CN111097452A - Preparation method of graphene-loaded ferrous sulfide nano material and application of graphene-loaded ferrous sulfide nano material in electrocatalytic nitrogen reduction - Google Patents
Preparation method of graphene-loaded ferrous sulfide nano material and application of graphene-loaded ferrous sulfide nano material in electrocatalytic nitrogen reduction Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 76
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 57
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 38
- 230000009467 reduction Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000002086 nanomaterial Substances 0.000 title abstract description 8
- 239000011858 nanopowder Substances 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 239000000243 solution Substances 0.000 claims abstract description 55
- 238000012360 testing method Methods 0.000 claims abstract description 27
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 12
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 11
- 229920000557 Nafion® Polymers 0.000 claims description 10
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 10
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 238000011056 performance test Methods 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000005485 electric heating Methods 0.000 claims description 4
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 238000005987 sulfurization reaction Methods 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 2
- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims 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 claims 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 63
- 229910021529 ammonia Inorganic materials 0.000 abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 5
- 238000004073 vulcanization Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000012670 alkaline solution Substances 0.000 abstract 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 16
- 238000001035 drying Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- -1 transition metal sulfide Chemical class 0.000 description 13
- 238000002835 absorbance Methods 0.000 description 12
- 238000002484 cyclic voltammetry Methods 0.000 description 12
- 238000003760 magnetic stirring Methods 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 238000005406 washing Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000011161 development Methods 0.000 description 9
- 238000009210 therapy by ultrasound Methods 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 239000005708 Sodium hypochlorite Substances 0.000 description 8
- 238000007664 blowing Methods 0.000 description 8
- SPBWMYPZWNFWES-UHFFFAOYSA-N disodium;azanylidyneoxidanium;iron(2+);pentacyanide;dihydrate Chemical compound O.O.[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].[O+]#N SPBWMYPZWNFWES-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 8
- 229960004889 salicylic acid Drugs 0.000 description 8
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 8
- 239000012086 standard solution Substances 0.000 description 8
- 229910021642 ultra pure water Inorganic materials 0.000 description 8
- 239000012498 ultrapure water Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000009620 Haber process Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 4
- 238000002211 ultraviolet spectrum Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- 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
-
- 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
Abstract
Ammonia has become one of the important raw materials in industries such as world industry, agriculture, pharmaceutical industry and the like. Given the high consumption of ammonia and the drawbacks of the current industrial ammonia production industry, the synthesis of ammonia under mild conditions has become a significant concern for the research of scientists worldwide. Therefore, the electrocatalytic reduction of nitrogen to ammonia has received much attention from researchers. In view of the above, on the basis of a large number of experimental tests, the graphene-supported ferrous sulfide nanomaterial prepared by the invention has extremely high yield and Faraday efficiency in the field of electrocatalytic nitrogen reduction. Firstly, adding an iron source reagent into an alkaline solution to prepare a pre-reaction solution, and heating the pre-reaction solution to obtain the sesquioxideIron nano powder; and then, mixing ferric oxide and self-made graphene oxide for a vulcanization reaction to finally obtain the graphene-loaded ferrous sulfide. The catalyst shows excellent activity in the field of electro-catalytic nitrogen reduction, and the ammonia yield under-0.2V (relative to a standard hydrogen electrode) is as high as 86.9 mu g h–1mg–1 cat.The Faraday efficiency reaches 5.3%.
Description
Technical Field
The invention relates to the field of preparation and application of inorganic nano powder, in particular to a method for preparing graphene-loaded sodium ferrous sulfide based on a solvothermal method and application of the method in the field of electro-catalytic nitrogen reduction.
Background
As is well known, ammonia (NH)3) As an important chemical raw material, the compound plays an irreplaceable role in the fertilizer manufacturing industry, the plastic rubber manufacturing industry and the pharmaceutical industry. Worldwide, 1.45 million metric tons of ammonia are manufactured and put into use each year. Therefore, the preparation of ammonia is significant to the development of mankind and social progress in the world today. However, the currently widely used ammonia process in the world is the Haber-Bosch process (Haber-Bosch), which releases large amounts of carbon dioxide (1.6% CO worldwide) due to the harsh reaction conditions (high temperature, high pressure), large scale2Emission comes from the emission) and consumes a large amount of energy (1% -3% of the energy is used for preparing ammonia by the Haber-Bosch process every year in the world), which causes further development of significant challenges. In response to the sustainable development concept and the national call for new and old energy conversion, the realization of mass preparation of ammonia under mild conditions becomes the focus of current research. Therefore, a great number of scientists in the world today are striving to explore designing new processes to achieve mass production of ammonia.
Among a plurality of novel processes, the electrocatalytic nitrogen reduction for preparing ammonia successfully attracts the attention of a large number of domestic and foreign research institutions due to the advantages of mild reaction conditions, safe process flows, green and pollution-free process processes and the like. This process also constitutes one of the most promising alternatives to the haber-bosch process. However, the electrocatalytic nitrogen reduction also faces a series of problems which are difficult to solve, thus making the industrial implementation of the electrocatalytic ammonia production process to be a bottleneck. Specifically, the half-reaction of water splitting in the electrocatalytic process: electrocatalytic hydrogen production (HER) is overpotential similar to the nitrogen reduction process making it difficult to separate. Thus, generally, electrocatalytic nitrogen reduction processes are accompanied by non-negligible hydrogen evolution reactions, resulting in very poor faradaic efficiency and low electron utilization for electrocatalytic nitrogen reduction. In response to this problem, scientists have proposed several regulatory strategies to achieve highly selective electrocatalytic nitrogen reduction. Recently, the group of the university of china, scheimpflug, discovered that, thanks to the strong coupling effect between the nanoparticles and the graphene lamellae, a bridge (between the nanoparticles and the graphene) was created. Further research finds that the bridge bond can be used as a channel with good charge transfer to greatly promote the charge transfer rate in the electrocatalytic nitrogen reduction process so as to realize the electrocatalytic nitrogen reduction with high yield, high selectivity and high stability, and the finding provides a theoretical basis for the industrial application of the electrocatalytic nitrogen reduction. In addition, the Cheng Jiangsheng project group of Shanghai university of transportation reports that selective adsorption and reduction of nitrogen can be realized by purposefully regulating and controlling the surface charge of the material, so that the Faraday efficiency of electrocatalysis nitrogen reduction is greatly improved. In consideration of the promotion effect of the bridge bond between the graphene and the nano-particles on charge transfer and the capability of the graphene to inject electrons into the nano-material, the preparation of the graphene-loaded nano-particle material is very hopeful to realize high activity and high selectivity of electro-catalytic nitrogen reduction. Therefore, the selection of proper materials to load on graphene can make a great contribution to the industrial production of the electrocatalytic nitrogen reduction.
The transition metal is unique3dElectronic structures (which can both donate and accept electrons) have made significant breakthroughs in the field of electrocatalysis. Meanwhile, in consideration of the unique size effect of the nanomaterial and the high conductivity of the sulfide, the development of the graphene-supported transition metal sulfide is expected to realize excellent electrocatalytic nitrogen reduction performance. In view of this, a series of experiments and characterization are carried out, and it is found that the yield and selectivity of the electrocatalytic nitrogen reduction can be improved to the greatest extent by loading ferrous sulfide on graphene. Therefore, the invention provides a graphene-supported ferrous sulfide nano material as a high-efficiency and high-selectivity electricityThe catalyst is reduced by catalytic nitrogen. The yield was 86.9 μ g h at-0.2V (vs. standard hydrogen electrode) in acid electrolyte–1mg–1 cat.The Faraday efficiency is as high as 5.3%, compared with the electrocatalysts studied at home and abroad, the yield and the selectivity of the electrocatalysts are further improved, and the successful synthesis of the material opens up a new path for the research and the development of the electrocatalyst nitrogen reduction catalyst.
Disclosure of Invention
The invention aims to provide a preparation method of graphene-loaded ferrous sulfide nano powder and application of the graphene-loaded ferrous sulfide nano powder in electrocatalytic nitrogen reduction. In order to solve the problems, the technical scheme of the invention is as follows:
1. a preparation method of graphene-loaded ferrous sulfide nano powder comprises the following preparation steps: (1) adding a proper amount of iron source reagent into an alkaline aqueous solution to prepare a pre-reaction solution, placing the pre-reaction solution into an electric heating blast drying oven to be heated for a certain time, naturally cooling to room temperature, washing, centrifuging, collecting, and freeze-drying to obtain self-made ferric oxide nano powder; (2) putting a certain amount of ferric oxide nano powder and a proper amount of self-made graphene into an absolute ethyl alcohol solvent, adding a certain amount of sulfur source reagent to prepare a reaction solution, heating the reaction solution for a certain time, cooling to room temperature, centrifugally collecting, and drying in vacuum to obtain black graphene-loaded ferrous sulfide nano powder.
2. The preparation method of the graphene-supported ferrous sulfide nanopowder according to claim 1, wherein in the step (1), the pH of the alkaline aqueous solution is 9-11; the optimal ratio is 9-10.
3. The method for preparing graphene-supported ferrous sulfide nanopowder according to claim 1, wherein in the step (1), the alkaline regulator is: one or more of ammonia water, sodium hydroxide, potassium hydroxide and sodium carbonate; most preferably ammonia water and trisodium citrate.
4. The method for preparing graphene-supported ferrous sulfide nanopowder according to claim 1, wherein in the step (1), the iron source reagent is ferric nitrate nonahydrate, ferric chloride hexahydrate, ferric ammonium sulfate, ferric acetylacetonate; most preferably ferric chloride hexahydrate and ferric nitrate nonahydrate.
5. The preparation method of the graphene-supported ferrous sulfide nano-powder according to claim 1, wherein in the step (1), the concentration of iron in a pre-reaction solution is 0.01-0.10 mol/L; the optimal ratio is 0.04-0.08 mol/L.
6. The method for preparing graphene-supported ferrous sulfide nanopowder according to claim 1, wherein in the step (1), the reaction temperature of the pre-reaction solution is 100%oC~ 180oC, the reaction time is 5-30 h; the optimal method is as follows: 150oC ~160oC，12 h ~ 24 h。
7. The preparation method of the graphene-supported ferrous sulfide nanopowder according to claim 1, wherein in the step (2), the mass ratio of the ferric oxide nanopowder to the self-made graphene oxide (mass concentration: 0.11 g/mL) is 1-3: 100-300; the optimal method is as follows: 1: 200.
8. The method for preparing the graphene-supported ferrous sulfide nanopowder according to claim 1, wherein in the step (2), the used sulfurization reagent is one or a combination of two of thioacetamide, sodium sulfide, sodium thiosulfate and thiourea, and the optimal is thioacetamide and thiourea.
9. The preparation method of the graphene-supported ferrous sulfide nanopowder according to claim 1, wherein in the step (2), the mass ratio of the ferric oxide to the vulcanizing agent is 1-3: 8-10, and preferably 1-2: 8-9.
10. The method for preparing graphene-supported ferrous sulfide nanopowder according to claim 1, wherein in the step (2), the reaction temperature of the sulfurization reaction solution is 150%oC~ 200oC, the reaction time is 10-20 h; the optimal method is as follows: 180oC ~ 190oC，15 h ~ 18 h。
11. The preparation method is characterized in that a three-electrode system is adopted for testing, an electro-catalytic nitrogen reduction performance test is carried out on an electrochemical workstation, carbon paper coated with graphene-loaded ferrous sulfide nano powder is used as a working electrode, a carbon rod is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode; 0.1mol/L hydrochloric acid solution is taken as electrolyte; an H-shaped glass electrolytic tank is taken as an electrolytic reaction device; and a Nafion membrane (117) separates the anode compartment from the cathode compartment.
Detailed description of the preferred embodiments
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and to the accompanying drawings, which are included to further illustrate features and advantages of the invention, and not to limit the scope of the invention as claimed.
Self-making graphene oxide: adding a certain amount of carbon powder into 70 mL of sulfuric acid, stirring for 30 min, adding a certain amount of sodium nitrate in an ice bath, continuously stirring for 30 min, slowly adding a proper amount of potassium permanganate in the ice bath, continuously stirring until the potassium permanganate is fully dissolved to form a uniformly dispersed mixed solution, and then heating to 40 DEG CoC, stirring is continued for a period of time. Then, 40 mL of deionized water was added slowly in a close-coupled state in an ice bath, and then 100 mL of deionized water was rapidly added and stirred for a while, and then taken out. After warming to room temperature, 20 mL of H was added slowly2O2And (3) uniformly stirring, taking out, washing for several times by using dilute hydrochloric acid, adding a proper amount of deionized water into the obtained solution after washing until the pH value is close to neutral, performing ultrasonic treatment for 6 hours, then centrifuging (4500 r/min, 30 min), and centrifuging to obtain supernatant to obtain the self-made graphene oxide for subsequent reaction. The mass concentration of the homemade graphene is calculated to be 0.11 g/mL.
Example 1
The first step is as follows: a50 mL hydrothermal high-pressure reaction kettle for a laboratory is taken, and the hydrothermal high-pressure reaction kettle is provided with a polytetrafluoroethylene inner container. 40 mL of ultrapure water was added to a 50 mL polytetrafluoroethylene liner, and sodium hydroxide (0.5150 g, 12.9 mmol) was added with magnetic stirring and stirred until fully dissolved (pH = 8.5). Next, iron sulfate (0.2399 g, 0.6 mmol) was added with magnetic stirring. After stirring for 12 h, the magnetons are sucked out and the hydrothermal autoclave is sealed, and then the hydrothermal autoclave is placed in an electrothermal blowing drying oven at 110 ℃ and kept warm for 6 h. After natural cooling, centrifugally washing with ultrapure water for a plurality of times, and freeze-drying to obtain the ferric oxide nano powder.
The second step is that: 35.5 mL of absolute ethyl alcohol and 4.5 mL of self-made graphene are placed in a 50 mL beaker, and are transferred to a 50 mL polytetrafluoroethylene inner container after being subjected to ultrasonic treatment for 6 hours. And sequentially adding 50mg of ferric oxide nano powder and 150mg of sodium sulfide under magnetic stirring, and continuously stirring for 2 hours to obtain a vulcanization reaction solution. Sealing the reaction kettle and placing the reaction kettle at 150 DEG CoAnd C, preserving heat for 12 hours in the electrothermal blowing drying box. After reaction, after cooling to room temperature, washing with absolute ethyl alcohol for several times, and vacuum drying to obtain black graphene-loaded ferrous sulfide nano powder.
The third step: application of graphene-loaded ferrous sulfide nano powder in electrocatalytic nitrogen reduction
1. Weighing 5 mg of graphene-loaded ferrous sulfide nano powder, adding 0.5 mL of ethanol and 0.5 mL of deionized water, and then adding 50 mu L of Nafion solution for ultrasonic treatment for 1 h to obtain a uniform dispersion liquid. And (3) coating 20 mu L of the dispersion liquid on the surface of clean and dry carbon paper, wherein the surface area of the carbon paper is controlled to be 0.5 cm multiplied by 1 cm by using a raw material tape, and naturally drying.
2. A three-electrode system is adopted to carry out the electro-catalytic nitrogen reduction performance test on a Chenghua 660E electrochemical workstation. The carbon paper coated with the graphene loaded ferrous sulfide nano powder is used as a working electrode, a carbon rod is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode. Taking 0.1mol/L hydrochloric acid solution as electrolyte and an H-shaped glass electrolytic tank as a reaction device; and a Nafion membrane (117) separates the anode compartment from the cathode compartment.
3. And (3) taking the carbon paper coated with the graphene loaded ferrous sulfide nano powder as a working electrode, and carrying out cyclic voltammetry test in a three-electrode system to activate the sample. The cyclic voltammetry test voltage interval is 0 to-1.0V (relative to an Ag/AgCl electrode), the highest potential is 0V, the lowest potential is-1.0V, the initial potential is 0V, and the final potential is-1.0V. The scanning rate was 0.05V/s. The sampling interval is 0.001V, the standing time is 2 s, and the number of scanning segments is 500.
4. After cyclic voltammetry activation, carbon paper coated with graphene-supported ferrous sulfide nano powder is used as a working electrode, long-time nitrogen reduction test is carried out on the catalyst, and the operating time of the catalyst is 7200 s when the potential is respectively set to-0.1V, -0.1V, -0.3V, -0.4V, -0.5V and-0.6V (relative to a standard hydrogen electrode).
The fourth step: ammonia production test
1. Drawing a working curve: 0.0. mu.g/mL, 0.1. mu.g/mL, 0.2. mu.g/mL, 0.3. mu.g/mL, 0.4. mu.g/mL, 0.5. mu.g/mL, 0.6. mu.g/mL, 0.7. mu.g/mL, 0.8. mu.g/mL, 0.9. mu.g/mL, 1.0. mu.g/mL of a standard solution was prepared in a hydrochloric acid solution of 0.1mol/L using ammonium chloride as a standard reagent and subjected to a color reaction to test the absorbance. The specific color development process comprises the following steps: 2 mL of the standard solution was added with 2 mL of 1mol/L sodium hydroxide solution (containing 5 wt% salicylic acid and 5 wt% sodium citrate dihydrate), 1 mL of 0.05 mol/L sodium hypochlorite solution was added, and 0.2 mL of 5 wt% sodium nitroprusside dihydrate solution was added. Standing and developing for 2 h at room temperature in a dark place, performing spectral scanning in a wavelength range of 550-800 nm by using an ultraviolet-visible spectrophotometer, recording an absorbance value at 655 nm, and drawing with concentration to obtain a working curve.
2. And (3) testing the yield of ammonia: 2 mL of the electrolyte after running for 2 h at each potential was taken, 2 mL of 1 mol/sodium hydroxide solution (containing 5 wt% salicylic acid and 5 wt% sodium citrate dihydrate) was added, 1 mL of 0.05 mol/L sodium hypochlorite solution was added, and 0.2 mL of 5 wt% sodium nitroprusside dihydrate was added. Standing and developing for 2 h at room temperature in a dark place, performing spectrum scanning within 550-800 nm by using an ultraviolet spectrum, recording an absorbance value at 655 nm, and contrasting with a working curve to finally obtain the concentration of ammonia. After data processing and calculation, the graphene-loaded ferrous sulfide nano powder has excellent NRR effect, and the ammonia yield reaches 83.7 mu g h under-0.3V (relative to a standard hydrogen electrode)–1mg–1 cat.The Faraday efficiency reaches 5.0%.
Example 2
The first step is as follows: a50 mL hydrothermal high-pressure reaction kettle for a laboratory is taken, and the hydrothermal high-pressure reaction kettle is provided with a polytetrafluoroethylene inner container. 40 mL of ultrapure water was added to a 50 mL polytetrafluoroethylene liner, and trisodium citrate (3.1762 g, 10.8 mmol) was added with magnetic stirring and stirred until fully dissolved (pH = 9.5). Next, ferric chloride hexahydrate (0.8646 g, 3.2 mmol) was added continuously with magnetic stirring. After stirring for 12 h, the magnetons are sucked out and the hydrothermal autoclave is sealed, and then the hydrothermal autoclave is placed in an electrothermal blowing drying oven at 110 ℃ and kept warm for 6 h. After natural cooling, centrifugally washing with ultrapure water for a plurality of times, and freeze-drying to obtain the ferric oxide nano powder.
The second step is that: and (3) putting 31 mL of absolute ethyl alcohol and 9 mL of self-made graphene into a 50 mL beaker, carrying out ultrasonic treatment for 6 hours, and transferring the treated product into a 50 mL polytetrafluoroethylene inner container. Under magnetic stirring, 50mg of ferric oxide nano powder and 200 mg of thioacetamide are sequentially added, and stirring is continued for 2 hours to obtain a vulcanization reaction solution. Sealing the reaction kettle and placing the reaction kettle at 180 DEGoAnd C, preserving heat for 17 hours in the electrothermal blowing drying box. After reaction, after cooling to room temperature, washing with absolute ethyl alcohol for several times, and vacuum drying to obtain black graphene-loaded ferrous sulfide nano powder.
The third step: application of graphene-loaded ferrous sulfide nano powder in electrocatalytic nitrogen reduction
1. Weighing 5 mg of graphene-loaded ferrous sulfide nano powder, adding 0.5 mL of ethanol and 0.5 mL of deionized water, and then adding 50 mu L of Nafion solution for ultrasonic treatment for 1 h to obtain a uniform dispersion liquid. And (3) coating 20 mu L of the dispersion liquid on the surface of clean and dry carbon paper, wherein the surface area of the carbon paper is controlled to be 0.5 cm multiplied by 1 cm by using a raw material tape, and naturally drying.
2. A three-electrode system is adopted to carry out the electro-catalytic nitrogen reduction performance test on a Chenghua 660E electrochemical workstation. The carbon paper coated with the graphene loaded ferrous sulfide nano powder is used as a working electrode, a carbon rod is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode. Taking 0.1mol/L hydrochloric acid solution as electrolyte and an H-shaped glass electrolytic tank as a reaction device; and a Nafion membrane (117) separates the anode compartment from the cathode compartment.
3. And (3) taking the carbon paper coated with the graphene loaded ferrous sulfide nano powder as a working electrode, and carrying out cyclic voltammetry test in a three-electrode system to activate the sample. The cyclic voltammetry test voltage interval is 0 to-1.0V (relative to an Ag/AgCl electrode), the highest potential is 0V, the lowest potential is-1.0V, the initial potential is 0V, and the final potential is-1.0V. The scanning rate was 0.05V/s. The sampling interval is 0.001V, the standing time is 2 s, and the number of scanning segments is 500.
4. After cyclic voltammetry activation, carbon paper coated with graphene-supported ferrous sulfide nano powder is used as a working electrode, long-time nitrogen reduction test is carried out on the catalyst, and the operating time of the catalyst is 7200 s when the potential is respectively set to-0.1V, -0.1V, -0.3V, -0.4V, -0.5V and-0.6V (relative to a standard hydrogen electrode).
The fourth step: ammonia production test
1. Drawing a working curve: 0.0. mu.g/mL, 0.1. mu.g/mL, 0.2. mu.g/mL, 0.3. mu.g/mL, 0.4. mu.g/mL, 0.5. mu.g/mL, 0.6. mu.g/mL, 0.7. mu.g/mL, 0.8. mu.g/mL, 0.9. mu.g/mL, 1.0. mu.g/mL of a standard solution was prepared in a hydrochloric acid solution of 0.1mol/L using ammonium chloride as a standard reagent and subjected to a color reaction to test the absorbance. The specific color development process comprises the following steps: 2 mL of the standard solution was added with 2 mL of 1mol/L sodium hydroxide solution (containing 5 wt% salicylic acid and 5 wt% sodium citrate dihydrate), 1 mL of 0.05 mol/L sodium hypochlorite solution was added, and 0.2 mL of 5 wt% sodium nitroprusside dihydrate solution was added. Standing and developing for 2 h at room temperature in a dark place, performing spectral scanning in a wavelength range of 550-800 nm by using an ultraviolet-visible spectrophotometer, recording an absorbance value at 655 nm, and drawing with concentration to obtain a working curve.
2. And (3) testing the yield of ammonia: 2 mL of the electrolyte after running for 2 h at each potential was taken, 2 mL of 1 mol/sodium hydroxide solution (containing 5 wt% salicylic acid and 5 wt% sodium citrate dihydrate) was added, 1 mL of 0.05 mol/L sodium hypochlorite solution was added, and 0.2 mL of 5 wt% sodium nitroprusside dihydrate was added. Standing and developing for 2 h at room temperature in a dark place, performing spectrum scanning within 550-800 nm by using an ultraviolet spectrum, recording an absorbance value at 655 nm, and contrasting with a working curve to finally obtain the concentration of ammonia. After data processing and calculation, the graphene-loaded ferrous sulfide nano powder has excellent NRR effect, and the ammonia yield reaches 86.9 mu g h under-0.3V (relative to a standard hydrogen electrode)–1mg–1 cat.The Faraday efficiency reaches 5.3%.
Example 3
The first step is as follows: a50 mL hydrothermal high-pressure reaction kettle for a laboratory is taken, and the hydrothermal high-pressure reaction kettle is provided with a polytetrafluoroethylene inner container. 40 mL of ultrapure water was added to a 50 mL polytetrafluoroethylene liner, and 1 mL of aqueous ammonia was added thereto with magnetic stirring and stirred for 30 min (pH = 10). Next, iron nitrate nonahydrate (0.8080 g, 2.0 mmol) was added with magnetic stirring. After stirring for 12 h, the magnetons are sucked out and the hydrothermal autoclave is sealed, and then the hydrothermal autoclave is placed in an electrothermal blowing drying oven at 160 ℃ for heat preservation for 12 h. After natural cooling, centrifugally washing with ultrapure water for a plurality of times, and freeze-drying to obtain the ferric oxide nano powder.
The second step is that: and (3) putting 31 mL of absolute ethyl alcohol and 9 mL of self-made graphene into a 50 mL beaker, carrying out ultrasonic treatment for 6 hours, and transferring the treated product into a 50 mL polytetrafluoroethylene inner container. And sequentially adding 50mg of ferric oxide nano powder and 400 mg of thiourea under magnetic stirring, and continuously stirring for 2 hours to obtain a vulcanization reaction solution. Sealing the reaction kettle and placing the reaction kettle at 190oAnd C, keeping the temperature in the electric heating blowing drying box for 15 hours. After reaction, after cooling to room temperature, washing with absolute ethyl alcohol for several times, and vacuum drying to obtain black graphene-loaded ferrous sulfide nano powder.
The third step: application of graphene-loaded ferrous sulfide nano powder in electrocatalytic nitrogen reduction
1. Weighing 5 mg of graphene-loaded ferrous sulfide nano powder, adding 0.5 mL of ethanol and 0.5 mL of deionized water, and then adding 50 mu L of Nafion solution for ultrasonic treatment for 1 h to obtain a uniform dispersion liquid. And (3) coating 20 mu L of the dispersion liquid on the surface of clean and dry carbon paper, wherein the surface area of the carbon paper is controlled to be 0.5 cm multiplied by 1 cm by using a raw material tape, and naturally drying.
2. A three-electrode system is adopted to carry out the electro-catalytic nitrogen reduction performance test on a Chenghua 660E electrochemical workstation. The carbon paper coated with the graphene loaded ferrous sulfide nano powder is used as a working electrode, a carbon rod is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode. Taking 0.1mol/L hydrochloric acid solution as electrolyte and an H-shaped glass electrolytic tank as a reaction device; and a Nafion membrane (117) separates the anode compartment from the cathode compartment.
3. And (3) taking the carbon paper coated with the graphene loaded ferrous sulfide nano powder as a working electrode, and carrying out cyclic voltammetry test in a three-electrode system to activate the sample. The cyclic voltammetry test voltage interval is 0 to-1.0V (relative to an Ag/AgCl electrode), the highest potential is 0V, the lowest potential is-1.0V, the initial potential is 0V, and the final potential is-1.0V. The scanning rate was 0.05V/s. The sampling interval is 0.001V, the standing time is 2 s, and the number of scanning segments is 500.
4. After cyclic voltammetry activation, carbon paper coated with graphene-supported ferrous sulfide nano powder is used as a working electrode, long-time nitrogen reduction test is carried out on the catalyst, and the operating time of the catalyst is 7200 s when the potential is respectively set to-0.1V, -0.1V, -0.3V, -0.4V, -0.5V and-0.6V (relative to a standard hydrogen electrode).
The fourth step: ammonia production test
1. Drawing a working curve: 0.0. mu.g/mL, 0.1. mu.g/mL, 0.2. mu.g/mL, 0.3. mu.g/mL, 0.4. mu.g/mL, 0.5. mu.g/mL, 0.6. mu.g/mL, 0.7. mu.g/mL, 0.8. mu.g/mL, 0.9. mu.g/mL, 1.0. mu.g/mL of a standard solution was prepared in a hydrochloric acid solution of 0.1mol/L using ammonium chloride as a standard reagent and subjected to a color reaction to test the absorbance. The specific color development process comprises the following steps: 2 mL of the standard solution was added with 2 mL of 1mol/L sodium hydroxide solution (containing 5 wt% salicylic acid and 5 wt% sodium citrate dihydrate), 1 mL of 0.05 mol/L sodium hypochlorite solution was added, and 0.2 mL of 5 wt% sodium nitroprusside dihydrate solution was added. Standing and developing for 2 h at room temperature in a dark place, performing spectral scanning in a wavelength range of 550-800 nm by using an ultraviolet-visible spectrophotometer, recording an absorbance value at 655 nm, and drawing with concentration to obtain a working curve.
2. And (3) testing the yield of ammonia: 2 mL of the electrolyte after running for 2 h at each potential was taken, 2 mL of 1 mol/sodium hydroxide solution (containing 5 wt% salicylic acid and 5 wt% sodium citrate dihydrate) was added, 1 mL of 0.05 mol/L sodium hypochlorite solution was added, and 0.2 mL of 5 wt% sodium nitroprusside dihydrate was added. Standing and developing for 2 h at room temperature in a dark place, performing spectrum scanning within 550-800 nm by using an ultraviolet spectrum, recording an absorbance value at 655 nm, and contrasting with a working curve to finally obtain the concentration of ammonia. After data processing and calculation, the graphene-loaded ferrous sulfide nano powder has excellent NRR effect, and the ammonia yield reaches 86.3 mu g h under-0.3V (relative to a standard hydrogen electrode)–1mg–1 cat.The Faraday efficiency reaches 5.3%.
Example 4
The first step is as follows: a50 mL hydrothermal high-pressure reaction kettle for a laboratory is taken, and the hydrothermal high-pressure reaction kettle is provided with a polytetrafluoroethylene inner container. 40 mL of ultrapure water was added to a 50 mL polytetrafluoroethylene inner container, and sodium carbonate (2.1763 g, 20.5 mmol) was added with magnetic stirring and stirred until fully dissolved (pH = 11). Next, ammonium iron sulfate (1.0641 g, 2.0 mmol) was added with magnetic stirring. After stirring for 12 h, the magnetons are sucked out and the hydrothermal autoclave is sealed, and then the hydrothermal autoclave is placed in an electrothermal blowing drying oven at 180 ℃ for heat preservation for 28 h. After natural cooling, centrifugally washing with ultrapure water for a plurality of times, and freeze-drying to obtain the ferric oxide nano powder.
The second step is that: and (3) putting 26.3 mL of absolute ethyl alcohol and 13.5 mL of self-made graphene in a 50 mL beaker, carrying out ultrasonic treatment for 6h, and transferring the treated mixture to a 50 mL polytetrafluoroethylene inner container. And sequentially adding 50mg of ferric oxide nano powder and 500 mg of sodium thiosulfate under magnetic stirring, and continuously stirring for 2 hours to obtain a vulcanization reaction solution. Sealing the reaction kettle and placing the reaction kettle at 200 DEG CoAnd C, preserving the heat in the electric heating blowing drying box for 19 hours. After reaction, after cooling to room temperature, washing with absolute ethyl alcohol for several times, and vacuum drying to obtain black graphene-loaded ferrous sulfide nano powder.
The third step: application of graphene-loaded ferrous sulfide nano powder in electrocatalytic nitrogen reduction
1. Weighing 5 mg of graphene-loaded ferrous sulfide nano powder, adding 0.5 mL of ethanol and 0.5 mL of deionized water, and then adding 50 mu L of Nafion solution for ultrasonic treatment for 1 h to obtain a uniform dispersion liquid. And (3) coating 20 mu L of the dispersion liquid on the surface of clean and dry carbon paper, wherein the surface area of the carbon paper is controlled to be 0.5 cm multiplied by 1 cm by using a raw material tape, and naturally drying.
2. A three-electrode system is adopted to carry out the electro-catalytic nitrogen reduction performance test on a Chenghua 660E electrochemical workstation. The carbon paper coated with the graphene loaded ferrous sulfide nano powder is used as a working electrode, a carbon rod is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode. Taking 0.1mol/L hydrochloric acid solution as electrolyte and an H-shaped glass electrolytic tank as a reaction device; and a Nafion membrane (117) separates the anode compartment from the cathode compartment.
3. And (3) taking the carbon paper coated with the graphene loaded ferrous sulfide nano powder as a working electrode, and carrying out cyclic voltammetry test in a three-electrode system to activate the sample. The cyclic voltammetry test voltage interval is 0 to-1.0V (relative to an Ag/AgCl electrode), the highest potential is 0V, the lowest potential is-1.0V, the initial potential is 0V, and the final potential is-1.0V. The scanning rate was 0.05V/s. The sampling interval is 0.001V, the standing time is 2 s, and the number of scanning segments is 500.
4. After cyclic voltammetry activation, carbon paper coated with graphene-supported ferrous sulfide nano powder is used as a working electrode, long-time nitrogen reduction test is carried out on the catalyst, and the operating time of the catalyst is 7200 s when the potential is respectively set to-0.1V, -0.1V, -0.3V, -0.4V, -0.5V and-0.6V (relative to a standard hydrogen electrode).
The fourth step: ammonia production test
1. Drawing a working curve: 0.0. mu.g/mL, 0.1. mu.g/mL, 0.2. mu.g/mL, 0.3. mu.g/mL, 0.4. mu.g/mL, 0.5. mu.g/mL, 0.6. mu.g/mL, 0.7. mu.g/mL, 0.8. mu.g/mL, 0.9. mu.g/mL, 1.0. mu.g/mL of a standard solution was prepared in a hydrochloric acid solution of 0.1mol/L using ammonium chloride as a standard reagent and subjected to a color reaction to test the absorbance. The specific color development process comprises the following steps: 2 mL of the standard solution was added with 2 mL of 1mol/L sodium hydroxide solution (containing 5 wt% salicylic acid and 5 wt% sodium citrate dihydrate), 1 mL of 0.05 mol/L sodium hypochlorite solution was added, and 0.2 mL of 5 wt% sodium nitroprusside dihydrate solution was added. Standing and developing for 2 h at room temperature in a dark place, performing spectral scanning in a wavelength range of 550-800 nm by using an ultraviolet-visible spectrophotometer, recording an absorbance value at 655 nm, and drawing with concentration to obtain a working curve.
2. And (3) testing the yield of ammonia: 2 mL of the electrolyte after running for 2 h at each potential was taken, 2 mL of 1 mol/sodium hydroxide solution (containing 5 wt% salicylic acid and 5 wt% sodium citrate dihydrate) was added, 1 mL of 0.05 mol/L sodium hypochlorite solution was added, and 0.2 mL of 5 wt% sodium nitroprusside dihydrate was added. Standing at room temperature in dark place for 2 h, performing spectrum scanning at 550-800 nm with ultraviolet spectrum, recording the value of absorbance at 655 nm, and comparing with the working curveThe final ammonia concentration was obtained. After data processing and calculation, the graphene-loaded ferrous sulfide nano powder has excellent NRR effect, and the ammonia yield reaches 84.3 mu g h under-0.2V (relative to a standard hydrogen electrode)–1mg–1 cat.The Faraday efficiency reaches 5.1%.
Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (7)
1. A preparation method of graphene-loaded ferrous sulfide nano powder is characterized by comprising the following preparation steps: (1) adding an iron source reagent into an alkaline aqueous solution to prepare a pre-reaction solution, heating the pre-reaction solution in an electric heating forced air drying box for a certain time, naturally cooling to room temperature, centrifugally collecting, and freeze-drying to obtain ferric oxide nano powder; (2) placing a proper amount of ferric oxide nano powder and self-made graphene oxide in an absolute ethyl alcohol solvent, adding a certain amount of sulfur source reagent to obtain a reaction solution, heating the reaction solution for a certain time, cooling to room temperature, centrifuging and collecting to obtain the graphene-loaded ferrous sulfide nano powder.
2. The method for preparing graphene-supported ferrous sulfide nanopowder according to claim 1, wherein in the step (1), the pH of the alkaline aqueous solution is 9-11, and the alkaline regulator is: one or more of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate and trisodium citrate.
3. The preparation method of the graphene-supported ferrous sulfide nano-powder according to claim 1, wherein in the step (1), the iron source reagent is one or a combination of several of ferric nitrate nonahydrate, ferric chloride hexahydrate, ferric ammonium sulfate, ferric sulfate and ferric acetylacetonate, and the concentration of iron in the pre-reaction solution is 0.01-0.10 mol/L.
4. The method for preparing graphene-supported ferrous sulfide nano-powder according to claim 1, wherein in the step (1), the reaction temperature of the pre-reaction solution is 100%oC~ 180oAnd C, the reaction time is 5-30 h.
5. The preparation method of the graphene-supported ferrous sulfide nano powder according to claim 1, wherein in the step (2), the mass ratio of the ferric oxide nano powder to the self-made graphene oxide (the mass concentration is 1.11 mg/mL) is 1-3: 100-300, the used vulcanizing agent is one or a combination of two of thioacetamide, sodium sulfide, sodium thiosulfate and thiourea, and the mass ratio of the ferric oxide to the vulcanizing agent is 1-3: 8-10.
6. The method for preparing graphene-supported ferrous sulfide nano-powder according to claim 1, wherein in the step (2), the reaction temperature of the sulfurization reaction solution is 150%oC~ 200oAnd C, the reaction time is 10-20 h.
7. The preparation method is characterized in that a three-electrode system is adopted for testing, an electro-catalytic nitrogen reduction performance test is carried out on an electrochemical workstation, carbon paper coated with graphene-loaded ferrous sulfide nano powder is used as a working electrode, a carbon rod is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode; 0.1mol/L hydrochloric acid solution is taken as electrolyte; an H-shaped glass electrolytic tank is taken as an electrolytic reaction device; and a Nafion membrane (117) separates the anode compartment from the cathode compartment.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113089016A (en) * | 2021-03-10 | 2021-07-09 | 西南科技大学 | Preparation method of high-performance single-center uranium-based supported catalyst |
| CN113593921A (en) * | 2021-06-11 | 2021-11-02 | 青岛科技大学 | Sandwich structure multiphase nanocomposite material and preparation method and application thereof |
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