CN110628038A - Covalent triazine organic framework, limited-area metal catalyst, preparation method and application - Google Patents
Covalent triazine organic framework, limited-area metal catalyst, preparation method and application Download PDFInfo
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- CN110628038A CN110628038A CN201910887666.6A CN201910887666A CN110628038A CN 110628038 A CN110628038 A CN 110628038A CN 201910887666 A CN201910887666 A CN 201910887666A CN 110628038 A CN110628038 A CN 110628038A
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- organic framework
- covalent triazine
- metal catalyst
- triazine organic
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000013384 organic framework Substances 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 46
- 239000002184 metal Substances 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 12
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000006722 reduction reaction Methods 0.000 claims description 30
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- UHAGMGPUCFRHSM-UHFFFAOYSA-N 4-(4-carbamimidoylphenyl)benzenecarboximidamide Chemical compound C1=CC(C(=N)N)=CC=C1C1=CC=C(C(N)=N)C=C1 UHAGMGPUCFRHSM-UHFFFAOYSA-N 0.000 claims description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- GRXRSNXVJUQKDL-UHFFFAOYSA-N 6-(5-carbamimidoylpyridin-2-yl)pyridine-3-carboximidamide Chemical compound C1=CC(=NC=C1C(=N)N)C2=NC=C(C=C2)C(=N)N GRXRSNXVJUQKDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 claims description 3
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims description 3
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 3
- 229910021576 Iron(III) bromide Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- DTMHTVJOHYTUHE-UHFFFAOYSA-N thiocyanogen Chemical compound N#CSSC#N DTMHTVJOHYTUHE-UHFFFAOYSA-N 0.000 claims description 3
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 230000009467 reduction Effects 0.000 abstract description 12
- 230000001105 regulatory effect Effects 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- -1 dimethyl amidino compound Chemical class 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 238000009795 derivation Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004873 anchoring Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910017488 Cu K Inorganic materials 0.000 description 4
- 229910017541 Cu-K Inorganic materials 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 238000001144 powder X-ray diffraction data Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000013354 porous framework Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- DVXJDRMCWWERRO-UHFFFAOYSA-N [6-[5-(hydroxymethyl)pyridin-2-yl]pyridin-3-yl]methanol Chemical compound N1=CC(CO)=CC=C1C1=CC=C(CO)C=N1 DVXJDRMCWWERRO-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000002253 near-edge X-ray absorption fine structure spectrum Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- VIESAWGOYVNHLV-UHFFFAOYSA-N 1,3-dihydropyrrol-2-one Chemical compound O=C1CC=CN1 VIESAWGOYVNHLV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000012088 reference solution Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- IWOKCMBOJXYDEE-UHFFFAOYSA-N sulfinylmethane Chemical compound C=S=O IWOKCMBOJXYDEE-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
The invention provides a covalent triazine organic framework, a limited metal catalyst, a preparation method and application, wherein the covalent triazine organic framework comprises a heteroatom N, metal ions are anchored through the heteroatom, the limited metal catalyst is prepared, the density and the relative distance of metal active centers can be regulated and controlled by regulating and controlling the structure of the covalent triazine organic framework and the relative content of coordination heteroatoms, and the structure derivation of the limited metal in the in-situ reaction process is realized by utilizing a porous skeleton structure with coordination heteroatom N sites, so that high-activity and high-selectivity catalytic sites are formed; the covalent triazine organic framework is synthesized by precursors of a dimethyl alcohol-based compound and a dimethyl amidino compound, and the preparation method is mild and can be largeThe method has the advantages of quantitative synthesis and wide applicability; application of confined metal catalyst in electrocatalysis of CO2The reaction has good activity and selectivity for generating multi-electron transfer products in CO reduction.
Description
Technical Field
The invention belongs to the field of electrochemical catalysis, and relates to a covalent triazine organic framework, a limited-area metal catalyst, a preparation method and an application.
Background
Electrochemical CO2The reduction (ERC) technique is to utilize electric energy to convert CO2Reduction to various organic chemicals to realize CO2A technique for resource utilization which can convert CO under mild conditions2The conversion into fuel or chemical with high added value has important practical significance.
But at present, electrochemical CO2The reduction has the bottleneck problems of poor catalytic activity of the electrochemical catalyst, high overpotential of ERC reaction, low Faraday efficiency and the like, and related theories are to be further developed to develop efficient catalysts. Wherein the preparation of the metal-based catalyst by anchoring metal atoms/ions with catalytic activity on an inorganic or organic material substrate is to improve the electrocatalysis of CO by the catalyst2One of the methods for reducing the performance of the reaction. However, the nitrogen-doped carbon-anchored metal monatomic material (M-NC) which is currently most widely studied in electrocatalytic CO2In reduction, the product is mainly CO, in multiple electrons: (>2e-) transfer product (e.g. CH)4，C2H4Etc.) are not satisfactory in terms of production activity and selectivity.
Therefore, a novel and efficient catalyst is developed and applied to electrocatalysis of CO2The reduction of CO and the improvement of the generation activity and selectivity of multi-electron transfer products are really necessary.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention provides a covalent triazine organic framework, a limited-area metal catalyst, a preparation method and applications thereof, so as to provide a novel and efficient catalyst for electrocatalysis of CO2/CO reduction, solving the problem of electrochemical CO in the prior art2The multiple electron transfer product generation activity of the/CO reduction catalyst is low and the selectivity is poor.
To achieve the above and other related objects, the present invention provides a covalent triazine organic framework having the general structural formula:
wherein X, Y are each independently a C atom or a N atom, at least one of X and Y is a N atom, and the N atom is a heteroatom of the covalent triazine organic framework.
The invention also provides a method for preparing the covalent triazine organic framework, which comprises the following steps:
providing precursors of a dimethyl alcohol-based compound and a diamidino compound;
and (2) carrying out oxidation and polycondensation reaction on the precursor in a solvent under the catalysis of an alkaline reagent to prepare the covalent triazine organic framework, wherein at least one of the dimethyl alcohol-based compound and the diamidinyl compound contains a heterocyclic ring, the heterocyclic ring is 2, 2-bipyridine, and the covalent triazine organic framework contains a heteroatom N.
Optionally, the diamidino compound comprises one of 2,2' -bipyridine-5, 5' -dicarboxamidine and 1, 1-biphenyl 4,4' -dicarboxamidine; the dimethyl alcohol-based compound comprises one of 1, 1-biphenyl 4,4' -dimethyl alcohol and 2,2' -bipyridyl-5, 5' -dimethyl alcohol.
The present invention also provides a confined metal catalyst prepared by coordinating the heteroatom N in the covalent triazine organic framework prepared by the above method to anchor metal ions.
Optionally, the metalThe ions comprise one or more of Cu, Co, Ni and Fe; the metal source of the metal ion comprises CuCl2、CuCl、CuBr2、CuI、Cu(NO3)2、Cu(OAc)2、CuSO4、FeCl3、FeBr3、FeCl2、FeBr2、 Fe(OAc)3、Co(OAc)2、Fe(NO3)2、Co(SCN)2、CoCl3、CoCl2、Co(OAc)2、CoSO4、NiCl2、NiBr2、 NiSO4、Ni(SCN)2One or more of (a).
The invention also provides an application of the limited-area metal catalyst, and the limited-area metal catalyst is applied to electrocatalysis of CO2and/CO reduction reaction.
Optionally, the electrocatalytic CO2The electrolyte for the reduction reaction of/CO comprises KOH and KHCO3One of KCl, KBr and KI; the electrocatalytic CO2The concentration range of the electrolyte for the/CO reduction reaction comprises 0.1M-10M.
Optionally, the electrocatalytic CO2The working electrode substrate material for the/CO reduction reaction includes one of a porous electrode, a PTFE treated or untreated carbon paper electrode.
Optionally, the electrocatalytic CO2The preparation method of the working electrode for the/CO reduction reaction comprises one of quantitative spraying, blade coating and quantitative dripping.
Optionally, the electrocatalytic CO2The electrolytic cell for the/CO reduction reaction comprises one of a flow electrolytic cell, a membrane reactor and an H-shaped electrolytic cell.
As mentioned above, the covalent triazine organic framework, the limited domain metal catalyst, the preparation method and the application of the catalyst are provided, the covalent triazine organic framework comprises heteroatom N, metal ions are anchored through the heteroatom, the limited domain metal catalyst is prepared, wherein, the density and the relative distance of metal active centers can be regulated and controlled by regulating and controlling the structure of the covalent triazine organic framework and the relative content of coordination heteroatoms, the structure derivation of the limited domain metal in the in-situ reaction process is realized by utilizing a porous framework structure with N sites of the coordination heteroatoms,a catalytic site with high activity and high selectivity is formed, and the catalyst is mild and has wide applicability; the covalent triazine organic framework is synthesized by precursors of a dimethyl carbinol compound and a dimethyl amidino compound, the preparation method is mild, a large amount of covalent triazine organic framework can be synthesized, and the application is wide; limited-domain metal catalyst prepared by anchoring metal ions by covalent triazine organic framework and application of limited-domain metal catalyst to electrocatalysis of CO2The reaction has good activity and selectivity for generating multi-electron transfer products in CO reduction.
Drawings
Fig. 1 shows an infrared spectrum of CTF synthesized in example 1 and its precursor.
FIG. 2 shows a PXRD pattern of the CTF synthesized in example 1 and its theoretical calculated PXRD pattern.
Fig. 3 is a graph showing nitrogen adsorption of the CTF synthesized in example 1.
Fig. 4 shows the BET pore size distribution of the CTF synthesized in example 1.
FIG. 5 shows a transmission electron micrograph of the CTF synthesized in example 1.
FIG. 6 shows the thermogravimetric analysis of the CTF and CTF-Cu-4.8% synthesized in example 1 in a nitrogen atmosphere.
FIG. 7 is an SEM image of the spherical aberration correction of the CTF-Cu-4.8% synthesized in example 1.
FIG. 8 shows the electron microscope and elemental distribution plots of the CTF-Cu-4.8% synthesized in example 1.
FIG. 9 shows a high resolution XPS spectrum of N1s as the CTF-Cu-4.8% synthesized in example 1.
FIG. 10 shows a Cu 2p high resolution XPS spectrum of the CTF-Cu-4.8% synthesized in example 1.
FIG. 11 shows a Cu-K edge XANES spectrum of CTF-Cu-4.8% synthesized in example 1.
FIG. 12 shows the Cu-K side EXAFS spectrum of CTF-Cu-4.8% synthesized in example 1.
FIG. 13 is a view showing an H-type electrolytic cell apparatus used in example 2.
FIG. 14 shows the presence of CTF and CTF-Cu (1.7%, 2.4%, 4.8%) in CO in example 22Saturated 0.3M KCLSV profile in solution.
FIG. 15 shows the potential-dependent CH of CTF-Cu (1.7%, 2.4%, 4.8%) in example 24Faraday efficiency plot.
FIG. 16 shows the potential-dependent C of CTF-Cu (1.7%, 2.4%, 4.8%) in example 22H4Faraday efficiency plot.
FIG. 17 is a graph showing the mass activity of CTF-Cu (1.7%, 2.4%, 4.8%) to hydrocarbons in example 2.
Figure 18 shows the faradaic efficiency plot of the CORR product at-1.44V vs. she for CTF-Cu (1.7%, 2.4%, 4.8%) in example 2.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1 to 18. It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and the components related to the present invention are only shown in the drawings rather than drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of the components in actual implementation may be changed at will, and the layout of the components may be more complex.
The invention provides a covalent triazine organic framework, which has a structural general formula as follows:wherein X, Y are each independently a C atom or a N atom, at least one of X and Y is a N atom, and the N atom is a heteroatom of the covalent triazine organic framework.
In this embodiment, the covalent triazine organic framework has the advantages of adjustable structure and adjustable relative content of coordination heteroatom N, and can adjust and control the density and relative distance of metal active centers, and a porous framework structure with coordination heteroatom N sites can be used for structure derivatization of subsequent confined-domain metals in an in-situ reaction process to form high-activity and high-selectivity catalytic sites, so that the catalyst is mild and has wide applicability. By regulating the structure of the covalent triazine organic framework, the content of the anchoring metal ions of the covalent triazine organic framework can be conveniently regulated and controlled subsequently.
The present example also provides a method of making the covalent triazine organic framework, comprising the steps of:
providing precursors of a dimethyl alcohol-based compound and a diamidino compound;
and (2) carrying out oxidation and polycondensation reaction on the precursor in a solvent under the catalysis of an alkaline reagent to prepare the covalent triazine organic framework, wherein at least one of the dimethyl alcohol-based compound and the diamidinyl compound contains a heterocyclic ring, the heterocyclic ring is 2, 2-bipyridine, and the covalent triazine organic framework contains a heteroatom N.
In the embodiment, the covalent triazine organic framework containing heteroatom N is synthesized by precursors of a dimethyl alcohol-based compound and a dimethyl amidino compound, the preparation method is mild, a large amount of covalent triazine organic framework catalysts can be synthesized, and the prepared covalent triazine organic framework catalysts are suitable for large-scale application.
The diamidino compound includes, as an example, one of 2,2' -bipyridine-5, 5' -dicarboxamidine and 1, 1-biphenyl-4, 4' -dicarboxamidine; the dimethyl alcohol-based compound comprises one of 1, 1-biphenyl 4,4' -dimethyl alcohol and 2,2' -bipyridyl-5, 5' -dimethyl alcohol.
As an example, the alkaline agent may include Cs2CO3、Et3N、KOH、NaOH、K2CO3、Na2CO3One of (1); the solvent comprises one of N, N-dimethylacetamide, dimethyl sulfoxide and N-pyrrolidone; the synthesis temperature comprises 100-200 ℃.
This example also provides a confined metal catalyst prepared by coordinating the heteroatom N in the covalent triazine-organic framework to anchor metal ions. Wherein the content of the metal ion anchored in the covalent triazine organic framework can be adjusted by one or a combination of adjusting the structure of the covalent triazine organic framework and the amount of the metal source of the metal ion.
As an example, the metal ions include one or more of Cu, Co, Ni, Fe; the metal source of the metal ion comprises CuCl2、CuCl、CuBr2、CuI、Cu(NO3)2、Cu(OAc)2、CuSO4、FeCl3、FeBr3、FeCl2、FeBr2、 Fe(OAc)3、Co(OAc)2、Fe(NO3)2、Co(SCN)2、CoCl3、CoCl2、Co(OAc)2、CoSO4、NiCl2、NiBr2、 NiSO4、Ni(SCN)2One or more of (a).
As an example, the conditions for anchoring the metal ions include one or more of ultrasound, thermal refluxing, standing, stirring; the solvent for anchoring the metal ions comprises one or more of water, ethanol, methanol, N-dimethylformamide and dimethyl sulfoxide.
The embodiment also provides application of the limited-area metal catalyst, and the limited-area metal catalyst is applied to electrocatalysis of CO2and/CO reduction reaction. In which electrocatalysis of CO is carried out2During the CO reduction, the structure and the metal active catalytic center of the covalent triazine organic framework are adjusted, and meanwhile, the porous structure of the covalent triazine organic framework and the structure derivation of the coordination N site limited domain metal in an in-situ reaction state are utilized to form a high-activity reaction site, so that the CO reduction is accelerated2The hydrogenation and C-C coupling capacity of the intermediate product are reduced, the selectivity of methane and C2 products is improved, CO is directly used as reaction gas, the CO coverage on the surface of an active site is increased, the C-C coupling probability is increased, the C2 selectivity is further improved, and high hydrocarbon and acetic acid selectivity is shown, so that the problem of high selectivity of the existing electrocatalysis CO and the existing electrocatalysis CO is solved2In the reduction of CO, in multiple electronsThe transfer product has low activity and poor selectivity.
As an example, the electrocatalytic CO2The electrolyte for the reduction reaction of/CO comprises KOH and KHCO3One of KCl, KBr and KI; the electrocatalytic CO2The concentration range of the electrolyte for the/CO reduction reaction comprises 0.1M-10M, such as 0.1M, 1M, 5M, 10M and the like; the electrocatalytic CO2The working electrode substrate material of the/CO reduction reaction comprises one of a porous electrode, a PTFE treated or untreated carbon paper electrode; the electrocatalytic CO2The preparation method of the working electrode for the/CO reduction reaction comprises one of quantitative spraying, blade coating and quantitative dripping; the electrocatalytic CO2The electrolytic cell for the/CO reduction reaction comprises one of a flow electrolytic cell, a membrane reactor and an H-shaped electrolytic cell.
The following is illustrated in detail by specific examples, but is not limited thereto:
example 1
2,2' -bipyridine-5, 5' -dimethanol (PCM) (216mg, 1mmol), 1, 1-biphenyl 4,4' -dicarboxamidine (BPM) (476mg, 2mmol), cesium carbonate (975mg, 3mmol) were accurately weighed, added to 50ml of methylene sulfoxide in this order, and subjected to an open reaction at 100 ℃ for 24 hours and then at 185 ℃ for 36 hours under magnetic stirring. And after the reaction is finished, cooling to room temperature, filtering, sequentially washing filter residues with dilute hydrochloric acid (the concentration is 1M, the washing is carried out for three times, 20ml each time), deionized water (the washing is carried out for three times, 20ml each time), tetrahydrofuran (the washing is carried out for three times, 20ml each time), and ethanol (the washing is carried out for three times, 20ml each time), carrying out vacuum drying on the obtained solid at 100 ℃ to obtain the covalent triazine organic framework material of 450mg, wherein the yield is 72%, and the product of the covalent triazine organic framework material is marked as CTF.
The synthetic route for CTF is as follows:
20mg of CTF from example 1 were accurately weighed and 12.5mL of 0.5mM CuCl were added2Dispersing the obtained mixture in ultrasonic wave, stirring at room temperature for 12 hr, filtering, and washing the filter residue with ethanol for three times (20 m each time)l. The resulting solid was dried under vacuum at 100 ℃ and the product was designated as CTF-Cu-1.7% (1.7% represents the mass percent of Cu in CTF-Cu, the same applies hereinafter).
20mg of CTF from example 1 were accurately weighed and 25mL of 0.5mM CuCl were added2The resulting mixture was dispersed in ultrasound, followed by stirring at room temperature for 12 hours, filtration, and the filter residue was washed with ethanol dispersion three times, 20ml each time. The resulting solid was dried under vacuum at 100 ℃ and the product was noted as CTF-Cu-2.4%.
20mg of CTF from example 1 are weighed out accurately, 50mL of a 0.5mM ethanol solution of CuCl2 are added, the mixture is dispersed by ultrasound and subsequently stirred at room temperature for 12 hours, filtered and the filter residue is washed three times with 20mL of ethanol each time. The resulting solid was dried under vacuum at 100 ℃ and the product was noted as CTF-Cu-4.8%.
The obtained initial CTF and CTF-Cu were subjected to the relevant physical characterization as shown in fig. 1 to 12, wherein:
FIG. 1 is an infrared spectrum of synthesized CTF and its precursor, which is at 1373cm-1And 1508cm-1The formation of the triazine structure is evidenced by the appearance of a vibrational peak.
Fig. 2 is a PXRD pattern of the synthesized CTF and its theoretical calculated PXRD pattern, indicating that the synthesized CTF has a good crystal form and that the interlayer stacking pattern may be AB stacking.
FIG. 3 is a graph of nitrogen adsorption versus pressure P/P for the synthesized CTF0The obvious increase of the adsorption volume in the interval of 0-0.2 indicates more micropores, and the specific surface area of the synthesized CTF is 488m by software analysis2(ii)/g, wherein the specific surface area of the micropores is 435m2/g。
FIG. 4 is a BET pore size distribution plot of the synthesized CTF showing the presence of two pore sizes in the CTF, i.e.Andindicating that both AA and AB stacking forms exist in CTF.
FIG. 5 is a transmission electron micrograph of the synthesized CTF, illustrating that the CTF is mainly in a lamellar structure.
FIG. 6 is a graph of the thermogravimetric analysis of the synthesized CTF and CTF-Cu-4.8% in a nitrogen atmosphere, wherein it is shown that the degradation of CTF and CTF-Cu-4.8% is started at 600 ℃, indicating good thermal stability.
FIG. 7 is an SEM image of the spherical aberration of the synthesized CTF-Cu-4.8% with a size of aboutThe presence of a bright spot indicates that the initial presence of Cu in CTF-Cu is in the form of a single atom.
FIG. 8 is an electron microscope and elemental distribution plot of the synthesized CTF-Cu-4.8%, which shows that the Cu element and N element are uniformly distributed in the CTF-Cu-4.8%.
Fig. 9 is a synthesized CTF-Cu-4.8% N1s high resolution XPS spectrum, which illustrates that after bipyridine N coordinates with Cu, the electronic structure of bipyridine N in CTF is affected, and partial electrons on N are transferred to Cu, so that the 1s peak of partial N in CTF moves toward high binding energy.
FIG. 10 is a Cu 2p high resolution XPS spectrum of synthesized CTF-Cu-4.8%, Cu2+The presence of satellite co-peaks and a main peak at 934.9eV indicates that Cu is predominantly in the divalent form in CTF-Cu.
FIG. 11 is a Cu-K edge XANES spectrum of synthesized CTF-Cu-4.8%, the proximity of the near edge structure to divalent Cu, illustrating the Cu proximity to divalent in CTF-Cu.
FIG. 12 is a Cu-K edge EXAFS spectrum of 4.8% synthesized CTF-Cu, and the control shows the absence of Cu-Cu bond and possible Cu-N and Cu-Cl coordination in CTF-Cu.
Example 2
Accurately weighing 5mg of CTF-Cu (1.7%, 2.4%, 4.8%), quantitatively transferring 0.98mL of ethanol and 0.02mL of Nafion solution (5 wt.%) by a pipette, placing in a 100W ultrasonic instrument, and ultrasonically dispersing for 60 min. Then 50. mu.L of the dispersion was applied to 1cm by using a 100. mu.L pipette2The carbon paper electrode (20 wt.% PTFE treatment) was baked dry under an infrared lamp, and then the other side of the carbon paper was dip coated quantitatively and baked dry in the same manner for future use. Adopts a closed H-shaped electrolytic tank, one side of a cathode chamber,fixing the prepared electrode on an electrode clamp as a working electrode, and using an Ag/AgCl electrode (saturated potassium chloride is used as an internal reference solution) as a reference electrode; on one side of the anode chamber, a platinum mesh electrode is taken as a counter electrode; both sides of the cathode chamber and the anode chamber adopt 0.3M KCl solution as electrolyte; the cathode and anode chambers are separated by a Nafion 115 ion exchange membrane. High-purity CO is respectively introduced into the two sides of the cathode and the anode2And controlling the flow rate of the gas to be 20sccm by adopting a mass flow meter respectively. And carrying out constant temperature water bath at 25 ℃ on the cathode side, and carrying out magnetic stirring at the rotation speed of 600 rpm. CO 22After the gas saturated the electrolyte for 30min, constant potential electrolysis was started. Gas Cl is carried out by connecting the gas outlet of the anode chamber into 1M NaOH solution2Absorbing, and accessing an air outlet of the cathode chamber into an online gas chromatograph to analyze the composition and content of a gas product.
FIG. 13 is a diagram of an H-type electrolytic cell apparatus used, which employs a three-electrode system, divided into a working electrode WE, a counter electrode CE, and a reference electrode RE.
FIG. 14 shows CTF and CTF-Cu (1.7%, 2.4%, 4.8%) in CO2LSV pattern in saturated 0.3M KCl solution, CTF-Cu activity was significantly enhanced compared to the base carbon paper material and CTF, and increased with increasing Cu content, indicating that Cu is the main active center.
FIG. 15 is the potential-dependent CH of CTF-Cu (1.7%, 2.4%, 4.8%)4Faraday efficiency map, the studied CTF-Cu all showed excellent CH4Selective (FE CH)4>50%) of which CTF-Cu-4.8% of the highest CH4The Faraday efficiency reaches 70 percent.
FIG. 16 is C of CTF-Cu (1.7%, 2.4%, 4.8%) potential dependence2H4Faraday efficiency map, C as Cu content increases2H4The selectivity is remarkably improved, and strong content dependence is shown.
FIG. 17 is a mass activity diagram of CTF-Cu (1.7%, 2.4%, 4.8%) produced hydrocarbons, which is more consistent with LSV activity law and shows Cu content dependence.
FIG. 18 is a graph of the Faraday efficiency of the CORR product at-1.46V vs. SHE for CTF-Cu (1.7%, 2.4%, 4.8%), the C2 product (C2)2H4And Cu content in HAc) and CTFA positive correlation was shown, with a C2 selectivity of CTF-Cu-4.8% being optimally 68.3%.
In summary, the covalent triazine organic framework comprises heteroatom N, and metal ions are anchored by the heteroatom to prepare the confined metal catalyst, wherein the density and relative distance of metal active centers can be regulated by regulating the structure of the covalent triazine organic framework and the relative content of coordination heteroatoms, and the structure derivation of the confined metal in the in-situ reaction process is realized by utilizing a porous framework structure with coordination heteroatom N sites to form high-activity and high-selectivity catalytic sites, so that the catalyst is mild and has wide applicability; the covalent triazine organic framework is synthesized by precursors of a dimethyl carbinol compound and a dimethyl amidino compound, the preparation method is mild, a large amount of covalent triazine organic framework can be synthesized, and the application is wide; limited-domain metal catalyst prepared by anchoring metal ions by covalent triazine organic framework and application of limited-domain metal catalyst to electrocatalysis of CO2The reaction has good activity and selectivity for generating multi-electron transfer products in CO reduction. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which may be accomplished by those skilled in the art without departing from the spirit and scope of the present invention as set forth in the appended claims.
Claims (10)
1. A covalent triazine organic framework, characterized by: the structural general formula of the covalent triazine organic framework is as follows:
x, Y are independently C atom or N atom, and at least one of X and YOne is a N atom and the N atom serves as a heteroatom of the covalent triazine organic framework.
2. A process for the preparation of the covalent triazine organic framework of claim 1, comprising the steps of:
providing precursors of a dimethyl alcohol-based compound and a diamidino compound;
and (2) carrying out oxidation and polycondensation reaction on the precursor in a solvent under the catalysis of an alkaline reagent to prepare the covalent triazine organic framework, wherein at least one of the dimethyl alcohol-based compound and the diamidinyl compound contains a heterocyclic ring, the heterocyclic ring is 2, 2-bipyridine, and the covalent triazine organic framework contains a heteroatom N.
3. Process for the preparation of a covalent triazine organic framework according to claim 2, characterized in that: the diamidino compound comprises one of 2,2' -bipyridine-5, 5' -dicarboxamidine and 1, 1-biphenyl 4,4' -dicarboxamidine; the dimethyl alcohol-based compound comprises one of 1, 1-biphenyl 4,4' -dimethyl alcohol and 2,2' -bipyridyl-5, 5' -dimethyl alcohol.
4. A confined metal catalyst characterized by: the constrained metal catalyst is prepared by coordinating the heteroatom N in the covalent triazine organic framework prepared by the method of any of claims 1-3 to anchor metal ions.
5. The confined metal catalyst of claim 4, wherein: the metal ions comprise one or more of Cu, Co, Ni and Fe; the metal source of the metal ion comprises CuCl2、CuCl、CuBr2、CuI、Cu(NO3)2、Cu(OAc)2、CuSO4、FeCl3、FeBr3、FeCl2、FeBr2、Fe(OAc)3、Co(OAc)2、Fe(NO3)2、Co(SCN)2、CoCl3、CoCl2、Co(OAc)2、CoSO4、NiCl2、NiBr2、NiSO4、Ni(SCN)2One or more of (a).
6. The application of a limited-area metal catalyst is characterized in that: use of the constrained-metal catalyst of any of claims 4-5 for electrocatalytic CO2and/CO reduction reaction.
7. Use of a confined metal catalyst according to claim 6, characterized in that: the electrocatalytic CO2The electrolyte for the reduction reaction of/CO comprises KOH and KHCO3One of KCl, KBr and KI; the electrocatalytic CO2The concentration range of the electrolyte for the/CO reduction reaction comprises 0.1M-10M.
8. Use of a confined metal catalyst according to claim 6, characterized in that: the electrocatalytic CO2The working electrode substrate material for the/CO reduction reaction includes one of a porous electrode, a PTFE treated or untreated carbon paper electrode.
9. Use of a confined metal catalyst according to claim 6, characterized in that: the electrocatalytic CO2The preparation method of the working electrode for the/CO reduction reaction comprises one of quantitative spraying, blade coating and quantitative dripping.
10. Use of a confined metal catalyst according to claim 6, characterized in that: the electrocatalytic CO2The electrolytic cell for the/CO reduction reaction comprises one of a flow electrolytic cell, a membrane reactor and an H-shaped electrolytic cell.
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