CN111482185B - Self-supporting FeS x Electrocatalyst, preparation method and application thereof - Google Patents
Self-supporting FeS x Electrocatalyst, preparation method and application thereof Download PDFInfo
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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
- 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
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
- B01J37/20—Sulfiding
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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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
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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
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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
- 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
- C25B11/075—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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- Optics & Photonics (AREA)
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Abstract
The invention discloses a self-supporting FeS x An electrocatalyst, a method for preparing the same and use thereof, the method comprising: providing an iron substrate; subjecting the iron substrate to a plasma treatment, the plasma comprising H 2 S, feS is formed on the surface of the iron matrix x Obtaining the self-supporting FeS x Electrocatalyst, wherein x=0.5-2. The invention provides a simple, economical and effective plasma vulcanization method for preparing a novel self-supporting FeS x Electrocatalysts, such FeS when applied to electrocatalytically reducing nitrogen at ambient conditions x the/Fe electrode proved to show excellent ammonia production of 4.25X10 ‑10 mol·s ‑1 ·cm ‑2 And a very high faraday efficiency of 18.1%, significantly better than other non-noble metal catalysts. FeS synthesized in consideration of plasma sulfidation method x The Fe has good performance and lower cost, and has wide application prospect in electrochemical ammonia synthesis.
Description
Technical Field
The invention relates to the technical field of electrocatalysts, in particular to a self-supporting FeS x Electrocatalyst and its preparation method and application are provided.
Background
Ammonia (NH) 3 ) Is the largest chemical product in the world, and the annual yield of the world is up to 1.5 hundred million tons. More than 90% of the synthetic ammonia is currently produced by the industrial Haber-Bosch process, i.e. using N 2 And H 2 The gas synthesizes ammonia on the surface of the iron-based catalyst under the conditions of high temperature (400-500 ℃) and high pressure (150-200 atm). This process requires 1% of the global supply energy and generates a significant amount of CO 2 . In sharp contrast, many natural plants and bacteria carry metallo-nitrogen fixation enzymes that are capable of being exposed to environmental conditionsThe strong N.ident.N triple bond (941 kj/mol) is activated and the nitrogen in the air is reduced to ammonia. Inspired by this biological process, much work has begun to investigate how nitrogen is reduced to ammonia under mild conditions. Recently, electrochemical nitrogen reduction of ammonia synthesis at room temperature in aqueous phase has attracted extensive research interest. The electrochemical process directly utilizes abundant water resources as a hydrogen source, and can be easily combined with intermittent renewable energy sources (such as wind energy, solar energy or ocean energy) to provide required electric power, so that the electrochemical process is very suitable for being used in areas where traffic is inconvenient and large-scale chemical plants are not suitable to be built. However, activation of the n≡n bond under mild conditions is a significant challenge, not only because of its very high bond energy but also because of the lack of dipole moment, this electrochemical process requires the help of an electrocatalyst. In addition, electrochemical reduction of Nitrogen (NRR) in the aqueous phase also faces the challenge of competing with electrochemical Hydrogen Evolution (HER). Because the reduction potentials of these two reactions are very close, this places more stringent demands on the selectivity of the nitrogen reduction catalyst.
Recently reported monoatomic ruthenium (Ru) based and gold (Au) nanoparticle catalysts exhibit very high ammonia yields and faradaic efficiencies. However, the use of single-atom Ru and nano-particle Au, which are complicated and expensive in synthetic method, severely limit the large-scale use thereof. And other non-noble metal catalyst materials (e.g., fe 2 O 3 ，Bi 4 V 2 O 11 ，MoS 2 ) And carbon materials, although also widely studied, the reported ammonia yields and faraday efficiencies remain quite low. Thus, there is an urgent need to develop a non-noble metal nitrogen reduction catalyst that is simple to synthesize, economical and efficient.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, it is an object of the present invention to provide a self-supporting FeS x Electrocatalyst, preparation method and application thereof, aiming at solving the problems that the existing metal catalyst material synthesis method is complex and expensive, but not noble metal catalyst materialThe ammonia yield and faraday efficiency are quite low.
The technical scheme of the invention is as follows:
self-supporting FeS x A method of preparing an electrocatalyst comprising:
providing an iron substrate;
subjecting the iron substrate to a plasma treatment, the plasma comprising H 2 S, feS is formed on the surface of the iron matrix x Obtaining the self-supporting FeS x Electrocatalyst, wherein x=0.5-2.
The self-supporting FeS x The preparation method of the electrocatalyst comprises the step of preparing an iron base material from foam iron, an iron sheet or a stainless steel sheet.
The self-supporting FeS x Preparation method of electrocatalyst, wherein the plasma is H 2 S or H 2 S and inert gas.
The self-supporting FeS x A method for preparing an electrocatalyst, wherein the temperature of the treatment is from 25 ℃ to 300 ℃.
The self-supporting FeS x The preparation method of the electrocatalyst comprises the step of treating for 5-180min.
The self-supporting FeS x The preparation method of the electrocatalyst comprises the steps of performing plasma treatment of the foam iron in a quartz tube in a tube furnace system, wherein the plasma is H 2 S, the processing procedure comprises the following steps: firstly, cutting foam iron into fragments with the size of 1cm multiplied by 2cm, and then placing the fragments in the central area of a quartz tube; quartz tube at H 2 Heating to 160 ℃ during the S plasma treatment; continuously introducing 50sccm of H 2 S, entering a quartz tube, and maintaining the pressure in the tube at 600mtorr through a vacuum pump; the upstream portion of the quartz tube is wrapped with a copper coil through which 60W of RF power is supplied to generate H in the upstream region of the tube 2 S plasma; the plasma power supply is in a pulse mode, the pulse length of each plasma is 15s, and the whole H is 2 The S plasma treatment process comprises 200H 2 S plasma pulse cycle.
Self-supplying deviceSupport FeS x Electrocatalyst, wherein the self-supporting FeS x The electrocatalyst comprises an iron substrate and FeS on the surface of the iron substrate x The self-supporting FeS x The electrocatalyst adopts the self-supporting FeS x The electrocatalyst is prepared by a preparation method.
The self-supporting FeS x Electrocatalyst, wherein the self-supporting FeS x The electrocatalyst is self-supporting FeS 2 An electrocatalyst.
The self-supporting FeS provided by the invention x The application of the electrocatalyst in electrochemical reduction of nitrogen to ammonia.
The beneficial effects are that: the invention provides a new method for simply carrying out H on the surface of an iron substrate 2 S plasma treatment to form FeS x Nitrogen reduces the catalytic material. Through H 2 S plasma vulcanization treatment can form a layer of FeS on the surface of foam iron x And exhibits excellent properties of nitrogen reduction and ammonia production. With such FeS x the/Fe is directly used as a working electrode, and shows excellent ammonia yield up to 4.25X10 at a potential of-0.30V relative to a Reversible Hydrogen Electrode (RHE) -10 mol·s -1 ·cm -2 And a very high faraday efficiency of 18.1%, which is significantly higher than the non-noble metal catalysts already reported. Notably, the site of activated nitrogen of biological nitrogen fixation enzyme is located on the Fe-S molecular cluster. They are compatible with the pure inorganic FeS of the present invention x Catalysts have similarities which make this work more interesting as it can provide important help to simulate natural nitrogen fixation processes.
Drawings
In FIG. 1, (a) is an example FeS x SEM pictures of/Fe, (b) corresponding EDS, (c) STEM HADDF pictures of cross-section, (d-g) corresponding EDS element profile, (h) XPS measurement spectrum, (i) corresponding high resolution spectrum Fe 2p, (j) corresponding high resolution spectrum S2 p.
FIG. 2 is a representation of electrocatalytic nitrogen reduction performance in an example: (a) Is FeS x Electrochemical polarization curves of the Fe electrode in saturated solutions of nitrogen and argon, the inset shows the measurement in briefA device; (b) is a potentiostatic time ampere curve; (c) Photographs and absorption spectra for determining nitrogen reduction products using the indophenol blue method; (b) (c) and (d) adopt the same line color for the yield of ammonia under different potentials; (e) The Faraday efficiency of ammonia and the potential corresponding to Δj/j nitrogen; (f) Is Fe, fe 2 O 3 、FeS x Is compared to the faraday efficiency.
FIG. 3 is a graph of (a) Nyquist and (b) Bote obtained in the examples at-0.30V (vs. RHE) in saturated solutions of nitrogen and argon, respectively; (c) For RNRR at various potentials -1 /(RNRR -1 +RHER -1 ) The curve and the inset are the equivalent circuit obtained by fitting.
FIG. 4 shows steady state currents measured under saturated nitrogen and argon solutions, respectively, using chronoamperometry in examples, each potential being maintained for 120s, respectively.
FIG. 5 shows absolute standard curves (a, b) for the analysis of ammonia production (e, f) and the indophenol blue method (c, d) for the analysis of hydrazine production by the Watt-Christp method, respectively, in the examples.
FIG. 6 is a photograph of ammonia production analyzed by the Neisserial method and an absorption spectrum measured in the examples.
FIG. 7 is a photograph and absorption spectrum of hydrazine yield by the Watt-Christp method in the example.
Fig. 8 is a nyquist (a, c, e, g) and baud diagram (b, d, f, h) under nitrogen saturation and argon saturation conditions in the examples.
Fig. 9 is a comparison of SEM and EDS before and after the reaction in the examples.
FIG. 10 shows FeS before and after the reaction in the examples x And raman comparison of synthetic pure FeS.
FIG. 11 shows XPS analysis after nitrogen reduction in the examples.
FIG. 12 is a cyclic voltammetry test FeS in an example x (a) And Fe (Fe) 2 O 3 (b) The calculated electric double layer capacitance size (c).
Detailed Description
The invention provides a self-supporting FeS x An electrocatalyst, a preparation method and application thereof,the present invention will be described in further detail below in order to make the objects, technical solutions and effects of the present invention more clear and distinct. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The invention provides a self-supporting FeS x A method of preparing an electrocatalyst comprising:
providing an iron substrate;
subjecting the iron substrate to a plasma treatment, the plasma comprising H 2 S, feS is formed on the surface of the iron matrix x Obtaining the self-supporting FeS x Electrocatalyst, wherein x=0.5-2.
The invention provides a new method for simply carrying out H on the surface of an iron substrate 2 S plasma treatment to form FeS x Nitrogen reduces the catalytic material. Through H 2 S plasma vulcanization treatment can form a layer of FeS on the surface of the iron base material x And exhibits excellent properties of nitrogen reduction and ammonia production. With such FeS x the/Fe is directly used as a working electrode, and shows excellent ammonia yield up to 4.25X10 at a potential of-0.30V relative to a Reversible Hydrogen Electrode (RHE) -10 mol·s -1 ·cm -2 And a very high faraday efficiency of 18.1%, which is significantly higher than the non-noble metal catalysts already reported. Notably, the site of activated nitrogen of biological nitrogen fixation enzyme is located on the Fe-S molecular cluster. They are compatible with the pure inorganic FeS of the present invention x Catalysts have similarities which make this work more interesting as it can provide important help to simulate natural nitrogen fixation processes.
Preferably, the iron matrix is foam iron, iron sheet or stainless steel sheet. More preferably, the iron matrix is foam iron. The excellent porosity is beneficial to electrocatalysis, because they can rapidly diffuse active substances, promote effective permeation of electrolyte, and significantly enlarge the surface area of electrochemical reaction.
Preferably, the plasma is H 2 S or H 2 S with an inert gas (e.g., argon, etc.).
Preferably, the temperature of the treatment is 25-300 ℃. More preferably, the temperature of the treatment is 150-170 ℃ (e.g. 160 ℃). The temperature is selected for the plasma treatment in the present invention to limit diffusion of sulfur in the iron and thus limit its sulfidation depth.
Preferably, the treatment is for a period of time ranging from 5 to 180 minutes. More preferably, the treatment is for a period of 40-60 minutes (e.g., 50 minutes). The plasma treatment of the invention for the above time can finally form a FeS with uniform thickness on the surface of the iron matrix x 。
Specifically, the plasma treatment of the foam iron is carried out in a quartz tube in a tube furnace system, and the plasma is H 2 S, the processing procedure comprises the following steps: firstly, cutting foam iron into fragments with the size of 1cm multiplied by 2cm, and then placing the fragments in the central area of a quartz tube; quartz tube at H 2 Heating to 160 ℃ during the S plasma treatment; continuously introducing 50sccm of H 2 S, entering a quartz tube, and maintaining the pressure in the tube at 600mtorr through a vacuum pump; the upstream portion of the quartz tube is wrapped with a copper coil through which 60W of RF power is supplied to generate H in the upstream region of the tube 2 S plasma; the plasma power supply is in a pulse mode, the pulse length of each plasma is 15s, and the whole H is 2 The S plasma treatment process comprises 200H 2 S plasma pulse cycle.
The invention also provides a self-supporting FeS x Electrocatalyst, wherein the self-supporting FeS x The electrocatalyst comprises an iron substrate and FeS on the surface of the iron substrate x The self-supporting FeS of the invention is adopted x The electrocatalyst is prepared by a preparation method.
In the invention, the self-supporting FeS x The electrocatalyst may be self-supporting FeS 2 An electrocatalyst.
The invention also provides the self-supporting FeS x The application of the electrocatalyst in electrochemical reduction of nitrogen to ammonia.
The present invention will be described in detail with reference to examples.
1、H 2 S plasma treatment of foam iron (FeS preparation) x Fe electrode) H is carried out in a quartz tube in a self-made tube furnace system 2 S plasma treatment. The commercial foam iron was first cut into pieces of 1cm x 2cm size, and then the sample was placed in the central region of the quartz tube. The tube needs to be heated to 160 ℃ during plasma processing. Continuously introducing 50sccm of H 2 S (3% Ar dilution) into a quartz tube, the pressure in the tube was maintained at 600mtorr by a vacuum pump. The upstream portion of the quartz tube was wrapped with a copper coil through which 60W of radio frequency power (13.56 MHz) was supplied to generate H in the upstream region of the tube 2 S plasma. The plasma power supply is pulsed to avoid overheating of the tube. Each plasma pulse length is 15s, and the whole vulcanization process is completed by 200H 2 S plasma pulse cycle.
2. Electrochemical nitrogen reduction test: as shown in fig. 2a, the entire test was performed in a double chamber cell, with a Nafion 211 exchange membrane in between. Before the experiment, the Nafion film is subjected to pretreatment, and is continuously immersed in 5% hydrogen peroxide solution and ultrapure water, and the temperature is maintained at 80 ℃ for 1 hour. Electrochemical data were tested using the CHI604E workstation under a three electrode system. Pt is used as a counter electrode, hg/HgO is used as a reference electrode, and the electrolyte is 0.1M KOH aqueous solution. All the potentials shown were iR corrected, corresponding to Reversible Hydrogen Electrodes (RHE), and the electrochemical polarization curves were obtained by potentiostatic chronoamperometry, maintaining 120s at each potential to achieve steady state current. To characterize nitrogen reduction, pure nitrogen (99.999%, 1 atm) was continuously vented to the working electrode in aqueous solution, and nitrogen was vented for 30 minutes prior to data collection. By way of comparison, argon (99.999%, 1 atm) replaced nitrogen, all other tests being identical to that in nitrogen.
3. Electrochemical impedance test (EIS): the frequencies tested were 0.1Hz to 10kHz, with bias voltages set at-0.14, -0.22, -0.30, -0.38 and-0.42V vs. RHE, respectively, with an alternating amplitude of 5mV, and impedance fitting with ZView software.
4. Preparation of Fe 2 O 3 /Fe electrode: heating foam iron in air at 600 ℃ for 1h to obtain Fe on the surface of the foam iron 2 O 3 。
The experimental results are as follows:
through H 2 After the S plasma treatment, the color of the whole foam iron is uniformly changed, which indicates FeS x The coverage on Fe is completely uniform, indicating that this plasma sulfidation process is easily scalable. After that for FeS x The microstructure of/Fe was subjected to Scanning Electron Microscope (SEM) testing. Fig. 1a, b show typical SEM images and corresponding energy dispersive x-ray spectroscopy (EDS). H 2 After S plasma treatment, the porous foam has complete structure and FeS on the surface x The layer is even and smooth. Excellent porosity and surface uniformity for conversion to FeS x Are important for electrocatalysis because they can rapidly diffuse active species, promote efficient penetration of electrolyte, and significantly expand the surface area of electrochemical reactions.
FeS of opposite surface x The layers were further subjected to a cross-sectional Scanning Transmission Electron Microscope (STEM) test. To prepare STEM samples, one first takes place in FeS x And depositing a Pt protective layer on the surface of the Fe. FIG. 1c shows FeS x Large angle annular dark field (HAADF) STEM pictures of layers. Fig. 1d-g show the corresponding element distributions obtained by EDS. These results clearly show that a layer of FeS about 70nm thick is uniformly formed on the surface of the foam iron x . Further investigation of FeS by X-ray photoelectron spectroscopy (XPS) x Composition of the layers. FIG. 1h shows the full spectrum of XPS, and FIGS. 1i, j show the high resolution lines of Fe 2p and S2 p. The spectrum of Fe shows a pair of peaks of spin orbitals at 707.3 (2 p 3/2) and 720.0eV (2 p 1/2), and the spectrum of S shows a pair of peaks of spin orbitals at 162.5 (2 p 3/2) and 163.7eV (2 p 1/2), the values of these binding energies being the same as FeS 2 Is consistent with that of FeS to illustrate surface formation x May be FeS 2 . Meanwhile, the integral of the peak areas of the Fe and S2 p spectral lines can find that the atomic ratio of S/Fe is listed as 2.03+/-0.03, which indicates that FeS is formed 2 . Raman spectroscopy (FIG. 11) further showed that FeS formed 2 Is pyrite-pyrite mixed FeS 2 Similar to the use of H 2 S plasma atomic layer deposition FeS 2 But no raman signal of element S was observed.
The pair of cells was operated with a double chamber cell at room temperature of 21℃in 0.1M KOH solutionFeS x Three electrode tests were performed for electrocatalytic nitrogen reduction. FeS (FeS) x the/Fe is used directly as working electrode, pure nitrogen being continuously led to the electrolyte. To investigate its competing process with electrochemical hydrogen evolution, pure argon was used as a control group instead of nitrogen. The electrochemical polarization curve reaches steady state current by stepping up potentials (-0.14 to-0.42 vvs. Rhe), each potential held for 120s (fig. 4). The values of the steady state current are then used to generate a polarization curve measured under nitrogen or argon bubbling as shown in figure 2 a. The current density generated under nitrogen (j nitrogen) was found to be greater than that generated under argon (j argon), particularly in the interval of potential from-0.22 to-0.38V (vs. Assuming that the current under argon bubbling should correspond to electrochemical hydrogen evolution, and assuming that electrochemical hydrogen evolution and nitrogen reduction are two independent competing processes, the difference between the two upper curves (Δj=j nitrogen-j argon) should correspond to nitrogen reduction. The results showed that the difference in current density reached a maximum of-138. Mu.A/cm when the potential was at-0.30V (vs. RHE) 2 Under nitrogen bubbling conditions, this value represents up to 19.1% of the total current density. The Δj/j nitrogen in the column of the aspect ratio means that a large portion of the cathode current is used to reduce the nitrogen.
Products of nitrogen reduction (e.g. NH 3 And N 2 H 4 ) Quantization was performed in the following manner. Firstly, in order to obtain a sufficient quantity of products for quantitative analysis, feS is added x the/Fe electrode is biased for 20h under a certain constant potential, and FeS is collected x The electrolyte on the electrode side was analyzed for the accumulated product quantity. This procedure was repeated at each constant potential-0.14, -0.22, -0.30, -0.38 and-0.42V (vs. rhe), respectively, while recording the current density as a function of potential over the 20 h. As shown in fig. 2b, the current density remains fairly constant over time, indicating FeS x The Fe electrode has good electrocatalytic stability. At the same time, a negligible small change in current density also indicates that the rate of formation of the reaction product is constant, so the rate of formation of the product can be calculated by dividing the total amount formed by the total reaction time. Ammonia was quantitatively analyzed as the main product of nitrogen reduction by the indophenol blue method and the nervilia reagent method, respectively. FIG. 2c showsThe photograph and absorption spectrum curves obtained by the indophenol blue method are shown in FIG. 5, and the corresponding absolute calibration curves are shown to obtain the concentration of ammonia in the reaction product solution. Likewise, the photographs and absorption spectra measured by the Neisserial method are shown in FIG. 9, and the absolute calibration curve is shown in FIG. 5. The ammonia concentration obtained from the absolute calibration curve can be used to calculate FeS x The electrocatalyst gives ammonia yields at different potentials. As shown in table 1, the values obtained for the two methods are very similar (within 4%) and therefore their average value is simply used as the ammonia yield. FIG. 2d shows a graph of ammonia production versus the corresponding potential (see Table 2), it can be seen that at potential-0.30V (vs. RHE) the ammonia yield reaches a maximum of 4.25X10 -10 mol·s -1 ·cm -2 . This ammonia yield was quite high, essentially one of the most recently reported optimal values (Table 3). The Faraday efficiency of ammonia was also calculated in this example, as shown in FIG. 2e, and was as high as 18.1% at potential-0.30V (vs. RHE), which is one of the best values reported. (Table 3). In addition, FIG. 2e also shows a comparison between Faraday efficiency and Δj/j nitrogen, by which it can be found that Δj/j nitrogen is only higher (0.3-2.7%) than ammonia-producing Faraday efficiency, indicating that the catalyst has a very high selectivity for ammonia in electrochemical reduction over other reduction products. In fact, N was also quantified by Watt-Christp spectrophotometry 2 H 4 N was found by the yield of (FIG. 5 and FIG. 7) 2 H 4 Is the main byproduct, thus explaining the source of minor errors between Faraday efficiency and Δj/j nitrogen (see Table 2). In summary, the FeS prepared by the plasma treatment x The method has good performance of preparing ammonia by electrocatalytic reduction of nitrogen under the environmental condition, and has high ammonia yield, high Faraday efficiency and good stability.
To gain insight into the electrocatalytic mechanism, feS was separated in argon and nitrogen saturated solutions x the/Fe electrode was subjected to Electrochemical Impedance Spectroscopy (EIS) measurement. Figures 3a, b show nyquist and baud curves at-0.30V (vs. rhe). The nyquist diagram shows that in both cases, a single semicircle is used, but the diameter of the semicircle is smaller than that of the argon saturation case when the nitrogen is saturated; wave-guideThe special graph shows a single peak in the frequency range of 0.1Hz-10khz, and the peak frequency of nitrogen saturation is greater than that of argon saturation. Similar results were also observed for other potentials (fig. 8), with single nyquist semicircles and baud peaks representing a single equivalent charge transfer process in the frequency range of 0.1Hz-10khz, indicating that electrochemical nitrogen reduction does have a reaction rate competing relationship with hydrogen evolution, perhaps seen as two parallel processes. Therefore, the EIS data in the nitrogen saturated solution is fitted by adopting a slightly modified equivalent circuit, as shown in the inset of fig. 3c, wherein the charge transfer resistor (Rct) is divided into two reaction channels of RHER and RNRR which are connected in parallel, and the RHER value only takes the EIS data without nitrogen reduction in the argon saturated solution. Fitting results are detailed in table 4. Further calculation of RNRR at each potential -1 /(RNRR -1 +RHER -1 ) Values and correspond to the percentage of nitrogen reduction current. As shown in FIG. 3c, RNRR -1 /(RNRR -1 +RHER -1 ) The same trend was shown for Δj/j nitrogen (FIG. 2 e), which shows good consistency under DC and AC testing.
Further reducing FeS after nitrogen x Is characterized by the material. As shown in FIG. 9, after nitrogen reduction, feS x The surface morphology of the/Fe electrode remains substantially unchanged. However, raman spectroscopy shows FeS x After the crystal structure of the surface was changed to that of the marinote FeS by nitrogen reduction (fig. 10), this conclusion was also verified by XPS, and it was found that the peak positions of Fe 2p and S2 p were shifted to the marinote FeS (fig. 11). Thus, the markeno FeS is likely to be the actual electrocatalyst. In addition, XPS spectra also showed the presence of nitrogen-containing species on the catalyst surface after nitrogen reduction (fig. 11): the observed N1 s binding energy is 399.6eV, which may correspond to the formation of nitrogen hydride (e.g., NH) x Or N x H y )。
Finally, feS is also compared with x With Fe 2 O 3 Nitrogen reduction properties of Fe 2 O 3 Is a very good nitrogen reduction electrocatalyst recently reported. The Fe is obtained on the surface of the same foam iron by oxidation 2 O 3 Catalysts, by testingObtaining FeS x Fe electrode and Fe 2 O 3 The surface area of the/Fe electrode was substantially the same (FIG. 12). The same measurement process is adopted to obtain Fe 2 O 3 Maximum nitrogen yield and faraday efficiency of the electrocatalyst, as shown in fig. 2 f. Note that pure foam iron did not show any measurable ammonia product. In fact, fe 2 O 3 The catalyst showed a good ammonia yield of 4.25X10 -10 mol·s -1 ·cm -2 (-0.3V vs. RHE), and Faraday efficiency 2.2%, which are consistent with previous reports. These values are then significantly lower than FeS in this example x A catalyst.
Table 1, comparison of ammonia yields of indophenol blue method and Neisseria reagent method, average, unit order of 10 -10 mol·s -1 ·cm -2
TABLE 2 Faraday efficiency for ammonia and hydrazine production
TABLE 3 FeS x Performance comparison of Fe with other catalysts
Table 4, fitting results of EIS, electric double layer capacitor (C dl ) By passing through
And (5) calculating. T and->
Parameters corresponding to CPE
In summary, the present invention provides a simple, cost-effective plasma sulfidation process for preparing a self-supporting FeS x Electrocatalysts, such FeS when applied to electrocatalytically reducing nitrogen at ambient conditions x the/Fe electrode proved to show excellent ammonia production of 4.25X10 -10 mol·s -1 ·cm -2 And a very high faraday efficiency of 18.1%, significantly better than other non-noble metal catalysts. FeS synthesized in consideration of plasma sulfidation method x The Fe has good performance and lower cost, and has wide application prospect in electrochemical ammonia synthesis. Furthermore, feS x The catalyst is somewhat similar to the Fe-S cluster in biological nitrogen fixation enzymes, which may provide important insight into mimicking the natural nitrogen fixation process.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (2)
1. Self-supporting FeS x Use of an electrocatalyst for electrochemical reduction of nitrogen to ammonia, comprising:
providing an iron substrate;
subjecting the iron substrate to a plasma treatment, the plasma comprising H 2 S, feS is formed on the surface of the iron matrix x Obtaining the self-supporting FeS x Electrocatalyst, wherein x=2;
the saidSelf-supporting FeS x The electrocatalyst comprises an iron substrate and FeS on the surface of the iron substrate x ；
The iron base material is foam iron, an iron sheet or a stainless steel sheet;
the plasma is H 2 S or H 2 S and inert gas mixed gas;
the temperature of the treatment is 25-300 ℃;
the treatment time is 5-180min.
2. The self-supporting FeS of claim 1 x The application of the electrocatalyst in the electrochemical reduction of nitrogen to prepare ammonia is characterized in that the plasma treatment of foam iron is carried out in a quartz tube in a tube furnace system, and the plasma is H 2 S, the processing procedure comprises the following steps: firstly, cutting foam iron into fragments with the size of 1cm multiplied by 2 and cm, and then placing the fragments in the central area of a quartz tube; quartz tube at H 2 Heating to 160 ℃ during the S plasma treatment; continuously introducing 50sccm of H 2 S, entering a quartz tube, and maintaining the pressure in the tube at 600mtorr through a vacuum pump; the upstream portion of the quartz tube is wrapped with a copper coil through which 60W of the RF power is supplied to generate H in the upstream region of the tube 2 S plasma; the plasma power supply is in a pulse mode, the pulse length of each plasma is 15s, and the whole H 2 The S plasma treatment process comprises 200H 2 S plasma pulse cycle.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011125398A1 (en) * | 2010-04-01 | 2011-10-13 | 株式会社神戸製鋼所 | Method for purifying polluted water |
| CN103495427A (en) * | 2013-10-17 | 2014-01-08 | 大连理工大学 | Method for using low-temperature plasma to prepare supported metal sulfide catalyst |
| WO2014207156A1 (en) * | 2013-06-26 | 2014-12-31 | Centre National De La Recherche Scientifique (Cnrs) | Iron sulfide based catalyst for electrolytic water reduction into hydrogen gas |
| CN108201893A (en) * | 2016-12-20 | 2018-06-26 | 北京大学深圳研究生院 | FeSxFilm, hydrazo phenyl compound and deposition method and preparation method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011125398A1 (en) * | 2010-04-01 | 2011-10-13 | 株式会社神戸製鋼所 | Method for purifying polluted water |
| WO2014207156A1 (en) * | 2013-06-26 | 2014-12-31 | Centre National De La Recherche Scientifique (Cnrs) | Iron sulfide based catalyst for electrolytic water reduction into hydrogen gas |
| CN103495427A (en) * | 2013-10-17 | 2014-01-08 | 大连理工大学 | Method for using low-temperature plasma to prepare supported metal sulfide catalyst |
| CN108201893A (en) * | 2016-12-20 | 2018-06-26 | 北京大学深圳研究生院 | FeSxFilm, hydrazo phenyl compound and deposition method and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| Deep eutectic-solvothermal synthesis of nanostructured Fe3S4 for electrochemical N2 fixation under ambient conditions;Xinhui Zhao et al.;《Chem. Comm.》;20181026;第54卷;摘要 * |
| 马世宁等.现代设备维修技术.《现代设备维修技术》.中国计划出版社,2006, * |
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