CN116219477A - Nano hybrid material and preparation method and application thereof - Google Patents
Nano hybrid material and preparation method and application thereof Download PDFInfo
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- CN116219477A CN116219477A CN202310516995.6A CN202310516995A CN116219477A CN 116219477 A CN116219477 A CN 116219477A CN 202310516995 A CN202310516995 A CN 202310516995A CN 116219477 A CN116219477 A CN 116219477A
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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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- Y02E60/30—Hydrogen technology
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Abstract
The invention provides a nano hybrid material, a preparation method and application thereof, belonging to the field of water electrolysis hydrogen evolution catalytic materials. The nano hybrid material is a catalyst prepared by taking tungsten salt or hydrate thereof, rhodium salt or hydrate thereof, urea and conductive carbon black as raw materials, wherein the mass ratio of the tungsten salt or hydrate thereof, the rhodium salt or hydrate thereof, the urea and the conductive carbon black is (10-30) to (0.5-10) to (10-30) to (1-3). The nanometer hybrid material can be efficiently applied to acidic, neutral and alkaline environments, and is an efficient HER catalyst with a full pH range. Compared with the prior art, the consumption of rhodium in the nano hybrid material is greatly reduced, the catalyst cost is greatly reduced, the catalytic intrinsic activity is greatly improved, and the nano hybrid material has wide application prospect in the field of hydrogen electrolysis of water as a water and electricity hydrogen desorption catalyst.
Description
Technical Field
The invention belongs to the field of water electrolysis hydrogen evolution catalytic materials, and particularly relates to a nano hybrid material, a preparation method and application thereof.
Background
H 2 Has higher environmental benefit (no carbon emission) and mass energy density, and is one of the energy carriers suitable for the later fossil fuel era. Among the numerous hydrogen production technologies, the hydropower-analysis hydrogen reaction (HER) is considered to be a highly efficient and promising method for large-scale production of high purity hydrogen without additional carbon emissions. Exchange current density of Pt-based HER catalyst (j 0 ) Large, low Tafel slope, thus being one of the most advanced acidic hydrogen evolution reaction electrocatalysts at present. However, the problems of high cost, reduced activity in alkaline medium, poor electrochemical stability and the like greatly prevent the industrial application of the catalyst. Furthermore, in view of practical water splitting applications, the ideal electrocatalyst needs to be satisfactory for operation in both strongly acidic proton exchange membrane cells, near neutral microbial cells and alkaline cells. Therefore, developing a low cost hydrogen evolution material in the full pH range makes it significant to surpass Pt/C in HER activity and stability.
Chinese patent application CN112501631A discloses a rhodium oxide-nickel-based phosphate-carbon carrier hydrogen evolution electrocatalyst, which is prepared byThe preparation process comprises the following steps: (1) Loading a carbon carrier on a conductive substrate to obtain a conductive substrate loaded with the carbon carrier; (2) Adopting the conductive substrate loaded with the carbon carrier obtained in the step (1) as a working electrode, a graphite rod as a counter electrode, and an aqueous solution containing a nickel salt precursor and a phosphorus precursor as a deposition solution, and forming the conductive substrate loaded with the nickel-based phosphate-carbon carrier by an electrodeposition method; (3) The conductive matrix of the supported nickel-based phosphate-carbon carrier obtained in the step (2) is used as a working electrode, rhodium wires are used as a counter electrode, sulfuric acid is used as a deposition solution, and the conductive matrix of the supported rhodium oxide-nickel-based phosphate-carbon carrier is formed through an electrodeposition method. The rhodium oxide-nickel-based phosphate-carbon carrier hydrogen evolution electrocatalyst shows excellent HER activity in both acidic and basic media: at a current density of 10 mA cm -2 A lower overpotential of 30 mV (in acidic medium), 43 mV (in basic medium) was achieved, comparable to commercial Pt/C catalysts. However, the HER activity of the rhodium oxide-nickel-based phosphate-carbon supported hydrogen evolution electrocatalyst in both acidic and basic media is still to be further improved.
Disclosure of Invention
The invention aims to provide a nano hybrid material, and a preparation method and application thereof.
The invention provides a nano hybrid material which is prepared from tungsten salt or a hydrate thereof, rhodium salt or a hydrate thereof, urea and conductive carbon black as raw materials, wherein the mass ratio of the tungsten salt or the hydrate thereof, the rhodium salt or the hydrate thereof, the urea and the conductive carbon black is (10-30) to (0.1-10) to (10-30) to (1-3).
Further, the mass ratio of the tungsten salt or the hydrate thereof to the rhodium salt or the hydrate thereof to the urea to the conductive carbon black is 20 (0.5-2): 20:2.
Further, the mass ratio of the tungsten salt or the hydrate thereof to the rhodium salt or the hydrate thereof to the urea to the conductive carbon black is 20:1:20:2.
Further, the tungsten salt is tungsten hexachloride, the rhodium salt is rhodium trichloride, and the conductive carbon black is ketjen black.
The invention also provides a method for preparing the nano hybrid material, which comprises the following steps:
(1) Adding tungsten salt or hydrate thereof, rhodium salt or hydrate thereof, urea and conductive carbon black into an organic solvent, uniformly mixing, and standing to obtain a precursor;
(2) And heating the precursor, pyrolyzing, cooling to room temperature, and standing to obtain the water and electricity hydrogen desorption catalyst.
Further, in the step (1), the organic solvent is an alcohol solvent; the standing time is 8-16 hours;
in the step (2), the pyrolysis temperature is 500-900 ℃ and the pyrolysis time is 2-4 hours; the heating rate is that the temperature is firstly increased to 60-80 ℃ at a heating rate of 0.5-2 ℃/min and kept at a constant temperature of 1-3 h, and then the temperature is continuously increased to the pyrolysis temperature at a heating rate of 0.5-2 ℃/min.
Further, in the step (1), the alcohol solvent is ethanol; the standing time is 12 hours;
in the step (2), the pyrolysis temperature is 600 ℃ and the pyrolysis time is 3 hours; the heating rate is that the temperature is firstly increased to 70 ℃ at a heating rate of 1 ℃/min and kept at a constant temperature of 2 h, and then the temperature is continuously increased to the pyrolysis temperature at the heating rate of 1 ℃/min.
Further, the step (1) is carried out under anhydrous and anaerobic conditions; step (2) is performed under the protection of inert gas.
The invention also provides application of the nano hybrid material in preparing a water electrolysis hydrogen evolution catalyst.
Further, the hydro-power hydrogen desorption catalyst is suitable for use in acidic, neutral and/or alkaline conditions.
According to the invention, rhodium chloride, tungsten chloride and urea are mixed in ethanol, and a nano hybrid material of an Rh-loaded WNO and nitrogen-doped carbon interconnection structure is prepared through a two-step method. Wherein, urea plays an important role as a complexing agent and a nitrogen source, and can prevent the aggregation of Rh species, thereby greatly improving the utilization rate of noble metal Rh catalytic active sites and the catalytic quality activity. During calcination, rhodium chloride and tungsten chloride are reduced by the reducing species dissociated by urea calcination, and a nitrogen-doped carbon layer is formed. In addition, the external nitrogen-doped carbon layer can further enhance the conductivity of the material while protecting the material from electrolyte corrosion.
The nano hybrid material provided by the invention has the advantages that the charge is redistributed in the form of Rh species transferring to WNO electrons, and the electron density of Rh atom center is reduced. Due to the favorable valence state of the active site, the nanostructure of the nano hybrid material is 10 mA cm in acid, neutral and alkaline -2 The overpotential of the catalyst is 22, 19 and 143 mV respectively, can efficiently produce hydrogen in the full pH range, and is a high-efficiency HER catalyst in the full pH range. Compared with Rh10mg-WNO-NC and Rh20mg-WNO-NC, the electrocatalytic HER performance of Rh5mg-WNO-NC is better; compared with Rh-W-NC-500, rh-W-NC-700, rh-W-NC-800 and Rh-W-NC-900, the electrocatalytic HER performance of Rh-W-NC-600 of the invention is optimal.
In the nano hybrid material Rh-WNO-NC provided by the invention, the mass fraction of XPS of Rh is only 2.58%, but the conversion frequency value Pt/C of Rh-WNO-NC at the overpotential of 100 mV is 8.7 times higher. Compared with the prior art, the dosage of Rh in the nano hybrid material Rh-WNO-NC is greatly reduced, the cost of the catalyst is greatly reduced, the catalytic intrinsic activity is greatly improved, and the catalytic nano hybrid material has wide application prospect in the field of hydrogen electrolysis of water as a HER catalyst.
It should be apparent that, in light of the foregoing, various modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
The above-described aspects of the present invention will be described in further detail below with reference to specific embodiments in the form of examples. It should not be understood that the scope of the above subject matter of the present invention is limited to the following examples only. All techniques implemented based on the above description of the invention are within the scope of the invention.
Drawings
FIG. 1 (a) bright field TEM image of the same region of Rh-WNO-NC; (b) dark field TEM image of the same region of Rh-WNO-NC; (c, d, g) HAADF-STEM map of Rh-WNO-NC at different magnifications; (e, f) HAADF-STEM map at Rh-WNO-NC 2nm magnification; (h-m) EDS element map of Rh-WNO-NC.
FIG. 2 (a) XRD pattern of Rh-WNO-NC; (b) XPS survey scan of Rh-WNO-NC; (c-f) XPS spectrum of Rh 3d,W 4f,N 1s,O 1s of Rh-WNO-NC.
FIG. 3 (a, b) Rh-WNO-NC and Rh K-edge XANES spectra of the standard samples; (c) Fourier transform K3 weighted EXAFS spectrogram of Rh-WNO-NC and standard sample; (d-f) WT analysis maps of Rh K edges of different samples.
FIG. 4 shows a graph of HER (a) polarization and (b) Tafel in 1M KOH for different catalysts; (c) Tafel slope, 10 mA cm -2 Is a graph of the overpotential for different catalysts in terms of mass activity; (d) TOF plots deduced from CV curves of Rh-WNO-NC, pt/C and Rh/C; (e) Cdl plots deduced from CV curves of Rh-WNO-NC, WNO-NC and Rh/C; (f) Rh-WNO-NC vs. HER at 10 mA cm −2 The following long-term stability test results are shown.
FIG. 5 samples at 0.5M H 2 SO 4 (a) Linear Sweep Voltammetry (LSV) and (b) Tafel, (c) Rh-WNO-NC at 0.5. 0.5M H 2 SO 4 、10 mA cm -2 The lower overpotential and Tafel slope plot; (d) Linear Sweep Voltammetry (LSV) and (e) Tafel plots of samples in 1M PBS, (f) Rh-WNO-NC in 1M PBS, 10 mA cm -2 The overpotential and Tafel slope plots below.
FIG. 6 is a schematic diagram of a metal-urea precursor.
FIG. 7 EDS spectrum of Rh-WNO-NC.
FIG. 8 XRD spectra of Rh-WNO-NC-without urea and KB.
FIG. 9 EDS spectrum of Rh-WNO-NC.
FIG. 10 (a) W4 f XPS spectra of Rh-WNO-NC and WNO-NC; (b) Rh 3d XPS spectra of Rh-WNO-NC and Rh/C.
FIG. 11 LSV graphs of Rh-WNO-NC, rh-NC and Pt/C.
FIG. 12 LSV graphs of Rh5mg-WNO-NC, rh10mg-WNO-NC, rh20mg-WNO-NC, pt/C.
FIG. 13 catalyst at 10 mA cm −2 A comparison plot of overpotential is below.
Fig. 14 shows the exchange current density for different catalysts.
Fig. 15. TOF plots (overpotential 100 mV) for different electrocatalysts.
FIG. 16. (a) Cdl plot inferred from CV curves; (b) Cyclic voltammograms of Rh-WNO-NC, (C) WNO-NC and (d) Rh/C in 1M KOH at different scan rates in the non-Faraday potential region (0.88-0.98V vs RHE).
FIG. 17 LSV graphs of Rh-W-NC-500, rh-W-NC-600, rh-W-NC-700, rh-W-NC-800, rh-W-NC-900.
FIG. 18 Rh-WNO-NC and Pt/C at 1M KOH and 0.5M H 2 SO 4 HER polarization profile in (a).
Detailed Description
The raw materials and equipment used in the invention are all known products and are obtained by purchasing commercial products.
TABLE 1 materials and reagents
| Raw materials | Purity of | Source |
| Tungsten hexachloride (WCl) 6 ） | 99% | Alatine |
| Rhodium trichloride hydrate (RhCl) 3 ·xH 2 O） | 98% | Alatine |
| Urea | 99.5% | Alatine |
| Potassium hydroxide (KOH) | 85% | Alatine |
| Ethanol | 99.7% | Alatine |
| Keqin Black (KB) | 99.9% | Ke Lide Co Ltd |
| Platinum carbon (Pt/C) containing 20. 20 wt% Pt | - | Alfa Aesar |
| Rhodium carbon (Rh/C) containing 10 wt% Rh | - | An Naiji chemistry |
In the present invention, room temperature means 25.+ -. 5 ℃.
Example 1: preparation of Rh-WNO-NC
200 mg tungsten hexachloride (WCl) 6 ) And 10mg rhodium chloride hydrate (RhCl) 3 ·x H 2 O) the powder was dispersed in 2 ml ethanol to form a stable, clear solution. 200 mg urea is added and stirred for dissolution. Adding 20mg Keqin Black (KB), stirring for 30 min, transferring into crucible, and standing to rhodium complex for 12 h to obtain gel solid (also called metal-urea precursor) (FIG. 6). The above operations were completed in a dry and oxygen-free glove box. The gel-like solid was placed in a tube furnace (flow 100 mL min) under argon (Ar) atmosphere -1 ) The temperature is raised to 70 ℃ at a heating rate of 1 ℃/min and kept constant at 2 h; after that, the process is carried out,the temperature was continuously raised to 600℃at a heating rate of 1℃per minute and pyrolysed at constant temperature of 3 h. Then cooled to room temperature under the same argon flow and left for 2 hours, the product is ground into powder to obtain the target product, which is named Rh-WNO-NC (also known as Rh10mg-WNO-NC or Rh-W-NC-600).
Example 2: preparation of Rh-WNO-NC-500 catalyst
The preparation method of reference example 1 was different only in that the constant temperature was pyrolyzed to change the temperature from 600℃to 500℃to obtain the target product, designated Rh-W-NC-500.
Example 3: preparation of Rh-WNO-NC-700 catalyst
The preparation method of reference example 1 was different only in that the constant temperature was pyrolyzed to change the temperature from 600 to 700 ℃ to obtain the target product, designated Rh-W-NC-700.
Example 4: preparation of Rh-WNO-NC-800 catalyst
The preparation method of reference example 1 was different only in that the constant temperature was pyrolyzed to change the temperature from 600 to 800 ℃ to obtain the target product, designated Rh-W-NC-800.
Example 5: preparation of Rh-WNO-NC-900 catalyst
The preparation method of reference example 1 was different only in that the constant temperature was pyrolyzed to change the temperature from 600℃to 900℃to obtain the target product designated Rh-W-NC-900.
Example 6: preparation of Rh5mg-WNO-NC catalyst
The preparation method of reference example 1 is only different in that RhCl is prepared 3 ·x H 2 The dosage of O is changed from 10mg to 5mg, and the target product is obtained and named Rh5mg-WNO-NC.
Example 7: preparation of Rh20mg-WNO-NC catalyst
The preparation method of reference example 1 is only different in that RhCl is prepared 3 ·x H 2 The dosage of O is changed from 10mg to 20mg, and the target product is obtained and named Rh20mg-WNO-NC.
The following is a method for preparing a control sample.
Comparative example 1: preparation of WNO-NC catalyst
The preparation method of reference example 1 is different only in that it does not causeUsing RhCl as a raw material 3 ·x H 2 O, a control sample was obtained and designated WNO-NC.
Comparative example 2: preparation of Rh-WNO-NC-urea-free catalyst
The preparation method of reference example 1 was different only in that urea as a raw material was not used, and a control sample was obtained and designated Rh-WNO-NC-urea-free.
Comparative example 3: preparation of Rh-NC catalyst
The preparation process according to example 1 differs only in that no starting material WCl is used 6 And RhCl is added 3 ·x H 2 The amount of O added was changed from 10 to mg to 3mg, and a control sample was obtained and designated Rh-NC.
The following experiments prove the beneficial effects of the invention.
Experimental example 1: structural characterization test
1. Experimental method
(1) The microstructure of Rh-WNO-NC was characterized by Transmission Electron Microscopy (TEM).
(2) The unique morphology of Rh-WNO-NC was further studied using a high angle annular dark field scanning TEM (HAADF-STEM).
(3) The morphology of the precursor and final materials was observed with a high resolution FE-SEM (Thermo Fisher Scientific (FEI) Apreo SHiVoc).
(4) STEM uses a JEOL JEM-ARM 200F scanning transmission electron microscope equipped with a cold field emission electron source and a DCOR probe corrector (CEOS GmbH), one 100 mm 2 JEOL Centurio EDS detector, and a Gatan GIF quantum ERS electron energy loss spectrometer, operating at 200 kV.
(5) XPS at K-Alpha ™ The measurement was performed on a +X-ray photoelectron spectrometer system (thermo scientific) using a dual focal spot analyzer with 128 channel detector and hemispherical 180 deg.. The X-ray monochromator is a micro-focused alkα radiation. The X-ray spot size of the collected data was 400 μm,5 scans for investigation and 20 scans for specific areas. The powder XRD test was performed on the prepared samples under Cu ka radiation (λ=1.54 a) using a Rigaku type-ulma IV instrument at a voltage of 40 kV and a current of 50 mA. X-rayAbsorption spectra were collected on the BL07A1 beam line of the National Synchrotron Radiation Research Center (NSRRC).
2. Experimental results
The microstructure of Rh-WNO-NC was first characterized by Transmission Electron Microscopy (TEM). By comparing bright field and dark field TEM images of the same region of Rh-WNO-NC, it was found that the metal composite and the carbon layer formed an interconnected nano-hybrid structure (FIGS. 1a and 1 b). The unique morphology of Rh-WNO-NC was further studied using a high angle annular dark field scanning TEM (HAADF-STEM). As can be seen from fig. 1c and 1d, the flocculated Rh-loaded tungsten nitride oxide is spatially discontinuous and the surface is not smooth, indicating that the Rh-loaded WNO nanonetworks are interpenetrating crosslinked with the carbon nanonetworks. HAADF-STEM images showed that the WNO catalyst consisted of carbon-coated WNO nanocrystals. The roughened surface may expose more active sites for HER.
The morphology of the precursor and final material was observed with a high resolution FE-SEM and the thickness of the gold deposit was about 1nm. From the atomic resolution STEM images of fig. 1e and 1f, it can be seen that nanoparticles with lattice distances of about 0.24 nm and 0.21nm match the (111) and (200) planes of WNO, respectively. The surface of the WNO was decorated with a number of bright spots, and to confirm that the bright spots were Rh clusters, it was better observed at higher magnification (fig. 1 g), and EDS element mapping was performed (fig. 1h-m, fig. 7) to demonstrate the presence of rhodium in the catalyst. As shown in fig. 1l, rhodium is primarily distributed in the center of the WNO nanonetwork, indicating that rhodium nanoclusters are primarily anchored on the WNO nanonetwork. In addition, the uniform distribution of W, N, O elements (FIGS. 1j, k, m) verifies the composition and nanonetwork structure of WNO. Carbon (fig. 1 i) was dispersed throughout the test area, demonstrating that Rh-WNO nanocrystals were surrounded by carbon flakes.
The prepared Rh-WNO-NC catalyst is characterized by adopting a powder X-ray diffraction technology. As shown in FIG. 2a, the diffraction peaks of Rh-WNO-NC are at 37.62 °, 43.72 °, 63.54 °, 76.23 ° and 80.27 °, corresponding to (111), (200), (220), (311) and (222) characteristic lattice planes of W0.62 (N0.62O0.38), respectively (JCDF No. 25-1254). It was confirmed that the W precursor was pyrolyzed to partially nitrided in the presence of urea. Rh or RhO was not found in XRD patterns x Peaks, again verifying that most Rh species exist in the form of highly dispersed clusters of atoms, and that the crystallinity of the sample is relatively small, consistent with HRTEM analysis. The broad peak occurring at about 24 deg. is attributed to carbon, again verifying the presence of a carbon layer in the catalyst. For comparison, rh-WNO-NC-urea-free was prepared using the same process but without urea. As shown in FIG. 8, for Rh-WNO-NC-urea-free prepared without urea addition, all major XRD peaks were compared with WO 3 The characteristic peaks of (JCDF No. 46-1096) correspond, while Rh metal peaks (JCDF No. 05-0685) occur due to the presence of agglomerated metal Rh particles. In order to gain an insight into the chemical composition and valence state, XPS was used to characterize catalytic materials. As shown in FIG. 2b, the XPS spectrum results of Rh-WNO-NC further confirm that the catalyst, as shown in FIG. 9, consisted of C, W, N, rh and O elements, consistent with the EDS results. As shown in FIG. 2c and FIG. 10b, the Rh 3d XPS fine spectrum of Rh-WNO-NC can be divided into two groups of peaks, namely a metallic peak (307.57, 312.17 eV) and an oxidized peak Rh (309.47, 314.17). The results show that the annealing treatment can convert Rh 3+ Partially reduced to Ru 0 . As shown in FIG. 2d, FIG. 10a, the high resolution W4 f spectrum of Rh-WNO-NC has mainly 4 peaks, divided into two pairs of 32.72, 34.79 eV and 35.72, 37.87 eV. The first pair corresponds to the W-N bond of WNO and the pair at high binding energy is attributed to the W-O bond. The presence of WN and WO bonds at the same time means the presence of WNO, not WN x Or WO x . In the high resolution N1 s spectrum of Rh-WNO-NC (FIG. 2 e), the peak with binding energy 397.38 eV corresponds to the metal N bond (M-N), confirming the formation of WNO. In addition, the peaks at 398.4, 399.82, 401.08 and 402.11 eV belong to pyridine N, pyrrole N, graphite N and oxide N, respectively, indicating that the nitrogen heteroatom is doped in carbon. As shown in FIG. 2f, the O1 s spectra of Rh-WNO-NC fit well, showing two oxygen species. 530.87 The fitted peak at eV means that the metallo-oxygen (M-O) is related to the W-O bond of WNO. The peak at 531.65 eV is c=o, because the carbon shell of the outer layer is oxidized.
X-ray absorption structure (XAS) spectroscopy was performed on the Rh K side, analyzing the electronic structural properties of Rh-WNO-NC, reflecting the Rh doping in WNO nanoparticles. The normalized X-ray absorption near edge structure (XANES) spectra of Rh-WNO-NC and the Rh K edge of the standard sample are shown in fig. 3a and 3 b. Compared with the Rh foil and RhO standard reference samples, a significant forward shift occurred at the absorption edge of Rh-WNO-NC, and Rh exhibited higher average valence states (+2 to +3), which is consistent with XPS results. The extended X-ray absorption fine structure (EXAFS) spectrum of Rh-WNO-NC and the reference sample provides further structural information (FIG. 3 c). The peak at about 1.5 a is attributed to Rh-O or Rh-N coordination, thereby validating the oxidation state of the Rh species. The relatively weak peak at about 2.3 a corresponds to Rh-Rh. The oxidation state of the Rh species was also confirmed in Wavelet Transform (WT) data analysis of the Rh K side (FIGS. 3 d-f).
The experimental result shows that the Rh-WNO-NC provided by the invention has an interconnected nano-hybrid structure, wherein Rh-WNO nanocrystals are surrounded by carbon sheets, and Rh exists in the form of highly dispersed atomic clusters.
Experimental example 2 HER Performance test of catalyst
1. Experimental method
(1) Preparation of Ink-like slurry (catalyst Ink) formed by catalyst and solvent under ultrasonic conditions: catalyst ink was prepared by mixing catalyst powder (10 mg) with 100 μl Nafion solution (5 wt%) and 900 μl ethanol in an ultrasonic bath. Then 5 μL of catalyst ink was transferred to the GC surface with a catalyst loading of 0.25 mg cm -2 . Commercially available 20 wt% Pt/C (Alfa Aesar) was measured at the same loading for comparison.
(2) Electrode and measurement: all electrochemical measurements were performed at room temperature in a conventional three-electrode cell using a Gamry reference 600 workstation. A Reversible Hydrogen Electrode (RHE) or silver/silver chloride (Ag/AgCl) and graphite rod were used as reference and counter electrodes, respectively. The reference electrode (Ag/AgCl) was calibrated with RHE and the relative potential was 1.010V in 1M potassium hydroxide (KOH). In an area of 0.196 to 0.196 cm -2 As a substrate for the working electrode, a glassy carbon Rotating Disk Electrode (RDE) to evaluate HER activity of various catalysts. Electrochemical experiments were performed in 1M KOH saturated with Ar. All fresh electrolyte was bubbled with pure argon for 30 minutes before measurement. RDE measurements were performed at 1600 rpm with a scan rate of 10 mV s −1 。
(3) Electrochemical specific surface area (ECSA): the specific surface area of electrochemical activity was estimated by measuring the capacitance of the solid-liquid interface bilayer membrane by cyclic voltammetry. The measurement is performed within a potential window of 0.13-0.23V relative to RHE, where the faraday current on the working electrode is negligible. 20-320 mV s is adopted -1 The charge current density difference at a fixed potential of 0.18V is plotted against the scan rate. The resulting linear curve slope was 2 times the double layer capacitance (Cdl) and was used to estimate ECSA.
(4) Electrochemical Impedance Spectroscopy (EIS): EIS was performed using a potentiostatic EIS method, with a DC voltage of-0.042V vs RHE, in Ar saturated 1M KOH electrolyte, at frequencies of 100 kHz to 0.1 Hz,10 mV AC potential, and rotational speed of 1600 rpm.
(5) Electrochemical specific surface area (ECSA): the electrochemical activity specific surface area is estimated by measuring the capacitance of the solid-liquid interface double-layer film through cyclic voltammetry. The measurement is performed within a potential window of 0.13-0.23V relative to RHE, where the faraday current on the working electrode is negligible. Adopting 40-200 mV s -1 And (3) establishing a graph of the charge current density difference at a fixed potential of 0.4V versus the scan rate. The resulting linear curve slope was 2 times the double layer capacitance (Cdl) and was used to estimate ECSA.
2. Experimental results
This experiment evaluates the electrocatalytic HER performance of the catalyst at different Rh loadings in alkaline medium, and it can be seen that Rh5mg-WNO-NC has the best electrocatalytic HER performance compared to Rh10mg-WNO-NC and Rh20mg-WNO-NC (FIG. 12).
Experiments were then further performed using commercial catalysts Pt/C (20 wt% Pt) and Rh/C (10 wt% Rh) as reference catalysts. FIG. 4a shows a scan rate of 10 mV s in 1.0M KOH aqueous solution −1 Representative polarization curves for Rh-WNO-NC, rh/C and Pt/C. Obviously, rh-WNO-NC showed higher HER activity than Rh/C and Pt/C. Specifically, the current density was 10 mA cm −2 Rh-WNO-NC required an overpotential of 22 mV, well below that of WNO-NC (229 mV), rh/C (79 mV) and Pt/C (38 mV) (FIG. 13). WNO-NC and Rh/CNot ideal HER catalytic activity, indicating that the synergy of highly dispersed Rh nanoclusters and WNO-NC plays a crucial role in the high activity of Rh-WNO-NC. These results demonstrate that anchoring of Rh nanoclusters to the WNO surface can significantly enhance the hydrolytic reactivity, thereby greatly promoting hydrogen evolution activity. It is worth mentioning that the Rh-WNO-NC catalyst of the present invention has smaller overpotential and higher HER activity than the reported advanced electrocatalyst shown in Table 2.
TABLE 2 comparison of HER Activity of Rh-WNO-NC with reported catalysts
To gain a deeper understanding of HER dynamics, the Tafel slope was further analyzed in this experiment. As shown in FIG. 4b, the ratio of the catalyst to Rh/C (150 mV dec -1 ) And Pt/C (88 mV dec -1 ) Rh-WNO-NC showed a smaller Tafel slope (34.7 mV dec -1 ). The intrinsic activity of the catalyst was evaluated by measuring the exchange current density (fig. 14). Obviously, rh-WNO-NC (1.547 mA cm) −2 ) Ratio WNO-NC (0.199 mA cm) −2 )、Rh/C (1.478 mA cm −2 ) And Pt/C has better intrinsic HER activity. As can be seen from FIG. 4c, rh-WNO-NC (containing 2.58. 2.58 wt.% Rh) has the highest mass activity at an overpotential of 100 mV of 547 mA mg -1 Higher than 20% Pt/C (300 mA mg -1 ) And 10% Rh/C (114 mA mg -1 ). As shown in FIG. 4d, rh-WNO-NC showed 7.84H at an overpotential of 100 mV 2 s −1 Is significantly higher than Pt/C (0.9H) 2 s −1 ) And Rh/C (0.77H) 2 s −1 ) As well as some reported HER catalysts (fig. 4c and 15). These results indicate that the synergy between the highly dispersed Rh nanoclusters and the WNO nanonetworks plays a critical role in the high catalytic activity of Rh-WNO-NC.
Electrochemical surface area (ECSA) was further measured using a typical Cyclic Voltammetry (CV). Electrochemical double layer capacitance (Cdl) of Rh-WNO-NC was 4.3 mF cm −2 Less than 5.1 mF cm of Rh/C −2 But much higher than 2 of WNO-NC.7 mF cm −2 It was demonstrated that Rh-WNO-NC could expose more catalytically active sites (FIGS. 4e and 16). In FIG. 4f, at 10 mA cm −2 Before and after 10 hours of HER testing at the high current density of (c) the HER polarization curve did not shift significantly (fig. 4 f), indicating that Rh-WNO-NC has good electrochemical durability, which explains the presence of N-doped carbon shells in the interconnected nanostructures.
TABLE 3 determination of atomic weight ratio of sample surfaces by XPS
| Sample of | C | N | O | Rh | W |
| Rh-WNO-NC | 40.97 | 2.23 | 13.30 | 2.58 | 40.92 |
| Rh-NC | 92.57 | 1.19 | 3.67 | 2.57 | - |
As shown in table 3, the Rh content of Rh-NC was 2.57 wt%, the Rh content of Rh-WNO-NC was 2.58 wt%, and the Rh contents of both were almost the same. As shown in FIG. 11, the temperature was set at 10 mA cm -2 When Rh-NC over-potential was 16 mV lower than Rh-WNO-NC (22 mV); and at 200 mA cm -2 Under the condition of larger current density, rh-WNO-NC only needs the overpotential of 119 mV, which is far lower than 213 mV of Rh-NC, thus greatly reducing the cost of electrolyzed water. The results show that the kinetics of Rh-WNO-NC reaction is significantly better than Rh-NC due to the unique interconnected nanohybrid structure and optimized composition of WNO in Rh-WNO-NC.
The effect of calcination temperature on the HER performance of the catalyst was studied from characterization and testing of Rh-W-NC-500, rh-W-NC-600, rh-W-NC-700, rh-W-NC-800, rh-W-NC-900 (FIG. 17). Experimental data indicate that Rh-W-NC-600 has the best HER performance.
It has been demonstrated hereinbefore that Rh-WNO-NC exhibits higher HER activity than Pt/C under alkaline conditions. To reveal the pH prevalence of Rh-WNO-NC interconnected nanohybrid structure to catalyze HER, this experiment further investigated its pH at 0.5M H 2 SO 4 HER performance in solution and 1.0M Phosphate Buffered Saline (PBS). As shown in FIGS. 5 (a-f), at 0.5M H 2 SO 4 In solution and 1.0M PBS solution, rh-WNO-NC was at 10 mA cm -2 The lower overpotential was 19 mV and 143 mV, respectively. It can be seen that Rh-WNO-NC shows higher current density than Pt/C under alkaline or neutral conditions at different overpotential; the current densities of Rh-WNO-NC and Pt/C were not significantly different even in the acidic solution. Rh-WNO-NC is shown to be a high-efficiency HER catalyst suitable for the full pH range. Unlike Pt/C, pH did not greatly affect the HER catalytic performance of Rh-WNO-NC, indicating that Rh-WNO-NC was able to overcome the water dissociation energy barrier well, which is very important for HER catalysts that need to be used under non-acidic conditions (FIG. 18).
The experimental result shows that the Rh-WNO-NC catalyst can be efficiently applied to acidic, neutral and alkaline environments, and is an efficient HER catalyst in a full pH range. Compared with Rh10mg-WNO-NC and Rh20mg-WNO-NC, the Rh5mg-WNO-NC catalyst has better electrocatalytic HER performance; compared with Rh-W-NC-500, rh-W-NC-700, rh-W-NC-800 and Rh-W-NC-900, the Rh-W-NC-600 catalyst of the invention has the best electrocatalytic HER performance.
In summary, the invention provides a nano hybrid material, a preparation method and application thereof. The nanometer hybrid material can be efficiently applied to acidic, neutral and alkaline environments, and is an efficient HER catalyst with a full pH range. Compared with the prior art, the consumption of rhodium in the nano hybrid material is greatly reduced, the catalyst cost is greatly reduced, the catalytic intrinsic activity is greatly improved, and the nano hybrid material has wide application prospect in the field of hydrogen electrolysis of water as a water and electricity hydrogen desorption catalyst.
Claims (10)
1. A nano hybrid material is characterized in that the nano hybrid material is prepared from tungsten salt or hydrate thereof, rhodium salt or hydrate thereof, urea and conductive carbon black as raw materials, wherein the mass ratio of the tungsten salt or hydrate thereof, the rhodium salt or hydrate thereof, the urea and the conductive carbon black is (10-30) to (0.1-10) to (10-30) to (1-3).
2. The nano-hybrid material according to claim 1, wherein the mass ratio of the tungsten salt or the hydrate thereof, the rhodium salt or the hydrate thereof, the urea and the conductive carbon black is 20 (0.5-2): 20:2.
3. The nano-hybrid material according to claim 2, wherein the mass ratio of the tungsten salt or the hydrate thereof, the rhodium salt or the hydrate thereof, the urea and the conductive carbon black is 20:1:20:2.
4. A nano-hybrid material according to any one of claims 1-3, wherein the tungsten salt is tungsten hexachloride, the rhodium salt is rhodium trichloride, and the conductive carbon black is ketjen black.
5. A method of preparing the nanohybrid material of any of claims 1-4, comprising the steps of:
(1) Adding tungsten salt or hydrate thereof, rhodium salt or hydrate thereof, urea and conductive carbon black into an organic solvent, uniformly mixing, and standing to obtain a precursor;
(2) And heating the precursor, pyrolyzing, cooling to room temperature, and standing to obtain the water and electricity hydrogen desorption catalyst.
6. The method according to claim 5, wherein in step (1), the organic solvent is an alcohol solvent; the standing time is 8-16 hours;
in the step (2), the pyrolysis temperature is 500-900 ℃ and the pyrolysis time is 2-4 hours; the heating rate is that the temperature is firstly increased to 60-80 ℃ at a heating rate of 0.5-2 ℃/min and kept at a constant temperature of 1-3 h, and then the temperature is continuously increased to the pyrolysis temperature at a heating rate of 0.5-2 ℃/min.
7. The method of claim 6, wherein in step (1), the alcoholic solvent is ethanol; the standing time is 12 hours;
in the step (2), the pyrolysis temperature is 600 ℃ and the pyrolysis time is 3 hours; the heating rate is that the temperature is firstly increased to 70 ℃ at a heating rate of 1 ℃/min and kept at a constant temperature of 2 h, and then the temperature is continuously increased to the pyrolysis temperature at the heating rate of 1 ℃/min.
8. The method according to any one of claims 5 to 7, wherein step (1) is carried out under anhydrous and anaerobic conditions; step (2) is performed under the protection of inert gas.
9. Use of the nanohybrid material according to any one of claims 1 to 4 for the preparation of a catalyst for the electrolytic hydrogen evolution of water.
10. Use according to claim 9, wherein the hydro-power analysis hydrogen catalyst is suitable for acidic, neutral and/or basic conditions.
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