃ for 2 hours to obtain a roasted product;
wherein, the mol ratio of the template product to the dopamine hydrochloride is 1:2, and the mol ratio of the template product to the Tris-buffer is 1:2;
(4) Stirring and mixing the roasting product and 1mol/L hydrochloric acid solution, and performing heat treatment at 170 ℃ for 20 hours to remove the ferric oxide template;
(5) 0.72g of the heat treated product and 1.736g of Ce (NO 3 ) 3 ·6H 2 O was placed in 15mL of deionized water, 20.0g of NaOH was placed in 65mL of deionized waterObtaining alkali liquor in water, dripping the alkali liquor into the water containing the heat-treated product and Ce (NO) 3 ) 3 Stirring for 1h at room temperature after the dripping is finished, transferring to a 100mL hydrothermal kettle with a polytetrafluoroethylene lining, performing hydrothermal crystal growth treatment at 100 ℃ for 20h, washing with water and washing with alcohol to be neutral, drying at 70 ℃ for 12h, and then performing secondary roasting at 500 ℃ for 2h to obtain the composite nitrogen-doped carbon catalyst with a core-shell structure, wherein the core is the nitrogen-doped carbon catalyst with a hollow columnar structure, and the shell is cerium dioxide;
wherein the heat treated product and Ce (NO 3 ) 3 ·6H 2 The molar ratio of O is 5.5:1, ce (NO 3 ) 3 ·6H 2 The mol ratio of O to NaOH is 1:125, and the hydroxide ion concentration of the alkali liquor is 6mol/L.
The embodiment also provides a method for synthesizing the cyclic carbonate by adopting the composite nitrogen-doped carbon catalyst, which comprises the following steps:
9.6g of linear carbonate, 4.8g of 1, 2-butanediol and 0.048g of composite nitrogen-doped carbon catalyst are added into a 50mL reaction kettle, continuously stirred at 500rpm, heated at 120 ℃ and reacted for 30min to obtain cyclic carbonate;
Wherein, the mol ratio of the linear carbonic ester to the 1, 2-butanediol is 2:1, and the mass ratio of the composite nitrogen-doped carbon catalyst to the vicinal diol is 0.01:1.
Example 2
The present embodiment differs from embodiment 1 in that the method for synthesizing a cyclic carbonate provided in the present embodiment includes the steps of:
9.6g of linear carbonate, 3.3g of ethylene glycol and 0.03g of composite nitrogen-doped carbon catalyst are added into a 50mL reaction kettle, continuously stirred at 500rpm, heated at 140 ℃ and reacted for 40min to obtain cyclic carbonate;
wherein, the mol ratio of the linear carbonic ester to the ethylene glycol is 2:1, and the mass ratio of the composite nitrogen-doped carbon catalyst to the ethylene glycol is 0.01:1.
The remaining preparation methods and parameters remain the same as in example 1.
Example 3
The present embodiment differs from embodiment 1 in that the method for synthesizing a cyclic carbonate provided in the present embodiment includes the steps of:
9.6g of linear carbonate, 4.9g of ethylene glycol and 0.049g of composite nitrogen-doped carbon catalyst are added into a 50mL reaction kettle, continuously stirred at 500rpm, heated at 150 ℃ and reacted for 80min to obtain cyclic carbonate;
wherein, the mol ratio of the linear carbonic ester to the ethylene glycol is 1.3:1, and the mass ratio of the composite nitrogen-doped carbon catalyst to the ethylene glycol is 0.01:1.
The remaining preparation methods and parameters remain the same as in example 1.
Example 4
The present embodiment differs from embodiment 1 in that the method for synthesizing a cyclic carbonate provided in the present embodiment includes the steps of:
18g of linear carbonic ester, 4.05g of 1, 2-propylene glycol and 0.04g of composite nitrogen-doped carbon catalyst are added into a 50mL reaction kettle, continuously stirred at 750rpm, heated at 150 ℃ and reacted for 40min to obtain cyclic carbonic ester;
wherein, the mol ratio of the linear carbonic ester to the 1, 2-propylene glycol is 3.8:1, and the mass ratio of the composite nitrogen-doped carbon catalyst to the 1, 2-propylene glycol is 0.01:1.
The remaining preparation methods and parameters remain the same as in example 1.
Example 5
The present embodiment differs from embodiment 1 in that the method for synthesizing a cyclic carbonate provided in the present embodiment includes the steps of:
18g of linear carbonic ester, 4.05g of 1, 2-propylene glycol and 0.04g of composite nitrogen-doped carbon catalyst are added into a 50mL reaction kettle, continuously stirred at 500rpm, heated at 160 ℃ and reacted for 60min to obtain cyclic carbonic ester;
wherein, the mol ratio of the linear carbonic ester to the 1, 2-propylene glycol is 3.8:1, and the mass ratio of the composite nitrogen-doped carbon catalyst to the 1, 2-propylene glycol is 0.01:1.
The remaining preparation methods and parameters remain the same as in example 1.
Example 6
The present embodiment differs from embodiment 1 in that the method for synthesizing a cyclic carbonate provided in the present embodiment includes the steps of:
18g of linear carbonate, 4.8g of 2, 3-butanediol and 0.048g of composite nitrogen-doped carbon catalyst are added into a 50mL reaction kettle, continuously stirred at 500rpm, and subjected to heating treatment at 160 ℃ for 60min to obtain cyclic carbonate;
wherein, the mol ratio of the linear carbonic ester to the 2, 3-butanediol is 3.8:1, and the mass ratio of the composite nitrogen-doped carbon catalyst to the 2, 3-butanediol is 0.01:1.
The remaining preparation methods and parameters remain the same as in example 1.
Example 7
The difference between this example and example 1 is that in the method for synthesizing carbonate, the catalyst used in example 1 is selected as the composite nitrogen-doped carbon catalyst, and the catalyst is recycled five times after being washed and dried for a plurality of times.
The remaining preparation methods and parameters remain the same as in example 1.
Example 8
The embodiment provides a preparation method of a composite nitrogen-doped carbon catalyst, which comprises the following steps:
(1) 20.21g of ferric nitrate nonahydrate and 30mL of deionized water are stirred and mixed for 5min at 70 ℃ to obtain ferric nitrate solution, 7.56g of KOH and 30mL of deionized water are mixed for 20min, and 0.213g of NaHSO is obtained 4 Mixing with 5mL of deionized water for 10min to obtain an alkali solution and a template solution respectively, sequentially dripping the alkali solution and the template solution into an iron nitrate solution, and continuously stirring and mixing for 30min to obtain mixed slurry;
wherein, the mol ratio of the ferric nitrate nonahydrate to the KOH is 0.37:1, and the ferric nitrate nonahydrate and the NaHSO are prepared 4 The molar ratio of the alkali solution to the solution is 1:0.04, the hydroxide ion concentration of the alkali solution is 2mol/L, and the dripping rate is 60 drops/min;
(2) Transferring the mixed slurry into a 100mL hydrothermal kettle with a polytetrafluoroethylene lining, performing hydrothermal crystal growth treatment on the mixed slurry at 80 ℃ for 110 hours, performing solid-liquid separation after the reaction is finished, washing the obtained solid to be neutral by using water and ethanol, and drying at 60 ℃ for 24 hours to obtain a template product, namely ferric oxide particles;
(3) Adding the template product into a Tris-buffer solution with the concentration of 15mmol/L, then adding 2.5mmol of dopamine hydrochloride, carrying out a polymerization reaction at the temperature of 30 ℃ for 6 hours, washing the template product with ethanol and water after the reaction is finished, drying the template product at the temperature of 50 ℃ for 18 hours, and then roasting the template product at the temperature of 450 ℃ for 7 hours to obtain a roasted product;
wherein, the mol ratio of the template product to the dopamine hydrochloride is 1:1, and the mol ratio of the template product to the Tris-buffer is 1:2;
(4) Stirring and mixing the roasting product and 2mol/L hydrochloric acid solution, and performing heat treatment at 160 ℃ for 36 hours to remove the ferric oxide template;
(5) Placing 0.72g of the heat-treated product and 0.986g of cerium chloride in 15mL of deionized water, placing 13.44g of KOH in 65mL of deionized water to obtain an alkali liquor, dripping the alkali liquor into a solution containing the heat-treated product and cerium chloride, stirring at room temperature for 0.5h after dripping, transferring into a 100mL hydrothermal kettle with a polytetrafluoroethylene lining, performing hydrothermal crystal growth treatment at 80 ℃ for 36h, washing with water and washing with alcohol to neutrality, drying at 90 ℃ for 10h, and performing secondary roasting at 300 ℃ for 8h to obtain a composite nitrogen-doped carbon catalyst with a core-shell structure, wherein the core is a nitrogen-doped carbon catalyst with a hollow columnar structure, and the shell is cerium dioxide;
wherein the molar ratio of the product after heat treatment to cerium chloride is 7:1, the molar ratio of cerium chloride to KOH is 1:60, and the hydroxide ion concentration of alkali liquor is 2mol/L.
The embodiment also provides a method for synthesizing the cyclic carbonate by adopting the composite nitrogen-doped carbon catalyst, which comprises the following steps:
9.6g of linear carbonate, 4.8g of 1, 2-butanediol and 0.0048g of composite nitrogen-doped carbon catalyst are added into a 50mL reaction kettle, continuously stirred at 500rpm, heated at 120 ℃ for 30min, and then the cyclic carbonate is obtained;
wherein, the mol ratio of the linear carbonic ester to the 1, 2-butanediol is 2:1, and the mass ratio of the composite nitrogen-doped carbon catalyst to the vicinal diol is 0.001:1.
Example 9
The embodiment provides a preparation method of a composite nitrogen-doped carbon catalyst, which comprises the following steps:
(1) Mixing 20.00g of ferric sulfate and 30mL of deionized water at 70 ℃ for 5min to obtain a ferric sulfate solution, mixing 6.0g of urea and 30mL of deionized water for 20min, mixing 0.213g of sodium dodecyl sulfate and 5mL of deionized water for 10min to respectively obtain an alkali solution and a template solution, sequentially dripping the alkali solution and the template solution into the ferric sulfate solution, and continuously stirring and mixing for 30min to obtain mixed slurry;
wherein, the mol ratio of ferric sulfate to urea is 0.5:1, the mol ratio of ferric sulfate to sodium dodecyl sulfate is 1:0.05, the hydroxide ion concentration of alkali liquor is 10mol/L, and the dripping rate is 150 drops/min;
(2) Transferring the mixed slurry into a 100mL hydrothermal kettle with a polytetrafluoroethylene lining, performing hydrothermal crystal growth treatment on the mixed slurry at 120 ℃ for 80 hours, performing solid-liquid separation after the reaction is finished, washing the obtained solid to be neutral by using water and ethanol, and drying at 120 ℃ for 8 hours to obtain a template product, namely ferric oxide particles;
(3) Adding the template product into a Tris-buffer solution with the concentration of 20mmol/L, then adding dopamine hydrochloride with the concentration of 5mmol, carrying out a polymerization reaction at room temperature for 24 hours, washing the template product with ethanol and water after the reaction is finished, drying the template product at 100 ℃ for 18 hours, and roasting the template product at 500 ℃ for 6 hours to obtain a roasted product;
wherein, the mol ratio of the template product to the dopamine hydrochloride is 1:4, and the mol ratio of the template product to the Tris-buffer is 1:4;
(4) Stirring and mixing the roasting product and 1mol/L hydrochloric acid solution, and performing heat treatment at 200 ℃ for 12 hours to remove the ferric oxide template;
(5) Placing 0.72g of the heat-treated product and 3.13g of cerium sulfate in 15mL of deionized water, placing 46.25g of KOH in 65mL of deionized water to obtain an alkali liquor, dripping the alkali liquor into a solution containing the heat-treated product and cerium sulfate, stirring at 30 ℃ for 2 hours after dripping, transferring the solution into a 100mL hydrothermal kettle with a polytetrafluoroethylene lining, performing hydrothermal crystal growth treatment at 160 ℃ for 12 hours, washing with water and washing with alcohol to neutrality, drying at 120 ℃ for 8 hours, and roasting at 600 ℃ for three times for 2 hours to obtain the composite nitrogen-doped carbon catalyst with a core-shell structure, wherein the core is the nitrogen-doped carbon catalyst with a hollow columnar structure and the shell is cerium dioxide;
Wherein, the mol ratio of the product after heat treatment to cerium sulfate is 5:1, the mol ratio of cerium sulfate to KOH is 1:150, and the hydroxide ion concentration of alkali liquor is 10mol/L.
The embodiment also provides a method for synthesizing the cyclic carbonate by adopting the composite nitrogen-doped carbon catalyst, which comprises the following steps:
48.0g of linear carbonate, 4.8g of 1, 2-butanediol and 0.096g of composite nitrogen-doped carbon catalyst are added into a 50mL reaction kettle, continuously stirred at 500rpm, heated at 120 ℃ for 30min, and then the cyclic carbonate is obtained;
wherein, the mol ratio of the linear carbonic ester to the 1, 2-butanediol is 10:1, and the mass ratio of the composite nitrogen-doped carbon catalyst to the vicinal diol is 0.02:1.
Example 10
This example differs from example 1 in that step (4) is not performed, i.e., the iron oxide template is not removed.
The remaining preparation methods and parameters remain the same as in example 1.
Fig. 1 and 2 show SEM images of the composite nitrogen-doped carbon catalysts prepared in examples 1 and 10, respectively, and it is understood that the columnar structure of the catalyst obtained in example 10 is more stable and complete.
Example 11
This example differs from example 1 in that the molar ratio of template product to dopamine hydrochloride in step (3) is 1:0.5.
The remaining preparation methods and parameters remain the same as in example 1.
Example 12
This example differs from example 1 in that the molar ratio of template product to dopamine hydrochloride in step (3) is 1:5.
The remaining preparation methods and parameters remain the same as in example 1.
Example 13
This example differs from example 1 in that the calcination product of step (5) and Ce (NO) 3 ) 3 ·6H 2 The molar ratio of O is 1:1.
The remaining preparation methods and parameters remain the same as in example 1.
Example 14
This example differs from example 1 in that the calcination product of step (5) and Ce (NO) 3 ) 3 ·6H 2 The molar ratio of O was 10:1.
The remaining preparation methods and parameters remain the same as in example 1.
Comparative example 1
This comparative example differs from example 1 in that steps (3) - (5) are not performed.
The remaining preparation methods and parameters remain the same as in example 1.
Comparative example 2
This comparative example differs from example 1 in that step (5) was not performed.
The remaining preparation methods and parameters remain the same as in example 1.
Comparative example 3
The comparative example provides a method for preparing a composite nitrogen-doped carbon catalyst, comprising the following steps:
(1) Adding 2.5mmol of dopamine hydrochloride into 10mmol/L Tris-buffer solution, performing polymerization treatment at room temperature for 10 hours, washing with ethanol and water, drying at 80 ℃ for 12 hours, and roasting at 450 ℃ for 2 hours to obtain a carbon nitride catalyst;
(2) Mixing 0.72g of the carbon nitride catalyst obtained in the step (1) with 1.736g of Ce (NO) 3 ) 3 ·6H 2 O is placed in 15mL of deionized water, 20g of NaOH is placed in 65mL of deionized water to obtain alkali liquor, and the alkali liquor is dropwise added to the carbon nitride catalyst and Ce (NO) 3 ) 3 After the dripping is finished, placing the mixture in a room temperature environment for continuous stirring for 1h, transferring the mixture into a 100mL hydrothermal kettle with a polytetrafluoroethylene lining, performing hydrothermal crystal growth treatment at 100 ℃ for 20h, washing with water and alcohol to be neutral, drying at 70 ℃ for 12h, and performing secondary roasting at 500 ℃ for 2h to obtain the composite nitrogen-doped carbon catalyst with a core-shell structure, wherein the core is the nitrogen-doped carbon catalyst with a hollow columnar structure, and the shell is cerium dioxide.
The remaining preparation methods and parameters remain the same as in example 1.
Performance testing
The cyclic carbonate solutions obtained in examples 1 to 14 and comparative examples 1 to 3 were centrifuged at 3000rpm for 3min, and an appropriate amount of the supernatant was added to biphenyl and quantitatively analyzed by a gas chromatography internal standard method.
The test results are shown in Table 1.
TABLE 1
Analysis:
as can be seen from the table, when the composite nitrogen-doped carbon catalyst prepared by the invention is applied to the synthesis of the cyclic carbonate, the o-diol conversion rate is more than or equal to 97.8%, the selectivity of the cyclic carbonate is more than or equal to 99%, and the yield of the cyclic carbonate is more than 97%.
As can be seen from the data of example 1 and example 7, the composite nitrogen-doped carbon catalyst prepared by the invention has good catalytic effect when being recycled for 5 times, and the yield of the cyclic carbonate is still more than or equal to 97%.
From the data of examples 1-5, it can be seen that the composite nitrogen-doped carbon catalyst prepared by the invention can achieve quite high selectivity and yield for the corresponding cyclic carbonate product, whether for ethylene glycol, 1, 2-propylene glycol, glycerol, 2, 3-butylene glycol or 1, 2-propylene glycol.
From the data of examples 1 and 10, it is clear that the resulting composite nitrogen-doped carbon catalyst can maintain a stable columnar nitrogen-doped carbon structure and form a strong interaction with ferric oxide when the core nitrogen-doped carbon catalyst does not remove the internal ferric oxide template.
From the data of examples 1 and 11-12, it is clear that if the molar ratio of the template product to dopamine hydrochloride is too small, part of polydopamine grows into spheres alone, and cannot grow on the template, so that the catalytic effect is affected; if the molar ratio of the template product to the dopamine hydrochloride is too large, a part of the wood board surface cannot obtain a perfect nitrogen-doped carbon coating structure, and the catalytic effect is affected.
As is clear from the data of example 1 and examples 13 to 14, if the calcined product and Ce (NO 3 ) 3 ·6H 2 If the molar ratio of O is too small, partial ceria can form a rod-shaped structure, and nitrogen-doped carbon cannot be completely coated; if the product is calcined and Ce (NO) 3 ) 3 ·6H 2 When the molar ratio of O is too large, a completely coated ceria structure cannot be formed on the surface of the partially nitrogen-doped carbon, and the catalytic activity is reduced.
From the data of example 1 and comparative example 1, it is apparent that if the prepared composite nitrogen-doped carbon catalyst is columnar ferric oxide particles, the selectivity and yield of the cyclic carbonate are low in the process of synthesizing the cyclic carbonate due to the single active site of ferric oxide and poor catalytic activity.
As is apparent from the data of example 1 and comparative example 2, if the prepared composite nitrogen-doped carbon catalyst is columnar nitrogen-doped carbon (no ceria), the acid-base double active site is weak and the catalytic activity is poor due to the presence of only a single nitrogen-doped carbon active site, so that the selectivity and yield of the cyclic carbonate are low in the process of synthesizing the cyclic carbonate.
From the data of example 1 and comparative example 3, it is understood that when the composite nitrogen-doped carbon catalyst is prepared by the non-template method, the columnar nitrogen-doped carbon structure cannot be obtained, the specific surface area is small, the active sites are few, and thus the selectivity and the yield of the cyclic carbonate are low in the process of synthesizing the cyclic carbonate.
The applicant states that the technical solution of the present invention is illustrated by the above embodiments, but the present invention is not limited to the above embodiments, i.e. it does not mean that the present invention must be implemented by the above embodiments. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A method for preparing a composite nitrogen-doped carbon catalyst, which is characterized by comprising the following steps:
(1) Mixing an iron source, alkali liquor, a template agent and a solvent, performing hydrothermal crystal growth treatment, and drying to obtain a template product;
(2) Mixing the template product with a nitrogen-containing carbon source, performing polymerization reaction, and roasting for the first time to obtain a roasting product;
(3) Mixing the roasting product, a cerium source, alkali liquor and a solvent, performing hydrothermal crystallization growth treatment, and roasting for the second time to obtain the composite nitrogen-doped carbon catalyst;
the template agent in the step (1) comprises any one or a combination of at least two of sodium sulfate, sodium bisulfate or sodium dodecyl sulfate;
The temperature of the hydrothermal crystal growth treatment in the step (1) is 80-160 ℃; the time of the hydrothermal crystal growth treatment in the step (1) is 60-120h;
the nitrogen-containing carbon source in the step (2) comprises dopamine hydrochloride;
the temperature of the polymerization reaction in the step (2) is 20-50 ℃; the polymerization reaction time in the step (2) is 6-24 hours;
the temperature of the primary roasting in the step (2) is 300-600 ℃; the time of the primary roasting in the step (2) is 1-8 hours;
the temperature of the hydrothermal crystal growth treatment in the step (3) is 80-160 ℃; the time of the hydrothermal crystal growth treatment in the step (3) is 12-36h;
the temperature of the secondary roasting in the step (3) is 300-600 ℃; and (3) the secondary roasting time is 2-8h.
2. The method of claim 1, wherein the iron source in step (1) is a soluble iron salt;
in the alkali liquor in the step (1), the concentration of hydroxide ions is 2-10mol/L;
the molar ratio of the iron source to the alkali liquor in the step (1) is (0.25-0.5): 1;
the molar ratio of the iron source to the template agent in the step (1) is 1 (0.025-0.05).
3. The method of claim 1, wherein the temperature of the mixing in step (1) is 60-100 ℃;
The mixing mode in the step (1) comprises the following steps: stirring and mixing an iron source and a solvent to obtain an iron source solution, sequentially adding an alkali liquor and a template agent into the iron source solution, and continuously stirring and mixing to obtain mixed slurry;
washing the crystals after the hydrothermal crystal growth treatment in the step (1) and before drying;
the drying temperature in the step (1) is 60-120 ℃;
the drying time in the step (1) is 8-24h.
4. The method of claim 1, wherein a buffer is further added during the mixing of step (2);
the molar ratio of the template product to the nitrogen-containing carbon source in the step (2) is 1 (1-4);
the molar ratio of the template product and the buffer solution in the step (2) is 1 (2-4).
5. The process according to claim 1, wherein after the polymerization reaction in step (2) is completed, the mixture is washed and dried, and then calcined.
6. The method of claim 1, wherein the cerium source of step (3) is a soluble cerium salt;
the soluble cerium salt comprises any one or a combination of at least two of cerium nitrate, cerium chloride, cerium sulfate or cerium acetate;
The hydroxide ion concentration of the alkali liquor in the step (3) is 2-10mol/L;
the molar ratio of the cerium source to the solute in the alkali liquor in the step (3) is 1 (60-150);
the molar ratio of the roasting product and the cerium source in the step (3) is (2-8): 1;
and (3) after the hydrothermal crystal growth treatment, washing and drying are carried out, and then secondary roasting is carried out.
7. The method according to claim 1, wherein the step (3) is performed by mixing the calcined product with a cerium source, an alkali solution and a solvent, followed by the steps of:
mixing the roasting product with an acid solution, and performing heat treatment;
the concentration of hydrogen ions in the acid solution is 1-10mol/L;
the temperature of the heat treatment is 150-200 ℃;
the heat treatment time is 12-36h.
8. The preparation method according to any one of claims 1 to 7, characterized in that the preparation method comprises the steps of:
stirring and mixing soluble ferric salt and deionized water at 60-100 ℃ for 2-30min to obtain an iron source solution, then sequentially dripping alkali liquor and a template agent into the iron source solution, and continuously stirring and mixing for 10-30min to obtain mixed slurry;
wherein, the mol ratio of the soluble ferric salt to the alkali solution is (0.25-0.5) 1, the mol ratio of the soluble ferric salt to the template agent is (0.025-0.05), the concentration of hydroxide ion of the alkali solution is 2-10mol/L, and the dripping rate is 60-150 drops/min;
(II) carrying out hydrothermal crystallization growth treatment on the mixed slurry for 80-110h at 80-120 ℃, then carrying out solid-liquid separation, washing the obtained solid to be neutral, and drying at 60-120 ℃ for 8-24h to obtain a template product;
(III) stirring and mixing the template product, the buffer solution and the nitrogen-containing carbon source, carrying out polymerization reaction at 25-50 ℃ for 6-24 hours, washing and drying after the reaction is finished, and then roasting at 300-600 ℃ for 1-8 hours to obtain a roasting product;
wherein, the molar ratio of the template product to the nitrogen-containing carbon source is 1 (1-4), the molar ratio of the template product to the buffer solution is 1 (2-4), the drying temperature is 50-100 ℃, and the drying time is 8-18h;
(IV) stirring and mixing the roasting product and the acid solution, and performing heat treatment at 160-200 ℃ for 12-36h;
wherein the concentration of hydrogen ions in the acid solution is 1-10mol/L;
(V) stirring and mixing the heat-treated product with soluble cerium salt, alkali liquor and solvent for 0.5-2h, performing hydrothermal crystal growth treatment, washing and drying, and performing secondary roasting at 300-600 ℃ for 2-8h to obtain the composite nitrogen-doped carbon catalyst;
wherein the mole ratio of the product after heat treatment to the soluble cerium salt is (2-8): 1, the mole ratio of the soluble cerium salt to the solute in the alkali solution is (60-150), the hydroxide ion concentration of the alkali solution is 2-10mol/L, the temperature of the hydrothermal crystal growth treatment is 80-160 ℃, the time of the hydrothermal crystal growth treatment is 12-36h, the drying temperature is 60-120 ℃, and the drying time is 8-18h.
9. A composite nitrogen-doped carbon catalyst, characterized in that the composite nitrogen-doped carbon catalyst is prepared by the preparation method according to any one of claims 1 to 8;
the composite nitrogen-doped carbon catalyst has a core-shell structure, the inner core of the composite nitrogen-doped carbon catalyst is a nitrogen-doped carbon catalyst with a columnar structure, and the outer shell of the composite nitrogen-doped carbon catalyst is cerium dioxide.
10. Use of the composite nitrogen-doped carbon catalyst according to claim 9 for the synthesis of cyclic carbonates;
the specific steps of the synthesis of the cyclic carbonate comprise:
mixing linear carbonic ester, o-diol and the composite nitrogen-doped carbon catalyst, and performing heating treatment to obtain cyclic carbonic ester;
the molar ratio of the linear carbonic ester to the vicinal diol is (1-10): 1;
the mass ratio of the composite nitrogen-doped carbon catalyst to the vicinal diol is (0.001-0.2): 1;
the temperature of the heating treatment is 80-200 ℃;
the heating treatment time is 20-300min.
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