CN116334683B - Fe doped MoS for bionic electrochemical nitrogen fixation 2 Preparation method of base nano material - Google Patents
Fe doped MoS for bionic electrochemical nitrogen fixation 2 Preparation method of base nano material Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 9
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims abstract description 9
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 239000004332 silver Substances 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 229920000557 Nafion® Polymers 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000007704 transition Effects 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract description 2
- 238000005554 pickling Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 49
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 19
- 229910021529 ammonia Inorganic materials 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000000833 X-ray absorption fine structure spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000003592 biomimetic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000009623 Bosch process Methods 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229910017108 Fe—Fe Inorganic materials 0.000 description 1
- 229910017116 Fe—Mo Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910004616 Na2MoO4.2H2 O Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004178 biological nitrogen fixation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010959 commercial synthesis reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/27—Ammonia
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of electrocatalytic energy storage, and aims to provide Fe doped MoS for bionic electrochemical nitrogen fixation 2 A preparation method of a base nano material. The method comprises the following steps: weighing ferric trichloride, sodium molybdate dihydrate and thioacetamide according to a molar ratio of 0.2:1:5, adding the ferric trichloride, the sodium molybdate dihydrate and the thioacetamide into a hydrothermal reaction kettle, reacting for 20 hours at 190 ℃, and then naturally cooling to room temperature; washing and drying the reactant to obtain silver gray powder which is Fe doped MoS 2 And (3) a base nanomaterial. The invention realizes MoS through doping Fe 2 2H phase to 1T phase transition of the material, optimizing the conductivity of the material; bionic Fe-Mo-S synergistic center promotes N 2 Activation of (C) to thereby increase electrocatalytic reduction of N 2 NH formation 3 Is a compound of formula (I). Atomically dispersed Fe provides a large number of catalytically active sites, enabling high atomic utilization. The invention adopts a one-step hydrothermal method, has no complicated steps of pretreatment, post-treatment pickling and the like, has rich raw material reserves and low cost, and is suitable for industrialized production.
Description
Technical Field
The invention relates to Fe doping for bionic electrochemical nitrogen fixationMoS 2 A preparation method of a base nano material, belonging to the field of electrocatalytic energy storage.
Background
Ammonia (NH) 3 ) The catalyst is widely applied as an important chemical raw material and a clean fuel carrier. However, commercial synthesis of ammonia still relies on the conventional high temperature and pressure Harber-Bosch process (N 2 +H 2 →NH 3 450-550 ℃ and 20-50 MPa), the process consumes about 2% of energy source worldwide, and the raw material gas H 2 Also produces 1% CO in the production process 2 And (5) discharging. Therefore, the development of the high-efficiency, clean and low-energy-consumption ammonia synthesis technology has important significance for the development of human society.
In recent years electrocatalytic nitrogen fixation (ENRR) was carried out by water (H 2 O) and nitrogen (N) 2 ) As a raw material, ammonia production is realized at normal temperature and normal pressure, and is considered as a most promising technology for synthesizing ammonia, and the advantages are represented in the following three aspects: (1) Will H 2 O is used as a hydrogen source, so that the source is wide, and the use of fossil energy is reduced; (2) The reaction condition is mild, the energy consumption is reduced, and the process has higher safety; (3) The process equipment is simple, and the on-demand preparation and the accurate preparation of ammonia can be realized. But due to N 2 Is of low solubility, high dissociation energy of N.ident.N (941 kJ mol -1 ) The Hydrogen Evolution (HER) competing reactions present at the cathode cause NRR to face bottlenecks in yield and energy consumption efficiency. Therefore, how to design an efficient and economical catalyst to increase N 2 Electrochemical synthesis of NH 3 Is critical to the selectivity and reaction rate.
Although metallic elements such as ruthenium, rhodium, cobalt, iron, molybdenum, nickel, tin, etc. have been widely developed and applied to ENRR, for example, the descriptions of patent publication nos. CN 111604048A, CN 110699705A, CN 113388858A. However, the noble metal and the catalyst of the noble metal are complex in synthesis steps and low in atom utilization rate, and indirectly increase the industrialized application cost.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects in the prior art and providing the Fe doped MoS for bionic electrochemical nitrogen fixation 2 A preparation method of a base nano material.
In order to solve the technical problems, the invention adopts the following solutions:
providing Fe doped MoS for biomimetic electrochemical nitrogen fixation 2 The preparation method of the base nanomaterial is characterized by comprising the following steps:
(1) Weighing ferric trichloride, sodium molybdate dihydrate and thioacetamide according to a molar ratio of 0.2:1:5, adding the ferric trichloride, the sodium molybdate dihydrate and the thioacetamide into a hydrothermal reaction kettle, reacting for 20 hours at 190 ℃, and then naturally cooling to room temperature;
(2) Washing and drying the reactant to obtain silver gray powder which is Fe doped MoS 2 And (3) a base nanomaterial.
As a preferable scheme of the invention, the hydrothermal reaction kettle is placed in a hydrothermal oven for heating.
As a preferable scheme of the invention, the washing is carried out by adopting a suction filtration mode, and deionized water and ethanol are used for washing for a plurality of times.
In a preferred embodiment of the present invention, the drying is performed by freezing.
The invention further provides the Fe doped MoS prepared by the method 2 The application method of the base nano material in bionic electrochemical nitrogen fixation comprises the following steps:
(1) Doping powdered Fe into MoS 2 Dispersing the base nano material in the dispersion liquid to obtain slurry; coating the slurry on hydrophobic carbon paper, and airing to obtain Fe@MoS 2 An electrode sheet;
(2) Using Fe@MoS as working electrode 2 Electrode sheet, pt sheet as counter electrode, ag/AgCl electrode as reference electrode to build three-electrode H-type electrolytic cell with LiClO of 0.25M 4 The solution is used as electrolyte;
(3) Bubbling for 30 min N 2 Then the H-type electrolytic cell is electrified and continuously electrified into N 2 At Fe@MoS 2 N at catalytic cathode 2 Is catalytically reduced to NH 3 。
As a preferable scheme of the invention, the dispersion liquid is a mixed liquid prepared by mixing deionized water, ethylene glycol and Nafion according to a volume ratio of 47:2:1, namely the concentration of Nafion solution is 1wt per mill.
As a preferred embodiment of the invention, fe in the slurry is doped with MoS 2 The mass volume ratio of the base nano material to the dispersion liquid is 2 mg/1 mL.
As a preferred embodiment of the present invention, the voltage applied to the working electrode ranges from-0.2V to-0.8V vs. RHE.
Description of the inventive principles:
according to the records of the prior research results, biological nitrogen fixation enzyme in nature contains Fe, mo, S and other elements, and forms a Fe-Mo-S center with synergistic catalysis. The invention optimizes the coordination structure based on atomic level by the bionic design of Fe-Mo-S center, and reserves the unoccupied d orbit atoms of Mo to adsorb N 2 Thereby obtaining an electrocatalyst with high performance.
The invention utilizes a hydrothermal one-pot method to prepare the bionic Fe@MoS 2 Electrocatalyst, moS is achieved by doping Fe atoms 2 Optimization of 2H to 1T phases, the synergistic active sites of Fe-Mo-S facilitate N 2 To thereby increase N 2 Catalytic reduction to NH 3 Is not limited to the above-described embodiments.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention realizes MoS through doping Fe 2 2H phase to 1T phase transition of the material, optimizing the conductivity of the material; bionic Fe-Mo-S synergistic center promotes N 2 Activation of (C) to thereby increase electrocatalytic reduction of N 2 NH formation 3 Is a compound of formula (I).
(2) Fe@MoS prepared by the method 2 The catalyst can realize 6.32mg h at-0.6V vs. RHE and-0.2V vs. RHE respectively -1 mg -1 Ammonia production rate and faraday efficiency of 28.2%. Atomically dispersed Fe provides a large number of catalytically active sites, enabling high atomic utilization.
(3) The invention adopts a one-step hydrothermal method, has no complicated steps of pretreatment, post-treatment pickling and the like, has rich raw material reserves of the used precursor and low cost, and is suitable for industrialized production.
Drawings
FIG. 1 is a schematic illustration of an embodiment of the present inventionFe@MoS in example 1 2 Is a schematic representation of the preparation of (a);
FIG. 2 is a chart showing the process of Fe@MoS in example 1 of the present invention 2 Is a Raman spectrum of (c);
FIG. 3 is a chart showing the process of Fe@MoS in example 1 of the present invention 2 A TEM image of (a);
FIG. 4 is a chart showing the process of Fe@MoS in example 1 of the present invention 2 STEM diagram of (a);
FIG. 5 is a chart showing the process of Fe@MoS in example 1 of the present invention 2 Is an EDS plot of (2);
FIG. 6 is a chart showing the process of Fe@MoS in example 1 of the present invention 2 Is a XAFS graph of (c);
FIG. 7 is a chart showing the process of Fe@MoS in example 1 of the present invention 2 Is a XAFS fit graph of (b);
FIG. 8 is MoS of comparative example 1 2 Ammonia yield and faraday efficiency;
FIG. 9 is a graph showing the comparison of ammonia yield and Faraday efficiency of Fe@MoS2 in example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following examples, but the scope of the present invention is not limited to these examples.
The iron trichloride, sodium molybdate dihydrate, thioacetamide used in the examples below were all purchased from sigma aldrich limited and analytically pure.
Preparation and application of first part catalyst
Example 1 Fe@MoS 2 Is prepared from
Fe doped MoS 2 The preparation method of the base nano material comprises the following steps:
(1) Weighing 32mg of ferric chloride (FeCl) at a molar ratio of 0.2:1:5 3 ) 242mg sodium molybdate dihydrate (Na) 2 MoO 4 .2H 2 O) and 376mg of thioacetamide (C) 2 H 5 NS)。
(2) The reactants were added to a hydrothermal reaction kettle, then placed in a hydrothermal oven and set at 190 ℃ for 20h.
(3) And naturally cooling to room temperature after the reaction is finished, taking out a reaction product, and sequentially carrying out suction filtration washing by using deionized water and ethanol.
(4) Freeze drying the powder obtained by suction filtration, and recovering to obtain silver gray powder which is Fe doped MoS 2 Base nanomaterial, abbreviated as Fe@MoS 2 。
Application method example:
Fe@MoS obtained by preparation of example 1 2 The method can be used for biomimetic electrochemical nitrogen fixation, and the application method comprises the following steps:
(1) Adding 1mL of Nafion into 2mL of glycol and 47mL of deionized water, and carrying out ultrasonic treatment for 5min to prepare 50mL of 1 wt%o Nafion solution;
(2) 2mg of prepared Fe@MoS are taken respectively 2 And MoS 2 In 1mL of 1 wt%Nafion solution, carrying out ultrasonic treatment for 2 hours to prepare evenly dispersed catalyst slurry with the concentration of 2 mg/mL;
(3) Cutting 1.5cm×1cm hydrophobic carbon paper, respectively dripping 100uL of the prepared catalyst onto 1cm 2 Is naturally dried to obtain 0.2mg/cm 2 Electrode plates of the catalyst;
(4) Three-electrode system is built in H-shaped groove to electrically reduce N 2 Synthesis of NH 3 The reaction, the working electrode (catalyst electrode plate), the reference electrode (Ag/AgCl electrode) and the counter electrode (Pt plate) are placed in the cathode tank, the anode tank and the electrolyte solution are 0.25M LiClO 4 The voltage applied to the working electrode ranges from-0.2V to-0.8V vs. rhe.
Performance testing and analysis of the second part catalyst
1. Comparative example 1 MoS 2 Is prepared from
Reference to Fe@MoS in example 1 2 Is prepared by mixing 242mg of sodium molybdate dihydrate (Na 2 MoO 4 .2H 2 O), 376mg of thioacetamide (C) 2 H 5 NS) is placed in a hydrothermal reaction kettle, the subsequent treatment steps are consistent, and black powder is obtained, namely MoS 2 。
2. The performance test method comprises the following steps:
(1) Referring to the procedure in the application example of example 1, coated Fe@MoS was prepared separately 2 Catalyst and coated MoS 2 A carbon paper electrode of the catalyst;
(2) Referring to the application example of example 1, electrochemical test was performed in an H-cell three-electrode system using a carbon paper electrode as a working electrode;
(3) The electrochemical workstation CHI 660E is adopted to evaluate the performance of the electrochemical ammonia synthesis;
(4) Electrochemical N-electrode system built by using working electrodes coated with different catalysts 2 Reduction to NH 3 Performance test, in which Ag/AgCl electrodes were converted to standard hydrogen electrodes (RHE), the conversion relationship was: e (E) RHE ＝E Ag/AgCl +0.0591 ph+0.199, ph=6.8. The voltage test of ENRR takes 0.2V as interval, and the test interval is-0.2V to-0.8V vs. RHE.
(5) N was introduced into the electrolyte at 50sccm (air flow unit, standard ml/min) for 30 min before the test 2 Continuously introducing N at 20sccm during test 2 . Loading voltages in a range from-0.2V to-0.8V vs. RHE by using a constant voltage method at intervals of 0.2V, and applying each voltage for 30 minutes; replacing the new electrolyte and introducing N 2 The new voltage is tested.
(6) The electrolyte for constant pressure test is reserved, and NH in the reaction liquid is quantified by ultraviolet spectrophotometry 3 Content of N 2 Conversion to NH 3 The faraday efficiency calculation formula of (2) is as follows:
wherein n is the number of transferred electrons; f Faraday constant, 96485C mol -1 ；C:NH 3 Concentration; v is the volume of electrolyte; m is NH 3 Relative mole fraction of NH 3 Is 18; q is the total amount of electrolytic charge.
NH 3 The yield of (2) is calculated as follows:
C:NH 3 concentration; v is the volume of electrolyte; t is the reaction time; m is the mass of the catalyst.
3. Analysis and conclusion
FIG. 1 depicts Fe@MoS in the present invention 2 Is a synthetic scheme of (2).
In the pair Fe@MoS 2 And MoS 2 After raman spectroscopy, fe@mos can be seen from fig. 2 2 Relative to MoS 2 In addition to having the original 2H characteristic peak, a new 1T phase J is generated 1 (150cm -1 ) And J 3 (344cm -1 ) Two characteristic peaks, illustrating the doping of Fe atoms to make MoS of 2H phase 2 Generation of MoS to 1T 2 Is a phase transition of (c).
FIG. 3 characterizes the catalyst material Fe@MoS 2 From TEM image, the synthesized nano-particle Fe@MoS 2 And presents a two-dimensional petal-shaped structure. Further, the defect on the surface of the two-dimensional structure can be seen by a dark field transmission electron microscope STEM image, and atomic-level Fe replaces part of Mo atomic distribution two-dimensional material MoS 2 Is shown (fig. 4).
FIG. 5 shows a catalyst Fe@MoS 2 In which strong signals of Mo and S are observed, while the signals of Fe are weaker and Fe is uniformly distributed in MoS 2 And (3) upper part.
To further explore the coordination structure of Fe, the method was used for Fe@MoS 2 By performing XAFS analysis, fe@MoS can be found by FIG. 6 2 Only Fe-S bonds are present and Fe-Fe bonds and Fe-Mo bonds are absent.
The coordination number of Fe was found to be 5.5 by fitting in FIG. 7, which illustrates the position where Fe replaced part of Mo, 5S atoms were coordinated around it, and an S defect was constructed to indirectly connect with Mo atoms.
FIG. 8 statistics of Fe@MoS 2 And MoS 2 The catalyst reduces N under different potentials 2 The Faraday efficiency and ammonia production efficiency of (C) can be seen as Fe@MoS 2 Yield and Faraday efficiency of (2) are much greater than MoS 2 ，Fe@MoS 2 The maximum Faraday efficiency (28.2%) and the maximum yield were achieved at-0.2V vs. RHE and-0.6V vs. RHE, respectively The Faraday efficiency and the yield are both larger than those of the noble metal Pd/C catalyst (CN 112647093A) and the Ni-based catalyst (CN 113388858A) reported in the prior publication.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (4)
1. Fe doped MoS for bionic electrochemical nitrogen fixation 2 The preparation method of the base nano material is characterized by comprising the following steps:
(1) Weighing ferric trichloride, sodium molybdate dihydrate and thioacetamide according to a molar ratio of 0.2:1:5, and adding the ferric trichloride, the sodium molybdate dihydrate and the thioacetamide into a hydrothermal reaction kettle; heating the hydrothermal reaction kettle in a hydrothermal oven, reacting at 190 ℃ for 20h, and naturally cooling to room temperature;
(2) Washing the reactant for multiple times by using deionized water and ethanol in a suction filtration mode, and drying by adopting a freezing mode to obtain silver gray powder, namely Fe doped MoS 2 And (3) a base nanomaterial.
2. The Fe-doped MoS prepared by the method of claim 1 2 The application method of the base nano material in bionic electrochemical nitrogen fixation is characterized by comprising the following steps:
(1) Doping powdered Fe into MoS 2 Dispersing the base nano material in the dispersion liquid to obtain slurry; coating the slurry on hydrophobic carbon paper, and airing to obtain Fe@MoS 2 An electrode sheet; the dispersion liquid is a mixed liquid prepared by mixing deionized water, glycol and Nafion according to a volume ratio of 47:2:1, namely the concentration of Nafion solution is 1wt per mill;
(2) Using Fe@MoS as working electrode 2 Electrode sheet, pt sheet as counter electrode, ag/AgCl electrode as reference electrode to build three-electrode H-type electrolytic cell with LiClO of 0.25M 4 The solution is used as electrolyte;
(3) Bubbling for 30 min N 2 Then the H-type electrolytic cell is electrified and continuously electrified into N 2 At Fe@MoS 2 N at catalytic cathode 2 Is catalytically reduced to NH 3 。
3. The method of claim 2, wherein Fe in the slurry is doped with MoS 2 The mass volume ratio of the base nano material to the dispersion liquid is 2: 2 mg:1 mL.
4. The method according to claim 2, wherein the voltage applied to the working electrode is in the range of-0.2V to-0.8Vvs. RHE。
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