阅读说明：本技术 钼氧硫化物/硫化镍/泡沫镍复合体及其制备方法和应用 (Molybdenum oxysulfide/nickel sulfide/foamed nickel complex and preparation method and application thereof ) 是由 马淑兰 于梓洹 姚惠琴 于 2021-09-15 设计创作，主要内容包括：本发明提供了一种MoO-(x)S-(y)/Ni-(3)S-(2)/NF复合体,其以三维泡沫镍为基底材料,三维泡沫镍的表面生长有Ni-(3)S-(2)颗粒和无定型MoO-(x)S-(y)微米球；其中,2＜x+y＜3,0<y<2。本发明提供的复合体,含有的Mo为+(5+δ)(0<δ<1)价,无定型钼氧硫化物生长为微米球,暴露更多活性位点的同时增强了机械稳定性；MoO-(x)S-(y)主要以Mo＝O为活性位点,且从Ni-(3)S-(2)到MoO-(x)S-(y)的电子转移活化了Mo＝O,降低了氢吸附自由能,提升催化活性；此外,复合体中还存在具有催化活性的硫化镍,未被硫化的单质Ni作基底增强了复合体的导电性；制备得到的复合体具有极高的析氢催化活性和耐久的电化学稳定性,呈现卓越的催化析氢性能。(The invention provides a MoO x S y /Ni 3 S 2 the/NF composite body takes three-dimensional foam nickel as a base material, and Ni is grown on the surface of the three-dimensional foam nickel 3 S 2 Particles and amorphous MoO x S y Micro-balls; wherein x + y is more than 2 and less than 3, 0<y<2. The composite provided by the invention contains Mo of plus (5+ delta) (0)<δ<1) The amorphous molybdenum oxysulfide grows into microspheres, so that mechanical stability is enhanced while more active sites are exposed; MoO x S y Mo ═ O as active site, and Ni 3 S 2 To MoO x S y The electron transfer of (A) activates Mo ═ O, and reducesHydrogen adsorbs free energy, and the catalytic activity is improved; in addition, nickel sulfide with catalytic activity is also present in the composite body, and the conductivity of the composite body is enhanced by using an unsulfided simple substance Ni as a substrate; the prepared complex has extremely high hydrogen evolution catalytic activity and durable electrochemical stability, and shows excellent catalytic hydrogen evolution performance.)

1. MoO (MoO)_xS_y/Ni₃S₂the/NF composite body takes three-dimensional foam nickel as a base material, and Ni is grown on the surface of the three-dimensional foam nickel₃S₂Particles and amorphous MoO_xS_yMicro-balls; wherein x + y is more than 2 and less than 3, and y is more than 0 and less than 2.

2. The MoO of claim 1_xS_y/Ni₃S₂/NF Complex wherein the amorphous MoO_xS_yFrom molybdenum dimers [ Mo ]₂O₂(S,O)₄]Composition, and Mo is + (5+ delta) valence, wherein 0<δ<1。

3. The MoO of claim 1_xS_y/Ni₃S₂/NF Complex wherein the amorphous MoO_xS_yThe diameter of the micro-spheres is 2-3 μm.

4. The MoO of any of claims 1-3_xS_y/Ni₃S₂A method for preparing a/NF complex, comprising:

(1) dissolving molybdate and hexadecyl trimethyl ammonium bromide in a mixed solvent of water and ethanol, and adding a sulfur source for dissolving to obtain a precursor;

(2) carrying out hydrothermal reaction on the precursor and the pretreated nickel foam at the temperature of 150-180 ℃ for 18-24 hours to obtain the MoO_xS_y/Ni₃S₂a/NF complex.

5. The method of claim 4, wherein the molar ratio of molybdenum, sulfur, cetyltrimethylammonium bromide is 1 (8-12) to (1-4).

6. The method according to claim 4, wherein the volume ratio of water to ethanol is 1 (0.8-1.2).

7. The method according to claim 4, wherein the concentration of the molybdate in the mixed solvent is 30 to 50 mmol/L.

8. The method of claim 4, wherein the molybdate is selected from at least one of sodium molybdate and ammonium molybdate; the sulfur source is at least one selected from thiourea and sodium thiosulfate.

9. The method of claim 4, wherein the pre-processing comprises: soaking with 4.5-5.5% (w/w) hydrochloric acid for 20-40 min, and ultrasonic cleaning with acetone, deionized water and ethanol for 10-20 min.

10. The MoO of any of claims 1-3_xS_y/Ni₃S₂The use of/NF complexes in electrocatalytic hydrogen evolution.

Technical Field

The invention relates to the technical field of electrocatalysts, in particular to MoO_xS_y/Ni₃S₂The preparation method and application of the/NF complex.

Background

The hydrogen is a clean and renewable novel fuel, and has important significance for replacing the traditional fossil fuel and realizing the upgrading of industrial technology. The combustion value of hydrogen is extremely high, and the combustion product is only H₂O, does not generate any pollutant and greenhouse gas such as CO₂. More importantly, the hydrogen can be directly obtained through electrolytic water Hydrogen Evolution Reaction (HER), and the raw materials are rich. However, the overpotential of the hydrogen evolution reaction is high, and platinum noble metals are generally needed to be used as catalysts to reduce the overpotential, and the noble metal catalysts are expensive and lack resources, so that the wide application of hydrogen production by water electrolysis in industry is limited.

Among the numerous non-platinum hydrogen evolution electrocatalysts, the most studied in recent years have been transition metal chalcogenide electrocatalysts, such as molybdenum, tungsten and nickel sulfides, of which molybdenum sulfide catalysts have received much attention because they are inexpensive and readily available and have high catalytic efficiency. MoS₂The 2D layer edge unsaturated sulfur active sites of (a) play an important catalytic role in HER. Conductivity is also an important factor influencing catalytic performance, and the conductivity is high and electron transmission is fast. However, MoS₂Poor conductivity due to large band gap affects the rate of HER reaction. Therefore, new hydrogen evolution reaction electrocatalysts have to be found.

Disclosure of Invention

The embodiment of the invention aims to provide a MoO_xS_y/Ni₃S₂a/NF complex to achieve high catalytic performance for hydrogen evolution reactions.

In a first aspect, the present application provides a MoO_xS_y/Ni₃S₂the/NF composite body takes three-dimensional foam nickel as a base material, and Ni is grown on the surface of the three-dimensional foam nickel₃S₂Particles and amorphous MoO_xS_yMicro-balls; wherein x + y is more than 2 and less than 3, 0<y<2。

In a second aspect, the present application provides a MoO as provided in the first aspect of the present application_xS_y/Ni₃S₂A method for preparing a/NF complex, comprising:

(1) dissolving molybdate and hexadecyl trimethyl ammonium bromide in a mixed solvent of water and ethanol, and adding a sulfur source for dissolving to obtain a precursor;

(2) carrying out hydrothermal reaction on the precursor and the pretreated nickel foam at the temperature of 150-180 ℃ for 18-24 hours to obtain the MoO_xS_y/Ni₃S₂a/NF complex.

In a third aspect, the present application provides the MoO provided in the first aspect of the present application_xS_y/Ni₃S₂The use of/NF complexes in electrocatalytic hydrogen evolution.

The MoO provided by the invention_xS_y/Ni₃S₂/NF composite, amorphous molybdenum oxysulfide (MoO)_xS_y) From Mo dimer [ Mo ]₂O₂(S,O)₄]Composition, and Mo contained is + (5+ delta) valence, 0<δ<1, with the known MoS₂And MoO₃The materials are significantly different; the amorphous molybdenum oxysulfide grows into microspheres in shape, so that mechanical stability is enhanced while more active sites are exposed; MoO_xS_yMo ═ O as active site, and Ni₃S₂To MoO_xS_yThe electron transfer of (1) effectively activates Mo ═ O and reduces the hydrogen adsorption free energy Δ G_HIncreasing catalytic activity; further, the MoO_xS_y/Ni₃S₂The presence of catalytically active nickel sulfide (Ni) in the/NF composite₃S₂) The elemental Ni which is not vulcanized is used as a substrate to enhance the conductivity of the composite; prepared MoO_xS_y/Ni₃S₂the/NF complex has extremely high hydrogen evolution catalytic activity (eta)₁₀58mV) and durable electrochemical stability: (>200h) And the catalyst has excellent catalytic hydrogen evolution performance.

MoO of the present application_xS_y/Ni₃S₂the/NF complex can be obtained by a one-step hydrothermal method, the preparation method is simple, the reaction condition is mild, and the method is suitable for industrial production.

Drawings

In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, it is obvious that the drawings in the following description are only one embodiment of the present invention, and other embodiments can be obtained by those skilled in the art according to the drawings.

FIG. 1A is an XRD spectrum of the products of example 2 and comparative example 1;

FIG. 1B is an XRD spectrum of the products of examples 1, 3, 4;

figure 1C is an XRD spectrum of the products of example 5 and comparative example 2;

FIG. 2A is an SEM photograph of the product of comparative example 1;

FIG. 2B is an SEM photograph of the composite of example 2;

FIG. 2C is an SEM photograph of the composite of example 5;

FIG. 2D is an SEM photograph of the product of comparative example 2;

FIG. 3 is a Transmission Electron Microscope (TEM) photograph of the composite of example 2;

FIG. 4A shows Mo 3d XPS spectra of the products of examples 2, 5 and comparative examples 1, 2; and Raman (c) and FT-IR (d) spectra of the products of example 2 and comparative example 1.

Figure 4B shows S2 p XPS spectra of the products of examples 2, 5 and comparative examples 1, 2.

Figure 4C shows Ni 2p XPS spectra of the products of examples 2, 5 and comparative examples 1, 2.

FIG. 5 shows MoO in the composite of example 2_xS_yAnd MoO₃And MoS₂Mo of (3)₃-edge XANES (graph a); mo K-edge XANES (panel b); MoO_xS_yLinear fitting graph (c diagram) of Mo valence state and MoO_xS_y、MoO₃And MoS₂Graph (d) of Mo K-edge FT-EXAFS.

FIG. 6 shows [ Mo ]₄O₈S₄]@Ni₃S₂(101) Front view (figure a) and top view (figure b) of the model.

FIG. 7 shows the complexes of examples 1-4 at 0.5M H₂SO₄LSV curve of (1)

FIG. 8, panel a, is 160-2CTAB,160-no CTAB, Ni₃S₂LSV curves for/NF, 180-2CTAB and Pt-C/NF; b shows 160-2CTAB,160-no CTAB and Ni₃S₂Tafel slopes for/NF and Pt-C/NF; c is 160-2CTAB,160-no CTAB and Ni₃S₂Nyquist plot for/NF; graph d is CV diagram of 160-2 CTAB; e is a plot of capacitance current density difference versus scan rate for 160-2 CTAB; f picture is H precipitation in 160-2CTAB Faraday efficiency test process₂Theoretical volume and experimental volume versus time.

Fig. 9 is an equivalent circuit diagram for nyquist plot fitting.

FIG. 10, panel a, is a 160-2CTAB stability test (I-t) diagram; b is a partial enlarged view of the 45.4-45.75h interval in the diagram a; c is a comparison of LSV before and after 160-2CTAB stability test; and d and e are SEM morphology comparison before and after stability test of 160-CTAB respectively.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and examples. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in this application are within the scope of protection of this application.

In a first aspect, the present application provides a MoO_xS_y/Ni₃S₂/NF composite (molybdenum oxysulfide/nickel sulfide/foamed nickel complex)Composite body, hereinafter may be simply referred to as composite body) using three-dimensional foamed nickel as a base material, the surface of which is grown with Ni₃S₂Particles and amorphous MoO_xS_yMicro-balls; wherein x + y is more than 2 and less than 3, 0<y<2。

Currently reported oxygen insertion molybdenum disulfide is crystal molybdenum disulfide, the oxygen content is low, the disorder is low, and the maximized exposure of edge sulfur and Mo ═ O active sites is difficult. The inventor finds that amorphous molybdenum sulfide (MoS) in research_x) The disorder is higher, more edge sulfur active sites are provided, and the catalytic activity is higher; the disorder can be increased by inserting oxygen element into amorphous molybdenum sulfide, and Mo ═ O of the end group can become a new hydrogen evolution active site, so that the hydrogen evolution performance of the catalyst is greatly improved. Furthermore, the inventors have found that MoS contains tetravalent molybdenum₂The catalytic activity is higher, the electrochemical stability of the molybdenum oxide containing hexavalent molybdenum is strong, and the pure phase of the application contains intermediate-state Moⁿ⁺(+4<n<+6) amorphous molybdenum oxysulfide (MoO)_xS_y) Can maximize the exposure of active sites and can be used as a highly active, continuously durable electrocatalyst.

In addition, the foamed nickel (abbreviated as NF) of the present application is used as a base material, which can improve the conductivity of the catalyst, and is directly used as an electrode; a composite material with a specific morphology can be constructed by using a NF special three-dimensional framework; the foamed nickel has high specific surface area and can synthesize MoO_xS_yGood dispersion is obtained, and catalytic active sites are fully exposed; furthermore, sulfur source is introduced in the synthesis process, so that Ni can be partially vulcanized and grow in situ to obtain nickel sulfide (Ni)₃S₂) The catalytic activity is synergistically improved, and the catalytic activity of the complex is further improved.

In certain embodiments of the first aspect of the present application, the amorphous molybdenum oxysulfide is formed from molybdenum dimer [ Mo₂O₂(S,O)₄]Composition, and Mo is + (5+ delta) valence, wherein 0<δ<1。

In some embodiments of the first aspect of the present application, the amorphous MoO_xS_yGrowing into micron spheres with uniform diameter, wherein the diameter of the micron spheres is 2-3 mu m.

The inventors have found that when the amorphous molybdenum oxysulfide microspheres are regular microspheres with a diameter of 2-3 μm, it is advantageous to expose more active sites while enhancing the mechanical stability of the composite.

In a second aspect, the present application provides a MoO as provided in the first aspect of the present application_xS_y/Ni₃S₂A method for preparing a/NF complex, comprising:

(1) dissolving molybdate and Cetyl Trimethyl Ammonium Bromide (CTAB) in a mixed solvent of water and ethanol, and adding a sulfur source for dissolving to obtain a precursor;

(2) carrying out hydrothermal reaction on the precursor and the pretreated nickel foam at the temperature of 150-180 ℃ for 18-24 hours to obtain the MoO_xS_y/Ni₃S₂a/NF complex.

The inventors have surprisingly found in their studies that it is possible to obtain intermediate Mo when the reaction takes place in the presence of CTABⁿ⁺(+4<n<+6) amorphous MoO_xS_yThe reaction temperature also affected the product formation and the inventors found that MoS began to appear when the reaction temperature reached 180 deg.C₂The valence of Mo is Mo⁴⁺And intermediate Moⁿ⁺(+4<n<+ 6); when the reaction temperature is lower than 150 ℃, the temperature can not meet the vulcanization requirement, and the product mainly contains Mo⁶⁺Of MoO_x(ii) a When the reaction temperature is between 150 ℃ and 180 ℃, the synthesized product is intermediate Moⁿ⁺(+4<n<+6) amorphous MoO_xS_yAnd does not contain MoS₂。

In some embodiments of the second aspect of the present application, the molar ratio of molybdenum, sulfur, cetyltrimethylammonium bromide is 1 (8-12) to (1-4); preferably 1 (8-12) to 1.5-2.5.

The inventors have unexpectedly found in their studies that the amount of CTAB has a large influence on the electrocatalytic properties of the product, when the ratio of the amount of molybdenum to CTAB is in the range of 1: (1.5-2.5), the resulting composite has higher catalytic performance.

In some embodiments of the second aspect of the present application, the volume ratio of water to ethanol is 1 (0.8-1.2).

In some embodiments of the second aspect of the present application, the concentration of the molybdate in the mixed solvent is from 30 to 50 mmol/L.

In some embodiments of the second aspect of the present application, the molybdate is selected from at least one of sodium molybdate and ammonium molybdate; the sulfur source is at least one selected from thiourea and sodium thiosulfate.

The inventors have found that the use of the above molybdate, a sulfur source, and further a specific amount ratio is advantageous for obtaining MoO having uniform amorphous molybdenum oxysulfide microspheres_xS_y/Ni₃S₂a/NF complex.

In some embodiments of the second aspect of the present application, the pre-treating comprises: soaking with 4.5-5.5% (w/w) hydrochloric acid for 20-40 min, and ultrasonic cleaning with acetone, deionized water and ethanol for 10-20 min.

In a third aspect, the present application provides the MoO provided in the first aspect of the present application_xS_y/Ni₃S₂The use of/NF complexes in electrocatalytic hydrogen evolution.

MoO_xS_y/Ni₃S₂Synthesis of/NF Complex

Example 1

1. Foam nickel pretreatment

Shearing 2 × 2cm of foamed nickel, soaking in 5% (w/w) hydrochloric acid solution for 30min, and sequentially ultrasonic cleaning with acetone, deionized water and ethanol for 15 min. The weight of the now bare nickel foam is weighed and recorded as m₀。

2、MoO_xS_y/Ni₃S₂Synthesis of/NF Complex

0.483g (1.0mmol) of Na was weighed₂MoO₄·2H₂O and 0.364g (1.0mmol) CTAB (C)₁₆H₃₃(CH₃)₃NBr), dissolved in 30mL of a mixture of ethanol and deionized water (volume ratio 1:1), and magnetically stirred for 30 min. Further, 0.760g (10mmol) of thiourea (CH) was added₄N₂S), magnetically stirring for 30min to form a clear and transparent precursor solution, and transferring to 50mL of solution containing polytetrafluoroethyleneAnd (3) immersing the pretreated foamed nickel in a stainless steel hot reaction kettle with an ethylene lining, and putting the immersed foamed nickel into an oven to react for 18 to 24 hours at 160 ℃. After the reaction is finished, naturally cooling the reaction kettle to room temperature, washing the product for a plurality of times by using deionized water and ethanol, drying at 45 ℃, weighing, and recording the mass as m₁，(m₁-m₀)/4cm²I.e. the loading of the active material. The product was noted as 160-1CTAB (160 denotes reaction temperature of 160 ℃ C., 1CTAB denotes moles of CTAB of 1 mmol).

Example 2

The product was taken as 160-2CTAB, identical to example 1, except that CTAB was used in an amount of 0.728g (2.0 mmol).

Example 3

The product was taken as 160-3CTAB, identical to example 1, except that the amount of CTAB used was adjusted to 1.092g (3.0 mmol).

Example 4

The product was taken as 160-4CTAB, identical to example 1, except that the amount of CTAB was adjusted to 1.456g (4.0 mmol).

Example 5

The product was recorded as 180-2CTAB, the same as in example 2, except that the reaction temperature was adjusted to 180 ℃.

Comparative example 1

The reaction was carried out in the same manner as in example 2 except that CTAB was not added to the reaction system, and the product was designated as 160-nocTAB.

Comparative example 2

The reaction was carried out in the same manner as in example 5 except that CTAB was not added to the reaction system, and the product was designated as 180-nocTAB.

Ni₃S₂Synthesis of/NF

2g (26.27mmol) Thiourea (CH)₄N₂S) is dissolved in a mixed solution of 33mL deionized water and 16mL hydrazine hydrate, a piece of foam nickel after 2X 2cm pretreatment is added, the mixture is transferred to an 80mL reaction kettle and reacts for 24 hours at 200 ℃ to obtain a comparative sample Ni₃S₂/NF。

The loading of the products obtained in each example and comparative example are shown in table 1.

TABLE 1 catalyst loading on foamed nickel substrate

	Sample name	Load (mg/cm)2)
			Example 1	160-1CTAB	3.79
Example 2	160-2CTAB	3.82
			Example 3	160-3CTAB	3.82
Example 4	160-4CTAB	3.82
			Example 5	180-2CTAB	3.82
Comparative example 1	160-no CTAB	3.81
			Comparative example 2	180-no CTAB	3.81
Commercial catalysts	Pt-C/NF	3.82

MoO_xS_y/Ni₃S₂Characterization of/NF

X-ray diffraction (XRD) analysis

The results of XRD analysis of the products of examples 1-5 and comparative examples 1, 2 are shown in FIGS. 1A-1C. As can be seen from FIGS. 1A-1C, all the products showed diffraction peaks at 21.8 °, 31.2 °, 37.8 °, 50.2 ° and 55.2 °, corresponding to Ni₃S₂(PDF card number 44-1418) (101), (110), (003), (113) and (122) indicating that the added sulfur source reacted with the Ni in the nickel foam to form Ni₃S₂. In addition, diffraction peaks of cubic phase Ni (PDF 04-0850) were also observed, which were assigned to elemental nickel. As can be seen in FIGS. 1A and 1B, MoS was not observed in all products synthesized at 160 deg.C_xOr MoO_xCorresponding diffraction peaks, indicating molybdenum oxysulfide (MoO)_xS_y) Present in amorphous form. As can be seen from FIG. 1C, when the temperature was increased to 180 ℃, a weak peak appeared at 16.0 ° (designated by '■' in the figure), indicating a small amount of crystalline phase MoS₂And (4) generating.

2. Analysis of electron microscope results

Scanning Electron Microscope (SEM) photographs of the products of examples 2 and 5 and comparative examples 1 and 2 are shown in FIGS. 2A to 2D, and it can be seen from FIGS. 2A and 2D that, without CTAB added, the products 160-noctaB and 180-noctaB are irregular particles, and in FIG. 2B, the composite 160-2CTAB is a regular micron sphere (2-3 μm in diameter), indicating that the addition of CTAB promotes amorphous MoO_xS_yAnd (4) producing the micro-spheres. As can be seen in FIG. 2C, the increase in reaction temperature causes the non-uniform size of the microspheres formed by 180-2CTAB of the composite.

Transmission Electron Microscopy (TEM) micrograph of the composite of example 2As shown in fig. 3. As can be seen from the B-plot, the average diameter of the composite 160-2CTAB microspheres was 2 μm, consistent with the SEM results of FIG. 2B. The a and c images are High Resolution Transmission Electron Microscopy (HRTEM) images of the b image, in which Ni of 0.28 and 0.40nm can be observed, respectively₃S₂(110) And (101) no discernible lattice of the other phase is observed, indicating that the other species may be amorphous; amorphous phase and Ni₃S₂The phase boundary is clearly visible (as shown by the dotted lines in panels a and c), indicating MoO in the product_xS_yAnd Ni₃S₂Staggered growth with abundant MoO_xS_yAnd Ni₃S₂A heterogeneous interface therebetween. The results of high-angle annular dark field-high resolution transmission electron microscopy (HAADF-STEM) show the element distribution in the composite 160-2CTAB, and the results are shown in a d chart, which shows that S and O exist besides Mo and Ni, and the product contains S and O, namely molybdenum oxysulfide is obtained.

3. Analysis of complex valence state

The valence states of Mo, S and Ni elements in the products of examples 2 and 5 and comparative examples 1 and 2 were analyzed by X-ray photoelectron spectroscopy (XPS), and the results are shown in FIGS. 4A to 4C. As can be seen from the a diagram of FIG. 4A, 233.9(Mo 3 d) in 160-2CTAB_3/2) And 230.7(Mo 3 d)_5/2) Bonding energy of the corresponding Mo⁵⁺Implying the intermediate valence of Moⁿ⁺(4<n<6, n is close to 5), since only one pair of peaks is observed in the figure, the MoO is proved to be contained_xS_yIs a pure phase. The a' plot shows that if CTAB is not added in the reaction, 160-no CTAB prepared has only one pair of Mo at 235.6 and 232.4eV⁶⁺Peak of (1), Mo is 160-2CTAB (-Mo)⁵⁺) And 160-no CTAB (Mo)⁶⁺) The different valence states between them highlight the role of CTAB in controlling the redox process. In contrast, the b plot shows that at 180 deg.C, there are two sets of peaks for 180-2CTAB, and the binding energy is higher, 234.1 and 230.9eV, indicating that Mo^m+(m>n), and furthermore, the binding energies of 232.4 and 229.2eV correspond to Mo⁴⁺3d_3/2And Mo⁴⁺3d_5/2The product synthesized under the high temperature condition is proved to contain MoS₂. As can be seen from the b' diagram, pair 180-no CTAB, except Mo⁶⁺In addition to the peaks (235.6 and 232.4eV), there is a pair of peaks at 232.0 and 228.8eV assigned to MoS₂Mo of⁴⁺Indicates that higher temperatures favor MoS₂And (4) generating. FIG. 4B is an XPS spectrum of S2 p demonstrating that all products contain S^2-And S₂ ^2-. FIG. 4C is an XPS spectrum of Ni, demonstrating that the products all contain Ni²⁺And Ni⁰Derived from Ni₃S₂And a foamed nickel substrate.

The Raman spectrum (Raman) results of the products of example 2 and comparative example 1 are shown in the c diagram of FIG. 4A, and are 250-350 cm^-1The peak of (A) belongs to ν (Mo-S); 800-950cm^-1The peak at (A) was assigned to v (Mo-O), and the peak was observed only in 160-2CTAB, confirming the presence of Mo-O bonds in 160-2 CTAB. The combination of X-ray photoelectron spectroscopy shows that Mo is added into the product without CTAB⁶⁺Derived from MoS₄ ^2-Rather than MoO₄ ^2-。

Infrared (FT-IR) spectra are shown in d of FIG. 4A, 945 and 875cm in 160-2CTAB^-1The absorption peaks at (a) are derived from the vibrations of Mo ═ O and Mo — O, respectively. While neither IR nor Raman of 160-nocctab found the presence of Mo ═ O or Mo — O, demonstrating that the addition of CTAB promotes the doping of oxygen into the molybdenum sulphide, thereby producing molybdenum oxysulphide.

4. Analysis of product Structure

To further study Mo in MoO_xS_yThe present example characterizes the 160-2CTAB complex of example 2 by an X-ray absorbing near-edge structure (XANES). The results are shown in FIG. 5. As can be seen from diagram a of FIG. 5, MoO_xS_yL of₃Shape of edge and MoS₂(Mo⁴⁺) Different, illustrate MoO_xS_yThe oxidation state of medium Mo is not + 4. MoO_xS_yAnd MoO₃Mo of (3)₃The edge has a split, which can be explained as the first peak (t) of the splitting of the ligand field of the d orbital_2gPeak) decreases linearly with electron fill. With MoO₃(Mo⁶⁺) In contrast, MoO_xS_yT of_2gThe weaker peak means that the oxidation state of Mo is below + 6. Diagram b of FIG. 5 is MoO_xS_y，MoO₃(Mo⁶⁺) And MoS₂(Mo⁴⁺) Normalized Mo K-edge XANES graph of (1). The energy shift of the absorption edge of Mo K-edge indicates the change of Mo oxidation state. As can be seen, MoO_xS_yHas an absorption edge energy higher than that of MoS₂To be lower than MoO₃(inset in b of FIG. 5), illustrating MoO_xS_yIn which Mo is in an oxidation state of>4 and<6. as shown in the c diagram of FIG. 5, MoO_xS_yThe average valence of medium Mo is +5.24, which can be written in general as + (5+ δ) in view of the amorphous nature of the material, indicating that the Mo oxidation state is in an intermediate state, not the common 4 or 6 valence. An extended X-ray absorption fine structure (EXAFS) analysis method is adopted, the coordination structure and the local bond length of Mo are researched and are shown in a d diagram of fig. 5, and good fitting of Fourier transform in an R space is obtained. MoS₂、MoO₃、MoO_xS_yThe local structural parameters of (a) are shown in table 2. For MoS₂In aThe peak at (uncorrected phase shift) corresponds to the Mo-S bond, MoO₃Are respectively two main peaks ofAndcorresponding to Mo-O_IAnd Mo-O_IIBond, with reported Mo-O bond length rangeAnd (5) the consistency is achieved. The Mo-O distances of MoOxSy are respectively 1.68 (Mo-O)_I)And(Mo-O_II) At a Mo-S distance ofMo-O_I、Mo-O_IIAnd the coordination numbers of Mo-S are 1.2, 1.7 and 2.0, respectively.

TABLE 2MoO_xS_y(160-2CTAB) and MoS as standard₂And MoO₃Mo EXAFS fitting results

5. Construction of a structural model

By DFT calculation, using [ Mo ]₄O₈S₄]Chain as model for amorphous MoO_xS_yLocal structural features of (1). The model of 160-2CTAB is shown in FIG. 6, wherein, a is a front view, b is a top view, [ Mo ]₄S₈O₄]Chain and Ni₃S₂The (101) crystal face of (A) has an effect of forming Ni-O and Ni-S bonds (the model is marked as [ Mo ]₄O₈S₄]@Ni₃S₂(101) Forming a heterojunction. Due to [ Mo ]₄O₈S₄]The distances between the S and O atoms and the Ni atoms are different, and the partially bridged O atoms cannot be connected with Ni₃S₂Ni leads to Ni₃S₂The most recent Mo at the surface has a higher oxidation state. The model structure obtains the average charge state of Mo to be +5.32, which is very close to the average valence state of Mo obtained by XANES test to be +5.24, and the reasonability of the structural model is shown. This Mo valence state greater than 5 leads to Mo ═ O instability, these double bonds being activated in favor of H⁺Adsorption of (2) and H produced₂Desorption of (3).

Electrocatalytic performance test

1. Test for catalytic Activity

The electrocatalytic Hydrogen Evolution (HER) performance of the products of examples 1-5 and comparative example 1 was tested and compared to a commercial Pt/C catalyst (20 wt% Pt/C) and Ni₃S₂The control was/NF. The test adopts a standard three-electrode system, the obtained 1 multiplied by 2cm product is clamped on an electrode clamp to be used as a working electrode, and a counter electrode is a graphite electrodeAnd the reference electrode is a saturated Ag/AgCl electrode. Electrolyte solution of 0.5M H₂SO₄. The polarization curves were measured by Linear Sweep Voltammetry (LSV) at a sweep rate of 2mV/s, with the products of examples 1-5 and comparative example 1 at 0.5M H₂SO₄The LSV curves in (a) are shown in fig. 7 and a graph in fig. 8, where the voltages have been converted to potential values with respect to the reversible hydrogen electrode. As can be seen from the graph, when the current density reached 10mA/cm²Sample 160-no CTAB requires an overpotential (. eta.) of₁₀) Is 128 mV; eta of 160-1CTAB₁₀Reduced to 82 mV; eta of 160-2CTAB₁₀Only 58 mV; eta of 160-3CTAB₁₀Is 100 mV; eta of 160-4CTAB₁₀Is 107 mV; it can be seen that compared with the product without CTAB, the overpotential is reduced after CTAB is added, the catalytic performance is obviously improved, and the overpotential is firstly reduced and then increased with the increase of the adding amount of CTAB, wherein 160-2CTAB has the optimal performance, eta is optimal₁₀Is only 58mV, and therefore, in preparing the MoO of the present application_xS_y/Ni₃S₂In the case of the/NF composite, the molar ratio of Mo to CTAB is 1 (1-4), preferably 1: (1.5-2.5). Meanwhile, HER performance of 180-2CTAB is shown in graph a of FIG. 8, eta₁₀86mV compared with 160-2CTAB catalytic performance, which shows that excessive reaction temperature can cause the catalytic hydrogen evolution performance of the composite body to be reduced, so the reaction temperature of the application is 150-180 ℃. Wherein, when the reaction temperature is 160 ℃ and the CTAB addition amount is 2mmol, the performance of the obtained catalyst is optimal.

In addition, the MoO prepared in example 2 of the present application will be_xS_y/Ni₃S₂Commercial Pt/C catalysts with the same/NF loading were loaded on NF (Pt-C/NF), with η₁₀At 48mV, the MoO synthesized in example 2 of the present application can be seen_xS_y/Ni₃S₂The catalytic performance of the catalyst is close to that of a commercial Pt/C catalyst, and the catalyst is molybdenum-sulfur oxide, so that the cost is greatly reduced compared with noble metal Pt, and the catalyst has a good commercial application prospect.

FIG. 8, panel b, shows that the Tafel slope of 160-2CTAB is only 43mV/dec, close to that of Pt/C catalyst (36mV/dec), confirming that it possesses fast HER reaction kinetics, which in turn demonstrates its excellent electrical propertiesCatalytic performance. FIG. 8 c is a graph of 160-2CTAB,160-no CTAB and Ni tested in the frequency range of 0.01Hz to 100kHz₃S₂Nyquist plot of/NF from the equivalent circuit diagram (FIG. 9) fit, the charge transfer resistance (R) is known_ct) The resistance values and the results are shown in Table 3. It is known that R of 160-2CTAB_ctThe lowest value, only 2.52 Ω, confirms its excellent conductivity, which is beneficial for improving HER performance. To further confirm the excellent electrocatalytic performance of 160-2CTAB, the double layer capacitance (C) was tested in this example_dl) Value of (A), C_dlProportional to the electrochemically active surface area of the electrocatalyst, C_dlCan be used to measure the electrochemically active surface area of the electrode. The current density difference is plotted against the sweep rate (e diagram in FIG. 8) by testing the cyclic voltammetry (CV, d diagram in FIG. 8) of 160-2CTAB in the non-faradaic region, and half of the slope of the linear fit is C_dValue, as shown, of 160-2CTAB C_dIs 81.5mF/cm²The value is far greater than the value reported in most literatures, and the 160-2CTAB is proved to have a large electrochemical active surface area, expose more active sites and be beneficial to the improvement of HER performance. Meanwhile, the Faraday efficiency of 160-2CTAB was also measured in this example, as shown in the f-diagram of FIG. 8, and the results show that the MoO of the present application_xS_y/Ni₃S₂Actual H evolution from NF₂The volume is very close to the theoretical value, and the Faraday efficiency is close to 100%.

TABLE 3.160-2 CTAB,160-no CTAB and Ni₃S₂Nf Nyquist diagram parameter fitting according to equivalent circuit diagram

2. Evaluation of electrochemical stability

Electrochemical stability is another important factor in evaluating catalyst performance, and the results of the chemical stability test of 160-2CTAB of example 2 of the present application are shown in FIG. 10. Wherein, the graph a of FIG. 10 is a current density graph (I-t) of 160-2CTAB with time under a constant voltage of 120mV, which can be seen to be stably maintainedThe electrolysis is continued for more than 200h, and the current density retention rate is nearly 99 percent, which proves that 160-2CTAB has very high stability. The inset in a is the generation of H on the electrode when water is electrolyzed and reacted for 10H₂Photograph of bubbles, very many bubbles were visible, H₂The yield is rich. And b, the graph is an enlargement of the graph a in the interval of 45.40-45.75h, and the accumulation-release process of the bubbles is shown. In addition, the present application tested the Linear Sweep Voltammetry (LSV) curves of 160-2CTAB before and after I-t test, and the results are shown in the c diagram of FIG. 10, which shows that the HER reaction is over 200h, the overpotential change is not large under the same current density, the HER activity is almost not attenuated, and the excellent electrochemical stability of 160-2CTAB is confirmed. FIG. 10 d and e are scanning electron microscope photographs of the 160-2CTAB complex before and after the test, and it can be seen that there is no significant change in morphology before and after the I-t test, further proving the superior stability of 160-2 CTAB.

The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.