CN114797922A - Preparation method of monatomic iron-carbon electrode with two-electron oxygen reduction selectivity - Google Patents
Preparation method of monatomic iron-carbon electrode with two-electron oxygen reduction selectivity Download PDFInfo
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- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 title claims abstract description 106
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000001301 oxygen Substances 0.000 title claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 37
- 230000009467 reduction Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- 229910001567 cementite Inorganic materials 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims description 87
- 239000002243 precursor Substances 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 claims description 10
- 239000005416 organic matter Substances 0.000 claims description 10
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 claims description 8
- 230000020477 pH reduction Effects 0.000 claims description 7
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 claims description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims 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 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 238000002791 soaking Methods 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011261 inert gas Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000019635 sulfation Effects 0.000 description 6
- 238000005670 sulfation reaction Methods 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229960005404 sulfamethoxazole Drugs 0.000 description 5
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- -1 phenol organic compound Chemical class 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Abstract
The invention belongs to the technical field of electrode preparation, and particularly relates to a preparation method of a monatomic iron-carbon electrode with two-electron oxygen reduction selectivity. The invention provides an iron-carbon integrated electrode, wherein the mass fraction of monatomic iron in the iron-carbon integrated electrode is 0.1-0.5%, and the mass fraction of iron carbide is 0.1-0.5%. The iron-carbon integrated electrode provided by the invention has the advantages of high selectivity of two electrons, high catalytic activity, simple preparation method and good electrochemical stability.
Description
Technical Field
The invention belongs to the technical field of electrode preparation, and particularly relates to a preparation method of a monatomic iron-carbon electrode with two-electron oxygen reduction selectivity.
Background
Molecular oxygen is an ideal oxidant from an economic and environmental point of view, because it is abundant and inexpensive. The molecular oxygen electrocatalytic reduction technology is fuel cell technologyThe important components have wide prospects in the aspect of meeting the requirements of environment-friendly energy sources. In addition, two electrons (2 e) are selected - ) Oxygen Reduction Reaction (ORR) enables continuous in situ generation of H under mild conditions 2 O 2 . The electrochemically generated hydrogen peroxide, as an environment-friendly oxidant, can be activated by an additionally added homogeneous (ferrous ions) or heterogeneous (nano zero-valent iron, iron oxide, metal alloy, etc.) fenton reagent to generate strongly oxidizing hydroxyl radicals, i.e., a variant of the Huron-Dow process, and is widely applied to the aspects of environmental remediation, wastewater treatment, etc. The iron-based catalyst has the advantages of high activity, abundant reserves, low cost and the like, and is used for decomposing H 2 O 2 An ideal catalyst for the production of HO. But the additional addition of chemicals is likely to cause secondary pollution. Therefore, the iron catalyst grows in situ in the carbon-based electrode to prepare the integrated iron-based carbon electrode, so that the application of the molecular oxygen reduction technology in a water environment can be further promoted.
However, conventional iron-based catalysts typically follow a four electron path (O) 2 +4H + +4e - ＝2H 2 O) water is produced during the oxygen reduction process. For example: chinese patent CN111952608A discloses a preparation method of a monatomic iron oxide reduction catalyst, which is characterized in that ZIF-8 doped with zeolite imidazole material Fe is used as a precursor, a nitrogen source is added for the second time, and then pyrolysis is carried out in an inert gas atmosphere to obtain the monatomic iron catalyst with four-electron selectivity. Chinese patent CN107346826B discloses a method for utilizing g-C 3 N 4 The surface active agent and the iron source are added into the raw materials, and the monatomic iron-dispersed electrocatalyst is obtained through high-temperature pyrolysis and shows electrochemical performance equivalent to platinum carbon.
However, most of the iron-carbon-based catalysts in the prior art have low selectivity of two electrons in the oxygen reduction reaction process, and the selectivity control from four electrons to two electrons is difficult to realize, so that the yield of hydrogen peroxide is low, and the requirement of water pollution control cannot be met.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that in most of the oxygen reduction reaction processes of the iron-carbon-based catalyst in the prior art, the selectivity of two electrons is low, the selectivity regulation from four electrons to two electrons is difficult to realize, the yield of hydrogen peroxide is low, and the water pollution control requirement cannot be met, so that the iron-carbon integrated electrode with high selectivity of two electrons in the oxygen reduction reaction, and the preparation method and the application thereof are provided.
Therefore, the invention provides the following technical scheme,
the invention provides a preparation method of a monoatomic iron-carbon electrode with two-electron oxygen reduction selectivity, which comprises the following steps,
(1) mixing, reacting and drying a phenolic organic matter, an aldehyde organic matter, a nitrogen source, sodium carbonate, an iron-nitrogen precursor and water to obtain an iron-carbon integrated electrode precursor;
(2) and calcining, acidifying and drying the iron-carbon integrated electrode precursor to obtain the iron-carbon integrated electrode.
Optionally, the phenolic organic matter is one or more of resorcinol, pyrocatechol, hydroquinone and phenol;
and/or the aldehyde organic matter is one or more of formaldehyde, acetaldehyde and propionaldehyde.
Optionally, the nitrogen source is one or more of acetonitrile, urea, dicyandiamide and melamine;
and/or the iron-nitrogen precursor is one or more of iron phthalocyanine, iron porphyrin and iron sulfide phthalocyanine.
Optionally, the mass ratio of the phenolic organic matter, the aldehyde organic matter, the nitrogen source, the iron-nitrogen precursor and the sodium carbonate is (30-45): (45-55): (1-5): (1-7): (0.001-0.05).
Optionally, the mass ratio of the phenolic organic matter to the water is 1: (1.5-3.0).
Optionally, the reaction conditions are: the reaction is carried out for 20-30h at 20-30 ℃, then for 20-30h at 40-60 ℃ and finally for 60-90h at 80-100 ℃.
Optionally, the drying time is 24-72 h;
and/or the drying temperature is 20-30 ℃.
Optionally, the calcination mode is two-stage calcination;
the first-stage calcination temperature is 300-500 ℃, and the calcination time is 120-480 min;
the second-stage calcination temperature is 700-1000 ℃, and the calcination time is 120-480 min;
and/or the heating rate is 2-10 ℃/min.
Optionally, the preparation method satisfies at least one of the following (1) to (6):
(1) the concentration of the acidizing acid solution is 0.1-2.0 mol/L;
(2) the acid solution is one of sulfuric acid, hydrochloric acid and nitric acid;
(3) the temperature of the acidification treatment is 20-90 ℃;
(4) the time of the acidification treatment is 4-12 h;
(5) the drying mode is vacuum drying;
(6) the drying time is 24-96 h.
Optionally, the mass fraction of monatomic iron in the iron-carbon integrated electrode is 0.1-0.5%, and the mass fraction of iron carbide is 0.1-0.5%.
The technical proposal provided by the invention has the advantages that,
1. the invention provides an iron-carbon integrated electrode, wherein the mass fraction of monatomic iron in the iron-carbon integrated electrode is 0.1-0.5%, and the mass fraction of iron carbide is 0.1-0.5%. The iron-carbon integrated electrode provided by the invention has the advantages of high selectivity of two electrons, high catalytic activity, simple preparation method and good electrochemical stability.
2. Compared with the traditional iron-carbon catalyst, the iron-carbon integrated electrode provided by the invention has the advantages that 2e of the integrated monatomic iron-carbon integrated electrode - The oxygen reduction selectivity is improved from 10% to 90%, and the conversion from four-electron to two-electron oxygen reduction is realized.
3. The invention provides an iron-carbon integrated electrode, wherein Fe 3 C as an electron donor provides electrons for the active site of the monoatomic iron through long-range action to realize the regulation and control of the electron structure, thereby optimizing the junction of the OOH intermediateSynthesis energy, increase ORR activity, and thus increase electrocatalytic generation of H 2 O 2 Selectivity of (2).
4. The invention provides a preparation method of a monatomic iron-carbon electrode with two-electron oxygen reduction selectivity, which comprises the following steps of (1) mixing, reacting and drying a phenol organic compound, an aldehyde organic compound, a nitrogen source and an iron-nitrogen precursor to obtain an iron-carbon integrated electrode precursor; (2) and calcining, acidifying and drying the iron-carbon integrated electrode precursor to obtain the iron-carbon integrated electrode. By adopting acidification treatment, elemental iron and iron oxide can be etched, so that the selectivity of two electrons in the oxygen reduction process is improved.
5. The iron-carbon integrated electrode provided by the invention is adjustable in size and shape, can be directly used as a working electrode, can be better applied in a large scale, and avoids secondary forming and addition of a binder.
6. The invention also provides an iron-carbon integrated electrode or application of the iron-carbon integrated electrode prepared by the preparation method in wastewater treatment and environmental remediation. The electrode provided by the invention meets the economic, flexible and sustainable water purification requirement and enables the electrode to be implemented in remote communities and regions.
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, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a spherical aberration electron microscope of a monoatomic iron electrode prepared in example 1 of the present invention;
FIG. 2 is a 0.05mol/LNa of FeCA and FeNCA electrodes at pH 3 2 SO 4 LSV curve and H determined in solution 2 O 2 And (4) selectivity.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1 (supplementary data is best, the best electrode prepared)
This example provides an iron-carbon integrated electrode having a monoatomic iron mass fraction of 0.18 ± 0.02% and an iron carbide mass fraction of 0.16 ± 0.02%.
The embodiment also provides a preparation method of the monatomic iron-carbon electrode with two-electron oxygen reduction selectivity, which comprises the following steps,
(1) preparing an iron-carbon integrated electrode precursor: 66g resorcinol, 93g formaldehyde, 3g acetonitrile, 0.05g sodium carbonate and 13.5g iron phthalocyanine were dissolved in 116g water, mechanically stirred for 25min, reacted first at 25 ℃ for 25h, then at 50 ℃ for 25h and finally at 90 ℃ for 75 h. And after the reaction is finished, soaking the electrode in acetone at 25 ℃ for 72h, replacing the solvent every 24h, replacing the water in the electrode, and standing and drying the electrode at 30 ℃ for 72h after the soaking is finished to obtain the iron-carbon integrated electrode precursor.
(2) Preparing an iron-carbon integrated electrode: calcining the obtained iron-carbon integrated electrode precursor under the protection of inert gas (argon) (the gas flow rate is 100mL/min, the calcining mode is a two-section calcining mode, the first section of calcining is calcining at 300 ℃ for 120min, the second section of calcining is calcining at 850 ℃ for 120min), cooling to room temperature after calcining, then carrying out sulfation treatment on the obtained product for 8h at 80 ℃ by adopting 0.1mol/L, and drying the obtained acidified electrode in a vacuum drying oven at 30 ℃ for 24h to obtain the iron-carbon integrated electrode.
Example 2 (end point values using range data compared to example 1)
This example provides an iron-carbon integrated electrode in which the mass fraction of monoatomic iron is 0.4 ± 0.02%, and the mass fraction of iron carbide is 0.16 ± 0.02%.
The embodiment also provides a preparation method of the monatomic iron-carbon electrode with two-electron oxygen reduction selectivity, which comprises the following steps,
(1) preparing an iron-carbon integrated electrode precursor: 45g resorcinol, 45g formaldehyde, 5g acetonitrile, 0.05g sodium carbonate and 2g iron phthalocyanine were dissolved in 67g water, mechanically stirred for 25min, reacted first at 25 ℃ for 25h, then at 50 ℃ for 25h and finally at 90 ℃ for 75 h. And after the reaction is finished, soaking the electrode in acetone at 25 ℃ for 72h, replacing the solvent every 24h, replacing the water in the electrode, and standing and drying the electrode at 30 ℃ for 72h after the soaking is finished to obtain the iron-carbon integrated electrode precursor.
(2) Preparing an iron-carbon integrated electrode: calcining the obtained iron-carbon integrated electrode precursor under the protection of inert gas (argon) (the gas flow rate is 100mL/min, the calcining mode is a two-section calcining mode, the first section of calcining is calcining at 30 ℃ for 120min, the second section of calcining is calcining at 750 ℃ for 120min), cooling to room temperature after calcining, then carrying out sulfation treatment on the obtained product for 8h at 80 ℃ by adopting 0.1mol/L, and drying the obtained acidified electrode in a vacuum drying oven at 30 ℃ for 24h to obtain the iron-carbon integrated electrode.
Example 3 (comparing with example 1, using the other endpoint value of the range data)
This example provides an iron-carbon integrated electrode having a monoatomic iron mass fraction of 0.1 ± 0.02% and an iron carbide mass fraction of 0.17 ± 0.02%.
The embodiment also provides a preparation method of the monatomic iron-carbon electrode with two-electron oxygen reduction selectivity, which comprises the following steps,
(1) preparing an iron-carbon integrated electrode precursor: 30g resorcinol, 55g formaldehyde, 2g acetonitrile, 0.05g sodium carbonate and 5g iron phthalocyanine were dissolved in 90g water, mechanically stirred for 25min, reacted first at 25 ℃ for 25h, then at 50 ℃ for 25h and finally at 90 ℃ for 75 h. And after the reaction is finished, soaking the electrode in acetone for 72 hours at 25 ℃, replacing the solvent once every 24 hours, replacing the water in the electrode, and standing and drying the electrode for 24 hours at 30 ℃ after the soaking is finished to obtain the iron-carbon integrated electrode precursor.
(2) Preparing an iron-carbon integrated electrode: calcining the obtained iron-carbon integrated electrode precursor under the protection of inert gas (argon) (the gas flow rate is 100mL/min, the calcining mode is a two-section calcining mode, the first section of calcining is calcining at 300 ℃ for 120min, the second section of calcining is calcining at 950 ℃ for 120min), cooling to room temperature after calcining, then carrying out sulfation treatment on the obtained product for 8h at 80 ℃ by adopting 0.1mol/L, and drying the obtained acidified electrode in a vacuum drying oven at 30 ℃ for 24h to obtain the iron-carbon integrated electrode.
Example 4 (comparison with example 1, using the remaining materials in the claims)
This example provides an iron-carbon integrated electrode having a monoatomic iron mass fraction of 0.1 ± 0.02% and an iron carbide mass fraction of 0.17 ± 0.02%.
The embodiment also provides a preparation method of the monatomic iron-carbon electrode with two-electron oxygen reduction selectivity, which comprises the following steps,
(1) preparing an iron-carbon integrated electrode precursor: 66g of pyrocatechol, 93g of acetaldehyde, 3g of melamine, 0.05g of sodium carbonate and 13.5g of iron phthalocyanine sulfide are dissolved in 116g of water, mechanically stirred for 25min, reacted at 25 ℃ for 25h, then at 50 ℃ for 25h and finally at 90 ℃ for 75 h. And after the reaction is finished, soaking the electrode in acetone for 72 hours at 25 ℃, replacing the solvent once every 24 hours, replacing the water in the electrode, and standing and drying the electrode for 24 hours at 30 ℃ after the soaking is finished to obtain the iron-carbon integrated electrode precursor.
(2) Preparing an iron-carbon integrated electrode: calcining the obtained iron-carbon integrated electrode precursor under the protection of inert gas (nitrogen) (the gas flow rate is 100mL/min, the calcining mode is a two-section calcining mode, the first section of calcining is calcining at 300 ℃ for 120min, the second section of calcining is calcining at 850 ℃ for 120min), cooling to room temperature after calcining, then carrying out sulfation treatment on the obtained product for 8h at 30 ℃ by adopting 0.1mol/L, and drying the obtained acidified electrode in a vacuum drying oven at 30 ℃ for 24h to obtain the iron-carbon integrated electrode.
Example 5 (comparison with example 1, using the remaining materials in the claims)
This example provides an iron-carbon integrated electrode having a monoatomic iron mass fraction of 0.2 ± 0.02% and an iron carbide mass fraction of 0.18 ± 0.02%.
The embodiment also provides a preparation method of the monatomic iron-carbon electrode with two-electron oxygen reduction selectivity, which comprises the following steps,
(1) preparing an iron-carbon integrated electrode precursor: 66g of phenol, 93g of propionaldehyde, 3g of urea, 0.05g of sodium carbonate and 13.5g of iron porphyrin are dissolved in 116g of water, mechanically stirred for 25min, reacted at 25 ℃ for 25h, then at 50 ℃ for 25h and finally at 90 ℃ for 75 h. And after the reaction is finished, soaking the electrode in acetone at 25 ℃ for 75h, replacing the solvent every 24h, replacing the water in the electrode, and standing and drying the electrode at 30 ℃ for 24h after the soaking is finished to obtain the iron-carbon integrated electrode precursor.
(2) Preparing an iron-carbon integrated electrode: calcining the obtained iron-carbon integrated electrode precursor under the protection of inert gas (argon) (the gas flow rate is 100mL/min, the calcining mode is a two-section calcining mode, the first section of calcining is calcining at 300 ℃ for 120min, the second section of calcining is calcining at 850 ℃ for 120min), cooling to room temperature after calcining, then carrying out sulfation treatment on the obtained product for 8h at 80 ℃ by adopting 0.1mol/L, and drying the obtained acidified electrode in a vacuum drying oven at 30 ℃ for 24h to obtain the iron-carbon integrated electrode.
Example 6 (different value ranges and material compositions compared to example 1)
This example provides an iron-carbon integrated electrode in which the monoatomic iron mass fraction is 0.4 ± 0.02%, and the iron carbide mass fraction is 0.38 ± 0.02%.
The embodiment also provides a preparation method of the monatomic iron-carbon electrode with two-electron oxygen reduction selectivity, which comprises the following steps,
(1) preparing an iron-carbon integrated electrode precursor: 40g of hydroquinone, 45g of formaldehyde, 2g of acetonitrile, 0.05g of sodium carbonate and 2g of iron phthalocyanine are dissolved in 60g of water, mechanically stirred for 25min, reacted at 25 ℃ for 25h, then at 50 ℃ for 25h and finally at 90 ℃ for 75 h. And after the reaction is finished, soaking the electrode in acetone for 72 hours at 25 ℃, replacing the solvent once every 24 hours, replacing the water in the electrode, and standing and drying the electrode for 24 hours at 30 ℃ after the soaking is finished to obtain the iron-carbon integrated electrode precursor.
(2) Preparing an iron-carbon integrated electrode: calcining the obtained iron-carbon integrated electrode precursor under the protection of inert gas (nitrogen) (the gas flow rate is 100mL/min, the calcining mode is a two-section calcining mode, the first section of calcining is calcining at 300 ℃ for 120min, the second section of calcining is calcining at 850 ℃ for 120min), cooling to room temperature after calcining, then carrying out sulfation treatment on the obtained product for 8h at 80 ℃ by adopting 0.1mol/L, and drying the obtained acidified electrode in a vacuum drying oven at 30 ℃ for 24h to obtain the iron-carbon integrated electrode.
Example 7 (different value ranges and material compositions compared to example 1)
This example provides an iron-carbon integrated electrode in which the monoatomic iron mass fraction is 0.4 ± 0.02%, and the iron carbide mass fraction is 0.38 ± 0.02%.
The embodiment also provides a preparation method of the monatomic iron-carbon electrode with two-electron oxygen reduction selectivity, which comprises the following steps,
(1) preparing an iron-carbon integrated electrode precursor: 45g hydroquinone, 54g formaldehyde, 3g acetonitrile, 0.05g sodium carbonate and 2g iron phthalocyanine were dissolved in 80g water, mechanically stirred for 25min, reacted first at 25 ℃ for 25h, then at 50 ℃ for 25h and finally at 90 ℃ for 75 h. And after the reaction is finished, soaking the electrode in acetone for 72 hours at 25 ℃, replacing the solvent once every 24 hours, replacing the water in the electrode, and standing and drying the electrode for 24 hours at 30 ℃ after the soaking is finished to obtain the iron-carbon integrated electrode precursor.
(2) Preparing an iron-carbon integrated electrode: calcining the obtained iron-carbon integrated electrode precursor under the protection of inert gas (nitrogen) (the gas flow rate is 200mL/min, the calcining mode is a two-section calcining mode, the first section of calcining is calcining at 400 ℃ for 120min, the second section of calcining is calcining at 900 ℃ for 480min), cooling to room temperature after calcining, then carrying out acidification treatment on the obtained product for 6h by adopting 0.5mol/L of hydrochloride at 70 ℃, and drying the acidified electrode in a vacuum drying oven at 25 ℃ for 24h to obtain the iron-carbon integrated electrode.
Comparative example 1 (No acidification compared with example 1)
The comparative example also provides a method for preparing a monatomic iron-carbon electrode with two-electron oxygen reduction selectivity, comprising the steps of,
(1) preparing an iron-carbon integrated electrode precursor: 66g of resorcinol, 93g of formaldehyde, 3g of acetonitrile, 0.05g of sodium carbonate and 13.5g of iron phthalocyanine were dissolved in 116g of water and mechanically stirred for 25min, reacted first for 25h at 25 ℃, then for 25h at 50 ℃ and finally for 75h at 90 ℃. And after the reaction is finished, soaking the electrode in acetone at 25 ℃ for 72h, replacing the solvent every 24h, replacing the water in the electrode, and standing and drying the electrode at 30 ℃ for 72h after the soaking is finished to obtain the iron-carbon integrated electrode precursor.
(2) Preparing an iron-carbon integrated electrode: calcining the obtained iron-carbon integrated electrode precursor under the protection of inert gas (argon) (the gas flow rate is 100mL/min, the calcining mode is a two-section calcining mode, the first section of calcining is calcining at 300 ℃ for 120min, the second section of calcining is calcining at 850 ℃ for 120min), and cooling to room temperature after calcining to obtain the iron-carbon integrated electrode.
Comparative example 2 (mass ratio of iron-nitrogen precursor out of the range of protection as compared with example 1)
The comparative example also provides a method for preparing a monatomic iron-carbon electrode with two-electron oxygen reduction selectivity, comprising the steps of,
(1) preparing an iron-carbon integrated electrode precursor: 66g of resorcinol, 93g of formaldehyde, 3g of acetonitrile, 0.05g of sodium carbonate and 30g of iron phthalocyanine were dissolved in 116g of water, mechanically stirred for 25min, reacted first at 25 ℃ for 25h, then at 50 ℃ for 25h and finally at 90 ℃ for 75 h. And after the reaction is finished, soaking the electrode in acetone at 25 ℃ for 72h, replacing the solvent every 24h, replacing the water in the electrode, and standing and drying the electrode at 30 ℃ for 72h after the soaking is finished to obtain the iron-carbon integrated electrode precursor.
(2) Preparing an iron-carbon integrated electrode: calcining the obtained iron-carbon integrated electrode precursor under the protection of inert gas (argon) (the gas flow rate is 100mL/min, the calcining mode is a two-section calcining mode, the first-section calcining is calcining at 300 ℃ for 120min, the second-section calcining is calcining at 850 ℃ for 120min), and cooling to room temperature after calcining to obtain the iron-carbon integrated electrode.
Test example 1
The electrodes prepared in examples 1 to 7 and comparative examples 1 to 2 were subjected to performance tests, the contents of which are the yield of hydrogen peroxide. The specific test method is as follows:
method for measuring yield of hydrogen peroxide: the electrodes prepared in examples 1 to 7 and comparative examples 1 to 2 were ground, then 0.4ml of 0.05M naphthol solution was added to a container containing 2mg of catalyst powder, ultrasonic dispersion was performed for 10min, 10. mu.l of the mixed solution was measured with a pipette, dropped on the surface of a rotating disk electrode, and then naturally dried at room temperature, followed by electrochemical testing. The counter electrode is platinum wire, the reference electrode is saturated calomel electrode, and the electrolyte solution is 0.05MNa with pH 3 2 SO 4 . And (3) performing a rotating disc electrode test by adopting an electrochemical workstation, continuously introducing oxygen into an electrolyte solution for 20-30min before performing the electrochemical test, wherein the oxygen flow rate is 50-200 mL/min, and performing a rotating disc linear scanning voltammetry curve test after oxygen saturation.
The test results were as follows:
and (4) conclusion: the electrodes prepared in examples 1 to 7 and comparative examples 1 to 2 were subjected to a rotating disk electrode test, and then the selectivity of the two electrons was calculated to be between 90% and 55%, and the optimum sample, example 1, had a selectivity of 90%, both of which were much higher than those of the conventional iron-carbon based catalysts.
Test example 2
The electrodes prepared in examples 1 to 7 and comparative examples 1 to 2 were applied to a simulated contaminated wastewater treatment process, and the specific test method was:
the indexes of wastewater inlet are as follows: 10mg/L sulfamethoxazole 0.05M sodium sulfate solution.
The test method comprises the following steps: degradation tests were carried out using a potentiostat at a constant current of 30mA for 20 to 30min with an oxygen flow rate of 200mL/min with the electrodes prepared in examples 1 to 7 and comparative examples 1 to 2 being the cathode and the platinum sheet being the anode, and the aeration rate was kept constant during the degradation process before the degradation reaction. After 30 minutes of degradation, a sample was taken and the sulfamethoxazole content was tested by liquid chromatography.
The test results were as follows:
and (4) conclusion: the sulfamethoxazole degradation tests are respectively carried out on the electrodes prepared in the examples 1-7 and the comparative examples 1-2, the sulfamethoxazole removal rate is between 100% and 68%, the removal rate of the optimal sample example 1 can reach 100%, and the sulfamethoxazole removal rate is far higher than that of the traditional iron-carbon-based catalyst.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A preparation method of a monoatomic iron-carbon electrode with two-electron oxygen reduction selectivity is characterized by comprising the following steps,
(1) mixing, reacting and drying a phenolic organic matter, an aldehyde organic matter, a nitrogen source, sodium carbonate, an iron-nitrogen precursor and water to obtain an iron-carbon integrated electrode precursor;
(2) and calcining, acidifying and drying the iron-carbon integrated electrode precursor to obtain the iron-carbon integrated electrode.
2. The method for preparing the monatomic iron-carbon electrode with two-electron oxygen reduction selectivity according to claim 1, wherein the phenolic organic substance is one or more of resorcinol, pyrocatechol, hydroquinone and phenol;
and/or the aldehyde organic matter is one or more of formaldehyde, acetaldehyde and propionaldehyde.
3. The method for preparing the monatomic iron-carbon electrode with two-electron oxygen reduction selectivity according to claim 1, wherein the nitrogen source is one or more of acetonitrile, urea, dicyandiamide, and melamine;
and/or the iron-nitrogen precursor is one or more of iron phthalocyanine, iron porphyrin and iron sulfide phthalocyanine.
4. The method for preparing the monatomic iron-carbon electrode with two-electron oxygen reduction selectivity according to claim 1, wherein the mass ratio of the phenolic organic substance, the aldehyde organic substance, the nitrogen source, the iron-nitrogen precursor and the sodium carbonate is (30-45): (45-55): (1-5): (1-7): (0.001-0.05).
5. The method for preparing a monatomic iron-carbon electrode with two-electron oxygen reduction selectivity according to claim 1, wherein the mass ratio of the phenolic organic substance to water is 1: (1.5-3.0).
6. The method for preparing a monatomic iron-carbon electrode with two-electron oxygen reduction selectivity according to any one of claims 1 to 5, wherein the reaction conditions are: the reaction is carried out for 20-30h at 20-30 ℃, then for 20-30h at 40-60 ℃ and finally for 60-90h at 80-100 ℃.
7. The method for preparing a monatomic iron-carbon electrode with two-electron oxygen reduction selectivity according to any one of claims 1 to 6, wherein the drying time is 24 to 72 hours;
and/or the drying temperature is 20-30 ℃.
8. The method for preparing a monatomic iron-carbon electrode with two-electron oxygen reduction selectivity according to any one of claims 1 to 7, wherein the calcination manner is two-stage calcination;
the first-stage calcination temperature is 300-500 ℃, and the calcination time is 120-480 min;
the second-stage calcination temperature is 700-1000 ℃, and the calcination time is 120-480 min;
and/or the heating rate is 2-10 ℃/min.
9. The method for producing a monatomic iron-carbon electrode having two-electron oxygen reduction selectivity according to any one of claims 1 to 8, wherein at least one of the following (1) to (6) is satisfied:
(1) the concentration of the acidizing acid solution is 0.1-1 mol/L;
(2) the acid solution is one of sulfuric acid, nitric acid and hydrochloric acid;
(3) the temperature of the acidification treatment is 20-90 ℃;
(4) the time of the acidification treatment is 4-12 h;
(5) the drying mode is vacuum drying;
(6) the drying time is 24-96 h.
10. The preparation method of the monatomic iron-carbon electrode with the two-electron oxygen reduction selectivity is characterized in that the mass fraction of monatomic iron in the iron-carbon integrated electrode is 0.1-0.5%, and the mass fraction of iron carbide is 0.1-0.5%.
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