CN115976567A - Chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel catalyst, and preparation method and application thereof - Google Patents

Chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel catalyst, and preparation method and application thereof Download PDF

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CN115976567A
CN115976567A CN202211718119.3A CN202211718119A CN115976567A CN 115976567 A CN115976567 A CN 115976567A CN 202211718119 A CN202211718119 A CN 202211718119A CN 115976567 A CN115976567 A CN 115976567A
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nickel
doped
chromium
double hydroxide
foamed nickel
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张素风
魏宁
姚雪
周秋生
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Shaanxi University of Science and Technology
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Abstract

The invention provides a chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel catalyst, and a preparation method and application thereof 3 ) 3 ·9H 2 O and Cr (NO) 3 ) 3 ·9H 2 Dissolving O in deionized water to obtain a mixed solution; immersing nickel foam into the mixed solution, and then adding Na 2 S 2 O 3 Carrying out reaction, and growing the chromium-sulfur double-doped nickel-iron layered double hydroxide on the surface of the foamed nickel in situ to obtain a mixture; and washing and drying the mixture to obtain the chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel catalyst. The electrolyte used in the water electrolysis and hydrogen evolution of the catalyst is a mixed solution of glucose and KOH, so that the synthesis time of the catalyst is greatly shortened, and the external requirement for water electrolysis is reducedThe electric potential is added, so that the efficiency of preparing high-purity hydrogen by electrolyzing water is improved.

Description

Chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel catalyst, and preparation method and application thereof
Technical Field
The invention belongs to the field of electrocatalytic hydrogen and oxygen production, and particularly relates to a chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel catalyst, and a preparation method and application thereof.
Background
The method for preparing high-purity hydrogen by electrolyzing water is an environment-friendly hydrogen preparation method so far, can realize clean production and sustainable supply, and effectively solves the energy crisis and environmental problems. The electrolyzed water contains two half reactions of anodic Oxygen Evolution (OER) and cathodic Hydrogen Evolution (HER) and has larger overpotential, so that the electrolyzed water needs to be additionally applied with larger potential in the practical application process, and the large-scale application of the technology is severely limited.
Currently, noble metals platinum (Pt) and ruthenium oxide (RuO) are used separately 2 ) Iridium oxide (IrO) 2 ) As efficient catalysts for HER and OER, these excellent catalysts are high cost, low inventory, and limited commercial use. Therefore, the development of low-cost and high-activity non-noble metal catalysts is a key technical problem for promoting the development of electrolyzed water.
At present, a great number of reports have been made on the use of advanced transition metal-based catalysts for high-efficiency electrolysis of water instead of conventional noble metal catalysts, such as transition metal oxides, hydroxides, phosphides, sulfides, etc. Wherein, the layered double hydroxide LDH has been developed into a very promising bifunctional catalyst in an alkaline medium by virtue of larger specific surface area, adjustable components and excellent electrochemical characteristics. However, methods for directly synthesizing LDH include a coprecipitation method and a sol-gel method, and methods for indirectly synthesizing LDH include a baking method and an ion exchange method. At present, the application of the nickel-iron layered double hydroxide in the layered double hydroxide is relatively wide, the shapes of the nickel-iron layered double hydroxide prepared by a hydrothermal method, a coprecipitation method and other methods comprise a lamellar wrinkle shape, a plate shape and the like, the nickel-iron layered double hydroxide prepared by the methods usually needs a longer time, and the catalytic performance needs to be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the chromium-sulfur double-doped nickel-iron layered double hydroxide/foamed nickel catalyst, the preparation method and the application thereof, so that the synthesis time of the catalyst is greatly shortened, the external potential required by water electrolysis is reduced, and the efficiency of preparing high-purity hydrogen by water electrolysis is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel catalyst comprises the following steps:
s1, according to the weight ratio of (3.5-4.5): (0.05-0.5) by mass ratio of Fe (NO) 3 ) 3 ·9H 2 O and Cr (NO) 3 ) 3 ·9H 2 Dissolving O in deionized water to obtain a mixed solution;
s2, soaking the foamed nickel into the mixed solution, and then adding Na 2 S 2 O 3 Reaction is carried out, na 2 S 2 O 3 With Fe (NO) in S1 3 ) 3 ·9H 2 The mass ratio of O is (0.5-1.5): (3.5-4.5), growing the chromium-sulfur double-doped nickel-iron layered double hydroxide on the surface of the foamed nickel in situ to obtain a mixture;
and S3, washing and drying the mixture to obtain the chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel catalyst.
Preferably, the foamed nickel described in S2 is obtained by the following process:
immersing the foamed nickel to be treated into acetone for ultrasonic cleaning for 10-20 min to obtain preliminarily cleaned foamed nickel, then immersing the preliminarily cleaned foamed nickel into 2-4 mol/L hydrochloric acid for ultrasonic cleaning for 10-20 min, then alternately washing with absolute ethyl alcohol and deionized water for 2-5 times in sequence, and finally vacuum drying for 8-12 h at 20-35 ℃ to obtain the foamed nickel.
Preferably, deionized water and Fe (NO) in S1 3 ) 3 ·9H 2 The proportion of O is 100mL: (3.5-4.5) g.
Preferably, S1 will be Fe (NO) 3 ) 3 ·9H 2 O and Cr (NO) 3 ) 3 ·9H 2 And adding O into deionized water, and magnetically stirring for 5-20 min to obtain a mixed solution.
Preferably, in S2, the reaction is carried out at room temperature.
Further, in S2, the reaction is carried out for 2 to 10min.
Preferably, S3, the mixture in the reaction solution is washed with absolute ethyl alcohol and deionized water for 2 to 6 times respectively and then dried.
Preferably, S3 dries the washed mixture under vacuum at room temperature for 8-15 h.
The chromium-sulfur double-doped nickel-iron layered double hydroxide/foamed nickel catalyst obtained by the preparation method of any one of the above chromium-sulfur double-doped nickel-iron layered double hydroxide/foamed nickel catalyst.
The application of the chromium-sulfur double-doped nickel-iron layered double hydroxide/foamed nickel catalyst in water electrolysis hydrogen evolution is characterized in that an electrolyte of the double hydroxide/foamed nickel catalyst in water electrolysis hydrogen evolution is a mixed solution of glucose and KOH, the concentration of the KOH is 0.5-1.5M, and the concentration of the glucose is 20-40 mM.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to a preparation method of a chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel catalyst 3 ) 3 ·9H 2 O and Cr (NO) 3 ) 3 ·9H 2 Dissolving O in deionized water to obtain a mixed solution, then soaking foamed nickel in the mixed solution, and finally adding Na 2 S 2 O 3 The reaction is carried out using the standard electrode potential Eq (Fe) 3+ /Fe 2+ )>Eq(Ni 2+ /Ni 0 ) In the case where the redox reaction spontaneously proceeds, a cation Cr is introduced for doping while binding Na 2 S 2 O 3 Dissolving the mixture in water to form a weak alkaline solution, and forming the chromium-sulfur double-doped nickel-iron layered double hydroxide on the surface of the foamed nickel in situ to obtain the chromium-sulfur double-doped nickel-iron layered double hydroxide/foamed nickel catalyst. The preparation method has the advantages of simple preparation process, rapid synthesis, cheap and easily-obtained raw materials, low cost, high yield, environmental friendliness and suitability for large-scale production. The chromium-sulfur-doped nickel-iron layered double hydroxide takes foamed nickel as a nickel source, and the chromium-sulfur-doped nickel-iron layered double hydroxide grows on a foamed nickel substrate in situ to form a three-dimensional porous nanosheet array structure. The chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel as a bifunctional electrolytic water catalyst can be used at the anodeOxygen evolution and cathodic hydrogen evolution, has excellent oxygen evolution reaction activity and lower hydrogen evolution overpotential, and shows excellent water electrolysis performance.
When the chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel catalyst is applied to the hydrogen evolution by electrolyzing water, the electrolyte is a mixed solution of glucose and KOH, so that the glucose is an anodic oxidation substrate, the glucose is subjected to an oxidation reaction at the anode, the glucose is upgraded and converted at the anode, the generation of oxygen at the anode is avoided, and the danger of mixing the oxygen and hydrogen is avoided. Meanwhile, the potential required by the electrolytic cell can be obviously reduced, so that the hydrogen production energy consumption is reduced, the development of water electrolysis can be promoted, and efficient hydrogen production is realized.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a layered double hydroxide of chromium-sulfur double-doped nickel-iron (Cr-Ni) grown in situ on the surface of a foamed nickel substrate prepared in example 3 of the present invention.
FIG. 2 is an X-ray photoelectron spectroscopy (XPS) of chromium-sulfur double-doped nickel-iron layered double hydroxide grown in situ on the surface of a foamed nickel substrate prepared in example 3 of the present invention.
FIG. 3 shows the foamed nickel NF prepared in example 3 of the present invention, and the Cr-S double-doped Ni-Fe layered double hydroxide and RuO grown in situ on the bottom surface of the foamed nickel NF 2 Performance plot of oxygen evolution polarization curve (LSV).
Fig. 4 is a graph of hydrogen evolution polarization curve (LSV) performance of the nickel foam NF prepared in example 3 of the present invention and the chromium sulfur double doped nickel iron layered double hydroxide grown in situ on the bottom surface of the nickel foam.
FIG. 5 is a graph of electrolytic water and glucose electrooxidation assisted electrolytic water polarization curve (LSV) performance of chromium-sulfur double-doped nickel-iron layered double hydroxide grown in situ on the surface of a foam nickel substrate prepared in example 3 of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention relates to a preparation method for quickly forming a chromium-sulfur double-doped nickel-iron layered double hydroxide/foamed nickel catalyst, which comprises the following steps:
step 1, immersing foamed nickel into acetone for ultrasonic cleaning for 10-20 min, then immersing preliminarily cleaned foamed nickel into 2-4 mol/L hydrochloric acid for ultrasonic cleaning for 10-20 min, finally alternately washing with absolute ethyl alcohol and deionized water for 2-5 times in sequence, and finally drying in vacuum for 8-12 h at 20-35 ℃ to obtain foamed nickel with an oxide layer removed;
step 2, weighing (3.5-4.5) g of Fe (NO) 3 ) 3 ·9H 2 O and (0.05-0.5) g Cr (NO) 3 ) 3 ·9H 2 Adding O into 100mL of deionized water, and magnetically stirring for 5-20 min at room temperature to form a uniform solution;
step 3, soaking the nickel foam obtained in the step 1 into the solution obtained in the step 2 at room temperature, and then adding (0.5-1.5) g of Na 2 S 2 O 3 Reacting at room temperature for 2-10 min.
And 4, after the reaction is finished, taking out a black product, sequentially washing the black product with absolute ethyl alcohol and deionized water for 2 to 6 times respectively, and performing vacuum drying for 8 to 15 hours at room temperature to obtain the chromium-sulfur double-doped nickel-iron layered double hydroxide/foamed nickel dual-functional electrocatalyst. The bifunctional electrocatalyst is a catalyst which can simultaneously act on the oxygen evolution of the anode and the hydrogen evolution of the cathode.
Example 1
The invention relates to a preparation method for rapidly forming a chromium-sulfur double-doped nickel-iron-doped layered double hydroxide/foamed nickel catalyst, which comprises the following steps:
step 1, immersing foamed nickel into pure acetone for ultrasonic cleaning for 15min, then immersing the primarily cleaned foamed nickel into 3mol/L hydrochloric acid for ultrasonic cleaning for 15min, finally alternately washing for 3 times by using absolute ethyl alcohol and deionized water in sequence, and performing vacuum drying for 12h at room temperature to obtain foamed nickel with an oxide layer removed;
step 2, 3.5g of Fe (NO) are weighed 3 ) 3 ·9H 2 O and 0.05g Cr (NO) 3 ) 3 ·9H 2 Adding O into 100mL of deionized water, and magnetically stirring at room temperature for 10min to form a uniform solution;
(3) At room temperature, the foamed nickel in the step (1) is put intoImmersing in the solution obtained in step (2), followed by addition of 0.5g of Na 2 S 2 O 3 The reaction was carried out at room temperature for 2min.
(4) And after the reaction is finished, taking out a black product, sequentially washing the black product by using absolute ethyl alcohol and deionized water for 3 times respectively, and performing vacuum drying for 12 hours at room temperature to obtain the chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel double-function electrocatalyst.
Example 2
The invention relates to a preparation method for rapidly forming a chromium-sulfur double-doped nickel-iron-doped layered double hydroxide/foamed nickel catalyst, which comprises the following steps:
step 1, immersing foamed nickel into pure acetone for ultrasonic cleaning for 15min, then immersing the preliminarily cleaned foamed nickel into 3mol/L hydrochloric acid for ultrasonic cleaning for 15min, finally alternately washing for 3 times by using absolute ethyl alcohol and deionized water in sequence, and carrying out vacuum drying for 12h at room temperature to obtain foamed nickel with an oxide layer removed;
step 2, weigh 4.5g of Fe (NO) 3 ) 3 ·9H 2 O and 0.1g Cr (NO) 3 ) 3 ·9H 2 Adding O into 100mL of deionized water, and magnetically stirring at room temperature for 10min to form a uniform solution;
(3) Immersing the nickel foam obtained in the step (1) into the solution obtained in the step (2) at room temperature, and then adding 1g of Na 2 S 2 O 3 The reaction was carried out at room temperature for 4min.
(4) And after the reaction is finished, taking out a black product, sequentially washing the black product by using absolute ethyl alcohol and deionized water for 3 times respectively, and performing vacuum drying for 12 hours at room temperature to obtain the chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel double-function electrocatalyst.
Example 3
The invention relates to a preparation method for rapidly forming a chromium-sulfur double-doped nickel-iron-doped layered double hydroxide/foamed nickel catalyst, which comprises the following steps:
step 1, immersing foamed nickel into pure acetone for ultrasonic cleaning for 15min, then immersing the primarily cleaned foamed nickel into 3mol/L hydrochloric acid for ultrasonic cleaning for 15min, finally alternately washing for 3 times by using absolute ethyl alcohol and deionized water in sequence, and performing vacuum drying for 12h at room temperature to obtain foamed nickel with an oxide layer removed;
step 2, weigh 4.5g of Fe (NO) 3 ) 3 ·9H 2 O and 0.3g Cr (NO) 3 ) 3 ·9H 2 Adding O into 100mL of deionized water, and magnetically stirring at room temperature for 10min to form a uniform solution
(3) Immersing the nickel foam obtained in the step (1) into the solution obtained in the step (2) at room temperature, and then adding 1g of Na 2 S 2 O 3 The reaction was carried out at room temperature for 6min.
(4) And after the reaction is finished, taking out a black product, sequentially washing the black product by using absolute ethyl alcohol and deionized water for 3 times respectively, and performing vacuum drying for 12 hours at room temperature to obtain the chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel double-function electrocatalyst.
As can be seen from the SEM of fig. 1, the chromium-sulfur double-doped nickel-iron layered double hydroxide has a three-dimensional porous nanosheet array structure.
As can be seen from the X-ray photoelectron spectroscopy of FIG. 2, the chromium-sulfur double-doped nickel-iron layered double hydroxide mainly contains Ni, fe, cr, O and S elements, and the present invention utilizes the standard electrode potential Eq (Fe) 3+ /Fe 2+ )>Eq(Ni 2+ /Ni 0 ) In the case where the redox reaction spontaneously proceeds, a cation Cr is introduced for doping, and Na is bonded 2 S 2 O 3 The chromium-sulfur double-doped nickel-iron layered double hydroxide can be proved to be successfully prepared by dissolving the chromium-sulfur double-doped nickel-iron layered double hydroxide in water to form a weak alkaline solution.
FIG. 3 shows foamed nickel NF, chromium-sulfur double doped nickel-iron layered double hydroxide and RuO grown in situ on the bottom surface of foamed nickel base 2 Oxygen evolution polarization curves measured in 1M KOH in a three electrode system with nickel foam NF, chromium sulfur double doped nickel iron layered double hydroxide (being a self-supporting catalyst) grown in situ on the surface of the nickel foam substrate, and RuO 2 As a working electrode, the chromium-sulfur double-doped ferronickel layered double hydroxide prepared in situ has excellent oxygen evolution reaction activity at 100mA/cm 2 The overpotential of oxygen evolution is 252mV, which is obviously lower than that of foamed nickel and commercial RuO 2 The required overpotential.
As can be seen from the hydrogen evolution polarization curves of the nickel foam NF of FIG. 4 and the Cr-S double-doped Ni-Fe layered double hydroxide grown in situ on the bottom surface of the nickel foam substrate, the Cr-S double-doped Ni-Fe layered double hydroxide has a lower hydrogen evolution overpotential reaching 10mA/cm 2 And 50mA/cm 2 The overpotential at the current density is 132mV and 214mV respectively, and the overpotential at the current density is 10mA/cm for foamed nickel 2 And 50mA/cm 2 The overpotential at the current density is significantly reduced compared to the prior art.
As can be seen from the polarization curve of the electrolyzed water and the glucose electrooxidation assisted electrolyzed water of the chromium-sulfur double-doped nickel-iron layered double hydroxide growing on the bottom surface of the foam nickel base in situ in FIG. 5, the oxygen evolution reaction of the anode can be replaced by the glucose oxidation reaction, when the electrolyte is only 1M KOH solution, the oxygen evolution reaction and the hydrogen evolution reaction occur, and the electrolytic cell reaches 10mA/cm 2 And 50mA/cm 2 The overpotential of the electrolytic cell is 1.614V and 1.722V respectively, when the electrolyte is a mixed solution of glucose and KOH, the concentration of KOH is 1M, the glucose is 30mM, the glucose is an anodic oxidation substrate, the glucose is subjected to an anodic oxidation reaction, and at the moment, the electrolytic cell reaches 10mA/cm 2 And 50mA/cm 2 The overpotentials are respectively 1.337V and 1.56V, and the glucose realizes upgrading and conversion at the anode, so that the oxygen generation at the anode is avoided, and the danger of mixing the oxygen and the hydrogen is avoided. Therefore, the glucose oxidation reaction is used for replacing the oxygen evolution reaction of the anode, so that the potential required by the electrolytic cell can be obviously reduced, and the energy consumption for hydrogen production is reduced.
Example 4
The invention relates to a preparation method for rapidly forming a chromium-sulfur double-doped nickel-iron-doped layered double hydroxide/foamed nickel catalyst, which comprises the following steps:
step 1, immersing foamed nickel into pure acetone for ultrasonic cleaning for 15min, then immersing the primarily cleaned foamed nickel into 3mol/L hydrochloric acid for ultrasonic cleaning for 15min, finally alternately washing for 3 times by using absolute ethyl alcohol and deionized water in sequence, and performing vacuum drying for 12h at room temperature to obtain foamed nickel with an oxide layer removed;
step 2, weigh 4.5g of Fe (NO) 3 ) 3 ·9H 2 O and 0.2g Cr (NO) 3 ) 3 ·9H 2 Adding O into 100mL of deionized water, and magnetically stirring at room temperature for 10min to form a uniform solution;
(3) Immersing the nickel foam obtained in the step (1) into the solution obtained in the step (2) at room temperature, and then adding 1g of Na 2 S 2 O 3 The reaction was carried out at room temperature for 8min.
(4) And after the reaction is finished, taking out a black product, sequentially washing the black product by using absolute ethyl alcohol and deionized water for 3 times respectively, and performing vacuum drying for 12 hours at room temperature to obtain the chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel double-function electrocatalyst.
Example 5
The invention relates to a preparation method for rapidly forming a chromium-sulfur double-doped nickel-iron-doped layered double hydroxide/foamed nickel catalyst, which comprises the following steps:
step 1, immersing foamed nickel into pure acetone for ultrasonic cleaning for 15min, then immersing the primarily cleaned foamed nickel into 3mol/L hydrochloric acid for ultrasonic cleaning for 15min, finally alternately washing for 3 times by using absolute ethyl alcohol and deionized water in sequence, and performing vacuum drying for 12h at room temperature to obtain foamed nickel with an oxide layer removed;
step 2, 4.5g of Fe (NO) is weighed 3 ) 3 ·9H 2 O and 0.3g Cr (NO) 3 ) 3 ·9H 2 Adding O into 100mL deionized water, and magnetically stirring at room temperature for 10min to form a uniform solution
(3) Immersing the nickel foam obtained in the step (1) into the solution obtained in the step (2) at room temperature, and then adding 1g of Na 2 S 2 O 3 The reaction was carried out at room temperature for 10min.
(4) And after the reaction is finished, taking out a black product, sequentially washing the black product by using absolute ethyl alcohol and deionized water for 3 times respectively, and performing vacuum drying for 12 hours at room temperature to obtain the chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel double-function electrocatalyst.
Example 6
The invention relates to a preparation method for quickly forming a chromium-sulfur double-doped nickel-iron-doped layered double hydroxide/foamed nickel catalyst, which comprises the following steps:
step 1, immersing foamed nickel into pure acetone for ultrasonic cleaning for 20min, then immersing the primarily cleaned foamed nickel into 4mol/L hydrochloric acid for ultrasonic cleaning for 20min, finally alternately washing for 5 times by using absolute ethyl alcohol and deionized water in sequence, and performing vacuum drying for 12h at room temperature to obtain foamed nickel with an oxide layer removed;
step 2, 4.5g of Fe (NO) is weighed 3 ) 3 ·9H 2 O and 0.25g Cr (NO) 3 ) 3 ·9H 2 Adding O into 100mL deionized water, and magnetically stirring at room temperature for 10min to form a uniform solution
(3) Immersing the nickel foam obtained in the step (1) into the solution obtained in the step (2) at room temperature, and then adding 0.5g of Na 2 S 2 O 3 The reaction was carried out at room temperature for 6min.
(4) And after the reaction is finished, taking out a black product, sequentially washing the black product by using absolute ethyl alcohol and deionized water for 3 times respectively, and performing vacuum drying for 12 hours at room temperature to obtain the chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel double-function electrocatalyst.
Example 7
The invention relates to a preparation method for rapidly forming a chromium-sulfur double-doped nickel-iron-doped layered double hydroxide/foamed nickel catalyst, which comprises the following steps:
step 1, immersing foamed nickel into pure acetone for ultrasonic cleaning for 15min, then immersing the primarily cleaned foamed nickel into 3mol/L hydrochloric acid for ultrasonic cleaning for 15min, finally alternately washing for 3 times by using absolute ethyl alcohol and deionized water in sequence, and performing vacuum drying for 12h at room temperature to obtain foamed nickel with an oxide layer removed;
step 2, weigh 4.5g of Fe (NO) 3 ) 3 ·9H 2 O and 0.35g Cr (NO) 3 ) 3 ·9H 2 Adding O into 100mL deionized water, and magnetically stirring at room temperature for 10min to form a uniform solution
(3) Immersing the nickel foam obtained in the step (1) into the solution obtained in the step (2) at room temperature, and then adding 1.5g of Na 2 S 2 O 3 The reaction was carried out at room temperature for 2min.
(4) And after the reaction is finished, taking out a black product, sequentially washing the black product by using absolute ethyl alcohol and deionized water for 6 times respectively, and performing vacuum drying for 15 hours at room temperature to obtain the chromium-sulfur double-doped nickel-iron layered double hydroxide/foamed nickel dual-functional electrocatalyst.
Example 8
The invention relates to a preparation method for quickly forming a chromium-sulfur double-doped nickel-iron-doped layered double hydroxide/foamed nickel catalyst, which comprises the following steps:
step 1, immersing foamed nickel into pure acetone for ultrasonic cleaning for 15min, then immersing the preliminarily cleaned foamed nickel into 3mol/L hydrochloric acid for ultrasonic cleaning for 15min, finally alternately washing for 3 times by using absolute ethyl alcohol and deionized water in sequence, and carrying out vacuum drying for 12h at room temperature to obtain foamed nickel with an oxide layer removed;
step 2, 3.5g of Fe (NO) are weighed 3 ) 3 ·9H 2 O and 0.4g Cr (NO) 3 ) 3 ·9H 2 Adding O into 100mL of deionized water, and magnetically stirring at room temperature for 10min to form a uniform solution;
(3) Immersing the nickel foam obtained in the step (1) into the solution obtained in the step (2) at room temperature, and then adding 1g of Na 2 S 2 O 3 The reaction was carried out at room temperature for 6min.
(4) And after the reaction is finished, taking out a black product, sequentially washing the black product by using absolute ethyl alcohol and deionized water for 3 times respectively, and performing vacuum drying for 12 hours at room temperature to obtain the chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel double-function electrocatalyst.
Example 9
The invention relates to a preparation method for rapidly forming a chromium-sulfur double-doped nickel-iron-doped layered double hydroxide/foamed nickel catalyst, which comprises the following steps:
step 1, immersing foamed nickel into pure acetone for ultrasonic cleaning for 15min, then immersing the primarily cleaned foamed nickel into 3mol/L hydrochloric acid for ultrasonic cleaning for 15min, finally alternately washing for 3 times by using absolute ethyl alcohol and deionized water in sequence, and performing vacuum drying for 12h at room temperature to obtain foamed nickel with an oxide layer removed;
step 2, weighing 4g of Fe (NO) 3 ) 3 ·9H 2 O and 0.45g Cr (NO) 3 ) 3 ·9H 2 Adding O into 100mL of deionized water, and magnetically stirring at room temperature for 10min to form a uniform solution;
(3) Immersing the nickel foam obtained in the step (1) into the solution obtained in the step (2) at room temperature, and then adding 1g of Na 2 S 2 O 3 The reaction was carried out at room temperature for 4min.
(4) And after the reaction is finished, taking out a black product, sequentially washing the black product with absolute ethyl alcohol and deionized water for 2 times respectively, and performing vacuum drying for 8 hours at room temperature to obtain the chromium-sulfur double-doped nickel-iron layered double hydroxide/foamed nickel dual-functional electrocatalyst.
Example 10
The invention relates to a preparation method for rapidly forming a chromium-sulfur double-doped nickel-iron-doped layered double hydroxide/foamed nickel catalyst, which comprises the following steps:
step 1, immersing foamed nickel into pure acetone for ultrasonic cleaning for 10min, then immersing the primarily cleaned foamed nickel into 2mol/L hydrochloric acid for ultrasonic cleaning for 10min, finally alternately washing for 2 times by using absolute ethyl alcohol and deionized water in sequence, and performing vacuum drying for 8h at room temperature to obtain foamed nickel with an oxide layer removed;
step 2, weigh 4.5g of Fe (NO) 3 ) 3 ·9H 2 O and 0.15g Cr (NO) 3 ) 3 ·9H 2 Adding O into 100mL of deionized water, and magnetically stirring at room temperature for 10min to form a uniform solution;
(3) Immersing the nickel foam obtained in the step (1) into the solution obtained in the step (2) at room temperature, and then adding 1.5g of Na 2 S 2 O 3 The reaction was carried out at room temperature for 2min.
(4) And after the reaction is finished, taking out a black product, sequentially washing the black product by using absolute ethyl alcohol and deionized water for 3 times respectively, and performing vacuum drying for 12 hours at room temperature to obtain the chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel double-function electrocatalyst.

Claims (10)

1. A preparation method of a chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel catalyst is characterized by comprising the following steps:
s1, according to the weight ratio of (3.5-4.5): (0.05-0.5) by mass ratio of Fe (NO) 3 ) 3 ·9H 2 O and Cr (NO) 3 ) 3 ·9H 2 O dissolves in the deionizationObtaining mixed solution by water;
s2, soaking the foamed nickel into the mixed solution, and then adding Na 2 S 2 O 3 Reaction is carried out, na 2 S 2 O 3 With Fe (NO) in S1 3 ) 3 ·9H 2 The mass ratio of O is (0.5-1.5): (3.5-4.5), growing the chromium-sulfur double-doped nickel-iron layered double hydroxide on the surface of the foamed nickel in situ to obtain a mixture;
and S3, washing and drying the mixture to obtain the chromium-sulfur double-doped nickel-iron layered double hydroxide/foamed nickel catalyst.
2. The process for preparing a chromium-sulfur double doped ferronickel layered double hydroxide/nickel foam catalyst according to claim 1, wherein the nickel foam in S2 is obtained by the following process:
immersing the foam nickel to be treated into acetone for ultrasonic cleaning for 10-20 min to obtain preliminarily cleaned foam nickel, then immersing the preliminarily cleaned foam nickel into 2-4 mol/L hydrochloric acid for ultrasonic cleaning for 10-20 min, then alternately washing for 2-5 times by using absolute ethyl alcohol and deionized water in sequence, and finally vacuum drying for 8-12 h at 20-35 ℃ to obtain the foam nickel.
3. The method of claim 1, wherein the deionized water and Fe (NO) are mixed in S1 to form the layered double hydroxide/nickel foam catalyst 3 ) 3 ·9H 2 The proportion of O is 100mL: (3.5-4.5) g.
4. The process for the preparation of the chromium-sulfur double doped ferronickel layered double hydroxide/nickel foam catalyst according to claim 1, wherein S1 is Fe (NO) mixed with Fe (NO) 3 ) 3 ·9H 2 O and Cr (NO) 3 ) 3 ·9H 2 And adding the O into deionized water, and magnetically stirring for 5-20 min to obtain a mixed solution.
5. The process for preparing a chromium-sulfur double doped nickel iron layered double hydroxide/foamed nickel catalyst according to claim 1, wherein in S2, the reaction is carried out at room temperature.
6. The method for preparing the chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel catalyst according to claim 5, wherein in S2, the reaction is performed for 2 to 10min.
7. The preparation method of the chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel catalyst according to claim 1, wherein S3 is to wash the mixture in the reaction solution with absolute ethyl alcohol and deionized water for 2 to 6 times respectively and then dry the mixture.
8. The method for preparing the chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel catalyst according to claim 1, wherein S3 is to vacuum-dry the washed mixture at room temperature for 8 to 15 hours.
9. The chromium-sulfur double-doped ferronickel layered double hydroxide/nickel foam catalyst obtained by the method for preparing a chromium-sulfur double-doped ferronickel layered double hydroxide/nickel foam catalyst according to any one of claims 1 to 8.
10. The application of the chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel catalyst in hydrogen evolution by electrolysis of water as claimed in claim 9, wherein the electrolyte of the double hydroxide/foamed nickel catalyst in hydrogen evolution by electrolysis of water is a mixed solution of glucose and KOH, the concentration of KOH is 0.5-1.5M, and the concentration of glucose is 20-40 mM.
CN202211718119.3A 2022-12-29 2022-12-29 Chromium-sulfur double-doped ferronickel layered double hydroxide/foamed nickel catalyst, and preparation method and application thereof Pending CN115976567A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117488357A (en) * 2023-12-29 2024-02-02 中石油深圳新能源研究院有限公司 Oxygen evolution electrode material and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117488357A (en) * 2023-12-29 2024-02-02 中石油深圳新能源研究院有限公司 Oxygen evolution electrode material and preparation method and application thereof
CN117488357B (en) * 2023-12-29 2024-03-15 中石油深圳新能源研究院有限公司 Oxygen evolution electrode material and preparation method and application thereof

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