CN115928102B - Iron-doped nickel-cobalt phosphide and molybdenum trioxide composite electrolytic water bifunctional catalyst and preparation method thereof - Google Patents
Iron-doped nickel-cobalt phosphide and molybdenum trioxide composite electrolytic water bifunctional catalyst and preparation method thereof Download PDFInfo
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- 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 discloses an iron-doped nickel-cobalt phosphide and molybdenum trioxide composite electrolytic water dual-function catalyst and a preparation method thereof. The method adopts a one-step hydrothermal method to synthesize Mo firstly 7 O 24 6‑ Layered double hydroxide Fe-NiCo-LDHs-Mo with ion intercalation structure 7 O 24 6‑ And synthesizing the iron-doped nickel cobalt phosphide and molybdenum trioxide composite material by adopting a low-temperature phosphating method. The preparation process is simple, the cost is low, and the Fe-NiCoP and MoO are used 3 The special interface formed by the compounding and the coupling effect of multiple metals lead to Fe-NiCoP-MoO 3 Exhibits excellent catalytic performance.
Description
Technical Field
The invention belongs to the field of electrolytic water catalysts, and relates to an iron-doped nickel-cobalt phosphide and molybdenum trioxide composite electrolytic water dual-function catalyst and a preparation method thereof.
Background
Electrocatalytic water splitting involves two half-cell reactions: oxygen Evolution Reactions (OER) occurring at the anode and Hydrogen Evolution Reactions (HER) occurring at the cathode. However, OER and HER cannot occur at standard electrode potentials (HER is 0V vs RHE, OER is 1.23V vs RHE), requiring an additional potential, called overpotential, compared to the theoretical potential, which makesIt is a great energy waste in the actual production process, so that it is highly demanded to find an excellent catalyst to improve this phenomenon. Currently, most of the excellent catalytic performance of electrolyzed water are noble metal catalysts (Pt/C and RuO 2 ) However, it is expensive and has a low reserve, which is difficult to use on a large scale. Therefore, high-efficiency non-noble metal catalysts have been a popular choice for research in recent years. Transition Metal Phosphides (TMPs) have attracted considerable attention due to their excellent electrical conductivity. Nickel cobalt phosphide (NiCoP) as a typical transition metal phosphide has great potential in electrocatalysis due to its good metallic properties.
Document 1 reports that Fe doped NiCoP synthesized by electroplating and gas-solid reaction method has more plane defects caused by Fe doping, and simultaneously adjusts the adsorption of HER/OER intermediate by the catalyst, so that Fe-NiCoP has good catalytic activity, and HER can reach 10mA/cm only by 60mV overpotential 2 At the same time, the OER overvoltage of 293mV can reach 50mA/cm 2 The catalyst can reach 10mA/cm only by an overpotential of 1.61mV when being used as the cathode and anode of an electrolytic cell for full hydrolysis 2 Is used for the current density of the battery. However, the electroplating process makes it difficult to control the surface morphology of the material, so that the repeatability of the properties of the synthesized end product is poor (M.Guo, S.Song, S.Zhang, et al, fe-cooled Ni-Co Phosphide Nanoplates with Planar Defects as an Efficient Bifunctional Electrocatalyst for Overall Water Splitting, ACS Sustainable Chemistry)&Engineering,2020,8(19):7436-7444)。
Despite extensive research, the modification techniques of NiCoP reported so far are relatively complex and the electrocatalytic activity is far from satisfactory.
Disclosure of Invention
The invention aims to provide an electrolytic water dual-function catalyst compounded by iron-doped nickel cobalt phosphide and molybdenum trioxide and a preparation method thereof. The method adopts a one-step hydrothermal method and a low-temperature phosphating method, which not only avoids a complex modification process, but also ensures that the prepared iron-doped nickel-cobalt phosphide and molybdenum trioxide composite material has excellent catalytic activity and stability.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the iron-doped nickel cobalt phosphide and molybdenum trioxide composite electrolytic water bifunctional catalyst comprises the following specific steps:
step 1, fe-NiCo-LDHs-Mo 7 O 24 6- Preparing a precursor: ni (NO) 3 ) 2 ·6H 2 O，Co(NO 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 O、(NH 4 ) 6 Mo 7 O 24 ·4H 2 Dissolving O, urea and trisodium citrate dihydrate in deionized water, stirring to be uniformly mixed, placing the mixture in 120+/-10 ℃ for hydrothermal reaction for more than 12 hours, and after the reaction is finished, carrying out suction filtration, washing and vacuum drying to obtain Mo 7 O 24 6- Layered double hydroxide Fe-NiCo-LDHs-Mo with ion intercalation structure 7 O 24 6- A precursor;
step 2, for Fe-NiCo-LDHs-Mo 7 O 24 6- And (3) phosphating: fe-NiCo-LDHs-Mo 7 O 24 6- The precursor is put into a ceramic boat, and NaH is placed at the upstream 2 PO 2 Placing the mixture into a tube furnace, heating to 350-400 ℃ under the protection of nitrogen atmosphere for phosphating, and obtaining the iron-doped nickel-cobalt phosphide and molybdenum trioxide composite catalyst (Fe-NiCoP-MoO after the phosphating is finished 3 )。
Preferably, in step 1, ni (NO 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 The molar ratio of O, urea and trisodium citrate dihydrate is 3:3:18:1.
Preferably, in step 1, fe (NO 3 ) 3 ·9H 2 O and Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 1:18 to 3, more preferably 1:9.
Preferably, in step 1, (NH 4 ) 6 Mo 7 O 24 ·4H 2 O and Ni (NO) 3 ) 2 ·6H 2 Molar ratio of OFrom 0.33 to 3.33:1, more preferably 1:1.
Preferably, in step 1, the stirring time is 30min or more.
Preferably, in step 1, water and absolute ethanol are used for washing for more than 3 times respectively.
Preferably, in step 1, the vacuum drying temperature is 60±5 ℃, and the drying time is 12 hours or more.
Preferably, in step 2, N is introduced into the quartz tube before the temperature is raised 2 Purging for 1h, exhausting air in the quartz tube, and then maintaining N 2 The flow rate is unchanged.
Preferably, in step 2, the rate of temperature increase is 2 to 5 ℃/min.
Preferably, in step 2, the incubation time is 4 to 6 hours.
Furthermore, the invention also provides application of the iron-doped nickel cobalt phosphide and molybdenum trioxide composite bifunctional electrocatalyst in water electrolysis.
Compared with the prior art, the invention has the following advantages:
(1) Compared with NiCoP catalyst prepared by similar method (HEReta 10 ＝199mV，OERη 50 ＝343mV)，Fe-NiCoP-MoO 3 HER performance (. Eta.) 10 =65 mV) and OER performance (η 50 =343 mV).
(2)Fe-NiCoP-MoO 3 Full hydrolysis system Fe-NiCoP-MoO respectively formed by cathode and anode for electrocatalytic water decomposition 3 //Fe-NiCoP-MoO 3 An overpotential of only 1.586mV is required to reach 10mA/cm 2 While NiCoP// NiCoP requires 1.689mV to achieve the same current density.
(3) Compared with the prior electroplating of the NiCoP doped with Fe, the invention realizes doping by a one-step simple hydrothermal method, greatly reduces unnecessary energy loss in the electroplating process, and has the advantages of 50mA/cm 2 The oxygen evolution overpotential was reduced by 40mV.
Drawings
FIG. 1 is a diagram of Fe-NiCoP-MoO 3 X-ray diffraction pattern of the composite material.
FIG. 2 is a diagram of Fe-NiCo-LDHs-Mo 7 O 24 6- And FT-IR patterns of Fe-NiCo-LDHs.
FIG. 3 is a diagram of Fe-NiCoP-MoO 3 X-ray photoelectron spectroscopy of the composite material.
FIG. 4 is a diagram of Fe-NiCoP-MoO 3 Scanning electron microscopy and transmission electron microscopy of the composite material.
FIG. 5 is a diagram of Fe-NiCoP-MoO 3 HER performance spectrum of composite material and series of catalysts and Fe-NiCoP-MoO 3 The composite material is 10mA/cm 2 Stability graph at current density for 24 h.
FIG. 6 is a diagram of Fe-NiCoP-MoO 3 OER performance spectrum and Fe-NiCoP-MoO of composite material and series of catalysts 3 The composite material is at 50mA/cm 2 Stability graph at current density for 24 h.
FIG. 7 is a diagram of Fe-NiCoP-MoO 3 Composite material and double hydrolysis performance spectrum of a series of catalysts and Fe-Fe-NiCoP-MoO 3 //Fe-NiCoP-MoO 3 The double hydrolysis system is 10mA/cm 2 Stability graph at current density for 24 h.
Fig. 8 is a series of HER performance and OER performance profiles for catalysts synthesized by varying the feed amount of Fe.
Figure 9 is a graph of HER performance and OER performance of a series of catalysts synthesized by varying the phosphating temperature.
Detailed Description
The invention will be described in further detail with reference to specific embodiments and drawings.
Example 1
1.Fe-NiCo-LDHs-Mo 7 O 24 6- Synthesis of precursors
3mmol of Ni (NO) 3 ) 2 ·6H 2 O, 3mmol Co (NO) 3 ) 2 ·6H 2 O, 0.33mmol Fe (NO) 3 ) 3 ·9H 2 O, 3mmol (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 18mmol of urea and 1mmol of trisodium citrate dihydrate are dissolved in 60mL of deionized water, a transparent solution is obtained after stirring for 30min, and then the obtained transparent solution is transferred into a 100mL high-pressure hydrothermal kettle, and the solution is prepared in a state of being 12Reacting at 0deg.C for 12 hr, naturally cooling to room temperature, vacuum filtering, washing with deionized water anhydrous ethanol for three times, and drying in vacuum oven at 60deg.C overnight to obtain reddish brown powder called Fe-NiCo-LDHs-Mo 7 O 24 6- A precursor.
2.Fe-NiCoP-MoO 3 Is synthesized by (a)
50mg of Fe-NiCo-LDHs-Mo 7 O 24 6- The precursor was carefully placed in a ceramic boat with 250mg NaH placed upstream 2 PO 2 First using N 2 Purge for 1h, then at N 2 Annealing for 4 hours at 350 ℃ under the atmosphere, wherein the heating rate is 5 ℃/min. And after the phosphating process is finished, naturally cooling the hearth to room temperature. N (N) 2 The flow rate (15 sccm) was kept constant throughout the process to give a black powder, designated Fe-NiCoP-MoO 3 。
3. Preparation of working electrode
Cutting commercially available foam nickel into 1X 2cm pieces 2 Size, and then sonicated in 3mol/L HCl, acetone, absolute ethanol, and deionized water, respectively, for 15min. The nickel foam was dried overnight in a vacuum oven at 60 ℃. Weighing 4mg of Fe-NiCoP-MoO 3 0.5mg of acetylene black and 0.5mg of PVDF are ground for 10min to uniformly mix the powder, then 20 mu L of N, N-dimethyl pyrrolidone is dripped, and then the mixture is quickly ground to form uniform slurry, the obtained slurry is uniformly smeared on the surface of the nickel foam which is activated before, and a layer of extremely thin 1X 1cm is formed on the surface of the nickel foam 2 After which the coated nickel foam was dried overnight in a vacuum oven at 60℃with a catalyst loading of about 2mg/cm 2 。
Comparative example 1
Fe-NiCoP-MoO in reference example 1 3 In the synthesis step of (2), ni (NO) is not added in the reaction charging stage 3 ) 2 ·6H 2 O, without Co (NO) 3 ) 2 ·6H 2 O, not adding Fe (NO) 3 ) 3 ·9H 2 O, not added (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O and at the same time NO Fe (NO) 3 ) 3 ·9H 2 O and (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O synthesis series of catalysts, respectively named CoFeP-MoO 3 ，NiFeP-MoO 3 ，NiCoP-MoO 3 Fe-NiCoP and NiCoP.
Comparative example 2
Fe-NiCoP-MoO in reference example 1 3 The synthesis step of (2) keeps the feeding amount of other metal elements unchanged in the reaction feeding stage, and changes the Fe (NO) 3 ) 3 ·9H 2 The dosage of O is controlled to control Fe (NO 3 ) 3 ·9H 2 O and Ni (NO) 3 ) 2 ·6H 2 The mol ratio of O is 1:18-3, and a series of catalysts are synthesized.
Comparative example 3
Fe-NiCoP-MoO in reference example 1 3 During the phosphating reaction, a series of catalysts, respectively named Fe-NiCoP-MoO, are synthesized by changing the annealing temperature 3 -300、Fe-NiCoP-MoO 3 -350、Fe-NiCoP-MoO 3 -400 and Fe-NiCoP-MoO 3 -450。
Application example 1
Electrochemical testing was performed in a typical three-electrode system that was used in conjunction with the CHI 760E electrochemical workstation. The electrolyte used was 1.0M aqueous KOH (ph=14). The working electrode and the reference electrode are graphite rod and Hg/HgO electrode respectively. The overpotential for HER and OER is calculated as follows, η=e (vs. rhe) -0V and η=e (vs. rhe) -1.23V. Prior to each test, cyclic Voltammetry (CV) was performed at a scan rate of 100mV/s for 100 cycles to bring the working electrode to steady state. Linear Sweep Voltammetry (LSV) curves for HER and OER were performed at low scan rates (2 mV/s). All LSV curves were compensated with 95% IR unless otherwise indicated. R is R s The ohmic resistance of the solution is represented and obtained by Electrochemical Impedance Spectroscopy (EIS) techniques. According to the Nernst formula (E RHE ＝E Hg/HgO +E 0 Hg/HgO +0.059 pH) to reversible hydrogen electrode, wherein E 0 Hg/HgO Is the standard potential of Hg/HgO at 25 ℃. HER and OER were tested with overpotential (vs. RHE) of-0.0746V and 1.5254V, respectively, in the range of 0.01 to 100000HzElectrochemical Impedance Spectroscopy (EIS) of the sample. Electrochemically active surface area (ECSA) is measured by measuring electrochemical double layer capacitance (C dl ) The scan rates were 20, 40, 60, 80 and 100mV/s. In a 1.0M KOH electrolyte double electrode system, the catalyst produced as HER and OER catalyst, with 2mV/s scan rate record polarization curve. Respectively at 10mA/cm by time potential method (CP) 2 And 50mA/cm 2 The stability of HER and OER of the resulting catalyst was determined at the current density.
FIG. 1 is a diagram of Fe-NiCoP-MoO 3 X-ray diffraction pattern of the composite material. The presence of NiCoP in the samples was confirmed from peaks at 41.0 °, 44.7 °, 47.6 ° and 54.8 °. No diffraction peaks for the iron-containing phase were observed from the figure, indicating that iron doping did not form any new crystalline phase. Furthermore, as shown in the close-up view on the right side of fig. 1, doping Fe shifts the peak that would otherwise occur at 44.7 ° to 44.3 °, possibly because Fe can be doped as a substitutional atom in the NiCoP lattice. Demonstration of Fe-NiCoP-MoO 3 Is successful.
FIG. 2 is a diagram of Fe-NiCo-LDHs-Mo 7 O 24 6- And FT-IR patterns of Fe-NiCo-LDHs, illustrating the incorporation of Mo 7 O 24 6- 1360cm in FT-IR chart -1 CO at site 3 2- The stretching vibration peak of the ion disappears at 800cm -1 Obvious Mo appears at left and right parts 7 O 24 6- And MoO 4 2- A peak. Description of Mo in combination with XRD and FT-IR changes 7 O 24 6- Substituted for CO 3 2- The intercalation is between Fe-NiCo-LDHs layers.
FIG. 3 is a diagram of Fe-NiCoP-MoO 3 X-ray photoelectron spectroscopy of the composite material. From XPS full spectrum, fe-NiCoP-MoO 3 Mainly consists of Ni, co, mo, fe and P elements. The XPS spectrum of Ni 2p can be deconvoluted to 5 peaks, and the binding energy of two main peaks around 874.7eV and 856.8eV can be attributed to Ni 2p1/2 and Ni 2p 3/2. It can be seen from the P1P XPS plot that a peak around 852.9eV may be associated with Ni-P bonds. The high resolution XPS spectrum of Co shows peak pairs at 782.0eV and 798.2eV, respectivelyPeaks corresponding to Co 2P3/2 and Co 2P1/2, around 778eV, may be associated with Co-P bonds. In the Fe 2p spectrum, it represents Fe 2+ Peaks at 712.7eV and 722.7eV, representing Fe 3+ The peaks of (2) lie in 717eV and 727eV. Fe (Fe) 2+ The presence of peaks is the pH generated during phosphating 3 Fe is added to 3+ Reduction to Fe 2+ As a result of (a). Meanwhile, according to the P2P XPS diagram of fig. 3f, a peak around 707eV can be assigned to fe—p. The XPS profile of Mo 3d can be deconvoluted into four peaks. Peaks at 235.03eV and 233.34eV respectively belong to Mo 6+ Mo 3d5/2 and Mo 3d3/2 of (C) are derived from MoO 3 . Two peaks, additionally located at 230.36eV and 232.23eV, correspond to Mo, respectively 4+ Mo 3d5/2 and Mo 3d3/2, which are the pH during the phosphating process 3 And (3) a result of reduction. The peak in the P2P spectrum of 129.4eV is mainly due to metal-phosphorus.
FIG. 4 is a diagram of Fe-NiCoP-MoO 3 Scanning electron microscopy of the composite material. A large number of vertically grown nano-plates can be observed, which are intertwined to form a network. Fe-NiCoP-MoO 3 The EDS of Ni, co, fe, mo and P elements confirm a uniform distribution. To better observe Fe-NiCoP and MoO 3 For Fe-NiCoP-MoO 3 HRTEM and SEAD characterization was performed. Only the (111) and (300) crystal planes of NiCoP can be clearly observed from the SEAD test results, from which MoO can be inferred 3 Is amorphous. Furthermore, as seen from the previous report, the doping of Fe reduces the crystallinity of NiCoP, rendering NiCoP amorphous. From the analysis of the results of HRTEM, the amorphous state is divided into two parts: white and gray. White amorphous MoO 3 While gray is amorphous Fe-NiCoP. To sum up, fe-NiCoP-MoO 3 From amorphous MoO 3 Amorphous Fe-NiCoP and NiCoP.
FIG. 5 is a diagram of Fe-NiCoP-MoO 3 HER performance spectrum of composite material and series of catalysts and Fe-NiCoP-MoO 3 The composite material is 10mA/cm 2 Stability at current density for 24 h. Fe-NiCoP-MoO 3 Good performance in HER (HER) reaching 10mA/cm 2 Only 65mV of overvoltage is needed, and Fe-NiCoP, niCoP and NiCoP-MoO 3 Requiring a higher level of oversteppingThe potential can reach the same current density. It can be seen that doping of Fe and MoO 3 Can improve the activity of the catalyst. Fe is doped in the NiCo-LDHs skeleton, more surface defects are formed after phosphating, and more active sites are exposed. MoO (MoO) 3 The NiCo-LDHs form special TMPs and MoO in the high-temperature collapse process 3 And a heterogeneous interface accelerates electron transport.
FIG. 6 is a diagram of Fe-NiCoP-MoO 3 OER performance spectrum and Fe-NiCoP-MoO of composite material and series of catalysts 3 The composite material is at 50mA/cm 2 Stability at current density for 24 h. FeNiCoP-MoO compared with other electrodes 3 Has the best OER performance, and the working current density is 50mA/cm 2 Only 253mV overpotential is needed, and the working current density is 200mA/cm 2 Only 288mV is needed, which is superior to the commercial RuO 2 。
FIG. 7 is a diagram of Fe-NiCoP-MoO 3 Composite material and double hydrolysis performance spectrum of a series of catalysts and Fe-Fe-NiCoP-MoO 3 //Fe-NiCoP-MoO 3 The double hydrolysis system is 10mA/cm 2 Stability at current density for 24 h. Fe-NiCoP-MoO 3 //Fe-NiCoP-MoO 3 A low overpotential of only 1.586V (iR correction) is required to drive 10mA/cm 2 Exhibits satisfactory catalytic activity for the overall water decomposition. In addition to Fe-NiCoP-MoO 3 //Fe-NiCoP-MoO 3 Is studied. For a fixed current density of 100mA/cm 2 The potential curve still maintains very excellent performance after 120 hours of continuous overall water splitting. The above results indicate that Fe-NiCoP-MoO 3 Is a double-function electric catalyst with extremely high stability and catalytic activity, and can be used as a high-efficiency catalyst for industrial electrolytic water.
Fig. 8 is a series of HER performance and OER performance profiles of catalysts synthesized by varying the Fe dosing, notably the electrocatalytic HER and OER performance exhibited a trend of increasing followed by decreasing with varying Fe salt dosing. Fe-NiCoP-MoO 3 In the method, the activity is optimal when the feeding mole ratio of the ferric salt to the nickel salt is 1:9.
Figure 9 is a graph of HER performance and OER performance of a series of catalysts synthesized by varying the phosphating temperature. With increasing annealing temperature during phosphating, the catalytic performance of the catalyst tends to increase and decrease, with the best catalyst performance obtained at 350 ℃.
Claims (10)
1. The preparation method of the iron-doped nickel cobalt phosphide and molybdenum trioxide composite electrolytic water bifunctional catalyst is characterized by comprising the following specific steps:
step 1, fe-NiCo-LDHs-Mo 7 O 24 6- Preparing a precursor: ni (NO) 3 ) 2 ·6H 2 O，Co(NO 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 ·9H 2 O、(NH 4 ) 6 Mo 7 O 24 ·4H 2 Dissolving O, urea and trisodium citrate dihydrate in deionized water, stirring to be uniformly mixed, placing the mixture in 120+/-10 ℃ for hydrothermal reaction for more than 12 hours, and after the reaction is finished, carrying out suction filtration, washing and vacuum drying to obtain Mo 7 O 24 6- Layered double hydroxide Fe-NiCo-LDHs-Mo with ion intercalation structure 7 O 24 6- A precursor;
step 2, for Fe-NiCo-LDHs-Mo 7 O 24 6- And (3) phosphating: fe-NiCo-LDHs-Mo 7 O 24 6- The precursor is put into a ceramic boat, and NaH is placed at the upstream 2 PO 2 And (3) placing the catalyst in a tube furnace, heating to 350-400 ℃ under the protection of nitrogen atmosphere, and performing phosphating to obtain the iron-doped nickel-cobalt phosphide and molybdenum trioxide composite catalyst after the phosphating is finished.
2. The method according to claim 1, wherein in step 1, ni (NO 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 The molar ratio of O, urea and trisodium citrate dihydrate is 3:3:18:1.
3. The method according to claim 1, wherein in step 1, fe (NO 3 ) 3 ·9H 2 O and Ni (NO) 3 ) 2 ·6H 2 The mol ratio of O is 1:18-3.
4. The method according to claim 1, wherein in step 1, fe (NO 3 ) 3 ·9H 2 O and Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O was 1:9.
5. The method according to claim 1, wherein in step 1, (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O and Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 0.33-3.33:1.
6. The method according to claim 1, wherein in step 1, (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O and Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 1:1.
7. The preparation method according to claim 1, wherein in step 1, the stirring time is more than 30min, water and absolute ethyl alcohol are respectively used for washing for more than 3 times in turn, the vacuum drying temperature is 60+/-5 ℃, and the drying time is more than 12 h.
8. The method according to claim 1, wherein N is introduced into the quartz tube before the temperature is raised in step 2 2 Purging for 1h, exhausting air in the quartz tube, and then maintaining N 2 The flow rate is unchanged; the temperature rising rate is 2-5 ℃/min; the heat preservation time is 4-6 h.
9. The iron-doped nickel cobalt phosphide and molybdenum trioxide composite bifunctional electrocatalyst produced by the production process according to any one of claims 1 to 8.
10. The use of the iron-doped nickel cobalt phosphide and molybdenum trioxide composite bifunctional electrocatalyst according to claim 9 in the electrolysis of water.
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| CN108654658A (en) * | 2018-05-28 | 2018-10-16 | 北京工业大学 | A kind of efficient water decomposition bifunctional electrocatalyst NiCoP and preparation method thereof |
| CN109174162A (en) * | 2018-10-26 | 2019-01-11 | 江苏大学 | A kind of Fe2O3 doping double-metal phosphide elctro-catalyst and its preparation method and application |
| CN113136603A (en) * | 2021-04-26 | 2021-07-20 | 云南大学 | Foam nickel-based erbium-doped nickel-cobalt bimetallic phosphide nano-array and preparation method and application thereof |
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| CN108654658A (en) * | 2018-05-28 | 2018-10-16 | 北京工业大学 | A kind of efficient water decomposition bifunctional electrocatalyst NiCoP and preparation method thereof |
| CN109174162A (en) * | 2018-10-26 | 2019-01-11 | 江苏大学 | A kind of Fe2O3 doping double-metal phosphide elctro-catalyst and its preparation method and application |
| CN113136603A (en) * | 2021-04-26 | 2021-07-20 | 云南大学 | Foam nickel-based erbium-doped nickel-cobalt bimetallic phosphide nano-array and preparation method and application thereof |
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| Stacked Porous Iron-Doped Nickel Cobalt Phosphide Nanoparticle:An Efficient and Stable Water Splitting Electrocatalyst;Chaiti Ray;ACS Sustainable Chem. Eng.;实验部分 * |
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