CN111330599A - Composite nano material electrocatalyst for high-efficiency hydrogen evolution reaction and preparation method thereof - Google Patents
Composite nano material electrocatalyst for high-efficiency hydrogen evolution reaction and preparation method thereof Download PDFInfo
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a composite nano material electrocatalyst for high-efficiency hydrogen evolution reaction and a preparation method thereof. The electrocatalyst is MoS2Composite nanomaterials with B-doped graphene, i.e. composed of a high proportion of MoS with defects and/or edges2The layer uniformly supports the heterogeneous composite nanomaterial formed on the B-doped graphene. The preparation method comprises the steps of oxidizing graphene and boric acid in hydrothermal solution in the presence of Na2MoO4And L-cysteine, and obtaining MoS through one-step hydrothermal reaction2A/B-graphene-doped composite nano material serving as an electrocatalyst of hydrogen evolution reaction, and the prepared MoS2Doped stone/B-stoneThe graphene composite nanomaterial showed a relatively high electrocatalytic activity and a low Tafel slope (46.3 mV/dec). MoS of the invention2the/B-doped graphene composite nano material is used as an electrocatalyst of a hydrogen evolution reaction with high efficiency and low cost, and has wide application prospect in the aspect of hydrogen production by water electrolysis.
Description
Technical Field
The invention relates to a composite nano material electrocatalyst for high-efficiency hydrogen evolution reaction and a preparation method thereof, in particular to MoS2A/B-doped graphene composite nano material electrocatalyst and a preparation method thereof belong to the technical field of new energy materials and application.
Background
MoS2The laminated structure is a typical laminated structure, and the laminated structure is formed by connecting and superposing S-Mo-S layers of a sandwich structure through van der Waals force. Nanoscale MoS2Has good electrocatalytic activity on Hydrogen Evolution Reaction (HER). Although Pt and Pt-based nanomaterials have optimal electrocatalytic properties for HER, the scarcity and high price of their resources limit the scale-up applications in the production of hydrogen by electrolysis of water. MoS2The electrocatalytic HER activity of (A) is mainly derived from its border sites (YAN Y, XIA B Y, GE X M, equivalent. Ultrathin MoS)2nanoplates with rich active sites as highly efficientcatalyst for hydrogen evolution[J].ACS Applied Materials&Interfaces,2013,5(24): 12794-. At the same time, MoS2The low conductivity limits its application as an electrocatalyst.
Mixing MoS2Compounding with carbon nanomaterials with high conductivity and flexibility (e.g., graphene, carbon nanotubes, etc.) is an effective approach to solve the above-mentioned problems in electrochemical applications (LI Y G, WANG H L, XIE L M, equivalent2nanoparticles grown on graphene:an advanced catalyst for the hydrogenevolution reaction[J].Journal of the American Chemical Society,2011,133(19):7296-7299；YAN Y,GE X M,LIU Z L,et al.Facile synthesis of low crystallineMoS2nanosheet-coated CNTs for enhanced hydrogen evolution reaction[J]Nanoscale,2013,5(17): 7768-7771). Graphene has high electron conductivity and charge mobility, as well as a very large specific surface area and inherently good flexibility. Graphene and MoS2The compounding not only obviously improves the conductivity of the composite material, but also can better inhibit MoS2Stacking or agglomerating the layers to obtain MoS with fewer layers and more active sites at the edges2And (3) a layer. Due to MoS2The interaction between the nanosheets and the graphene can enhance the electrochemical application performance of the prepared composite material.
Researches show that heterogeneous atom (such as N, S and the like) doped graphene can modify the electronic structure of graphene and change the physical and chemical properties of graphene, so that the electrocatalytic activity, electrochemical lithium storage performance and other performances of graphene and the composite material thereof (YE J B, YU Z T, CHEN W X, et al2/nitrogen-doped graphenecomposites for enhanced electrocatalytic hydrogen evolution andelectrochemical lithium storage[J]Carbon 2016,107:711 and 722). Compared with undoped graphene, the doped graphene can not only accelerate electron transfer of electrode reaction, but also form a new electrocatalytic active center. Duan et al found that N-doped graphene reduced the adsorption energy of hydrogen, showing better electrocatalytic HER performance than undoped graphene(DUANJ, CHEN S, JARONIEC M, et al. Heteroatom-based materials for energy-derived electrochemical processes. ACS Catalysis,2015,5(9): 5207) and 5234). MoS prepared by one-step hydrothermal method2the/S, N co-doped graphene composite material also shows higher electrocatalytic HER activity (REN X P, REN X D, PANG L Q, et al2(iii)/sulfur and nitro co-produced graphene oxide nanocomposite for enhanced electrochemical hydrogenation. International Journal of Hydrogen Energy,2016,41(2): 916-. B is less electronegative (even lower than carbon) than the N and S elements. B doping will form p-type carriers in graphene, thus changing some physical and chemical properties of the graphene surface, making graphene more suitable for applications in sensors, electrocatalysis, electrochemical energy storage, etc. (HAN J, ZHANG LL, LEEs, et al].ACS Nano,2013,7(1):19-26；SHENG Z H,GAO H L,BAO W J,et al.Synthesis ofboron doped graphene for oxygen reduction reaction in fuel cells[J].Journalof Materials Chemistry,2012,22(2):390-395；KONG X K,HUANG Y M,LIU Q C.Two-dimensional boron-doped graphyne nanosheet:Anew metal-free catalyst foroxygen evolution reaction[J].Carbon,2017,123:558-564；SAHOO M,SREENAKP,VINAYANBP,et al.Green synthesis of boron doped graphene and its application as highperformance anode material in Li ion battery[J]Materials Research Bulletin,2015,61: 383-. As a metal-free oxygen reduction reaction electrocatalyst, the B-doped graphene and the related nanostructure thereof have high-efficiency and stable electrocatalytic performance and better CO tolerance. Sathe et al, by a wet chemical method, substitute B atoms for C atoms of defect sites on graphene to prepare B-doped graphene, show good electrocatalytic HER activity, and boron-doped graphene can provide a lower energy reaction path (SATHEBR, ZOU X, ASEFAT, metal-free B-doped graphene with an effective electrochemical activity for hydrogen ion reduction [ J ] reaction].Catalysis Science&Technology,2014,4(7):2023-2030；NACHIMUTHU S,LAI P J,JIANG J C.Efficient hydrogen storage in boron dopedgraphene decorated by transition metals–A first-principles study[J]Carbon,2014,73: 132-.
The invention provides a composite nano material electrocatalyst for high-efficiency hydrogen evolution reaction and a preparation method thereof, wherein the catalyst is composed of MoS with more defects or edges2The layer is uniformly loaded on the B-doped graphene to form a composite structure, and is prepared through a one-step hydrothermal reaction approach. And MoS2And MoS2Compared with graphene composite materials, the MoS of the invention2the/B-doped graphene composite nano material is used as an electrocatalyst of hydrogen evolution reaction, and has remarkably high electrocatalytic activity and lower Tafel slope. However, so far, the composite nanomaterial electrocatalyst MoS for such a high-efficiency hydrogen evolution reaction2the/B-doped graphene composite nano material and the preparation method thereof are not reported in a public way.
Disclosure of Invention
The invention aims to provide a composite nano material electrocatalyst for high-efficiency hydrogen evolution reaction and a preparation method thereof.
The composite nano material electrocatalyst for high-efficiency hydrogen evolution reaction is prepared from MoS2The layer is compounded with B-doped graphene, wherein the doping amount of B element in the graphene is 3.2-6.6% in mol percentage, and the preparation method comprises the following steps:
(1) ultrasonically dispersing graphene oxide in deionized water to obtain uniform suspension, dropwise adding metered boric acid solution into the suspension containing the graphene oxide under stirring, continuously stirring for 12h, and then adding Na-containing solution2MoO4And L-cysteine, adding the mixed solution into the mixed suspension under stirring;
(2) transferring the hydrothermal reaction mixture obtained in the step (1) into a hydrothermal reaction kettle with a polytetrafluoroethylene inner container, adjusting the volume of a hydrothermal reaction mixture system to be about 80% of the nominal volume of the inner container of the hydrothermal reaction kettle by using deionized water, and controlling the concentration of boric acid in the hydrothermal reaction compound system to be 0.0125-0.0625 mol/L;
(3) sealing the hydrothermal reaction kettle, reacting at 180 ℃ for 24h, naturally cooling to room temperature, centrifugally separating a precipitate obtained by the hydrothermal reaction, fully washing with deionized water and absolute ethyl alcohol, and freeze-drying for 48h to obtain MoS2The composite nanometer material of/B-doped graphene, wherein the doping amount of B element in the graphene is 3.2-6.6% of molar ratio.
With hydrothermally prepared MoS2And MoS2Compared with the composite material of undoped graphene, the MoS of the invention2the/B-doped graphene composite nanomaterial has larger electrochemical activity specific surface area, and MoS loaded on B-doped graphene2The layer has more defects and/or edges.
Compared with the prior art:
the composite nano material electrocatalyst for high-efficiency hydrogen evolution reaction is prepared from MoS with more defects or edges2The layer and B-doped graphene are compounded, wherein the doping amount of B element in the graphene is 3.2-6.6% by mole ratio. The composite nano material electrocatalyst for high-efficiency hydrogen evolution reaction and the preparation method thereof have the following remarkable advantages:
despite the nanoscale MoS2Has good electrocatalytic activity on hydrogen evolution reaction, and the electrocatalytic activity is mainly derived from MoS2But the S-Mo-S layer is easily stacked due to van der Waals' force, resulting in a decrease in its edge active sites, and at the same time, MoS2The low conductivity limits its application as an electrocatalyst. MoS2Compounding with graphene is an effective way to better solve the 2 disadvantages. Graphene has high electron conductivity and charge mobility, as well as a very large specific surface area and inherently good flexibility. Graphene and MoS2The compounding can obviously improve the conductivity of the composite material and can well inhibit MoS2Stacking or agglomerating the layers to obtain MoS with fewer layers and more active sites at the edges2And (3) a layer.
Graphite modified by doping heterogeneous atoms (such as N, S and the like) with grapheneThe electronic structure of the graphene changes the physical and chemical properties of the graphene, so that the electrocatalytic activity of the graphene and the composite material thereof is enhanced. Compared with undoped graphene, the doped graphene can not only accelerate electron transfer of electrode reaction, but also form a new electrocatalytic active center. For example, N-doped graphene reduces the adsorption energy of hydrogen, showing better electrocatalytic hydrogen evolution reaction performance than undoped graphene; MoS2the/S, N co-doped graphene composite material also shows higher electrocatalytic HER activity. The B element is less electronegative (even lower than carbon) than the N and S elements. The doping B forms p-type carriers in the graphene, so that some physical and chemical properties of the surface of the graphene are changed, the graphene is more suitable for application in aspects of electrocatalysis, electrochemical energy storage and the like, and the graphene has better application performance. For example, B-doped graphene and its related nanostructures have efficient and stable electrocatalytic properties for oxygen reduction reactions, as well as better CO tolerance; the B-doped graphene also shows good electrocatalytic activity on hydrogen evolution reaction, and the boron-doped graphene can provide a lower energy reaction path for hydrogen ion reduction, but the Tafel slope of the electrocatalytic hydrogen evolution reaction is still higher (99 mV/dec).
The composite nano material electrocatalyst for high-efficiency hydrogen evolution reaction is prepared from MoS with more defects or edges2The layer is compounded with B-doped graphene and is prepared by a one-step hydrothermal reaction method. Under the condition of hydrothermal reaction, the graphene oxide is reduced to graphene, and is doped by B element released in situ by boric acid to obtain B-doped graphene, and Na is added2MoO4Hydrothermal reaction with L-cysteine to MoS2A layer, and uniformly supported on the B-doped graphene. Compared with undoped graphene, B-doping forms p-type carriers in graphene, so that some physical and chemical properties of the surface of the graphene are changed, and the electron transfer capacity of the graphene is enhanced. The boron-doped graphene also can provide a lower energy reaction path for hydrogen ion reduction, and is beneficial to improving the dynamic performance of the electrocatalytic hydrogen evolution reaction. Compared with undoped graphene, the B-doped graphene has a better open porous framework structure and is higherAnd lower electron transfer resistance of electrode reaction. In addition, the B-doped graphene with a better open porous framework structure can enable MoS loaded on the surface of the B-doped graphene2The layer has more defects and/or edges, providing more catalytically active sites for the hydrogen evolution reaction. The electrochemical test result shows that the metal oxide and the metal oxide are in contact with MoS2，MoS2Compared with graphene composite materials, the MoS of the invention2the/B-doped graphene composite nanomaterial has larger electrochemical activity specific surface area, shows remarkably improved electrocatalytic activity and lower Tafel slope for hydrogen evolution reaction as an electrocatalyst, and remarkably reduces electron transfer impedance of electrode reaction.
The composite nano material electrocatalyst for high-efficiency hydrogen evolution reaction mainly comprises elements such as Mo, S, C and B which are abundant in reserves on the earth, and does not contain noble metal elements such as Pt, so that the low cost can be realized.
The one-step hydrothermal preparation method for preparing the composite nano material electrocatalyst with high-efficiency hydrogen evolution reaction also has the characteristics of simple process, convenience and easy expanded application.
Drawings
FIG. 1: MoS2And XRD patterns of different composite nanomaterial electrocatalysts, (a) MoS2,(b)MoS2Graphene, (c) MoS2(B) -doped graphene-1, (d) MoS2(e) MoS of/B-doped graphene-22B-doped graphene-3;
FIG. 2: MoS2And SEM images of different composite nanomaterial electrocatalysts, (a) MoS2,(b)MoS2Graphene, (c) MoS2(B) -doped graphene-1, (d) MoS2(e) MoS of/B-doped graphene-22B-doped graphene-3;
FIG. 3: MoS2And TEM/HRTEM images of different composite nanomaterial electrocatalysts, (a, b) MoS2,(c,d)MoS2Graphene, (e, f) MoS2(g, h) MoS of/B-doped graphene-12(ii)/B-doped graphene-2, (i, j) MoS2B-doped graphene-3;
FIG. 4: (a) MoS2,MoS2Graphene，MoS2[ solution ] B-doped graphene-1, MoS2[ B ] -doped graphene-2 and MoS2A polarization curve of hydrogen evolution reaction on the/B-doped graphene-3 electrocatalyst electrode; (b) MoS2Stability test of electrocatalysis performance of hydrogen evolution reaction on/B-doped graphene-2 catalyst (room temperature, electrolyte is 0.5M H)2SO4)；
FIG. 5: (a) MoS2,(b)MoS2Graphene, (c) MoS2(B) -doped graphene-1, (d) MoS2(ii)/B-doped graphene-2 and (e) MoS2Tafel curve of hydrogen evolution reaction on/B-doped graphene-3 electrocatalyst electrode (room temperature, electrolyte is 0.5M H2SO4)；
FIG. 6: (a) MoS2,(b)MoS2Graphene, (c) MoS2(B) -doped graphene-1, (d) MoS2(ii)/B-doped graphene-2 and (e) MoS2Nyquist diagram of electrochemical impedance spectrum of hydrogen evolution reaction on/B-doped graphene-3 electrocatalyst electrode (room temperature, electrolyte is 0.5mol/L H2SO4) The inset in the figure is the equivalent circuit of electrochemical impedance analysis, where RsIs the resistance of the electrolyte, RctFor electron transfer resistance, CPE1 is a constant phase element associated with the catalyst-electrolyte interface.
Detailed Description
The invention is further illustrated below with reference to examples and figures.
Example 1
Uniformly dispersing graphene oxide in deionized water under the action of ultrasonic waves to obtain uniform suspension, dropwise adding metered boric acid solution into the suspension containing graphene oxide under stirring, continuously stirring for 12h, and then adding Na-containing solution2MoO4And L-cysteine were added to the above mixed suspension with stirring to obtain a hydrothermal reaction mixture containing 1.5mmol of Na2MoO47.5mmol of L-cysteine, 3.0mmol of graphene oxide (measured as carbon element), the amount of boric acid-containing substance being 1.0,2.0 or 5.0 mmol; transferring the mixture of the hydrothermal reaction into a 100mL hydrothermal reaction kettle, and carrying out hydrothermal reaction by using deionized waterAdjusting the volume of the mixture to about 80mL, sealing the hydrothermal reaction kettle, preserving heat at 180 ℃ for 24h, naturally cooling the reaction kettle to room temperature after the reaction is finished, washing the reaction kettle with deionized water for 5-6 times, performing centrifugal separation to obtain black precipitate, and performing freeze drying for 48h to obtain MoS2a/B-doped graphene composite material. The amounts of boric acid in the hydrothermal reaction mixed solution were 1.0,2.0 and 5.0mmol, respectively, and the prepared composite nanomaterial electrocatalysts were named MoS2[ solution ] B-doped graphene-1, MoS2[ B ] -doped graphene-2 and MoS2and/B-doped graphene-3.
Comparative example 1: MoS was prepared by a similar hydrothermal method without the addition of boric acid2A graphene composite material.
Uniformly dispersing graphene oxide in deionized water under the action of ultrasonic waves to obtain uniform suspension, and then adding Na2MoO4And L-cysteine under stirring to obtain a hydrothermal reaction mixture containing 1.5mmol of Na2MoO47.5mmol of L-cysteine, 3.0mmol of graphene oxide (in terms of carbon) without addition of boric acid; transferring the obtained hydrothermal reaction mixture into a 100mL hydrothermal reaction kettle, adjusting the volume of the hydrothermal reaction mixture to about 80mL by using deionized water, sealing the hydrothermal reaction kettle, keeping the temperature at 180 ℃ for 24h, naturally cooling the reaction kettle to room temperature after the reaction is finished, washing the reaction kettle for 5-6 times by using the deionized water, obtaining a black precipitate by centrifugal separation, and freeze-drying the black precipitate for 48h to obtain MoS2A graphene composite material.
Comparative example 2: MoS was prepared by a similar hydrothermal reaction method in the absence of graphene oxide and without the addition of boric acid2And (3) nano materials.
The MoS prepared above was subjected to X-ray diffraction (XRD), Scanning Electron Microscope (SEM), Transmission Electron microscope/high resolution Transmission Electron microscope (TEM/HRTEM), and XPS2，MoS2Graphene and MoS2And (3) carrying out characterization and analysis on the/B-doped graphene composite material sample.
Electro-catalyst pair evolution of hydrogenTesting of electrocatalytic performance of the reaction: adopting a three-electrode system, Pt as a counter electrode, a reference electrode as a Saturated Calomel Electrode (SCE), and 0.5mol/L electrolyte of H2SO4And (3) solution. Preparation of a working electrode: 4.0mg of the catalyst was dispersed in 80. mu.L of a 5 wt% Nafion solution and 1.0mL of a water/ethanol mixture (volume ratio 4:1), and sonicated for 1h to obtain a uniform catalyst slurry. And transferring 5.0 mu L of catalyst slurry to be coated on a glassy carbon electrode with the diameter of 3.0mm, and drying at 60 ℃ to obtain the working electrode. The electrocatalytic hydrogen evolution performance of the comparative catalysts was tested using Linear Sweep Voltammetry (LSV), cyclic voltammetry and electrochemical impedance techniques on a CHI660E electrochemical workstation. The potential values of the hydrogen evolution reactions are relative to the Reversible Hydrogen Electrode (RHE), i.e. the potential value is equal to the potential value relative to the SCE plus 0.272V. The electron transfer impedance of the hydrogen evolution reaction on the different composite nanomaterial electrocatalyst electrodes was tested with electrochemical impedance. To compare MoS2，MoS2Graphene and MoS2The electrochemical activity specific surface area of the/B-doped graphene composite nano material is tested by cyclic voltammetry, and the electrochemical activity specific surface area and differential capacitance of the/B-doped graphene composite nano material are tested by cyclic voltammetry. The electrochemical active specific surface area of the composite nano material is in direct proportion to the differential capacitance value, so that the measured differential capacitance value can be used for comparing the electrochemical active specific surface area.
The microstructure and morphology characterization results of different electrocatalysts are as follows:
figure 1 is an XRD pattern of different electrocatalyst samples. The results showed that all samples exhibited 4 diffraction peaks at 2 θ of 32.8 °,35.3 °,43.0 °, and 56.8 °, corresponding to 2H — MoS, respectively2The (100), (103), (006) and (110) crystal planes of (c). However, it corresponds to MoS2The (002) plane of (a) showed no diffraction peak at 2 θ of 14.4 °, while the sample showed a relatively distinct broadened diffraction peak at 2 θ of 9.3 ° (# sign), which corresponds to a layer spacing of 0.95 nm. 3 MoS2the/B-graphene composite nanomaterial showed a weak diffraction peak at 24.5 ° 2 θ, corresponding to the (002) plane of graphene. This is because pi-pi stacking between layers of B-doped graphene is enhanced to some extent, and B atoms form sp in carbon lattice2Hybridization, hydrothermal reduction of sp in graphene oxide2The conjugated structure is partially restored, and the pi-pi accumulation or crosslinking superposition degree of the graphene sheet is improved.
SEM microscopic morphology characterization results of different catalyst samples in FIG. 2 show that MoS alone2The sample presents a flower-shaped appearance formed by staggered and superposed nano sheets; MoS2The/graphene composite nano material shows the morphology of flaky graphene-like, MoS2The nano sheets are uniformly loaded on the graphene; 3 MoS2the/B-doped graphene composite nano material also shows the appearance of similar graphene, and the B-doped graphene has more folds and MoS2The layer is better evenly dispersed on the B-doped graphene.
The TEM/HRTEM characterization results of FIG. 3 show that MoS2The sample consists of MoS2The nano sheets are staggered; for MoS2(iv) composite nanomaterial of/G, MoS2The layer can be uniformly dispersed on the graphene; and MoS2Graphene and MoS2In contrast, MoS2In the/B-doped graphene composite nano material, MoS2The layer shows shorter length and more exposed edges and is uniformly dispersed on the B-doped graphene, especially MoS2[ solution ] B-doped graphene-2 composite nanomaterial, in which MoS2The lattice fringes of (a) show more disordered structures or defects, exposing more edges or defect sites.
XPS analysis showed that for MoS2[ solution ] B-doped graphene-1, MoS2[ B ] -doped graphene-2 and MoS2The amount of B element doped in the graphene is 3.2%, 4.6% and 6.6%, the amount ratio of Mo to S is 1:1.9,1:2.1 and 1:2.1, which is consistent with MoS2The stoichiometric ratio of (a).
The test comparison of the electrocatalysis performance of different electrocatalysts on the hydrogen evolution reaction:
the results of comparing the electrocatalytic performance tests of different electrocatalysts to the hydrogen evolution reaction in FIG. 4(a) show that MoS alone2The catalyst exhibited a relatively high initial overpotential (185mV), even at a high overpotential of 300mV, with a current density of only 16mA/cm2(ii) a And MoS2Catalyst phase MoS2The initial overpotential of the hydrogen evolution reaction on the graphene catalyst is reduced to 153mV, and the current density is also obviously increased; and MoS2MoS/graphene comparison2the/B-doped graphene shows remarkably improved catalytic activity of electrocatalytic hydrogen evolution reaction, particularly MoS2The initial overpotential of the hydrogen evolution reaction of the/B-doped graphene-2 is reduced to 130mV, and the current density of the graphene-2 reaches 180mA/cm under the overpotential of 300mV2Higher than reported MoS2Current Density of/N-doped graphene (136.3 mA/cm)2)。
Stability is also an important factor in evaluating the performance of electrocatalysts. At 0.5M H2SO4In the electrolyte, MoS is subjected to cyclic voltammetry at a sweep rate of 5mV/s2the/B-doped graphene-2 was cycled 1000 times. As shown in FIG. 5(b), the polarization curve of the hydrogen evolution reaction obtained after 1000 cycles almost coincides with the initial polarization curve, indicating that MoS is present in the acid electrolyte2the/B-doped graphene is stable to the electrocatalytic properties of HER.
FIG. 5 is a Tafel slope analysis of the polarization curve of the hydrogen evolution reaction, the Tafel formula can be expressed as η ═ a + blogj, b is the Tafel slope, j is the current density, the hydrogen evolution reaction in acid electrolyte comprises 3 basic steps, the Volmer reaction (H++e→Had,HadRepresenting the adsorption of a hydrogen atom), Heyrovsky reaction (H)++e→H2) And Tafel reaction (H)ad+Had→H2). At room temperature, the Tafel slopes of these 3 steps were around 120mV/dec,40mV/dec and 30mV/dec, respectively. FIG. 6 shows, MoS2Exhibits a higher Tafel slope (100.5mV/dec), indicating that the Volmer reaction is the rate determining step of its hydrogen evolution reaction, due to MoS2Has relatively limited active sites and low conductivity, and is in MoS2Volmer reactions on the electrode are very difficult, resulting in a higher Tafel slope; MoS2The Tafel slope of the/graphene is 75.6mV/dec, which is lower than MoS2The hydrogen evolution reaction is controlled by the mixture of the Volmer reaction and the Heyrovsky reaction, and the composite material is compounded with the graphene to improve the conductive capability and increase MoS2The edge active site of (1), modificationThe Volmer reaction process of the hydrogen evolution reaction is improved; MoS2The Tafel slope of the/B-doped graphene composite material is further reduced to 46-50mV/dec, and the lower Tafel slope is caused by the unique electronic structure and surface characteristics of boron-doped graphene and MoS with more edges or defects2The nano-sheets are uniformly loaded on the B-doped graphene, so that the composite material catalyst has a large number of electrocatalytic active centers and obviously increased electrocatalytic active sites, and has better electron transfer capacity in hydrogen evolution electrode reaction, especially MoS2the/B-doped graphene-2 has the smallest Tafel slope (46.3mV/dec), indicating that its HER is performed by the Volmer-Heyrovsky step, where the Heyrovsky reaction is the rate determining step.
Fig. 6 is a Nyquist plot of the electrochemical resistance of the hydrogen evolution reaction at different electrocatalyst electrodes, and table 1 is the results of fitting electrochemical resistance test data to the electrochemical kinetic parameters of the hydrogen evolution reaction. The results show that the MoS is due to2Lower conductivity, MoS2The electrode showed maximum electron transfer (R)ct＝1131Ω)；MoS2R of graphene electrodectThe conductivity of the composite material electrocatalyst is improved due to graphene compounding, and the electron transfer capacity in the hydrogen evolution reaction electrode process is improved; MoS2R of/B-doped graphene electrodectWith a further reduction in which MoS2the/B-doped graphene catalyst electrode shows the minimum Rct(87. omega.) and a value of MoS225.6% for graphene electrode, demonstrate MoS2The hydrogen evolution reaction on the/B-doped graphene-2 electrode has better electron transfer capability.
TABLE 1 kinetic parameters of hydrogen evolution reaction electrode obtained by fitting electrochemical impedance data
The results of the cyclic voltammetry test on the differential capacitance show that MoS2，MoS2Graphene, MoS2[ solution ] B-doped graphene-1, MoS2[ B ] -doped graphene-2 and MoS2/B-doped graphene-3 complexThe differential capacitance of the nano material electrode is 3.5mF/cm2，5.3mF/cm2，8.8mF/cm2，16.2mF/cm2And 12.0mF/cm2. And MoS2，MoS2MoS/graphene comparison2The electrode of the/B-doped graphene composite nano material has larger differential capacitance, wherein MoS2the/B-doped graphene-2 has the largest differential capacitance, which is shown to be related to MoS2，MoS2MoS/graphene comparison2the/B-doped graphene composite nano material has larger electrochemical activity specific surface area, wherein MoS2the/B-doped graphene-2 has the largest electrochemical activity specific surface area.
Claims (2)
1. The composite nano material electrocatalyst for efficient hydrogen evolution reaction is characterized in that the composite nano material electrocatalyst is prepared from MoS2The layer is compounded with B-doped graphene, wherein the doping amount of B element in the B-doped graphene is 3.2-6.6% in mol percentage, and the layer is compared with simple MoS2And MoS2MoS compared with composite nano material of undoped graphene2the/B-doped graphene composite nanomaterial has larger electrochemical activity specific surface area, and MoS loaded on B-doped graphene2The layer has more defects and/or edges.
2. A method for preparing the composite nano-material electrocatalyst for high-efficiency hydrogen evolution reaction according to claim 1, which comprises the following steps:
(1) ultrasonically dispersing graphene oxide in deionized water to obtain uniform suspension, dropwise adding metered boric acid solution into the suspension containing the graphene oxide under stirring, continuously stirring for 12h, and then adding Na-containing solution2MoO4And L-cysteine, adding the mixed solution into the mixed suspension under stirring;
(2) transferring the hydrothermal reaction mixture obtained in the step (1) into a hydrothermal reaction kettle with a polytetrafluoroethylene inner container, adjusting the volume of a hydrothermal reaction mixture system to 80% of the nominal volume of the inner container of the hydrothermal reaction kettle by using deionized water, and controlling the concentration of boric acid in the hydrothermal reaction mixture system to be 0.0125-0.0625 mol/L;
(3) sealing the hydrothermal reaction kettle, reacting at 180 ℃ for 24h, naturally cooling to room temperature, centrifugally separating a precipitate obtained by the hydrothermal reaction, fully washing with deionized water and absolute ethyl alcohol, and freeze-drying for 48h to obtain MoS2a/B-graphene-doped composite nanomaterial.
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