CN110124673B - Boron-induced amorphous layered double hydroxide electrocatalyst and preparation and application thereof - Google Patents
Boron-induced amorphous layered double hydroxide electrocatalyst and preparation and application thereof Download PDFInfo
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- CN110124673B CN110124673B CN201910430592.3A CN201910430592A CN110124673B CN 110124673 B CN110124673 B CN 110124673B CN 201910430592 A CN201910430592 A CN 201910430592A CN 110124673 B CN110124673 B CN 110124673B
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 91
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 73
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- 239000013078 crystal Substances 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 183
- 229910052759 nickel Inorganic materials 0.000 claims description 88
- 239000002135 nanosheet Substances 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000002243 precursor Substances 0.000 claims description 33
- 229910052723 transition metal Inorganic materials 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 23
- 239000006260 foam Substances 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 238000009210 therapy by ultrasound Methods 0.000 claims description 18
- -1 transition metal salt Chemical class 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- 239000012046 mixed solvent Substances 0.000 claims description 12
- 150000003624 transition metals Chemical class 0.000 claims description 12
- 238000011065 in-situ storage Methods 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 9
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000001939 inductive effect Effects 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 229910003266 NiCo Inorganic materials 0.000 description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- 229910006030 NiCoCu Inorganic materials 0.000 description 5
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- VDGMIGHRDCJLMN-UHFFFAOYSA-N [Cu].[Co].[Ni] Chemical compound [Cu].[Co].[Ni] VDGMIGHRDCJLMN-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005271 boronizing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004098 selected area electron diffraction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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Abstract
The invention relates to a boron-induced amorphous layered double hydroxide electrocatalyst, and preparation and application thereof. Compared with the prior art, the method for inducing the layered double hydroxide crystal to be amorphous by doping the boron atoms ensures that the electrocatalyst has more active sites, lower electron transfer impedance and better corrosion resistance, and when the electrocatalyst is used in a hydrogen evolution reaction, the electrocatalyst can show excellent electrocatalytic activity and stability under the condition of extremely high current density.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by water electrolysis, and relates to a boron-induced amorphous unitary or multi-element transition metal-based layered double hydroxide nanosheet electrocatalyst for hydrogen evolution reaction under high current, and preparation and application thereof.
Background
The hydrogen energy is taken as a ring in the current renewable energy distribution system, so that the problem of uneven distribution of the renewable energy in space and time is solved; on the other hand, the energy-saving device has the advantages of high energy density, freshness, no pollution and the like, and can be effectively used as a substitute of the traditional fossil energy. For the production of hydrogen, electrolysis of water is a practical technique that meets the requirements of sustainable development, where the Hydrogen Evolution (HER) reaction is one of the two half-reactions at its core. However, due to the slow thermodynamic and kinetic processes of the hydrogen evolution reaction, a high overpotential is required to deliver a certain amount of current density. In order to reduce the overpotential on the electrode, a novel hydrogen evolution electrocatalyst with high efficiency needs to be developed to reduce the reaction energy barrier and promote the exchange process of electrons and protons. At present, the hydrogen evolution reaction electrocatalyst used as a high-efficiency commercial electrode is mainly noble metal platinum/carbon, and although the catalyst performance is excellent and high-efficiency, the hydrogen evolution reaction electrocatalyst is limited by the defects of limited storage capacity and high cost in the nature, and cannot be applied to large-scale industrialization. Therefore, researchers need to develop a non-noble metal electrocatalyst with low cost, excellent performance and simple synthesis process.
Among numerous non-noble metal electrocatalysts, 3d transition metal electrocatalysts (such as Ni, Co and the like) have the advantages of low hydrogen evolution overpotential, high efficiency, stability, low cost and the like, and particularly, the transition metal-based layered double hydroxide is concerned due to unique structure, excellent catalytic activity and simple preparation process. However, almost all transition metal-based layered double hydroxide electrocatalysts fail to exhibit and maintain excellent electrocatalytic hydrogen evolution performance at relatively large current densities. Coupled with the relatively complicated preparation process and high cost, it is not suitable for large-scale industrial production and commercialization.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a boron-induced amorphous layered double hydroxide electrocatalyst, and preparation and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a boron-induced amorphous layered double hydroxide electrocatalyst comprises the following steps:
1) generating a layered double hydroxide nanosheet crystal precursor on the foamed nickel by adopting an in-situ growth method;
2) the amorphous layered double hydroxide electrocatalyst is formed by utilizing boron induction.
Further, the step 1) is specifically as follows:
1-1) dissolving transition metal salt and urotropine in a mixed solvent to obtain a mixed solution;
1-2) immersing the pretreated foamed nickel in the mixed solution obtained in the step 1-1), and then reacting for 6-10h at 80-100 ℃;
1-3) taking out the foamed nickel, and washing and drying to obtain a layered double hydroxide nanosheet crystal precursor loaded on a foamed nickel substrate.
Further, in step 1-1), the transition metal salt includes one or more of a nickel salt, a cobalt salt, or a copper salt.
Further, in the step 1-1), the transition metal salt is a nitrate of a transition metal.
Further, in the step 1-1), the mixed solvent comprises water and ethanol.
Further, in the step 1-2), the pretreatment process of the nickel foam is as follows: and sequentially carrying out ultrasonic treatment on the foamed nickel by using deionized water, acetone and ethanol for 10-20min, taking out the foamed nickel, washing and drying.
Further, the step 2) is specifically as follows: placing the foam nickel loaded with the layered double hydroxide nanosheet crystal precursor in the step 1) into NaBH4Reacting in the solution at room temperature for 8-30h to obtain the amorphous layered double hydroxide electrocatalyst.
The boron-induced amorphous layered double hydroxide electrocatalyst is prepared by the method.
An application of boron-induced amorphous layered double hydroxide electrocatalyst is disclosed, wherein the electrocatalyst is used in hydrogen evolution reaction of electrolyzed water.
Further, when the electrocatalyst is used for catalyzing the hydrogen evolution reaction process, the electrocatalyst is used as a working electrode, a mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode.
According to the invention, a crystalline layered double hydroxide nanosheet precursor directly grows in situ on three-dimensional blank foamed nickel, and then is doped with boron atoms to induce and form the amorphous layered double hydroxide nanosheet electrocatalyst. The prepared hydrogen evolution reaction electrocatalyst benefits from a process of boron doping to induce the amorphization of the crystalline layered double hydroxide nanosheets, has more active sites and better chemical corrosion resistance, and promotes better synergistic effect between multiple transition metals (such as nickel and cobalt). In addition, the ultrathin nanosheet shape is more beneficial to the transmission of protons and electrons, so that the nanosheet has a larger electrochemical active area and more exposed active sites; and unique open three-dimensional support knotThe structure makes it have higher conductivity, avoids adopting any macromolecular binder, prevents the jam to the active site, improves the efficiency that produces the gas and discharges. The advantages promote the electrocatalyst to show excellent electrocatalytic activity and stability under high current density, and meet the requirement of current density required by large-scale industrial production (more than 500mA cm)–2) The HER overpotentials of the electrocatalyst are η for 1 mol per liter of KOH solution10mA cm-2=22mV,η100mA cm-2=140mV,η500mA cm-2=275mV,η1000mA cm-2370 mV. And at 1000mA cm–2Can be maintained without significant fading for up to 72 hours at the current density of (2). The preparation process of the electrocatalyst is very simple, the raw material sources are convenient and cheap (the preparation raw materials only relate to blank foamed nickel, nickel nitrate, cobalt nitrate, copper nitrate, urotropine, sodium borohydride and other common reagents), the cost is low, the product purity is high, the electrocatalyst can be stably catalyzed under various current density conditions, the extremely low reaction energy consumption is kept, and the large-scale industrial production is easy to realize. The method for inducing the amorphous crystalline layered double hydroxide nanosheet to be amorphous has high universality, can be applied to the preparation of one-element, two-element, three-element and other multi-element transition metal layered double hydroxide nanosheet crystals, and the obtained amorphous layered double hydroxide nanosheet electrocatalyst has excellent hydrogen evolution electrocatalytic activity.
Compared with the prior art, the invention has the following characteristics:
1) the invention provides a boron-induced amorphous layered double hydroxide nanosheet electrocatalyst for hydrogen evolution reaction under high current, which is prepared by firstly synthesizing a transition metal layered double hydroxide nanosheet crystal precursor on a foamed nickel substrate by using an in-situ growth method, and then amorphizing the crystal precursor by using a room-temperature boronizing method. The method for inducing the layered double hydroxide crystal to be amorphous by doping boron atoms enables the electrocatalyst to have more active sites, lower electron transfer resistance and better corrosion resistance. When the electrocatalyst is used in hydrogen evolution reaction, excellent electrocatalytic activity and stability can be shown under the condition of extremely high current density.
2) The amorphous layered double hydroxide nanosheet electrocatalyst prepared by the invention has the advantages of excellent electrocatalytic performance, simple preparation process and low cost, can perform stable and efficient electrocatalytic hydrogen evolution reaction under high current density, and is suitable for large-scale production of hydrogen production by water electrolysis.
Drawings
FIG. 1 is a Scanning Electron Micrograph (SEM) of 3D A-NiCo LDH/NF electrocatalyst prepared in example 1, wherein (a) is a graph at 2 μm and (b) is a graph at 500 nm;
FIG. 2 is a Transmission Electron Micrograph (TEM) of the 3D NiCo LDH/NF and 3D A-NiCo LDH/NF electrocatalysts prepared in example 1, wherein (a) to (c) are maps of the 3D NiCo LDH/NF and (D) to (f) are maps of the 3D A-NiCo LDH/NF electrocatalysts;
FIG. 3 is an X-ray diffraction energy spectrum (XRD) analysis of 3D NiCo LDH/NF and 3D A-NiCo LDH/NF electrocatalysts prepared in example 1;
in FIG. 4, (a) is an Atomic Force Microscope (AFM) of the 3D A-NiCo LDH/NF electrocatalyst prepared in example 1, and (b) is a line scan thickness map of the corresponding region in (a) (the nanosheets have an average thickness of about 2.7 nm);
FIG. 5 is a plot of HER linear sweep voltammograms at a sweep rate of 5 millivolts per second in 1.0 moles per liter of potassium hydroxide electrolyte for a 3DA-NiCo LDH/NF electrocatalyst prepared in example 1;
FIG. 6 is a graph showing the 3D A NiCo LDH/NF electrocatalyst prepared in example 1, loaded at 1000mA cm–2Current density, current density in 1.0 mole per liter of potassium hydroxide electrolyte versus time graph.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
the preparation of the boron-induced amorphous nickel-cobalt layered double hydroxide nanosheet electrocatalyst (3D A-NiCo LDH/NF) comprises the following steps:
(1) generating a crystal nickel-cobalt layered double hydroxide nanosheet precursor (3D NiCo LDH/NF) on blank foamed nickel with a three-dimensional structure by adopting an in-situ growth method: intercepting blank foam nickel for pretreatment, including sequentially performing ultrasonic treatment on the blank foam nickel by using deionized water, acetone and ethanol for 15min, then washing the blank foam nickel by using the deionized water, and drying at room temperature; subsequently, 8.8g of Ni (NO) were weighed out3)2·6H2O, 4.4g of Co (NO)3)2·6H2O and 5g of urotropin are dissolved in a mixed solvent of 50mL of deionized water and 150mL of ethanol, and the mixture is transferred into a beaker after being subjected to ultrasonic treatment for 30 min. Putting the pretreated blank foamed nickel into the solution to be completely immersed, putting the blank foamed nickel into a drying oven, reacting for 9 hours at 90 ℃, cooling at room temperature, taking out the foamed nickel, cleaning and drying to obtain a crystal nickel-cobalt layered double hydroxide ultrathin nanosheet precursor (3D NiCo LDH/NF) loaded on a foamed nickel substrate;
(2) adopting boron-doped atom to induce and form an amorphous nickel-cobalt layered double hydroxide nanosheet electrocatalyst (3D A-NiCoLDH/NF): 1.8915g of NaBH was weighed out4Dissolving in 50mL of deionized water, and performing ultrasonic treatment for 2 min; and standing the prepared 3D NiCoLDH/NF precursor in the solution, and reacting for 25 hours at room temperature to obtain the final 3D A-NiCoLDH/NF electrocatalyst.
When the 3D A-NiCo LDH/NF electrocatalyst prepared by the embodiment is used for catalyzing a hydrogen evolution reaction process, the specific steps are as follows: the prepared 3D A-NiCo LDH/NF electrocatalyst is used as a working electrode, a mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode. HER was tested for electrochemical performance in 1 mole per liter KOH solution saturated with hydrogen, including linear sweep voltammetry and time-current density tests.
As can be seen from FIG. 1, the 3D A-NiCo LDH/NF nanosheet array is vertically and densely distributed on the surface of the foamed nickel, and the nanosheets have an ultrathin structure.
As can be seen from fig. 2(a), 3D NiCo LDH/NF possesses an ultrathin nanosheet structure, which is consistent with the results of SEM in fig. 1. From the selected area electron diffraction pattern (SAED) of 3D NiCo LDH/NF in FIG. 2(b), it can be observed that there are many concentric diffraction circles, demonstrating that it exists as a polycrystalline phase. The high power transmission electron micrograph (HRTEM) of fig. 2(c) shows the well-defined lattice striations of 3D NiCoLDH/NF with lattice spacings of 0.272 and 0.158 nm, corresponding to the (100) and (003) planes of crystalline NiCoLDH, respectively. FIG. 2(a-c) illustrates that the precursor 3D NiCo LDH/NF is of polycrystalline structure. As can be seen from the TEM image of 3D A-NiCoLDH/NF in FIG. 2(d), the sheet structure remains after the boron atoms are doped into the precursor; however, complete disappearance of both diffraction rings and lattice fringes was observed in the SAED plot of FIG. 2(e) and the HRTEM plot of FIG. 2(f), indicating that the crystalline NiCo LDH underwent an amorphous phase change after boron atom incorporation, resulting in the formation of fully amorphous 3D A-NiCo LDH/NF.
As can be seen from fig. 3, the blank nickel foam has three diffraction peaks at 44.3 °, 51.8 ° and 76.3 °, respectively, corresponding to the (111), (200) and (220) crystal planes of nickel. Except three diffraction peaks of the foam nickel, the other diffraction peaks of the precursor 3D NiCo LDH/NF are respectively at 19.3 degrees, 33.26 degrees, 37.8 degrees and 59.9 degrees and respectively correspond to (001), (100), (101) and (003) crystal planes of the crystal NiCo LDH. In the XRD diffraction pattern of 3D A-NiCo LDH/NF, only three diffraction characteristic peaks of blank foam nickel exist, which shows that with the doping of boron atoms, the crystal NiCo LDH is subjected to amorphous phase change to form completely amorphous 3D A-NiCo LDH/NF.
As can be seen from FIG. 4, the average thickness of 3D A-NiCo LDH/NF was only about 2.7nm, confirming that it possesses a sheet structure of an ultra-thin structure.
As can be seen from FIG. 5, 3D A-NiCo LDH/NF required up to 10mA cm at 140mV overpotential–2Current density of (d); thereby achieving a high current density of 500mA cm–2And 1000mA cm–2Then 275 and 370mV overpotentials were required, respectively, indicating excellent electrocatalytic activity (especially at high current densities).
As can be seen from FIG. 6, 3D A-NiCo LDH/NF could be maintained at 1000mA cm at a stable voltage of-0.37V (relative to a reversible hydrogen electrode)–2Current density reaches 72 hours and is almostThere was no attenuation, indicating its excellent stability at high current densities.
Example 2:
the preparation of the boron-induced amorphous nickel layered double hydroxide nanosheet electrocatalyst (3D A-Ni LDH/NF) comprises the following steps:
(1) generating a crystal nickel layered double hydroxide nanosheet precursor (3D Ni LDH/NF) on blank foam nickel with a three-dimensional structure by adopting an in-situ growth method: intercepting blank foam nickel for pretreatment, including sequentially performing ultrasonic treatment on the blank foam nickel by using deionized water, acetone and ethanol for 15min, then washing the blank foam nickel by using the deionized water, and drying at room temperature; 13.2g of Ni (NO) are subsequently weighed out3)2·6H2O and 5g of urotropin are dissolved in a mixed solvent of 50mL of deionized water and 150mL of ethanol, and the mixture is transferred into a beaker after being subjected to ultrasonic treatment for 30 min. Putting the pretreated blank foamed nickel into the solution to be completely immersed, putting the blank foamed nickel into a drying oven, reacting for 9 hours at 90 ℃, cooling at room temperature, taking out the foamed nickel, cleaning and drying to obtain a crystal nickel layered double hydroxide ultrathin nanosheet precursor (3D Ni LDH/NF) loaded on a foamed nickel substrate;
(2) adopting boron-doped atom to induce and form an amorphous nickel layered double hydroxide nanosheet electrocatalyst (3D A-NiLDH/NF): 1.8915g of NaBH was weighed out4Dissolving in 50mL of deionized water, and performing ultrasonic treatment for 2 min; and standing the prepared 3D NiLDH/NF precursor in the solution, and reacting for 25h at room temperature to obtain the final 3D A-Ni LDH/NF electrocatalyst.
When the 3D A-Ni LDH/NF electrocatalyst prepared by the embodiment is used for catalyzing the hydrogen evolution reaction process, the specific steps are as follows: the prepared 3D A-Ni LDH/NF electrocatalyst is used as a working electrode, a mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode. HER was tested for electrochemical performance in 1 mole per liter KOH solution saturated with hydrogen, including linear sweep voltammetry and time-current density tests.
Example 3:
the preparation of the boron-induced amorphous cobalt layered double hydroxide nanosheet electrocatalyst (3D A-Co LDH/NF) comprises the following steps:
(1) generating a crystal cobalt layered double hydroxide nanosheet precursor (3D Co LDH/NF) on blank foam nickel with a three-dimensional structure by adopting an in-situ growth method: intercepting blank foam nickel for pretreatment, including sequentially performing ultrasonic treatment on the blank foam nickel by using deionized water, acetone and ethanol for 15min, then washing the blank foam nickel by using the deionized water, and drying at room temperature; then weighing 10-15g of Co (NO)3)2·6H2Dissolving O and 3-8g of urotropin in a mixed solvent of 50mL of deionized water and 150mL of ethanol, carrying out ultrasonic treatment for 30min, and transferring the solution into a beaker. Putting the pretreated blank foamed nickel into the solution to be completely immersed, putting the blank foamed nickel into a drying oven, reacting for 9 hours at 90 ℃, cooling at room temperature, taking out the foamed nickel, cleaning and drying to obtain a crystal cobalt layered double hydroxide ultrathin nanosheet precursor (3D Co LDH/NF) loaded on a foamed nickel substrate;
(2) adopting boron-doped atoms to induce and form an amorphous nickel layered double hydroxide nanosheet electrocatalyst (3D A-CoLDH/NF): weighing 2-4g of NaBH4Dissolving in 50mL of deionized water, and performing ultrasonic treatment for 2 min; and standing the prepared 3D Co LDH/NF precursor in the solution, and reacting for 25h at room temperature to obtain the final 3D A-Co LDH/NF electrocatalyst.
When the 3D A-Co LDH/NF electrocatalyst prepared by the embodiment is used for catalyzing the hydrogen evolution reaction process, the specific steps are as follows: the prepared 3D A-Co LDH/NF electrocatalyst is used as a working electrode, a mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode. HER was tested for electrochemical performance in 1 mole per liter KOH solution saturated with hydrogen, including linear sweep voltammetry and time-current density tests.
Example 4:
the preparation of the boron-induced amorphous nickel-cobalt-copper layered double hydroxide nanosheet electrocatalyst (3D A-NiCoCu LDH/NF) comprises the following steps:
(1) generating a crystal nickel-cobalt-copper layered double hydroxide nanosheet precursor (3D NiCoCu LDH/NF) on blank foamed nickel with a three-dimensional structure by adopting an in-situ growth method: intercepting blank foam nickel for pretreatment, sequentially performing ultrasonic treatment on the blank foam nickel by using deionized water, acetone and ethanol for 15min, and then subjecting the blank foam nickel to ultrasonic treatmentWashing with deionized water, and drying at room temperature; then weighing 8-10g of Ni (NO)3)2·6H2O, 3-5g of Co (NO)3)2·6H2O and 5g of urotropin are dissolved in a mixed solvent of 50mL of deionized water and 150mL of ethanol, and the mixture is transferred into a beaker after being subjected to ultrasonic treatment for 30 min. And putting the pretreated blank foamed nickel into the solution to be completely immersed, putting the blank foamed nickel into a drying oven, reacting for 9 hours at 70-100 ℃, cooling at room temperature, taking out the foamed nickel, cleaning and drying to obtain the crystal nickel-cobalt layered double hydroxide ultrathin nanosheets (3D NiCo LDH/NF) loaded on the foamed nickel substrate. Then 3-5g of Cu (NO) are weighed3)2·3H2Dissolving O in a mixed solvent of 50mL of deionized water and 150mL of ethanol, carrying out ultrasonic treatment for 10min, putting the prepared 3D NiCo LDH/NF into the solvent at room temperature, standing for reaction for 6h, taking out, cleaning and drying to obtain a crystal nickel-cobalt-copper layered double hydroxide ultrathin nanosheet precursor (3D NiCoCuLDH/NF) loaded on a foamed nickel substrate;
(2) adopting boron-doped atoms to induce and form an amorphous nickel-cobalt-copper layered double hydroxide nanosheet electrocatalyst (3D A-NiCoCu LDH/NF): weighing 1-3g of NaBH4Dissolving in 50mL of deionized water, and performing ultrasonic treatment for 2 min; and standing the prepared 3DNiCoCu LDH/NF precursor in the solution, and reacting at room temperature for 25h to obtain the final 3D A-NiCoCuLDH/NF electrocatalyst.
When the 3D A-NiCoCu LDH/NF electrocatalyst prepared by the embodiment is used for catalyzing a hydrogen evolution reaction process, the specific steps are as follows: the prepared 3D A-NiCoCu LDH/NF electrocatalyst is used as a working electrode, a mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode. HER was tested for electrochemical performance in 1 mole per liter KOH solution saturated with hydrogen, including linear sweep voltammetry and time-current density tests.
Example 5:
a preparation method of the electrocatalyst of boron-induced amorphous layered double hydroxide comprises the following steps:
1) generating a layered double hydroxide nanosheet crystal precursor on the foamed nickel by adopting an in-situ growth method:
1-1) dissolving transition metal salt and urotropine in a mixed solvent of water and ethanol to obtain a mixed solution, wherein the transition metal salt is nickel salt and copper salt, and the transition metal salt is nitrate of transition metal;
1-2) pretreating foamed nickel: sequentially carrying out ultrasonic treatment on the foamed nickel for 10min by using deionized water, acetone and ethanol, then taking out the foamed nickel, washing and drying; immersing the pretreated foamed nickel in the mixed solution obtained in the step 1-1), and then reacting for 6 hours at 100 ℃;
1-3) taking out the foamed nickel, and washing and drying to obtain a layered double hydroxide nanosheet crystal precursor loaded on a foamed nickel substrate.
2) Amorphous layered double hydroxide electrocatalyst formation induced by boron:
placing the foam nickel loaded with the layered double hydroxide nanosheet crystal precursor in the step 1) into NaBH4Reacting in the solution at room temperature for 30h to obtain the amorphous layered double hydroxide electrocatalyst.
The prepared electro-catalyst is used in the hydrogen evolution reaction of electrolyzed water, and when the electro-catalyst is used in the catalytic hydrogen evolution reaction process, the electro-catalyst is used as a working electrode, a mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode.
Example 6:
a preparation method of the electrocatalyst of boron-induced amorphous layered double hydroxide comprises the following steps:
1) generating a layered double hydroxide nanosheet crystal precursor on the foamed nickel by adopting an in-situ growth method:
1-1) dissolving transition metal salt and urotropine in a mixed solvent of water and ethanol to obtain a mixed solution, wherein the transition metal salt is cobalt salt and copper salt, and the transition metal salt is nitrate of transition metal;
1-2) pretreating foamed nickel: sequentially carrying out ultrasonic treatment on the foamed nickel for 20min by using deionized water, acetone and ethanol, then taking out the foamed nickel, washing and drying; immersing the pretreated foamed nickel in the mixed solution obtained in the step 1-1), and then reacting for 10 hours at 80 ℃;
1-3) taking out the foamed nickel, and washing and drying to obtain a layered double hydroxide nanosheet crystal precursor loaded on a foamed nickel substrate.
2) Amorphous layered double hydroxide electrocatalyst formation induced by boron:
placing the foam nickel loaded with the layered double hydroxide nanosheet crystal precursor in the step 1) into NaBH4Reacting in the solution at room temperature for 8h to obtain the amorphous layered double hydroxide electrocatalyst.
The prepared electro-catalyst is used in the hydrogen evolution reaction of electrolyzed water, and when the electro-catalyst is used in the catalytic hydrogen evolution reaction process, the electro-catalyst is used as a working electrode, a mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode.
Example 7:
a preparation method of the electrocatalyst of boron-induced amorphous layered double hydroxide comprises the following steps:
1) generating a layered double hydroxide nanosheet crystal precursor on the foamed nickel by adopting an in-situ growth method:
1-1) dissolving transition metal salt and urotropine in a mixed solvent of water and ethanol to obtain a mixed solution, wherein the transition metal salt is copper salt, and the transition metal salt is nitrate of transition metal;
1-2) pretreating foamed nickel: sequentially carrying out ultrasonic treatment on the foamed nickel by using deionized water, acetone and ethanol for 15min, taking out the foamed nickel, washing and drying; immersing the pretreated foamed nickel in the mixed solution obtained in the step 1-1), and then reacting for 8 hours at 90 ℃;
1-3) taking out the foamed nickel, and washing and drying to obtain a layered double hydroxide nanosheet crystal precursor loaded on a foamed nickel substrate.
2) Amorphous layered double hydroxide electrocatalyst formation induced by boron:
placing the foam nickel loaded with the layered double hydroxide nanosheet crystal precursor in the step 1) into NaBH4Reacting in the solution at room temperature for 20h to obtain the amorphous layered doubleA hydroxide electrocatalyst.
The prepared electro-catalyst is used in the hydrogen evolution reaction of electrolyzed water, and when the electro-catalyst is used in the catalytic hydrogen evolution reaction process, the electro-catalyst is used as a working electrode, a mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. A preparation method of a boron-induced amorphous layered double hydroxide electrocatalyst is characterized by comprising the following steps of:
1) generating a layered double hydroxide nanosheet crystal precursor on the foamed nickel by adopting an in-situ growth method:
1-1) dissolving transition metal salt and urotropine in a mixed solvent to obtain a mixed solution;
1-2) immersing the pretreated foamed nickel in the mixed solution obtained in the step 1-1), and then reacting for 6-10h at 80-100 ℃;
1-3) taking out the foamed nickel, washing and drying to obtain a layered double hydroxide nanosheet crystal precursor loaded on a foamed nickel substrate;
2) amorphous layered double hydroxide electrocatalyst formation induced by boron:
placing the foam nickel loaded with the layered double hydroxide nanosheet crystal precursor in the step 1) into NaBH4Reacting in the solution at room temperature for 8-30h to obtain the amorphous layered double hydroxide electrocatalyst;
in step 1-1), the transition metal salt includes one or more of a nickel salt, a cobalt salt, or a copper salt.
2. The method for preparing a boron-induced amorphous layered double hydroxide electrocatalyst according to claim 1, wherein in step 1-1), the transition metal salt is a nitrate of a transition metal.
3. The method for preparing a boron-induced amorphous layered double hydroxide electrocatalyst according to claim 1, wherein in step 1-1), the mixed solvent comprises water and ethanol.
4. The method for preparing the boron-induced amorphous layered double hydroxide electrocatalyst according to claim 1, wherein in step 1-2), the pretreatment process of the foamed nickel is as follows: and sequentially carrying out ultrasonic treatment on the foamed nickel by using deionized water, acetone and ethanol for 10-20min, taking out the foamed nickel, washing and drying.
5. A boron-induced layered double hydroxide electrocatalyst, characterized in that it is prepared by a method according to any one of claims 1 to 4.
6. Use of the boron-induced layered double hydroxide electrocatalyst according to claim 5, wherein the electrocatalyst is used in hydrogen evolution reactions for electrolysis of water.
7. The application of the boron-induced amorphous layered double hydroxide electrocatalyst according to claim 6, wherein when the electrocatalyst is used for catalyzing a hydrogen evolution reaction process, the electrocatalyst is used as a working electrode, a mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode.
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