CN115233250A - Sulfur-rich vacancy nickel sulfide nanosheet array structure catalyst material and preparation method and application thereof - Google Patents

Sulfur-rich vacancy nickel sulfide nanosheet array structure catalyst material and preparation method and application thereof Download PDF

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CN115233250A
CN115233250A CN202210713874.6A CN202210713874A CN115233250A CN 115233250 A CN115233250 A CN 115233250A CN 202210713874 A CN202210713874 A CN 202210713874A CN 115233250 A CN115233250 A CN 115233250A
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sulfur
array structure
nickel
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郑灵霞
郑华均
吕卓清
徐鹏辉
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses a sulfur-rich vacancy nickel sulfide nanosheet array structure catalyst material, and a preparation method and application thereof 3 S 2 Introducing sulfur vacancy into an ultrathin nanosheet precursor by a high-temperature calcination method in an inert atmosphere to prepare V s ‑Ni 3 S 2 The preparation method of the nano-sheet array structure material has the advantages of simple process, low cost, environmental friendliness and the like, and the introduction of sulfur vacancies effectively regulates and controls the electronic structure and carrier concentration of the materialThe intrinsic conductivity of the material, the diversity of redox reactions and the adsorption performance of reactants are improved; the defect state catalyst can be used for preparing benzoic acid by electrocatalytic oxidation of benzyl alcohol, the conversion rate can reach 99%, and the selectivity can reach 99%.

Description

Sulfur-rich vacancy nickel sulfide nanosheet array structure catalyst material and preparation method and application thereof
Technical Field
The invention belongs to the field of catalytic preparation technology and organic electro-catalysis, and particularly relates to a sulfur vacancy-rich nickel sulfide nanosheet array structure catalyst material, a preparation method thereof, and application thereof in an electrocatalytic oxidation benzyl alcohol reaction.
Background
At present, the production of benzoic acid on an industrial scale almost entirely depends on a resource and energy intensive toluene oxidation process, which usually requires high temperature (150 ℃ to 170 ℃), high pressure (1 MPa) and the use of toxic chemical oxidants, and has the problems of harsh reaction conditions, high cost and serious environmental pollution. Therefore, the development of new sustainable, environmentally friendly methods for benzoic acid production is of great importance to alleviate the increasingly prominent energy and environmental problems. The electrocatalytic oxidation of the benzyl alcohol in a water system has the advantages of mild reaction conditions, low thermodynamic barrier, greenness and energy conservation, and the main competitive reaction is the anode Oxygen Evolution Reaction (OER) of water cracking. How to effectively improve the selectivity of the reaction and improve the yield of the target product benzoic acid is a key problem which needs to be solved urgently. Based on this, the rational design of the electrocatalyst becomes crucial.
Transition metal sulfides are considered to be the most promising candidates for replacing noble metal-based catalysts due to their lower cost, abundant phase structure and good stability. Wherein nickel sulfide Ni 3 S 2 Materials are favored for their excellent conductivity, low cost and good intrinsic catalytic activity. To further increase Ni 3 S 2 The catalytic activity of the material, ni can be modified by making vacancy defects 3 S 2 The electronic structure realizes the regulation and control of the adsorption energy of the organic substrate on the surface of the catalyst, and finally promotes the high-efficiency operation of the catalytic reaction. For the regulation of the vacancy in nickel sulfide, it has been reported (patent CN 108677207 a) to regulate the oxygen vacancy of the precursor oxide to realize Ni 3 S 2 The concentration of the middle sulfur vacancy is easy to change in the process of preparing sulfide through the subsequent vulcanization treatment in consideration of the instability of oxygen vacancy defects, and in addition, the content of the oxygen vacancy cannot represent the concentration of the sulfur vacancy.
In view of the above, the present invention prepares Ni by direct in-situ growth on a foamed nickel substrate 3 S 2 Nanosheet arrayStructural precursor, and then directly preparing Ni rich in sulfur vacancy by annealing treatment under the protection of inert gas 3 S 2 Catalyst (V) s -Ni 3 S 2 ). The method has simple process and strong operability, and the foam nickel is used as a supporting substrate material and a nickel source to participate in the reaction, thereby saving the cost. The prepared defect-state catalyst material can realize the high-efficiency electrooxidation of benzyl alcohol to produce benzoic acid under a lower potential, the yield is as high as 99.99%, and the Faraday efficiency is 99.99%.
Disclosure of Invention
The invention provides Ni rich in sulfur vacancy 3 S 2 The catalyst with the nano-sheet array structure and the preparation method thereof are applied to the organic synthesis reaction for producing benzoic acid by electrooxidation of benzyl alcohol.
The method takes the nickel sulfide nanosheet material grown in situ as a precursor, introduces sulfur vacancy in a calcining mode in an inert gas atmosphere, and prepares Ni rich in sulfur vacancy 3 S 2 Nanosheet array structure catalyst V s -Ni 3 S 2 (ii) a The introduction of the sulfur vacancy can effectively regulate and control the electronic structure and the carrier concentration of the metal sulfide material, and improve the intrinsic conductivity and the diversity of oxidation reduction reaction, thereby improving the adsorption capacity to organic reactants and further promoting the high-efficiency catalytic reaction.
The preparation method provided by the invention has the advantages of simple process, short time consumption, low cost and the like. The material is used as an organic micromolecular electrocatalyst, and shows excellent benzyl alcohol electrocatalysis performance and catalytic stability.
The technical scheme of the invention is as follows:
a sulfur vacancy-rich nickel sulfide nanosheet array structure catalyst material is prepared by growing Ni with sulfur vacancies on a foam nickel substrate in situ 3 S 2 A nanosheet array structure;
the Ni having a sulfur vacancy 3 S 2 The nano-sheet array structure is obtained by adopting thiourea as a sulfur source, deionized water as a solvent and foamed nickel as a current collector substrate and a nickel source and growing the materials on the foamed nickel substrate in situ by a hydrothermal methodTo Ni 3 S 2 And the precursor material is formed by introducing sulfur vacancy in a calcining mode under the protection of inert atmosphere.
The preparation method of the sulfur-rich vacancy nickel sulfide nanosheet array structure catalyst material comprises the following steps:
(1) Dissolving thiourea in deionized water, adding a foam Nickel (NF) substrate, carrying out hydrothermal reaction for 1-10 h at 100-160 ℃, taking out, washing and drying to obtain Ni on the foam nickel substrate 3 S 2 Precursor material (denoted as Ni) 3 S 2 )；
The foam nickel substrate needs to be cleaned before use, and the method specifically comprises the following steps: ultrasonically cleaning the mixture for 15 minutes by using acetone, deionized water, a 3M HCl solution, deionized water and ethanol in sequence, and drying the mixture in vacuum for later use;
the concentration of the solution obtained by dissolving the thiourea in the deionized water is 1-5 mmol/L;
(2) Will be loaded with Ni 3 S 2 Putting the foam nickel of the precursor material into a tube furnace, heating to 250-450 ℃ under the protection of inert gas, calcining for 0.5-4.5 h to obtain the sulfur-rich vacancy nickel sulfide nanosheet array structure catalyst material (marked as V) s -Ni 3 S 2 )；
The inert gas is nitrogen, argon or helium;
the temperature rise rate of the calcination is 5-15 ℃/min.
Particularly preferably, the preparation method of the sulfur-rich vacancy nickel sulfide nanosheet array structure catalyst material comprises the following steps:
weighing thiourea, adding the thiourea into deionized water to form a reaction solution, wherein the concentration of the thiourea in the reaction solution is 1.445mM, then magnetically stirring for 30min at the rotating speed of 600rpm to obtain a uniform solution, and transferring the uniform solution into a hydrothermal kettle; then dry clean nickel foam (area of nickel foam is 1X 3 cm) 2 ) Heating to 150 ℃ for reaction for 5h, naturally cooling the hydrothermal kettle to room temperature, taking out foamed nickel, washing with deionized water and ethanol, and drying in a vacuum drying oven to obtain the Ni-loaded material 3 S 2 Foamed nickel of precursor material is put into a tube furnace and maintained in argon atmosphereAnd (3) heating to 300 ℃ under protection, and calcining for 0.5h to obtain the sulfur-rich vacancy nickel sulfide nanosheet array structure catalyst material.
The sulfur-rich vacancy nickel sulfide nanosheet array structure catalyst material can be applied to the reaction of generating benzoic acid through electrooxidation of benzyl alcohol, the conversion rate of the benzyl alcohol reaches 100%, and the yield of the benzoic acid reaches 99%.
In the reaction, the catalyst material with the sulfur-rich vacancy nickel sulfide nanosheet array structure can be directly used as an electrode material and can also be used as a catalyst.
Compared with the prior anode oxidation electrode material, the invention has the following beneficial effects:
(1) The foam nickel is used as a support material to ensure the excellent conductivity of the whole material, and is also used as a nickel source precursor to participate in the reaction for preparing the nickel sulfide catalyst, so that the use of a conductive agent and a binder is avoided, the material cost is effectively reduced, and the stability of the catalyst material is also improved.
(2) Directly calcining the sulfide to prepare sulfur vacancies, and directly adjusting the vacancy concentration by regulating and controlling the calcining temperature and the calcining time so as to optimize the catalytic activity.
(3) The calcination treatment method under inert atmosphere changes Ni 3 S 2 The exposed crystal face of the material and the optimized crystal face enhance the adsorption capacity of the material to the organic micromolecular substrate, so that the benzyl alcohol oxidation performance of the material is greatly improved.
(4) The nickel sulfide material prepared by the invention is a three-dimensional hierarchical structure stacked by two-dimensional nanosheets, the increased specific surface area is beneficial to exposing more active sites, and the interface contact resistance of the electrolyte and the catalytic material is effectively reduced.
(5) The preparation method has the advantages of simple operation, good reproducibility, low cost and environmental friendliness. The prepared V s -Ni 3 S 2 The catalyst material is used for the benzene methanol electrooxidation reaction, shows lower overpotential, higher yield, selectivity and Faraday efficiency in a 20mM benzene methanol solution, and has wider application prospect.
Drawings
FIG. 1 shows (a, b) Ni obtained in example 1 3 S 2 5h and (c, d) V s -Ni 3 S 2 Scanning Electron Micrographs (SEM) of the electrode material.
FIG. 2 shows (a) Ni obtained in example 1 3 S 2 -5h and (b) V s -Ni 3 S 2 X-ray diffraction pattern (XRD) of the electrode material.
FIG. 3 shows Ni obtained in example 1 3 S 2 5h and V s -Ni 3 S 2 Raman map of the material.
FIG. 4 shows Ni obtained in example 1 3 S 2 5h and V s -Ni 3 S 2 X-ray photoelectron spectroscopy (XPS) of a material.
FIG. 5 shows Ni obtained in example 1 3 S 2 5h and Vs-Ni 3 S 2 Electron paramagnetic resonance spectroscopy (EPR) of a material.
FIG. 6 shows (a, c) Ni obtained in example 1 3 S 2 5h and (b, d) Vs-Ni 3 S 2 Linear voltammetric scan (LSV) and Tafel plots of the material.
FIG. 7 shows Ni obtained in example 1 3 S 2 5h and V s -Ni 3 S 2 BA conversion of the material at different potentials, yield of benzaldehyde and benzoic acid as oxidation products are shown.
FIG. 8 shows V obtained in example 1 s -Ni 3 S 2 Stability profile of electrochemical oxidation of benzyl alcohol of electrode material.
FIG. 9 shows (a, b) Ni obtained in example 3 3 S 2 8h and (c, d) V s -Ni 3 S 2 SEM images of 8h material at different magnifications.
FIG. 10 shows Ni (a) obtained in example 3 3 S 2 -8h and (b) V s -Ni 3 S 2 Linear voltammetric scan (LSV) and Tafel plot of 8h material.
FIG. 11 shows Ni obtained in example 3 3 S 2 8h and Vs-Ni 3 S 2 -8h material after electrolysis at 1.35Vvs. RHE for 120 min, minEliminating power consumption 95C (a) and 137C (b); (c) Ni 3 S 2 8h and (d) Vs-Ni 3 S 2 BA conversion of-8 h material at 1.35V vs. RHE potential, yield plot of oxidation products benzaldehyde and benzoic acid.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be further illustrated with reference to specific examples, which are provided for illustration only and are not intended to limit the scope of the invention. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
The nickel foam used in the examples below was purchased from Tianjin Avicent chemical technology, inc., and had a thickness of 1.5mm and a porosity of 98%.
Example 1: sulfur-rich vacancy Ni 3 S 2 Preparation of nanosheet array structure catalyst
Dissolving 1.1mg of thiourea in 10mL of deionized water, uniformly stirring, and transferring the solution to a 25mL hydrothermal kettle; adding pretreated 1X 3cm 2 A nickel foam matrix was reacted at 150 ℃ for 5 hours. Naturally cooling to room temperature after the reaction is finished, taking out the foam nickel substrate, washing with deionized water and absolute ethyl alcohol for a plurality of times, and drying overnight under vacuum at 60 ℃ to obtain Ni 3 S 2 5h. Loading the obtained precursor material Ni 3 S 2 Putting the foamed nickel of-5 h into a tube furnace, heating to 300 ℃ under the protection of Ar gas, and calcining for 0.5h to finally obtain V s -Ni 3 S 2 Electrocatalyst samples.
Ni can be clearly seen in the SEM of FIG. 1 (a, b) 3 S 2 The-5 h sample exhibited a three-dimensional hierarchical structure of two-dimensional nanoplate stacking. V obtained after high-temperature treatment s -Ni 3 S 2 The morphology of the nanosheet array of the material remains substantially intact. XRD chart of FIG. 2 shows Ni 3 S 2 5h and V s -Ni 3 S 2 The diffraction peak of the material corresponds to that of PDF card JCPDS No.44-1418, the nickel sulfide is in a hexagonal system, and for Ni 3 S 2 -5h samples at 2 θ values of 31.1 °, 38.3 °, 50.1 ° and 54.6 °, respectivelyThe diffraction peak of (A) corresponds to Ni 3 S 2 The (110), (021), (211) and (104) crystal planes of (A). And V s -Ni 3 S 2 The diffraction peaks of the material at 2 theta values of 31.1 degrees, 37.7 degrees, 38.3 degrees, 50.1 degrees and 54.6 degrees respectively correspond to Ni 3 S 2 The (110), (003), (021), (211) and (104) planes of (A). Comparing the two figures, it can be seen that calcination causes a change in the exposed crystal planes of the nickel sulfide: the (110) plane peak became strong and the (003) plane peak became clear.
FIG. 3 shows Ni obtained in example 1 3 S 2 5h and V s -Ni 3 S 2 Raman map of the material. 200,220,274,322, and 355cm -1 These characteristic peaks indicate that hexagonal nickel sulfide materials are successfully prepared, and are consistent with XRD results. Comparing the two materials, the characteristic peaks shift to low wave number direction and become wider, which indicates that V is s -Ni 3 S 2 The degree of disorder in the medium-short range increases, indicating the generation of defects.
FIG. 4 shows Ni obtained in example 1 3 S 2 5h and V s -Ni 3 S 2 S2 p XPS plot of material. From the figure, it can be seen that S2 p 1/2 And 2p 3/2 The bond energy shifts to the lower bond energy direction, indicating an increased concentration of S vacancies. FIG. 5 shows Ni obtained in example 1 3 S 2 5h and Vs-Ni 3 S 2 EPR map of material. An increase in the intensity of the characteristic peak at g =0.2003 indicates that more sulfur vacancies are generated.
Example 2: ni rich in sulfur vacancies 3 S 2 Application of nanosheet catalyst in preparation of benzoic acid by electrooxidation of benzyl alcohol
In a 1M KOH solution, the performance of the catalyst material for electrooxidation catalysis of Benzyl Alcohol (BA) is systematically studied in an H-type electrolytic cell by using the catalyst material prepared in example 1 as a working electrode, a platinum sheet as a counter electrode and an Hg/HgO electrode as a reference electrode. In FIG. 6, a and b show Ni, respectively 3 S 2 5h and V s -Ni 3 S 2 Linear Sweep Voltammetry (LSV) curves for BA oxidation catalyzed in 1.0M KOH and oxygen evolution reaction of water (OER). In the absence of BA, both catalysts were observedA distinct anodic peak with strong oxygen bubbles released at positive potentials above 1.4v vs. rhe. Ni 3 S 2 5h and V s -Ni 3 S 2 At 10mA cm -2 Are 1.448 and 1.436vvs.rhe, indicating that they both have good water oxidizing ability. The anodic peak current sharply increased after the addition of 30mM BA. Ni 3 S 2 5h reached 74.8mA cm at 1.343Vvs. RHE -2 ，V s -Ni 3 S 2 Reaches 94.2 mA cm at 1.336Vvs -2 This means that the defective nickel sulphide material contributes to the oxidation capability of BA. Namely, the abundant sulfur vacancy is beneficial to promoting the electro-oxidation reaction of the organic small molecular alcohol. This electrochemical process is also demonstrated on the tafel slope (c, d in fig. 6). V s -Ni 3 S 2 And Ni 3 S 2 Tafel slope of BAOR of-5 h was 33.45mV dec -1 And 57.52mV dec -1 106.21 mV · dec, lower than OER -1 And 114.83mV dec -1 。V s -Ni 3 S 2 Shows a smaller Tafel slope of BA electrooxidation and also shows V s -Ni 3 S 2 Has excellent electrooxidation reaction kinetics of benzyl alcohol.
FIG. 7 is Ni 3 S 2 5h and V s -Ni 3 S 2 BA conversion of the material at different potentials, yield of the oxidation products benzaldehyde and benzoic acid (initial reaction system with 30mM BA added in 1M KOH). By contrast, V is shown at 1.325Vvs s -Ni 3 S 2 Shows more excellent BA electro-oxidation reaction: by constant potential electrolysis for 100 min, ni 3 S 2 The electrolysis on the-5 h material resulted in a conversion of BA of 83.8%, a yield of benzoic acid of 67.8%, and a Faraday efficiency of 88.5% (a in FIG. 7), while V s -Ni 3 S 2 The electrolysis on the material resulted in 100% conversion of BA, 97.8% yield of benzoic acid and faradaic efficiency close to 100% (b in figure 7). Ni when the electrolytic potential is increased to 1.35Vvs 3 S 2 5h (c in FIG. 7) and V s -Ni 3 S 2 (d in FIG. 7) can achieve nearly 100% conversion of BA to benzoic acid. FIG. 8 is V s -Ni 3 S 2 Stability profile of the material at 1.35v vs. rhe in cyclic electrolysis. It can be seen from the figure that good BAOR performance (conversion, yield, selectivity and faraday efficiency all approach 99%) is still achieved after 5 cycles. This indicates that the catalyst can be recycled many times.
Example 3: sulfur-rich vacancy Ni 3 S 2 Preparation and application of nanosheet array structure catalyst
Dissolving 1.1mg of thiourea in 10mL of deionized water, uniformly stirring, and transferring the solution to a 25mL hydrothermal kettle; adding pretreated 1X 3cm 2 A nickel foam matrix, and reacting at 150 ℃ for 8 hours. Naturally cooling to room temperature after the reaction is finished, taking out the foam nickel substrate, washing with deionized water and absolute ethyl alcohol for a plurality of times, and drying overnight under vacuum at 60 ℃ to obtain Ni 3 S 2 8h is carried out. Loading the obtained precursor material Ni 3 S 2 Putting the foamed nickel of-8 h into a tube furnace, heating to 300 ℃ under the protection of argon gas, and calcining for 0.5h to finally obtain V s -Ni 3 S 2 -8h electrocatalyst sample.
FIG. 9 shows Ni obtained in example 3 3 S 2 -8h and V s -Ni 3 S 2 SEM images of 8h material at different magnifications. Ni can be clearly seen from SEM 3 S 2 Double-sheet stacking of the nanosheet array in the 8h sample (a, b in FIG. 9), and calcining with argon gas to obtain V s -Ni 3 S 2 The nanosheet surface in the 8h material became rough and thick (c, d in fig. 9).
In a 1M KOH solution, the performance of the catalyst material for electrooxidation and catalysis of Benzyl Alcohol (BA) is systematically researched in an H-shaped electrolytic cell by taking the prepared catalyst material as a working electrode, a platinum sheet as a counter electrode and an Hg/HgO electrode as a reference electrode. In FIG. 10, a and b show Ni, respectively 3 S 2 -8h and V s -Ni 3 S 2 -8h Linear Sweep Voltammetry (LSV) curve of BA oxidation catalyzed in 1.0M KOH and oxygen evolution reaction of water (OER). In the absence of BA, a distinct anodic peak was observed for both catalysts, also at positive potentials above 1.4v vs. rheStrong oxygen bubbles are released. The anodic peak current increased dramatically after the addition of 30mM BA. Ni 3 S 2 8h reached 68.8mA cm at 1.327Vvs. RHE -2 ，V s -Ni 3 S 2 RHE reached 74.6 mA-cm at 1.322Vvs -2 This means that the nickel sulfide material in a defect state has more excellent BA electrooxidability.
FIG. 11 shows Ni obtained in example 3 3 S 2 -8h and V s -Ni 3 S 2 Plot of electrolytic I-t of-8 h material at 1.35V vs. RHE and the BA conversion, yield of oxidation products benzaldehyde and benzoic acid (initial reaction system with 30mM BA added in 1M KOH). By comparison, ni was found to be present after 120 minutes of electrolysis at 1.35Vvs. RHE 3 S 2 -8h and V s -Ni 3 S 2 The-8 h material consumed electric charge 95C (a in FIG. 11) and 137C (b in FIG. 11), respectively, and the Faraday Efficiencies (FE) were 78.78% and 96.14%, respectively. V s -Ni 3 S 2 The-8 h material shows higher catalytic activity: BA conversion was 69.9%, yield was 65.89%, selectivity was 94.26% (d in FIG. 11), higher than Ni 3 S 2 61.54%,38.69% and 62.87% of 8h (c in fig. 11).

Claims (7)

1. The catalyst material with the sulfur vacancy-rich nickel sulfide nanosheet array structure is characterized by comprising a foamed nickel substrate, and Ni with sulfur vacancies and growing on the foamed nickel substrate in situ 3 S 2 A nanosheet array structure;
the Ni having a sulfur vacancy 3 S 2 The nano-sheet array structure adopts thiourea as a sulfur source, deionized water as a solvent, and foamed nickel as a current collector substrate and a nickel source, and Ni is obtained by in-situ growth on the foamed nickel substrate by a hydrothermal method 3 S 2 And the precursor material is formed by introducing sulfur vacancy in a calcining mode under the protection of inert atmosphere.
2. The preparation method of the sulfur-rich vacancy nickel sulfide nanosheet array structure catalyst material of claim 1, wherein the preparation method comprises:
(1) Dissolving thiourea in deionized water, adding a foam nickel substrate, carrying out hydrothermal reaction for 1-10 h at 100-160 ℃, taking out, washing and drying to obtain Ni on the foam nickel substrate 3 S 2 A precursor material;
(2) Will be loaded with Ni 3 S 2 Putting the foam nickel of the precursor material into a tube furnace, heating to 250-450 ℃ under the protection of inert gas, and calcining for 0.5-4.5 h to obtain the sulfur-rich vacancy nickel sulfide nanosheet array structure catalyst material.
3. The preparation method of the sulfur-rich vacancy nickel sulfide nanosheet array structure catalyst material of claim 2, wherein in step (1), the concentration of the solution obtained by dissolving thiourea in deionized water is 1 to 5mmol/L.
4. The method for preparing the sulfur-rich vacancy nickel sulfide nanosheet array structure catalyst material of claim 2, wherein in step (2), the temperature increase rate of the calcination is from 5 to 15 ℃/min.
5. The preparation method of the sulfur-rich vacancy nickel sulfide nanosheet array structure catalyst material of claim 2, wherein the preparation method comprises:
weighing thiourea, adding the thiourea into deionized water to form a reaction solution, wherein the concentration of the thiourea in the reaction solution is 1.445mM, then magnetically stirring for 30min at the rotating speed of 600rpm to obtain a uniform solution, and transferring the uniform solution into a hydrothermal kettle; adding dry and clean foamed nickel, heating to 150 ℃, reacting for 5 hours, naturally cooling the hydrothermal kettle to room temperature, taking out the foamed nickel, washing with deionized water and ethanol, and drying in a vacuum drying oven to obtain the Ni-loaded Ni 3 S 2 And putting the foam nickel of the precursor material into a tubular furnace, heating to 300 ℃ under the protection of argon gas, and calcining for 0.5h to obtain the sulfur-rich vacancy nickel sulfide nanosheet array structure catalyst material.
6. The application of the sulfur-rich vacancy nickel sulfide nanosheet array structure catalyst material as defined in claim 1 in the reaction of electrooxidation of benzyl alcohol to produce benzoic acid.
7. The use of claim 6, wherein the sulfur-rich vacancy nickel sulfide nanosheet array structure catalyst material is used directly as an electrode material or as a catalyst.
CN202210713874.6A 2022-06-22 2022-06-22 Sulfur-rich vacancy nickel sulfide nanosheet array structure catalyst material and preparation method and application thereof Pending CN115233250A (en)

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