CN114990580A - Composite heterostructure nanosheet, preparation method and application - Google Patents

Composite heterostructure nanosheet, preparation method and application Download PDF

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CN114990580A
CN114990580A CN202210833561.4A CN202210833561A CN114990580A CN 114990580 A CN114990580 A CN 114990580A CN 202210833561 A CN202210833561 A CN 202210833561A CN 114990580 A CN114990580 A CN 114990580A
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CN114990580B (en
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戴正飞
刘耀达
刘倩旖
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Guilin University of Electronic Technology
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Abstract

The invention discloses a composite heterostructure nanosheet, a preparation method and application, and relates to the technical field of electrocatalytic water decomposition. The invention discloses a metal-loaded NiPS 3 The preparation method of the heterostructure nanosheet adopts a one-step electrochemical stripping synchronous doping technology, and can efficiently mix the bulk NiPS 3 The material is stripped into two-dimensional nanosheets with thin thickness and large transverse dimension (mum level), and simultaneously metal atoms are doped in the nanosheets, so that the hydrogen evolution performance of the nanosheets under alkaline conditions is greatly improved. The invention dopes metal atoms in NiPS 3 In NiPS, the metal atom acts as a dopant 3 On one hand, the defects produced in the crystal lattice cause the conversion of an electronic structure and the redistribution of charges, so that the conductivity of the system is enhanced, the carrier transmission is promoted, and the improvement of the catalytic performance is facilitated.

Description

Composite heterostructure nanosheet, preparation method and application
Technical Field
The invention relates to the technical field of electrocatalytic water decomposition, in particular to a composite heterostructure nanosheet, a preparation method and application.
Background
The hydrogen energy is a clean and pollution-free secondary energy source and has higher mass energy density. Abundant water resources on earth provide prerequisites for sustainable hydrogen production. The electric energy required by water decomposition can be converted from renewable energy sources, and the decomposition products are free from pollution. However, during the electrocatalytic decomposition of water, the cathodic Hydrogen Evolution Reaction (HER) involves multiple electron transfer processes, resulting in overpotentials and energy losses. Therefore, high performance electrocatalysts are required to reduce the overpotential for water decomposition. Currently, the best catalyst for the preparation of HER is a platinum-based material, but the global reserves of platinum are small and expensive, which greatly limits its commercial application. Therefore, the development of an efficient and cheap electrocatalyst or the reduction of the loading of noble metals makes the hydrogen production process by water electrolysis more economical and efficient, and is an urgent scientific problem.
Ternary nickel phosphorus sulfide (NiPS) 3 ) Is a novel HER electrocatalyst material and has excellent performance. For example, the unique layered structure enables it to be exfoliated into two-dimensional materials, providing a more active surface for electrocatalytic reactions; has a moderate bandgap (-1.6 eV) and a suitable electronic bandgap; excellent activity and high stability in alkaline medium; the electronegativity difference of phosphorus and sulfur makes the in-plane electronic structure rich and diverse, and can meet various electronic requirements. Despite the foregoing features and advantages, NiPS 3 Many scientific issues remain for catalytic research, as embodied by: the traditional liquid phase stripping has low efficiency and can not synthesize nanosheets with large transverse sizes; NiPS 3 The intrinsic conductivity of the material is poor, and the charge transmission is not facilitated; further improvement of the catalytic performance is limited by the inert surface, and a suitable substrate surface activation method is required.
Currently, in order to obtain two-dimensional materials with optimal surface chemistry and electronic state, many efforts have been made to develop effective synthetic strategies such as atomic doping, controlling elemental composition, adjusting the crystalline phase, changing the number of atomic layers, reducing lateral dimensions, exposing appropriate atoms, and creating potential defects. Atomic doping is considered to be an effective strategy to both enhance charge carrier transfer and modulate adsorption energy. In particular, the introduction of metal dopants can provide rich active sites, introduce new energy levels, and adjust hydrogen adsorption/desorption balances, all of which are critical to the development of efficient two-dimensional electrocatalysts. Although methods such as atomic layer deposition and magnetron sputtering are successful metal doping techniques for mechanically stripped two-dimensional materials, they are not suitable for liquid-stripped two-dimensional materials. Therefore, in order to meet the yield requirements for mass production, a more efficient mass production technique that synchronizes metal doping and stripping is highly desirable.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a composite heterostructure nanosheet, a preparation method and application.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
metal-loaded NiPS 3 The preparation method of the composite heterostructure nanosheet comprises the following steps:
(1) dissolving tetrabutylammonium tetrafluoroborate and metal salt in N, N-dimethylformamide to obtain electrolyte;
(2) NiPS is prepared 3 The block body is arranged between Pt nets and is used as a working electrode, a platinum wire electrode is used as a counter electrode, and the working electrode and the counter electrode are arranged in electrolyte;
the working electrode and the counter electrode are respectively and electrically connected with the negative electrode and the positive electrode of a power supply, voltage is applied between the working electrode and the counter electrode, and NiPS is subjected to electric field 3 Stripping and doping the block until NiPS 3 Loose spongy tissue appears in the block;
(3) NiPS is prepared 3 Subjecting the block to ultrasonic treatment in electrolyte, stripping loose spongy tissue under the action of ultrasonic treatment to form suspension, centrifuging, collecting, cleaning, and drying to obtain powdered metal-loaded NiPS 3 Nanosheets.
Further, in the step (1), the metal salt is cobalt chloride hexahydrate, molybdenum pentachloride, rhodium chloride trihydrate, palladium dichloride, ferrous chloride tetrahydrate or ruthenium chloride trihydrate.
Further, in the step (1), the concentration of the metal salt in the electrolyte is 5X 10 -3 ～5×10 -2 M。
Further, applying a static bias voltage of-5 to-10V on the working electrode in the step (2).
Further, the time was 6 hours.
Metal-loaded NiPS 3 Composite heterostructure nanosheets prepared according to any one of the preparation methods of the present invention.
Metal-loaded NiPS 3 The application of the composite heterostructure nanosheet is a cathode hydrogen evolution reaction catalyst for electrocatalytic water decomposition.
Further, the method is used in alkaline environment.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a metal-loaded NiPS 3 The preparation method of the heterostructure nanosheet adopts a one-step electrochemical stripping synchronous doping technology, and can efficiently mix the bulk NiPS 3 The material is stripped into two-dimensional nanosheets with thin thickness and large transverse dimension (mum level), and simultaneously metal atoms are doped in the nanosheets, so that the hydrogen evolution performance of the nanosheets under alkaline conditions is greatly improved.
The metal-loaded NiPS of the invention 3 Composite heterostructure nano-sheet, doping Co, Mo, Fe, Rh, Pd, Ru metal atoms in NiPS 3 In NiPS, the metal atom acts as a dopant 3 On one hand, the defects produced in the crystal lattice cause the conversion of an electronic structure and the redistribution of charges, thereby enhancing the conductivity of the system, promoting the transmission of carriers and being beneficial to the improvement of catalytic performance, and on the other hand, the metal atoms can be used as active sites, thereby increasing the number of the active sites of the system and influencing the intrinsic activity of the system; transition metals such as Co, Mo, Fe and the like have d orbitals, can meet the requirement of giving or obtaining electrons, and can optimize the adsorption/desorption energy of H adsorption and H desorption by introducing the transition metals, thereby optimizing the thermodynamic process of hydrogen evolution reaction. The precious metals such as Rh, Pd, Ru and the like have excellent intrinsic catalytic activity and are applied to NiPS 3 Sufficient dispersion on the substrate can reduce the amount of noble metal used, while having high catalytic activity.
The metal-loaded NiPS of the invention 3 The composite heterostructure nanosheet is used as an electrocatalytic water decomposition catalyst and shows equivalent effectHigh level of hydrogen evolution performance. Various metal supported nano sheets are synthesized by one-step electrochemical synchronous stripping with a very simple synthesis technology. In an alkaline medium (1M KOH) at 10mA cm –2 Overpotential (η) of HER at current density 10 ) All with different degrees of improvement. Specifically, NiPS stripping with pure electrochemical 3 Eta of 10 Compared with 257mV, the electrochemical stripping is synchronously doped with Co-NiPS 3 Eta of 10 Is 199mV of Mo-NiPS 3 156mV of Rh-NiPS 3 151mV of Pd-NiPS 3 Is 52mV of Fe-NiPS 3 Is 161mV of Ru-NiPS 3 The 191mV metal supported nanosheets exhibited far greater catalytic activity than the pure material.
Drawings
FIG. 1 is a SEM photograph of example 1, in which FIG. 1(a) NiPS 3 SEM image of bulk, FIG. 1(b) is electrochemical stripping NiPS 3 Scanning electron microscope images of the nanosheets;
FIG. 2 shows the electrochemical stripping of Co-NiPS for simultaneous doping in example 2 3 Microscopic characterization of the nanoplatelets, wherein FIG. 2(a) SEM pictures, FIG. 2(b-c) EDS spectra pictures and results;
FIG. 3 shows the electrochemical stripping of synchronously doped Mo-NiPS prepared in example 3 3 Microscopic characterization of the nanoplatelets, wherein FIG. 3(a) SEM pictures, FIG. 3(b-c) EDS spectra and results;
FIG. 4 shows the electrochemical stripping of the simultaneous doping of Rh-NiPS prepared in example 4 3 Microscopic characterization of the nanoplatelets, wherein FIG. 4(a) SEM pictures, FIG. 4(b-c) EDS spectra and results;
FIG. 5 shows the electrochemical stripping of synchronously doped Pd-NiPS prepared in example 5 3 Microscopic characterization of the nanoplatelets, wherein FIG. 5(a) SEM pictures, FIG. 5(b-c) EDS spectra and results;
FIG. 6 is a microscopic characterization of the electrochemical stripping codoped products prepared in examples 6 and 7, wherein FIG. 6(a) is Fe-NiPS of example 6 3 Nanosheets, FIG. 6(b) being the Ru-NiPS of example 7 3 SEM photograph of nanosheets;
FIG. 7 shows electrochemical stripping NiPS prepared in example 1 3 Of nanosheetsHydrogen evolution linear voltammetry;
FIG. 8 shows the electrochemical stripping of Co-NiPS for simultaneous doping in example 2 3 Hydrogen evolution linear voltammetry of the nanosheets;
FIG. 9 shows the electrochemical stripping of synchronously doped Mo-NiPS prepared in example 3 3 Hydrogen evolution linear voltammetry of the nanosheets;
FIG. 10 shows the electrochemical stripping of the simultaneous doping of Rh-NiPS prepared in example 4 3 Hydrogen evolution linear voltammetry of the nanosheets;
FIG. 11 shows the electrochemical stripping of synchronously doped Pd-NiPS prepared in example 5 3 Hydrogen evolution linear voltammetry of the nanosheets;
FIG. 12 shows the electrochemical stripping of synchronously doped Fe-NiPS prepared in example 6 3 Hydrogen evolution linear voltammetry of the nanosheets;
FIG. 13 shows the electrochemical exfoliation of synchronously doped Ru-NiPS prepared in example 7 3 Hydrogen evolution linear voltammogram of the nanosheets.
Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in other sequences than those illustrated or described herein. Moreover, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides an electrochemical stripping synchronous doping method based on a ternary nickel-phosphorus sulfide system, which can realize synchronous metal doping during crystal stripping and produce metal-loaded NiPS (nickel-phosphorus sulfide) with high yield 3 A composite heterostructure nanoplate. The results show that the metal-supported NiPS 3 The nano-sheet has more excellent hydrogen evolution performance than a pure material. The invention provides a more efficient and low-cost electrochemical stripping synchronous doping method for efficiently producing metal-loaded NiPS with excellent hydrogen evolution performance 3 A composite heterostructure nanosheet aims to solve the problems of low stripping efficiency, complex doping process and low catalytic activity.
The invention is described in further detail below with reference to the accompanying drawings:
metal-loaded NiPS 3 A method of making a composite heterostructure electrocatalyst, comprising the steps of:
1) preparing an electrolyte
Preparing N, N-Dimethylformamide (DMF) solution of tetrabutylammonium Tetrafluoroborate (TBAB) with the concentration of 0.05M, and dissolving a metal salt in the DMF solution of TBAB, wherein the metal salt is cobalt chloride hexahydrate, molybdenum pentachloride, rhodium chloride trihydrate, palladium dichloride, ferrous chloride tetrahydrate or ruthenium chloride trihydrate, and the concentration of the metal salt is 5 x 10 –3 ～5×10 –2 M, performing ultrasonic treatment for 20min, and stirring for 60min to obtain the electrolyte.
2) Preparation of metal-loaded NiPS by electrochemical stripping synchronous doping method 3 Nano-sheet
Bulk NiPS was performed using an electrochemical workstation consisting of a two-electrode system (CHI 650, Chenghua instruments works, Shanghai, China) 3 The electrochemical peeling of the crystal is synchronously doped with the metal. Mixing NiPS 3 The bulk crystal is sandwiched between metal platinum meshes, and the platinum meshes are sandwiched on platinum clamps to serve as working electrodes. A platinum wire electrode was used as the counter electrode. Electrolyte is used as a step oneAnd (3) preparing an electrolyte in advance. A static bias voltage of-5 to-10V is applied to the working electrode, and the reaction time is 6 h. In the electrochemical stripping synchronous doping process, a large amount of NiPS 3 The crystals expand and flake off, forming a suspension. Subsequently, the suspension was collected and subjected to ice-water bath sonication for 10 min. The resulting product was washed 3 times with absolute ethanol, centrifuged to remove large, non-exfoliated masses, and the rest was collected, followed by drying under vacuum at 60 ℃ for 10 h. For comparison, NiPS was prepared in the same manner 3 Bulk crystals were stripped electrochemically only, except that the electrolyte was a 0.05M TBAB in DMF (30ml) and contained no metal salts.
3) Electrochemical Performance test
Acetylene black (1mg) and catalyst material (4mg) were mixed and ground into a mortar and placed in a 1ml vial. Then, isopropyl alcohol (450. mu.L), ultrapure water (50. mu.L) and 5 wt% Nafion (20. mu.L) were added to the bottle, and ultrasonic treatment was performed for 2 hours to form a catalytic ink. Subsequently, catalytic ink (10 μ L) was uniformly deposited on a glassy carbon (GC, 3mm) working electrode and dried for several hours to form a uniform catalytic film. The catalysts were tested for HER performance in alkaline solution (1M KOH) using an Autolab PGSTAT204 workstation. The three-electrode system consists of a reference electrode (Ag/AgCl), a graphite rod counter electrode and a GC working electrode. The scanning test speed of the Linear Scanning Voltammetry (LSV) curve is 5mV s -1 The potential range is-0.6-0.1V (vs RHE, HER, 1M KOH). Before a stable LSV curve was obtained, each electrode was measured at 100mV s -1 Was subjected to 20 cyclic voltammetry tests (CV).
Example 1
1) Preparing electrolyte
A solution of 0.05M tetrabutylammonium Tetrafluoroborate (TBAB) in N, N-Dimethylformamide (DMF) (30ml) was prepared, sonicated for 20min and stirred at high speed for 60min to form a homogeneous solution.
2) Preparation of metal-loaded NiPS by electrochemical stripping synchronous doping method 3 Nano-sheet
NiPS is clamped between the metal platinum nets 3 Bulk crystals, and platinum mesh was clamped on a platinum clamp as the working electrode. A platinum wire electrode was used as the counter electrode. Electrolyte is prepared by the following stepsAnd (3) preparing an electrolyte in advance. The bulk NiPS was completed using an electrochemical workstation (Shanghai Hua instruments factory CHI 650, China) 3 Electrochemical peeling of the crystal, a static bias of-5V is applied to the working electrode, and the reaction time is 6 h. Large amount of NiPS during electrochemical stripping 3 The crystals expand and flake off, forming a suspension. Subsequently, the suspension was collected and subjected to sonication in a mild ice bath for 10 min. The resulting product was washed 3 times with absolute ethanol, centrifuged to remove large, non-exfoliated blocks, and the remainder was collected, then dried under vacuum at 60 ℃ for 10 h.
3) Electrochemical performance test
The catalyst material (4mg) and acetylene black (1mg) were mixed and ground into a mortar, which was then dispersed in a solution consisting of isopropyl alcohol (450. mu.L), ultrapure water (50. mu.L) and 5 wt% Nafion (20. mu.L), and sonicated for 2 h. Subsequently, catalytic ink (10 μ L) was uniformly deposited and dried on a glassy carbon (GC, 3mm) working electrode for several hours to form a thin film consisting of a catalyst. HER performance in alkaline solution (1M KOH) was tested on the Autolab PGSTAT204 workstation.
Example 2
1) Preparing an electrolyte
A0.05M solution of tetrabutylammonium Tetrafluoroborate (TBAB) in N, N-Dimethylformamide (DMF) (30ml) was prepared and dissolved at 5X 10 –3 And (3) carrying out ultrasonic treatment on the cobalt chloride hexahydrate of the M for 20min, and stirring at a high speed for 60min to form a homogeneous solution.
2) Preparation of metal-loaded NiPS by electrochemical stripping synchronous doping method 3 Nano-sheet
NiPS is clamped between the metal platinum nets 3 Bulk crystals, platinum mesh was clamped on a platinum clamp as the working electrode. A platinum wire electrode was used as the counter electrode. The electrolyte is prepared in advance in the step one. The bulk NiPS was completed using an electrochemical workstation (Shanghai Hua instruments factory CHI 650, China) 3 Electrochemical peeling of the crystal, a static bias of-5V is applied to the working electrode, and the reaction time is 6 h. In the electrochemical stripping process, a large amount of NiPS 3 The crystals expand and flake off, forming a suspension. Subsequently, the suspension was collected and subjected to mild ice bath sonication for 10 min.The resulting product was washed 3 times with absolute ethanol, centrifuged to remove large, non-exfoliated blocks, and the remainder was collected, then dried under vacuum at 60 ℃ for 10 h.
3) Electrochemical performance test
The catalyst material (4mg) and acetylene black (1mg) were mixed and ground into a mortar, which was then dispersed in a solution composed of isopropyl alcohol (450. mu.L), ultrapure water (50. mu.L) and 5 wt% Nafion (20. mu.L), and subjected to ultrasonic treatment for 2 hours. Subsequently, catalytic ink (10 μ L) was uniformly deposited and dried on a glassy carbon (GC, 3mm) working electrode for several hours to form a thin film consisting of a catalyst. HER performance in alkaline solution (1M KOH) was tested on the Autolab PGSTAT204 workstation.
Example 3
1) Preparing an electrolyte
A0.05M solution of tetrabutylammonium Tetrafluoroborate (TBAB) in N, N-Dimethylformamide (DMF) (30ml) was prepared and dissolved at 5X 10 –3 M molybdenum pentachloride, sonicated for 20min, and stirred at high speed for 60min to form a homogeneous solution.
2) Preparation of metal-loaded NiPS by electrochemical stripping synchronous doping method 3 Nano-sheet
NiPS is clamped between the metal platinum nets 3 Bulk crystals, and platinum mesh was clamped on a platinum clamp as the working electrode. A platinum wire electrode was used as the counter electrode. The electrolyte is prepared in advance in the first step. The electrochemical workstation (CHI 650, Shanghai Hua apparatus, China) was used to complete a large block of NiPS 3 Electrochemical peeling of the crystal, a static bias of-5V is applied to the working electrode, and the reaction time is 6 h. In the electrochemical stripping process, a large amount of NiPS 3 The crystals expanded and exfoliated to form a suspension. Subsequently, the suspension was collected and subjected to sonication in a mild ice bath for 10 min. The resulting product was washed 3 times with absolute ethanol, centrifuged to remove large, non-exfoliated blocks, and the remainder was collected, then dried under vacuum at 60 ℃ for 10 h.
3) Electrochemical performance test
The catalyst material (4mg) and acetylene black (1mg) were mixed and ground into a mortar, which was then dispersed in a solution consisting of isopropyl alcohol (450. mu.L), ultrapure water (50. mu.L) and 5 wt% Nafion (20. mu.L), and sonicated for 2 h. Subsequently, catalytic ink (10 μ L) was uniformly deposited and dried on a glassy carbon (GC, 3mm) working electrode for several hours to form a thin film consisting of a catalyst. HER performance in alkaline solution (1M KOH) was tested on the Autolab PGSTAT204 workstation.
Example 4
1) Preparing electrolyte
A0.05M solution of tetrabutylammonium Tetrafluoroborate (TBAB) in N, N-Dimethylformamide (DMF) (30ml) was prepared and dissolved at 5X 10 –3 M rhodium chloride trihydrate, sonicated for 20min, and stirred at high speed for 60min to form a homogeneous solution.
2) Preparation of metal-loaded NiPS by electrochemical stripping synchronous doping method 3 Nano-sheet
NiPS is clamped between the metal platinum nets 3 Bulk crystals, platinum mesh was clamped on a platinum clamp as the working electrode. A platinum wire electrode was used as the counter electrode. The electrolyte is prepared in advance in the step one. The bulk NiPS was completed using an electrochemical workstation (Shanghai Hua instruments factory CHI 650, China) 3 And (4) electrochemically peeling off the crystals, applying a static bias of-5V to the working electrode, and reacting for 6 h. In the electrochemical stripping process, a large amount of NiPS 3 The crystals expand and flake off, forming a suspension. Subsequently, the suspension was collected and subjected to mild ice bath sonication for 10 min. The resulting product was washed 3 times with absolute ethanol, centrifuged to remove large, non-exfoliated blocks, and the remainder was collected, then dried under vacuum at 60 ℃ for 10 h.
3) Electrochemical performance test
The catalyst material (4mg) and acetylene black (1mg) were mixed and ground into a mortar, which was then dispersed in a solution composed of isopropyl alcohol (450. mu.L), ultrapure water (50. mu.L) and 5 wt% Nafion (20. mu.L), and subjected to ultrasonic treatment for 2 hours. Subsequently, the catalytic ink (10 μ L) was uniformly deposited and dried on a glassy carbon (GC, 3mm) working electrode for several hours to form a thin film consisting of the catalyst. HER performance in alkaline solution (1M KOH) was tested on an Autolab PGSTAT204 workstation.
Example 5
1) Preparing an electrolyte
A0.05M solution of tetrabutylammonium Tetrafluoroborate (TBAB) in N, N-Dimethylformamide (DMF) (30ml) was prepared and dissolved at 5X 10 –3 M Palladium dichloride, sonicated for 20min, and stirred at high speed for 60min to form a homogeneous solution.
2) Preparation of metal-loaded NiPS by electrochemical stripping synchronous doping method 3 Nano-sheet
NiPS is clamped between the metal platinum nets 3 Bulk crystals, platinum mesh was clamped on a platinum clamp as the working electrode. A platinum wire electrode was used as the counter electrode. The electrolyte is prepared in advance in the step one. The electrochemical workstation (CHI 650, Shanghai Hua apparatus, China) was used to complete a large block of NiPS 3 And (4) electrochemically peeling off the crystals, applying a static bias of-5V to the working electrode, and reacting for 6 h. In the electrochemical stripping process, a large amount of NiPS 3 The crystals expand and flake off, forming a suspension. Subsequently, the suspension was collected and subjected to mild ice bath sonication for 10 min. The resulting product was washed 3 times with absolute ethanol, centrifuged to remove large, non-exfoliated blocks, and the remainder was collected, then dried under vacuum at 60 ℃ for 10 h.
3) Electrochemical performance test
The catalyst material (4mg) and acetylene black (1mg) were mixed and ground into a mortar, which was then dispersed in a solution composed of isopropyl alcohol (450. mu.L), ultrapure water (50. mu.L) and 5 wt% Nafion (20. mu.L), and subjected to ultrasonic treatment for 2 hours. Subsequently, the catalytic ink (10 μ L) was uniformly deposited and dried on a glassy carbon (GC, 3mm) working electrode for several hours to form a thin film consisting of the catalyst. HER performance in alkaline solution (1M KOH) was tested on the Autolab PGSTAT204 workstation.
Example 6
1) Preparing an electrolyte
A0.05M solution of tetrabutylammonium Tetrafluoroborate (TBAB) in N, N-Dimethylformamide (DMF) (30ml) was prepared and dissolved at 5X 10 –3 M ferrous chloride tetrahydrate, ultrasonic sound for 20min, high speed stirring for 60min to form homogeneous solution.
2) Preparation of metal-loaded NiPS by electrochemical stripping synchronous doping method 3 Nano-sheet
In metalNiPS sandwiched between platinum nets 3 Bulk crystals, platinum mesh was clamped on a platinum clamp as the working electrode. A platinum wire electrode was used as the counter electrode. The electrolyte is prepared in advance in the step one. The bulk NiPS was completed using an electrochemical workstation (Shanghai Hua instruments factory CHI 650, China) 3 Electrochemical peeling of the crystal, a static bias of-5V is applied to the working electrode, and the reaction time is 6 h. In the electrochemical stripping process, a large amount of NiPS 3 The crystals expand and flake off, forming a suspension. Subsequently, the suspension was collected and subjected to mild ice bath sonication for 10 min. The resulting product was washed 3 times with absolute ethanol, centrifuged to remove large, non-exfoliated masses, and the rest was collected, followed by drying under vacuum at 60 ℃ for 10 h.
3) Electrochemical Performance test
The catalyst material (4mg) and acetylene black (1mg) were mixed and ground into a mortar, which was then dispersed in a solution composed of isopropyl alcohol (450. mu.L), ultrapure water (50. mu.L) and 5 wt% Nafion (20. mu.L), and subjected to ultrasonic treatment for 2 hours. Subsequently, the catalytic ink (10 μ L) was uniformly deposited and dried on a glassy carbon (GC, 3mm) working electrode for several hours to form a thin film consisting of the catalyst. HER performance in alkaline solution (1M KOH) was tested on the Autolab PGSTAT204 workstation.
Example 7
1) Preparing an electrolyte
A0.05M solution of tetrabutylammonium Tetrafluoroborate (TBAB) in N, N-Dimethylformamide (DMF) (30ml) was prepared and dissolved at 5X 10 –3 M ruthenium chloride trihydrate, sonicated for 20min, stirred at high speed for 60min to form a homogeneous solution.
2) Preparation of metal-loaded NiPS by electrochemical stripping synchronous doping method 3 Nano-sheet
NiPS is clamped between the metal platinum nets 3 Bulk crystals, and platinum mesh was clamped on a platinum clamp as the working electrode. A platinum wire electrode was used as the counter electrode. The electrolyte is prepared in advance in the step one. The bulk NiPS was completed using an electrochemical workstation (Shanghai Hua instruments factory CHI 650, China) 3 Electrochemical peeling of the crystal, a static bias of-5V is applied to the working electrode, and the reaction time is 6 h. In electrochemical strippingDuring the separation process, a large amount of NiPS 3 The crystals expand and flake off, forming a suspension. Subsequently, the suspension was collected and subjected to mild ice bath sonication for 10 min. The resulting product was washed 3 times with absolute ethanol, centrifuged to remove large, non-exfoliated blocks, and the remainder was collected, then dried under vacuum at 60 ℃ for 10 h.
3) Electrochemical performance test
The catalyst material (4mg) and acetylene black (1mg) were mixed and ground into a mortar, which was then dispersed in a solution composed of isopropyl alcohol (450. mu.L), ultrapure water (50. mu.L) and 5 wt% Nafion (20. mu.L), and subjected to ultrasonic treatment for 2 hours. Subsequently, catalytic ink (10 μ L) was uniformly deposited and dried on a glassy carbon (GC, 3mm) working electrode for several hours to form a thin film consisting of a catalyst. HER performance in alkaline solution (1M KOH) was tested on the Autolab PGSTAT204 workstation.
The samples prepared in examples 1-7 were subjected to characterization tests and the results were as follows:
referring to FIG. 1, bulk NiPS prepared in example 1 3 And electrochemical stripping of NiPS 3 The NiPS can be seen from the Scanning Electron Microscope (SEM) picture of the nano sheet 3 The bulk is typically a layer, and NiPS of the bulk is achieved by electrochemical lift-off technology 3 Can be well stripped to form micrometer-scale flake.
Referring to FIG. 2, FIG. 2 shows the electrochemical stripping of Co-NiPS for simultaneous doping in example 2 3 SEM photograph (a) of nanosheet, EDS energy spectrum photograph (b-c) and results. Co-NiPS 3 Visible granular substances exist on the nanosheets, the nanosheet surfaces are not smooth any more, and the energy spectrum result shows that Co element exists.
Referring to FIG. 3, FIG. 3 shows the electrochemical stripping of the synchronously doped Mo-NiPS prepared in example 3 3 SEM photograph (a) of the nanosheets, and EDS energy spectrum photograph (b-c) and the results. Mo-NiPS 3 NiPS with relatively pure stripped nano sheets 3 The transverse size of the nano-sheet is reduced, and the energy spectrum result shows that Mo element exists.
Referring to FIG. 4, FIG. 4 shows the electrochemical stripping of the simultaneous doping of Rh-NiPS prepared in example 4 3 SEM photograph (a) of the nanosheets, and EDS energy spectrum photograph (b-c) and the results. Rh-NiPS 3 Granular substances exist on the surfaces of the nano sheets, the nano sheets are stacked, and the energy spectrum result shows that Rh elements exist.
Referring to FIG. 5, FIG. 5 shows the electrochemical stripping of synchronously doped Pd-NiPS prepared in example 5 3 SEM photograph (a) of nanosheet, EDS energy spectrum photograph (b-c) and results. Pd-NiPS 3 The nano-sheet has obvious granular substances, the whole nano-sheet structure is complete, and the energy spectrum result shows the existence of Pd elements.
Referring to FIG. 6, FIG. 6 shows the electrochemical stripping simultaneous doping (a) of Fe-NiPS prepared in examples 6 and 7 3 Nanosheet and (b) Ru-NiPS 3 SEM photograph of nanoplatelets. Exfoliated Fe-NiPS 3 Nanosheet and Ru-NiPS 3 The nanoplatelets are all relatively small in lateral dimension.
Referring to FIGS. 7-13, electrochemical stripping NiPS is shown, respectively 3 Nano sheet and electrochemical stripping synchronous doping Co-NiPS 3 ，Mo-NiPS 3 ，Rh-NiPS 3 ，Pd-NiPS 3 ，Fe-NiPS 3 ，Ru-NiPS 3 Hydrogen evolution linear voltammogram of the nanosheets. In 1M KOH, NiPS is stripped from pure electrochemical 3 (257mV) comparison, electrochemical stripping Co-NiPS doping 3 (199mV)，Mo-NiPS 3 (156mV)，Rh-NiPS 3 (151mV)，Pd-NiPS 3 (52mV)，Fe-NiPS 3 (161mV)，Ru-NiPS 3 (191mV) Gem at 10mA –2 Over potential (η) of 10 ) All have different degrees of reduction, which indicates that the electrochemical stripping synchronously doped nano-sheet has excellent HER activity, and the technology is advantageous compared with single doping.
Example 8
1) Preparing electrolyte
A0.05M solution of tetrabutylammonium Tetrafluoroborate (TBAB) in N, N-Dimethylformamide (DMF) (30ml) was prepared and dissolved at 1X 10 –2 And (3) carrying out ultrasonic treatment on the cobalt chloride hexahydrate of the M for 20min, and stirring at a high speed for 60min to form a homogeneous solution.
2) Preparation of metal-loaded NiPS by electrochemical stripping synchronous doping method 3 Nano-sheet
On the middle clip of the metal platinum netNiPS 3 Bulk crystals, platinum mesh was clamped on a platinum clamp as the working electrode. A platinum wire electrode was used as the counter electrode. The electrolyte is prepared in advance in the step one. The bulk NiPS was completed using an electrochemical workstation (Shanghai Hua instruments factory CHI 650, China) 3 Electrochemical peeling of the crystal, a static bias of-10V is applied to the working electrode, and the reaction time is 6 h. In the electrochemical stripping process, a large amount of NiPS 3 The crystals expand and flake off, forming a suspension. Subsequently, the suspension was collected and subjected to mild ice bath sonication for 10 min. The resulting product was washed 3 times with absolute ethanol, centrifuged to remove large, non-exfoliated blocks, and the remainder was collected, then dried under vacuum at 60 ℃ for 10 h.
3) Electrochemical Performance test
The catalyst material (4mg) and acetylene black (1mg) were mixed and ground into a mortar, which was then dispersed in a solution composed of isopropyl alcohol (450. mu.L), ultrapure water (50. mu.L) and 5 wt% Nafion (20. mu.L), and subjected to ultrasonic treatment for 2 hours. Subsequently, catalytic ink (10 μ L) was uniformly deposited and dried on a glassy carbon (GC, 3mm) working electrode for several hours to form a thin film consisting of a catalyst. HER performance in alkaline solution (1M KOH) was tested on the Autolab PGSTAT204 workstation.
Example 9
1) Preparing an electrolyte
A0.05M solution of tetrabutylammonium Tetrafluoroborate (TBAB) in N, N-Dimethylformamide (DMF) (30ml) was prepared and dissolved at 5X 10 –2 M cobalt chloride hexahydrate, ultrasonically treated for 20min, and stirred at a high speed for 60min to form a homogeneous solution.
2) Preparation of metal-loaded NiPS by electrochemical stripping synchronous doping method 3 Nano-sheet
NiPS is clamped between the metal platinum nets 3 Bulk crystals, platinum mesh was clamped on a platinum clamp as the working electrode. A platinum wire electrode was used as the counter electrode. The electrolyte is prepared in advance in the first step. The electrochemical workstation (CHI 650, Shanghai Hua apparatus, China) was used to complete a large block of NiPS 3 Electrochemical peeling of the crystal, a static bias of-5V is applied to the working electrode, and the reaction time is 6 h. In the electrochemical stripping process, is largeQuantitative NiPS 3 The crystals expand and flake off, forming a suspension. Subsequently, the suspension was collected and subjected to mild ice bath sonication for 10 min. The resulting product was washed 3 times with absolute ethanol, centrifuged to remove large, non-exfoliated blocks, and the remainder was collected, then dried under vacuum at 60 ℃ for 10 h.
3) Electrochemical performance test
The catalyst material (4mg) and acetylene black (1mg) were mixed and ground into a mortar, which was then dispersed in a solution composed of isopropyl alcohol (450. mu.L), ultrapure water (50. mu.L) and 5 wt% Nafion (20. mu.L), and subjected to ultrasonic treatment for 2 hours. Subsequently, the catalytic ink (10 μ L) was uniformly deposited and dried on a glassy carbon (GC, 3mm) working electrode for several hours to form a thin film consisting of the catalyst. HER performance in alkaline solution (1M KOH) was tested on the Autolab PGSTAT204 workstation.
Example 10
1) Preparing an electrolyte
A0.05M solution of tetrabutylammonium Tetrafluoroborate (TBAB) in N, N-Dimethylformamide (DMF) (30ml) was prepared and dissolved at 5X 10 –3 M molybdenum pentachloride, sonicated for 20min, and stirred at high speed for 60min to form a homogeneous solution.
2) Preparation of metal-loaded NiPS by electrochemical stripping synchronous doping method 3 Nano-sheet
NiPS is clamped in the middle of the metal platinum net 3 Bulk crystals, and platinum mesh was clamped on a platinum clamp as the working electrode. A platinum wire electrode was used as the counter electrode. The electrolyte is prepared in advance in the first step. The bulk NiPS was completed using an electrochemical workstation (Shanghai Hua instruments factory CHI 650, China) 3 And (4) electrochemically peeling off the crystals, applying a static bias of-10V to the working electrode, and reacting for 6 h. In the electrochemical stripping process, a large amount of NiPS 3 The crystals expanded and exfoliated to form a suspension. Subsequently, the suspension was collected and subjected to mild ice bath sonication for 10 min. The resulting product was washed 3 times with absolute ethanol, centrifuged to remove large, non-exfoliated blocks, and the remainder was collected, then dried under vacuum at 60 ℃ for 10 h.
3) Electrochemical performance test
The catalyst material (4mg) and acetylene black (1mg) were mixed and ground into a mortar, which was then dispersed in a solution composed of isopropyl alcohol (450. mu.L), ultrapure water (50. mu.L) and 5 wt% Nafion (20. mu.L), and subjected to ultrasonic treatment for 2 hours. Subsequently, catalytic ink (10 μ L) was uniformly deposited and dried on a glassy carbon (GC, 3mm) working electrode for several hours to form a thin film consisting of a catalyst. HER performance in alkaline solution (1M KOH) was tested on the Autolab PGSTAT204 workstation.
Example 11
1) Preparing electrolyte
A0.05M solution of tetrabutylammonium Tetrafluoroborate (TBAB) in N, N-Dimethylformamide (DMF) (30ml) was prepared and dissolved at 5X 10 –2 M rhodium chloride hydrate, ultrasonic 20min, high speed stirring for 60min to form homogeneous solution.
2) Preparation of metal-loaded NiPS by electrochemical stripping synchronous doping method 3 Nano-sheet
NiPS is clamped between the metal platinum nets 3 Bulk crystals, platinum mesh was clamped on a platinum clamp as the working electrode. A platinum wire electrode was used as the counter electrode. The electrolyte is prepared in advance in the step one. The electrochemical workstation (CHI 650, Shanghai Hua apparatus, China) was used to complete a large block of NiPS 3 And (4) electrochemically peeling off the crystals, applying a static bias of-5V to the working electrode, and reacting for 6 h. In the electrochemical stripping process, a large amount of NiPS 3 The crystals expand and flake off, forming a suspension. Subsequently, the suspension was collected and subjected to mild ice bath sonication for 10 min. The resulting product was washed 3 times with absolute ethanol, centrifuged to remove large, non-exfoliated masses, and the rest was collected, followed by drying under vacuum at 60 ℃ for 10 h.
3) Electrochemical Performance test
The catalyst material (4mg) and acetylene black (1mg) were mixed and ground into a mortar, which was then dispersed in a solution composed of isopropyl alcohol (450. mu.L), ultrapure water (50. mu.L) and 5 wt% Nafion (20. mu.L), and subjected to ultrasonic treatment for 2 hours. Subsequently, catalytic ink (10 μ L) was uniformly deposited and dried on a glassy carbon (GC, 3mm) working electrode for several hours to form a thin film consisting of a catalyst. HER performance in alkaline solution (1M KOH) was tested on the Autolab PGSTAT204 workstation.
Example 12
1) Preparing an electrolyte
A0.05M solution of tetrabutylammonium Tetrafluoroborate (TBAB) in N, N-Dimethylformamide (DMF) (30ml) was prepared and dissolved at 1X 10 –2 M ferrous chloride tetrahydrate, ultrasonic sound for 20min, high speed stirring for 60min to form homogeneous solution.
2) Preparation of metal-loaded NiPS by electrochemical stripping synchronous doping method 3 Nano-sheet
NiPS is clamped in the middle of the metal platinum net 3 Bulk crystals, platinum mesh was clamped on a platinum clamp as the working electrode. A platinum wire electrode was used as the counter electrode. The electrolyte is prepared in advance in the step one. The electrochemical workstation (CHI 650, Shanghai Hua apparatus, China) was used to complete a large block of NiPS 3 Electrochemical peeling of the crystal, a static bias of-10V is applied to the working electrode, and the reaction time is 6 h. In the electrochemical stripping process, a large amount of NiPS 3 The crystals expand and flake off, forming a suspension. Subsequently, the suspension was collected and subjected to mild ice bath sonication for 10 min. The resulting product was washed 3 times with absolute ethanol, centrifuged to remove large, non-exfoliated blocks, and the remainder was collected, then dried under vacuum at 60 ℃ for 10 h.
3) Electrochemical performance test
The catalyst material (4mg) and acetylene black (1mg) were mixed and ground into a mortar, which was then dispersed in a solution consisting of isopropyl alcohol (450. mu.L), ultrapure water (50. mu.L) and 5 wt% Nafion (20. mu.L), and sonicated for 2 h. Subsequently, catalytic ink (10 μ L) was uniformly deposited and dried on a glassy carbon (GC, 3mm) working electrode for several hours to form a thin film consisting of a catalyst. HER performance in alkaline solution (1M KOH) was tested on the Autolab PGSTAT204 workstation.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (8)

1. Metal-loaded NiPS 3 The preparation method of the composite heterostructure nanosheet is characterized by comprising the following steps:
(1) dissolving tetrabutylammonium tetrafluoroborate and metal salt in N, N-dimethylformamide to obtain electrolyte;
(2) NiPS is prepared 3 The block body is arranged between Pt nets and is used as a working electrode, a platinum wire electrode is used as a counter electrode, and the working electrode and the counter electrode are arranged in electrolyte;
the working electrode and the counter electrode are respectively and electrically connected with the negative electrode and the positive electrode of a power supply, voltage is applied between the working electrode and the counter electrode, and NiPS is subjected to electric field treatment 3 Stripping and doping the block until NiPS 3 Loose spongy tissue appears in the block;
(3) NiPS is prepared 3 The block is subjected to ultrasonic treatment in electrolyte, loose spongy tissue is stripped under the ultrasonic action to form suspension, then centrifugal collection is carried out, and after cleaning and drying, powdery metal-loaded NiPS is obtained 3 A composite heterostructure nanoplate.
2. Metal supported NiPS according to claim 1 3 The preparation method of the composite heterostructure nanosheet is characterized in that in step (1), the metal salt is cobalt chloride hexahydrate, molybdenum pentachloride, rhodium chloride trihydrate, palladium dichloride, ferrous chloride tetrahydrate or ruthenium chloride trihydrate.
3. Metal supported NiPS according to claim 1 3 The preparation method of the composite heterostructure nanosheet is characterized in that in step (1), the concentration of the metal salt in the electrolyte is 5 x 10 -3 ～5×10 -2 M。
4. Metal-loaded NiPS according to claim 1 3 The preparation method of the composite heterostructure nanosheet is characterized in that a static bias of-5 to-10V is applied to the working electrode in the step (2).
5. Metal-loaded NiPS according to claim 4 3 The preparation method of the composite heterostructure nanosheet is characterized in that the voltage application time is 6 h.
6. Metal-loaded NiPS 3 Composite heterostructure nanoplatelets prepared according to the preparation process of any of claims 1 to 5.
7. Metal supported NiPS according to claim 6 3 The application of the composite heterostructure nanosheet is characterized in that the catalyst is used for a cathodic hydrogen evolution reaction for electrocatalytic water decomposition.
8. Metal-loaded NiPS according to claim 7 3 Use of a composite heterostructured nanoplate, characterized by its use in an alkaline environment.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018111191A1 (en) * 2016-12-12 2018-06-21 Nanyang Technological University Activating transition metal phosphochalcogenide for highly efficient hydrogen evolution
CN109052495A (en) * 2018-11-06 2018-12-21 深圳大学 A kind of NiPS3Nanometer sheet and preparation method thereof
CN109772386A (en) * 2019-03-22 2019-05-21 哈尔滨工业大学 The NiPS of self supporting structure3The preparation method and applications of nanometer sheet
CN110359059A (en) * 2018-04-11 2019-10-22 中国科学院金属研究所 Electro-catalysis produces oxygen NiPS3/ graphene composite catalyst and preparation method thereof
CN113151857A (en) * 2021-03-29 2021-07-23 浙江大学衢州研究院 Two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018111191A1 (en) * 2016-12-12 2018-06-21 Nanyang Technological University Activating transition metal phosphochalcogenide for highly efficient hydrogen evolution
CN110359059A (en) * 2018-04-11 2019-10-22 中国科学院金属研究所 Electro-catalysis produces oxygen NiPS3/ graphene composite catalyst and preparation method thereof
CN109052495A (en) * 2018-11-06 2018-12-21 深圳大学 A kind of NiPS3Nanometer sheet and preparation method thereof
CN109772386A (en) * 2019-03-22 2019-05-21 哈尔滨工业大学 The NiPS of self supporting structure3The preparation method and applications of nanometer sheet
CN113151857A (en) * 2021-03-29 2021-07-23 浙江大学衢州研究院 Two-dimensional ultrathin nickel-doped molybdenum disulfide nanosheet and preparation method and application thereof

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