CN111632606A - Multilayer stacked nanosheet CoS-CeO2Preparation method of nitrogen reduction catalyst - Google Patents
Multilayer stacked nanosheet CoS-CeO2Preparation method of nitrogen reduction catalyst Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 230000009467 reduction Effects 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000002135 nanosheet Substances 0.000 title claims description 29
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 41
- -1 cobalt sulfide cerium oxide Chemical compound 0.000 claims abstract description 22
- 239000012695 Ce precursor Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 238000012360 testing method Methods 0.000 claims description 39
- 239000012528 membrane Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 29
- 239000003792 electrolyte Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- MNUSFSHFJMPRIV-UHFFFAOYSA-N [Co].[Ce] Chemical compound [Co].[Ce] MNUSFSHFJMPRIV-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 229920000557 Nafion® Polymers 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 238000011946 reduction process Methods 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000011056 performance test Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005987 sulfurization reaction Methods 0.000 claims 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims 1
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 229940011182 cobalt acetate Drugs 0.000 claims 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims 1
- 229940044175 cobalt sulfate Drugs 0.000 claims 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims 1
- KPZSTOVTJYRDIO-UHFFFAOYSA-K trichlorocerium;heptahydrate Chemical compound O.O.O.O.O.O.O.Cl[Ce](Cl)Cl KPZSTOVTJYRDIO-UHFFFAOYSA-K 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 51
- 238000006722 reduction reaction Methods 0.000 abstract description 32
- 229910021529 ammonia Inorganic materials 0.000 abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000009620 Haber process Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 abstract description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 2
- 230000002411 adverse Effects 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 229910052709 silver Inorganic materials 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 48
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000002835 absorbance Methods 0.000 description 12
- 239000012086 standard solution Substances 0.000 description 12
- 238000011161 development Methods 0.000 description 10
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000003086 colorant Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 8
- 229960004025 sodium salicylate Drugs 0.000 description 8
- 230000003595 spectral effect Effects 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 8
- 239000002243 precursor Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
Abstract
NH3The synthesis is mainly controlled by the traditional energy-consuming Haber-Bosch process, but the process has the great disadvantage of discharging a large amount of CO2Causing a greenhouse effect and requiring severe reaction conditions such as high temperature, high pressure. Electrochemical nitrogen reduction reaction under ambient conditions provides us with the artificial synthesis of NH3A friendly route, however stable and efficient catalysts are required for nitrogen reduction reactions. Noble metals such as Au, Ru, Ag and Rh are effective for electrolytic nitrogen reduction, and the expensive price of these catalysts limits their use. Transition metal oxides happen to solve this expensive and non-toxic and easy to prepare, but the problem with them is that their poor electrical conductivity adversely affects the catalytic performance. The invention provides a multilayer stacked nanosheetCatalyst material cobalt sulfide cerium oxide hybrid CoS-CeO2And its electrocatalytic nitrogen reduction application. Firstly, adding cobalt and cerium reagents with a specific proportion into a special reaction solution, and heating and reacting by using a hydrothermal synthesis method to obtain cobalt and cerium precursors; then placing the cobalt and cerium precursors in a tubular furnace at a specific nitrogen flow rate for vulcanization treatment to finally obtain cobalt sulfide cerium oxide hybrid CoS-CeO2. The CoS-CeO2The catalyst shows excellent catalytic activity in the field of electrocatalytic nitrogen reduction (NRR), and when the catalyst is arranged under a standard hydrogen electrode and under a standard-0.2V, the ammonia yield reaches 40.6 mu g h–1mg–1 catThe Faraday efficiency reaches 10.2%.
Description
Technical Field
The invention relates to the field of preparation and application of inorganic nano materials, in particular to a multilayer stacked nanosheet catalyst material prepared based on a hydrothermal method, namely cobalt sulfide cerium oxide hybrid CoS-CeO2The method and the application in the field of electrocatalytic nitrogen reduction are realized.
Background
NH3As one of the most important industrial chemicals, it has been used for pharmaceuticals, fertilizers, fuels, explosives, and the like; as a precursor of nitrogen compounds, it plays an important role in agriculture, pharmaceuticals and textile industries. Meanwhile, ammonia gas is a new energy carrier, the hydrogen content in liquid ammonia is 17.6%, while the methanol content is 12.5%, and the ammonia gas is likely to be a promising candidate for the future hydrogen energy economy. Therefore, ammonia gas occupies an indispensable position in the future population development. Statistically, over 1.4 million tons of ammonia gas are produced industrially every year, and the demand is still increasing. Today, a large demand for ammonia gasThe development of the ammonia gas generating device is an urgent social problem, which stimulates the intensive research of the artificial ammonia gas mass production technology.
However, due to the chemical inertness of nitrogen and the high energy barrier for N.ident.N bond cleavage, the synthesis of ammonia gas relies mainly on the conventional energy-intensive Haber-Bosch process, but the process conditions are severe and must be carried out at 350-2The input and energy consumption of (a) is mainly from fossil fuels, which results in a large carbon dioxide emission, on average 1.87 tons of carbon dioxide per ton of ammonia gas, which is not negligible. The traditional Haber-Bosch process reportedly consumes about 2% of the global energy supply, accounting for 1.5% of global greenhouse gas emissions. Therefore, the search for sustainable and efficient ammonia production processes under mild conditions remains a great driving force.
In recent years, electrochemical nitrogen reduction NRR has attracted much attention. Compared to the traditional Haber-Bosch process, NRR has the following advantages: ambient working conditions, rich soil feedstocks, i.e. nitrogen and water, simplified equipment, very low carbon emissions, but it requires an efficient nitrogen reduction electrocatalyst. To date, theoretical and experimental research on NRR for heterogeneous catalysts has focused primarily on noble metals, transition metal oxides/nitrides/carbides/chalcogenides, and metal-free catalysts. Many noble metals, such as Au, Ru, Rh, and Pd, are effective in catalyzing nitrogen reduction reactions and have high yields, but the expense of these catalysts is a limiting condition for their widespread use. Accordingly, much attention has been focused on the design and study of non-noble metal catalysts, particularly transition metals, which are distinguished by their advantages, stability, non-toxicity, low cost and ease of preparation.
The nano material has many novel properties due to the unique size, and shows excellent activity when being applied to the field of electrocatalysis. In addition, doping is used as a common regulation and control means, and metal synergistic effect is added, so that the generated catalytic performance is applied to electrocatalytic nitrogen reduction, and further breakthrough is certainly achieved. In view of the above, the present invention provides a multilayer stacked nanosheet catalyst material, cobalt sulfide cerium oxide hybrid CoS-CeO2The application is a high-efficiency electrocatalytic nitrogen reduction catalyst.
Disclosure of Invention
One of the purposes of the invention is to stack the nanosheet CoS-CeO in multiple layers2A novel preparation method of a nitrogen reduction catalyst.
The other purpose of the invention is to apply the synthesized multilayer stacked nanosheet catalyst to an electro-catalytic nitrogen reduction system.
The invention also aims to design a brand-new single-chamber membrane electrode nitrogen reduction electrocatalysis test system by repeated test processing.
Drawings
FIG. 1 is a schematic structural diagram of a self-designed single-chamber membrane electrode nitrogen reduction electro-catalysis test system provided by the invention.
The technical scheme of the invention is as follows:
1. multilayer stacked nanosheet catalyst material cobalt sulfide cerium oxide hybrid CoS-CeO2The preparation method is characterized by comprising the following steps:
(1) adding cobalt and cerium reagents with a fixed ratio of 10: 1-1: 1 into a specific reaction solution, namely a mixed solution of urea and thiourea to prepare a pre-reaction solution, heating the pre-reaction solution at a certain temperature by using a hydrothermal synthesis method for a certain time, naturally cooling, washing, drying and collecting the obtained cobalt and cerium precursor, wherein in the process, the use of the mixed solution of urea and thiourea can effectively adjust the pH value of the solution, promote the generation of multilayer stacked nanosheets, and simultaneously regulate the morphology of a nanomaterial to enable the generated cobalt and cerium precursor to present a very thin physical structure;
(2) placing a cobalt-cerium precursor in a tube furnace, fixing the nitrogen flow rate at 10-50 mL/min and the calcination temperature at 300oC ~600oAnd C, adding sublimed sulfur as a vulcanizing agent to perform a vulcanizing reaction, wherein the mass ratio of the vulcanizing agent to the cobalt-cerium precursor is 1: 10-1: 100, and the vulcanizing temperature is 300oC ~ 600oC, vulcanizing for 1-6 h at a heating rate of 0.5oC/min to obtain multilayer stacked nanosheets CoS-CeO2In the process, sublimed sulfur is used as a vulcanizing agent and can promoteMultilayer stacked nanosheet CoS-CeO2Can improve the conductivity of the catalyst and simultaneously enable the formed CoS-CeO2More catalytic active sites are exposed, which is beneficial to the subsequent electrocatalytic process.
2. Multilayer stacked nanosheet CoS-CeO2The preparation method of the nitrogen reduction catalyst is characterized in that a single-chamber membrane electrode nitrogen reduction electrocatalysis performance test is adopted, and the steps are as follows:
(1) adding CoS-CeO2Preparing 0.1-5 mg/mL ink liquid, dripping the ink liquid on a proton exchange membrane, and slightly drying the ink liquid at room temperature; preparing 0-1 mg/mL Nafion solution, and dripping the solution on the micro-dried CoS-CeO2The surface is prepared into an electrocatalytic nitrogen reduction membrane electrode, and in the process, the proton exchange membrane only allows H+The directional permeation is directly acted with the catalyst on the membrane electrode in the nitrogen atmosphere, so that the reaction time is greatly shortened;
(2) the membrane electrode is used as a working electrode, the graphite electrode is used as a counter electrode, the Ag/AgCl electrode is used as a reference electrode, the 0.1-2 mol/L sodium sulfate-lithium perchlorate mixed solution is used as electrolyte, the electrocatalytic nitrogen reduction process is carried out, the sodium sulfate-lithium perchlorate mixed solution is used as electrolyte in the process, the reaction selectivity is improved, the hydrogen evolution reaction can be effectively inhibited, the nitrogen reduction reaction is promoted, the mixed solution of the sodium sulfate and the lithium perchlorate is applied to the nitrogen reduction electrocatalytic test for the first time, and the result shows that the effect is excellent.
3. The novel single-chamber membrane electrode nitrogen reduction electrocatalysis test system is used, wherein a proton exchange membrane is used as a working electrode, and CoS-CeO2The catalyst is dripped on the outer side of the membrane electrode, and H is continuously provided by the mixed electrolyte of sodium sulfate and lithium perchlorate+Supply, the ammonia solution that produces is collected to the miniature funnel receiver, and this test system can improve the utilization ratio of electro-catalytic nitrogen gas reduction catalyst, prevents that the catalyst from excessively consuming, can effectively improve the faraday efficiency of reaction simultaneously.
4.CoS-CeO2The performance of the multilayer stacked nanosheets and the ammonia yield of the electrocatalytic nitrogen reduction reaction reach 40.6 mu g h–1mg–1The Faraday efficiency is as high as 10.2 percent, and the method hasBetter ammonia yield and faraday efficiency.
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.
Example 1
The first step is as follows: adding 100 mL of deionized water into a beaker, adding urea (0.781 g, 13 mmol), stirring for 30min to form a clear transparent solution, sequentially adding cobalt nitrate hexahydrate (0.582 g, 2 mmol) and cerium nitrate hexahydrate (0.434 g, 1.0 mmol) while continuing stirring, stirring for 30min, and transferring 40 mL of the solution into a polytetrafluoroethylene liner. Sealing the hydrothermal autoclave, and then placing the hydrothermal autoclave in an oven at 100 ℃ for heat preservation for 8 h. And after natural cooling, washing with deionized water and absolute ethyl alcohol respectively, and drying in vacuum to obtain the cobalt-cerium precursor loaded on the titanium mesh.
The second step is that: taking a cobalt-cerium precursor and 1 g of sublimed sulfur, placing the precursor and the 1 g of sublimed sulfur in a tube furnace, and placing the precursor and the sublimed sulfur in the tube furnace under the nitrogen atmosphere for 300 goCalcining C for 1h at a temperature rise rate of 0.5oC/min, nitrogen flow 10 mL/min. Obtaining multilayer stacked nanosheets CoS-CeO2。
The third step: multilayer stacked nanosheet CoS-CeO2Application of electrolytic water
1. Adding CoS-CeO2Preparing 0.1-5 mg/mL ink liquid, dripping the ink liquid on a proton exchange membrane, and slightly drying the ink liquid at room temperature; preparing 0-1 mg/mL Nafion solution, and dripping the solution on the micro-dried CoS-CeO2And (5) preparing the electrocatalytic nitrogen reduction membrane electrode on the surface.
2. The membrane electrode is used as a working electrode, the graphite electrode is used as a counter electrode, the Ag/AgCl electrode is used as a reference electrode, and the 0.1-2 mol/L sodium sulfate-lithium perchlorate mixed solution is used as electrolyte to perform an electrocatalytic nitrogen reduction process. The cyclic voltammetry test voltage interval is 0 to-1.0V, 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.
3. And performing linear voltage scanning test, wherein the voltage interval is 0 to-1.0V. The initial potential was 0V and the final potential was-1.0V. The scan rate was 5 mV/s. The sampling interval was 0.001V. The standing time was 2 s. Firstly, introducing argon into the electrolyte for 30min, and carrying out a first linear voltage scanning test after the argon is saturated. And then introducing nitrogen into the electrolyte for 30min, and carrying out a second linear voltage scanning test after the nitrogen is saturated.
4. And (3) performing a long-time nitrogen reduction test on the catalyst by using a membrane electrode as a working electrode, wherein the potentials are respectively set to be-0.35V, -0.45V, -0.55V, -0.65V and-0.75V, and the running time is 7200 s.
The fourth step: ammonia production test
1. Drawing a working curve: by NH40.0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 and 1.0 mu g/mL of standard solution is prepared in 0.1 mol/L of sodium sulfate-lithium perchlorate mixed solution by taking Cl as a standard reagent, and the standard solution is subjected to chromogenic reaction to test absorbance. To 4 mL of the standard solution were added 50. mu.L of an oxidizing agent (containing 75 wt% NaOH and 75 wt% NaClO), 500. mu.L of a coloring agent (containing 40 wt% sodium salicylate and 32 wt% NaOH), and 50. mu.L of a catalyst (5 wt% Na) in this order2[Fe(NO)(CN)5]·2H2O). Standing at room temperature in a dark place for color development for 1h, performing spectral scanning in a wavelength range of 550 nm-800 nm by using an ultraviolet visible spectrophotometer, and recording the absorbance value at 660nm and the concentration to obtain a standard curve by mapping.
2. And (3) testing the yield of ammonia: after running for 2 hours at each potential, 4 mL of each electrolyte was taken, and 50. mu.L of an oxidizing agent (containing 75 wt% of NaOH and 75 wt% of NaClO), 500. mu.L of a coloring agent (containing 40 wt% of sodium salicylate and 32 wt% of NaOH), and 50. mu.L of a catalyst (5 wt% of Na) were sequentially added2[Fe(NO)(CN)5]·2H2O). Standing at room temperature in a dark place for color development for 1h, performing spectral scanning in a wavelength range of 550 nm-800 nm by using an ultraviolet visible spectrophotometer, and recording an absorbance value at 660nm to finally obtain the concentration of ammonia. After data processing and calculation, multilayer stacked nanosheet CoS-CeO2Excellent application to NRR (relative to standard hydrogen) -0.2VElectrode) ammonia yield reaches 40.6 mu g h–1mg–1 cat.The Faraday efficiency is as high as 10.2%.
Example 2
The first step is as follows: 100 mL of deionized water is added into a beaker, urea (0.901 g, 15 mmol) is added, the mixture is stirred for 30min to form a clear and transparent solution, cobalt chloride hexahydrate (0.476 g, 2 mmol) and cerium nitrate hexahydrate (0.434 g, 1.0 mmol) are sequentially added under the condition of continuous stirring, 40 mL of the solution is taken and transferred into a polytetrafluoroethylene inner container after the mixture is stirred for 30 min. After the hydrothermal autoclave is sealed, the hydrothermal autoclave is placed in an oven at 110 ℃ and kept warm for 10 hours. And after natural cooling, washing with deionized water and absolute ethyl alcohol respectively, and drying in vacuum to obtain the cobalt-cerium precursor.
The second step is that: taking a cobalt-cerium precursor and 1.5 g of sublimed sulfur, placing the precursor and the sublimed sulfur in a tube furnace in a nitrogen atmosphere of 350oCalcining C for 1h at a temperature rise rate of 0.5oC/min, nitrogen flow 10 mL/min. Obtaining multilayer stacked nanosheets CoS-CeO2。
The third step: multilayer stacked nanosheet CoS-CeO2Application of electrolytic water
1. Adding CoS-CeO2Preparing 0.1-5 mg/mL ink liquid, dripping the ink liquid on a proton exchange membrane, and slightly drying the ink liquid at room temperature; preparing 0-1 mg/mL Nafion solution, and dripping the solution on the micro-dried CoS-CeO2And (5) preparing the electrocatalytic nitrogen reduction membrane electrode on the surface.
2. The membrane electrode is used as a working electrode, the graphite electrode is used as a counter electrode, the Ag/AgCl electrode is used as a reference electrode, and the 0.1-2 mol/L sodium sulfate-lithium perchlorate mixed solution is used as electrolyte to perform an electrocatalytic nitrogen reduction process. The cyclic voltammetry test voltage interval is 0 to-1.0V, 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.
3. And performing linear voltage scanning test, wherein the voltage interval is 0 to-1.0V. The initial potential was 0V and the final potential was-1.0V. The scan rate was 5 mV/s. The sampling interval was 0.001V. The standing time was 2 s. Firstly, introducing argon into the electrolyte for 30min, and carrying out a first linear voltage scanning test after the argon is saturated. And then introducing nitrogen into the electrolyte for 30min, and carrying out a second linear voltage scanning test after the nitrogen is saturated.
4. And (3) performing a long-time nitrogen reduction test on the catalyst by using a membrane electrode as a working electrode, wherein the potentials are respectively set to be-0.35V, -0.45V, -0.55V, -0.65V and-0.75V, and the running time is 7200 s.
The fourth step: ammonia production test
1. Drawing a working curve: by NH40.0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 and 1.0 mu g/mL of standard solution is prepared in 0.1 mol/L of sodium sulfate-lithium perchlorate mixed solution by taking Cl as a standard reagent, and the standard solution is subjected to chromogenic reaction to test absorbance. To 4 mL of the standard solution were added 50. mu.L of an oxidizing agent (containing 75 wt% NaOH and 75 wt% NaClO), 500. mu.L of a coloring agent (containing 40 wt% sodium salicylate and 32 wt% NaOH), and 50. mu.L of a catalyst (5 wt% Na) in this order2[Fe(NO)(CN)5]·2H2O). Standing at room temperature in a dark place for color development for 1h, performing spectral scanning in a wavelength range of 550 nm-800 nm by using an ultraviolet visible spectrophotometer, and recording the absorbance value at 660nm and the concentration to obtain a standard curve by mapping.
2. And (3) testing the yield of ammonia: after running for 2 hours at each potential, 4 mL of each electrolyte was taken, and 50. mu.L of an oxidizing agent (containing 75 wt% of NaOH and 75 wt% of NaClO), 500. mu.L of a coloring agent (containing 40 wt% of sodium salicylate and 32 wt% of NaOH), and 50. mu.L of a catalyst (5 wt% of Na) were sequentially added2[Fe(NO)(CN)5]·2H2O). Standing at room temperature in a dark place for color development for 1h, performing spectral scanning in a wavelength range of 550 nm-800 nm by using an ultraviolet visible spectrophotometer, and recording an absorbance value at 660nm to finally obtain the concentration of ammonia. After data processing and calculation, multilayer stacked nanosheet CoS-CeO2When the method is applied to NRR, the effect is excellent, and the ammonia yield reaches 40.2 mu g h under the condition of minus 0.2V (relative to a standard hydrogen electrode)–1mg–1 cat.The Faraday efficiency is as high as 10.1%.
Example 3
The first step is as follows: adding 100 mL of deionized water into a beaker, adding urea (0.961 g, 16 mmol), stirring for 30min to form a clear transparent solution, sequentially adding cobalt nitrate hexahydrate (0.582 g, 2 mmol) and cerium sulfate (0.498 g, 1.5 mmol) while continuing stirring, stirring for 30min, and transferring 40 mL of the solution into a polytetrafluoroethylene liner. The hydrothermal autoclave is sealed and then placed in an oven at 110 ℃ for heat preservation for 8 h. And after natural cooling, washing with deionized water and absolute ethyl alcohol respectively, and drying in vacuum to obtain the cobalt-cerium precursor.
The second step is that: taking a cobalt-cerium precursor and 2 g of sublimed sulfur, placing the precursor and the sublimed sulfur in a tube furnace in a nitrogen atmosphere for 300 goCalcining C for 1h at a temperature rise rate of 0.5oC/min, nitrogen flow 10 mL/min. Obtaining multilayer stacked nanosheets CoS-CeO2。
The third step: multilayer stacked nanosheet CoS-CeO2Application of electrolytic water
1. Adding CoS-CeO2Preparing 0.1-5 mg/mL ink liquid, dripping the ink liquid on a proton exchange membrane, and slightly drying the ink liquid at room temperature; preparing 0-1 mg/mL Nafion solution, and dripping the solution on the micro-dried CoS-CeO2And (5) preparing the electrocatalytic nitrogen reduction membrane electrode on the surface.
2. The membrane electrode is used as a working electrode, the graphite electrode is used as a counter electrode, the Ag/AgCl electrode is used as a reference electrode, and the 0.1-2 mol/L sodium sulfate-lithium perchlorate mixed solution is used as electrolyte to perform an electrocatalytic nitrogen reduction process. The cyclic voltammetry test voltage interval is 0 to-1.0V, 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.
3. And performing linear voltage scanning test, wherein the voltage interval is 0 to-1.0V. The initial potential was 0V and the final potential was-1.0V. The scan rate was 5 mV/s. The sampling interval was 0.001V. The standing time was 2 s. Firstly, introducing argon into the electrolyte for 30min, and carrying out a first linear voltage scanning test after the argon is saturated. And then introducing nitrogen into the electrolyte for 30min, and carrying out a second linear voltage scanning test after the nitrogen is saturated.
4. And (3) performing a long-time nitrogen reduction test on the catalyst by using a membrane electrode as a working electrode, wherein the potentials are respectively set to be-0.35V, -0.45V, -0.55V, -0.65V and-0.75V, and the running time is 7200 s.
The fourth step: ammonia production test
1. Drawing a working curve: by NH40.0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 and 1.0 mu g/mL of standard solution is prepared in 0.1 mol/L of sodium sulfate-lithium perchlorate mixed solution by taking Cl as a standard reagent, and the standard solution is subjected to chromogenic reaction to test absorbance. To 4 mL of the standard solution were added 50. mu.L of an oxidizing agent (containing 75 wt% NaOH and 75 wt% NaClO), 500. mu.L of a coloring agent (containing 40 wt% sodium salicylate and 32 wt% NaOH), and 50. mu.L of a catalyst (5 wt% Na) in this order2[Fe(NO)(CN)5]·2H2O). Standing at room temperature in a dark place for color development for 1h, performing spectral scanning in a wavelength range of 550 nm-800 nm by using an ultraviolet visible spectrophotometer, and recording the absorbance value at 660nm and the concentration to obtain a standard curve by mapping.
2. And (3) testing the yield of ammonia: after running for 2 hours at each potential, 4 mL of each electrolyte was taken, and 50. mu.L of an oxidizing agent (containing 75 wt% of NaOH and 75 wt% of NaClO), 500. mu.L of a coloring agent (containing 40 wt% of sodium salicylate and 32 wt% of NaOH), and 50. mu.L of a catalyst (5 wt% of Na, respectively) were sequentially added2[Fe(NO)(CN)5]·2H2O). Standing at room temperature in a dark place for color development for 1h, performing spectral scanning in a wavelength range of 550 nm-800 nm by using an ultraviolet visible spectrophotometer, and recording an absorbance value at 660nm to finally obtain the concentration of ammonia. After data processing and calculation, multilayer stacked nanosheet CoS-CeO2When the method is applied to NRR, the effect is excellent, and the ammonia yield reaches 40.3 mu g h under the condition of minus 0.2V (relative to a standard hydrogen electrode)–1mg–1 cat.The Faraday efficiency is as high as 10.2%.
Example 4
The first step is as follows: 100 mL of deionized water is added into a beaker, urea (1.051 g, 17.5 mmol) is added, the mixture is stirred for 30min to form a clear transparent solution, cobalt nitrate hexahydrate (1.019 g, 3.5 mmol) and cerium nitrate hexahydrate (0.76 g, 1.75 mmol) are sequentially added under the condition of continuous stirring, 40 mL of the solution is taken and transferred into a polytetrafluoroethylene inner container after the mixture is stirred for 30 min. Sealing the hydrothermal autoclave, and then placing the hydrothermal autoclave in an oven at 120 ℃ for heat preservation for 10 hours. And after natural cooling, washing with deionized water and absolute ethyl alcohol respectively, and drying in vacuum to obtain the cobalt-cerium precursor.
The second step is that: taking a cobalt-cerium precursor and 1 g of sublimed sulfur, placing the precursor and the 1 g of sublimed sulfur in a tube furnace, and placing the precursor and the sublimed sulfur in the tube furnace under the nitrogen atmosphere of 400 DEGoCalcining C for 1h at a temperature rise rate of 0.5oC/min, nitrogen flow 10 mL/min. Obtaining multilayer stacked nanosheets CoS-CeO2。
The third step: multilayer stacked nanosheet CoS-CeO2Application of electrolytic water
1. Adding CoS-CeO2Preparing 0.1-5 mg/mL ink liquid, dripping the ink liquid on a proton exchange membrane, and slightly drying the ink liquid at room temperature; preparing 0-1 mg/mL Nafion solution, and dripping the solution on the micro-dried CoS-CeO2And (5) preparing the electrocatalytic nitrogen reduction membrane electrode on the surface.
2. The membrane electrode is used as a working electrode, the graphite electrode is used as a counter electrode, the Ag/AgCl electrode is used as a reference electrode, and the 0.1-2 mol/L sodium sulfate-lithium perchlorate mixed solution is used as electrolyte to perform an electrocatalytic nitrogen reduction process. The cyclic voltammetry test voltage interval is 0 to-1.0V, 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.
3. And performing linear voltage scanning test, wherein the voltage interval is 0 to-1.0V. The initial potential was 0V and the final potential was-1.0V. The scan rate was 5 mV/s. The sampling interval was 0.001V. The standing time was 2 s. Firstly, introducing argon into the electrolyte for 30min, and carrying out a first linear voltage scanning test after the argon is saturated. And then introducing nitrogen into the electrolyte for 30min, and carrying out a second linear voltage scanning test after the nitrogen is saturated.
4. And (3) performing a long-time nitrogen reduction test on the catalyst by using a membrane electrode as a working electrode, wherein the potentials are respectively set to be-0.35V, -0.45V, -0.55V, -0.65V and-0.75V, and the running time is 7200 s.
The fourth step: ammonia production test
1. Drawing a working curve: by NH40.0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 and 1.0 mu g/mL of standard solution is prepared in 0.1 mol/L of sodium sulfate-lithium perchlorate mixed solution by taking Cl as a standard reagent, and the standard solution is subjected to chromogenic reaction to test absorbance. To 4 mL of the standard solution were added 50. mu.L of an oxidizing agent (containing 75 wt% NaOH and 75 wt% NaClO), 500. mu.L of a coloring agent (containing 40 wt% sodium salicylate and 32 wt% NaOH), and 50. mu.L of a catalyst (5 wt% Na) in this order2[Fe(NO)(CN)5]·2H2O). Standing at room temperature in a dark place for color development for 1h, performing spectral scanning in a wavelength range of 550 nm-800 nm by using an ultraviolet visible spectrophotometer, and recording the absorbance value at 660nm and the concentration to obtain a standard curve by mapping.
2. And (3) testing the yield of ammonia: after running for 2 hours at each potential, 4 mL of each electrolyte was taken, and 50. mu.L of an oxidizing agent (containing 75 wt% of NaOH and 75 wt% of NaClO), 500. mu.L of a coloring agent (containing 40 wt% of sodium salicylate and 32 wt% of NaOH), and 50. mu.L of a catalyst (5 wt% of Na) were sequentially added2[Fe(NO)(CN)5]·2H2O). Standing at room temperature in a dark place for color development for 1h, performing spectral scanning in a wavelength range of 550 nm-800 nm by using an ultraviolet visible spectrophotometer, and recording an absorbance value at 660nm to finally obtain the concentration of ammonia. After data processing and calculation, multilayer stacked nanosheet CoS-CeO2When the method is applied to NRR, the effect is excellent, and the ammonia yield reaches 40.5 mu g h under the condition of minus 0.2V (relative to a standard hydrogen electrode)–1mg–1 cat.The Faraday efficiency is as high as 10.1%.
Claims (4)
1. Multilayer stacked nanosheet CoS-CeO2The preparation method of the nitrogen reduction catalyst is characterized by comprising the following preparation steps:
(1) adding a cobalt reagent and a cerium reagent in a fixed proportion into a specific reaction solution to prepare a pre-reaction solution, heating the pre-reaction solution at a certain temperature for a certain time by using a hydrothermal synthesis method, naturally cooling, washing, drying and collecting the obtained cobalt-cerium precursor;
(2) placing the cobalt-cerium precursor in a tube furnace, and fixing nitrogenAdding sulfur powder as a sulfurizing reagent at the flow rate and the calcination temperature for sulfurization reaction to obtain a multilayer stacked nanosheet catalyst material, namely a cobalt sulfide cerium oxide hybrid CoS-CeO2。
2. Multilayer stacked nanosheet CoS-CeO according to claim 12The preparation method of the nitrogen reduction catalyst is characterized by comprising the following steps:
in the step (1), a mixed solution of urea and thiourea is specified; the cobalt source reagent is one or more of cobalt nitrate hexahydrate, cobalt chloride, cobalt acetylacetonate, cobalt sulfate and cobalt acetate, and the concentration of the cobalt source solution is 0.005-0.04 mol/L; the cerium source is one or more of ammonium ceric nitrate, cerium nitrate hexahydrate, cerium chloride heptahydrate, cerium sulfate and cerium acetate, and the concentration of the cerium source solution is 0.002-0.02 mol/L; the molar ratio of the cobalt source to the cerium source is 10: 1-1: 1; the reaction temperature of the cobalt-cerium pre-reaction liquid is 100 DEGoC ~ 180oC, the reaction time is 6-14 h;
in the step (2), the nitrogen flow rate is 10-50 mL/min; the used sulfuration reagent is sublimed sulfur, wherein the mass ratio of the sulfuration reagent to the cobalt-cerium precursor is 1: 10-1: 100; the sulfurization temperature of the cobalt-cerium precursor in the tube furnace is 300oC ~600oC, vulcanizing for 1-6 h at a heating rate of 0.5oC/min。
3. Multilayer stacked nanosheet CoS-CeO2The preparation method of the nitrogen reduction catalyst is characterized in that a single-chamber membrane electrode nitrogen reduction electrocatalysis performance test is adopted, and the steps are as follows:
(1) adding CoS-CeO2Preparing 0.1-5 mg/mL ink liquid, dripping the ink liquid on a proton exchange membrane, and slightly drying the ink liquid at room temperature; preparing 0-1 mg/mL Nafion solution, and dripping the solution on the micro-dried CoS-CeO2The surface is prepared into the electrocatalytic nitrogen reduction membrane electrode;
(2) the membrane electrode is used as a working electrode, the graphite electrode is used as a counter electrode, the Ag/AgCl electrode is used as a reference electrode, and the 0.1-2 mol/L sodium sulfate-lithium perchlorate mixed solution is used as electrolyte to perform an electrocatalytic nitrogen reduction process.
4. Multilayer stacked nanosheet CoS-CeO2The preparation method of the nitrogen reduction catalyst is characterized in that the single-chamber membrane electrode nitrogen reduction electrocatalysis test system is shown in figure 1, wherein (1) is a fixed base; (2) is a membrane electrode in which CoS-CeO2The catalyst is arranged outside the single-chamber electrolytic cell; (3) is a micro funnel receiver; (4) is an ammonia solution storage tank; (5) the sodium sulfate-lithium perchlorate mixed electrolyte is prepared; (6) is a single-chamber electrolytic cell; (7) is a liquid inlet pipe; (8) is a counter electrode; (9) is a reference electrode; (10) is an air pressure balance outlet; (11) is a working electrode lead; (12) is a micro-drip device; (13) is a nitrogen gas delivery channel.
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