CN117661025B - Preparation method of urea electrolysis hydrogen production catalyst for clean energy - Google Patents
Preparation method of urea electrolysis hydrogen production catalyst for clean energy Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000001257 hydrogen Substances 0.000 title claims abstract description 88
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 88
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000004202 carbamide Substances 0.000 title claims abstract description 70
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 229910003296 Ni-Mo Inorganic materials 0.000 claims abstract description 44
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims abstract description 44
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 39
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 38
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011733 molybdenum Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- ZVVSSOQAYNYNPP-UHFFFAOYSA-N olaflur Chemical compound F.F.CCCCCCCCCCCCCCCCCCN(CCO)CCCN(CCO)CCO ZVVSSOQAYNYNPP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229960001245 olaflur Drugs 0.000 claims abstract description 8
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- 239000000843 powder Substances 0.000 claims description 92
- 239000000243 solution Substances 0.000 claims description 83
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- 238000003756 stirring Methods 0.000 claims description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 64
- 238000001035 drying Methods 0.000 claims description 41
- 238000005406 washing Methods 0.000 claims description 32
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- 229920001690 polydopamine Polymers 0.000 claims description 30
- 239000012153 distilled water Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 239000007983 Tris buffer Substances 0.000 claims description 15
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 15
- 229910015667 MoO4 Inorganic materials 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
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- 229910021641 deionized water Inorganic materials 0.000 description 41
- 238000001291 vacuum drying Methods 0.000 description 27
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 229910017855 NH 4 F Inorganic materials 0.000 description 14
- 229910004616 Na2MoO4.2H2 O Inorganic materials 0.000 description 14
- -1 polytetrafluoroethylene Polymers 0.000 description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 description 14
- 229910001415 sodium ion Inorganic materials 0.000 description 14
- 229910001220 stainless steel Inorganic materials 0.000 description 14
- 239000010935 stainless steel Substances 0.000 description 14
- 238000011010 flushing procedure Methods 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 229960003638 dopamine Drugs 0.000 description 12
- 230000001965 increasing effect Effects 0.000 description 11
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- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229910017299 Mo—O Inorganic materials 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 238000010248 power generation Methods 0.000 description 5
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910015417 Mo2 C Inorganic materials 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
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- 239000012798 spherical particle Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910005809 NiMoO4 Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
-
- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a clean energy urea electrolysis hydrogen production catalyst, which is characterized in that a novel Ni-Mo 2 C@NC catalyst is prepared by a two-step method: mixing a nickel source, a molybdenum source and amine fluoride, and obtaining a bimetallic oxide nickel molybdate precursor after hydrothermal reaction; mixing a nickel molybdate precursor with dopamine hydrochloride, and carrying out a polymerization reaction, and then carrying out a heat treatment reaction on a polymer to obtain the catalyst for producing hydrogen by urea electrolysis. The catalyst has more active sites, and can improve electrochemical catalytic efficiency; meanwhile, due to the synergistic effect of the Ni-Mo 2 C@NC core-shell, the catalyst can effectively reduce the overpotential of the electrochemical reaction, so that the energy consumption cost is reduced. Therefore, the Ni-Mo 2 C@NC catalyst is an efficient and low-cost catalyst for producing hydrogen by urea electrolysis.
Description
Technical Field
The invention relates to the field of renewable energy sources, in particular to a preparation method of a catalyst for producing hydrogen by urea electrolysis for clean energy sources.
Background
The development of clean energy represented by wind power is an important means for completing the targets of carbon neutralization and carbon peak reaching in China, and in recent years, the development of wind power industry in China is rapid, and along with the continuous expansion of the installed scale of a fan, the influence of wind power generation on a power system is more obvious. The most obvious problem is the stability of wind power generation. Under conventional control, in order to improve economic benefit of the wind farm to the greatest extent, all wind generators work under control of maximum power point tracking (Maximum Power Point Tracking, MPPT), so that power output of the wind farm is changed continuously along with change of wind speed, change of wind speed is randomly fluctuated, the wind farm is caused to continuously inject randomly fluctuated electric power into a power system, frequency oscillation accidents are easily caused by the unstable power, and stability of the power system is seriously reduced. In addition, wind power generation is not controlled by human beings, and the anti-peaking performance is shown in certain time periods, so that the electric power generation is not favored. Based on the reasons, large-scale 'waste wind' phenomenon appears in succession in China, and serious waste of wind energy resources is caused.
In order to solve the problem, related scholars propose to utilize wind power generation to produce hydrogen and convert unstable and uncontrollable wind energy into stable and controllable hydrogen energy. However, after many years of development, the electric hydrogen production technology also faces a technical bottleneck problem, and in the actual water electrolysis process, a large amount of electric energy is required to drive the reaction to occur, which severely restricts the hydrogen production efficiency of the electrolyzed water. To address this problem, researchers have used some easily oxidized molecules (e.g., glycerol, ethanol, hydrazine, urea, etc.) as additives to adjust the anode terminal to reduce the theoretical potential of the anode terminal and thereby reduce the energy consumption for hydrogen production.
Urea is one of easily oxidized molecules and has the advantages of low toxicity, high hydrogen content, easy storage and transportation, low cost and the like. Furthermore, the theoretical potential of the urea electrooxidation reaction (UOR) is only 0.37V (relative to RHE). Thus, the Oxygen Evolution Reaction (OER) can be replaced at the anode side by UOR and combined with the Hydrogen Evolution Reaction (HER) at the cathode side to form a urea electrolysis hydrogen production system (HER & UOR). Compared with the hydrogen production by water electrolysis, the energy consumption of the hydrogen production by urea electrolysis is reduced by 30 percent, and the economic cost is reduced by 36 percent. Therefore, in the electrocatalytic energy conversion technology for replacing the traditional fossil energy in the future, the UOR is an important supplement to the electrolytic water OER, and the system has potential significance, can provide a new solution for sustainable energy production and environmental protection, and brings new possibility for future energy conversion and hydrogen energy application.
Although electrolysis of water reduces the energy consumption of hydrogen production to some extent, in practical hydrogen production processes, there is still a need to overcome the reaction activation energy barrier in Hydrogen Evolution Reactions (HER) and urea electrooxidation reactions (UOR). Meanwhile, impedance factors such as contact resistance, solution resistance and the like caused by the inside of the electrolytic cell also need to be solved. Therefore, in the actual hydrogen production process, a voltage higher than the theoretical voltage needs to be applied. At present, the most effective method for solving the problem is to utilize a high-efficiency catalyst to accelerate the dynamic process of the urea electrolysis reaction, thereby improving the hydrogen production efficiency and reducing the hydrogen production cost. Therefore, the design and development of the catalyst are key to improving the conversion efficiency of the urea electrolysis hydrogen production, and are core problems to be solved in the current field for realizing large-scale industrial application.
Disclosure of Invention
The technical problems to be solved are as follows: the invention aims to overcome the defects of the prior art and provides a preparation method of a clean energy urea electrolysis hydrogen production catalyst, which comprises the following steps: mixing a nickel source, a molybdenum source and amine fluoride, and obtaining a bimetallic oxide nickel molybdate precursor after hydrothermal reaction; mixing a nickel molybdate precursor with dopamine hydrochloride, and carrying out a polymerization reaction, and then carrying out a heat treatment reaction on a polymer to obtain the catalyst for producing hydrogen by urea electrolysis. The catalyst for producing hydrogen by urea electrolysis can accelerate the dynamic process of urea electrolysis reaction, and improve the hydrogen production efficiency, thereby reducing the hydrogen production cost.
The technical scheme is as follows: the preparation method of the catalyst for producing hydrogen by urea electrolysis for clean energy comprises the following steps:
s1, mixing a nickel source, a molybdenum source and amine fluoride, and obtaining a bimetallic oxide nickel molybdate precursor after hydrothermal reaction;
s2, mixing the nickel molybdate precursor with dopamine hydrochloride, and carrying out polymerization reaction on the mixture to obtain the catalyst for preparing hydrogen by urea electrolysis through heat treatment reaction on the polymer.
Further, in the step S1, the nickel source is Ni (any one of NO 3)2·6H2O、Ni(CH3COO)2·4H2 O and NiCl 2·6H2 O), and the molybdenum source is Na 2MoO4·2H2 O.
Further, the step S1 specifically includes the following steps:
S11, respectively weighing a nickel source and Na 2MoO4·2H2 O, respectively adding the nickel source and the Na 2MoO4·2H2 O into an ethanol and distilled water mixed solvent, and uniformly mixing the two solutions after ultrasonic stirring for 0.5-1: 1h to obtain a mixed solution;
S12, slowly adding a reducing agent of amine fluoride into the mixed solution obtained in the step S11, and stirring for 2-3 h to obtain a pre-reaction solution;
S13, transferring the pre-reaction solution into an autoclave for hydrothermal reaction; after the reaction is finished, collecting the precipitate, washing and drying to obtain NiMoO 4 powder.
Further, the step S2 specifically includes the following steps:
S1-1, weighing NiMoO 4 powder and dopamine hydrochloride with the mass ratio of 1:1-1:5, respectively adding the powder and the dopamine hydrochloride into distilled water solution, uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5-1h to obtain a mixed solution, and regulating the pH value of the mixed solution to 8.5 by using 0.1M Tris buffer reagent;
S1-2, carrying out polymerization reaction on the mixed solution obtained in the step S1-1 under the stirring condition; after the reaction is finished, collecting the precipitate, washing and drying to obtain NiMoO 4 @polydopamine;
S1-3, performing heat treatment on NiMoO 4 @polydopamine under inert gas, and cooling to room temperature to obtain the Ni-Mo 2 C@NC urea electrolytic hydrogen production catalyst.
Further, the molar ratio of the nickel source, na 2MoO4·2H2 O and amine fluoride is 1-5: 1 to 5:1 to 10.
Further, the hydrothermal reaction temperature in the step S13 is 150-220 ℃, and the reaction time is 6-20 h.
Further, in the step S13, the drying temperature is 60-90 ℃ and the drying time is 12-24 hours.
Further, in the step S1-2, the stirring temperature is 30-60 ℃ and the stirring time is 6-12 h.
Further, in the step S1-2, the drying temperature is 60-90 ℃ and the drying time is 12-24 h.
Further, the heat treatment temperature in the step S1-3 is 500-900 ℃, and the drying time is 2-4 h.
Advantageous effects
The preparation method takes common and low-cost Ni and Mo as raw materials, prepares the bimetallic oxide precursor by using a hydrothermal method, and pyrolyzes the precursor and biomass dopamine to form the nitrogen-doped carbon. The biomass dopamine is a natural organic matter, can provide a nitrogen source, and has good carbon loading capacity. The whole preparation process is relatively simple, complex equipment and conditions are not needed, and the hydrogen precipitation performance and stability of the urea electrolysis hydrogen production catalyst are improved, so that the invention has potential of industrialized mass production in the field of clean energy application;
The preparation method of the catalyst for producing hydrogen by urea electrolysis comprises the following two steps: firstly, generating spherical bimetal nickel molybdate oxide through a molybdenum source and a nickel source, wherein the preparation method is mainly used for preparing the spherical bimetal oxide, improving the specific surface area of the material and preparing for constructing a Ni and Mo 2 C heterojunction in the next step; and secondly, ni-Mo 2 C@NC is generated through the reaction of nickel molybdate and polydopamine, and firstly, the heterojunction constructed by Ni and Mo 2 C can enhance the coupling effect of the nickel molybdate and the polydopamine, so that electrons in Ni are transferred to Mo 2 C, the center position of d-band of Mo atoms is downwards moved, the electron filling degree of d-orbit of the Mo atoms is increased, and the adsorption strength of Mo 2 C on H is improved. However, mo 2 C is easily oxidized to molybdenum-based oxides or hydroxides in UOR reaction, resulting in deterioration of Mo 2 C stability, and thus, the use of Mo 2 C in UOR is severely limited. In addition, ni and Mo 2 C are also corroded by the strongly alkaline solution. In order to solve the problems, the acid and alkali resistant graphite C cage is coated on the surface of the Ni-Mo 2 C, so that the corrosion rate of the Ni/Mo 2 C can be slowed down. Meanwhile, the N atoms are doped into the graphite C cage, so that the catalytic activity of Ni/Mo 2 C@C can be further improved, and the N atoms not only can adjust the electronic structure of the adjacent graphite C atoms, but also can provide additional active sites for a reaction intermediate, so that a core-shell structure Ni-Mo 2 C@NC is constructed;
According to the invention, the spherical NiMoO 4 bimetallic oxide is synthesized by a hydrothermal method, the spherical particles have lower surface energy, the spherical particles are easier to form in the synthesis process, and the lower surface energy is beneficial to reducing the free energy of the material. The smaller free energy of the catalyst has the following benefits for the performance of the electrolytic urea: (1) reducing the reaction activation energy: the catalyst with smaller free energy can reduce the activation energy of the urea electrolysis hydrogen production reaction, so that the reaction is easier to occur. This means that the urea electrolysis hydrogen production reaction can be carried out at lower temperature and voltage, thereby improving the efficiency of urea electrolysis; (2) increasing the reaction rate: the catalyst with smaller free energy is beneficial to reducing the free energy of the transition state of the reaction, thereby accelerating the reaction rate. In addition, the spherical particles have higher symmetry, and a stable structure is easier to form. Therefore, the molybdenum source and the nickel source generate nano-sphere-shaped bimetallic oxide which is beneficial to the catalytic performance of urea electrolysis hydrogen production;
The catalyst for preparing hydrogen by urea electrolysis can realize high current density under low overpotential, which means that the catalyst has higher catalytic activity and efficiency; meanwhile, the catalyst has high stability and can maintain the catalytic performance for a long time.
Drawings
FIG. 1 is an X-ray diffraction pattern of a catalyst prepared in accordance with example 1 of the present invention;
FIG. 2 is an SEM image of a catalyst prepared according to the invention, wherein a is example 1; b is comparative example 4;
FIG. 3 is an elemental distribution diagram of a catalyst prepared according to example 1 of the present invention;
FIG. 4 is an LSV curve of urea electrolysis for the catalyst prepared according to example 1 of the present invention;
FIG. 5 is an i-t curve for a catalyst prepared according to the invention, where a is example 1 and b is comparative example 8;
fig. 6 is an LSV curve of HER for catalysts prepared according to comparative examples 1, 2, 3 of the present invention;
fig. 7 is a Tafel plot of HER for catalysts prepared according to comparative examples 1,2,3 of the present invention;
FIG. 8 is an LSV curve of the UOR for the catalysts prepared according to comparative examples 1,2, 3 of the present invention;
FIG. 9 is Tafel curves for UOR for catalysts prepared according to comparative examples 1,2, 3 of the present invention;
FIG. 10 is a graph showing the catalytic activity of the catalysts prepared according to example 1 and comparative example 5 of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The preparation method of the catalyst for producing hydrogen by urea electrolysis for clean energy comprises the following steps:
s1, respectively weighing 3 mol Na 2MoO4 .2H2 O and 3 mol Ni (NO 3)2 .2H2 O, respectively adding into 30mL deionized water, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution;
S2, slowly adding 1 mol NH 4 F into the mixed solution, and stirring 2h to obtain a pre-reaction solution;
S3, transferring the pre-reaction solution into a stainless steel autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction, putting into an oven, and reacting at 160 ℃ for 6 h;
S4, centrifugally collecting a powder sample after the hydrothermal reaction is finished, washing with deionized water and ethanol for 3 times, washing out NO 3 - and Na + ions in the powder sample, reserving a solid part, placing the solid part into a vacuum drying oven at 80 ℃, and drying 12 h to obtain NiMoO 4 powder;
S5, weighing NiMoO 4 powder and dopamine hydrochloride with the mass ratio of 1:3, respectively adding the powder and the dopamine hydrochloride into distilled water solutions, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution; adjusting the pH of the mixed solution to 8.5 with 0.1M Tris buffer;
s6, stirring the mixed solution at 35 ℃ for 8 hours, and carrying out polymerization reaction;
S7, after the polymerization reaction is finished, centrifugally collecting a powder sample, flushing with deionized water and ethanol for 3 times, reserving a solid part, placing the solid part into a vacuum drying oven at 90 ℃, and drying 12 h to obtain NiMoO 4 @polydopamine;
S8, placing NiMoO 4 @polydopamine into a magnetic boat in a tube furnace, heating to 800 ℃ at a speed of 2 ℃ per minute under Ar atmosphere, then keeping for 2 hours, and cooling to room temperature to obtain the Ni-Mo 2 C@NC urea electrolytic hydrogen production catalyst.
Example 2
The preparation method of the catalyst for producing hydrogen by urea electrolysis for clean energy comprises the following steps:
s1, respectively weighing 3 mol Na 2MoO4 .2H2 O and 3 mol Ni (NO 3)2 .2H2 O, respectively adding into 30mL deionized water, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution;
S2, slowly adding 1 mol NH 4 F into the mixed solution, and stirring 2h to obtain a pre-reaction solution;
S3, transferring the pre-reaction solution into a stainless steel autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction, putting into an oven, and reacting at 160 ℃ for 6 h;
S4, centrifugally collecting a powder sample after the hydrothermal reaction is finished, washing with deionized water and ethanol for 3 times, washing out NO 3 - and Na + ions in the powder sample, reserving a solid part, placing the solid part into a vacuum drying oven at 80 ℃, and drying 12 h to obtain NiMoO 4 powder;
S5, weighing NiMoO 4 powder and dopamine hydrochloride with the mass ratio of 1:1, respectively adding the powder and the dopamine hydrochloride into distilled water solutions, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution; adjusting the pH of the mixed solution to 8.5 with 0.1M Tris buffer;
s6, stirring the mixed solution at 35 ℃ for 8 hours, and carrying out polymerization reaction;
S7, after the polymerization reaction is finished, centrifugally collecting a powder sample, flushing with deionized water and ethanol for 3 times, reserving a solid part, placing the solid part into a vacuum drying oven at 90 ℃, and drying 12 h to obtain NiMoO 4 @polydopamine;
S8, placing NiMoO 4 @polydopamine into a magnetic boat in a tube furnace, heating to 800 ℃ at a speed of 2 ℃ per minute under Ar atmosphere, then keeping for 2 hours, and cooling to room temperature to obtain the Ni-Mo 2 C@NC urea electrolytic hydrogen production catalyst.
Example 3
The preparation method of the catalyst for producing hydrogen by urea electrolysis for clean energy comprises the following steps:
S1, respectively weighing 3 mol Na 2MoO4 .2H2 O and 3 mol Ni (NO 3)2 .2H2 O, respectively adding into a mixed solvent of 15 mL deionized water and 15 mL ethanol, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution;
S2, slowly adding 5 mol NH 4 F into the mixed solution, and stirring 2h to obtain a pre-reaction solution;
S3, transferring the pre-reaction solution into a stainless steel autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction, putting into an oven, and reacting at 160 ℃ for 6 h;
S4, centrifugally collecting a powder sample after the hydrothermal reaction is finished, washing with deionized water and ethanol for 3 times, washing out NO 3 - and Na + ions in the powder sample, reserving a solid part, placing the solid part into a vacuum drying oven at 80 ℃, and drying 12 h to obtain NiMoO 4 powder;
S5, weighing NiMoO 4 powder and dopamine hydrochloride with the mass ratio of 1:5, respectively adding the powder and the dopamine hydrochloride into distilled water solutions, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 1: 1h to obtain a mixed solution; adjusting the pH of the mixed solution to 8.5 with 0.1M Tris buffer;
s6, stirring the mixed solution at 35 ℃ for 8 hours, and carrying out polymerization reaction;
s7, centrifugally collecting a powder sample after the polymerization reaction is finished, flushing with deionized water and ethanol for 5 times, reserving a solid part, placing the solid part into a vacuum drying oven at 90 ℃, and drying 12h to obtain NiMoO 4 @polydopamine;
S8, placing NiMoO 4 @polydopamine into a magnetic boat in a tube furnace, heating to 800 ℃ at a speed of 2 ℃ per minute under Ar atmosphere, then keeping for 3 hours, and cooling to room temperature to obtain the Ni-Mo 2 C@NC urea electrolytic hydrogen production catalyst.
Example 4
The preparation method of the catalyst for producing hydrogen by urea electrolysis for clean energy comprises the following steps:
S1, respectively weighing 3 mol Na 2MoO4 .2H2 O and 3 mol Ni (NO 3)2 .2H2 O, respectively adding into a mixed solvent of 15 mL deionized water and 15 mL ethanol, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution;
S2, slowly adding 5 mol NH 4 F into the mixed solution, and stirring 2h to obtain a pre-reaction solution;
S3, transferring the pre-reaction solution into a stainless steel autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction, placing the pre-reaction solution into an oven, and reacting at 180 ℃ for 12 h;
S4, centrifugally collecting a powder sample after the hydrothermal reaction is finished, washing with deionized water and ethanol for 5 times, washing out NO 3 - and Na + ions in the powder sample, reserving a solid part, placing the solid part into a vacuum drying oven at 80 ℃, and drying 12 h to obtain NiMoO 4 powder;
S5, weighing NiMoO 4 powder and dopamine hydrochloride with the mass ratio of 1:3, respectively adding the powder and the dopamine hydrochloride into distilled water solutions, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 1:1 h to obtain a mixed solution; adjusting the pH of the mixed solution to 8.5 with 0.1M Tris buffer;
s6, stirring the mixed solution at 35 ℃ for 8 hours, and carrying out polymerization reaction;
s7, centrifugally collecting a powder sample after the polymerization reaction is finished, flushing with deionized water and ethanol for 3 times, reserving a solid part, placing the solid part into a vacuum drying oven at 90 ℃, and drying 12h to obtain NiMoO 4 @polydopamine;
S8, placing NiMoO 4 @polydopamine into a magnetic boat in a tube furnace, heating to 800 ℃ at a speed of 2 ℃ per minute under Ar atmosphere, then keeping for 3 hours, and cooling to room temperature to obtain the Ni-Mo 2 C@NC urea electrolytic hydrogen production catalyst.
Example 5
The preparation method of the catalyst for producing hydrogen by urea electrolysis for clean energy comprises the following steps:
s1, respectively weighing 3 mol Na 2MoO4 .2H2 O and 3 mol Ni (NO 3)2 .2H2 O, respectively adding into 30mL deionized water, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution;
S2, slowly adding 2 mol NH 4 F into the mixed solution, and stirring 2h to obtain a pre-reaction solution;
S3, transferring the pre-reaction solution into a stainless steel autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction, putting into an oven, and reacting at 160 ℃ for 6 h;
S4, centrifugally collecting a powder sample after the hydrothermal reaction is finished, washing with deionized water and ethanol for 3 times, washing out NO 3 - and Na + ions in the powder sample, reserving a solid part, placing the solid part into a vacuum drying oven at 80 ℃, and drying 12 h to obtain NiMoO 4 powder;
S5, weighing NiMoO 4 powder and dopamine hydrochloride with the mass ratio of 1:3, respectively adding the powder and the dopamine hydrochloride into distilled water solutions, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution; adjusting the pH of the mixed solution to 8.5 with 0.1M Tris buffer;
s6, stirring the mixed solution at 35 ℃ for 8 hours, and carrying out polymerization reaction;
s7, centrifugally collecting a powder sample after the polymerization reaction is finished, flushing with deionized water and ethanol for 3 times, reserving a solid part, placing the solid part into a vacuum drying oven at 90 ℃, and drying 12h to obtain NiMoO 4 @polydopamine;
S8, placing NiMoO 4 @polydopamine into a magnetic boat in a tube furnace, heating to 800 ℃ at a speed of 2 ℃ per minute under Ar atmosphere, then keeping for 2 hours, and cooling to room temperature to obtain the Ni-Mo 2 C@NC urea electrolytic hydrogen production catalyst.
Example 6
The preparation method of the catalyst for producing hydrogen by urea electrolysis for clean energy comprises the following steps:
s1, respectively weighing 3 mol Na 2MoO4 .2H2 O and 3 mol Ni (NO 3)2 .2H2 O, respectively adding into 30mL deionized water, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution;
S2, slowly adding 1 mol NH 4 F into the mixed solution, and stirring 2h to obtain a pre-reaction solution;
S3, transferring the pre-reaction solution into a stainless steel autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction, putting into an oven, and reacting at 160 ℃ for 6 h;
S4, centrifugally collecting a powder sample after the hydrothermal reaction is finished, washing with deionized water and ethanol for 3 times, washing out NO 3 - and Na + ions in the powder sample, reserving a solid part, placing the solid part into a vacuum drying oven at 80 ℃, and drying 12 h to obtain NiMoO 4 powder;
S5, weighing NiMoO 4 powder and dopamine hydrochloride with the mass ratio of 1:3, respectively adding the powder and the dopamine hydrochloride into distilled water solutions, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5: 0.5 h to obtain a mixed solution; adjusting the pH of the mixed solution to 8.5 with 0.1M Tris buffer;
S6, stirring the mixed solution at 60 ℃ for 8 hours to perform polymerization reaction;
s7, centrifugally collecting a powder sample after the polymerization reaction is finished, flushing with deionized water and ethanol for 3 times, reserving a solid part, placing the solid part into a vacuum drying oven at 90 ℃, and drying 12h to obtain NiMoO 4 @polydopamine;
S8, placing NiMoO 4 @polydopamine into a magnetic boat in a tube furnace, heating to 800 ℃ at a speed of 2 ℃ per minute under Ar atmosphere, then keeping for 2 hours, and cooling to room temperature to obtain the Ni-Mo 2 C@NC urea electrolytic hydrogen production catalyst.
Example 7
The preparation method of the catalyst for producing hydrogen by urea electrolysis for clean energy comprises the following steps:
s1, respectively weighing 3 mol Na 2MoO4 .2H2 O and 3 mol Ni (NO 3)2 .2H2 O, respectively adding into 30mL deionized water, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution;
S2, slowly adding 1 mol NH 4 F into the mixed solution, and stirring 2h to obtain a pre-reaction solution;
S3, transferring the pre-reaction solution into a stainless steel autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction, putting into an oven, and reacting at 160 ℃ for 6 h;
S4, centrifugally collecting a powder sample after the hydrothermal reaction is finished, washing with deionized water and ethanol for 3 times, washing out NO 3 - and Na + ions in the powder sample, reserving a solid part, placing the solid part into a vacuum drying oven at 80 ℃, and drying 12 h to obtain NiMoO 4 powder;
S5, weighing NiMoO 4 powder and dopamine hydrochloride with the mass ratio of 1:3, respectively adding the powder and the dopamine hydrochloride into distilled water solutions, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5: 0.5 h to obtain a mixed solution; adjusting the pH of the mixed solution to 8.5 with 0.1M Tris buffer;
s6, stirring the mixed solution at 35 ℃ for 8 hours, and carrying out polymerization reaction;
s7, centrifugally collecting a powder sample after the polymerization reaction is finished, flushing with deionized water and ethanol for 3 times, reserving a solid part, placing the solid part into a vacuum drying oven at 90 ℃, and drying 12h to obtain NiMoO 4 @polydopamine;
S8, placing NiMoO 4 @polydopamine into a magnetic boat in a tube furnace, heating to 500 ℃ at a speed of 2 ℃ per minute under Ar atmosphere, then keeping for 2 hours, and cooling to room temperature to obtain the Ni-Mo 2 C@NC urea electrolytic hydrogen production catalyst.
Example 8
The preparation method of the catalyst for producing hydrogen by urea electrolysis for clean energy comprises the following steps:
s1, respectively weighing 3 mol Na 2MoO4 .2H2 O and 3 mol Ni (NO 3)2 .2H2 O, respectively adding into 30mL deionized water, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution;
S2, slowly adding 1 mol NH 4 F into the mixed solution, and stirring 2h to obtain a pre-reaction solution;
S3, transferring the pre-reaction solution into a stainless steel autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction, putting into an oven, and reacting at 160 ℃ for 6 h;
S4, centrifugally collecting a powder sample after the hydrothermal reaction is finished, washing with deionized water and ethanol for 3 times, washing out NO 3 - and Na + ions in the powder sample, reserving a solid part, placing the solid part into a vacuum drying oven at 80 ℃, and drying 12 h to obtain NiMoO 4 powder;
S5, weighing NiMoO 4 powder and dopamine hydrochloride with the mass ratio of 1:3, respectively adding the powder and the dopamine hydrochloride into distilled water solutions, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5: 0.5 h to obtain a mixed solution; adjusting the pH of the mixed solution to 8.5 with 0.1M Tris buffer;
s6, stirring the mixed solution at 35 ℃ for 8 hours, and carrying out polymerization reaction;
s7, centrifugally collecting a powder sample after the polymerization reaction is finished, flushing with deionized water and ethanol for 3 times, reserving a solid part, placing the solid part into a vacuum drying oven at 90 ℃, and drying 12h to obtain NiMoO 4 @polydopamine;
S8, placing NiMoO 4 @polydopamine into a magnetic boat in a tube furnace, heating to 800 ℃ at a speed of 2 ℃ per minute under Ar atmosphere, then keeping for 3 hours, and cooling to room temperature to obtain the Ni-Mo 2 C@NC urea electrolytic hydrogen production catalyst.
Comparative example 1
The preparation method of the catalyst for producing hydrogen by urea electrolysis for clean energy comprises the following steps:
s1, respectively weighing 3 mol Na 2MoO4 .2H2 O and 3 mol Ni (NO 3)2 .2H2 O, respectively adding into 30mL deionized water, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution;
S2, slowly adding 1 mol NH 4 F into the mixed solution, and stirring 2h to obtain a pre-reaction solution;
S3, transferring the pre-reaction solution into a stainless steel autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction, putting into an oven, and reacting at 160 ℃ for 6 h;
S4, centrifugally collecting a powder sample after the hydrothermal reaction is finished, washing with deionized water and ethanol for 3 times, washing out NO 3 - and Na + ions in the powder sample, reserving a solid part, placing the solid part into a vacuum drying oven at 80 ℃, and drying 12 h to obtain NiMoO 4 powder;
S5, weighing NiMoO 4 powder and dopamine hydrochloride with the mass ratio of 1:5, respectively adding the powder and the dopamine hydrochloride into distilled water solutions, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution; adjusting the pH of the mixed solution to 8.5 with 0.1M Tris buffer;
s6, stirring the mixed solution at 35 ℃ for 8 hours, and carrying out polymerization reaction;
S7, after the polymerization reaction is finished, centrifugally collecting a powder sample, flushing with deionized water and ethanol for 3 times, reserving a solid part, placing the solid part into a vacuum drying oven at 90 ℃, and drying 12 h to obtain NiMoO 4 @polydopamine;
s8, placing NiMoO 4 @polydopamine into a magnetic boat in a tube furnace, heating to 800 ℃ at a speed of 2 ℃ per minute under Ar atmosphere, then keeping for 2 hours, and cooling to room temperature to obtain the Ni-Mo 2 C@NC-4 urea electrolytic hydrogen production catalyst.
The catalyst for producing hydrogen by electrolysis of urea prepared in example 1 was named as Ni-Mo 2C@NC-3（NiMoO4 powder and dopamine hydrochloride with a mass ratio of 1:3, and the catalyst for producing hydrogen by electrolysis of urea prepared in example 2 was named as Ni-Mo 2C@NC-2（NiMoO4 powder and dopamine hydrochloride with a mass ratio of 1:1), respectively, as comparative example 2 and comparative example 3.
Comparative example 4
The preparation method of the catalyst for producing hydrogen by urea electrolysis for clean energy comprises the following steps:
s1, respectively weighing 3 mol Na 2MoO4 .2H2 O and 3 mol Ni (NO 3)2 .2H2 O, respectively adding into 30mL deionized water, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution;
S2, slowly adding 1 mol NH 4 F into the mixed solution, and stirring 2h to obtain a pre-reaction solution;
S3, transferring the pre-reaction solution into a stainless steel autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction, putting into an oven, and reacting at 160 ℃ for 6 h;
s4, centrifugally collecting a powder sample after the hydrothermal reaction is finished, washing with deionized water and ethanol for 3 times, washing out NO 3 - and Na + ions in the powder sample, reserving a solid part, placing the solid part into a vacuum drying oven at 80 ℃, and drying 12 h to obtain Ni-Mo-O powder;
S5, weighing Ni-Mo-O powder and dopamine hydrochloride with the mass ratio of 1:3, respectively adding the Ni-Mo-O powder and the dopamine hydrochloride into distilled water solution, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution; adjusting the pH of the mixed solution to 8.5 with 0.1M Tris buffer;
s6, stirring the mixed solution at 35 ℃ for 8 hours, and carrying out polymerization reaction;
S7, after the polymerization reaction is finished, centrifugally collecting a powder sample, flushing with deionized water and ethanol for 3 times, reserving a solid part, placing the solid part into a vacuum drying oven at 90 ℃, and drying 12h to obtain Ni-Mo-O@ polydopamine;
s8, placing Ni-Mo-O@ polydopamine into a magnetic boat in a tubular furnace, heating to 800 ℃ at a speed of 2 ℃ per minute under Ar atmosphere, then keeping for 2 hours, and cooling to room temperature to obtain the Ni-Mo-C@NC urea electrolytic hydrogen production catalyst.
Comparative example 5
The preparation method of the catalyst for producing hydrogen by urea electrolysis for clean energy comprises the following steps:
s1, respectively weighing 3 mol Na 2MoO4 .2H2 O and 3 mol Ni (NO 3)2 .2H2 O, respectively adding into 30mL deionized water, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution;
S2, slowly adding 1 mol NH 4 F into the mixed solution, and stirring 2h to obtain a pre-reaction solution;
S3, transferring the pre-reaction solution into a stainless steel autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction, putting into an oven, and reacting at 160 ℃ for 6 h;
S4, centrifugally collecting a powder sample after the hydrothermal reaction is finished, washing with deionized water and ethanol for 3 times, washing out NO 3 - and Na + ions in the powder sample, reserving a solid part, placing the solid part into a vacuum drying oven at 80 ℃, and drying 12 h to obtain NiMoO 4 powder;
S5, weighing NiMoO 4 powder and cellulose in a mass ratio of 1:3, respectively adding the powder and the cellulose into a distilled water solution and a cellulose water solution, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution; adjusting the pH of the mixed solution to 8.5 with 0.1M Tris buffer;
s6, stirring the mixed solution at 35 ℃ for 8 hours, and carrying out polymerization reaction;
S7, centrifugally collecting a powder sample after the polymerization reaction is finished, flushing with deionized water and ethanol for 3 times, reserving a solid part, placing the solid part into a vacuum drying oven at 90 ℃, and drying 12h to obtain NiMoO 4 @cellulose;
S8, placing NiMoO 4 @cellulose into a magnetic boat in a tube furnace, heating to 800 ℃ at a speed of 2 ℃ per minute under Ar atmosphere, then keeping for 2 hours, and cooling to room temperature to obtain the Ni-Mo-C@C urea electrolytic hydrogen production catalyst.
Comparative example 6
The preparation method of the catalyst for producing hydrogen by urea electrolysis for clean energy comprises the following steps:
s1, respectively weighing 3 mol Na 2MoO4 .2H2 O and 3 mol Ni (NO 3)2 .2H2 O, respectively adding into 30mL deionized water, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution;
S2, slowly adding 1 mol NH 4 F into the mixed solution, and stirring 2h to obtain a pre-reaction solution;
S3, transferring the pre-reaction solution into a stainless steel autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction, putting into an oven, and reacting at 160 ℃ for 6 h;
S4, centrifugally collecting a powder sample after the hydrothermal reaction is finished, washing with deionized water and ethanol for 3 times, washing out NO 3 - and Na + ions in the powder sample, reserving a solid part, placing the solid part into a vacuum drying oven at 80 ℃, and drying 12 h to obtain NiMoO 4 powder;
s5, weighing NiMoO 4 powder and dopamine hydrochloride with the mass ratio of 1:0.5, respectively adding the powder and the dopamine hydrochloride into distilled water solutions, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution; adjusting the pH of the mixed solution to 8.5 with 0.1M Tris buffer;
s6, stirring the mixed solution at 35 ℃ for 8 hours, and carrying out polymerization reaction;
S7, after the polymerization reaction is finished, centrifugally collecting a powder sample, flushing with deionized water and ethanol for 3 times, reserving a solid part, placing the solid part into a vacuum drying oven at 90 ℃, and drying 12 h to obtain NiMoO 4 @polydopamine;
S8, placing NiMoO 4 @polydopamine into a magnetic boat in a tube furnace, heating to 800 ℃ at a speed of 2 ℃ per minute under Ar atmosphere, then keeping for 2 hours, and cooling to room temperature to obtain the Ni-Mo 2 C@NC urea electrolytic hydrogen production catalyst.
Comparative example 7
The preparation method of the catalyst for producing hydrogen by urea electrolysis for clean energy comprises the following steps:
s1, respectively weighing 3 mol Na 2MoO4 .2H2 O and 3 mol Ni (NO 3)2 .2H2 O, respectively adding into 30mL deionized water, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution;
S2, slowly adding 1 mol NH 4 F into the mixed solution, and stirring 2h to obtain a pre-reaction solution;
S3, transferring the pre-reaction solution into a stainless steel autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction, putting into an oven, and reacting at 160 ℃ for 6 h;
S4, centrifugally collecting a powder sample after the hydrothermal reaction is finished, washing with deionized water and ethanol for 3 times, washing out NO 3 - and Na + ions in the powder sample, reserving a solid part, placing the solid part into a vacuum drying oven at 80 ℃, and drying 12 h to obtain NiMoO 4 powder;
S5, weighing NiMoO 4 powder and dopamine hydrochloride with the mass ratio of 1:6, respectively adding the powder and the dopamine hydrochloride into distilled water solutions, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution; adjusting the pH of the mixed solution to 8.5 with 0.1M Tris buffer;
s6, stirring the mixed solution at 35 ℃ for 8 hours, and carrying out polymerization reaction;
S7, after the polymerization reaction is finished, centrifugally collecting a powder sample, flushing with deionized water and ethanol for 3 times, reserving a solid part, placing the solid part into a vacuum drying oven at 90 ℃, and drying 12 h to obtain NiMoO 4 @polydopamine;
S8, placing NiMoO 4 @polydopamine into a magnetic boat in a tube furnace, heating to 800 ℃ at a speed of 2 ℃ per minute under Ar atmosphere, then keeping for 2 hours, and cooling to room temperature to obtain the Ni-Mo 2 C@NC urea electrolytic hydrogen production catalyst.
Comparative example 8
The preparation method of the catalyst for producing hydrogen by urea electrolysis for clean energy comprises the following steps:
s1, respectively weighing 3 mol Na 2MoO4 .2H2 O and 3 mol Ni (NO 3)2 .2H2 O, respectively adding into 30mL deionized water, and uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5h to obtain a mixed solution;
S2, slowly adding 1 mol NH 4 F into the mixed solution, and stirring 2h to obtain a pre-reaction solution;
S3, transferring the pre-reaction solution into a stainless steel autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction, putting into an oven, and reacting at 160 ℃ for 6 h;
S4, centrifugally collecting a powder sample after the hydrothermal reaction is finished, washing with deionized water and ethanol for 3 times, washing out NO 3 - and Na + ions in the powder sample, reserving a solid part, placing the solid part into a vacuum drying oven at 80 ℃, and drying 12 h to obtain NiMoO 4 powder;
S5, placing NiMoO 4 powder into a magnetic boat in a tube furnace for heat nitrogen treatment, taking ammonia gas as a nitrogen source, heating to 800 ℃ at a speed of2 ℃ per minute under Ar atmosphere, then keeping for 2 hours, and cooling to room temperature to obtain the Ni-Mo@N urea electrolytic hydrogen production catalyst.
Performance test:
1) Preparing KOH solution with the concentration of 1mol/L, sealing and placing in a dark place, and introducing high-purity nitrogen or argon to remove dissolved oxygen in water before electrochemical testing;
2) The model of an electrochemical workstation is CHI 660e, in a three-electrode system, a carbon rod is used as a counter electrode, an Hg/HgO (1M KOH) electrode is used as a reference electrode, an L-shaped glassy carbon electrode loaded with a catalyst is used as a working electrode, the HER electrochemical performance of Ni-Mo 2 C@NC is tested by adopting a Linear Scanning Voltammetry (LSV) in 1mol/L KOH electrolyte, and the UOR electrochemical performance of Ni-Mo 2 C@NC is tested by adopting a Linear Scanning Voltammetry (LSV) in a mixed electrolyte of 1M KOH and 0.5M urea;
3) To evaluate the stability of the catalyst in HER, we performed current density and time (i-t) tests on it. The test conditions were constant potential 0.088V, test time 24 h, and electrolyte was a mixed solution of 0.5. 0.5M urea and 1M KOH.
Through SEM image analysis, as shown in figure 2a, spherical bimetallic nickel molybdate oxide NiMoO 4 is generated through the reaction of a nickel source and a molybdenum source, and the external surface of Ni-Mo 2 C@NC is observed to be relatively flat, and no obvious concave-convex or rough area exists; and FIG. 2b shows that after other substances (Ni-Mo-O) are generated by the reaction of a nickel source and a molybdenum source, non-spherical bimetallic nickel molybdate oxide is generated, and Ni-Mo-C@NC is observed to be accumulated together in irregular particles, so that a larger aggregate structure is formed. In addition, EDS surface element distribution was performed on selected areas of the Ni-Mo 2 C@NC catalyst, as shown in FIG. 3. From the graph, ni element, mo element and C element are mainly concentrated at the central position of the composite material, and N element is mainly distributed on the surface of the whole composite material, which shows that the CN shell layer is uniformly coated on the Ni-Mo 2 C core. Such a distribution may protect the Ni-Mo 2 C core and provide a larger specific surface area and more active sites. The unique characteristic is that the core-shell interface effect induces electrons to flow from the inner core Ni/Mo 2 C to the N-doped graphite C shell, so that the electron state density of C atoms in the NC shell is increased, and the electron transport capacity of the NC shell is improved. Meanwhile, due to electron transfer between the Ni/Mo 2 C core and the C (N) shell, a contact potential difference is formed at the interface of the core and the shell, so that OH - in H 2 O tends to be adsorbed on positively charged Mo atoms in the Ni/Mo 2 C core, and H + is adsorbed on negatively charged NC shell, and cracking of H 2 O molecules is accelerated. In addition, the Mo 2 C core receives compressive strain from the C (N) shell, resulting in downward movement of the d-band center of the Mo atom of the core, increasing electron filling of the Mo atom counter-bond orbitals, and enhancing the adsorption strength of Mo 2 C to H. Moreover, the constraint effect of the shell NC can enrich reactants in the shell cavity, so that the NC shell can be ensured to fully adsorb the reactants.
As shown in fig. 5a, the current density of the Ni-Mo 2 c@nc prepared in example 1 is only attenuated by 3% after 24: 24 h, which fully proves that Ni/Mo 2 C has high stability under the protection of the N-doped graphite C shell; in fig. 5b, the comparative example 8 uses ammonia gas as nitrogen source to directly provide N atoms, and does not dope C atoms, so that the prepared Ni-mo@n catalyst is attenuated by 17% after 24 h, and the stability is worse than that of the Ni-Mo 2 c@nc.
The influence of different dopamine contents on the hydrogen evolution performance of Ni-Mo 2 C@NC is explored, as shown in figure 6, along with the increase of the mass concentration of the dopamine, the hydrogen evolution activity of the Ni-Mo 2 C@NC nanocapsule shows a change trend of increasing and then decreasing, and the specific relation is Ni-Mo 2C@NC-3>1:0.5>Ni-Mo2C@NC-4>Ni-Mo2 C@NC-2>1:6. From the above relationship, when the appropriate dopamine-built Ni-Mo 2 C@NC-3 catalyst has excellent hydrogen evolution activity, the hydrogen evolution activity of the nitrogen-doped carbon-built catalyst for pyrolysis of too little or excessive dopamine is weakened. From this, the mass concentration of the precursor dopamine hydrochloride can adjust the hydrogen evolution catalytic performance of the catalyst. The specific reasons are as follows: when the mass concentration of the dopamine is too low, namely the nitrogen doped carbon content formed by pyrolysis is not small, the number of coupling interfaces (Ni/Mo 2 C) formed in the Ni-Mo 2 C@NC is small, and the hydrogen evolution performance is adversely affected. On the other hand, when the nitrogen-doped carbon content is insufficient, most of the C shell coated on the surface of the Ni/MoO 2 preferentially reacts with MoO 2, so that NC shell coating is incomplete, and the synergistic effect of a core-shell structure cannot be exerted to the maximum value. However, when the mass concentration of dopamine is too large, the thickness of the C (N) shell layer coated on the surface of Ni/Mo 2 C is increased compared with Ni-Mo 2 C@NC-2. Excessive nitrogen-doped carbon shells slow down the diffusion of water molecules and adsorbed H from the C layer to the metal core, and at the same time, can also result in the inability of the outer N-doped C shell to complete rapid proton and electron exchange with the components within the core. Therefore, the hydrogen evolution reaction rate of the catalyst of Ni-Mo 2 C@NC-4 is obviously slowed down especially when the ratio of NiMoO 4 powder to dopamine hydrochloride is 1:6, and only a core-shell structure constructed by proper nitrogen doped carbon content is beneficial to the hydrogen evolution reaction of the catalyst. In the study, firstly, a unique core-shell interface effect induces electrons to flow from the inner core Ni/Mo 2 C to the N-doped graphite C shell, so that the electron state density of C atoms in the NC shell is increased, and the electron transport capacity of the NC shell is improved. Meanwhile, due to electron transfer between the Ni/Mo 2 C core and the C (N) shell, a contact potential difference is formed at the interface of the core and the shell, so that OH-in H 2 O tends to be adsorbed on positively charged Mo atoms in the Ni/Mo 2 C core, and H+ is adsorbed on negatively charged NC shell, and the cracking of H 2 O molecules is accelerated. In addition, the Mo 2 C core receives compressive strain from the C (N) shell, resulting in downward movement of the d-band center of the Mo atom of the core, increasing electron filling of the Mo atom counter-bond orbitals, and enhancing the adsorption strength of Mo 2 C to H. Moreover, the constraint effect of the shell NC can enrich reactants in the shell cavity, so that the NC shell can be ensured to fully adsorb the reactants.
FIG. 7 shows the Tafel slopes of three Ni-Mo 2 C@NC at a current density of-10 mA cm -2. As can be seen from the graph, the Tafel slope of Ni-Mo 2 C@NC-2 at a current density of-10 mA cm -2 was found to be 117 mV dec -1,Ni/Mo2 C@C (N) -3, and the Tafel slope was found to be significantly reduced to 97 mV dec -1. The research result shows that the heterogeneous interface effect of the inner core Ni/Mo 2 C can enhance the hydrogen evolution catalytic activity. In this case, when Ni makes coupling contact with Mo 2 C, since Mo 2 C is a p-type semiconductor, its work function (4.82 eV) is larger than that of Ni (4.6 eV). Thus, electrons will spontaneously transfer from Ni to Mo 2 C, forming a Ni/Mo 2 C schottky heterojunction. As a result, the C-terminal of Mo 2 is enriched with electrons, and the electron transport capacity of Mo 2 C for adsorbing H-intermediates is significantly improved.
Correspondingly, the core metal Ni is positively charged due to the lack of electrons, resulting in a built-in electric field directed from the metal Ni to Mo 2 C. The built-in electric field causes the surface energy bands of Mo 2 C to bend downward and form a contact potential difference, which polarizes the H 2 O molecules in the hydrogen evolution reaction. OH - in the H 2 O molecule would tend to adsorb at the active sites on the positively charged Ni surface, whereas H + would tend to adsorb at the active sites on the negatively charged Mo atom surface in Mo 2 C, resulting in the extension of the chemical bonds of the H 2 O molecule and eventually heterocleavage. Therefore, the Ni/Mo 2 C Schottky heterojunction interface can not only accelerate the electron transport of the reaction intermediate, but also accelerate the cracking of water molecules.
After the hydrogen evolution performance of the prepared catalyst was studied, the UOR performance was evaluated. The UOR performance of Ni-Mo 2 c@nc catalysts prepared with different dopamine content was investigated. As can be seen in FIG. 8, the potential of Ni-Mo 2 C@NC-2 at a current density of 10 mA cm -2 is 1.402V, corresponding to a Tafel slope of 41 mV dec -1 (shown in FIG. 9). The potential of Ni-Mo 2C@NC-3、Ni-Mo2 C@NC-4 at a current density of 10 mV cm -2 was 1.384V and the corresponding Tafel slopes of 1.395V were 36 mV dec -1、38 mV ·dec-1, respectively. It was found that the UOR performance of the three catalysts exhibited a law similar to its hydrogen evolution performance, i.e. increasing followed by decreasing, with increasing dopamine mass concentration. The result shows that the content of the pyrolytic carbon of the dopamine can also regulate the UOR performance of the Ni-Mo 2 C@NC.
When the content of the carbon doped by the pyrolysis nitrogen of the dopamine is low, the number of the formed Ni/Mo 2 C heterogeneous interfaces is small, and the Schottky effect caused by the heterogeneous interfaces is not obvious in improvement of the Ni-Mo 2 C@NC catalytic performance. On the other hand, the nitrogen doped carbon content is low, C firstly reacts with MoO 2, so that a C layer coated on Ni/Mo 2 C is incomplete, and the core-shell synergistic effect cannot be exerted. Compared with Ni/Mo 2 C@C (N) -2, the thickness of the C (N) shell layer is increased when the content of the pyrolytic nitrogen doped carbon of the dopamine is high, and the excessive thickness of the C shell layer can limit the speed of urea molecules and reaction intermediates diffusing from the surface of the C layer to a metal core, so that the UOR reaction rate of Ni-Mo 2 C@NC-4 is seriously influenced. According to the performance test result, when the mass ratio of the NiMoO 4 powder to the dopamine hydrochloride is 1:3, the Ni/Mo 2 C@NC-3 synthesized under the condition has the most reasonable interface matching, and the optimal UOR catalytic effect can be exerted.
As can be seen from fig. 10, after the dopamine hydrochloride is replaced by cellulose, the doping of N atoms cannot be provided, so that the catalytic activity of the prepared Ni-Mo-C@C is reduced, and the addition of the dopamine hydrochloride can dope the N atoms of the graphite C cage, so that the catalytic activity of Ni/Mo 2 C@C is further improved.
The above embodiments are only for illustrating the technical aspects of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those of ordinary skill in the art that: modifications and equivalents may be made to the specific embodiments of the invention without departing from the spirit and scope of the invention, which is intended to be covered by the claims.
Claims (5)
1. The preparation method of the catalyst for producing hydrogen by urea electrolysis for clean energy is characterized by comprising the following steps:
s1, mixing a nickel source, a molybdenum source and amine fluoride, and obtaining a bimetallic oxide nickel molybdate precursor after hydrothermal reaction;
S11, respectively weighing a nickel source and Na 2MoO4·2H2 O, respectively adding the nickel source and the Na 2MoO4·2H2 O into an ethanol and distilled water mixed solvent, and uniformly mixing the two solutions after ultrasonic stirring for 0.5-1: 1h to obtain a mixed solution;
S12, slowly adding a reducing agent of amine fluoride into the mixed solution in the step S11, wherein the molar ratio of the nickel source to Na 2MoO4·2H2 O to the amine fluoride is 1-5: 1 to 5: 1-10, stirring 2-3 h to obtain a pre-reaction solution;
S13, transferring the pre-reaction solution into an autoclave for hydrothermal reaction, wherein the hydrothermal reaction temperature is 150-220 ℃ and the reaction time is 6-20 h; after the reaction is finished, collecting the precipitate, washing and drying to obtain NiMoO 4 powder;
S2, mixing a nickel molybdate precursor with dopamine hydrochloride, and carrying out a polymerization reaction on the mixture to obtain a urea electrolysis hydrogen production catalyst through a heat treatment reaction on the polymer;
S1-1, weighing NiMoO 4 powder and dopamine hydrochloride with the mass ratio of 1:1-1:5, respectively adding the powder and the dopamine hydrochloride into distilled water solution, uniformly mixing the two solutions after ultrasonic auxiliary stirring for 0.5-1h to obtain a mixed solution, and regulating the pH value of the mixed solution to 8.5 by using 0.1M Tris buffer reagent;
S1-2, carrying out polymerization reaction on the mixed solution obtained in the step S1-1 under the stirring condition; after the reaction is finished, collecting the precipitate, washing and drying to obtain NiMoO 4 @polydopamine;
S1-3, performing heat treatment on NiMoO 4 @polydopamine under inert gas, wherein the heat treatment temperature is 500-900 ℃, the drying time is 2-4 h, and cooling to room temperature to obtain the Ni-Mo 2 C@NC urea electrolytic hydrogen production catalyst.
2. The method for preparing the clean energy urea electrolysis hydrogen production catalyst according to claim 1, which is characterized in that: in the step S1, the nickel source is Ni (any one of NO 3)2·6H2O、Ni(CH3COO)2·4H2 O and NiCl 2·6H2 O), and the molybdenum source is Na 2MoO4·2H2 O.
3. The method for preparing the clean energy urea electrolysis hydrogen production catalyst according to claim 1, which is characterized in that: the drying temperature in the step S13 is 60-90 ℃ and the drying time is 12-24 h.
4. The method for preparing the clean energy urea electrolysis hydrogen production catalyst according to claim 1, which is characterized in that: in the step S1-2, the stirring temperature is 30-60 ℃, and the stirring time is 6-12 h.
5. The method for preparing the clean energy urea electrolysis hydrogen production catalyst according to claim 1, which is characterized in that: the drying temperature in the step S1-2 is 60-90 ℃ and the drying time is 12-24 h.
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