CN115254193B - Palladium phthalocyanine molecular catalyst, preparation method and application of palladium phthalocyanine molecular catalyst supported by carbon substrate - Google Patents
Palladium phthalocyanine molecular catalyst, preparation method and application of palladium phthalocyanine molecular catalyst supported by carbon substrate Download PDFInfo
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- CN115254193B CN115254193B CN202210971908.1A CN202210971908A CN115254193B CN 115254193 B CN115254193 B CN 115254193B CN 202210971908 A CN202210971908 A CN 202210971908A CN 115254193 B CN115254193 B CN 115254193B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- MCTALTNNXRUUBZ-UHFFFAOYSA-N molport-000-691-724 Chemical compound [Pd+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MCTALTNNXRUUBZ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 51
- 239000000758 substrate Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000001914 filtration Methods 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 23
- 238000001291 vacuum drying Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- -1 nitrile organic compounds Chemical class 0.000 claims abstract description 9
- 150000002940 palladium Chemical class 0.000 claims abstract description 8
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 10
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 10
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims description 10
- 229920006391 phthalonitrile polymer Polymers 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- RRCAJFYQXKPXOJ-UHFFFAOYSA-N 4-aminobenzene-1,2-dicarbonitrile Chemical compound NC1=CC=C(C#N)C(C#N)=C1 RRCAJFYQXKPXOJ-UHFFFAOYSA-N 0.000 claims description 2
- NTZMSBAAHBICLE-UHFFFAOYSA-N 4-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(C#N)=C1 NTZMSBAAHBICLE-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 238000000944 Soxhlet extraction Methods 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical group [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 26
- 239000001569 carbon dioxide Substances 0.000 abstract description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 13
- 230000009467 reduction Effects 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000002041 carbon nanotube Substances 0.000 description 45
- 229910021393 carbon nanotube Inorganic materials 0.000 description 45
- 238000006722 reduction reaction Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 238000009210 therapy by ultrasound Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 8
- 239000011609 ammonium molybdate Substances 0.000 description 8
- 229940010552 ammonium molybdate Drugs 0.000 description 8
- 235000018660 ammonium molybdate Nutrition 0.000 description 8
- 239000012535 impurity Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- 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
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/23—Carbon monoxide or syngas
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
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- 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
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/085—Organic compound
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- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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Abstract
The invention discloses a palladium phthalocyanine molecular catalyst, a preparation method of a carbon substrate supported palladium phthalocyanine molecular catalyst and application thereof, wherein nitrile organic compounds, palladium salt, nitrogen source and solid phase reaction catalyst are fully mixed and then calcined at high temperature in inert atmosphere; cooling to room temperature, stirring strong acid solution for 0.2-2 h, washing with deionized water, filtering, and vacuum drying; stirring strong alkali solution for 0.2-2 h, washing with deionized water, filtering and vacuum drying; and (5) extracting and purifying, and then drying in vacuum again to obtain the high-yield palladium phthalocyanine molecular catalyst. Dispersing the palladium phthalocyanine molecular catalyst and the carbon substrate in an organic solvent, and stirring, washing, filtering and vacuum drying to obtain the palladium phthalocyanine molecular catalyst supported by the carbon substrate. The palladium phthalocyanine molecular catalyst and the palladium phthalocyanine molecular catalyst supported by the carbon substrate have high atom utilization rate palladium sites, can be used for reducing carbon dioxide, and have excellent catalytic activity and carbon dioxide reduction stability.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic carbon dioxide reduction, and relates to a palladium phthalocyanine molecular catalyst, a preparation method of a carbon substrate supported palladium phthalocyanine molecular catalyst and application thereof.
Background
Electrochemical reduction of carbon dioxide is an effective energy conversion technology for converting intermittent electrical energy into valuable chemicals and is of great interest. However, carbon dioxide is extremely stable in chemical nature, and a high overpotential is required by adopting a direct electroreduction method, so that a proper electrocatalyst is required to increase the current density and reduce the overpotential. The metal is firstly used for the electrocatalyst, and the metal palladium-based electrocatalyst has higher conversion rate on carbon dioxide reduction reaction in all metals. However, the material generally has the problems of poor product selectivity, metal electroreduction side effect, catalyst poisoning and other activity losses, high cost, limited availability and the like. In addition, the conventional method for preparing the bulk or sheet palladium-based catalyst has less exposed active sites due to a smaller electrochemical active area, so that the catalytic activity is not ideal. Therefore, the development of novel palladium-based electrocatalysts with high product selectivity, high atom utilization and high chemical stability remains a very challenging topic.
The metal phthalocyanine is a compound with a highly symmetrical structure, uniform electron distribution and excellent chemical stability, and is concerned in the fields of photoelectrocatalysis, solar cells, medicines and the like, and is widely applied to the treatment of diseases and the solving of the problems of environmental pollution, energy shortage and the like. Therefore, synthesizing palladium phthalocyanine is an effective way to improve the utilization rate of palladium atoms and obtain high catalytic activity. However, the traditional palladium phthalocyanine has the problems of excessively complex steps, long period, harsh conditions (preparation under the conditions of high-boiling-point organic solvent, anhydrous oxygen-free and organic alkali) and the like in the synthesis process, namely the preparation method, due to weaker coordination capability of palladium ions, so that the problems of low atom utilization efficiency, excessive impurities, low yield and the like are caused.
Disclosure of Invention
The embodiment of the invention aims to provide a palladium phthalocyanine molecular catalyst, a preparation method of a palladium phthalocyanine molecular catalyst supported by a carbon substrate and application thereof, so as to solve the problems of complicated preparation steps, long period and harsh conditions of the traditional palladium phthalocyanine catalyst, and the problems of low atomic utilization rate, more impurities and low yield of the traditional palladium phthalocyanine catalyst.
The first technical scheme adopted by the embodiment of the invention is as follows: the preparation method of the palladium phthalocyanine molecular catalyst comprises the following steps:
fully mixing the nitrile organic compound with palladium salt, nitrogen source and solid phase reaction catalyst, and calcining at high temperature in inert atmosphere to obtain the palladium phthalocyanine molecular catalyst.
Further, after calcination at high temperature in an inert atmosphere, the following operations are also performed:
cooling to room temperature;
stirring the strong acid solution for 0.2-2 h, washing with deionized water, filtering and drying in vacuum;
stirring strong alkali solution for 0.2-2 h, washing with deionized water, filtering and vacuum drying;
and (5) extracting and purifying, and then drying in vacuum again to obtain the palladium phthalocyanine molecular catalyst.
Further, the mass ratio of the nitrile organic compound to the palladium salt to the nitrogen source to the solid phase reaction catalyst is 1:0.05-0.5:1.5-10:0.01-0.05;
the nitrile organic compound is phthalonitrile, 4-nitrophthalonitrile or 4-amino phthalonitrile;
the palladium salt is palladium dichloride, palladium acetate, sodium tetrachloropalladate or palladium tetrammine dichloride;
the nitrogen source is urea, ammonium chloride, ammonium bicarbonate or ammonium nitrate;
the solid phase reaction catalyst is molybdate.
Further, the pH of the strong acid solution is <1, and the pH of the strong base solution is >13;
the extraction and purification adopts Soxhlet extraction and purification with methanol.
Further, the calcination temperature is between 100 and 300 ℃, the temperature rising speed is between 2 and 5 ℃ per minute, and the calcination time is between 6 and 10 h.
The second technical scheme adopted by the embodiment of the invention is as follows: the application of the palladium phthalocyanine molecular catalyst is used for reducing carbon dioxide.
The third technical scheme adopted by the embodiment of the invention is as follows: the preparation method of the carbon substrate supported palladium phthalocyanine molecular catalyst comprises the following steps:
dispersing the palladium phthalocyanine molecular catalyst and the pretreated carbon substrate in an organic solvent, and stirring, washing, filtering and vacuum drying to obtain the palladium phthalocyanine molecular catalyst supported by the carbon substrate.
Further, the organic solvent is N, N-dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone;
the mass ratio of the carbon substrate to the palladium phthalocyanine molecular catalyst to the organic solvent is 1:0.02-0.1: 100-1000.
Further, the pretreatment of the carbon substrate is to wash and filter the carbon substrate with deionized water after treating 6 to 24 to h with concentrated sulfuric acid at 70 to 90 ℃ and then dry the carbon substrate at 40 to 100 ℃ for 2 to 10 h;
after dispersing the palladium phthalocyanine molecular catalyst and the pretreated carbon substrate in an organic solvent, stirring the mixture for 20 to 30 h, and drying the mixture in vacuum at a temperature of between 60 and 100 ℃ for 8 to 12 h.
The fourth technical scheme adopted by the embodiment of the invention is as follows: the application of the carbon substrate supported palladium phthalocyanine molecular catalyst is used for reducing carbon dioxide.
The embodiment of the invention has the beneficial effects that:
1. compared with the traditional preparation method, the preparation method provided by the embodiment of the invention has the advantages that the yield is as high as more than 90%, the large-scale preparation can be performed, and the problem of low yield of the traditional palladium phthalocyanine preparation method is solved;
2. compared with the traditional palladium nano block or palladium nano sheet, the phthalocyanine palladium molecular catalyst prepared by the mode of chemical bonding of the organic ligand and palladium has higher atomic utilization rate, thereby having more excellent CO 2 RR activity, has solved the problem that the atomic utilization rate of the traditional palladium phthalocyanine preparation method is low;
3. the palladium phthalocyanine molecules prepared by the embodiment of the invention can be uniformly loaded on different types of carbon substrates to obtain various carbon substrate supported palladium phthalocyanine molecule catalysts, and the palladium phthalocyanine molecule catalysts can be used as excellent catalysts for electrocatalytic carbon dioxide reduction reaction, and can show excellent catalytic activity, excellent carbon dioxide reduction to carbon monoxide selectivity and excellent reaction stability;
in conclusion, the palladium phthalocyanine is obtained by calcining the palladium salt and the nitrile organic compound at high temperature, and the synthesis path of the palladium phthalocyanine material supported by the carbon substrate is further obtained by using a stirring method, so that the problems of severe conditions, more side reactions and the like of the traditional preparation method are avoided, and the method has the advantages of simplicity, high efficiency and capability of large-scale preparation, and has good application prospect.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an ultraviolet spectrum of the palladium phthalocyanine catalyst prepared in the present example 1.
FIG. 2 is a Raman spectrum of the palladium phthalocyanine catalyst obtained in the present example 1.
FIG. 3 is a scanning electron microscope image of the palladium phthalocyanine catalyst produced in the present example 1.
FIG. 4 is a scanning electron microscope image of a carbon nanotube-supported palladium phthalocyanine molecular catalyst prepared in example 1.
FIG. 5 is a carbon nanotube pretreated in example 1 and a prepared carbon nanotube-supported palladium phthalocyanine molecular catalyst for CO reduction 2 Is a graph comparing the polarization curves of CO.
FIG. 6 is a carbon nanotube-supported palladium phthalocyanine molecular catalyst prepared in example 1 for CO reduction at-0.6V, -0.7V, -0.8V and-0.9V potential 2 Is a potentiostatic stability diagram of CO.
FIG. 7 is a schematic diagram showing the reduction of CO by the carbon nanotube-supported palladium phthalocyanine molecular catalyst prepared in example 1 at potentials of-0.6V, -0.7V, -0.8V and-0.9V 2 Is the faraday efficiency of CO.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Preparation of a palladium phthalocyanine molecular catalyst:
step S1: uniformly grinding phthalonitrile, palladium dichloride, urea and ammonium molybdate with the mass ratio of 1:0.15:5:0.02, and calcining 8 h at 200 ℃ in argon atmosphere, wherein the heating speed is 3 ℃ per minute;
step S2: after cooling to room temperature, the obtained product was placed at 1 mol L -1 Hydrochloric acid solution (pH)<1) Stirring 1 and h, filtering, washing with a large amount of deionized water, and vacuum drying;
step S3: at 1 mol L -1 Sodium hydroxide solution (pH)>13 Stirring 1 h, suction filtering, washing with deionized water, filtering, and vacuum drying;
step S4: extracting and purifying by using methanol soxhlet, and then drying in vacuum again to obtain a high-yield palladium phthalocyanine molecular catalyst (PdPc);
(2) Based on the palladium phthalocyanine molecular catalyst, preparing a carbon nanotube supported palladium phthalocyanine molecular catalyst:
firstly, treating the carbon nano tube with concentrated sulfuric acid at 90 ℃ for 15 h, removing metal impurities of the carbon substrate, improving the oxygen content of the surface of the carbon substrate, washing and filtering with deionized water, and then drying at 60 ℃ for 8 h;
dispersing PdPc in an N, N-dimethylformamide solvent, carrying out ultrasonic treatment for 30min, then adding a carbon nano tube, continuing ultrasonic treatment for 30min, and stirring at room temperature for 24 h, wherein the mass ratio of the carbon nano tube to the PdPc to the N, N-dimethylformamide solvent is 1:0.05:500;
washing and filtering the mixed solution with deionized water, and finally vacuum drying at 80 ℃ for 10 h to obtain the carbon nanotube supported palladium phthalocyanine molecular catalyst (PbPc/CNT), namely the carbon substrate supported palladium phthalocyanine molecular catalyst.
The ultraviolet spectra of the PdPc catalyst prepared in this example are shown in FIG. 1, and are located at 600 and 690 cm -1 Is a characteristic peak of PdPc, which shows that the material prepared by the method is PdPc, and the PdPc has a certain CO 2 RR performance. The Raman spectrum of the prepared PdPc catalyst is shown in fig. 2, and the occurrence of Raman absorption peaks reflects the highly symmetrical molecular structure of PdPc, and further shows the synthesis of PdPc. The scanning electron microscope diagram of the prepared PdPc catalyst is shown in fig. 3, and the PdPc has a bulk morphology composed of nano particles.
The scanning electron microscope image of the carbon nanotube supported palladium phthalocyanine molecular catalyst prepared in this embodiment is shown in fig. 4, and it can be seen from fig. 4 that there are a large number of carbon nanotubes without massive PbPc, which indicates that the palladium phthalocyanine molecules can be uniformly dispersed on the surface of the carbon substrate, so as to obtain the carbon nanotube supported palladium phthalocyanine molecular catalyst.
Example 2
This example differs from example 1 only in that the mass ratio of phthalonitrile, palladium dichloride, urea, ammonium molybdate is 1:0.35:3.75:0.016.
Example 3
This example differs from example 1 only in that the mass ratio of phthalonitrile, palladium dichloride, urea, ammonium molybdate is 1:0.5:10:0.05.
Example 4
This example differs from example 1 only in that the mass ratio of phthalonitrile, palladium dichloride, urea, ammonium molybdate is 1:0.05:1.5:0.01.
Example 5
This example differs from example 1 only in that the mass ratio of phthalonitrile, palladium dichloride, urea, ammonium molybdate is 1:0.2:8:0.03.
Example 6
This example differs from example 1 only in that the mass ratio of nanotubes, pdPc to N, N-dimethylformamide solvent is 1:0.1:1000.
Example 7
This example differs from example 1 only in that the mass ratio of nanotubes, pdPc to N, N-dimethylformamide solvent is 1:0.02:100.
Example 8
This example differs from example 1 only in that the mass ratio of nanotubes, pdPc to N, N-dimethylformamide solvent is 1:0.08:700.
Example 9
The difference between this example and example 1 is that the carbon substrate is graphene, and a uniformly dispersed graphene-supported palladium phthalocyanine molecular catalyst (PbPc/GPE) is produced.
Example 10
This example differs from example 1 only in that the carbon substrate was acetylene black, and a uniformly dispersed acetylene black supported palladium phthalocyanine molecular catalyst (PbPc/ACET) was produced.
Example 11
This example differs from example 1 only in that the carbon substrate was ketjen black, and a uniformly dispersed ketjen black supported palladium phthalocyanine molecular catalyst (PbPc/ketjen black) was produced.
Example 12
The embodiment provides a preparation method of a carbon substrate supported palladium phthalocyanine molecular catalyst, which comprises the following steps:
(1) Preparation of a palladium phthalocyanine molecular catalyst:
step S1: mixing and grinding phthalonitrile, palladium dichloride, urea and ammonium molybdate uniformly in a mass ratio of 1:015:5:0.02, and calcining 10 h at 100 ℃ in argon atmosphere at a heating rate of 2 ℃ per minute;
step S2: after cooling to room temperature, the obtained product was placed at 1 mol L -1 Hydrochloric acid solution (pH)<1) Stirring for 0.2. 0.2h, filtering, cleaning with a large amount of deionized water, and vacuum drying;
step S3: at 1 mol L -1 Sodium hydroxide solution (pH)>13 Stirring for 0.2h, suction filtering, washing with deionized water, filtering, and vacuum drying;
step S4: extracting and purifying by using methanol soxhlet, and then drying in vacuum again to obtain a high-yield palladium phthalocyanine molecular catalyst (PdPc);
(2) Based on the palladium phthalocyanine molecular catalyst, preparing a carbon nanotube supported palladium phthalocyanine molecular catalyst:
firstly, treating the carbon nano tube with concentrated sulfuric acid at 80 ℃ for 10 h, removing metal impurities of the carbon substrate, improving the oxygen content of the surface of the carbon substrate, washing and filtering with deionized water, and then drying at 40 ℃ for 10 h;
dispersing PdPc in an N, N-dimethylformamide solvent, carrying out ultrasonic treatment for 30min, then adding a carbon nano tube, continuing ultrasonic treatment for 30min, and stirring at room temperature for 24 h, wherein the mass ratio of the carbon nano tube to the PdPc to the N, N-dimethylformamide solvent is 1:0.05:500;
washing and filtering the mixed solution with deionized water, and finally vacuum drying at 80 ℃ for 10 h to obtain the carbon nanotube supported palladium phthalocyanine molecular catalyst (PbPc/CNT), namely the carbon substrate supported palladium phthalocyanine molecular catalyst.
Example 13
The embodiment provides a preparation method of a carbon substrate supported palladium phthalocyanine molecular catalyst, which comprises the following steps:
(1) Preparation of a palladium phthalocyanine molecular catalyst:
step S1: mixing and grinding phthalonitrile, palladium dichloride, urea and ammonium molybdate uniformly in a mass ratio of 1:015:5:0.02, and calcining 6 h at 300 ℃ in argon atmosphere at a temperature rising speed of 5 ℃ per minute;
step S2: after cooling to room temperature, the obtained product was placed at 1 mol L -1 Hydrochloric acid solution (pH)<1) Stirring for 2h, filtering, washing with a large amount of deionized water, and vacuum drying;
step S3: at 1 mol L -1 Sodium hydroxide solution (pH)>13 Stirring 2h, suction filtering, washing with deionized water, filtering, and vacuum drying;
step S4: extracting and purifying by using methanol soxhlet, and then drying in vacuum again to obtain a high-yield palladium phthalocyanine molecular catalyst (PdPc);
(2) Based on the palladium phthalocyanine molecular catalyst, preparing a carbon nanotube supported palladium phthalocyanine molecular catalyst:
firstly, treating the carbon nano tube with concentrated sulfuric acid at 70 ℃ for 24 h, removing metal impurities of the carbon substrate, improving the oxygen content of the surface of the carbon substrate, washing and filtering with deionized water, and then drying at 100 ℃ for 2 hours;
dispersing PdPc in an N, N-dimethylformamide solvent, carrying out ultrasonic treatment for 30min, then adding a carbon nano tube, continuing ultrasonic treatment for 30min, and stirring at room temperature for 30 h, wherein the mass ratio of the carbon nano tube to the PdPc to the N, N-dimethylformamide solvent is 1:0.05:500;
washing and filtering the mixed solution with deionized water, and finally vacuum drying at 60 ℃ for 8 h to obtain the carbon nanotube supported palladium phthalocyanine molecular catalyst (PbPc/CNT), namely the carbon substrate supported palladium phthalocyanine molecular catalyst.
Example 14
(1) Preparation of a palladium phthalocyanine molecular catalyst:
step S1: mixing and grinding phthalonitrile, palladium dichloride, urea and ammonium molybdate uniformly in a mass ratio of 1:015:5:0.02, and calcining 10 h at 200 ℃ in argon atmosphere at a heating rate of 3 ℃ per minute;
step S2: after cooling to room temperature, the obtained product was placed at 1 mol L -1 Hydrochloric acid solution (pH)<1) Stirring 1.5 and h, filtering, cleaning with a large amount of deionized water, and vacuum drying;
step S3: at 1 mol L -1 Sodium hydroxide solution (pH)>13 Stirring for 1.5 to h, suction filtering, washing and filtering with deionized water, and vacuum drying;
step S4: extracting and purifying by using methanol soxhlet, and then drying in vacuum again to obtain a high-yield palladium phthalocyanine molecular catalyst (PdPc);
(2) Based on the palladium phthalocyanine molecular catalyst, preparing a carbon nanotube supported palladium phthalocyanine molecular catalyst:
firstly, treating the carbon nano tube with concentrated sulfuric acid at 90 ℃ for 6 h, removing metal impurities of the carbon substrate, improving the oxygen content of the surface of the carbon substrate, washing and filtering with deionized water, and then drying at 75 ℃ for 6 h;
dispersing PdPc in an N, N-dimethylformamide solvent, carrying out ultrasonic treatment for 30min, then adding a carbon nano tube, continuing ultrasonic treatment for 30min, and stirring at room temperature for 20 h, wherein the mass ratio of the carbon nano tube to the PdPc to the N, N-dimethylformamide solvent is 1:0.05:500;
washing and filtering the mixed solution with deionized water, and finally vacuum drying at 100 ℃ for 8 h to obtain the carbon nanotube supported palladium phthalocyanine molecular catalyst (PbPc/CNT), namely the carbon substrate supported palladium phthalocyanine molecular catalyst.
Example 15
The embodiment provides a preparation method of a PbPc/CNT electrode, which specifically comprises the following steps:
dispersing the carbon nanotube supported palladium phthalocyanine molecular catalyst PbPc/CNT prepared in the embodiment 1 of 5 mg into a mixed solution of Nafion, water and ethanol of 1 mL in a volume ratio of 0.062:1:1, and performing ultrasonic treatment for 30 minutes to obtain uniform black catalyst slurry;
mu.L of black catalyst slurry was pipetted into a surface area of 0.09cm 2 And (3) drying the carbon paper electrode under the wet room temperature condition to form a working electrode film, thereby forming the PbPc/CNT electrode.
Reduction of CO using PbPc/CNT catalyst prepared by three electrode cell testing 2 The performance of CO is that the PbPc/CNT electrode is a working electrode, the counter electrode is a platinum sheet electrode, the reference electrode is an Ag/AgCl electrode, and the electrolyte is 0.5M KHCO saturated by carbon dioxide 3 The test voltage range is-1-0.5V vs. RHE. PdPc/CNT electrode prepared in this example and pretreated Carbon Nanotube (CNT) reduction CO without Palladium phthalocyanine molecular catalyst in example 1 2 The polarization curve of CO is shown in FIG. 5, which shows that the Carbon Nanotube (CNT) without the supported palladium phthalocyanine molecular catalyst has almost no electrocatalytic carbon dioxide reduction current, while the PbPc/CNT supported by the carbon nanotube has better CO 2 RR performance. The PdPc/CNT electrodes produced reduce CO at voltages of-0.6, -0.7, -0.8 and-0.9V 2 The potentiostatic stability curve for CO is shown in FIG. 6, which shows that PbPc/CNT has better catalytic stability. The PdPc/CNT electrodes produced reduce CO at voltages of-0.6, -0.7, -0.8 and-0.9V 2 The Faraday efficiency for CO is shown in FIG. 7, which also shows that PbPc/CNT has good reduction efficiency.
According to the embodiment of the invention, the PdPc is synthesized by adopting a green method, an organic solvent and an organic base catalyst are not needed, and the carbon substrate supported/supported PdPc molecular catalyst is obtained by auxiliary dissolution and re-adsorption of the organic solvent, so that the utilization rate of metal atoms Pd is improved, and the carbon substrate supported PdPc molecular catalyst is firstly utilized for electrocatalytic carbon dioxide reduction, CO 2 The reduction to CO is efficient.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention are included in the protection scope of the present invention.
Claims (4)
1. The preparation method of the palladium phthalocyanine molecular catalyst is characterized by comprising the following steps of:
fully mixing the nitrile organic compound with palladium salt, nitrogen source and solid phase reaction catalyst, calcining at high temperature in inert atmosphere, and cooling to room temperature;
stirring the strong acid solution for 0.2-2 h, washing with deionized water, filtering and drying in vacuum;
stirring strong alkali solution for 0.2-2 h, washing with deionized water, filtering and vacuum drying;
extracting and purifying methanol by Soxhlet extraction and then drying in vacuum again to obtain a palladium phthalocyanine molecular catalyst;
the mass ratio of the nitrile organic compound to the palladium salt to the nitrogen source to the solid phase reaction catalyst is 1:0.05-0.5:1.5-10:0.01-0.05;
the nitrile organic compound is phthalonitrile, 4-nitrophthalonitrile or 4-amino phthalonitrile;
the palladium salt is palladium dichloride, palladium acetate, sodium tetrachloropalladate or palladium tetrammine dichloride;
the nitrogen source is urea, ammonium chloride, ammonium bicarbonate or ammonium nitrate;
the solid phase reaction catalyst is molybdate;
the PH of the strong acid solution is less than 1, and the PH of the strong base solution is more than 13;
the calcination temperature is 100-300 ℃, the temperature rising speed is 2-5 ℃/min, and the calcination time is 6-10 h.
2. The preparation method of the carbon substrate supported palladium phthalocyanine molecular catalyst is characterized by comprising the following steps of:
dispersing the palladium phthalocyanine molecular catalyst and the pretreated carbon substrate in an organic solvent, and stirring, washing, filtering and vacuum drying to obtain the palladium phthalocyanine molecular catalyst supported by the carbon substrate;
the palladium phthalocyanine molecular catalyst is prepared by the preparation method of the palladium phthalocyanine molecular catalyst as claimed in claim 1;
the organic solvent is N, N-dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone.
3. The method for preparing a carbon-supported palladium phthalocyanine catalyst according to claim 2, wherein the mass ratio of the carbon substrate, the palladium phthalocyanine catalyst and the organic solvent is 1:0.02-0.1:100-1000.
4. The method for preparing a carbon substrate supported palladium phthalocyanine molecular catalyst according to claim 2, wherein after dispersing the palladium phthalocyanine molecular catalyst and the pretreated carbon substrate in an organic solvent, stirring 20 to 30 h, and vacuum drying at 60 to 100 ℃ for 8 to 12 h.
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