CN115254193A - Palladium phthalocyanine molecular catalyst, preparation method of carbon substrate supported palladium phthalocyanine molecular catalyst and application of catalyst - Google Patents
Palladium phthalocyanine molecular catalyst, preparation method of carbon substrate supported palladium phthalocyanine molecular catalyst and application of catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 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 94
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- 239000000758 substrate Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005406 washing Methods 0.000 claims abstract description 27
- 238000001914 filtration Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000003756 stirring 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 16
- 230000009467 reduction Effects 0.000 claims abstract description 16
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 nitrile organic compounds Chemical class 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 150000002940 palladium Chemical class 0.000 claims abstract description 8
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- 238000003746 solid phase reaction Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 238000000605 extraction Methods 0.000 claims abstract description 5
- 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
- 238000000034 method Methods 0.000 claims description 12
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 12
- 239000004202 carbamide Substances 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
- 238000000944 Soxhlet extraction Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 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 claims description 4
- 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
- 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
- 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
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000002041 carbon nanotube Substances 0.000 description 36
- 229910021393 carbon nanotube Inorganic materials 0.000 description 36
- 238000006722 reduction reaction Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 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 9
- 239000002184 metal Substances 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
- 239000000203 mixture Substances 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 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
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 150000002739 metals Chemical class 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
- 238000012360 testing method 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
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 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
- 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
- 238000002474 experimental method Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
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- 238000001000 micrograph Methods 0.000 description 1
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- 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
- 239000002994 raw material Substances 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
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
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- 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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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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- 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
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Abstract
The invention discloses a preparation method and application of a palladium phthalocyanine molecular catalyst and a carbon substrate supported palladium phthalocyanine molecular catalyst, wherein nitrile organic compounds, palladium salt, a nitrogen source and a solid-phase reaction catalyst are fully mixed and then calcined at high temperature in an inert atmosphere; cooling to room temperature, stirring the strong acid solution for 0.2 to 2 hours, washing with deionized water, filtering, and drying in vacuum; stirring the strong alkali liquor for 0.2 to 2 hours, washing and filtering the strong alkali liquor by using deionized water, and drying the strong alkali liquor in vacuum; and (4) after extraction and purification, vacuum drying is carried out 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 carbon substrate supported palladium phthalocyanine molecular catalyst. The palladium phthalocyanine molecular catalyst and the carbon substrate supported palladium phthalocyanine molecular catalyst both have palladium sites with high atom utilization rate, 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 electrocatalysis carbon dioxide reduction, and relates to a preparation method and application of a palladium phthalocyanine molecular catalyst and a carbon substrate supported palladium phthalocyanine molecular catalyst.
Background
Electrochemical reduction of carbon dioxide is an efficient energy conversion technology for converting intermittent electrical energy into valuable chemicals and is therefore of great interest. However, carbon dioxide is chemically very stable, and a direct electrical reduction method requires a high overpotential, so that a suitable electrocatalyst is required to increase the current density and reduce the overpotential. The metals are first used in electrocatalysts, and among all metals, the palladium-based electrocatalysts have a higher conversion rate for the reduction reaction of carbon dioxide. However, the material generally has the problems of poor product selectivity, metal electro-reduction side effect, catalyst poisoning and other activity losses, high cost, limited availability and the like. In addition, the traditional method for preparing the blocky or flaky palladium-based catalyst has less electrochemical active area and less exposed active sites, so that the catalytic activity is not ideal. Therefore, the development of new palladium-based electrocatalysts with high product selectivity, high atom utilization and high chemical stability remains a very challenging issue.
The metal phthalocyanine is a compound with a highly symmetrical structure, has uniform electron distribution, has excellent chemical stability, receives attention from people in the fields of photoelectrocatalysis, solar cells, medicines and the like, and is widely applied to the treatment of diseases, the solution of the problems of environmental pollution, energy shortage and the like. Therefore, the synthesis of the palladium phthalocyanine is an effective way for improving the utilization rate of palladium atoms and obtaining high catalytic activity. However, the traditional palladium phthalocyanine has weak coordination capacity of palladium ions, so that the problems of complicated steps, long period, harsh conditions (preparation under the conditions of high-boiling-point organic solvent, anhydrous oxygen-free and organic alkali) and the like exist in the synthesis process, namely the preparation method, and 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 the carbon substrate supported palladium phthalocyanine molecular catalyst and application of the carbon substrate supported palladium phthalocyanine molecular catalyst, 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 atom utilization rate, more impurities and low yield of the traditional preparation method of the 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:
the nitrile organic compound is fully mixed with palladium salt, nitrogen source and solid phase reaction catalyst, and then is calcined at high temperature in inert atmosphere to obtain the phthalocyanine palladium molecular catalyst.
Further, after high-temperature calcination in an inert atmosphere, the following operations are also performed:
cooling to room temperature;
stirring the strong acid solution for 0.2 to 2 hours, washing with deionized water, filtering, and drying in vacuum;
stirring strong alkali liquor for 0.2 to 2 hours, washing with deionized water, filtering, and drying in vacuum;
and after extraction and purification, vacuum drying is carried out again to obtain the phthalocyanine palladium 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 1.05-0.5;
the nitrile organic compound is phthalonitrile, 4-nitro phthalonitrile or 4-amino phthalonitrile;
the palladium salt is palladium dichloride, palladium acetate, sodium tetrachloropalladate or tetraammine palladium 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 less than 1, and the pH of the strong alkali solution is more than 13;
the extraction and purification adopt methanol Soxhlet extraction and purification.
Furthermore, the calcination temperature is between 100 and 300 ℃, the temperature rise speed is between 2 and 5 ℃/min, and the calcination time is between 6 and 10 h.
The second technical scheme adopted by the embodiment of the invention is as follows: use of a palladium phthalocyanine molecular catalyst for the reduction of 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 carbon substrate supported palladium phthalocyanine molecular catalyst.
Further, the organic solvent is N, N-dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone;
the mass ratio of the carbon substrate, the palladium phthalocyanine molecular catalyst and the organic solvent is 1: 0.02-0.1: 100-1000.
Further, the pretreatment of the carbon substrate comprises the steps of treating 6-24 h by concentrated sulfuric acid at 70-90 ℃, washing by deionized water, filtering, and drying at 40-100 ℃ for 2-10 h;
dispersing the palladium phthalocyanine molecular catalyst and the pretreated carbon substrate in an organic solvent, stirring for 20-30 h, and vacuum drying at 60-100 ℃ for 8-12 h.
The fourth technical scheme adopted by the embodiment of the invention is as follows: application of a carbon substrate supported palladium phthalocyanine molecular catalyst for reducing carbon dioxide.
The embodiment of the invention has the beneficial effects that:
1. the raw materials are low in price, the synthesis route is simple and feasible, and compared with the traditional preparation method, the preparation method provided by the embodiment of the invention has the advantages that the yield is up to more than 90%, the large-scale preparation can be carried out, and the problem of low yield of the traditional preparation method of palladium phthalocyanine is solved;
2. compared with the traditional palladium nano-block or palladium nano-sheet, the palladium phthalocyanine molecular catalyst prepared by chemically bonding the organic ligand and palladium in the embodiment of the invention has higher atom utilization rate, so that the catalyst has more excellent CO 2 RR activity, solving the problem of low atom utilization rate of the traditional preparation method of palladium phthalocyanine;
3. the palladium phthalocyanine molecules prepared by the embodiment of the invention can be uniformly loaded on different types of carbon substrates, so that a plurality of carbon substrate supported palladium phthalocyanine molecular catalysts can be obtained, the palladium phthalocyanine molecular catalysts can be used as excellent catalysts for electrocatalytic carbon dioxide reduction reaction, and the palladium phthalocyanine molecular catalysts can show excellent catalytic activity, excellent selectivity for reducing carbon dioxide into carbon monoxide and excellent reaction stability;
in conclusion, the embodiment of the invention adopts the synthesis path of calcining palladium salt and nitrile organic compound at high temperature to obtain palladium phthalocyanine and further using a stirring method to obtain the carbon substrate supported palladium phthalocyanine material, thereby avoiding the problems of harsh conditions, more side reactions and the like of the traditional preparation method, having the advantages of simplicity, high efficiency and large-scale preparation, and having good application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a UV spectrum of the palladium phthalocyanine catalyst prepared in example 1.
FIG. 2 is a Raman spectrum of the palladium phthalocyanine catalyst obtained in example 1.
FIG. 3 is a scanning electron micrograph of the palladium phthalocyanine catalyst prepared in example 1.
Fig. 4 is a scanning electron micrograph of the carbon nanotube-supported palladium phthalocyanine molecular catalyst prepared in example 1.
FIG. 5 shows the reduction of CO by the carbon nanotubes pretreated in this example 1 and the prepared carbon nanotube-supported palladium phthalocyanine molecular catalyst 2 The polarization curve of CO is compared with that of CO.
FIG. 6 shows the carbon nanotube supported palladium phthalocyanine molecular catalyst prepared in this example 1 reducing CO at potentials of-0.6V, -0.7V, -0.8V and-0.9V 2 The potentiostatic stability of CO is plotted.
FIG. 7 shows that the carbon nanotube supported palladium phthalocyanine molecular catalyst prepared in this example 1 reduces CO at potentials of-0.6V, -0.7V, -0.8V and-0.9V 2 Is the faradaic efficiency of CO.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
(1) Preparation of palladium phthalocyanine molecular catalyst:
step S1: uniformly grinding phthalonitrile, palladium dichloride, urea and ammonium molybdate in a mass ratio of 1;
step S2: after cooling to room temperature, the product obtained is placed in 1 mol L -1 Hydrochloric acid solution (pH)<1) Stirring the mixture for 1 h, performing suction filtration, washing the mixture by using a large amount of deionized water, and performing vacuum drying;
and 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;
and step S4: carrying out soxhlet extraction and purification by methanol, and then carrying out vacuum drying again to obtain the high-yield palladium phthalocyanine molecular catalyst (PdPc);
(2) Preparing a carbon nanotube-supported palladium phthalocyanine molecular catalyst based on the palladium phthalocyanine molecular catalyst:
firstly, treating 15 h by concentrated sulfuric acid at 90 ℃, removing metal impurities from a carbon substrate, increasing the oxygen content of the surface of the carbon substrate, washing and filtering by deionized water, and then drying 8 h at 60 ℃;
dispersing PdPc in an N, N-dimethylformamide solvent, performing ultrasonic treatment for 30min, adding carbon nanotubes, continuing performing ultrasonic treatment for 30min, and stirring at room temperature for 24 h, wherein the mass ratio of the carbon nanotubes to the PdPc to the N, N-dimethylformamide solvent is 1;
washing the mixed solution with deionized water, filtering, and finally drying 10 h in vacuum at 80 ℃ to obtain the carbon nano tube supported palladium phthalocyanine molecular catalyst (PbPc/CNT), namely the carbon substrate supported palladium phthalocyanine molecular catalyst.
The UV spectrogram of the PdPc catalyst prepared in this example is shown in FIG. 1, and is located at 600 and 690 cm -1 The absorption peak is the characteristic peak of PdPc, which shows that the prepared material is PdPc, and the PdPc has certain CO proved by experiments 2 RR performance. The Raman spectrogram of the prepared PdPc catalyst is shown in figure 2, and the appearance of a Raman absorption peak reflects the highly symmetrical molecular structure of PdPc, further showing the synthesis of PdPc. The scanning electron microscope image of the prepared PdPc catalyst is shown in FIG. 3, and it can be seen that PdPc has a blocky morphology consisting of nanoparticles.
The scanning electron micrograph of the carbon nanotube-supported palladium phthalocyanine molecular catalyst prepared in this example is shown in fig. 4, and it can be seen from fig. 4 that a large number of carbon nanotubes exist without bulk PbPc, indicating that the palladium phthalocyanine molecules can be uniformly dispersed on the carbon substrate surface to obtain the carbon nanotube-supported palladium phthalocyanine molecular catalyst.
Example 2
The difference between the present embodiment and embodiment 1 is only that the mass ratio of phthalonitrile, palladium dichloride, urea and ammonium molybdate is 1.
Example 3
The difference between the present example and example 1 is only that the mass ratio of phthalonitrile, palladium dichloride, urea and ammonium molybdate is 1.
Example 4
The difference between the present example and example 1 is only that the mass ratio of phthalonitrile, palladium dichloride, urea and ammonium molybdate is 1.
Example 5
The difference between the present example and example 1 is only that the mass ratio of phthalonitrile, palladium dichloride, urea and ammonium molybdate is 1.
Example 6
The present example differs from example 1 only in that the mass ratio of the nanotubes, pdPc, and N, N-dimethylformamide solvent is 1.
Example 7
The present example differs from example 1 only in that the mass ratio of the nanotubes, pdPc, and N, N-dimethylformamide solvent is 1.
Example 8
The present example differs from example 1 only in that the mass ratio of the nanotubes, pdPc, and N, N-dimethylformamide solvent is 1.
Example 9
This example differs from example 1 only in that the carbon substrate is graphene, producing a uniformly dispersed graphene-supported palladium phthalocyanine molecular catalyst (PbPc/GPE).
Example 10
This example differs from example 1 only in that the carbon substrate is acetylene black, resulting in a uniformly dispersed acetylene black supported palladium phthalocyanine molecular catalyst (PbPc/ACET).
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/Ketjenblack) was prepared.
Example 12
This example provides the preparation of a carbon substrate supported palladium phthalocyanine molecular catalyst by the following method:
(1) Preparation of palladium phthalocyanine molecular catalyst:
step S1: uniformly mixing and grinding phthalonitrile, l palladium dichloride, urea and ammonium molybdate in a mass ratio of 1;
step S2: after cooling to room temperature, the product obtained is placed in 1 mol L -1 Hydrochloric acid solution (pH)<1) Stirring the mixture for 0.2h, performing suction filtration, washing the mixture by using a large amount of deionized water, and performing vacuum drying;
and step S3: at 1 mol L -1 Sodium hydroxide solution (pH)>13 Stirring for 0.2h, performing suction filtration, washing with deionized water, filtering, and vacuum drying;
and step S4: carrying out soxhlet extraction and purification by methanol, and then carrying out vacuum drying again to obtain the high-yield palladium phthalocyanine molecular catalyst (PdPc);
(2) Preparing a carbon nanotube-supported palladium phthalocyanine molecular catalyst based on the palladium phthalocyanine molecular catalyst:
firstly, treating 10 h by concentrated sulfuric acid at 80 ℃, removing metal impurities from a carbon substrate, increasing the oxygen content of the surface of the carbon substrate, washing the carbon substrate with deionized water, filtering, and drying 10 h at 40 ℃;
dispersing PdPc in N, N-dimethylformamide solvent, performing ultrasonic treatment for 30min, adding carbon nanotubes, continuing ultrasonic treatment for 30min, and stirring at room temperature for 24 h, wherein the mass ratio of the carbon nanotubes to the PdPc to the N, N-dimethylformamide solvent is 1;
washing the mixed solution with deionized water, filtering, and finally drying in vacuum 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
This example provides the preparation of a carbon substrate supported palladium phthalocyanine molecular catalyst by the following method:
(1) Preparation of palladium phthalocyanine molecular catalyst:
step S1: uniformly mixing and grinding phthalonitrile, palladium dichloride, urea and ammonium molybdate in a mass ratio of 1;
step S2:after cooling to room temperature, the product obtained is placed in 1 mol L -1 Hydrochloric acid solution (pH)<1) Stirring the mixture for 2h, performing suction filtration, washing the mixture by using a large amount of deionized water, and performing vacuum drying;
and step S3: at 1 mol L -1 Sodium hydroxide solution (pH)>13 2h, then suction filtration, washing with deionized water, filtration and vacuum drying;
and step S4: performing Soxhlet extraction and purification by methanol, and then performing vacuum drying again to obtain the high-yield palladium phthalocyanine molecular catalyst (PdPc);
(2) Preparing a carbon nanotube-supported palladium phthalocyanine molecular catalyst based on the palladium phthalocyanine molecular catalyst:
firstly, treating 24 h by concentrated sulfuric acid at 70 ℃, removing metal impurities from a carbon substrate, increasing the oxygen content of the surface of the carbon substrate, washing and filtering by deionized water, and then drying for 2 hours at 100 ℃;
dispersing PdPc in an N, N-dimethylformamide solvent, performing ultrasonic treatment for 30min, adding carbon nanotubes, continuing performing ultrasonic treatment for 30min, and stirring at room temperature for 30 h, wherein the mass ratio of the carbon nanotubes to the PdPc to the N, N-dimethylformamide solvent is 1;
washing the mixed solution with deionized water, filtering, and finally drying 8 h in vacuum at 60 ℃ to obtain the carbon nano tube supported palladium phthalocyanine molecular catalyst (PbPc/CNT), namely the carbon substrate supported palladium phthalocyanine molecular catalyst.
Example 14
(1) Preparation of palladium phthalocyanine molecular catalyst:
step S1: uniformly mixing and grinding phthalonitrile, palladium dichloride, urea and ammonium molybdate in a mass ratio of 1;
step S2: after cooling to room temperature, the product obtained is placed in 1 mol L -1 Hydrochloric acid solution (pH)<1) Stirring the mixture for 1.5 h, then performing suction filtration, washing the mixture by using a large amount of deionized water, and performing vacuum drying;
and step S3: at 1 mol L -1 Sodium hydroxide solution (pH)>13 Stirring 1.5 h, suction filtering, washing with deionized water, filtering, and vacuum drying;
and step S4: performing Soxhlet extraction and purification by methanol, and then performing vacuum drying again to obtain the high-yield palladium phthalocyanine molecular catalyst (PdPc);
(2) Preparing a carbon nanotube-supported palladium phthalocyanine molecular catalyst based on a palladium phthalocyanine molecular catalyst:
firstly, treating 6 h by concentrated sulfuric acid at 90 ℃, removing metal impurities from a carbon substrate, increasing the oxygen content of the surface of the carbon substrate, washing and filtering by deionized water, and then drying 6 h at 75 ℃;
dispersing PdPc in N, N-dimethylformamide solvent, performing ultrasonic treatment for 30min, adding carbon nanotubes, continuing ultrasonic treatment for 30min, and stirring at room temperature for 20 h, wherein the mass ratio of the carbon nanotubes to the PdPc to the N, N-dimethylformamide solvent is 1;
washing the mixed solution with deionized water, filtering, and finally drying 8 h in vacuum at 100 ℃ 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 a carbon nanotube-supported palladium phthalocyanine molecular catalyst PbPc/CNT prepared in example 1 of 5 mg into a mixed solution of Nafion, water and ethanol of 1 mL in a volume ratio of 0.062;
suck 18. Mu.L of black catalyst slurry droplets to a surface area of 0.09cm 2 The carbon paper electrode is dried under the wet room temperature condition to form a working electrode film, and a PbPc/CNT electrode is formed.
Reduction of CO with PbPc/CNT catalyst prepared by three-electrode battery test 2 For CO performance, 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 with carbon dioxide 3 The test voltage range is-1-0.5V vs. PdPc/CNT electrode prepared in this example and Carbon Nanotube (CNT) without supported palladium phthalocyanine molecular catalyst pretreated in example 1 for CO reduction 2 Polarization curve for CO is shown in FIG. 5It is shown that the Carbon Nano Tube (CNT) without the supported palladium phthalocyanine molecular catalyst has almost no electrocatalytic carbon dioxide reduction current, and the carbon nano tube supported palladium phthalocyanine molecular catalyst PbPc/CNT has better CO 2 RR performance. The prepared PdPc/CNT electrode reduces CO at-0.6, -0.7, -0.8 and-0.9V voltages 2 The potentiostatic stability curve for CO is shown in FIG. 6, which indicates that PbPc/CNT has better catalytic stability. The prepared PdPc/CNT electrode reduces CO at-0.6, -0.7, -0.8 and-0.9V voltages 2 The Faraday efficiency for CO is shown in FIG. 7, which also indicates that PbPc/CNT has good reduction efficiency.
The embodiment of the invention synthesizes PdPc by adopting a green method, does not need an organic solvent and an organic base catalyst, obtains the PdPc molecular catalyst supported/loaded on the carbon substrate by the auxiliary dissolution and re-adsorption of the organic solvent, improves the utilization rate of metal atom Pd, and utilizes the PdPc molecular catalyst supported on the carbon substrate for electrocatalytic carbon dioxide reduction, CO reduction and CO reduction for the first time 2 The reduction to CO is efficient.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. The preparation method of the palladium phthalocyanine molecular catalyst is characterized by comprising the following steps:
the nitrile organic compound is fully mixed with palladium salt, nitrogen source and solid phase reaction catalyst, and then is calcined at high temperature in inert atmosphere to obtain the phthalocyanine palladium molecular catalyst.
2. The method for preparing a palladium phthalocyanine molecular catalyst according to claim 1, wherein the following operation is further performed after the calcination at a high temperature in an inert atmosphere:
cooling to room temperature;
stirring the strong acid solution for 0.2 to 2 hours, washing with deionized water, filtering and drying in vacuum;
stirring strong alkali liquor for 0.2 to 2 hours, washing with deionized water, filtering, and drying in vacuum;
and (4) after extraction and purification, vacuum drying is carried out again to obtain the palladium phthalocyanine molecular catalyst.
3. The method for preparing a palladium phthalocyanine molecular catalyst according to claim 1, wherein the mass ratio of the nitrile organic compound, the palladium salt, the nitrogen source and the solid-phase reaction catalyst is 1 (0.05-0.5) to 1.5-10 to 0.01-0.05;
the nitrile organic compound is phthalonitrile, 4-nitro phthalonitrile or 4-amino phthalonitrile;
the palladium salt is palladium dichloride, palladium acetate, sodium tetrachloropalladate or tetraammine palladium dichloride;
the nitrogen source is urea, ammonium chloride, ammonium bicarbonate or ammonium nitrate;
the solid phase reaction catalyst is molybdate.
4. The method for preparing the palladium phthalocyanine molecular catalyst according to claim 2, wherein the pH of the strong acid solution is less than 1, and the pH of the strong alkali solution is more than 13;
the extraction and purification adopt methanol Soxhlet extraction and purification.
5. The method of making a palladium phthalocyanine molecular catalyst as claimed in any one of claims 1~4 wherein the calcination temperature is between 100-300 ℃, the ramp rate is between 2-5 ℃/min, and the calcination time is between 6-10 h.
6. Use of a palladium phthalocyanine molecular catalyst, characterized in that it is used for the reduction of carbon dioxide.
7. The preparation method of the carbon substrate supported palladium phthalocyanine molecular catalyst is characterized by comprising 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 carbon substrate supported palladium phthalocyanine molecular catalyst.
8. The method of claim 7, wherein the organic solvent is N, N-dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone;
the mass ratio of the carbon substrate, the palladium phthalocyanine molecular catalyst and the organic solvent is 1 (0.02-0.1): (100-1000).
9. The method for preparing the carbon substrate supported palladium phthalocyanine molecular catalyst according to claim 7, wherein the pretreatment of the carbon substrate comprises the steps of treating 6-24 h with concentrated sulfuric acid at 70-90 ℃, washing with deionized water, filtering, and drying 2-10 h at 40-100 ℃;
dispersing a palladium phthalocyanine molecular catalyst and the pretreated carbon substrate in an organic solvent, stirring for 20-30 h, and performing vacuum drying at 60-100 ℃ for 8-12 h.
10. Use of a carbon substrate supported palladium phthalocyanine molecular catalyst for the reduction of carbon dioxide.
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