CN111545226A - Bifunctional carbon-based iron phosphide nano material based on microbial synthesis and preparation method and application thereof - Google Patents
Bifunctional carbon-based iron phosphide nano material based on microbial synthesis and preparation method and application thereof Download PDFInfo
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- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 title claims abstract description 92
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 77
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 71
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000000813 microbial effect Effects 0.000 title claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 12
- 238000001308 synthesis method Methods 0.000 title description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052742 iron Inorganic materials 0.000 claims abstract description 39
- 244000005700 microbiome Species 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- -1 iron ions Chemical class 0.000 claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 claims abstract description 17
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 14
- 238000010000 carbonizing Methods 0.000 claims abstract description 14
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 241000588724 Escherichia coli Species 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 244000063299 Bacillus subtilis Species 0.000 claims description 9
- 235000014469 Bacillus subtilis Nutrition 0.000 claims description 9
- 230000003321 amplification Effects 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 9
- 238000003199 nucleic acid amplification method Methods 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 8
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 8
- 241000672609 Escherichia coli BL21 Species 0.000 claims description 7
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 241001538194 Shewanella oneidensis MR-1 Species 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000001963 growth medium Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 241000894006 Bacteria Species 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 241001223867 Shewanella oneidensis Species 0.000 claims description 2
- 241001052560 Thallis Species 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 4
- 210000004027 cell Anatomy 0.000 description 11
- 239000010411 electrocatalyst Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
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- 239000000203 mixture Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000012137 tryptone Substances 0.000 description 3
- 239000012138 yeast extract Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 241000863430 Shewanella Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 210000005056 cell body Anatomy 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
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- 230000002588 toxic effect Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYRDHRYMAZWQJH-UHFFFAOYSA-N [P].P Chemical compound [P].P VYRDHRYMAZWQJH-UHFFFAOYSA-N 0.000 description 1
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- 238000005868 electrolysis reaction Methods 0.000 description 1
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- 238000010304 firing Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004832 voltammetry 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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Abstract
The invention discloses a bifunctional carbon-based iron phosphide nano material based on microbial synthesis, which comprises a carbon-based material and iron phosphide nano particles uniformly distributed on the surface of the carbon-based material, wherein the bifunctional carbon-based iron phosphide nano material is prepared by adsorbing iron ions by living microorganisms with phosphate groups on the surfaces and then carbonizing the living microorganisms. The catalyst has excellent OER and HER reaction catalytic activity in the same electrolyte, and has good catalytic performance and great application potential. The invention also discloses a preparation method of the carbon-based iron phosphide nano material, which takes the microorganisms as a carrier, utilizes the weak interaction force between rich groups on the surface of the microorganisms and iron ions as a link, tightly combines and uniformly disperses the metal on the surface of the microorganisms, and is prepared by high-temperature roasting. The invention also discloses application of the bifunctional carbon-based iron phosphide nano material.
Description
Technical Field
The invention belongs to the field of new material preparation, and particularly relates to a bifunctional carbon-based iron phosphide nano material based on microbial synthesis, a preparation method thereof and application thereof in electrocatalysis of OER and HER reactions.
Background
The increasing exhaustion of fossil fuels and the development and utilization of new energy are always the problems which puzzle the development of human beings, and the hydrogen production by electrolyzing water is an advanced new energy conversion technology and can produce clean and sustainable fuel. However, due to the problem of low efficiency of water electrolysis, an electrocatalyst with a lower overpotential is needed, which can still catalyze water cracking efficiently at high current density and low cell voltage. At present, the electrocatalyst with excellent application performance belongs to noble metal catalysts such as platinum, palladium, ruthenium, rubidium, iridium and the like, but the noble metal resources are low in reserve and high in cost, so that the development of a novel efficient non-noble metal-based electrocatalyst for catalyzing water cracking is urgently needed for commercial application. The non-noble metal catalyst is mainly used for catalyzing water cracking and comprises transition metal oxides, layered double hydroxides, sulfides, phosphides and the like, but most of the transition metal oxides, the layered double hydroxides, the sulfides, the phosphides and the like can normally operate only under low current density, and the OER and HER catalytic effects on the same electrolyte are difficult to realize.
Currently, graphene/activated carbon is mostly used as a carrier for synthesizing iron-based phosphide, and iron salt and phosphate or organic phosphorus (phosphine) are used for hydrothermal synthesis, high-temperature roasting or iron phosphide is synthesized by an electrodeposition method. Although the synthesis of iron phosphide by using biomass as a carrier currently exists, the hydrothermal synthesis reaction needs to be completed in a reaction kettle by adding a binder. The following problems are caused by the above method: adding organic solvent; ② the energy consumption is high. The conditions for synthesizing the carbon-based iron phosphide by the methods are very harsh, and the catalyst synthesized by the methods is difficult to meet the high-efficiency catalysis of the OER and HER reactions in the same solvent.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background art, provide a carbon-based iron phosphide nano material capable of efficiently catalyzing OER and HER reactions in the same electrolyte, provide a preparation method without adding a binder, and provide an application method of the carbon-based iron phosphide nano material.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the difunctional carbon-based iron phosphide nano material based on microbial synthesis comprises a carbon-based material and iron phosphide nano particles uniformly distributed on the surface of the carbon-based material, and is prepared by adsorbing iron ions by living microorganisms with phosphate groups on the surfaces and then carbonizing the living microorganisms. And (3) automatically transporting part of the adsorbed iron ions into cells through a transmembrane mode by using a microbial surface transporter, carrying out redox reaction inside and outside the cell body by using oxidoreductase in/outside the cell body, and carbonizing to obtain the bifunctional carbon-based iron phosphide nano material.
The invention synthesizes and prepares the carbon-based iron phosphide nano-material by using the microorganism as the carrier, and the carbon-based carrier and the metal are tightly combined by relying on a plurality of functional groups (mainly phosphate groups) on the surface of the microorganism superior to other biomasses and extremely strong weak interaction force between extracellular polymers and iron ions, thereby avoiding the addition of toxic reagents and the consumption of more energy, and simultaneously having excellent OER and HER reaction catalytic activity and better catalytic performance.
Preferably, the carbon-based material comprises one or more of carbon spheres, carbon nanotubes, rod-shaped nanocarbons and sheet-shaped nanocarbons; the particle size of the carbon spheres is 100-500 nm; the length of the carbon nano tube is 200 nm-1 mu m; the cross section diameter of the rod-shaped nano carbon is 200 nm-400 nm, and the length of the rod-shaped nano carbon is 500 nm-800 nm.
Preferably, the average particle size of the iron phosphide nano-particles is 3-40 nm; the living microorganisms with phosphate groups on the surface comprise any one or more of Escherichia coli (Escherichia coli BL21), Shewanella oneidensis MR-1 and Bacillus subtilis.
The invention relates to a nano catalytic material formed by carbonizing after adsorbing iron ions by living microorganisms, in particular to a method for preparing a metal-loaded catalyst precursor by putting cultured living microorganisms into iron ions for solution adsorption to obtain the metal-loaded catalyst precursor of the microorganisms; as abundant phosphate groups grow on the surfaces of microbial cells, iron ions are adsorbed to form a precursor, the precursor is placed in a tube furnace and is roasted under the protection of oxygen-free nitrogen or argon, the compound of the phosphate groups and the iron ions contained on the surfaces of the cells forms iron phosphide due to oxygen deficiency, and the microbial cells are carbonized to form carbon spheres, carbon nanotubes or irregular carbon fragments, so that the difunctional carbon-based iron phosphide nano material with high-efficiency OER and HER reaction electrocatalytic activity is obtained.
Based on a general inventive concept, the invention also provides a preparation method of the bifunctional carbon-based iron phosphide nano-material based on microbial synthesis, which comprises the following steps:
(1) inoculating living microorganisms with phosphate groups on the surfaces to an LB culture medium for amplification culture, and centrifuging after a logarithmic phase is reached to obtain wet bacteria;
(2) putting the wet thalli obtained in the step (1) into an iron ion solution for adsorption, and centrifuging to obtain an iron-loaded microorganism precursor after adsorption is completed;
(3) and (3) collecting the iron-loaded microbial precursor obtained in the step (2), preparing dry powder by vacuum freeze drying, and then carrying out carbonization roasting in an oxygen-free protective atmosphere to obtain the bifunctional carbon-based iron phosphide nano material.
In the preparation method, preferably, in the step (1), the living microorganisms with phosphate groups on the surfaces comprise any one or more of Escherichia coli (Escherichia coli BL21), Shewanella oneidensis (MR-1) and Bacillus subtilis (Bacillus subtilis), and the surfaces of the microorganisms contain abundant phosphate groups, hydroxyl groups, amino groups, carboxyl groups and other groups, can form extremely strong weak interaction force with iron ions, and tightly bond the carbon-based carrier and the metal after carbonization; the temperature of the amplification culture is 20-30 ℃, and the time of the amplification culture is 6-72 h; the rotating speed of the centrifugation is 5000-10000 rpm, and the centrifugation time is more than or equal to 15 min.
Preferably, in the step (2), the iron ion solution is FeCl3、FeSO4And Fe (NO)3)3Any one or more of them; the concentration of the iron ion solution is 50-300 mg/L; the adsorption temperature is 10-50 ℃, and the adsorption time is 0.5-6 h; the rotation speed adopted by the centrifugation is more than 6000rpm, and the centrifugation time is more than 10 min.
Preferably, in the step (3), the vacuum freeze-drying time is 0.5-12 hours, and the protective atmosphere is nitrogen or argon.
Preferably, in the step (3), the temperature of the carbonization roasting is 300-1200 ℃, the temperature rise rate of the carbonization roasting is 5-20 ℃/min, and the time of the carbonization roasting is 0.5-3 h.
The preparation method of the invention avoids the step of adding a phosphorus source, simplifies the synthesis step of ferric phosphide, avoids the harsh conditions required by the current hydrothermal synthesis method, the electrodeposition method and the like and toxic reagents added in the preparation process, and prevents the problems of metal nano-particle agglomeration and the like. Compared with the method for preparing the carbon-based iron phosphide nano-material by using other biomasses, the method has the advantages of simple preparation process, easily controlled reaction process, low preparation cost and environmental friendliness, and the prepared bifunctional carbon-based iron phosphide nano-material has huge catalytic application potential and can be directly carbonized after being adsorbed by microorganisms.
Based on a general inventive concept, the invention also provides an application of the bifunctional carbon-based iron phosphide nanomaterial, wherein the bifunctional carbon-based iron phosphide nanomaterial is added in an electrocatalytic HER and/or OER reaction for improving the electrocatalytic activity of the OER and HER reaction.
In the above application, preferably, the electrolyte used in the OER reaction and/or the HER reaction is a potassium hydroxide solution.
Compared with the prior art, the invention has the beneficial effects that:
1. the difunctional carbon-based iron phosphide nano material synthesized based on microorganisms has excellent OER and HER reaction catalytic activity in the same electrolyte, and is good in catalytic performance and huge in application potential.
2. The preparation method takes the microorganism as a biological carrier, utilizes the strong weak interaction force between the rich groups such as phosphate group, hydroxyl group, amino group, carboxyl group and the like on the surface of the microorganism and iron metal ions as a link, tightly combines and uniformly disperses the metal on the surface of the microorganism, and prepares the carbon-based iron phosphide nano material after high-temperature roasting.
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 introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a scanning electron microscope SEM image (50,000 magnification) of the bifunctional carbon-based iron phosphide nanomaterial of example 1;
FIG. 2 is a scanning electron microscope SEM image (300,000 magnification) of the bifunctional carbon-based iron phosphide nanomaterial of example 1;
FIG. 3 is a TEM image of the iron phosphide nanoparticle distribution of the bifunctional carbon-based iron phosphide nanomaterial of example 1;
FIG. 4 is a scanning electron microscopy-spectroscopy (SEM-EDS) spectrum of the bifunctional carbon-based iron phosphide nanomaterial of example 1;
FIG. 5 is an X-ray diffraction pattern (XRD) of the bifunctional carbon-based iron phosphide nanomaterial of example 1;
FIG. 6 is a TEM image of the iron phosphide nanoparticle distribution of the bifunctional carbon-based iron phosphide nanomaterial of example 2;
FIG. 7 is an SEM image of iron phosphide nanoparticle distribution of the bifunctional carbon-based iron phosphide nanomaterial of example 2;
FIG. 8 is a scanning electron microscopy-spectroscopy (SEM-EDS) spectrum of the bifunctional carbon-based iron phosphide nanomaterial of example 2;
FIG. 9 is a TEM image of the bifunctional carbon-based iron phosphide nanomaterial of example 3;
FIG. 10 is a TEM image of the iron phosphide nanoparticle distribution of the bifunctional carbon-based iron phosphide nanomaterial of example 3;
FIG. 11 is a statistical plot of current density data for different electrocatalysts in an OER reaction;
FIG. 12 is a statistically magnified view of current density data for different electrocatalysts in an OER reaction;
FIG. 13 is a statistical plot of overpotential data for different electrocatalysts in an OER reaction;
figure 14 is a statistical plot of overpotential data for different electrocatalysts in HER reactions;
figure 15 is a statistical plot of current density data for different electrocatalysts in HER reactions.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a bifunctional carbon-based iron phosphide nano material based on microbial synthesis comprises a carbon-based material obtained by carbonizing Escherichia coli (Escherichia coli BL21) and iron phosphide nano particles uniformly distributed on the surface of the carbon-based material. The difunctional carbon-based iron phosphide nano material is prepared by adsorbing iron ions in an iron chloride solution by using living microorganism Escherichia coli (Escherichia coli BL21), transferring the iron ions into cells through a membrane, carrying out redox reaction in vitro and in vivo, and then carbonizing the iron ions at high temperature.
The preparation method comprises the following steps:
1) inoculating Escherichia coli (Escherichia coli BL21) under aseptic condition, performing amplification culture to 1L LB culture medium, performing shake culture at 20 deg.C for 72h to logarithmic phase, and centrifuging at 10000rpm for 15min to obtain wet thallus;
the formulation of LB medium was as follows: tryptone 10g/L, yeast extract 5g/L, sodium chloride 10g/L, and NaOH to adjust the pH of the medium to 7.4;
2) FeCl with total iron ion concentration of 200mg/L is prepared3Adding wet thallus into the prepared FeCl3Adsorbing in the solution, stirring and adsorbing for 5h at 25 ℃; centrifuging for 15min under the condition of 10000rpm to obtain a precursor of the escherichia coli loaded iron;
3) collecting a precursor of the escherichia coli loaded iron, preparing the precursor into dry powder by vacuum freeze drying for 10h, then roasting and carbonizing at 700 ℃ under the condition of nitrogen protection atmosphere, wherein the heating rate is 5 ℃/min, the roasting time is 1.5h, and cooling to obtain the bifunctional carbon-based iron phosphide nano material.
As shown in FIG. 1, the cells in the bifunctional carbon-based iron phosphide nano-material are rod-shaped, the diameter of the cross section of the cells is 200 nm-400 nm, and the length of the cells is 500 nm-800 nm.
As shown in FIG. 2, the surface of the bifunctional carbon-based iron phosphide nano-material is loaded with uniformly dispersed iron phosphide nano-particles, the particle size distribution of the iron phosphide nano-material is 13-60 nm, and the average particle size of the iron phosphide nano-material is 33.4 nm.
As can be seen from FIG. 3, the bifunctional carbon-based iron phosphide nano-material is loaded with uniformly dispersed iron phosphide nano-particles, the particle size of the bifunctional carbon-based iron phosphide nano-material is distributed between 13nm and 60nm, and the average size of the bifunctional carbon-based iron phosphide nano-material is 35.94 nm.
As can be seen from FIG. 4, the distribution of the elements loaded on the surface of the bifunctional carbon-based iron phosphide nano-material is substantially uniform.
As shown in FIG. 5, the surface of the bifunctional carbon-based iron phosphide nano-material contains Fe3P and Fe2O3，Fe2O3Has better OER reaction catalytic activity, Fe3P has better HER catalytic activity, which indicates that the carbon-based iron phosphide nano material obtained by the invention has the double functions of catalyzing the reaction of OER and HER simultaneously.
Example 2:
a bifunctional carbon-based iron phosphide nano material based on microbial synthesis comprises a carbon-based material obtained by carbonizing Shewanella oneidensis MR-1 and iron phosphide nano particles uniformly distributed on the surface of the carbon-based material. The difunctional carbon-based iron phosphide nano material is prepared by adsorbing iron ions in a ferric sulfate solution by Shewanella oneidedensis MR-1, transferring the iron ions into cells through a transmembrane manner, carrying out redox reaction in vitro and in vivo, and carbonizing at high temperature.
The preparation method comprises the following steps:
1) inoculating Shewanella oneidensis MR-1 under aseptic condition, performing amplification culture to 1L LB culture medium, performing shake culture at30 deg.C for 48h to logarithmic phase, and centrifuging at 8000rpm for 15min to obtain wet thallus;
the formulation of LB medium was as follows: tryptone 10g/L, yeast extract 5g/L, sodium chloride 10g/L, and NaOH to adjust the pH of the medium to 7.4;
2) preparing FeSO with the total concentration of iron ions being 300mg/L4Adding wet thallus into the prepared FeSO4Adsorbing in the solution, stirring and adsorbing for 6h at30 ℃; centrifuging for 15min at 8000rpm to obtain precursor of the Escherichia coli loaded iron;
3) collecting the precursor of the shewanella iron-loaded precursor, preparing the precursor into dry powder by vacuum freeze drying for 12h, then roasting and carbonizing at the temperature of 500 ℃ under the condition of argon protective atmosphere, wherein the heating rate is 10 ℃/min, the roasting time is 1h, and cooling to obtain the bifunctional carbon-based iron phosphide nano material.
As can be seen from FIG. 6, the bifunctional carbon-based iron phosphide nano-material is loaded with uniformly dispersed iron phosphide nano-particles, the particle size distribution of which is 15 nm-60 nm, and the average particle size of which is 33.7 nm.
As can be seen from FIG. 7, the surface of the bifunctional carbon-based iron phosphide nano-material is loaded with uniformly dispersed iron phosphide nano-particles.
As can be seen from FIG. 8, the elements loaded on the surface of the bifunctional carbon-based iron phosphide nano-material are uniformly distributed.
Example 3:
a bifunctional carbon-based iron phosphide nano material based on microbial synthesis comprises a carbon-based material obtained by carbonizing Bacillus subtilis and iron phosphide nano particles uniformly distributed on the surface of the carbon-based material. The difunctional carbon-based iron phosphide nano material is prepared by adsorbing iron ions in an iron nitrate solution by using living microorganisms, namely Bacillus subtilis, transporting the iron ions to cells through a membrane, carrying out redox reaction inside and outside a body, and then carbonizing the iron ions at high temperature.
The preparation method comprises the following steps:
the preparation method of the carbon-based iron phosphide nano-material comprises the following steps:
1) inoculating Bacillus subtilis under aseptic condition, performing amplification culture to 1L LB culture medium, performing shake culture at 25 deg.C for 48h to logarithmic phase, and centrifuging at 10000rpm for 15min to obtain wet thallus;
the formulation of LB medium was as follows: tryptone 10g/L, yeast extract 5g/L, sodium chloride 10g/L, and NaOH to adjust the pH of the medium to 7.4;
2) preparing Fe (NO) with the total concentration of iron ions being 300mg/L3)3Adding wet bacteria to the prepared Fe (NO)3)3Adsorbing in the solution, stirring and adsorbing for 6h at 25 ℃; centrifuging for 15min under the condition of 10000rpm to obtain a precursor of the escherichia coli loaded iron;
3) collecting a precursor of the bacillus subtilis loaded with iron, preparing dry powder by vacuum freeze drying for 12h, roasting and carbonizing at 600 ℃ under the condition of argon protective atmosphere, wherein the heating rate is 5 ℃/min, the roasting time is 1.5h, and cooling to obtain the bifunctional carbon-based iron phosphide nano material.
As shown in FIG. 9, the bifunctional carbon-based iron phosphide nano-material is rod-shaped;
as can be seen from FIG. 10, the bifunctional carbon-based iron phosphide nano-material is loaded with uniformly dispersed iron phosphide nano-particles, the particle size distribution of which is 14 nm-60 nm, and the average particle size of which is 34.2 nm.
Example 4:
the application of the bifunctional carbon-based iron phosphide nano material prepared in the embodiment 1-3 as an electrocatalyst in electrocatalysis of HER and OER reactions specifically comprises the following steps:
ultrasonically dispersing 5mg of the prepared bifunctional carbon-based iron phosphide nano material in 2mL of ethanol and 50uL of Nafion to obtain a mixed suspension, then dripping the mixed suspension on a glassy carbon electrode (a working electrode), and drying in the air. The catalytic performance test is carried out on a Metrohm Autolab PGSTAT302N electrochemical workstation, the catalytic performance of the prepared bifunctional carbon-based iron phosphide nano-material is evaluated through cyclic voltammetry scanning, linear voltammetry scanning and alternating current impedance test, and the electrolyte is 0.1M KOH. The test results are shown in FIGS. 11-15, wherein S represents temperature, and S700, S600 and S500 represent test data of the bifunctional carbon-based iron phosphide nano-material prepared by roasting at 700 ℃ in example 1, at 600 ℃ in example 3 and at 500 ℃ in example 2, respectively.
FIGS. 11-13 show the firing at 700 deg.C (example 1) in an OER reaction to produce a bifunctional carbon-based iron phosphide nanomaterial at 10mAcm-2Current density of (2), overpotential and noble metal electrocatalyst (RuO)2) Close, 283 mV; at high current density, its overpotential is much lower than RuO2。
FIGS. 14-15 show the bifunctional carbon-based iron phosphide nanomaterials prepared by calcination (example 1) at 700 ℃ in the HER reaction at 10mA cm-2The overpotential is only 139mV at the current density of (1); at high current densities, the overpotential is similar to the performance of Pt/C.
In conclusion, the bifunctional carbon-based iron phosphide nano material prepared by the method disclosed by the invention has high-efficiency OER and HER electrocatalytic activities in the same electrolyte (0.1MKOH), and has good catalytic performance and huge application potential.
Claims (10)
1. The difunctional carbon-based iron phosphide nano material is characterized by comprising a carbon-based material and iron phosphide nano particles uniformly distributed on the surface of the carbon-based material, wherein the difunctional carbon-based iron phosphide nano material is prepared by adsorbing iron ions by living microorganisms with phosphate groups on the surfaces and then carbonizing the living microorganisms.
2. The bifunctional carbon-based iron phosphide nanomaterial according to claim 1, wherein the carbon-based material comprises any one or more of carbon spheres, carbon nanotubes, rod-shaped nanocarbons and sheet-shaped nanocarbons; the particle size of the carbon spheres is 100-500 nm; the length of the carbon nano tube is 200 nm-1 mu m; the cross section diameter of the rod-shaped nano carbon is 200 nm-400 nm, and the length of the rod-shaped nano carbon is 500 nm-800 nm.
3. The bifunctional carbon-based iron phosphide nano-material according to claim 1 or 2, wherein the average particle size of the iron phosphide nano-particles is 3-40 nm; the living microorganisms with phosphate groups on the surface comprise any one or more of Escherichia coli (Escherichia coli BL21), Shewanella oneidensis MR-1 and Bacillus subtilis.
4. A preparation method of a bifunctional carbon-based iron phosphide nano material based on microbial synthesis is characterized by comprising the following steps:
(1) inoculating living microorganisms with phosphate groups on the surfaces to an LB culture medium for amplification culture, and centrifuging after a logarithmic phase is reached to obtain wet bacteria;
(2) putting the wet thalli obtained in the step (1) into an iron ion solution for adsorption, and centrifuging to obtain an iron-loaded microorganism precursor after adsorption is completed;
(3) and (3) collecting the iron-loaded microbial precursor obtained in the step (2), preparing dry powder by vacuum freeze drying, and then carrying out carbonization roasting in an oxygen-free protective atmosphere to obtain the bifunctional carbon-based iron phosphide nano material.
5. The preparation method according to claim 4, wherein in the step (1), the living microorganisms having phosphate groups on the surface include any one or more of Escherichia coli (Escherichia coli BL21), Shewanella oneidensis (Shewanella oneidensis MR-1) and Bacillus subtilis; the temperature of the amplification culture is 20-30 ℃, and the time of the amplification culture is 6-72 h; the rotating speed of the centrifugation is 5000-10000 rpm, and the centrifugation time is more than or equal to 15 min.
6. The method according to claim 4, wherein in the step (2), the iron ion solution is FeCl3、FeSO4And Fe (NO)3)3Any one or more of them; the concentration of the iron ion solution is 50-300 mg/L; the adsorption temperature is 10-50 ℃, and the adsorption time is 0.5-6 h; the rotation speed adopted by the centrifugation is more than 6000rpm, and the centrifugation time is more than 10 min.
7. The preparation method according to claim 4, wherein in the step (3), the vacuum freeze-drying time is 0.5-12 h, and the protective atmosphere is nitrogen or argon.
8. The preparation method according to any one of claims 4 to 7, wherein in the step (3), the temperature of the carbonization roasting is 300 to 1200 ℃, the temperature rise rate of the carbonization roasting is 5 to 20 ℃/min, and the time of the carbonization roasting is 0.5 to 3 hours.
9. Use of the bifunctional carbon-based iron phosphide nanomaterial as defined in any one of claims 1 to 3 or prepared by the preparation method as defined in any one of claims 4 to 8, wherein the bifunctional carbon-based iron phosphide nanomaterial is added to an electrocatalytic HER and/or OER reaction.
10. Use according to claim 9, wherein the electrolyte used for the OER reaction and/or the HER reaction is potassium hydroxide solution.
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