CN114990580B - Composite heterostructure nanosheet, preparation method and application - Google Patents

Composite heterostructure nanosheet, preparation method and application Download PDF

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CN114990580B
CN114990580B CN202210833561.4A CN202210833561A CN114990580B CN 114990580 B CN114990580 B CN 114990580B CN 202210833561 A CN202210833561 A CN 202210833561A CN 114990580 B CN114990580 B CN 114990580B
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CN114990580A (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 disclosesA composite heterostructure nanosheet, a preparation method and application thereof relate to the technical field of electrocatalytic decomposition of water. The invention discloses a metal-loaded NiPS 3 The preparation method of the heterostructure nanosheets adopts a one-step electrochemical stripping synchronous doping technology, and can efficiently carry out NiPS on the block body 3 The material is stripped into a two-dimensional nano sheet with thin thickness and large transverse dimension (mu m level), and metal atoms are doped in the nano sheet, so that the hydrogen evolution performance of the nano sheet under alkaline conditions is greatly improved. The invention dopes metal atoms in NiPS 3 In which metal atoms act as dopants in NiPS 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 a system is enhanced, the carrier transmission is promoted, and the promotion 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 decomposition of water, in particular to a composite heterostructure nanosheet, a preparation method and application thereof.
Background
The hydrogen energy is a clean and pollution-free secondary energy source and has higher quality energy density. The abundant water resources on earth provide a prerequisite for sustainable hydrogen production. The electric energy required by water decomposition can be converted by renewable energy sources, and the decomposition products are pollution-free. However, in the electrocatalytic decomposition process of water, cathodic Hydrogen Evolution (HER) involves multiple electron transfer processes, resulting in overpotential and energy loss. Thus, high performance electrocatalysts are needed to reduce the overpotential for water decomposition. Currently, the best catalyst for HER production is platinum-based, but platinum has a small earth reserve and is expensive, which greatly limits its commercial use. Therefore, developing an efficient and low-cost electrocatalyst or reducing the noble metal loading amount, so that the water electrolysis hydrogen production process is more economical and efficient, is an urgent scientific problem.
Ternary nickel phosphorus sulfide (NiPS) 3 ) Is a novel HER electrocatalyst material with 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; with a medium bandgap (-1.6 eV) and a suitable electronic bandgap; has excellent activity and high stability in alkaline medium; electronegativity difference of phosphorus and sulfur makes in-plane electronic structure abundantIs rich and various, and can meet various electronic requirements. Despite the above features and advantages, niPS 3 Many scientific problems still face for catalytic research, embodied as: the traditional liquid phase stripping efficiency is low, and nano sheets with larger transverse size can not be synthesized; niPS (NiPS) 3 Is inherently less conductive and is not conducive to charge transport; further improvements in catalytic performance are limited by the inert surface, requiring appropriate substrate surface activation methods.
Currently, in order to obtain two-dimensional materials with optimal surface chemistry and electronic state, many efforts have been made to develop efficient synthesis strategies such as atomic doping, controlling elemental composition, adjusting the crystalline phase, changing the number of atomic layers, reducing lateral dimensions, exposing the appropriate atoms, and creating potential defects. Atomic doping is considered to be an effective strategy for both enhancing charge carrier transfer and modulating the adsorption energy. In particular, the introduction of metal dopants can provide rich active sites, introduce new energy levels, and adjust the hydrogen adsorption/desorption equilibrium, 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 exfoliated two-dimensional materials, they are not suitable for liquid-exfoliated two-dimensional materials. Therefore, in order to meet the yield requirements required for mass production, a more efficient mass production technique for simultaneously performing metal doping and stripping is highly desired.
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 is realized by adopting the following technical scheme:
metal-loaded NiPS 3 The preparation method of the composite heterostructure nanosheets comprises the following steps:
(1) Dissolving tetrabutylammonium tetrafluoroborate and metal salt in N, N-dimethylformamide to obtain electrolyte;
(2) NiPS is to 3 The block is arranged between Pt meshes as workThe electrode takes a platinum wire electrode as a counter electrode, and the working electrode and the counter electrode are placed in electrolyte;
the working electrode and the counter electrode are respectively electrically connected with the negative electrode and the positive electrode of a power supply, and a voltage is applied between the working electrode and the counter electrode to the NiPS 3 Stripping and doping the block until NiPS 3 The block body has loose spongy tissue;
(3) NiPS is to 3 The block is subjected to ultrasonic treatment in electrolyte, loose spongy tissue is stripped under the action of ultrasonic treatment to form suspension, and then centrifugal collection is carried out, and after washing and drying, powdered metal-loaded NiPS is obtained 3 A nano-sheet.
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, in the step (2), a static bias voltage of-5 to-10V is applied to the working electrode.
Further, the time was 6 hours.
Metal-loaded NiPS 3 The composite heterostructure nanosheets are prepared by the preparation method according to any one of the invention.
Metal-loaded NiPS 3 The application of the composite heterostructure nanosheets is used for 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 nanosheets adopts a one-step electrochemical stripping synchronous doping technology, and can efficiently carry out NiPS on the block body 3 The material is exfoliated into two-dimensional nanoplatelets of thin thickness, large transverse dimensions (μm scale), while the metal atoms are doped in the nanoplatelets so that theyThe hydrogen evolution performance under alkaline conditions is greatly improved.
The metal-loaded NiPS of the invention 3 The Co, mo, fe, rh, pd, ru metal atoms are doped in NiPS by the composite heterostructure nanosheets 3 In which metal atoms act as dopants in NiPS 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 a system, promoting the carrier transmission and being beneficial to the improvement of the catalytic performance, and on the other hand, metal atoms can be used as active sites, so that the number of the active sites of the system is increased, and the intrinsic activity of the system is influenced; the transition metals such as Co, mo, fe and the like have d orbits, can meet the requirements of electron giving or obtaining, 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. Noble metals such as Rh, pd, ru and the like have excellent intrinsic catalytic activity, and are used in NiPS 3 The full dispersion on the substrate can reduce the noble metal dosage and has high catalytic activity.
The metal-loaded NiPS of the invention 3 The composite heterostructure nanosheets, as electrocatalytic water splitting catalysts, exhibit a relatively high level of hydrogen evolution performance. The various metal-loaded nano-sheets are synthesized by electrochemical synchronous stripping in one step with very simple synthesis technology. In alkaline medium (1M KOH) at a temperature of up to 10mA.cm –2 Over potential (eta) of HER at current density 10 ) All have different degrees of improvement. Specifically, niPS is peeled off with pure chemical 3 η of (2) 10 Electrochemical stripping synchronous doping Co-NiPS for 257mV compared 3 η of (2) 10 For 199mV, mo-NiPS 3 156mV, rh-NiPS 3 151mV, pd-NiPS 3 52mV, fe-NiPS 3 161mV, ru-NiPS 3 Metallic supported nanoplatelets at 191mV exhibit catalytic activity far exceeding that of pure materials.
Drawings
FIG. 1 is an SEM image of example 1, wherein FIG. 1 (a) NiPS 3 SEM of the block and FIG. 1 (b) is an electrochemically stripped NiPS 3 Scanning electron microscope pictures of the nano-sheets;
FIG. 2 is an embodiment2, synchronously doping Co-NiPS by electrochemical stripping 3 A microscopic characterization map of the nanoplatelets, wherein fig. 2 (a) SEM photograph, fig. 2 (b-c) EDS spectroscopy photograph and results;
FIG. 3 is an electrochemical stripping synchronous doping Mo-NiPS prepared in example 3 3 A microscopic characterization map of the nanoplatelets, wherein fig. 3 (a) SEM photograph, fig. 3 (b-c) EDS spectroscopy photograph and results;
FIG. 4 is an electrochemical stripping synchronous doping Rh-NiPS prepared in example 4 3 A microscopic characterization map of the nanoplatelets, wherein fig. 4 (a) SEM photograph, fig. 4 (b-c) EDS spectra photograph and results;
FIG. 5 is an electrochemical stripping synchronous doping Pd-NiPS prepared in example 5 3 A microscopic characterization map of the nanoplatelets, wherein fig. 5 (a) SEM photograph, fig. 5 (b-c) EDS spectroscopy photograph and results;
FIG. 6 is a microscopic characterization of the electrochemical stripping synchronous doping product prepared in example 6 and example 7, wherein FIG. 6 (a) is the Fe-NiPS of example 6 3 Nanoplatelets, FIG. 6 (b) is Ru-NiPS of example 7 3 SEM photograph of nanoplatelets;
FIG. 7 is an electrochemically peeled NiPS prepared in example 1 3 Hydrogen evolution linear voltammetry curve of the nanosheets;
FIG. 8 is an electrochemical stripping synchronous doping Co-NiPS prepared in example 2 3 Hydrogen evolution linear voltammetry curve of the nanosheets;
FIG. 9 is an electrochemical stripping synchronous doping Mo-NiPS prepared in example 3 3 Hydrogen evolution linear voltammetry curve of the nanosheets;
FIG. 10 is an electrochemical stripping synchronous doping Rh-NiPS prepared in example 4 3 Hydrogen evolution linear voltammetry curve of the nanosheets;
FIG. 11 is an electrochemical stripping synchronous doping Pd-NiPS prepared in example 5 3 Hydrogen evolution linear voltammetry curve of the nanosheets;
FIG. 12 is an electrochemical stripping synchronous doping Fe-NiPS prepared in example 6 3 Hydrogen evolution linear voltammetry curve of the nanosheets;
FIG. 13 is an electrochemical stripping synchronous doping Ru-NiPS prepared according to example 7 3 Hydrogen evolution linear voltammetry curve of the nanoplatelets.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, 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 with high yield 3 Composite heterostructure nanoplatelets. The results show that the metal-loaded NiPS 3 The nano-sheet has more excellent hydrogen evolution performance than pure materials. 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 The nano sheet with the composite heterostructure solves 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 attached drawing figures:
metal-loaded NiPS 3 The preparation method of the composite heterostructure electrocatalyst comprises the following steps:
1) Preparing electrolyte
Preparing N, N-Dimethylformamide (DMF) solution with the concentration of 0.05M tetrabutylammonium Tetrafluoroborate (TBAB), dissolving 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 multiplied by 10 –3 ～5×10 –2 And M, carrying out 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 Nanosheets
Bulk NiPS using an electrochemical workstation (CHI 650 from Shanghai Chen Hua Instrument Co., china) consisting of a double electrode System 3 Electrochemical exfoliation of the crystal is synchronized with the metal doping. NiPS is put into 3 The bulk crystal is clamped in the middle of the metal platinum net, and the platinum net is clamped on the platinum clamp to be used as a working electrode. A platinum wire electrode was used as a counter electrode. The electrolyte is the electrolyte prepared in advance in the first step. And applying a static bias voltage of-5 to-10V to the working electrode, wherein the reaction time is 6h. In the process of electrochemical stripping synchronous doping, 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 pieces, and the remaining product was collected, followed by drying under vacuum at 60 ℃ for 10 hours. In contrast, niPS was prepared in the same manner 3 The bulk crystals were only electrochemically exfoliated, except that the electrolyte was a DMF solution (30 ml) at a concentration of 0.05M TBAB, containing no metal salts.
3) Electrochemical performance test
Acetylene black (1 mg) and catalyst material (4 mg) were mixed and ground to a mortar, placed in a 1ml vial. Isopropanol (450 μl), ultrapure water (50 μl) and 5wt% nafion (20 μl) were then added to the flask and sonicated for 2h to form catalytic ink. Subsequently, the catalytic ink (10 μl) was uniformly deposited on a glassy carbon (GC, 3 mm) working electrode and dried for several hours to form a uniform catalytic film. HER performance of the catalyst in alkaline solution (1M KOH) was tested using an Autolab PGSTAT204 workstation. The three electrode system consisted of a reference electrode (Ag/AgCl), a graphite rod counter electrode and a GC working electrode. The scan test speed of the Linear Sweep Voltammetry (LSV) curve is 5mV s -1 The potential range was selected to be-0.6-0.1V (vs RHE, HER,1M KOH). Before a stable LSV curve was obtained, each electrode was measured at 100mV s -1 Is subjected to 20 cyclic voltammetry tests (CV).
Example 1
1) Preparing electrolyte
An N, N-Dimethylformamide (DMF) solution (30 ml) was prepared at a concentration of 0.05M tetrabutylammonium Tetrafluoroborate (TBAB), 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 Nanosheets
Nip NiPS in the middle of metal platinum net 3 And (3) a large crystal, and clamping the platinum net on the platinum clamp to serve as a working electrode. A platinum wire electrode was used as a counter electrode. The electrolyte is the electrolyte prepared in advance in the first step. Large-scale NiPS was completed using an electrochemical workstation (CHI 650 from Shanghai Chen Hua Instrument Co., china) 3 The crystals were electrochemically exfoliated and a static bias of-5V was applied to the working electrode for a reaction time of 6h. 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 pieces, and the remaining product was collected, followed by drying under vacuum at 60 ℃ for 10 hours.
3) Electrochemical performance test
Catalyst material (4 mg) and acetylene black (1 mg) were mixed and ground into mortar, which was then dispersed in a solution consisting of isopropyl alcohol (450 μl), ultrapure water (50 μl) and 5wt% nafion (20 μl), and sonicated for 2 hours. Subsequently, catalytic ink (10 μl) was uniformly deposited and dried on a glassy carbon (GC, 3 mm) working electrode for several hours to form a thin film composed of the catalyst. HER performance in alkaline solution (1M KOH) was tested on an Autolab PGSTAT204 workstation.
Example 2
1) Preparing electrolyte
N, N-Dimethylformamide (DMF) solution (30 ml) at a concentration of 0.05M tetrabutylammonium Tetrafluoroborate (TBAB) was prepared and dissolved 5X 10 –3 M cobalt chloride hexahydrate, 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 Nanosheets
Nip NiPS in the middle of metal platinum net 3 And (3) a large crystal, and clamping the platinum net on the platinum clamp to serve as a working electrode. A platinum wire electrode was used as a counter electrode. The electrolyte is the electrolyte prepared in advance in the first step. Large-scale NiPS was completed using an electrochemical workstation (CHI 650 from Shanghai Chen Hua Instrument Co., china) 3 The crystals were electrochemically exfoliated and a static bias of-5V was applied to the working electrode for a reaction time of 6h. 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 pieces, and the remaining product was collected, followed by drying under vacuum at 60 ℃ for 10 hours.
3) Electrochemical performance test
Catalyst material (4 mg) and acetylene black (1 mg) were mixed and ground into mortar, which was then dispersed in a solution consisting of isopropyl alcohol (450 μl), ultrapure water (50 μl) and 5wt% nafion (20 μl), and sonicated for 2 hours. Subsequently, catalytic ink (10 μl) was uniformly deposited and dried on a glassy carbon (GC, 3 mm) working electrode for several hours to form a thin film composed of the catalyst. HER performance in alkaline solution (1M KOH) was tested on an Autolab PGSTAT204 workstation.
Example 3
1) Preparing electrolyte
N, N-Dimethylformamide (DMF) solution (30 ml) at a concentration of 0.05M tetrabutylammonium Tetrafluoroborate (TBAB) was prepared and dissolved 5X 10 –3 M molybdenum pentachloride, superbThe sound was applied 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 Nanosheets
Nip NiPS in the middle of metal platinum net 3 And (3) a large crystal, and clamping the platinum net on the platinum clamp to serve as a working electrode. A platinum wire electrode was used as a counter electrode. The electrolyte is the electrolyte prepared in advance in the first step. Large-scale NiPS was completed using an electrochemical workstation (CHI 650 from Shanghai Chen Hua Instrument Co., china) 3 The crystals were electrochemically exfoliated and a static bias of-5V was applied to the working electrode for a reaction time of 6h. 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 pieces, and the remaining product was collected, followed by drying under vacuum at 60 ℃ for 10 hours.
3) Electrochemical performance test
Catalyst material (4 mg) and acetylene black (1 mg) were mixed and ground into mortar, which was then dispersed in a solution consisting of isopropyl alcohol (450 μl), ultrapure water (50 μl) and 5wt% nafion (20 μl), and sonicated for 2 hours. Subsequently, catalytic ink (10 μl) was uniformly deposited and dried on a glassy carbon (GC, 3 mm) working electrode for several hours to form a thin film composed of the catalyst. HER performance in alkaline solution (1M KOH) was tested on an Autolab PGSTAT204 workstation.
Example 4
1) Preparing electrolyte
N, N-Dimethylformamide (DMF) solution (30 ml) at a concentration of 0.05M tetrabutylammonium Tetrafluoroborate (TBAB) was prepared and dissolved 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 Nanosheets
Nip NiPS in the middle of metal platinum net 3 And (3) a large crystal, and clamping the platinum net on the platinum clamp to serve as a working electrode. A platinum wire electrode was used as a counter electrode. The electrolyte being prepared in advance in step oneAnd (3) an electrolyte. Large-scale NiPS was completed using an electrochemical workstation (CHI 650 from Shanghai Chen Hua Instrument Co., china) 3 The crystals were electrochemically exfoliated and a static bias of-5V was applied to the working electrode for a reaction time of 6h. 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 pieces, and the remaining product was collected, followed by drying under vacuum at 60 ℃ for 10 hours.
3) Electrochemical performance test
Catalyst material (4 mg) and acetylene black (1 mg) were mixed and ground into mortar, which was then dispersed in a solution consisting of isopropyl alcohol (450 μl), ultrapure water (50 μl) and 5wt% nafion (20 μl), and sonicated for 2 hours. Subsequently, catalytic ink (10 μl) was uniformly deposited and dried on a glassy carbon (GC, 3 mm) working electrode for several hours to form a thin film composed of the catalyst. HER performance in alkaline solution (1M KOH) was tested on an Autolab PGSTAT204 workstation.
Example 5
1) Preparing electrolyte
N, N-Dimethylformamide (DMF) solution (30 ml) at a concentration of 0.05M tetrabutylammonium Tetrafluoroborate (TBAB) was prepared and dissolved 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 Nanosheets
Nip NiPS in the middle of metal platinum net 3 And (3) a large crystal, and clamping the platinum net on the platinum clamp to serve as a working electrode. A platinum wire electrode was used as a counter electrode. The electrolyte is the electrolyte prepared in advance in the first step. Large-scale NiPS was completed using an electrochemical workstation (CHI 650 from Shanghai Chen Hua Instrument Co., china) 3 The crystals were electrochemically exfoliated and a static bias of-5V was applied to the working electrode for a reaction time of 6h. 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. Anhydrous ethyl acetate for the obtained productThe alcohol was washed 3 times, centrifuged to remove large non-exfoliated pieces, and the remaining product was collected, followed by drying under vacuum at 60 ℃ for 10h.
3) Electrochemical performance test
Catalyst material (4 mg) and acetylene black (1 mg) were mixed and ground into mortar, which was then dispersed in a solution consisting of isopropyl alcohol (450 μl), ultrapure water (50 μl) and 5wt% nafion (20 μl), and sonicated for 2 hours. Subsequently, catalytic ink (10 μl) was uniformly deposited and dried on a glassy carbon (GC, 3 mm) working electrode for several hours to form a thin film composed of the catalyst. HER performance in alkaline solution (1M KOH) was tested on an Autolab PGSTAT204 workstation.
Example 6
1) Preparing electrolyte
N, N-Dimethylformamide (DMF) solution (30 ml) at a concentration of 0.05M tetrabutylammonium Tetrafluoroborate (TBAB) was prepared and dissolved 5X 10 –3 M ferrous chloride tetrahydrate, 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 Nanosheets
Nip NiPS in the middle of metal platinum net 3 And (3) a large crystal, and clamping the platinum net on the platinum clamp to serve as a working electrode. A platinum wire electrode was used as a counter electrode. The electrolyte is the electrolyte prepared in advance in the first step. Large-scale NiPS was completed using an electrochemical workstation (CHI 650 from Shanghai Chen Hua Instrument Co., china) 3 The crystals were electrochemically exfoliated and a static bias of-5V was applied to the working electrode for a reaction time of 6h. 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 pieces, and the remaining product was collected, followed by drying under vacuum at 60 ℃ for 10 hours.
3) Electrochemical performance test
Catalyst material (4 mg) and acetylene black (1 mg) were mixed and ground into mortar, which was then dispersed in a solution consisting of isopropyl alcohol (450 μl), ultrapure water (50 μl) and 5wt% nafion (20 μl), and sonicated for 2 hours. Subsequently, catalytic ink (10 μl) was uniformly deposited and dried on a glassy carbon (GC, 3 mm) working electrode for several hours to form a thin film composed of the catalyst. HER performance in alkaline solution (1M KOH) was tested on an Autolab PGSTAT204 workstation.
Example 7
1) Preparing electrolyte
N, N-Dimethylformamide (DMF) solution (30 ml) at a concentration of 0.05M tetrabutylammonium Tetrafluoroborate (TBAB) was prepared and dissolved 5X 10 –3 M ruthenium 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 Nanosheets
Nip NiPS in the middle of metal platinum net 3 And (3) a large crystal, and clamping the platinum net on the platinum clamp to serve as a working electrode. A platinum wire electrode was used as a counter electrode. The electrolyte is the electrolyte prepared in advance in the first step. Large-scale NiPS was completed using an electrochemical workstation (CHI 650 from Shanghai Chen Hua Instrument Co., china) 3 The crystals were electrochemically exfoliated and a static bias of-5V was applied to the working electrode for a reaction time of 6h. 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 pieces, and the remaining product was collected, followed by drying under vacuum at 60 ℃ for 10 hours.
3) Electrochemical performance test
Catalyst material (4 mg) and acetylene black (1 mg) were mixed and ground into mortar, which was then dispersed in a solution consisting of isopropyl alcohol (450 μl), ultrapure water (50 μl) and 5wt% nafion (20 μl), and sonicated for 2 hours. Subsequently, catalytic ink (10 μl) was uniformly deposited and dried on a glassy carbon (GC, 3 mm) working electrode for several hours to form a thin film composed of the catalyst. HER performance in alkaline solution (1M KOH) was tested on an Autolab PGSTAT204 workstation.
Characterization tests were performed on the samples prepared in examples 1-7, with the following results:
referring to FIG. 1, a bulk NiPS prepared in example 1 3 Electrochemical stripping of NiPS 3 Scanning Electron Microscope (SEM) pictures of nanoplatelets, one can see NiPS 3 The blocks are typically lamellar, with the NiPS of the block being by electrochemical stripping techniques 3 Can be well peeled off to form a micron-sized flake.
Referring to FIG. 2, FIG. 2 is an electrochemical stripping synchronous doped Co-NiPS prepared in example 2 3 (a) SEM photograph, (b-c) EDS spectroscopy photograph and results of the nanoplatelets. Co-NiPS 3 The nanosheets have visible granular substances, the surfaces of the nanosheets are not smooth any more, and the energy spectrum results show the existence of Co elements.
Referring to FIG. 3, FIG. 3 is an electrochemical stripping synchronous doped Mo-NiPS prepared in example 3 3 (a) SEM photograph, (b-c) EDS spectroscopy photograph and results of the nanoplatelets. Mo-NiPS 3 Nanoplatelet relatively pure exfoliated NiPS 3 The nanoplatelets have reduced lateral dimensions and the spectroscopic results indicate the presence of Mo elements.
Referring to FIG. 4, FIG. 4 is an electrochemical stripping synchronous doping Rh-NiPS prepared in example 4 3 (a) SEM photograph, (b-c) EDS spectroscopy photograph and results of the nanoplatelets. Rh-NiPS 3 Granular substances exist on the surfaces of the nano-sheets, the nano-sheets are stacked, and the energy spectrum result shows the existence of Rh element.
Referring to FIG. 5, FIG. 5 is an electrochemical stripping synchronous doped Pd-NiPS prepared in example 5 3 (a) SEM photograph, (b-c) EDS spectroscopy photograph and results of the nanoplatelets. Pd-NiPS 3 The nanosheets have obvious granular substances, the whole nanosheets have complete structures, and the energy spectrum results show the existence of Pd elements.
Referring to FIG. 6, FIG. 6 is an electrochemical stripping synchronous doping (a) Fe-NiPS prepared in example 6 and example 7 3 Nanoplatelets and (b) Ru-NiPS 3 SEM photograph of nanoplatelets. Stripped Fe-NiPS 3 Nanoplatelets and Ru-NiPS 3 The lateral dimensions of the nanoplatelets are relatively small.
Referring to FIGS. 7-13, the NiPS is electrochemically stripped, respectively 3 Nanosheets 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 voltammetry curve of the nanoplatelets. NiPS was stripped with pure chemical in 1M KOH 3 (257 mV) compared with the electrochemical stripping synchronous doping Co-NiPS 3 (199mV)，Mo-NiPS 3 (156mV)，Rh-NiPS 3 (151mV)，Pd-NiPS 3 (52mV)，Fe-NiPS 3 (161mV)，Ru-NiPS 3 (191 mV) nanosheets at 10mA cm –2 The overpotential (. Eta.) 10 ) There are various degrees of reduction, indicating that electrochemical stripping of synchronously doped nanoplates has superior HER activity, which is advantageous over single doping.
Example 8
1) Preparing electrolyte
N, N-Dimethylformamide (DMF) solution (30 ml) at a concentration of 0.05M tetrabutylammonium Tetrafluoroborate (TBAB) was prepared and dissolved 1X 10 –2 M cobalt chloride hexahydrate, 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 Nanosheets
Nip NiPS in the middle of metal platinum net 3 And (3) a large crystal, and clamping the platinum net on the platinum clamp to serve as a working electrode. A platinum wire electrode was used as a counter electrode. The electrolyte is the electrolyte prepared in advance in the first step. Large-scale NiPS was completed using an electrochemical workstation (CHI 650 from Shanghai Chen Hua Instrument Co., china) 3 The crystals were electrochemically exfoliated and a static bias of-10V was applied to the working electrode for a reaction time of 6h. 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 pieces, and the remaining product was collected, followed by drying under vacuum at 60 ℃ for 10 hours.
3) Electrochemical performance test
Catalyst material (4 mg) and acetylene black (1 mg) were mixed and ground into mortar, which was then dispersed in a solution consisting of isopropyl alcohol (450 μl), ultrapure water (50 μl) and 5wt% nafion (20 μl), and sonicated for 2 hours. Subsequently, catalytic ink (10 μl) was uniformly deposited and dried on a glassy carbon (GC, 3 mm) working electrode for several hours to form a thin film composed of the catalyst. HER performance in alkaline solution (1M KOH) was tested on an Autolab PGSTAT204 workstation.
Example 9
1) Preparing electrolyte
N, N-Dimethylformamide (DMF) solution (30 ml) at a concentration of 0.05M tetrabutylammonium Tetrafluoroborate (TBAB) was prepared and dissolved 5X 10 –2 M cobalt chloride hexahydrate, 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 Nanosheets
Nip NiPS in the middle of metal platinum net 3 And (3) a large crystal, and clamping the platinum net on the platinum clamp to serve as a working electrode. A platinum wire electrode was used as a counter electrode. The electrolyte is the electrolyte prepared in advance in the first step. Large-scale NiPS was completed using an electrochemical workstation (CHI 650 from Shanghai Chen Hua Instrument Co., china) 3 The crystals were electrochemically exfoliated and a static bias of-5V was applied to the working electrode for a reaction time of 6h. 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 pieces, and the remaining product was collected, followed by drying under vacuum at 60 ℃ for 10 hours.
3) Electrochemical performance test
Catalyst material (4 mg) and acetylene black (1 mg) were mixed and ground into mortar, which was then dispersed in a solution consisting of isopropyl alcohol (450 μl), ultrapure water (50 μl) and 5wt% nafion (20 μl), and sonicated for 2 hours. Subsequently, catalytic ink (10 μl) was uniformly deposited and dried on a glassy carbon (GC, 3 mm) working electrode for several hours to form a thin film composed of the catalyst. HER performance in alkaline solution (1M KOH) was tested on an Autolab PGSTAT204 workstation.
Example 10
1) Preparing electrolyte
The concentration is prepared as follows0.05M solution of tetrabutylammonium Tetrafluoroborate (TBAB) in N, N-Dimethylformamide (DMF) (30 ml) and dissolved 5X 10 –3 M molybdenum pentachloride, 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 Nanosheets
Nip NiPS in the middle of metal platinum net 3 And (3) a large crystal, and clamping the platinum net on the platinum clamp to serve as a working electrode. A platinum wire electrode was used as a counter electrode. The electrolyte is the electrolyte prepared in advance in the first step. Large-scale NiPS was completed using an electrochemical workstation (CHI 650 from Shanghai Chen Hua Instrument Co., china) 3 The crystals were electrochemically exfoliated and a static bias of-10V was applied to the working electrode for a reaction time of 6h. 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 pieces, and the remaining product was collected, followed by drying under vacuum at 60 ℃ for 10 hours.
3) Electrochemical performance test
Catalyst material (4 mg) and acetylene black (1 mg) were mixed and ground into mortar, which was then dispersed in a solution consisting of isopropyl alcohol (450 μl), ultrapure water (50 μl) and 5wt% nafion (20 μl), and sonicated for 2 hours. Subsequently, catalytic ink (10 μl) was uniformly deposited and dried on a glassy carbon (GC, 3 mm) working electrode for several hours to form a thin film composed of the catalyst. HER performance in alkaline solution (1M KOH) was tested on an Autolab PGSTAT204 workstation.
Example 11
1) Preparing electrolyte
N, N-Dimethylformamide (DMF) solution (30 ml) at a concentration of 0.05M tetrabutylammonium Tetrafluoroborate (TBAB) was prepared and dissolved 5X 10 –2 M rhodium chloride hydrate, 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 Nanosheets
Nip NiPS in the middle of metal platinum net 3 And (3) a large crystal, and clamping the platinum net on the platinum clamp to serve as a working electrode. A platinum wire electrode was used as a counter electrode. The electrolyte is the electrolyte prepared in advance in the first step. Large-scale NiPS was completed using an electrochemical workstation (CHI 650 from Shanghai Chen Hua Instrument Co., china) 3 The crystals were electrochemically exfoliated and a static bias of-5V was applied to the working electrode for a reaction time of 6h. 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 pieces, and the remaining product was collected, followed by drying under vacuum at 60 ℃ for 10 hours.
3) Electrochemical performance test
Catalyst material (4 mg) and acetylene black (1 mg) were mixed and ground into mortar, which was then dispersed in a solution consisting of isopropyl alcohol (450 μl), ultrapure water (50 μl) and 5wt% nafion (20 μl), and sonicated for 2 hours. Subsequently, catalytic ink (10 μl) was uniformly deposited and dried on a glassy carbon (GC, 3 mm) working electrode for several hours to form a thin film composed of the catalyst. HER performance in alkaline solution (1M KOH) was tested on an Autolab PGSTAT204 workstation.
Example 12
1) Preparing electrolyte
N, N-Dimethylformamide (DMF) solution (30 ml) at a concentration of 0.05M tetrabutylammonium Tetrafluoroborate (TBAB) was prepared and dissolved 1X 10 –2 M ferrous chloride tetrahydrate, 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 Nanosheets
Nip NiPS in the middle of metal platinum net 3 And (3) a large crystal, and clamping the platinum net on the platinum clamp to serve as a working electrode. A platinum wire electrode was used as a counter electrode. The electrolyte is the electrolyte prepared in advance in the first step. Large-scale NiPS was completed using an electrochemical workstation (CHI 650 from Shanghai Chen Hua Instrument Co., china) 3 The crystals were electrochemically exfoliated and a static bias of-10V was applied to the working electrode for a reaction time of 6h. 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 pieces, and the remaining product was collected, followed by drying under vacuum at 60 ℃ for 10 hours.
3) Electrochemical performance test
Catalyst material (4 mg) and acetylene black (1 mg) were mixed and ground into mortar, which was then dispersed in a solution consisting of isopropyl alcohol (450 μl), ultrapure water (50 μl) and 5wt% nafion (20 μl), and sonicated for 2 hours. Subsequently, catalytic ink (10 μl) was uniformly deposited and dried on a glassy carbon (GC, 3 mm) working electrode for several hours to form a thin film composed of the catalyst. HER performance in alkaline solution (1M KOH) was tested on an Autolab PGSTAT204 workstation.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to 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 nanosheets is characterized by comprising the following steps of:
(1) Dissolving tetrabutylammonium tetrafluoroborate and metal salt in N, N-dimethylformamide to obtain electrolyte;
(2) NiPS is to 3 The block is arranged between Pt meshes to be 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 electrically connected with the negative electrode and the positive electrode of a power supply, and a voltage is applied between the working electrode and the counter electrode to the NiPS 3 Stripping and doping the block until NiPS 3 The block body has loose spongy tissue;
(3) NiPS is to 3 The block is subjected to ultrasound in electrolyte, loose spongy tissue is peeled off under the action of ultrasound to form suspension, and thenCentrifugally collecting, cleaning and drying to obtain powdered metal-loaded NiPS 3 Composite heterostructure nanoplatelets.
2. The metal-loaded NiPS of claim 1 3 The preparation method of the composite heterostructure nanosheets is characterized in that 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.
3. The metal-loaded NiPS of claim 1 3 The preparation method of the composite heterostructure nanosheets is characterized in that in the step (1), the concentration of metal salt in the electrolyte is 5 multiplied by 10 -3 ～5×10 -2 M。
4. The metal-loaded NiPS of claim 1 3 The preparation method of the composite heterostructure nanosheets is characterized in that in the step (2), static bias voltage of-5 to-10V is applied to a working electrode.
5. The metal-loaded NiPS of claim 4 3 The preparation method of the composite heterostructure nanosheets is characterized by comprising the step of applying voltage for 6 hours.
6. Metal-loaded NiPS 3 The composite heterostructure nanosheets of any one of claims 1 to 5.
7. A metal-loaded NiPS as set forth in claim 6 3 The application of the composite heterostructure nanosheets is characterized by being a cathode hydrogen evolution reaction catalyst for electrocatalytic water decomposition.
8. The metal-loaded NiPS of claim 7 3 The application of the composite heterostructure nanosheets is characterized by being used in 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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