CN117904670A - Controllable preparation of amorphous selenium coating-coated nickel selenide nanoparticles for methanol electrooxidation - Google Patents
Controllable preparation of amorphous selenium coating-coated nickel selenide nanoparticles for methanol electrooxidation Download PDFInfo
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- 239000011669 selenium Substances 0.000 title claims abstract description 97
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 39
- 239000011248 coating agent Substances 0.000 title claims abstract description 33
- 238000000576 coating method Methods 0.000 title claims abstract description 33
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title abstract description 54
- 238000006056 electrooxidation reaction Methods 0.000 title description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 22
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000019253 formic acid Nutrition 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000002086 nanomaterial Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 3
- 239000002159 nanocrystal Substances 0.000 claims 7
- 238000001291 vacuum drying Methods 0.000 claims 2
- 238000011049 filling Methods 0.000 claims 1
- 239000012456 homogeneous solution Substances 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000010411 electrocatalyst Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 10
- 238000009792 diffusion process Methods 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 229910002640 NiOOH Inorganic materials 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 241000252073 Anguilliformes Species 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
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- 150000001450 anions Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 239000007772 electrode material Substances 0.000 description 1
- 238000005430 electron energy loss spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
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- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Abstract
The invention provides a one-step hydrothermal synthesis method of amorphous selenium-coated nickel selenide nano particles for preparing formic acid from methanol by electrocatalytic reaction, which comprises the following steps: (1) A preparation of solution: adding nickel nitrate into 10ml of deionized water, and performing ultrasonic treatment for 30 minutes to obtain a homogeneous transparent solution A; (2) preparation of B solution: adding selenium powder into 10ml of deionized water, adding 1g of sodium borohydride serving as a reducing agent, and performing ultrasonic treatment until the selenium powder is completely dissolved to obtain a solution B; (3) preparation of mixed solution: pouring the solution A into the solution B, rapidly stirring, and fully and uniformly mixing; (4) hydrothermal reaction: the obtained mixed solution is put into a hydrothermal kettle to react for 12, 16, 20 or 24 hours at 180 ℃; (5) washing and drying: the obtained black solid is centrifugally washed for many times, and is dried for 24 hours under 60 DEG vacuum, thus obtaining amorphous selenium coated nickel selenide nanoparticle material; (6) The coating proportion of amorphous selenium can be adjusted by changing the hydrothermal reaction time. The nano material prepared by the method has uniform morphology, adjustable coating proportion and excellent methanol electrocatalytic property, and provides a new scheme for preparing formic acid by taking non-noble metal compounds as electrocatalysts.
Description
Technical Field
The invention relates to the field of new energy materials, in particular to nickel selenide nano particles for electrocatalytic synthesis of formic acid, which are covered by a controllable amorphous selenium coating and are prepared by a one-step hydrothermal synthesis method.
Background
Hydrogen is considered one of the main energy sources in the 21 st century because of its environmental protection and sustainability properties, and has attracted great attention. Electrolysis of water is a key method for producing hydrogen gas, comprising two half reactions: cathodic hydrogen evolution (hydrogen evolution reaction, HER) and anodic oxygen evolution (oxygen evolution reaction, OER). However, OER involves a high overpotential and requires more energy to achieve a current density comparable to HER, which causes a major obstacle to water decomposition. Thus, there is a need for an effective strategy to replace OER with organic molecules having lower oxidation potential while improving HER and electrocatalytic efficiency. Among them, methanol is a basic organic compound, and has the advantages of low price, no toxicity, practicality, wide availability, etc. Studies have shown that nickel-rich electrocatalysts can convert methanol oxidation reactions (methanol oxidation reaction, MOR) to formate. At the same time, formate is a valuable chemical, widely used in the chemical and pharmaceutical industries. In recent years, research on nickel-based electrocatalysts has progressed rapidly, resulting in a variety of catalyst types including hydroxides, oxides, sulfides, aerogels, bimetallic alloys, and the like. Of particular interest are nickel-based sulfides, which are of interest due to their anions (mainly SeO x) generated during the electrocatalytic MOR process, increasing their performance.
Therefore, the nickel selenide nano particles with controllable amorphous selenium coating are prepared by a one-step hydrothermal synthesis method, and compared with the traditional vapor deposition method, the method is simpler and more convenient, has good controllability, and can be used as an anode electrode material of MOR in alkaline medium. Ion chromatography (ion chromatography, IC) technology shows that the methanol to formic acid (FARADAIC EFFICIENCY, FE) of the material has high Faraday efficiency.
Disclosure of Invention
The invention aims to provide a preparation method of nickel selenide nano particles for an amorphous selenium coating for preparing formic acid by electrocatalytic reaction, which aims to solve the technical problems of low yield and low selective conversion of the formic acid prepared by using nickel-based non-noble metal as an electrocatalyst. In order to solve the technical problems, the invention designs and develops a novel method for preparing formic acid in alkaline solution by electrocatalytic nickel selenide nano particles with an amorphous selenium coating, which comprises the following specific technical scheme:
a method for preparing nickel selenide nanoparticles for an amorphous selenium coating for electrocatalytically preparing formic acid, comprising the following steps:
(1) And (3) preparing a solution A: adding nickel nitrate into 10 ml of deionized water, and performing ultrasonic treatment for 30 minutes to obtain a homogeneous transparent solution A;
(2) And (2) preparing a solution B: adding selenium powder into 10 ml of deionized water, adding 1 g of sodium borohydride serving as a reducing agent, and performing ultrasonic treatment until the selenium powder is completely dissolved to obtain a solution B;
(3) Preparing a mixed solution: pouring the solution A into the solution B, rapidly stirring, and fully and uniformly mixing;
(4) Hydrothermal reaction: the obtained mixed solution is put into a hydrothermal kettle to react for 12, 16, 20 and 24 hours at 180 ℃;
(5) Washing and drying: the obtained black solid is centrifugally washed for many times, and vacuum dried for 24 hours at 60 ℃ to obtain a series of nickel selenide nano particles with amorphous selenium coating;
further, in the step (4), the obtained mixed solution is put into a hydrothermal kettle to react for 24 hours at 180 ℃ to obtain uncoated nickel selenide (Ni 3Se4) nano particles;
Further, in the step (4), the obtained mixed solution is put into a hydrothermal kettle to react for 20 hours at 180 ℃ to obtain nickel selenide nano particles with an amorphous selenium coating with a coating ratio of 8.1%;
Further, in the step (4), the obtained mixed solution is put into a hydrothermal kettle to react for 16 hours at 180 ℃ to obtain nickel selenide nano particles with an amorphous selenium coating with a coating ratio of 17.3%;
Further, in the step (4), the obtained mixed solution is put into a hydrothermal kettle to react for 12 hours at 180 ℃ to obtain nickel selenide nano particles with an amorphous selenium coating with a coating ratio of 22.3%;
The preparation method of the nickel selenide nano-particles for preparing the amorphous selenium coating of formic acid by electrocatalytic reaction has the following advantages: the morphology is uniform, the proportion of the selenium coating is adjustable, the electrocatalytic performance of the methanol is higher than most of reference values of the existing references, the yield and the speed of formic acid are improved, and the Faraday efficiency is close to 100%; the simple material synthesis method and the synthesis method of the formic acid with low cost at normal temperature and normal pressure have wide prospects in sustainable energy and environmental application.
Detailed Description
In order to better understand the purpose of the present invention and the structure and function of the synthesized nano material, the following describes in further detail the preparation method of the nickel selenide nano particles of the amorphous selenium coating for preparing formic acid by electrocatalytic action and the promotion of the electrocatalytic activity thereof with reference to the attached drawings. For the convenience of comparison and observation, three coating ratios, namely [email protected]%, [email protected]%, [email protected]%, and uncoated nickel selenide nanoparticles (Ni 3Se4) are mainly selected for comparison and display.
As shown in the synthesis flow chart of FIG. 1, the nickel selenide nanoparticles of the amorphous selenium coating of the invention adopts a simple one-step hydrothermal synthesis method. The coating proportion of amorphous selenium is changed by adjusting the time of hydrothermal reaction, nickel selenide nanometer materials with different coating ratios are obtained, and an X-ray diffraction pattern proves that the coated nickel selenide nanometer particles are Ni 3Se4, and the PDF card is 97-004-2558.
As shown in SEM-EDS of fig. 2, the coating ratio of amorphous selenium gradually decreased with longer reaction time, the ratio of 12 hours was 22.3%, the ratio of 16 hours was 17.3%, the ratio of 20 hours was 8.1%, and the amorphous selenium was completely disappeared for 24 hours, to obtain uncoated Ni 3Se4 nanoparticles.
FIG. 3a is a TEM image of [email protected]%. It is clearly seen that distinct nanoparticles with a diameter of 20.86nm are observed, and that there is a thin coating on the surface. Furthermore, figure 3b shows HRTEM analysis of nanoparticles with less selenium coating. It can be seen that there is a clear interface edge between crystalline Se and amorphous Se, indicating that a thin amorphous elemental selenium layer is present on the surface of the Ni 3Se4 nanoparticles. As shown in fig. 3b, the diffraction spots (up) and diffusion spots (down) further confirm the crystalline and amorphous features, respectively, in the corresponding selected region Fast Fourier Transform (FFT) map. In addition, the crystalline region exhibited lattice fringes with a spacing of 0.276nm, which closely matched the (-6 0-6) plane of the Ni 3Se4 crystal structure. Meanwhile, HAADF-STEM and EELS composition patterns showed that the crystalline and amorphous interface was clearly observed in [email protected]%, [email protected]% and [email protected]%, and Ni 3Se4 was the crystalline region only (FIG. 3 c). These evidence indicate that amorphous selenium-coated Ni 3Se4 nanoparticles are formed. The surface chemistry of the resulting nanoparticles was further studied by XPS analysis. FIG. 3d shows the entire XPS spectrum of the prepared [email protected]% in the Ni 2p, se 3d region. In the XPS spectrum of Ni 2p, ni 2p 1/2、Ni2 p3/2 and satellite peaks are shown. Specifically, the binding energies of 856.01 and 873.13eV may be related to Ni 3+, while the peaks of 853.52 and 871.57eV are from Ni 2+. For the [email protected]% Se 3d spectrum (FIG. 3 d), the two peaks at 53.9eV (Se 3d 5/2) and 54.7eV (Se 3d 3/2) represent Se 2- in the Ni-Se bond, respectively. Broad peaks around 58.2eV and 59.1eV can be attributed to the surface oxidation state of Se (SeO 2).
Electrocatalytic performance was performed on Corrtest workstation (CS 2350H) using a conventional three electrode system. By drying the slurry containing dry NPs on top of GC electrodes, a set of CVs was first measured in 1M KOH electrolyte at a potential ranging from 0.9-1.5v vs. rhe. As shown in fig. 4a, in alkaline electrolyte, the 1.411V anode peak measured in the forward scan corresponds to Ni (OH) 2/NiOOH oxidation, while the cathode peak at 1.266V in the backward scan is due to NiOOH/N (OH) 2 reduction. Among them, the [email protected]% NPs based electrode showed the highest redox peak current density at the same external potential due to the appropriate amorphous Se coating on the surface. When 1 mole of methanol was added to the electrolyte, a sharp rise in current density was observed at 1.4V (fig. 4 b), indicating an important step in the conversion of Ni (OH) 2 to NiOOH, which is widely recognized as the primary active species for electrooxidation of methanol. The current density of the Ni 3Se4 nano-particles without the amorphous selenium coating is 62.53mA cm -2, which is lower than that of the other three electrodes. The current density of the lowest [email protected]% of the selenium coating at 1.5V was as high as 99.69mA cm -2, and the net current density was increased by 93.36mA cm -2 due to the presence of methanol (FIGS. 4 c-d). In addition, the presence of amorphous Se provides more adsorption sites at the top of the original grains due to hydrophilicity, thereby maximizing efficiency of surface active sites and accelerating reaction kinetics, thereby improving catalytic performance.
The surface coverage (Γ) and apparent diffusion coefficient (D) of the [email protected]% electrocatalyst were determined at different scan rates (10-100 mV s -1) in alkaline medium (fig. 4 e). First, in the range of 10-50mV s -1, the peak current (I p) is proportional to the scan rate (v). The slope of the fit between IP and v allows to determine the surface coverage of the redox species (Γ) according to the following formula:
Wherein n, F, R, T and A are the number of transferred electrons (assumed to be 1), faraday constant (96845C mol -1), gas constant (8.314J K -1mol-1), temperature and geometric surface area of the GC electrode (0.196 cm 2), respectively. By averaging the results of the forward and reverse scans, the surface coverage of the redox species of the [email protected]% base electrode was calculated to be 1.81×10 - 7mol cm-2, almost twice that of the Ni 3Se4 NPs base electrode (fig. 4 f).
Proton diffusion is generally considered to control oxidation reactionsIs a step of limiting the speed. At high scan rates of 60-100mV s -1, the peak current increases linearly with the square root of the voltage scan rate, indicating the presence of a diffusion limited redox reaction. This value can be determined from the following formula:
Ip＝2.69×105n3/2AD1/2Cv1/2
Where D is the diffusion coefficient of the reaction-limiting species and C is the initial concentration of the redox species. Qualitatively, we observe that the slope of IP obtained from the Ni 3Se4 -based electrode increases with v 1/2 as hydrothermal time increases. From the fitting, the apparent diffusion coefficient of [email protected]% is 7.12X10 -9cm2 s-1, which is much higher than that of [email protected]% (4.45X10 -9cm2s-1)、[email protected]％(5.49×10-9cm2 s-1) and Ni 3Se4(1.56×10-9cm2 s-1) base electrodes (FIG. 4 f).
In alkaline media without methanol, the electrochemical surface area (ECSA) can be estimated by CV at different scan rates in the non-faraday region. This value can be estimated from the electrochemical double layer capacitance (C dl) based on CV recorded at different scan rates over the non-Faraday potential range 0.9-1.0V versus RHE (FIG. 4 g). Plotting the capacitance current (i) versus scan rate (v) to obtain a straight line with a slope equal to Cdl (fig. 4 h), ECSA for each electrode can be calculated by dividing C dl by the specific capacitance (Cs) using the following equation:
ECSA＝Cdl/Cs
Wherein C s is 0.04mF cm -2 in KOH solution. Thus, ni 3Se4 was found to have an ECSA of 22.74cm -2 and [email protected]% ECSA of 32.5cm -2 (FIG. 4 i). Overall, the MOR performance enhancement of [email protected]% is related to its higher active surface coverage, diffusion coefficient, ECSA and appropriate surface Se.
During catalysis, sufficient electrolyte contact can lead to better conductivity and higher catalytic efficiency. As shown in fig. 5, the electrolyte contact angle between the material and the electrolyte was measured in 1M KOH and 1M methanol solution, and it can be seen that the initial contact angle of [email protected]% was 27.85 °, followed by rapid diffusion, while the contact angle was measured to be 16.63 ° (fig. 5 a). In fact, the hydrophilic nature of the surface is very advantageous for rapid permeation of the electrolyte, thus improving the catalytic performance. Thus, the angular variation (Δθ) is 11.32 °, almost 3 times that of Ni 3Se4 NPs (Δθ=4.92°, fig. 5 b). The larger change in contact angle indicates an increase in hydrophilicity of [email protected]% in the presence of amorphous Se on the surface.
The present invention performed long term CA on this electrocatalyst as shown in fig. 6 a. The current density is slightly reduced in the whole electrochemical reaction process, but the current density is still kept at about 130mA cm -2 after 18 hours of electrolysis, and the current density is only reduced by 20 percent compared with the initial value. As can be seen in FIG. 6b, 399.78mg L -1 formate was determined and methanol to formate FE was 97.93% in 18 hours CA operation of MOR. Electrocatalytic properties stand out in similar nickel-based electrocatalysts. These results indicate that the electrocatalyst designed according to the invention has a long-term high conversion effect in industrial production.
Drawings
FIG. 1 is a schematic synthesis and XRD spectrum of nickel selenide nanoparticles of an amorphous selenium coating of the present invention;
FIG. 2 is a SEM and elemental energy spectrum of the invention: (a) is [email protected]%, (b) is [email protected]%, (c) is [email protected]%, and (d) is Ni 3Se4.
Fig. 3 (a) is a TEM image of the present invention and its size distribution; (b) HRTEM images of [email protected]%, and corresponding FFT modes for selected areas marked with squares; (c) HAADF-STEM images and crystal plane boundaries of [email protected]%, [email protected]% and Ni 3Se4, respectively; (d) XPS spectra of the peaks at [email protected]% for Ni 2p and Se 3 d.
FIG. 4 (a) is a CV curve in 1 mole KOH for an electrode based on [email protected]%, [email protected]%, [email protected]% and Ni 3Se4; (b) A CV curve of the material in 1 mole KOH and 1 mole methanol; (c) For CV comparison of [email protected]% in 1 mole KOH, 1 mole KOH and 1 mole methanol, respectively; (d) is a histogram for comparing the difference in current density; (e) For an electrode based on [email protected]%, the potential scanning rate is higher and higher in a1 mol KOH solution: CV curve of 10-100 mV s -1; (f) is the result of calculation of Γ and D. (g) A CV curve for scan rates of 10 to 100mV s -1 is [email protected]%, (h) is a slope fit for Cdl; (i) Results of calculations for C dl and ECSA;
FIG. 5 shows the contact angles of [email protected]% (a) and Ni 3Se4 (b) with an electrolyte in the present invention, with a spacing of 200ms.
FIG. 6 (a) is a CA response of [email protected]% at 1.6V, continuously electrolyzed in an electrolyte of 1 mole KOH and 1 mole methanol for 18 hours; (b) Formate standard curve (dashed line) and IC curve of electrolyte after electrode CA measurement (solid line).
Claims (7)
1. The preparation method and application of amorphous selenium coated nickel selenide nanometer material are characterized in that sodium borohydride is selected as a reducing agent, and a one-step hydrothermal synthesis method is adopted, and the preparation method comprises the following steps: (1) A preparation of solution: adding nickel nitrate into 10 ml of deionized water, and carrying out ultrasonic treatment for 30 minutes to obtain a uniform and transparent solution A; (2) preparation of B solution: adding selenium powder into 10 ml of deionized water, adding 1 g of sodium borohydride serving as a reducing agent, and performing ultrasonic treatment until the selenium powder is completely dissolved to obtain a solution B; (3) preparation of mixed solution: pouring the solution A into the solution B, and rapidly stirring to ensure that the solution A is fully and uniformly mixed; (4) hydrothermal reaction: filling the obtained mixed solution into a hydrothermal kettle, and reacting for 12, 16, 20 or 24 hours at 180 ℃; (5) washing and drying: centrifugally washing the obtained black solid substance for a plurality of times, and then vacuum drying at 60 ℃ for 12, 16, 20 or 24 hours, thereby obtaining nickel selenide nanocrystals with different amorphous selenium coating ratios; (6) The coating proportion of amorphous selenium can be adjusted by adjusting the hydrothermal reaction time.
2. The method for preparing amorphous selenium-coated nickel selenide nanocrystals for electrocatalytically preparing formic acid as claimed in claim 1, wherein in step (1), the nickel source used is nickel nitrate, and all solids are mixed in the form of a homogeneous solution.
3. The method for preparing amorphous selenium-coated nickel selenide nanocrystals for electrocatalytically preparing formic acid according to claim 2, wherein in step (2), the selenium source is elemental selenium powder, and the reducing agent is sodium borohydride.
4. The method for preparing amorphous selenium-coated nickel selenide nanocrystals for electrocatalytically preparing formic acid according to claim 3, wherein in step (3), both the nickel source and the selenium source coexist in the mixed solution in the form of ions.
5. The method of preparing amorphous selenium-coated nickel selenide nanocrystals for electrocatalytically preparing formic acid as claimed in claim 4, wherein the hydrothermal reaction in step (4) is carried out at 180 ℃ for 12, 16, 20 and 24 hours, the coating ratio being adjustable by a series of different reaction times.
6. The method for preparing amorphous selenium-coated nickel selenide nanocrystals for electrocatalytically preparing formic acid as claimed in claim 5, wherein the amorphous selenium-coated nickel selenide nanoparticles are finally obtained in the step (5) by centrifugal washing and vacuum drying at 60 degrees celsius for 24 hours.
7. The method for preparing amorphous selenium-coated nickel selenide nanocrystals for electrocatalytically preparing formic acid as claimed in claim 6, wherein in step (1-6), the synthesized coated nickel selenide (Ni 3Se4) nanomaterial is prepared.
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