CN117276562A - Two-electron catalyst and preparation method and application thereof - Google Patents
Two-electron catalyst and preparation method and application thereof Download PDFInfo
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- CN117276562A CN117276562A CN202311253900.2A CN202311253900A CN117276562A CN 117276562 A CN117276562 A CN 117276562A CN 202311253900 A CN202311253900 A CN 202311253900A CN 117276562 A CN117276562 A CN 117276562A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 33
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 13
- -1 iron-nitrogen-carbon-lead Chemical compound 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229940046892 lead acetate Drugs 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 19
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 239000000446 fuel Substances 0.000 abstract description 4
- 230000009466 transformation Effects 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 238000005457 optimization Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 14
- SEQUALWBCFCDGP-UHFFFAOYSA-N [C].[N].[Fe] Chemical compound [C].[N].[Fe] SEQUALWBCFCDGP-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000004448 titration Methods 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 229910002555 FeNi Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 5
- 229910052745 lead Inorganic materials 0.000 description 5
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical group [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229940032296 ferric chloride Drugs 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- GPFIZJURHXINSQ-UHFFFAOYSA-N acetic acid;nitric acid Chemical compound CC(O)=O.O[N+]([O-])=O GPFIZJURHXINSQ-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a two-electron catalyst, a preparation method and application thereof, belonging to the field of energy catalysis and the field of nano material performance optimization. The preparation method comprises the following steps: preparing a nitric acid solution of ferric salt and a nitric acid solution of lead salt with the same molar concentration, simultaneously dropwise adding the nitric acid solution of ferric salt and the nitric acid solution of lead salt into the nitric acid solution of carbon material at a certain temperature under a stirring state, controlling the dropwise adding speed to be the same, and carrying out heat preservation reaction for a certain time after the dropwise adding is finished; after the reaction is finished, separating and drying solids to obtain an iron-nitrogen-carbon-lead composite material; mixing and grinding the dried iron-nitrogen-carbon-lead composite material and urea, and then sintering in an inert atmosphere to obtain the composite material. The preparation method has high yield and stable performance. The cost is lower, the implementation of the energy industry transformation is strong, and the transformation potential is provided. Can be used as cathode catalyst in zinc-air cell and is widely applied in fuel cell and two-electron oxygen reaction process (ORR).
Description
Technical Field
The invention belongs to the field of energy catalysis and the field of nano material performance optimization, and particularly relates to a two-electron catalyst, a preparation method and application thereof.
Background
In recent years, as the residual storage amount of conventional fossil fuels is continuously reduced, more and more environmentally friendly energy programs are continuously rushing out, wherein a rechargeable zinc-air battery (ZAB) has the excellent characteristics of low cost, environmental friendliness, high theoretical energy density and the like, and is an emerging direction of energy conversion. Regarding the improvement of the performance of ZAB, the problem of slow dynamics of the air electrode is first solved, wherein the catalyst for catalyzing the oxygen reaction of the air electrode is mostly noble metal on the market, which makes the cost of ZAB battery increase continuously, so the use of non-noble metal catalyst is one of the main trend. In addition, the two-electron oxygen reaction in ZAB has faster electron transfer efficiency than the traditional four-electron oxygen reaction, but the two-electron high-selectivity catalyst in ZAB has the property of being difficult to combine with high catalytic performance, so that the development of a ZAB catalyst combining two performances is very important.
In the aspect of the current performance, the non-noble metal, especially the iron-nitrogen-carbon catalyst, is supported on the basis of the carbon material, so that the cost of the catalyst can be reduced, and the catalyst has better catalytic performance, but the performance of the iron-nitrogen-carbon catalyst still needs to be further improved, and meanwhile, the two-electron selectivity of the iron-nitrogen-carbon catalyst is not high, so that the problems of improving the catalytic activity and the high selectivity of the iron-nitrogen-carbon catalyst are all needed to be solved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a two-electron catalyst, a preparation method and application thereof, and the composite catalytic nanomaterial prepared by doping lead atoms in the iron-nitrogen-carbon catalyst can effectively regulate and control the adsorption and desorption capacity of the original active site to reactants, improve the selectivity of a reaction path, convert the original four-electron catalyst into the two-electron catalyst, convert the two-electron reaction into the four-electron reaction, and further improve the overall catalytic performance and high selectivity.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a two-electron catalyst, comprising the steps of:
(1) Preparing a nitric acid solution of ferric salt and a nitric acid solution of lead salt with the same molar concentration, simultaneously dropwise adding the nitric acid solution of ferric salt and the nitric acid solution of lead salt into the nitric acid solution of carbon material at a certain temperature under a stirring state, controlling the dropwise adding speed to be the same, and carrying out heat preservation reaction for a certain time after the dropwise adding is finished; after the reaction is finished, separating and drying solids to obtain an iron-nitrogen-carbon-lead composite material;
(2) Mixing and grinding the dried iron-nitrogen-carbon-lead composite material and urea, and then sintering in an inert atmosphere to obtain the composite material.
Further, in the step (1), the molar ratio of the iron salt, the lead salt and the carbon material is 1-1.2:1-1.2:8-9.2; wherein the molar amounts of the iron salt and the lead salt are the same.
Further, the iron salt comprises one of ferric chloride, ferric sulfate or ferric acetate; the lead salt comprises one of lead acetate or lead sulfate; the carbon material comprises carbon black, which is BP2000 or XC72.
Further, the molar concentration of the nitric acid solution is 6-15M, and the ferric salt is: lead salt: the molar ratio of nitric acid is 1:1:500-1200.
Further, the drop rates of the nitric acid solution of ferric chloride and the nitric acid solution of lead acetate are 130-150 mu L/min.
Further, the certain temperature is 80-85 ℃, and the certain time is 7-8 hours.
Further, the mass ratio of the iron-nitrogen-carbon-lead composite material to urea is 1:2-4.
Further, the inert atmosphere is nitrogen or argon.
Further, the sintering temperature is 900-950 ℃, the sintering time is 1-1.5h, and the heating rate is 5-6 ℃/min.
Further, after sintering is completed, the temperature is reduced to room temperature at a speed of 5-6 ℃/min.
In a second aspect, the invention provides a two-electron catalyst prepared by the preparation method.
In a third aspect, the present invention provides the use of a two-electron catalyst in a secondary metal-air battery.
The beneficial effects are that:
the invention provides a preparation method of a catalyst with high efficiency and high selectivity for regulating and controlling iron, nitrogen and carbon in a two-electron reaction by doping lead atoms and application of the catalyst in cathode catalysis in the field of zinc-air batteries. The invention ensures that iron atoms and lead atoms are added on the carbon material in a dropwise manner with the same molar quantity so as to be uniformly distributed on a carbon-nitrogen framework, thereby achieving the distribution of lead atoms on FeN 4 When the carbon-nitrogen skeleton is used, the adsorption capacity of active sites can be regulated and controlled, and then the added acid is used for oxidation, so that more oxygen-containing functional groups are formed on the surface of the carbon-nitrogen skeleton, and the increase of the oxygen-containing functional groups can attract more metal atoms to be adsorbed on the carbon-nitrogen skeleton
According to the method, the doped lead atoms are selected as the doped metal, and after the lead elements are added, the chemical energy required by the adsorption and desorption of the iron serving as the active site and the oxygen is smaller, so that the higher adsorption and desorption efficiency is achieved, the chemical energy required by the reaction of the two electrons and the oxygen is closer to the chemical energy required by the reaction of the two electrons, and the oxygen can be timely desorbed when the two protons are combined, so that the method has high selectivity. And sintering is carried out in the nitrogen atmosphere of the tubular furnace, so that iron ions in the catalyst are all ferric iron and form a target carbon skeleton structure, and the target catalyst FePb@NC is obtained. The preparation method has the advantages of simple process, easily obtained raw materials, low cost and stable performance of the prepared catalyst. The invention realizes strong energy industry conversion feasibility and has conversion potential. Can be used as cathode catalyst in zinc-air cell and is widely applied in fuel cell and two-electron oxygen reaction process (ORR).
The catalyst prepared by the method of the invention applies the oxygen reduction catalyst structure originally applied to four electrons to the two-electron oxygen reaction, and applies the lead element to the iron-nitrogen-carbon catalytic material for the first time. Besides being applied to hydrogen-oxygen fuel cells, the catalyst can also be applied to secondary batteries such as zinc-air batteries, and the like, so that the storage and discharge efficiency, organic catalytic reaction and the like of the original secondary batteries are improved.
The lead-doped iron-nitrogen-carbon structure high-selectivity two-electron catalyst FePb@NC prepared by the invention shows excellent ORR and OER difunctional catalytic performance, and can be obtained by using a rotating ring disk electrode test under the rotating speed of 1600rpm in oxygen saturated 0.1M KOH electrolyte, wherein the half-wave potential is 0.773V, and the initial potential is 0.698V.
The lead-doped iron-nitrogen-carbon structure high-selectivity two-electron catalyst FePb@NC prepared by the method has various applications in the field of energy catalysis, and can be applied to the field of zinc-air batteries and the field of organic catalysis.
Drawings
FIG. 1 is a graph of OER linear sweep voltammetry of FePb@NC on a glassy carbon electrode in example 2 of the present invention.
FIG. 2 is an OER Taphil plot of FePb@NC in example 2 of the present invention.
FIG. 3 is a plot of ORR linear sweep voltammetry for FePb@NC, fe@NC, feNi@NC and 20% Pt/C on a glassy carbon electrode in example 3 of the present invention.
FIG. 4 is a graph showing the number of electron transitions during the ORR reaction of FePb@NC in example 3 of the present invention.
Fig. 5 is a diagram of a battery clamp assembled with fepb@nc in example 4 of the present invention.
Fig. 6 is an illumination diagram of an LED panel assembled from 3 zinc-air cells in series, as per the fepb@nc in example 4 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments for better explaining the present invention.
According to the invention, lead element is used as an adjusting element for adjusting iron, nitrogen and carbon of a catalyst, ferric chloride hexahydrate and lead acetate are used as an Fe source and a Pb source, after nitric acid is added for dissolution, metal atoms are ensured to be uniformly dispersed on carbon BP2000 in a dropwise manner, a carbon material with double-atom distribution is synthesized, then urea is added to provide an N source, and finally high-temperature annealing sintering is carried out, so that the lead-doped iron, nitrogen and carbon structure high-selectivity two-electron catalyst FePb@NC is synthesized.
In the method for preparing the catalyst, the high-temperature annealing can remove impurity elements, ensure that metal atoms coat the surface of the carbon skeleton, provide effective conductivity, and introduce a large number of defects by the high-temperature annealing method. The method is simple to operate, the catalyst preparation method is simple and can be used for mass production, and active sites on the catalyst are uniformly distributed, so that more iron atoms are influenced by lead atoms, a better synergistic effect between diatomic atoms is presented, and the catalytic performance of the catalyst is improved. The catalyst after high-temperature sintering has a stable structure, so that the lead-doped iron-nitrogen-carbon structure high-selectivity two-electron catalyst FePb@NC is expected to be produced in a large scale in an industrialized manner.
Compared with the Fe-N-C catalyst without the doped lead atom, the Fe-N-C catalyst doped with lead atom of the invention has the advantages that 4 The lead atom doped iron nitrogen carbon has similar properties to those of iron nitrogen carbon, and comprises the following components: high specific surface area, low cost, high thermal stability and other excellent performances. The lead atoms can effectively regulate and control the iron-nitrogen-carbon structure, and can further regulate and control the catalytic performance of active site iron, thereby affecting the catalytic activity. Before the lead atom is not added, the original adsorption and desorption chemical energy of the active site is similar to the chemical energy required by the four-electron oxygen reaction process, so that the four-electron oxygen reaction is catalyzed, but after the lead atom is added, the original adsorption and desorption capacity is changed because the distribution of electrons in the orbit of the original active site is changed, and the original activation energy required by the four-electron reaction path is changed to be more similar to the activation energy required by the two-electron oxygen reaction path, so that the catalyst can be used in the two-electron ORR reaction, and the integral catalytic performance and high selectivity are improved.
The present invention will be described in detail with reference to examples, but the scope of the claims of the present invention is not limited to these examples. Meanwhile, the embodiments only give some conditions for achieving this, and do not mean that these conditions must be satisfied to achieve this.
Example 1: preparation of FePb@NC (BP 2000)
In this example, the molar ratio of ferric chloride hexahydrate, lead acetate to carbon black BP2000 was 1:1:8, respectively dissolving ferric chloride hexahydrate and lead acetate in 30mL of nitric acid solution, and stirring and dissolving for later use. BP2000 was added to 20mL of nitric acid, and after mixing well, transferred to a three-necked round bottom flask, and a titration funnel was placed on the three-necked flask, respectively, and a condenser was installed. Heating and stirring to mix under 80 ℃ oil bath, dripping ferric chloride nitric acid solution and lead acetate nitric acid solution into a three-neck flask at the titration speed of 140 mu L/min in a titration funnel, reacting for 8 hours at 80 ℃ after the dripping is finished, separating solids, and heating and drying to obtain the iron-nitrogen-carbon-lead composite material powder. And (3) placing the dried powder and urea (the mass ratio is 1:1) in a mortar for mixing and grinding, placing in a quartz boat, heating from room temperature to 950 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere for 1 hour, and then cooling to room temperature at a speed of 5 ℃/min to obtain the lead-doped iron-nitrogen-carbon structured catalyst FePb@NC (BP 2000).
Comparative example 1
Compared with example 1, the specific method of the comparative example is as follows:
in this comparative example, the molar ratio of ferric chloride hexahydrate to carbon black BP2000 was 1:8, dissolving ferric chloride hexahydrate in 30mL of nitric acid solution, and stirring for later use. BP2000 was added to 20mL of nitric acid, mixed well, transferred to a three-necked round bottom flask, and a titration funnel was placed on the three-necked flask, and a condenser was installed. Heating and stirring under 80 ℃ oil bath, adding ferric chloride nitric acid solution into a three-neck flask in a titration funnel at a titration speed of 140 mu L/min, reacting at 80 ℃ for 8 hours after the addition, separating solid, and heating and drying. And (3) placing the dried powder and urea (the mass ratio is 1:1) in a mortar for mixing and grinding, placing in a quartz boat, heating from room temperature to 950 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere for 1 hour, and then cooling to room temperature at a speed of 5 ℃/min to obtain Fe@NC (BP 2000).
Comparative example 2
The comparative example provides a preparation method of FeNi@NC (BP 2000), which comprises the following specific steps:
in this comparative example, the molar ratio of nickel acetate to carbon black BP2000 was 1:8, wherein nickel acetate is dissolved in 30mL of nitric acid solution, and stirred for later use. BP2000 was added to 20mL of nitric acid, mixed well, transferred to a three-necked round bottom flask, and a titration funnel was placed on the three-necked flask, and a condenser was installed. Heating and stirring under 80 ℃ oil bath, adding nickel acetate nitric acid solution into a three-neck flask in a titration funnel at a titration speed of 140 mu L/min, reacting at 80 ℃ for 8 hours after the addition, separating solid, and heating and drying. And (3) placing the dried powder and urea (the mass ratio is 1:1) in a mortar for mixing and grinding, placing in a quartz boat, heating from room temperature to 950 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere for 1 hour, and then cooling to room temperature at a speed of 5 ℃/min to obtain FeNi@NC (BP 2000).
Comparative example 3
Commercial catalyst at 20% pt/C for catalyst performance control.
Example 2: fePb@NC (BP 2000) electrocatalytic OER performance test
Electrocatalytic testing of the catalysts obtained in example 1 was carried out on an electrochemical workstation (Garmy 1010E) using a conventional three-electrode system. Wherein the electrolyte is 1.0M KOH aqueous solution, and the platinum sheet electrode and the Hg/HgO electrode are a counter electrode and a reference electrode respectively. 5mg FePb@NC was dispersed in 2000. Mu.L of a mixed solution of absolute ethanol and 50. Mu.L of Nafion, and after 1 hour of sonication, 25. Mu.L of the slurry was sampled dropwise onto a glassy carbon electrode using a microsyringe as a working electrode. As can be seen from FIG. 1, the catalyst FePb@NC of example 1 was driven at 10 mA.cm -2 Only 509mV is needed for the current density overpotential of (2), and the gradient is 217 mV.dec as can be seen from the Tafil curve of FIG. 2 -1 。
Example 3: electrocatalytic ORR Performance test of FePb@NC (BP 2000), undoped Pb Fe@NC (BP 2000) and FeNi@NC (BP 2000) and 20% Pt/C
The FePb@NC (BP 2000) obtained in example 1, the Fe@NC (BP 2000) obtained in comparative example 1 and the FeNi@NC@NC were electrocatalytic tests carried out on an electrochemical workstation (Pin WaveDriver 20-Basic) using a conventional three-electrode system. Wherein, the electrolyte is oxygen saturated 0.1M KOH aqueous solution, and a counter electrode and a reference electrode are respectively used for the platinum sheet electrode and the Hg/HgO electrode. 5mg FePb@NC was dispersed in 2000. Mu.L of a mixed solution of absolute ethanol and 50. Mu.L of Nafion, and after 1 hour of sonication, 25. Mu.L of the slurry was sampled dropwise onto a glass carbon disk electrode using a microsyringe as a working electrode. As can be seen from fig. 3, the half-wave potential of fepb@nc (BP 2000) is 0.94V V; the half-wave potential of Fe@NC (BP 2000) without Pb is 0.71V, and the half-wave potential of FeNi@NC (BP 2000) is 0.79V; since the 20% Pt/C half-wave potential is 0.89V, it is known that FePb@NC is the best catalytic activity, and as is apparent from FIG. 6, the number of electrons transferred by FePb@NC is 2.3, and it can be determined that the FePb@NC is the two-electron oxygen reaction. The FePb@NC (BP 2000) was found to have the best catalytic performance.
Example 4: zinc empty cell Performance test of FePb@NC (BP 2000) and Fe@NC (BP 2000) in comparative example 1
The FePb@NC (BP 2000) obtained in example 1 and the FeNi@NC (BP 2000) obtained in comparative example 1 were used as positive and negative electrodes of a zinc-air battery, respectively, and zinc-air battery performance was tested in a mixed electrolyte of 6.0M KOH and 0.1M zinc acetate.
It can be seen from fig. 5 and 6 that after linking three zinc-air batteries, the LED small bulb can be lit and can be maintained for 10min, in contrast to the other two catalysts: the Fe@NC (BP 2000) and FePb@NC (BP 2000) which are not doped with Pb are respectively maintained for 3min and 5min, so that the battery assembled by the catalytic FePb@NC (BP 2000) agent has better performance.
The invention provides a preparation method of a catalyst with high efficiency and high selectivity for regulating and controlling iron, nitrogen and carbon in a two-electron reaction by doping lead atoms and application of the catalyst in cathode catalysis in the field of zinc-air batteries. The invention ensures the even distribution of diatomic on the carbon-nitrogen skeleton by the dropping method, thereby achieving the distribution of lead atoms on FeN 4 Around the catalyst, the adsorption capacity of active sites is regulated, nitric acid is added for oxidation, all iron ions in the catalyst are ferric iron, and annealing sintering is carried out at 950 ℃ in the nitrogen atmosphere of a tube furnace to form the catalystForming a target carbon skeleton structure, thereby obtaining the target catalyst FePb@NC. The preparation method has high yield and stable performance. The cost is lower, the implementation of the energy industry transformation is strong, and the transformation potential is provided. Can be used as cathode catalyst in zinc-air cell and is widely applied in fuel cell and two-electron oxygen reaction process (ORR).
Many possible variations and modifications of the disclosed technology can be made by anyone skilled in the art without departing from the scope of the technology, or the technology can be modified to be equivalent. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention shall still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the two-electron catalyst is characterized by comprising the following steps of:
(1) Preparing a nitric acid solution of ferric salt and a nitric acid solution of lead salt with the same molar concentration, simultaneously dropwise adding the nitric acid solution of ferric salt and the nitric acid solution of lead salt into the nitric acid solution of carbon material at a certain temperature under a stirring state, controlling the dropwise adding speed to be the same, and carrying out heat preservation reaction for a certain time after the dropwise adding is finished; after the reaction is finished, separating and drying solids to obtain an iron-nitrogen-carbon-lead composite material;
(2) Mixing and grinding the dried iron-nitrogen-carbon-lead composite material and urea, and then sintering in an inert atmosphere to obtain the composite material.
2. The method according to claim 1, wherein in step (1), the molar ratio of iron salt, lead salt to carbon material is 1 to 1.2:1-1.2:8-9.2; wherein the molar amounts of the iron salt and the lead salt are the same.
3. The method of claim 1, wherein the iron salt comprises one of ferric chloride, ferric sulfate, or ferric acetate; the lead salt comprises one of lead acetate or lead sulfate; the carbon material comprises carbon black; the molar concentration of the nitric acid solution is 6-15M, and the ferric salt is: lead salt: the molar ratio of nitric acid is 1:1:500-1200.
4. The method according to claim 1, wherein the drop rates of the nitric acid solution of ferric chloride and the nitric acid solution of lead acetate are 130 to 150 μl/min.
5. The method according to claim 1, wherein the certain temperature is 80-85 ℃ and the certain time is 7-8 hours.
6. The preparation method according to claim 1, wherein the mass ratio of the iron-nitrogen-carbon-lead composite material to the urea is 1:2-4.
7. The method of claim 1, wherein the inert atmosphere is nitrogen or argon.
8. The method according to claim 1, wherein the sintering temperature is 900-950 ℃, the sintering time is 1-1.5h, and the heating rate is 5-6 ℃/min.
9. The two-electron catalyst prepared by the preparation method of any one of claims 1 to 8.
10. Use of the two-electron catalyst of claim 9 in a secondary metal-air battery.
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