CN110586156B - Preparation method for synthesizing mesoporous nitrogen-doped graphene-loaded molybdenum disulfide through laser irradiation and application of mesoporous nitrogen-doped graphene-loaded molybdenum disulfide in electro-catalysis hydrogen production - Google Patents
Preparation method for synthesizing mesoporous nitrogen-doped graphene-loaded molybdenum disulfide through laser irradiation and application of mesoporous nitrogen-doped graphene-loaded molybdenum disulfide in electro-catalysis hydrogen production Download PDFInfo
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- 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
- B01J27/24—Nitrogen compounds
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- B01J35/33—
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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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention relates to a preparation method for synthesizing mesoporous nitrogen-doped graphene-loaded molybdenum disulfide through laser irradiation and application of the mesoporous nitrogen-doped graphene-loaded molybdenum disulfide in electrocatalytic hydrogen production. Aiming at the problems that the transition metal oxide/sulfide composite mesoporous nitrogen-doped graphene rich in carbon pyridine nitrogen metal bonds can not be synthesized at low temperature and low pressure by the existing synthesis process and the content of the carbon pyridine nitrogen metal bonds in the composite system can not be effectively regulated, the problem that the content of the carbon pyridine nitrogen-molybdenum bonds in the composite catalyst can be improved by irradiating the graphene oxide with laser within the range of 177-315 mJ is found, and the loading amount of molybdenum disulfide on the mesoporous graphene can be optimized when the mass ratio of the raw material laser irradiation graphene oxide to tetrathiomolybdate is 1: 1-1: 8 in the hydrothermal process, so that the conductivity of the molybdenum disulfide is improved, the carbon pyridine nitrogen molybdenum bonds at the interface can also synergistically improve the intrinsic activity of the carbon pyridine nitrogen molybdenum bonds, and the electrocatalytic process of HER is promoted. The invention has simple process, ingenious design, safety, environmental protection and low cost.
Description
Technical Field
The invention relates to a method for improving electrocatalytic hydrogen production performance by taking graphene oxide irradiated by laser as a substrate, hydrothermally synthesizing a molybdenum disulfide/mesoporous nitrogen doped graphene compound, and taking carbon-pyridine nitrogen-molybdenum bonds formed by increased conductivity, exposed edge sites and an interface as high-activity sites. In particular to a preparation method for synthesizing mesoporous nitrogen doped graphene loaded molybdenum disulfide by laser irradiation and application thereof in electrocatalytic hydrogen production.
Background
Along with passingThe increasing consumption of fossil fuels and the resulting environmental degradation are severe, for example: CO 22Induced greenhouse effect, SO2The development and utilization of new clean energy by people are becoming reluctant due to the acid rain pollution and the haze caused by the exceeding of PM 2.5. Among the many clean energy sources, hydrogen energy is one of the most interesting clean energy sources. The application of electrocatalytic water decomposition and a fuel cell is two major ways of generating and utilizing hydrogen, however, in the hydrogen production by electrolyzing water, the key problems are energy consumption saving, cost reduction and yield and efficiency improvement to the maximum extent. The traditional hydrogen evolution electrode material is a platinum catalyst, which has strong corrosion resistance, good conductivity and excellent electrocatalytic performance, but due to high price and cost and poor mechanical strength, researchers at home and abroad successively develop a plurality of non-noble metal catalysts. In order to improve the performance of the non-noble metal catalysts, the modification can be carried out by means of morphological structure design, doping, defect vacancy manufacturing, interface creation and the like. The other half of the reaction OER is usually carried out in an alkaline environment for the purpose of full water splitting, so it is necessary to prepare a catalyst suitable for full pH hydrogen production, and Mo-based materials are advantageous in this respect.
MoS2Due to the unique structural characteristics and the appropriate gibbs free energy for hydrogen absorption, it is widely used in acidic HER, but its application is greatly limited due to few active sites, mainly concentrated at the edges and poor electrical conductivity. In general we can consider improvements from three aspects: (1) changing the MoS2The structure and the shape of the catalyst are used for increasing the number of active sites. See: xie J F, Zhang H, Li S, et al adv. Mater.,2013,25, 5807-one 5813. (2) MoS activation by doping of metals and non-metals, creation of sulfur vacancies to create defects2An inert base surface. See: wang H, Ouyang L Y, Zou G F, et al. ACS Catal.,2018,8, 9529-9536. (3) Mixing MoS2Growing on the substrate with good conductivity or compounding with the nano material with high conductivity. See: tan Y W, Liu P, Chen L Y, et al adv. Mater.,2014,26, 8023-8028. However, these existing preparation methods tend to be from a single perspective for MoS2Modification is carried out, namely, at present, no method exists for not damaging MoS2Under the condition of an internal structure, the inert basal plane can be activated, more active sites are created, and the conductivity is improved, so that the improvement of the intrinsic activity of the material is promoted.
For MoS2The combination with the carbon material generally improves the electrocatalytic performance from the following four aspects: firstly, the conductivity is increased, secondly, the specific surface area is increased, thirdly, more edge active sites are created, and fourthly, the free energy of H absorption is adjusted. See: li F, Li J, Gao Z, et al.J.Mater.chem.A,2015,3, 21772-21778; li Y G, Wang H L, Xie L M, et al.J.am.chem.Soc.,2011,133, 7296-; ma L B, Hu Y, Zhu G Y, et al. chem. mater, 2016,28, 5733-5742. For MoS 2With nitrogen-doped carbon composites, MoS has been reported2Loaded on nitrogen-doped carbon nano-box by virtue of excellent conductivity and unique hollow structure of nitrogen-doped carbon nano-box and dispersed ultrathin MoS2The high specific surface area of the nano-sheets promotes the transfer of electrons and protons, so that the hydrogen production catalytic activity is improved, however, carbon-pyridine nitrogen-molybdenum bonds which are active sites are not formed on the interface to activate MoS2Thus limiting further enhancement of its catalytic activity. See: yu X Y, Hu H, Wang Y W, et al, Angew, chem, int, Ed.2015,54, 7395-. Until later, Amiinu et al will MoS2Loaded on ZIF-8 to form Mo-N/C @ MoS2The structure of (1) is firstly proved by DFT theoretical calculation and comparative experiment that the formation of the interface molybdenum-nitrogen bond structure can lead the electron cloud on N/C to MoS2Transferring to enhance the adsorption energy of H, thereby improving the HER performance, but the high-temperature annealing method causes the nitrogen species and content to be unadjustable. See: amiinu I S, Pu Z H, Liu X B, et al adv Funct Mater, 2017,27, 1702300-1702310. In addition, it has been reported previously that the construction of carbon-pyridine nitrogen-metal bond is very helpful to improve the intrinsic activity of the material, see: wang X R, Liu J Y, Liu Z W, et al adv. Mater.,2018,30, 1800005-. Therefore, if a means for controllably adjusting the nitrogen contents of different types can be adopted to maximally improve the proportional content of carbon-pyridine nitrogen-molybdenum bonds, the MoS can be activated to the maximum extent 2A base surface ofMore reactive active sites are created on the surface, and the HER catalytic performance of the system is further improved. However, the conditions required for synthesizing the composite system are relatively strict, and the content of different types of carbon-nitrogen-molybdenum bonds cannot be controllably adjusted by direct hydrothermal or high-temperature annealing methods, so that no work is mentioned at present in MoS2The content of carbon-pyridine nitrogen-molybdenum bonds is increased by controllably adjusting the content of pyridine nitrogen in a nitrogen-doped graphene composite system, so that the HER catalytic performance is optimized. The laser irradiation of graphene oxide can generate a plurality of mesoporous structures under the quenching effect of rapid heating and quenching, the content of the mesoporous structures is increased along with the increase of laser energy, and the total nitrogen doping amount is slightly increased along with the increase of mesoporous density. In the nitrogen doping process, the pyridine N content is increased, the pyrrole N content is reduced, the graphite N content is basically unchanged, and the metal is easier to bond with the pyridine N. Therefore, the laser-irradiated graphene oxide is used as a matrix for hydrothermal nitrogen doping and MoS growth2More mesoporous structures are created on graphene through laser, so that the content of carbon-pyridine nitrogen-molybdenum bonds in the hydrothermal process is increased, the conductivity is increased, more active sites are exposed, and the formed carbon-pyridine nitrogen-molybdenum bonds synergistically promote the HER electrocatalytic activity of the system. The existing synthesis technology can synthesize the molybdenum disulfide MoS 2And molybdenum disulfide composite nitrogen-doped graphene (MoS)2/NG). Simple MoS2The acidic hydrogen production performance of the catalyst is 10mA cm-2The overpotential at (A) is 313.24mV, and the Tafel slope is 124.4mV dec-1Molybdenum disulfide composite nitrogen-doped graphene MoS2NG at 10mA cm-2The overpotential at (A) is 187.14mV, and the Tafel slope is 64.5mV dec-1. The performance of the mesoporous graphene subjected to laser irradiation is obviously improved after the mesoporous graphene is loaded with molybdenum disulfide, and the optimal performance can reach 10mA cm-2The overpotential at (A) is 110.58mV, the Tafel slope is 50.1mV dec-1The performance of the composite material is in the leading level in the current carbon material loaded molybdenum disulfide composite system.
Disclosure of Invention
Aiming at the problems that the existing synthesis process can not synthesize the transition metal oxide/sulfide composite mesoporous nitrogen-doped graphene rich in carbon pyridine nitrogen metal bonds at low temperature and low pressure and the content of the carbon pyridine nitrogen metal bonds in the composite system can not be effectively regulated, the invention discovers that the content of the carbon-pyridine nitrogen-molybdenum bonds in the composite catalyst can be increased by irradiating the graphene oxide with laser within the range of 177-315 mJ, and the loading amount of molybdenum disulfide on the mesoporous graphene can be optimized when the mass ratio of the raw material laser irradiation graphene oxide to tetrathiomolybdic acid is 1: 1-1: 8 in the hydrothermal process, so that the conductivity of the molybdenum disulfide is increased, the intrinsic activity of the carbon pyridine nitrogen molybdenum bonds at the interface can be synergistically increased, and the electrocatalytic process of HER is promoted. The invention has simple process, ingenious design, safety, environmental protection and low cost.
Preparation method for synthesizing mesoporous nitrogen-doped graphene-loaded molybdenum disulfide through laser irradiation and application of mesoporous nitrogen-doped graphene-loaded molybdenum disulfide in electro-catalysis hydrogen production
The invention provides a method for preparing a composite catalyst rich in carbon-pyridine nitrogen-molybdenum bonds by using laser irradiation to oxidize graphene to create more defect edges on the graphene, so that the number of doping sites of pyridine nitrogen is increased, and molybdenum disulfide is hydrothermally loaded on the nitrogen-doped graphene.
The technical scheme of the invention is as follows:
a preparation method for synthesizing mesoporous nitrogen-doped graphene loaded molybdenum disulfide by laser irradiation; the method comprises the following steps:
(1) putting graphene oxide into absolute ethyl alcohol, carrying out ultrasonic crushing, uniformly dispersing to obtain a suspension of 0.25-0.4 g/L, pouring the suspension into a reactor, and irradiating for 20-30 min by using nanosecond parallel pulse laser under continuous magnetic stirring to obtain the laser-irradiated graphene oxide;
(2) centrifuging the laser-irradiated graphene oxide obtained in the step (1), cleaning the graphene oxide with deionized water, and dispersing the precipitate into the deionized water for freeze-drying;
(3) dispersing the freeze-dried graphene oxide subjected to laser irradiation and the ammonium tetrathiomolybdate obtained in the step (2) in N, N-dimethylformamide according to the mass ratio of 1: 1-1: 8, wherein the mass ratio of the laser-irradiated graphene oxide obtained in the step (2) in the N, N-dimethylformamide is 0.5-1 g/L, then adding urea, the mass ratio of the urea to the laser-irradiated graphene oxide is 20: 1-70: 1, adding hydrazine hydrate after uniform ultrasonic dispersion, enabling the concentration of the ammonium tetrathiomolybdate in the hydrazine hydrate to be 100-200 g/L, and continuing ultrasonic treatment for 10-20 min to obtain a mixed solution;
(4) Pouring the mixed solution obtained in the step (3) into a reaction kettle, and reacting at 180-200 ℃ for 12-16 h to obtain a reaction product;
(5) and (4) centrifuging the product obtained in the step (4), cleaning the product with deionized water, and freeze-drying the product with a freeze dryer.
Preferred conditions are as follows:
the purity of the absolute ethyl alcohol used for dispersing the graphene oxide in the step (1) is analytically pure or higher.
When the nanosecond pulse laser in the step (1) is irradiated, the energy of the laser is 177-315 mJ, the wavelength is 1064nm, the repetition frequency of the laser is 10Hz, and the magnetic stirring speed is controlled at 300-500 rpm.
When the laser irradiation is carried out in the step (1), the liquid volume does not exceed 3/5 of the volume of the reactor, and the whole process is carried out in an ice-water bath.
And (3) when the step (2) and the step (5) are cleaned by deionized water, after centrifuging for 10-20 minutes at the rotating speed of 15000-20000 rpm, adding the deionized water and centrifuging for 10-20 minutes at the rotating speed of 15000-20000 rpm, and repeating for at least 3 times until the product is odorless.
The mesoporous nitrogen-doped graphene-loaded molybdenum disulfide composite material prepared by the invention is applied to electrocatalytic hydrogen production.
The specific application can comprise the following steps:
(1) placing mesoporous nitrogen-doped graphene-loaded molybdenum disulfide composite catalyst powder into an aqueous solution containing 4% -8% nafion solution, and performing ultrasonic dispersion after oscillation until uniform catalyst ink is obtained;
(2) Dropping the prepared catalyst ink on the hydrophilic carbon fiber to ensure that the loading capacity is 0.3-0.5 mg cm-2Naturally airing to obtain a working electrode; taking a mesoporous nitrogen-doped graphene-loaded molybdenum disulfide composite catalyst as a working electrode, a saturated calomel electrode as a reference electrode and a graphite rodThe electrolyte is used as a counter electrode to form a three-electrode system, and a sulfuric acid aqueous solution is used as the electrolyte.
Introducing N into the electrolyte2And testing Cyclic Voltammetry (CV), Linear Sweep Voltammetry (LSV), EIS impedance spectrum and i-t stability until saturation. All potentials are converted into the potential of the relatively reversible hydrogen electrode by means of a formula, ERHE＝ESaturated calomel+0.0592 × pH +0.242V + iR correction. Conversion frequency TOF calculation formula: TOF ═ I/2 nF; i denotes the current (A) at a certain overpotential, F denotes the Faraday constant (96485.3C/mol), and n denotes the number of moles (mol) of molybdenum atoms on the prepared electrode.
Finally obtaining the laser-irradiated mesoporous nitrogen-doped graphene molybdenum disulfide-loaded composite catalyst, wherein the hydrogen production catalysis efficiency is realized by the condition that the current in the LSV is not more than 10mA cm within the voltage range of 0-minus 0.45V vs RHE-2) Pure molybdenum disulfide (10 mA cm in LSV)-2The overpotential at (A) is 313.24 mV; tafel slope of 124.4mV dec -1) Molybdenum disulfide composite nitrogen-doped graphene (10 mA cm in LSV) obtained without laser action-2The overpotential at (A) is 187.14 mV; tafel slope of 64.5mV dec-1) Performance is improved to 10mA cm in LSV (laser-induced decomposition) of molybdenum disulfide composite mesoporous nitrogen-doped graphene-2The overpotential of the position is 110.58mV at the lowest and the Tafel slope is 50.1mV dec at the lowest-1It therefore has a lower reaction barrier and fastest reaction kinetics. And through the test of EIS impedance spectrum, the molybdenum disulfide composite mesoporous nitrogen doped graphene obtained under the action of laser can be found to have a smaller diameter similar to a semicircle than other products, so the electrochemical conductivity of the graphene is improved. In addition, through calculation of TOF (characterization of intrinsic catalytic activity), TOF of the molybdenum disulfide composite mesoporous nitrogen-doped graphene obtained by laser action can reach 0.21-2.54S-1Is obviously higher than 0.091S of the molybdenum disulfide composite nitrogen-doped graphene obtained without the action of laser-1Therefore, the molybdenum disulfide composite mesoporous nitrogen-doped graphene has more excellent intrinsic electrocatalytic hydrogen production activity. The molybdenum disulfide composite mesoporous nitrogen-doped graphene material can well keep the original composite structure characteristics after reaction And the catalyst also shows good catalytic stability for 80 hours in long-time test.
The nanosecond pulse laser wavelength acting on the graphene oxide is 1064nm, and the laser repetition frequency is 10 Hz. In order to ensure that the suspension is uniformly dispersed and the probability of each part being irradiated by laser is equal, the magnetic stirring is required to be carried out continuously in the irradiation process, the whole experiment process is carried out in an exposed environment, protective gas is not required to be introduced in an ice water bath, the product can be directly poured out after the irradiation, and the operation is simple.
The invention has the following advantages: nano-second laser is utilized to irradiate graphene oxide to create more defect edges on graphene, and the graphene oxide is used as a substrate for hydrothermal nitrogen doping and MoS growth2And the molybdenum disulfide/mesoporous nitrogen doped graphene composite material with high intrinsic activity is obtained by laser irradiation and optimization of the amount of raw materials in hydrothermal process to create more carbon-pyridine nitrogen-molybdenum bonds. The method firstly proposes that molybdenum in molybdenum disulfide preferentially forms a bond with pyridine nitrogen compared with other types of nitrogen (pyrrole nitrogen and graphite nitrogen), and the intrinsic activity of an electrocatalyst is positively correlated with the content of carbon-pyridine nitrogen-molybdenum bonds, so that the high-efficiency HER catalytic activity is realized, and a method for controllably regulating carbon-pyridine nitrogen metal bonds is proposed. In addition, the synthesis method adopted by the invention has the advantages of simple process, convenient operation, easy regulation and control, less toxic reaction raw materials and environmental-friendly green synthesis process. XPS tests show that when the laser energy is 177-315 mJ, the total nitrogen content and the pyridine nitrogen content in a sample are high, the pyridine nitrogen content is increased to 2.73-4.14 at% from the original 1.87 at% (molybdenum disulfide composite nitrogen-doped graphene obtained without laser action), and the catalytic hydrogen production performance of the molybdenum disulfide composite mesoporous nitrogen-doped graphene obtained by laser action is improved to 10mA cm in LSV -2The overpotential of the Tafel is 175.96-110.58 mV and the lowest Tafel slope is 50.1mV dec-1Compared with the pure nitrogen-doped graphene (the current in the LSV is less than 10mA cm within the voltage range of 0 to-0.45V vs RHE)-2) Pure molybdenum disulfide (10 mA cm in LSV)-2The overpotential at (A) is 313.24 mV; tafel slope of 124.4mV dec-1) Disulfide obtained without laser actionMolybdenum composite nitrogen doped graphene (10 mA cm in LSV)-2The overpotential at (A) is 187.14 mV; tafel slope of 64.5mV dec-1) There is a significant boost, and thus it has a lower reaction barrier and fastest reaction kinetics. And through the test of EIS impedance spectrum, the molybdenum disulfide composite mesoporous nitrogen doped graphene obtained under the action of laser can be found to have a smaller diameter similar to a semicircle than other products, so that the electrochemical conductivity of the graphene is improved. In addition, through calculation of TOF (characterization of intrinsic catalytic activity), TOF of the molybdenum disulfide composite mesoporous nitrogen-doped graphene obtained by laser action can reach 0.21-2.54S-1Is obviously higher than 0.091S of the molybdenum disulfide composite nitrogen-doped graphene obtained without the action of laser-1Therefore, the molybdenum disulfide composite mesoporous nitrogen-doped graphene has more excellent intrinsic electrocatalytic hydrogen production activity. The molybdenum disulfide composite mesoporous nitrogen-doped graphene material can well keep the original composite structure characteristics after reaction, and also shows good catalytic stability for 80 hours in long-time tests.
Drawings
Fig. 1 is a diagram of a process device for preparing mesoporous graphene oxide by nanosecond laser irradiation to expose more defect edges.
The nanosecond pulse laser wavelength acting on the graphene oxide is 1064nm, and the laser repetition frequency is 10 Hz. And (3) irradiating by using 177-315 mJ laser energy to improve the density of mesopores on the graphene oxide, and further obtaining more carbon-pyridine nitrogen-molybdenum bond composite materials in the next hydrothermal reaction. In order to ensure that the suspension is uniformly dispersed and the probability that each part is irradiated by laser is equal, magnetic stirring is required continuously in the irradiation process, the whole experiment process is carried out in an exposed environment, the whole device needs an ice water bath for avoiding that ethanol is heated and inflammable, protective gas is not required to be introduced, and the product can be directly poured out after irradiation, so that the operation is simple.
FIG. 2(a) shows molybdenum disulfide composite nitrogen-doped graphene (MoS)2NG) scanning electron microscope photographs; (b) for example 1 molybdenum disulfide composite mesoporous nitrogen doped graphene (MoS)2/NLG-270); (c) molybdenum disulfideComposite nitrogen-doped graphene (MoS)2/NG) and molybdenum disulfide composite mesoporous nitrogen-doped graphene (MoS) in example 12/NLG-270); (d) molybdenum disulfide composite nitrogen-doped graphene (MoS) 2/NG) and molybdenum disulfide composite mesoporous nitrogen-doped graphene (MoS) in example 12/NLG-270), inset: molybdenum disulfide composite nitrogen-doped graphene (MoS)2/NG) and molybdenum disulfide composite mesoporous nitrogen-doped graphene (MoS) in example 12/NLG-270).
FIG. 3(a) mechanically mixed molybdenum disulfide and mesoporous nitrogen doped graphene (MoS)2+ NLG-270), molybdenum disulfide composite nitrogen doped graphene (MoS)2/NG) and example 1 molybdenum disulfide composite mesoporous nitrogen doped graphene (MoS)2/NLG-270) from the N1s orbital photoelectron spectroscopy; (b) molybdenum disulfide, mechanically mixed molybdenum disulfide and mesoporous nitrogen doped graphene (MoS)2+ NLG-270) and example 1 molybdenum disulfide composite mesoporous nitrogen doped graphene (MoS)2/NLG-270) Mo 3d orbital X-ray photoelectron spectroscopy.
FIG. 4(a) molybdenum disulfide composite nitrogen doped graphene (MoS)2/NG) and 177-315 mJ of different laser energy to obtain molybdenum disulfide composite mesoporous nitrogen-doped graphene (example 2 MoS)2NLG-177, example 3MoS2NLG-220, example 1MoS2NLG-270, example 4MoS2NLG-315) at 0.5M H2SO4Comparing the electrocatalytic hydrogen production performance in the solution; (b) molybdenum disulfide composite nitrogen-doped graphene (MoS) 2/NG) and 177-315 mJ of different laser energy to obtain molybdenum disulfide composite mesoporous nitrogen-doped graphene (example 2 MoS)2NLG-177, example 3MoS2NLG-220, example 1MoS2NLG-270, example 4MoS2/NLG-315) as a function of the different types of nitrogen content; (c) molybdenum disulfide composite nitrogen-doped graphene (MoS)2/NG) and molybdenum disulfide composite mesoporous nitrogen-doped graphene with different loading amounts (example 1 MoS)2NLG-270, example 5MoS2-1/NLG-270, example 6MoS2-4/NLG-270, example 7MoS2-8/NLG-270) at 0.5M H2SO4Comparing the electrocatalytic hydrogen production performance in the solution.
Detailed Description
As shown in the synthesis device diagram of FIG. 1, a laser beam emitted by a laser device vertically irradiates the laser through a reflector, the position of the reaction container is adjusted to align the laser beam to the liquid level, and the magnetic stirring speed is suitably controlled between 300 r/min and 500 r/min. The nanosecond pulse laser wavelength acting on the graphene oxide is 1064nm, and the laser repetition frequency is 10 Hz. The whole experimental process is carried out in an exposed environment, and in order to avoid the flammability of the heated ethanol, the whole device needs an ice-water bath and does not need to be introduced with protective gas.
The present invention is further described in detail below by way of specific examples, which will enable those skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way.
Example 1:
(1) placing 10mg of graphene oxide in 30mL of absolute ethyl alcohol (purity is analytically pure), carrying out ultrasonic crushing to obtain uniformly dispersed turbid liquid, pouring the turbid liquid into a 50mL conical flask, controlling the magnetic stirring speed at 400 rpm, and irradiating for 25min by using 270mJ nanosecond parallel pulse laser in an ice-water bath to obtain the laser-irradiated graphene oxide.
(2) Centrifuging the laser-irradiated graphene oxide obtained in the step (1) for 15 minutes (18000 rpm), adding deionized water to wash and precipitate, centrifuging for 15 minutes at the rotating speed of 18000 rpm, adding deionized water to centrifuge for 15 minutes at the rotating speed of 18000 rpm, repeating the operation until the product smells odorless, and freeze-drying the product by using a freeze dryer.
(3) And (3) dispersing the freeze-dried graphene oxide subjected to laser irradiation and obtained in the step (2) and 20mg of ammonium tetrathiomolybdate in 10mL of N, N-dimethylformamide, then adding 200mg of urea, uniformly dispersing by ultrasonic, adding 100 mu L of hydrazine hydrate, and continuing to perform ultrasonic treatment for 10 min.
(4) And (4) pouring the mixed solution obtained in the step (3) into a reaction kettle, and reacting for 12 hours at 200 ℃.
(5) And (3) centrifuging the product obtained in the step (4) (18000 revolutions per minute) for 15 minutes, adding deionized water to wash the precipitate, centrifuging at 18000 revolutions per minute for 15 minutes, adding deionized water, centrifuging at 18000 revolutions per minute for 15 minutes, repeating the operation until the product smells odorless, and freeze-drying the product by using a freeze dryer.
The sample obtained in example 1 is recorded as MoS2The morphology under a scanning electron microscope is shown in FIG. 2b, the Raman test spectrum is shown in FIG. 2c, the results of testing the specific surface area, the mesoporous structure and the pore size by using a nitrogen adsorption-desorption isotherm are shown in FIG. 2d, and the XPS test results show that the N1s orbital X-ray photoelectron spectrum and the Mo 3d orbital X-ray photoelectron spectrum are respectively shown in FIG. 3a and FIG. 3b, which are respectively at 0.5M H2SO4LSV polarization curves in solution are shown in FIGS. 4a and 4c, the intrinsic TOF and contents of pyridine N, pyrollic N and graphite N are shown in FIG. 4b, the atomic percentages of N and Mo obtained by XPS test are shown in Table 1, the i-t stability is 10mA cm-2The test was carried out at a current density of up to 80 h.
Example 2:
(1) placing 7.5mg of graphene oxide in 30mL of absolute ethyl alcohol (purity is analytically pure), carrying out ultrasonic crushing to obtain uniformly dispersed turbid liquid, pouring the turbid liquid into a 50mL conical flask, controlling the magnetic stirring speed at 300 rpm, and irradiating for 30min by 177mJ nanosecond parallel pulse laser in an ice-water bath to obtain the laser-irradiated graphene oxide.
(2) And (2) centrifuging the laser-irradiated graphene oxide obtained in the step (1) for 20 minutes (15000 rpm), adding deionized water to wash and precipitate, centrifuging for 20 minutes at the rotating speed of 15000 rpm, adding deionized water to centrifuge for 20 minutes at the rotating speed of 15000 rpm, repeating the operation until the product smells odorless, and freeze-drying the product by using a freeze dryer.
(3) And (3) dispersing the freeze-dried graphene oxide subjected to laser irradiation and obtained in the step (2) and 15mg of ammonium tetrathiomolybdate in 10mL of N, N-dimethylformamide, then adding 150mg of urea, uniformly dispersing by using ultrasonic waves, adding 75 mu L of hydrazine hydrate, and continuing to perform ultrasonic waves for 11 min.
(4) And (4) pouring the mixed solution obtained in the step (3) into a reaction kettle, and reacting for 16h at 180 ℃. .
(5) And (3) centrifuging the product obtained in the step (4) (15000 rpm) for 20 minutes, adding deionized water to wash the precipitate, centrifuging at the rotating speed of 15000 rpm for 20 minutes, adding deionized water, centrifuging at the rotating speed of 15000 rpm for 20 minutes, repeating the operation until the product smells odorless, and freeze-drying the product by using a freeze dryer.
The sample obtained in example 2 was designated as MoS2NLG-177 at 0.5M H2SO4The LSV polarization curve in the solution is shown in FIG. 4a, the intrinsic activity TOF and the contents of pyridine N, pyrollic N and graphite N are shown in FIG. 4b, and the atomic percent contents of N and Mo obtained by the XPS test are shown in Table 1.
Example 3:
(1) placing 9.5mg of graphene oxide in 30mL of absolute ethyl alcohol (purity is analytically pure), ultrasonically crushing to obtain uniformly dispersed turbid liquid, pouring the turbid liquid into a 50mL conical flask, controlling the magnetic stirring speed at 400 revolutions per minute, and irradiating for 28min by 220mJ nanosecond parallel pulse laser in an ice-water bath to obtain the laser-irradiated graphene oxide.
(2) And (2) centrifuging the laser-irradiated graphene oxide obtained in the step (1) for 20 minutes (16000 rpm), adding deionized water to clean precipitates, centrifuging for 20 minutes at the rotating speed of 16000 rpm, adding deionized water, centrifuging for 20 minutes at the rotating speed of 16000 rpm, repeating the operation until the product smells odorless, and freeze-drying the product by using a freeze dryer.
(3) And (3) dispersing the freeze-dried graphene oxide subjected to laser irradiation and obtained in the step (2) and 19mg of ammonium tetrathiomolybdate in 10mL of N, N-dimethylformamide, then adding 190mg of urea, uniformly dispersing by ultrasonic, adding 95 mu L of hydrazine hydrate, and continuing to perform ultrasonic treatment for 13 min.
(4) And (4) pouring the mixed solution obtained in the step (3) into a reaction kettle, and reacting for 14 hours at 190 ℃.
(5) And (3) centrifuging the product obtained in the step (4) (16000 r/min) for 20 minutes, adding deionized water to wash the precipitate, centrifuging at 18000 r/min for 15 minutes, adding deionized water, centrifuging at 16000 r/min for 20 minutes, repeating the operation until the product smells odorless, and freeze-drying the product by using a freeze dryer.
The sample obtained in example 3 was designated as MoS2NLG-220, at 0.5M H2SO4The LSV polarization curve in the solution is shown in FIG. 4a, the content of intrinsic activity TOF and pyridine N, pyrollic N and graphite N is shown in FIG. 4b, and the atomic percentages of N and Mo obtained by XPS test are shown in Table 1.
Example 4:
(1) placing 12mg of graphene oxide in 30mL of absolute ethyl alcohol (purity is analytically pure), carrying out ultrasonic crushing to obtain uniformly dispersed turbid liquid, pouring the turbid liquid into a 50mL conical flask, controlling the magnetic stirring speed at 500 rpm, and carrying out irradiation for 20min by 315mJ nanosecond parallel pulse laser in an ice-water bath to obtain the laser-irradiated graphene oxide.
(2) Centrifuging the laser-irradiated graphene oxide obtained in the step (1) for 10 minutes (20000 rpm), adding deionized water to wash and precipitate, centrifuging for 10 minutes at the rotating speed of 20000 rpm, adding deionized water to centrifuge for 10 minutes at the rotating speed of 20000 rpm, repeating the operation until the product smells odorless, and freeze-drying the product by using a freeze dryer.
(3) And (3) dispersing the freeze-dried graphene oxide subjected to laser irradiation and obtained in the step (2) and 24mg of ammonium tetrathiomolybdate in 12mL of N, N-dimethylformamide, then adding 240mg of urea, uniformly dispersing by ultrasonic, adding 120 mu L of hydrazine hydrate, and continuing to perform ultrasonic treatment for 14 min.
(4) And (4) pouring the mixed solution obtained in the step (3) into a reaction kettle, and reacting for 12 hours at 200 ℃.
(5) And (3) centrifuging the product obtained in the step (4) (20000 rpm) for 10 minutes, adding deionized water to wash the precipitate, centrifuging at 20000 rpm for 10 minutes, adding deionized water, centrifuging at 20000 rpm for 10 minutes, repeating the operation until the product smells odorless, and freeze-drying the product by using a freeze dryer.
The sample obtained in example 4 was designated as MoS2NLG-315 at 0.5M H2SO4The LSV polarization curve in the solution is shown in FIG. 4a, the content of intrinsic activity TOF and pyridine N, pyrollic N and graphite N is shown in FIG. 4b, and the atomic percentages of N and Mo obtained by XPS test are shown in Table 1.
Example 5:
(1) placing 8mg of graphene oxide in 30mL of absolute ethyl alcohol (purity is analytically pure), carrying out ultrasonic crushing to obtain uniformly dispersed turbid liquid, pouring the turbid liquid into a 50mL conical flask, controlling the magnetic stirring speed at 350 revolutions per minute, and irradiating for 23min by 270mJ nanosecond parallel pulse laser in an ice water bath to obtain the laser-irradiated graphene oxide.
(2) And (2) centrifuging the laser-irradiated graphene oxide obtained in the step (1) for 15 minutes (17000 r/min), adding deionized water to wash and precipitate, centrifuging for 15 minutes at the rotating speed of 17000 r/min, adding deionized water, centrifuging for 15 minutes at the rotating speed of 17000 r/min, repeating the operation until the product smells odorless, and freeze-drying the product by using a freeze dryer.
(3) And (3) dispersing the freeze-dried graphene oxide subjected to laser irradiation and obtained in the step (2) and 8mg of ammonium tetrathiomolybdate in 16mL of N, N-dimethylformamide, then adding 560mg of urea, uniformly dispersing by ultrasonic, adding 80 mu L of hydrazine hydrate, and continuing to perform ultrasonic treatment for 12 min.
(4) And (4) pouring the mixed solution obtained in the step (3) into a reaction kettle, and reacting for 13h at 195 ℃.
(5) And (3) centrifuging the product obtained in the step (4) (17000 rpm) for 15 minutes, adding deionized water to wash the precipitate, centrifuging at 17000 rpm for 15 minutes, adding deionized water, centrifuging at 17000 rpm for 15 minutes, repeating the operation until the product smells odorless, and freeze-drying the product by using a freeze dryer.
The sample obtained in example 5 is reported as MoS 21/NLG-270 at 0.5M H2SO4In solutionThe LSV polarization curve is shown in fig. 4 c.
Example 6:
(1) placing 9mg of graphene oxide in 30mL of absolute ethyl alcohol (purity is analytically pure), carrying out ultrasonic crushing to obtain uniformly dispersed turbid liquid, pouring the turbid liquid into a 50mL conical flask, controlling the magnetic stirring speed at 320 rpm, and irradiating for 24min by using 270mJ nanosecond parallel pulse laser in an ice-water bath to obtain the laser-irradiated graphene oxide.
(2) Centrifuging the laser-irradiated graphene oxide obtained in the step (1) for 10 minutes (19000 r/min), adding deionized water to wash and precipitate, centrifuging for 10 minutes at 19000 r/min, adding deionized water, centrifuging for 10 minutes at 19000 r/min, repeating the operation until the product smells odorless, and freeze-drying the product by using a freeze dryer.
(3) And (3) dispersing the freeze-dried graphene oxide subjected to laser irradiation and obtained in the step (2) and 36mg of ammonium tetrathiomolybdate in 10mL of N, N-dimethylformamide, then adding 360mg of urea, uniformly dispersing by using ultrasonic waves, then adding 45 mu L of hydrazine hydrate, and continuing to perform ultrasonic waves for 15 min.
(4) And (4) pouring the mixed solution obtained in the step (3) into a reaction kettle, and reacting for 15 hours at 185 ℃.
(5) Centrifuging the product obtained in the step (4) (19000 r/min) for 10 minutes, adding deionized water to wash the precipitate, centrifuging at 19000 r/min for 10 minutes, adding deionized water, centrifuging at 19000 r/min for 10 minutes, repeating the operation until the product smells odorless, and freeze-drying the product by using a freeze dryer.
The sample obtained in example 6 is reported as MoS2-4/NLG-270 at 0.5M H2SO4The LSV polarization curve in solution is shown in figure 4 c.
Example 7:
(1) placing 11mg of graphene oxide in 30mL of absolute ethyl alcohol (purity is analytically pure), carrying out ultrasonic crushing to obtain uniformly dispersed turbid liquid, pouring the turbid liquid into a 50mL conical flask, controlling the magnetic stirring speed at 500 rpm, and irradiating for 26min by using 270mJ nanosecond parallel pulse laser in an ice-water bath to obtain the laser-irradiated graphene oxide.
(2) And (2) centrifuging the laser-irradiated graphene oxide obtained in the step (1) for 10 minutes (18000 revolutions per minute), adding deionized water to wash and precipitate, centrifuging for 10 minutes at the rotation speed of 18000 revolutions per minute, adding deionized water, centrifuging for 10 minutes at the rotation speed of 18000 revolutions per minute, repeating the operation until the product smells odorless, and freeze-drying the product by using a freeze dryer.
(3) And (3) dispersing the freeze-dried graphene oxide subjected to laser irradiation and obtained in the step (2) and 88mg of ammonium tetrathiomolybdate in 15mL of N, N-dimethylformamide, then adding 495mg of urea, uniformly dispersing by ultrasonic, adding 586 mu L of hydrazine hydrate, and continuing to perform ultrasonic treatment for 20 min.
(4) And (4) pouring the mixed solution obtained in the step (3) into a reaction kettle, and reacting for 12 hours at 200 ℃.
(5) And (3) centrifuging the product obtained in the step (4) (18000 revolutions per minute) for 10 minutes, adding deionized water to wash the precipitate, centrifuging at 18000 revolutions per minute for 10 minutes, adding deionized water, centrifuging at 18000 revolutions per minute for 10 minutes, repeating the operation until the product smells odorless, and freeze-drying the product by using a freeze dryer.
The sample obtained in example 7 was designated as MoS2-8/NLG-270 at 0.5M H2SO4The LSV polarization curve in solution is shown in figure 4 c.
The performance measurements are illustrated below:
the intrinsic activity and the conductivity of the reaction in the electrocatalytic hydrogen production of the embodiment 1 to the embodiment 4 are tested, and the method specifically comprises the following steps:
(1) weighing 5mg of mesoporous nitrogen-doped graphene-loaded molybdenum disulfide composite catalyst powder, adding 1000 mu L of aqueous solution containing 40 mu L of nafion (commercial weight percent of 5%) into the mesoporous nitrogen-doped graphene-loaded molybdenum disulfide composite catalyst powder, and oscillating and ultrasonically dispersing the mesoporous nitrogen-doped graphene-loaded molybdenum disulfide composite catalyst powder until uniform catalyst ink is obtained;
(2) then the area of the transverse direction is 0.15cm -29 mu L of the obtained catalyst ink is dripped on the hydrophilic carbon fiber, and the working electrode is obtained by natural airing. And was equipped with 0.5M H2SO4And (4) the electrolyte is for later use.
(3) To let throughCarbon fiber of the porous nitrogen-doped graphene-loaded molybdenum disulfide composite catalyst is used as a working electrode, a saturated calomel electrode is used as a reference electrode, and a graphite rod is used as a counter electrode, so that a three-electrode system is formed. Adding the electrolyte prepared in the step (2) into an electrolytic cell, and introducing N2And respectively testing cyclic voltammetry Curves (CV) after saturation, wherein the sweep rate is 50mV s-1And sweeping until stable. Then with 5mV s-1Linear Sweep Voltammetry (LSV) tests were performed and all data were corrected for iR compensation. EIS impedance spectrum at 0.1Hz to 106The test was carried out in the frequency range of Hz at a voltage of-0.12V.
XPS (XPS) characterization of molybdenum disulfide composite nitrogen-doped graphene (MoS)2/NG) and molybdenum disulfide composite mesoporous nitrogen-doped graphene obtained by changing laser energy from 177-315 mJ (example 2 MoS)2NLG-177, example 3MoS2NLG-220, example 1MoS2NLG-270, example 4MoS2/NLG-315) the atomic percentages of N and Mo are as follows:
table 1 molybdenum disulfide composite nitrogen doped graphene (MoS)2NG) and atomic percentages of N and Mo in examples 2, 3, 1 and 4
The analysis on the above table shows that when the laser energy is 177-315 mJ, the total nitrogen content and the pyridine nitrogen content in the sample are both improved, and the pyridine nitrogen content is increased from that of the original molybdenum disulfide composite nitrogen-doped graphene (MoS)2The 1.87 at% in/NG) rises to 4.14 at% in example 1, 2.73 at% in example 2, 3.35 at% in example 3, 3.70 at% in example 4, which indicates that the laser can increase the carbon-pyridine nitrogen-molybdenum bond content in the system.
When the pyridine nitrogen content is increased, the electrocatalytic hydrogen production performance is improved, and the LSV of the molybdenum disulfide composite mesoporous nitrogen-doped graphene sample obtained by the laser action is 10mA cm-2The overpotential of (d) is 175.96-110.58 mV (110.58 mV in example 1, 175.96mV in example 2, true) 151.56mV in example 3, 132.58mV in example 4) and Tafel slope is 50.1mV dec in example 1-1Compared with the pure molybdenum disulfide MoS2(10 mA cm in LSV)-2The overpotential at (A) is 313.24 mV; tafel slope of 124.4mV dec-1) The current of the pure nitrogen-doped graphene NG (in LSV, the current can not reach 10mA cm within the voltage range of 0 to-0.45V vs RHE-2) Molybdenum disulfide composite nitrogen-doped graphene MoS obtained without laser action2/NG (10 mA cm in LSV)-2The overpotential at (A) is 187.14 mV; tafel slope of 64.5mV dec-1) The carbon-pyridine nitrogen-molybdenum bond can improve the electrocatalytic hydrogen production activity of the compound. And through the test of EIS impedance spectrum, the molybdenum disulfide composite mesoporous nitrogen-doped graphene obtained by the laser action (example 1, example 2, example 3 and example 4) has more MoS than the pure molybdenum disulfide MoS2Pure nitrogen-doped graphene NG and molybdenum disulfide composite nitrogen-doped graphene MoS obtained without laser action2the/NG is smaller in diameter similar to a semicircle, so that the electrochemical conductivity of the conductive material is improved. In addition, through calculation of TOF (characterization of intrinsic catalytic activity), it can be found that TOF of the molybdenum disulfide composite mesoporous nitrogen-doped graphene obtained by laser action can reach 2.54S in example 1 -10.21S in example 2-10.53S in example 3-11.49S in example 4-1The content of the nitrogen-doped graphene MoS is higher than that of the molybdenum disulfide composite nitrogen-doped graphene MoS obtained without the action of laser20.091S of/NG-1Therefore, the molybdenum disulfide composite mesoporous nitrogen-doped graphene has more excellent intrinsic electrocatalytic hydrogen production activity. The molybdenum disulfide composite mesoporous nitrogen-doped graphene material can well keep the original composite structure characteristics after reaction, and also shows good catalytic stability in a long-time test, and the test example 1 is as long as 80 h.
Fig. 2a and 2b correspond to example 1 and molybdenum disulfide composite nitrogen-doped graphene (MoS), respectively2NG), and comparing the MoS2The mesoporous graphene loaded on the laser can obtain a porous structureAnd the defect-rich structure is beneficial to increasing the specific surface area of the material in the embodiment 1, so that MoS2The sheets are made finer and more discrete, thereby facilitating exposure of the edge active sites. As can be seen from the raman spectrum in fig. 2c, the nitrogen-doped graphene (MoS) is composited with the molybdenum disulfide in example 12/NG) all have MoS2Characteristic E of2g 1And Ag 1Peaks, as well as the D and G peaks attributed to graphene, indicate that both successfully synthesized the composite structure. In addition, the ratio of the intensity of the D peak to the G peak of graphene, i.e., I D/IGThe defect degree of the graphene is represented, the larger the ratio is, the more defects on the graphene are represented, and the molybdenum disulfide and nitrogen are compounded to dope the graphene (MoS)2I of/NG)D/IGValue 1.12, I of example 1D/IGThe value is 1.28, thus further illustrating that the laser can create more defects, which is consistent with the scanned picture results and is more favorable for nitrogen doping. As can be seen in fig. 2d, example 1 is compared to molybdenum disulfide composite nitrogen doped graphene (MoS)2/NG), the specific surface area, the mesoporous structure and the aperture size are slightly increased, and are consistent with the scanning and Raman obtaining results, which shows that more mesoporous structures and edge defects are actually created by laser. As can be seen by the shift of the N1s orbital X-ray photoelectron spectrum in fig. 3a, in contrast to molybdenum disulfide composite nitrogen-doped graphene (MoS)2/NG), mechanically mixed MoS2With the mesoporous nitrogen-doped graphene NLG-270, the peaks of pyritic N and pyrollic N of example 1 were shifted in the direction of low binding energy, while the peaks of graphitic N were not substantially changed, indicating that pyritic N and pyrollic N are bonded to Mo atom, and the electron of Mo shifts to pyritic N and pyrollic N, resulting in the peaks of pyritic N and pyrollic N being shifted in the direction of low binding energy, but continuing to compare example 1 with molybdenum disulfide compound nitrogen-doped graphene (MoS) 2Peak areas of pyridine N and pyrollic N in/NG), the larger the peak area is, the more the content is shown, and the nitrogen-doped graphene (MoS) can be found relative to molybdenum disulfide composite2/NG), the content of pyritic N in example 1 is significantly increased and the content of pyrollic N is significantly decreased, indicating thatThe laser did help to increase the pyridine nitrogen content, with more carbon-pyridine nitrogen-molybdenum bonds in example 1, which act as active sites to activate MoS2The base surface of the catalyst improves the performance of catalytic hydrogen production. Mo 3d orbital X-ray photoelectron Spectroscopy of FIG. 3b, in contrast to MoS2Mechanically mixed MoS2With mesoporous nitrogen-doped graphene NLG-270, Mo 3d of example 15/2And Mo 3d3/2The orbitals move in the direction of high binding energy, corresponding to the results in fig. 3a, and the electrons of Mo are shifted towards N, further confirming the formation of carbon-pyridine nitrogen-molybdenum bonds. FIG. 4a shows a molybdenum disulfide composite nitrogen-doped graphene (MoS)2/NG) and 177-315 mJ of different laser energy, wherein the amount of the molybdenum disulfide composite mesoporous nitrogen-doped graphene (example 2, example 3, example 1 and example 4) obtained by the method is 0.5M H2SO4LSV polarization curve in solution, the samples after laser action (examples 2, 3, 1, 4) compared to molybdenum disulfide composite nitrogen doped graphene (MoS) without laser action 2/NG) at 10mA cm-2With lower overpotential, examples 2, 3, 1, 4 obtained by laser action in LSV 10mA cm-2The overpotential of the graphene is 175.96-110.58 mV (110.58 mV in example 1, 175.96mV in example 2, 151.56mV in example 3 and 132.58mV in example 4)), which is obviously superior to molybdenum disulfide composite nitrogen-doped graphene (MoS)2NG) (187.14 mV). Fig. 4b illustrates that the intrinsic activity TOF of the catalyst has a positive correlation with the pyridine N content, that is, the more the carbon-pyridine nitrogen-molybdenum bond content is, the better the catalytic performance is, and the TOF of the molybdenum disulfide composite mesoporous nitrogen-doped graphene obtained by the laser effect can reach 2.54S in example 1-10.21S in example 2-10.53S in example 3-11.49S in example 4-1Is obviously higher than the molybdenum disulfide composite nitrogen-doped graphene MoS which is obtained without the action of laser2/NG(0.091S-1)。
We also refer to MoS2The load capacity of the catalyst is regulated, the catalytic hydrogen production activity of the catalyst in electrocatalytic hydrogen production of the embodiments 5 to 7 is tested, and the method specifically comprises the following steps:
(1) weighing 5mg of mesoporous nitrogen-doped graphene-loaded molybdenum disulfide composite catalyst powder, adding 1000 mu L of aqueous solution containing 60 mu L of nafion (commercial weight percent of 5%), oscillating, and performing ultrasonic dispersion until uniform catalyst ink is obtained;
(2) Then the area of the transverse direction is 0.15cm-2And dripping 12 mu L of the obtained catalyst ink on the hydrophilic carbon fiber, and naturally airing to obtain the working electrode. And was equipped with 0.5M H2SO4And (4) electrolyte is used for standby.
(3) The carbon fiber of the mesoporous nitrogen-doped graphene-loaded molybdenum disulfide composite catalyst is used as a working electrode, a saturated calomel electrode is used as a reference electrode, and a graphite rod is used as a counter electrode to form a three-electrode system. Adding the electrolyte prepared in the step (2) into an electrolytic cell, and introducing N2And respectively testing cyclic voltammetry Curves (CV) after saturation, wherein the sweep rate is 50mV s-1And sweeping until stable. Then with 5mV s-1Linear Sweep Voltammetry (LSV) tests were performed and all data were corrected for iR compensation.
FIG. 4c optimizes MoS in the system2The loading capacity of the mesoporous graphene oxide is found by comparison of LSV polarization curves, and MoS is facilitated when the mass ratio of the mesoporous graphene oxide to the ammonium tetrathiomolybdate raw materials is changed within 1: 1-1: 8 in the synthesis process2The dispersion growth is regulated and controlled in the range, and the molybdenum disulfide composite nitrogen-doped graphene MoS which is obtained without the laser effect is obtained2/NG (10 mA cm in LSV)-2Overpotential of 187.14mV) improved electrocatalytic performance (10 mA cm in LSV)-2The overpotential at (b) is 110.58mV in example 1, 127.18mV in example 5, 155.30mV in example 6, and 222.19mV in example 7).
Therefore, when graphene oxide is irradiated by laser within 177-315 mJ, and the mass ratio of graphene oxide irradiated by the laser to tetrathiomolybdic acid in the hydrothermal process is 1: 1-1: 8, the number of carbon-pyridine nitrogen-molybdenum bonds at active sites at the interface can be increased, and MoS is facilitated2The dispersion of the nanoplatelets thus leaves the active sites fully exposed.
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (7)
1. A preparation method of mesoporous nitrogen-doped graphene loaded molybdenum disulfide by laser irradiation synthesis; the method is characterized by comprising the following steps:
(1) putting graphene oxide into absolute ethyl alcohol, carrying out ultrasonic crushing, uniformly dispersing to obtain a suspension of 0.25-0.4 g/L, pouring the suspension into a reactor, and irradiating for 20-30 min by using nanosecond parallel pulse laser under continuous magnetic stirring to obtain the laser-irradiated graphene oxide;
(2) Centrifuging the laser-irradiated graphene oxide obtained in the step (1), cleaning the graphene oxide with deionized water, and dispersing the precipitate into the deionized water for freeze-drying;
(3) dispersing the freeze-dried graphene oxide subjected to laser irradiation and the ammonium tetrathiomolybdate obtained in the step (2) in N, N-dimethylformamide according to the mass ratio of 1: 1-1: 8, wherein the mass ratio of the laser-irradiated graphene oxide obtained in the step (2) in the N, N-dimethylformamide is 0.5-1 g/L, then adding urea, the mass ratio of the urea to the laser-irradiated graphene oxide is 20: 1-70: 1, adding hydrazine hydrate after uniform ultrasonic dispersion, enabling the concentration of the ammonium tetrathiomolybdate in the hydrazine hydrate to be 100-200 g/L, and continuing ultrasonic treatment for 10-20 min to obtain a mixed solution;
(4) pouring the mixed solution obtained in the step (3) into a reaction kettle, and reacting at 180-200 ℃ for 12-16 h to obtain a reaction product;
(5) and (4) centrifuging the product obtained in the step (4), cleaning the product with deionized water, and freeze-drying the product with a freeze dryer.
2. The preparation method according to claim 1, wherein the absolute ethanol used for dispersing graphene oxide in the step (1) has a purity of analytical purity or higher.
3. The preparation method according to claim 1, wherein when the nanosecond pulsed laser is irradiated in the step (1), the energy of the laser is 177-315 mJ, the wavelength is 1064nm, the repetition frequency of the laser is 10Hz, and the magnetic stirring speed is controlled to be 300-500 rpm.
4. The preparation method according to claim 1, wherein the liquid volume does not exceed 3/5 of the reactor volume when the laser is irradiated in the step (1), and the whole process is carried out in an ice-water bath.
5. The method according to claim 1, wherein the step (2) and the step (5) are performed by washing with deionized water, and after centrifuging at 15000-20000 rpm for 10-20 minutes, adding deionized water and centrifuging at 15000-20000 rpm for 10-20 minutes, and repeating at least 3 times until the product is odorless.
6. The mesoporous nitrogen-doped graphene-loaded molybdenum disulfide composite material prepared by the method in claim 1 is applied to electrocatalytic hydrogen production.
7. Use according to claim 6, characterised in that it comprises the following steps:
(1) placing mesoporous nitrogen-doped graphene-loaded molybdenum disulfide composite catalyst powder into an aqueous solution containing 4% -8% nafion solution, and performing ultrasonic dispersion after oscillation until uniform catalyst ink is obtained;
(2) dropping the prepared catalyst ink on the hydrophilic carbon fiber to ensure that the loading capacity is 0.3-0.5 mg cm-2Naturally airing to obtain a working electrode; a three-electrode system is formed by taking a mesoporous nitrogen-doped graphene-loaded molybdenum disulfide composite catalyst as a working electrode, a saturated calomel electrode as a reference electrode and a graphite rod as a counter electrode, and sulfuric acid is used The aqueous solution is used as electrolyte.
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