CN112007672B - A kind of CrP-Re2P hydrogen evolution and oxygen evolution electrocatalyst preparation method - Google Patents
A kind of CrP-Re2P hydrogen evolution and oxygen evolution electrocatalyst preparation method Download PDFInfo
- Publication number
- CN112007672B CN112007672B CN202010951396.3A CN202010951396A CN112007672B CN 112007672 B CN112007672 B CN 112007672B CN 202010951396 A CN202010951396 A CN 202010951396A CN 112007672 B CN112007672 B CN 112007672B
- Authority
- CN
- China
- Prior art keywords
- chromium
- crp
- composite material
- rhenium
- hydrothermal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000001257 hydrogen Substances 0.000 title claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000001301 oxygen Substances 0.000 title claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 19
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 15
- 239000011651 chromium Substances 0.000 claims abstract description 15
- SBOFHSLSQVFORB-UHFFFAOYSA-N [Cr].[Re] Chemical compound [Cr].[Re] SBOFHSLSQVFORB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 7
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004448 titration Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 15
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 229920000557 Nafion® Polymers 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 13
- 238000005406 washing Methods 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000005303 weighing Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 4
- 102000020897 Formins Human genes 0.000 description 3
- 108091022623 Formins Proteins 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 101100317222 Borrelia hermsii vsp3 gene Proteins 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/28—Phosphorising
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Catalysts (AREA)
Abstract
本发明涉及电催化水分解技术领域，具体为一种CrP‑Re2P析氢析氧电催化剂制备方法，通过水热和简单滴定以及低温磷化处理的方法得到的CrP‑Re2P复合材料，所述水热是将铬长在泡沫镍上，获得铬基前驱体；将所述铬基前驱体进行滴铼物种，获得铬铼复合材料前驱体，在氮气的气氛下进行低温磷化处理。本发明制备方法简单，通过在泡沫镍上进行水热和简单滴定以及低温磷化处理得到CrP‑Re2P复合材料，在碱性的条件下具有优异的电催化析氢和析氧性能，且使用寿命长。
The invention relates to the technical field of electrocatalytic water splitting, in particular to a method for preparing a CrP-Re 2 P hydrogen evolution and oxygen evolution electrocatalyst, and a CrP-Re 2 P composite material obtained by hydrothermal and simple titration and low-temperature phosphating treatment, The hydrothermal method is to grow chromium on the nickel foam to obtain a chromium-based precursor; drop rhenium species on the chromium-based precursor to obtain a chromium-rhenium composite material precursor, and perform low-temperature phosphating treatment in a nitrogen atmosphere. The preparation method of the invention is simple, the CrP-Re 2 P composite material is obtained by performing hydrothermal and simple titration and low-temperature phosphating treatment on nickel foam, and has excellent electrocatalytic hydrogen evolution and oxygen evolution performance under alkaline conditions, and uses long life.
Description
Technical Field
The invention belongs to the field of electrocatalytic total moisture decomposition, and particularly relates to CrP-Re2A preparation method of a P hydrogen evolution and oxygen evolution electrocatalyst.
Background
Water electrolysis is considered one of the most promising methods for producing high purity hydrogen from water. Despite the tremendous efforts of scientists, there are still some key bottlenecks that limit the practical applications of electrolytic water splitting. For example, as a half-reaction of water splitting, the kinetics of the oxygen evolution reaction are slow resulting in too high a potential. In recent years, the abundant transition metals on earth have attracted extensive research and attention of scientists, wherein iridium-based and platinum-based electrocatalysts show better electrocatalysts in oxygen evolution and hydrogen evolution reactions respectively, but the defects of scarcity, high cost and the like still limit the large-scale practical application of the electrocatalysts. Therefore, it is essential to develop a high-performance, cost-effective electrocatalyst to replace the conventional noble metal-based catalyst.
Disclosure of Invention
The invention aims to provide a CrP-Re2A preparation method of a P hydrogen evolution and oxygen evolution electrocatalyst solves the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
CrP-Re2The preparation method of the P hydrogen evolution and oxygen evolution electrocatalyst comprises the step of obtaining CrP-Re by hydrothermal, simple titration and low-temperature phosphating treatment methods2P composite material, wherein the hydrothermal method comprises the steps of growing chromium on foamed nickel to obtain a chromium-based precursor; and dropping rhenium species on the chromium-based precursor to obtain a chromium-rhenium composite material precursor, and carrying out low-temperature phosphating on the chromium-rhenium composite material precursor.
Further, the preparation of the chromium-based precursor comprises the step of ultrasonically dissolving chromium nitrate nonahydrate and urea in deionized water to obtain a chromium nitrate solution.
Further, the preparation of the chromium-rhenium composite material precursor comprises the step of dissolving the ammonium perrhenate solution in deionized water, absolute ethyl alcohol and Nafion in an ultrasonic mode to obtain the ammonium perrhenate solution.
Further, the concentration of the chromium nitrate solution is 0.03 mol/L, the temperature of the hydrothermal reaction is 120 ℃, and the reaction time is 12 hours.
Further, the concentration of the ammonium perrhenate solution is 0.36 mol/L.
Further, the temperature of the phosphating treatment is 350 ℃ in the atmosphere of nitrogen, and the time is 2 hours.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method is simple, and CrP-Re is obtained by simple hydrothermal, titration and low-temperature phosphating treatment on porous foamed nickel2The P composite material has excellent electro-catalytic hydrogen evolution and oxygen evolution performances under an alkaline condition, and has long service life.
Drawings
FIG. 1 is CrP-Re prepared in example 22An X-ray powder diffraction pattern of the P composite;
FIG. 2 shows the scanning electron microscope pictures (a), (b) and (c) TEM, (d) particle size distribution, (e) lattice spacing picture, (f) high resolution picture, and (g) element distribution picture, which correspond to example 2;
FIG. 3 is CrP-Re prepared in example 22P composite material and independent CrP and Re2An X-ray photoelectron spectrum of P;
FIG. 4 is CrP-Re prepared in example 22Two-electrode system composed of P composite material and noble metal Pt/C and RuO2Forming a two-electrode hydrolysis linear scanning curve;
FIG. 5 is CrP-Re prepared in example 22Stability of the P composite at high current density in 30% KOH;
FIG. 6 is a linear scanning curve of electrocatalytic hydrogen evolution under alkaline conditions for examples 1, 2 and 3;
FIG. 7 is a linear scan curve of electrocatalytic oxygen evolution under alkaline conditions for examples 1, 2, 3.
Detailed Description
The technical solution in the embodiment of the present invention will be described below with reference to fig. 1 to 7 in the embodiment of the present invention.
Firstly, preparing commercial Pt/C and RuO2As electrode samples, for comparison with examples of the present invention: weighing 2 mg of commercial Pt/C, dissolving the Pt/C in 200 muL of deionized water, 200 muL of absolute ethyl alcohol and 10 muL of Nafion solution, ultrasonically dissolving for 30 minutes, and then dropping Pt/C slurry subjected to uniform ultrasonic treatment in 1 cm2Dried at room temperature for use.
Preparation of RuO in the same manner as described above2Electrode sample, except commercial Pt/C was changed to RuO2And (4) finishing.
Second, example 1: preparation of CrP/NF material
Step (1), treating foamed nickel: cutting foamed nickel into 3 × 3 cm2Size. Then ultrasonic washing is respectively carried out in 0.5 mol/L sulfuric acid solution, deionized water and ethanol for 10 minutes, and the ultrasonic washing is carried out for three times and naturally aired for standby.
Preparing a chromium nitrate solution: weighing 2.5 mmol of chromium nitrate nonahydrate and 25 mmol of urea, dissolving in 80 mL of deionized water, and performing ultrasonic treatment for 10 minutes to obtain a chromium nitrate solution with the concentration of 0.03 mol/L.
Step (3) hydrothermal reaction: the foamed nickel was placed in a 100 mL reaction vessel and kept at 120 ℃ in an oven for 12 hours. After natural cooling, the foamed nickel is rinsed with a large amount of water and then dried at room temperature for use.
And (4) phosphating: putting the foamed nickel with the chromium precursor in the step (3) into the bottom of a quartz tube, weighing 1 g of sodium hypophosphite and putting the weighed foamed nickel into the opening of the quartz tube, and then heating the quartz tube at the temperature of 5 ℃ for min in a nitrogen atmosphere (20 sccm)-1) And calcining for 2 hours at 350 ℃, naturally cooling to room temperature, taking out, washing with a large amount of deionized water, and airing at room temperature to prepare the CrP/NF material.
Third, example 2: preparation of CrP-Re2P composite material
Step (1), treating foamed nickel: cutting foamed nickel into 3 × 3 cm2Size. Then ultrasonic washing is respectively carried out in 0.5 mol/L sulfuric acid solution, deionized water and ethanol for 10 minutes, and the ultrasonic washing is carried out for three times and naturally aired for standby.
Preparing a chromium nitrate solution: weighing 2.5 mmol of chromium nitrate nonahydrate and 25 mmol of urea, dissolving in 80 mL of deionized water, and performing ultrasonic treatment for 10 minutes to obtain a chromium nitrate solution with the concentration of 0.03 mol/L.
Step (3) hydrothermal reaction: the foamed nickel was placed in a 100 mL reaction vessel and kept at 120 ℃ in an oven for 12 hours. After natural cooling, the foamed nickel is rinsed with a large amount of water and then dried at room temperature for use.
Preparing an ammonium perrhenate solution in the step (4): weighing 0.15 mmol of ammonium perrhenate, adding 200 muL of water, 200 muL of ethanol and 10 muL of Nafion, wherein the concentration of the ammonium perrhenate solution is 0.36 mol/L, and dropping the ammonium perrhenate solution on the foamed nickel (1 cm multiplied by 1 cm) after ultrasonic dissolution.
And (5) dropping rhenium: and (4) dripping the ammonium perrhenate solution prepared in the step (4) on the foamed nickel with the chromium grown in the step (3) by using a liquid transfer gun, and naturally airing for later use.
And (6) phosphating: putting the foamed nickel with the chromium-rhenium precursor in the step (5) into the bottom of a quartz tube, weighing 1 g of sodium hypophosphite and putting the sodium hypophosphite into the opening of the quartz tube, and then heating the quartz tube at the temperature of 5 ℃ for min in a nitrogen atmosphere (20 sccm)-1) Calcining for 2 hours at 350 ℃, naturally cooling to room temperature, taking out, washing with a large amount of deionized water, and airing at room temperature to prepare the CrP-Re2P composite material.
Fourth, example 3: preparation of Re2P/NF material
Step (1), treating foamed nickel: cutting foamed nickel into 3 × 3 cm2Size. Then ultrasonic washing is respectively carried out in 0.5 mol/L sulfuric acid solution, deionized water and ethanol for 10 minutes, and the ultrasonic washing is carried out for three times and naturally aired for standby.
Preparing an ammonium perrhenate solution in the step (2): 0.15 mmol of ammonium perrhenate is weighed, 200 uL of water, 200 uL of ethanol and 10 uL of Nafion are added, and the mixture is dripped on the foamed nickel prepared in the step (1) (1 cm multiplied by 1 cm) after ultrasonic dissolution.
And (3) dropping rhenium: dripping the ammonium perrhenate solution prepared in the step (2) on the foamed nickel (1 multiplied by 1 cm) prepared in the step (1) by using a liquid transfer gun2) And (6) naturally airing for later use.
And (4) phosphating: putting the foamed nickel with the rhenium precursor in the step (3) in the bottom of a quartz tube, weighing 1 g of sodium hypophosphite and putting the weighed foamed nickel in the opening of the quartz tube, and then heating the foamed nickel in a nitrogen atmosphere (20 sccm) (5 ℃ for min)-1) Calcining at 350 deg.C for 2 hr, naturally cooling to room temperature, taking out, washing with deionized water, and air drying at room temperature to obtain Re2P/NF composite material.
Electrochemical test
Electrochemical testing: both hydrogen evolution and oxygen evolution tests were carried out on an electrochemical workstation (Bio-Logic VMP3, France) using a three-electrode system. The CrP-Re prepared in example 2 was used2The P/NF composite material is used as a working electrode, the graphite plate is used as a counter electrode, the saturated calomel electrode is used as a reference electrode, 1.0 mol/L potassium hydroxide solution is used as electrolyte, the test temperature is 25 ℃, the scanning speed is 10 mV/s, and the scanning range is-0.9 to-1.5V. The electrode potential was obtained by applying a saturated calomel electrode, and a Reversible Hydrogen Electrode (RHE) and impedance compensation correction were performed. All potentials herein were obtained according to the following nernst equation:
ERHE = ESCE+0.241+0.059pH-iR
whereiniFor the current tested, R is the solution impedance. The electrolyzed water test was carried out on an electrochemical workstation (Bio-Logic VMP3, France) using a two-electrode system.
Sixth, test results
FIG. 1 shows that the sample of example 2 has CrP and Re, respectively2Characteristic peak of typical X-ray powder diffraction of P.
FIG. 2 (a) is a scanning electron microscope image of example 2 showing a large amount of porous nanoparticles grown on the nickel foam; as shown in FIG. 2 (b) and FIG. 2 (c), transmission electron micrographs are shown; FIG. 2 (d) and FIG. 2 (e) are respectively a particle size distribution and a lattice fringe; FIG. 2 (f) is a high resolution view; the elements are uniformly distributed in the composite as shown in fig. 2 (g).
FIG. 3 shows the results in CrP-Re2The presence of CrP in P/NF composite and electron transfer effect, wherein CrP-Re in FIG. 3 (a)2The combination energy of CrP in the P/NF composite material generates positive offset, Crn+A negative bias is generated, CrP-Re in FIG. 3 (b)2Re in P/NF composite material2The binding energy of P produces a positive shift, Re4+The binding energy of (c) produces a negative bias. Thus, it was confirmed that CrP-Re2The P/NF composite material has electron synergistic effect, so that the conductivity of the catalyst is improved through the electron synergistic effectElectrical properties and intrinsic catalytic activity. FIG. 3 (c) demonstrates that both chromium and rhenium are present as phosphides.
FIG. 4 shows CrP-Re prepared according to the invention2The linear scanning polarization curve of the P/NF composite material under the industrial condition is that when the current density reaches 500 mA/cm2The cell voltage in 30% KOH solution is only 1.89V, when the current density reaches 1000 mA/cm2The cell voltage in 30% KOH solution was only 2.05V, illustrating the CrP-Re of the invention2The P/NF composite material has excellent catalytic performance.
FIG. 5 shows CrP-Re prepared according to the invention2The P/NF composite material is tested in a two-electrode system for 100 hours in 30 percent KOH solution at high current density, the potential has no obvious change, and the CrP-Re composite material shows that2The P/NF composite material has super stability under industrial conditions.
FIG. 6 and FIG. 7 show CrP-Re prepared by the present invention2The P/NF composite material is subjected to linear scanning polarization curve of hydrogen evolution and oxygen evolution in alkaline solution, and when the current density reaches-100 mA/cm2The overpotential for hydrogen evolution only needs 90 mV when the current density reaches 20 mA/cm2The overpotential for oxygen evolution needs only 255 mV to illustrate the CrP-Re of the present invention2The P/NF composite material has excellent electro-catalytic hydrogen evolution and oxygen evolution performances under alkaline conditions.
Comparing examples 1, 2 and 3, in example 1, only hydrothermal reaction is carried out, and the precursor only growing chromium is directly subjected to low-temperature phosphating treatment to obtain CrP/NF, while in example 3, ammonium perrhenate solution is dripped on pure nickel foam, and after natural airing, low-temperature phosphating treatment is carried out to obtain Re2P/NF. As shown in FIG. 6, the current densities of examples 1 and 3 under the alkaline condition reached 100 mA/cm2When the overpotential is 300 mV and 133 mV, the electrocatalytic hydrogen evolution performance is poorer than that of the example 2; as shown in FIG. 7, the current densities of examples 1 and 3 reached 20 mA/cm under the alkaline condition2The overpotentials were 285 mV and 312 mV, which showed inferior electrocatalytic oxygen evolution performance compared to example 2.
In conclusion, the invention simply carries out water on the foamed nickelThermal and simple titration and low-temperature phosphating treatment to obtain CrP-Re2The P composite material has excellent electro-catalytic hydrogen and oxygen evolution performances under an alkaline condition, and has long service life.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention, and it is to be understood that the invention is not limited thereto, but may be modified within the scope of the appended claims.
Claims (6)
1. CrP-Re2The preparation method of the P hydrogen evolution and oxygen evolution electrocatalyst is characterized by comprising the following steps: comprising CrP-Re obtained by hydrothermal and simple titration and low-temperature phosphating2P composite material, wherein the hydrothermal method comprises the steps of growing chromium on foamed nickel to obtain a chromium-based precursor; and dropping rhenium species on the chromium-based precursor to obtain a chromium-rhenium composite material precursor, and carrying out low-temperature phosphating on the chromium-rhenium composite material precursor.
2. The method of claim 1, wherein: the preparation of the chromium-based precursor comprises the step of ultrasonically dissolving chromium nitrate nonahydrate and urea in deionized water to obtain a mixed solution.
3. The method of claim 2, wherein: the preparation of the chromium-rhenium composite material precursor comprises the step of dissolving an ammonium perrhenate solution in deionized water, absolute ethyl alcohol and Nafion in an ultrasonic mode to obtain the ammonium perrhenate solution.
4. The production method according to claim 3, characterized in that: the concentration of the chromium nitrate solution is 0.03 mol/L, the temperature of the hydrothermal reaction is 120 ℃, and the reaction time is 12 hours.
5. The method of claim 4, wherein: the concentration of the ammonium perrhenate solution is 0.36 mol/L.
6. The method of claim 5, wherein: the temperature of the phosphating treatment is 350 ℃ in the atmosphere of nitrogen, and the time is 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010951396.3A CN112007672B (en) | 2020-09-11 | 2020-09-11 | A kind of CrP-Re2P hydrogen evolution and oxygen evolution electrocatalyst preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010951396.3A CN112007672B (en) | 2020-09-11 | 2020-09-11 | A kind of CrP-Re2P hydrogen evolution and oxygen evolution electrocatalyst preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112007672A CN112007672A (en) | 2020-12-01 |
| CN112007672B true CN112007672B (en) | 2021-08-17 |
Family
ID=73522457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010951396.3A Active CN112007672B (en) | 2020-09-11 | 2020-09-11 | A kind of CrP-Re2P hydrogen evolution and oxygen evolution electrocatalyst preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112007672B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2765839C1 (en) * | 2021-03-03 | 2022-02-03 | Герасимов Михаил Владимирович | Corrosion-resistant electrode for electrochemical production of hydrogen and method for its production |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105951123A (en) * | 2016-05-06 | 2016-09-21 | 湖北大学 | Preparation method for NiCoP nanowire electro-catalytic electrode |
| CN108499585A (en) * | 2017-02-27 | 2018-09-07 | 江南大学 | Phosphorous compound and its preparation and application |
| CN110433833A (en) * | 2019-08-14 | 2019-11-12 | 华南理工大学 | A kind of base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent and preparation method thereof based on modified synergic |
| CN111545227A (en) * | 2020-05-22 | 2020-08-18 | 辽宁大学 | 3D nanosheet network structure bimetallic phosphorus oxide electrocatalyst and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102188107B1 (en) * | 2018-11-22 | 2020-12-07 | 고려대학교 산학협력단 | Manufacturing method of cobalt sulfide based catalysts for hydrogen and oxygen production |
-
2020
- 2020-09-11 CN CN202010951396.3A patent/CN112007672B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105951123A (en) * | 2016-05-06 | 2016-09-21 | 湖北大学 | Preparation method for NiCoP nanowire electro-catalytic electrode |
| CN108499585A (en) * | 2017-02-27 | 2018-09-07 | 江南大学 | Phosphorous compound and its preparation and application |
| CN110433833A (en) * | 2019-08-14 | 2019-11-12 | 华南理工大学 | A kind of base metal Electrocatalytic Activity for Hydrogen Evolution Reaction agent and preparation method thereof based on modified synergic |
| CN111545227A (en) * | 2020-05-22 | 2020-08-18 | 辽宁大学 | 3D nanosheet network structure bimetallic phosphorus oxide electrocatalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| New Vesicular Carbon-based Rhenium Phosphides with All-pH Range Electrocatalytic Hydrogen Evolution Activity;Sun Fang et al.;《Applied Catalysis B: Environmental》;20191105;第256卷;第117851号 * |
| Trends in Alkaline Hydrogen Evolution Activity on Cobalt Phosphide Electrocatalysts Doped with Transition Metals;Men Yana et al.;《Cell Reports Physcial Science》;20200826;第1卷(第8期);第100136号 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112007672A (en) | 2020-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109659143B (en) | Nickel hydroxide/trinickel disulfide/foamed nickel compound and preparation method and application thereof | |
| CN109954503B (en) | Nickel selenide and ternary nickel-iron selenide composite electrocatalyst, preparation method and application | |
| CN111111716A (en) | Preparation and application of nickel-cobalt double-metal phosphide guided by MOF | |
| CN111111707A (en) | A selenium-doped nickel-iron spinel/nickel oxyhydroxide composite electrocatalyst material and its preparation method and application | |
| CN114875442A (en) | Ruthenium-modified molybdenum-nickel nanorod composite catalyst and preparation method and application thereof | |
| CN113275027A (en) | Preparation and application of bimetallic phosphide derived from prussian blue analogue as template and growing on foamed nickel | |
| CN113512738A (en) | Ternary iron-nickel-molybdenum-based composite catalyst for water electrolysis, preparation method and application thereof | |
| CN113789545B (en) | Electrolytic water catalyst and preparation method and application thereof | |
| CN113136597A (en) | Copper-tin composite material and preparation method and application thereof | |
| CN113637997A (en) | A kind of preparation method of Co2P/CuP2/NF hydrogen evolution and oxygen evolution electrocatalyst | |
| CN111111721A (en) | Preparation and application of a boron-doped carbon shell-wrapped CoNi nanoparticle composite | |
| CN114411195A (en) | A kind of nickel-manganese selenide heterojunction electrocatalyst and preparation method and application thereof | |
| CN110565113B (en) | Preparation method of composite electrocatalytic material for alkaline electrocatalytic hydrogen evolution | |
| CN112007672B (en) | A kind of CrP-Re2P hydrogen evolution and oxygen evolution electrocatalyst preparation method | |
| CN112680745B (en) | Tungsten nitride nano porous film integrated electrode with ruthenium nanocluster loaded in limited domain and preparation method and application thereof | |
| CN112501652B (en) | A tungsten-doped nickel sulfide catalyst using morphology and structure to control electrocatalytic oxygen production and its preparation method and application | |
| CN112007671B (en) | Fe1Co6-P @ CC electrocatalyst and preparation method thereof | |
| CN119177466A (en) | NiFe Prussian blue composite electrode with carbonized surface and preparation and application thereof | |
| CN113652708A (en) | Pt/Ni alloy3N@Mo2Preparation method of C hydrogen hydroxide evolution electrocatalyst | |
| CN118390103A (en) | A self-supporting nickel-iron hydrotalcite/graphene oxygen evolution electrocatalyst and its preparation method and application | |
| CN113249752B (en) | Fe2P-WOxPreparation method of oxygen evolution electrocatalyst | |
| CN112023926A (en) | Electro-catalytic hydrogen evolution material and preparation method and application thereof | |
| CN115627493A (en) | Platinum-doped catalyst electrode and preparation method and application thereof | |
| CN114196969A (en) | Ruthenium-based oxygen evolution reaction catalyst and preparation method and application thereof | |
| CN114956019B (en) | Method for one-step synthesis of cobalt phosphide by molten salt mediation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |