CN117865242B - OER electrocatalyst and preparation method and application thereof - Google Patents
OER electrocatalyst and preparation method and application thereof Download PDFInfo
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- 239000011572 manganese Substances 0.000 claims description 68
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- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
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- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 37
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- 229910052760 oxygen Inorganic materials 0.000 description 10
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910002640 NiOOH Inorganic materials 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002555 FeNi Inorganic materials 0.000 description 1
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- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention relates to an OER electrocatalyst, a preparation method and application thereof, and belongs to the field of electrocatalysts. The invention provides a preparation method of an OER electrocatalyst, which comprises the following steps: the OER electrocatalyst is prepared by using ferric salt, nickel salt and Mn-terephthalic acid coordination polymer as raw materials and preparing NiFeMn hydroxide through interfacial atom replacement. The resulting electrocatalyst required only 213mV and 251 mV overpotential in the electrolyte of 1M KOH and alkaline seawater NiFeMn to reach a current density of 100 mA cm ‑2.
Description
Technical Field
The invention relates to an OER electrocatalyst, a preparation method and application thereof, and belongs to the field of electrocatalysts.
Background
Electrochemical water electrolysis hydrogen production is used as a low-carbon green sustainable strategy, and can alleviate the problems of overwhelming fossil fuel exploitation, global atmospheric pollution and the like. The two-pole reactions of electrochemical water decomposition consist of an Oxygen Evolution Reaction (OER) at the anode and a Hydrogen Evolution Reaction (HER) at the cathode, respectively. In principle, OER kinetics involve multiple proton-coupled electron transfer steps, with slower kinetics, which limits the overall water splitting efficiency to a large extent. Electrochemical water splitting systems often require pure water as a feedstock. The fresh water resources required for large-scale industrialization are incompatible with pure water reserves on earth, which makes seawater electrolysis more attractive. However, the use of seawater places a number of challenging demands on the catalyst due to the complexity of the seawater composition. The presence of a significant amount of chloride ions in seawater (Cl -）,Cl- the oxidation reaction involved in the electrolysis of seawater is chlorine evolution chlorine reaction (CIER). The competition of OER and CIER at the anode hampers its large scale development in seawater electrolysis. Furthermore, the hypochlorite and Cl-corrosion effects of CIER reactions also impair the long-term operation of seawater electrolysis, thus inhibiting continuous hydrogen production in seawater electrolysis. Studies have shown that at ph=14 the theoretical potential of CIER is about 490mV higher than OER, which suggests that conducting alkaline seawater electrolysis can inhibit cier. For practical seawater electrolysis, the development of an anodic electrocatalyst capable of efficient and durable oxygen evolution at high current densities, and capable of avoiding chlorine evolution in alkaline seawater, remains a current challenge to be overcome.
Transition metal hydroxides, especially NiFe-based hydroxides, are the most effective OER catalysts among all the above candidates reported so far, and have also been demonstrated to be the true catalytically active species generated from the surface reconstruction of many types of oxygen evolving materials. However, the OER performance of hydroxides in seawater is still unsatisfactory due to insufficient long-term stability in Cl-containing media. Although some hydroxide electrocatalysts exhibit considerable stability, they do not exhibit sufficient catalytic capacity to conduct rapid electrolysis at low overpotential.
To date, the search for high performance catalysts with rich active centers and resistance to corrosion by salt electrolytes has been at the beginning of the study with great potential. In order to promote the OER activity of the NiFe hydroxide catalyst, researchers couple Ni/Fe hydroxide with other transition metal compounds, such as NiOOH/Ni 5P4、Ni2P/FeOOH、NiFe(OH)x/FeS, niFeOOH@FeNi, ni 3S2 @ NiFeOOH and the like, through interface engineering, and assemble the assembled interfaces, thereby achieving the purposes of optimizing the adsorption of oxygen intermediates and improving the OER activity.
However, there is no new OER electrocatalyst prepared by growing NiFe hydroxide on the surface of Mn-terephthalic acid coordination polymer (Mn TPA) as template and Mn source.
Disclosure of Invention
According to the invention, mn TPA is used as a template and a Mn source, niFe hydroxide grows on the surface of the Mn TPA, mn ions are leached out in the synthesis process and doped into hydroxide on the surface layer, so that the electrocatalyst (i.e. heterojunction electrocatalyst NiFeMn) with NiFeMn hydroxide-Mn TPA heterostructure is formed. The synergistic effect of the NiFeMn hydroxide on the surface layer and the Mn TPA substrate makes NiFeMn exhibit excellent OER activity and selectivity in seawater electrolyte. The resulting electrocatalyst required only 213mV and 251 mV overpotential in the electrolyte of 1M KOH and alkaline seawater NiFeMn to reach a current density of 100 mA cm -2. In addition, mn has a certain electronic regulation and control effect on the active site of Ni/Fe, which promotes the selectivity and activity of OER to a certain extent, and ensures that the Faraday efficiency of OER is as high as 91.89 percent. Also NiFeMn has high stability in the process of electrolyzing seawater, and the potential hardly decays after 88 hours of operation. Therefore, the invention not only has great practical value in the application of hydrogen evolution of the electrolytic seawater, but also provides an effective new strategy for researching the corrosion-resistant high-activity electrolytic seawater catalyst.
The technical scheme of the invention is as follows:
The first technical problem to be solved by the invention is to provide a preparation method of an OER electrocatalyst, which comprises the following steps: the OER electrocatalyst is prepared from ferric salt, nickel salt and Mn-terephthalic acid coordination polymer (Mn TPA) by preparing NiFeMn hydroxide with a heterostructure through interfacial atom substitution.
Further, the mass ratio of the raw materials is as follows: iron salt: nickel salt: mn-terephthalic acid coordination polymer=5-20:5-20:1-5.
Further, the iron salt is selected from: feSO 4·7H2 O or FeCl 2·4H2 O.
Further, the nickel salt is selected from: ni (NO 3）2·6H2O、NiSO4·6H2 O or NiCl 2·6H2 O).
Further, the Mn TPA is prepared by the following method: dissolving manganese salt and terephthalic acid (TPA) in a solvent to obtain a mixed solution, and then reacting the obtained mixed solution in corrosion-resistant reaction equipment at 100-150 ℃ for 20-30 h; naturally cooling to the ambient temperature after the reaction is finished; collecting the precipitate, and washing with alcohol and deionized water for at least 3 times; finally, vacuum drying is carried out to obtain Mn TPA (Mn-terephthalic acid coordination polymer).
Further, the manganese salt is selected from: mnCl 2·4H2O、MnSO4·xH2 O or Mn (NO 3)2·xH2 O).
Further, in the above method for producing Mn TPA, the solvent is selected from the group consisting of: deionized water, laboratory grade II pure water or ultrapure water; the alcohol substance is ethanol.
Further, the preparation method of the OER electrocatalyst comprises the following steps: mixing Mn-terephthalic acid coordination polymer and alcohol substances (ethanol), and performing ultrasonic treatment to form a uniformly dispersed suspension A; dissolving ferric salt and nickel salt in ultrapure water, and then adding urea for dissolving to obtain a solution B;
At normal temperature, the suspension A and the solution B are rapidly mixed and sealed, and are placed in 20-30 ℃ for reaction for 5-25 hours; and after the reaction is finished, washing with water and alcohol substances (ethanol) for 3-5 times respectively, and drying to obtain NiFeMn hydroxide with a heterostructure, namely the OER electrocatalyst.
Further, in the preparation method of the OER electrocatalyst, the mass ratio of the ferric salt to the nickel salt to the urea is: 5-20: 5-20: 10-40.
The second technical problem to be solved by the invention is to provide an OER electrocatalyst which is prepared by the preparation method.
Further, the resulting electrocatalyst requires only 213mV and 251 mV overpotential in the electrolyte of 1M KOH and alkaline seawater to achieve a current density of 100 mA cm -2.
The third technical problem to be solved by the present invention is to indicate the use of the OER electrocatalyst described above for the electrolysis of water or seawater.
The invention has the beneficial effects that:
According to the invention, a strategy of interfacial atom replacement is utilized to synthesize the NiFeMn hydroxide catalyst of the heterostructure for electrocatalytic oxygen evolution, mn TPA is taken as a template and Mn source, and NiFe hydroxide grows on the surface of the catalyst, so that controllable Mn replacement in NiFeMn is realized, and a heterojunction structure is constructed to obtain the OER electrocatalyst. As a result, it was found that the Ni and Fe electronic structures were controlled after Mn substitution incorporation, and Ni and Fe exhibited rich high valence states. Electrochemical tests show that NiFeMn loaded on carbon cloth in alkaline seawater medium can reach current density of 100mA cm -2 at over potential of 251mV and can stably work (> 80 h) at 50 and 100mA cm -2. The OER Faraday efficiency is as high as 91.89 percent, and the selectivity is high; it can be seen that the addition of a specific Mn source can promote high activity and high selectivity of NiFe hydroxide in alkaline seawater. Therefore, the NiFeMn catalyst with the atomic interface substitution has great practical value, which provides an effective strategy for realizing the high-activity and corrosion-resistant electrolytic alkaline seawater catalyst.
Drawings
FIG. 1 is a schematic diagram of the use of the NiFeMn heterojunction electrocatalyst OER according to the invention.
FIG. 2 (a) NiFe, (b) Mn TPA and (c) NiFeMn SEM of heterojunction electrocatalyst.
Fig. 3 a-e: a Transmission Electron Microscope (TEM) image of NiFeMn heterojunction electrocatalysts at different magnifications; and f, selecting an electron diffraction pattern of the region.
FIG. 4a NiFeMn is a HAADF diagram of a heterojunction electrocatalyst; b element map; element map of c-f Ni, fe, mn and O elements.
Figure 5 NiFeMn XRD patterns of electrocatalyst and NiFe, mnTPA.
FIG. 6 NiFeMn Fourier infrared spectra of heterojunction electrocatalyst and NiFe, mn TPA.
FIG. 7 a NiFeMn, XPS general plot of NiFe and Mn TPA; b-c NiFeMn high resolution XPS spectra of Ni 2p and Fe 2 p.
FIG. 8 is a LSV plot of OER for the a NiFeMn-CC electrocatalyst, niFe-CC and Mn TPA-CC at 1M KOH; b NiFeMn an overpotential statistical graph of the electrocatalyst and NiFe under different current densities; c. NiFeMn Tafel plot of electrocatalyst, niFe and MnTPA; ①、② and ③ in the figure represent Mn TPA, niFe and NiFeMn, respectively.
FIG. 9 LSV plots of NiFeMn electrocatalysts for different substrates (MnO 2、Mn3O4 and Mn TPA) in 1M KOH.
FIG. 10 NiFeMn is a graph of the stability results of electrocatalysts under alkaline conditions.
FIGS. 11 a-b NiFeMn are LSV and Tafel plots of electrocatalysts in alkaline seawater, ①、② and ③ representing Mn TPA, niFe and NiFeMn, respectively; c a overvoltage map at different current densities; d NiFeMn electrocatalyst and advanced electrolysis seawater OER catalyst activity statistics.
FIG. 12 NiFeMn is a graph of the stability results of electrocatalysts in alkaline seawater.
FIG. 13 NiFeMn Faraday efficiency and yield plot of OER of electrocatalyst in alkaline seawater; wherein the bar graph represents the yield and the wire graph represents the faraday efficiency.
Detailed Description
The invention takes Mn TPA as a template and Mn source, and grows NiFe hydroxide on the surface of the Mn TPA to form the electrocatalyst with NiFeMn hydroxide-Mn TPA heterostructure. The synergistic effect of the NiFeMn hydroxide on the surface layer and the Mn TPA substrate makes NiFeMn exhibit excellent OER activity and selectivity in seawater electrolyte. The resulting electrocatalyst required only 213mV and 251 mV overpotential in the electrolyte of 1M KOH and alkaline seawater NiFeMn to reach a current density of 100 mA cm -2.
The following describes the invention in further detail with reference to examples, which are not intended to limit the invention thereto.
Synthesis of example 1 Mn TPA
1.0Mmol of MnCl 2·4H2 O and 1.0mmol of terephthalic acid (PTA) were dissolved in 20ml of DMF (N, N-dimethylformamide) to obtain a mixed solution, and the above solution was put into a 50ml polytetrafluoroethylene liner, heated and kept at 120℃for reaction 24: 24 h. After the reaction is completed, naturally cooling to the ambient temperature. The resulting precipitate was collected by centrifugation and washed 3-5 times with ethanol and deionized water. Finally, vacuum drying is carried out for 6 hours at 70 ℃ to obtain the product of Mn TPA.
Synthesis of NiFeMn hydroxide of heterostructure
Mn TPA 20mg and ethanol 6 mL were mixed and sonicated for 30min to form a uniformly dispersed suspension A. Meanwhile, 50 mg FeSO 4·7H2 O and 150 mg Ni (NO 3）2·6H2 O was dissolved in 4mL ultrapure water, followed by 200 mg urea in the above salt solution to obtain solution B.
At normal temperature, rapidly mixing the suspension A and the solution B, and sealing the glass vial for reaction; placing the mixture in an oil bath at 80 ℃ for reaction for 20 hours; after the reaction is finished, washing the mixture with water and ethanol for 3-5 times respectively, and drying the mixture at 70 ℃ overnight to obtain NiFeMn hydroxide (abbreviated as NiFeMn) with a heterostructure.
FIG. 1 is a schematic diagram of the use of the NiFeMn heterojunction electrocatalyst OER according to the invention.
Example 2
The preparation was identical to example 1, except that the amount of Mn TPA added was 10mg.
Example 3
The preparation was identical to example 1, except that the amount of Mn TPA added was 15mg.
Comparative example 1
The preparation was identical to example 1, except that Mn TPA was replaced by MnO 2.
Comparative example 2
The preparation process was the same as in example 1, except that Mn TPA was replaced with Mn 3O4.
Comparative example 3
Synthesis of NiFe (NiFe hydroxide): 50 mg FeSO 4·7H2 O and 150 mg Ni O (NO 3）2·6H2 O is dissolved in 4 mL ultrapure water and 6ml ethanol, then 200 mg urea is weighed and dissolved in the above salt solution, and the mixture is placed in an oil bath at 80 ℃ for reaction for 20 hours, and after the reaction is finished, the mixture is washed with water and ethanol for 3-5 times respectively, and then dried at 70 ℃ overnight.
Microstructure and performance results
1. Structural characterization
SEM was used to characterize the basic morphology of NiFeMn hydroxides. FIG. 2 is an SEM topography of NiFe (FIG. 2 a), mn-TPA (FIG. 2 b) and NiFeMn (FIG. 2 c), respectively. From fig. 2c, it can be observed that uniform vertical growth of layered NiFe hydroxide on the surface of Mn TPA resulted in petal-like sphericity NiFeMn. The ultrathin petal-shaped morphology ensures that the material has large specific surface area and provides rich active sites for electrochemical reaction. In addition, the resulting high density of the spatial gap between the laminar sheet and the substrate may promote sufficient contact with the electrolyte, electron transfer and release of the generated gas. Therefore, mn TPA is used as a Mn source, mn ions are leached out in the growth process and slowly doped into hydroxide, so that controllable doping of Mn ions is realized.
The microstructure and its constituent components of NiFeMn were further studied using TEM and HRTEM. As can be seen from FIG. 3a, the morphology of NiFeMn is a layered petal sphere with a diameter of about 1.54 μm. And the flakes uniformly grown on the outer layer of the bulb are NiFeMn of hydroxide (see fig. 3 b-d). Obvious lattice fringes of NiFe hydroxide with lattice spacing of 0.197 nm and 0.230 nm, respectively, due to the (018) and (015) crystal planes of NiFe hydroxide can be observed in the HRTEM image (fig. 3 e). Selected Area Electron Diffraction (SAED) results showed distinct (110) and (012) diffraction rings, further demonstrating the NiFe hydroxide grown on the surface. Furthermore, the present invention speculates that the Mn ions do not disrupt the crystal structure of the NiFe hydroxide during substitutional doping (FIG. 3 f).
Fig. 4 is an energy dispersive X-ray spectroscopy (EDX) elemental profile of NiFeMn, reflecting primarily the spatial distribution of the different elements in the NiFeMn material. FIG. 4 a-b is a HAADF image of NiFeMn heterojunction catalyst, and FIG. 4 c-f is a map of the elements Ni, fe, mn, O, respectively. The results show that Ni and Fe elements are uniformly distributed in the whole petal sphere, and Mn elements are distributed in the petal sphere in a way of becoming thinner from the center to the outermost layer. It is inferred that the Mn element in the layered hydroxide is elution-doped in the Mn TPA substrate having the center, so that the Mn content of the outer layer is small. In combination with SEM and TEM results, the present invention considers that NiFe hydroxide grows uniformly on Mn TPA, and Mn ions slowly dissolve out during solvothermal reaction, thereby forming NiFeMn in place of NiFe hydroxide doped to the surface layer.
The phase composition of the material was characterized by XRD technique, and as a result, as shown in fig. 5, the diffraction peaks were located at 2θ=9.56 o,14.27o,18.20o, corresponding to the (200), (110), and (111) crystal planes of MnTPA, respectively. Characteristic peaks of MnTPA and NiFe hydroxide exist simultaneously on the XRD spectrum of NiFeMn synthesized on Mn TPA substrate. The diffraction peaks in which 2θ=11.39 o,23.06o,34.55o,38.81o,45.83o,60.08o correspond to the (003), (006), (012), (015), (018), (110), (019) crystal planes of NiFe hydroxide, respectively. But also has better crystallinity. This is sufficient to demonstrate that NiFe hydroxide and MnTPA are present simultaneously in the NiFeMn system. The characteristic peaks of NiFeMn are not significantly shifted and the crystallization properties are not changed compared to NiFe hydroxides and MnTPA, indicating that in situ doping of Mn does not have a significant effect on the structure of the material.
The structure of NiFeMn was further confirmed by fourier infrared spectroscopy (FTIR). FIG. 6 shows the infrared curves for Mn TPA, niFe and NiFeMn. In the infrared spectrum of NiFeMn, absorption peaks near 1574cm -1 and 1385cm -1 are assigned to asymmetric and symmetric tensile vibration peaks of the carboxylic acid group in MnTPA; the absorption peaks near 819cm -1 and 747cm -1 are related to the out-of-plane ring C-H bending vibrations of the TPA ligand. In addition, niFeMn also has a one-to-one correspondence with the characteristic peaks of NiFe hydroxide. Therefore, the infrared results further demonstrate the presence of MnTPA substrate and NiFe hydroxide in NiFeMn.
In order to investigate the elemental composition and valence structure of NiFeMn, XPS test was performed on the material, and the results are shown in FIG. 7. From XPS full spectrum, niFeMn and NiFe hydroxide materials contain Ni, fe, O, C and other elements (FIG. 7 a). In combination with EDX test results, the invention deduces that the Mn 2p is covered by Ni LMM probably because the Mn element content in NiFeMn system is relatively low, so that no obvious characteristic peak of Mn 2p exists in XPS full spectrum. In the XPS spectrum of high resolution Ni 2p (as in fig. 7 b), where the positions of the peaks at 855.28 and 860.78 eV correspond to Ni 2p 3/2 and Ni 2p 1/2, respectively, which are characteristic peaks of divalent Ni; ni 2p 3/2 of NiFeMn is offset 0.25eV to the high energy direction relative to Ni 2p 3/2 of NiFe hydroxide, indicating that Mn incorporation promotes conversion of Ni 2+ species to higher valence Ni, yielding NiOOH active species that enhance OER reactions. During electrolysis of seawater, competitive adsorption of Cl - and OH - may occur. The theory of the absolute soft acid hard base shows that the higher-valence Ni belongs to harder Lewis acid and is preferentially combined with the hard base OH -, so that the OER selectivity is enhanced. In the XPS spectrum of high resolution Fe2p (as in fig. 7 c), the characteristic peaks of Fe2p 3/2 and Fe2p 1/2 at 711.68 and 724.65eV belong to the trivalent oxidation peak of Fe, and the shift of Fe2p 3/2 to the high energy direction of 0.1eV occurs, i.e. Fe is in a higher valence state. Overall, the shift of these peaks suggests that in situ doping of Mn causes electron transfer of Ni and Fe with it, thus changing the local electron state of the active center, promoting OER activity optimization in the material.
The elemental content of the electrocatalyst was quantitatively analyzed NiFeMn by surface composition analysis of XPS and test results of a plasma spectrometer (ICP-OES). As can be seen from the results of XPS elemental analysis in FIG. 7, niFeMn and NiFe hydroxides have similar NiFe atomic ratios, and Ni/Fe is approximately 3/1. In the result of XPS analysis, since NiFeMn has a small Mn content, the characteristic peak is covered by the peak of Ni LM2, and the Mn content cannot be estimated. Therefore, the ICP-OES test is adopted to further accurately quantify Mn element. From the ICP-OES results, it was found that the Ni and Fe contents were consistent with the XPS results, and the Mn element content was about 1.97%.
2. Characterization of oxygen evolution catalytic performance in alkaline environments
To evaluate the catalytic activity of NiFeMn electrocatalysts (NiFeMn in the present invention, not specifically described, both refer to the electrocatalyst obtained in example 1) in 1M KOH electrolyte, a three electrode system was used to study the OER performance of the catalyst. 100 μl of NiFeMn ink is uniformly dispersed on 1cm -2 Carbon Cloth (CC) with good conductivity (load capacity is 1mg cm -2) to achieve the purpose of improving OER activity. As can be seen from fig. 8, niFeMn exhibits very excellent activity on carbon cloth. To achieve current densities of 100, 500 and 1000mAcm -2, niFeMn-CC only requires overpotentials of 213, 283 and 343 mV. Compared with NiFeMn-KB, niFeMn-CC can reach a current density of 1A cm -2 at a lower potential, so that an efficient OER reaction is realized (shown as a, b in FIG. 8); the Tafel slope (33.43 mV dec -1) is also significantly smaller than the Tafe slope of NiFe (59.30 mV dec -1) and MnTPA (306.85 mV dec -1) (see FIG. 8 c).
To further demonstrate that the NiFeMn hydroxide-Mn TPA heterostructure of NiFeMn electrocatalysts was able to enhance the OER activity of the material, niFeMn hydroxide (designated NiFeMn-MnO 2 and NiFeMn-Mn 3O4, respectively) was synthesized with MnO 2 and Mn 3O4 as substrates and tested for OER activity in 1M KOH electrolyte. As shown in FIG. 9, the overpotential of NiFeMn is much lower than NiFeMn-MnO 2 and NiFeMn-Mn 3O4, indicating that Mn TPA-based NiFeMn heterojunction plays an important role in the electrocatalytic process.
To evaluate the stability of NiFeMn-CC electrocatalysts, two current steps were used for chronopotentiometric measurements. Stability results as shown in fig. 10, niFeMn electrocatalysts can operate stably at 20 and 50mA cm -2 current densities. After 22h of operation at 20mA cm -2, only 20mV was attenuated. After this stage, the stabilization was carried out again at 50mA cm -2 for 22h, during which the potential was hardly decayed. Since CC has no OER activity, niFeMn-CC activities all contribute to NiFeMn. As can be seen, niFeMn catalysts have stable OER performance at 1M KOH.
3. Characterization of oxygen evolution catalytic performance in alkaline seawater environment
To investigate the OER performance of NiFeMn in alkaline seawater, the invention tested the OER activity of NiFeMn-CC in alkaline seawater using a three electrode system in an electrolyte. CC is known to be hardly active in alkaline seawater. It is therefore evident from FIG. 11a that NiFeMn-CC clearly exhibits better OER performance in the electrolyte than NiFe-CC and MnTPA-CC, allowing higher current densities to be achieved at lower potentials. The Tafel slope of NiFeMn-CC is only 24.66mV dec -1, and the dynamics is superior to that of NiFe-CC (35.88 mV dec -1) without doped Mn element. (as in FIG. 11 b) and MnTPA-CC have little activity, which suggests that Mn is not the active site of OER, but rather serves to regulate the electronic structure and optimize OER activity in NiFeMn. In alkaline seawater, niFeMn-CC only requires 403mV over-potential to achieve a current density of 500mA cm -2, while NiFe-CC requires 523mV. (FIG. 11 c) even in seawater containing a large amount of salt, niFeMn does not significantly attenuate OER activity, but is still superior to NiFe, presumably Mn doping is beneficial to some extent for OER selectivity in seawater. In summary, in situ doping of Mn promotes efficient OER of NiFeMn electrocatalysts in alkaline seawater (FIG. 11 d).
NiFeMn also has good stability in alkaline seawater. The invention tests the potential change for 88h at current densities of 50 and 100mA cm -2. At 50mA cm -2, the potential decayed from 1.647V to 1.663V, decaying 16mV. While at 100mA cm -2, the potential was changed from 1.818V to 1.790V with little decay. The side effect reflects less Cl 2 generated by CIER competing reactions, and less poisoning of the catalyst (see figure 12). The potential decay causes and the decay in alkaline medium always cause unstable dissolution of Ni and Fe atoms, resulting in reduction of active sites. The catalyst stability is almost unchanged after dissolution of the labile atoms.
To further verify that NiFeMn was able to suppress CIER reaction and enhance OER selectivity, the present invention calculated faraday efficiency based on the gas product produced by the catalyst at a current density of 50mA cm -2 collected by a drainage method. Cl 2 is a gas that is known to be yellowish green and readily soluble in water. The gas production and faraday efficiency over the cumulative time are shown in figure 13. The calculation results show that the FE% of NiFeMn in alkaline seawater is as high as 91.89%. This fully demonstrates that NiFeMn has good OER catalytic activity and can effectively inhibit CIER reaction in alkaline seawater solution.
In conclusion, niFeMn synthesized by the strategy of in-situ interface atom replacement can obviously optimize the electrolytic seawater OER performance of the NiFe catalyst. NiFeMn catalysts exhibit higher OER activity and stability compared to NiFe catalysts. Electron structural analysis shows that the Mn interface doped NiFe catalyst can enhance electron transfer of Ni and Fe to Mn species, so that high-valence Ni and Fe atoms exist in the catalyst. Tests of electrocatalyst have further demonstrated that NiFeMn catalyst only requires 213 and 251mV overpotential to reach a current density of 100mA cm -2 after doping in alkaline fresh water and seawater. And NiFeMn is able to resist Cl - attack in alkaline seawater media, exhibiting high OER selectivity (FE% = 91.56%) and long term stability (> 80 h).
Claims (8)
1. The preparation method of the OER electrocatalyst is characterized by comprising the following steps: preparing NiFeMn hydroxide by using ferric salt, nickel salt and Mn-terephthalic acid coordination polymer as raw materials through an interface atom replacement method, namely the OER electrocatalyst;
Wherein the Mn-terephthalic acid coordination polymer is prepared by the following method: dissolving manganese salt and terephthalic acid in a solvent to obtain a mixed solution, and then reacting the obtained mixed solution in corrosion-resistant reaction equipment at 100-150 ℃ for 20-30 h; naturally cooling to the ambient temperature after the reaction is finished; collecting the precipitate, and washing with alcohol and deionized water for at least 3 times; finally, vacuum drying to obtain the Mn-terephthalic acid coordination polymer;
And, the interface atom substitution method is as follows: mixing Mn-terephthalic acid coordination polymer and alcohol substances, and performing ultrasonic treatment to form a uniformly dispersed suspension A; dissolving ferric salt and nickel salt in ultrapure water, and then adding urea for dissolving to obtain a solution B; mixing the suspension A and the solution B at normal temperature, sealing, and reacting for 5-25 hours at 20-30 ℃; after the reaction is finished, washing with water and alcohol substances for 3-5 times respectively, and drying to obtain NiFeMn hydroxide.
2. The preparation method of the OER electrocatalyst according to claim 1, wherein the mass ratio of each raw material is: iron salt: nickel salt: mn-terephthalic acid coordination polymer=5 to 20: 5-20: 1-5.
3. The process for preparing an OER electrocatalyst according to claim 1 or 2, wherein the iron salt is selected from: feSO 4·7H2 O or FeCl 2·4H2 O;
the nickel salt is selected from: ni (NO 3）2·6H2O、NiSO4·6H2 O or NiCl 2·6H2 O).
4. The method for preparing an OER electrocatalyst according to claim 1, wherein the manganese salt is selected from the group consisting of: mnCl 2·4H2O、MnSO4·xH2 O or Mn (NO 3)2·xH2 O;
The solvent is selected from: deionized water, laboratory grade II pure water or ultrapure water;
the alcohol substance is ethanol.
5. The preparation method of the OER electrocatalyst according to claim 1, wherein the mass ratio of the iron salt, the nickel salt and the urea is: 5-20: 5-20: 10-40.
6. An OER electrocatalyst, characterised in that it is obtainable by a process according to any one of claims 1 to 5.
7. An OER electrocatalyst according to claim 6 wherein the electrocatalyst requires an overpotential of 213mV and 251 mV in the electrolyte of 1M KOH and alkaline seawater to reach a current density of 100 mA cm -2.
8. Use of the OER electrocatalyst produced by the production process of any one of claims 1 to 5 for the electrolysis of water or seawater.
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