CN110201670B - Ferronickel double-metal hydroxide/foamed nickel catalyst based on ferric trichloride/urea eutectic solvent, and preparation method and application thereof - Google Patents
Ferronickel double-metal hydroxide/foamed nickel catalyst based on ferric trichloride/urea eutectic solvent, and preparation method and application thereof Download PDFInfo
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- eutectic solvent
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 230
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000004202 carbamide Substances 0.000 title claims abstract description 82
- 239000002904 solvent Substances 0.000 title claims abstract description 59
- 230000005496 eutectics Effects 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 title claims abstract description 24
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 15
- 229910000863 Ferronickel Inorganic materials 0.000 title claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 98
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 22
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000002135 nanosheet Substances 0.000 claims abstract description 8
- 239000006260 foam Substances 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000002057 nanoflower Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- 235000019743 Choline chloride Nutrition 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical group [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 2
- 229960003178 choline chloride Drugs 0.000 description 2
- 239000000374 eutectic mixture Substances 0.000 description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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Abstract
The invention provides a nickel-iron bimetal hydroxide/foamed nickel catalyst based on an iron trichloride/urea eutectic solvent, and a preparation method and application thereof. The invention utilizes the eutectic solvent prepared by ferric trichloride hexahydrate and urea to prepare the nickel-iron bimetal hydroxide/foamed nickel catalyst, the used raw materials are cheap and easy to obtain, the cost is low, the operation process is extremely simple, the reaction condition is easy to realize, high-temperature conditions are not needed, the energy consumption is low, the preparation period is short, and the method is suitable for industrial production. The obtained catalyst is nickel-iron double metal hydroxide loaded on foamed nickel, wherein the catalytic active component is the nickel-iron double metal hydroxide (NiFe-LDH) which has a hierarchical structure, namely a nano flower-shaped structure consisting of nano sheets. The obtained catalyst has better performance of electrocatalysis electrolysis of water and urea.
Description
Technical Field
The invention relates to a nickel-iron bimetal hydroxide/foamed nickel catalyst based on an iron trichloride/urea eutectic solvent, a preparation method and application thereof, belonging to the technical field of energy materials.
Background
At present, the excessive use of traditional energy sources represented by petroleum and coal causes serious environmental pollution, and meanwhile, the problems of the risk of energy consumption, environmental pollution, energy shortage and the like attract wide attention of people. For this reason, development of green energy is required to meet human needs and reduce environmental pollution. Among them, hydrogen energy has the advantages of cleanness, high efficiency and the like, and electrocatalysis water cracking is one of important methods for producing hydrogen. However, in the electrocatalytic water splitting process, the theoretical voltage required for water splitting is 1.23V due to the presence of Oxygen Evolution Reaction (OER), greatly limiting the application of electrolyzed water. Therefore, it is desirable to reduce the voltage required to produce hydrogen, and therefore to produce hydrogen for use in the electrolysis of urea. Electrolysis of urea (UOR, CO (NH)2)2+H2O＝＝＝N2+3H2+CO2) The theoretical voltage required is only 0.37V; more particularly, the urea electrolysis can also treat urea wastewater, and has higher application value.
The research of electrocatalysts has been hot for more efficient electrolysis of water and urea. The nickel-iron double metal hydroxide (NiFe-LDH) is a common electrolytic water oxygen evolution catalyst, and has the advantages of good catalytic performance, easy preparation, adjustable structure and the like; the preparation method thereof includes a hydrothermal method, an electrodeposition method, an immersion method and the like. Chinese patent document CN108283926A discloses a method for preparing a layered ferronickel double metal hydroxide grown in situ on nickel foam; the method is characterized in that nickel nitrate hexahydrate, ferric nitrate nonahydrate, urea, ammonium fluoride and foamed nickel are used as main raw materials, the nickel nitrate hexahydrate, the ferric nitrate nonahydrate, the urea and the ammonium fluoride are added into water and mixed evenly, then the processed foamed nickel is added, and finally the nickel-based catalyst is prepared through hydrothermal reaction. The method adopts a hydrothermal method, so that the energy consumption is high, and the preparation time is long; the obtained catalyst used as an electrocatalytic oxygen production catalyst improves the OER catalytic performance under an alkaline condition to a certain extent, but the OER catalytic performance still needs to be further improved.
Meanwhile, the current reports based on double metal hydroxides in the aspect of urea electrolysis are still blank.
The eutectic solvent is a two-component or three-component eutectic mixture formed by combining hydrogen bond acceptors (such as quaternary ammonium salt) and hydrogen bond donors (such as amide, carboxylic acid, polyalcohol and other compounds) in a certain stoichiometric ratio, and the freezing point of the eutectic mixture is obviously lower than that of pure substances of each component. The most common eutectic solvent is choline chloride/urea, choline chloride/glycerol and the like. As an ionic liquid analogue, the eutectic solvent has the advantages of the ionic liquid, and simultaneously, the eutectic solvent also has the unique advantages of easy preparation, good biocompatibility, low toxicity and the like. Therefore, the eutectic solvent is widely applied to the preparation of inorganic nano materials. However, no report is available for preparing nickel-iron double metal hydroxide (NiFe-LDH) by using the eutectic solvent.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a nickel-iron bimetal hydroxide/foamed nickel catalyst based on an iron trichloride/urea eutectic solvent and a preparation method thereof. The invention utilizes the eutectic solvent prepared by ferric trichloride hexahydrate and urea to prepare the nickel-iron bimetal hydroxide/foamed nickel catalyst, the used raw materials are cheap and easy to obtain, the cost is low, the operation process is extremely simple, the reaction condition is easy to realize, high-temperature conditions are not needed, the energy consumption is low, the preparation period is short, and the method is suitable for industrial production. The resulting catalyst was nickel-iron double hydroxide supported on foamed nickel, the catalytically active component of which was nickel-iron double hydroxide (NiFe-LDH). The nickel-iron bimetal hydroxide prepared by the invention has a hierarchical structure, namely a nano flower-shaped structure consisting of nano sheets, and has larger specific surface area and better performance of electrocatalysis for electrolyzing water and urea.
The invention also provides an application of the nickel-iron bimetal hydroxide/foamed nickel catalyst based on the ferric trichloride/urea eutectic solvent in the electrocatalytic electrolysis of urea and water.
Description of terms:
nickel iron double metal hydroxide/nickel foam catalyst: the nickel-iron double metal hydroxide (NiFe-LDH) is loaded on foamed nickel, and the electrocatalytic active component is the nickel-iron double metal hydroxide (NiFe-LDH); the foamed nickel is mainly used as a carrier, and the electrocatalytic activity is poor.
The technical scheme of the invention is as follows:
a nickel-iron bimetal hydroxide/foamed nickel catalyst based on an iron trichloride/urea eutectic solvent is characterized in that the nickel-iron bimetal hydroxide in the catalyst is a catalytic active component, foamed nickel is a carrier, and the nickel-iron bimetal hydroxide is loaded on the surface of the foamed nickel; the microscopic morphology of the ferronickel bimetal hydroxide is a nanometer flower-shaped structure formed by nanometer sheets, wherein the diameter of the nanometer flower is 0.8-1.2 mu m, and the thickness of the nanometer sheets is 11-14 nm.
According to the invention, the catalyst is preferably prepared by placing foamed nickel in a eutectic solvent for reaction; the eutectic solvent is prepared from ferric trichloride hexahydrate and urea serving as raw materials.
The preparation method of the nickel-iron bimetal hydroxide/foamed nickel catalyst based on the ferric trichloride/urea eutectic solvent comprises the following steps:
(1) mixing ferric trichloride hexahydrate and urea, and heating at 40-100 ℃ for 10min-1h to obtain a eutectic solvent;
(2) soaking pure foam nickel into the eutectic solvent obtained in the step (1) to react for 10s-1min at the temperature of 40-100 ℃; then washing and drying to obtain the nickel-iron bimetal hydroxide/foamed nickel catalyst.
According to the invention, the mole ratio of ferric trichloride hexahydrate and urea in the step (1) is 1:3-3: 1; preferably, the molar ratio of ferric trichloride hexahydrate to urea is 2: 1.
According to the invention, the heating temperature in the step (1) is 60 ℃, and the heating time is 30 min.
According to the invention, the pure foam nickel in the step (2) is prepared by the following steps: and (3) putting the foamed nickel into 0.5-3mol/L hydrochloric acid for ultrasonic treatment for 5-20min, putting the foamed nickel into water for ultrasonic treatment for 5-15min, putting the foamed nickel into ethanol for ultrasonic treatment for 5-15min to remove impurities such as oxide on the surface of the foamed nickel, and then carrying out vacuum drying at room temperature to obtain the foamed nickel.
Preferably, the foam isThe nickel is 0.5 x 0.5cm in size2-2*2cm2Square of (2); further preferably, the nickel foam has a size of 1 x 1cm2。
Preferably, the molar concentration of the hydrochloric acid is 1mol/L, and the ultrasonic time in the hydrochloric acid is 10 min; ultrasonic treatment in water for 10 min; the ultrasonic treatment time in ethanol is 10 min; the drying time in vacuum at room temperature was 12 h.
Preferably, according to the invention, the reaction temperature in step (2) is 60 ℃ and the reaction time is 30 s.
Preferably according to the invention, the washing in step (2) is 3 times each with ethanol and water; the drying was carried out at room temperature under vacuum for 12 h.
The application of the nickel-iron double metal hydroxide/foamed nickel catalyst based on the ferric trichloride/urea eutectic solvent is applied to electrocatalytic electrolysis of urea or electrolyzed water. The catalyst is used as electrolytic urea or electrolytic water catalyst, and is applied to electrocatalysis, photoelectrocatalysis, alkaline hydrolysis hydrogen generators, urea wastewater treatment and the like.
The invention has the following technical characteristics and beneficial effects:
1. according to the invention, the eutectic solvent is prepared by simply and rapidly mixing ferric trichloride hexahydrate and urea; then simply immersing the pure nickel foam to quickly prepare the nickel-iron bimetal hydroxide/nickel foam catalyst. The raw materials used in the invention are cheap and easily available, and the cost is low; the method has the advantages of extremely simple process, simple and convenient operation, easy realization of reaction conditions, no need of high-temperature conditions, low energy consumption, extremely short preparation period and contribution to large-scale industrial production.
2. The invention successfully prepares the inorganic nano-material ferronickel bimetal hydroxide/foamed nickel catalyst by using a specific eutectic solvent such as ferric trichloride hexahydrate/urea which is used as an iron source and a solvent, and using foamed nickel as a nickel source and a carrier.
The reaction equation involved in the invention is as follows:
CO(NH2)2+H2O→2NH3+CO2(1)
NH3+H2O→NH4 ++OH-(2)
2Fe3++Ni→2Fe2++Ni2+(3)
Ni2++Fe3++OH-→NiFe-LDH (4)
h in urea and ferric chloride hexahydrate2O is reacted and hydrolyzed to NH4+And OH-(equations (1) and (2)). When the foam nickel as a sacrificial template and a substrate are immersed into a eutectic solvent, the foam nickel is coated with Fe3+Oxidation to Ni2+. Then Ni on the foamed nickel2+、Fe3+And OH-And (3) in-situ synthesis of the NiFe-LDH nano structure. During the reaction, the color of the nickel foam changed from the initial silver gray to dark yellow. The invention uses a specific eutectic solvent to prepare the nickel-iron bimetal hydroxide loaded on the surface of the foamed nickel. The ferronickel bimetal hydroxide is used as a catalytic active component, the microscopic morphology of the ferronickel bimetal hydroxide is a nano flower-shaped structure consisting of nano sheets, and the ferronickel bimetal hydroxide has a larger specific surface area; and the foamed nickel is mainly used as a carrier, can further increase the specific surface area and is beneficial to the transfer of electrons, but has weaker catalytic activity per se.
3. The catalyst prepared by the invention has excellent performance of electrolyzing urea and water. Especially the performance of urea oxidation and electrolytic water oxygen evolution is better than most of the reported catalysts at present. Under alkaline conditions, the current density was 10mA/cm2During the process, the voltage required by urea oxidation is as low as 1.32V, the voltage required by electrolysis of water for oxygen evolution is as low as 1.39V, the voltage required by urea electrolysis is as low as 1.52V, and the electrolysis voltage of total water is as low as 1.61V; from the above, the voltage required by urea oxidation is less than the voltage required by oxygen evolution from electrolyzed water, which shows that compared with the conventional alkaline electrolyzed water hydrogen production, the catalyst provided by the invention has lower voltage in alkaline electrolyzed urea reaction, thereby greatly reducing the power consumption of the electrolytic hydrogen production and improving the market competitiveness. Meanwhile, the electrocatalytic performance of the catalyst obtained by the invention is superior to that of the catalyst obtained without using a eutectic solvent (replaced by water), which shows the superiority of the specific eutectic solvent of the invention, and is beneficial to preparing the catalyst with high electrocatalytic activity. Preparation of the inventionThe catalyst applied to electrocatalysis electrolysis of water or urea has good catalytic performance and good stability.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of NiFe-LDH supported on the surface of foamed nickel in catalysts obtained in example 1 and comparative example 1; wherein NiFe-LDH in example 1 is abbreviated as NiFe-LDH _ D, and NiFe-LDH in comparative example 1 is abbreviated as NiFe-LDH _ W.
FIG. 2 is a scanning electron micrograph of NiFe-LDH in the catalysts prepared in example 1 (FIG. 2a) and comparative example 1 (FIG. 2 b).
FIG. 3 is a graph showing the comparison of the performance of the catalysts obtained in example 1, comparative example 1 and comparative example 2 in the electrocatalytic oxidation of urea and the evolution of oxygen by electrolytic water and a stability test.
FIG. 4 is a comparative plot of the polarization curves of urea electrolysis and total water electrolysis and a stability test plot of the catalyst obtained in example 1.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
In the examples, the nickel foam, Changshafen New materials, Inc. is available.
Example 1
A preparation method of a nickel-iron bimetal hydroxide/foamed nickel catalyst based on an iron trichloride/urea eutectic solvent comprises the following steps:
(1) synthesis of eutectic solvent: mixing ferric trichloride hexahydrate and urea in a molar ratio of 2:1, then heating for 30min at 60 ℃ in an oil bath to obtain reddish brown liquid with high viscosity, and cooling to room temperature to obtain the successfully synthesized ferric trichloride hexahydrate/urea eutectic solvent.
(2) Pretreatment of foamed nickel: cutting foamed nickel into 1 × 1cm2Then ultrasonic treating with 1mol/L hydrochloric acid for 10min, and respectively ultrasonic treating with water and ethanol for 10minTo remove surface oxides and impurities. Finally, vacuum drying is carried out for 12 hours at room temperature, and pure foam nickel is obtained.
(3) Preparation of NiFe-LDH/foamed nickel catalyst: and (2) soaking the pure foamed nickel in the eutectic solvent obtained in the step (1) to react for 30s at 60 ℃. And then taking out the foamed nickel (the surface of the foamed nickel is loaded with NiFe-LDH), washing the foamed nickel 3 times by using ethanol and water respectively, and drying the foamed nickel in vacuum at room temperature for 12 hours to obtain the NiFe-LDH/foamed nickel catalyst (NiFe-LDH _ D/NF for short).
The X-ray powder diffraction pattern of the powder loaded on the surface of the foamed nickel in the catalyst is shown in figure 1. As can be seen from FIG. 1, the substance loaded on the surface of the foamed nickel in the catalyst of the present invention is NiFe-LDH, and the catalyst is pure and free of impurities.
The scanning electron micrograph of NiFe-LDH in the catalyst prepared in this example is shown in FIG. 2 a. As can be seen from FIG. 2a, the microstructure of NiFe-LDH loaded on the surface of the foamed nickel is a nanoflower-like structure composed of nanosheets, wherein the diameter of the nanoflower is about 1 μm, and the thickness of the nanosheets is about 11.5-13.4 nm.
The catalyst prepared in the embodiment is applied to urea oxidation, and the specific application method is as follows:
the model of the electrochemical workstation used by the invention is Shanghai Chenghua 760E. Wherein the electrolyte is an aqueous solution of 1mol/L KOH and 0.5mol/L urea. The NiFe-LDH _ D/NF obtained by the invention is directly used as a working electrode, the saturated calomel electrode is used as a reference electrode, and the carbon rod is used as a counter electrode. Electrochemical measurements were performed using polarization curves with a scan rate of 5 mV/s.
The urea oxidation performance (UOR) of the catalyst obtained in this example is shown in FIG. 3a, and it can be seen from FIG. 3a that the current density is 10mA/cm2In the process, the required potential is only 1.32V, which shows that the catalyst prepared by the invention has higher catalytic activity.
Meanwhile, the catalyst prepared by the invention has good stability in catalyzing urea oxidation, and as can be seen from fig. 3c, the initial polarization curve is basically overlapped with the polarization curve after scanning for 1000 circles, which shows that the catalyst prepared by the invention has good stability.
The catalyst prepared in the embodiment is applied to water electrolysis Oxygen Evolution (OER), and the specific application method is as follows:
the test conditions and method were the same as for urea oxidation except that 1mol/LKOH of electrolyte was used.
The oxygen evolution performance of the catalyst obtained in this example by electrolyzing water is shown in FIG. 3b, and it is understood from FIG. 3b that the current density is 10mA/cm2In the case of the catalyst, the required potential is only 1.39V, which shows that the catalyst prepared by the invention has higher catalytic activity.
Meanwhile, the catalyst prepared by the invention has good stability of catalyzing oxygen generation, as shown in fig. 3d, and as can be seen from fig. 3d, the initial polarization curve is basically overlapped with the polarization curve after scanning for 1000 circles, which shows that the catalyst prepared by the invention has good stability.
The catalyst prepared by the embodiment is applied to urea electrolysis or total water electrolysis, and the specific application method is as follows:
the electrochemical workstation used was Shanghai Chenghua 760E, and the prepared catalyst was used as both cathode and anode. The electrolyte used was 1mol/L KOH, 0.5mol/L aqueous urea solution or 1mol/L aqueous KOH solution, and the scanning rate was 5 mV/s. .
The performance diagrams of the electrolytic urea of the catalyst obtained in this example are shown in fig. 4a and 4 b. As can be seen from FIG. 4a, the current density was 10mA/cm in the case of urea electrolysis2In this case, the required potential is only 1.52V. As can be seen from FIG. 4b, the curve obtained after 1000 scans substantially coincides with the initial curve, which shows that the catalyst prepared by the present invention can be used for urea electrolysis experiments and has good stability.
The performance graphs of the electrolyzed water of the catalyst obtained in this example are shown in FIGS. 4a and 4 c. As can be seen from FIG. 4a, the current density was 10mA/cm in the case of electrolyzing water2In this case, the required potential is only 1.61V. As can be seen from FIG. 4c, the curve obtained after 1000 cycles of scanning substantially coincides with the initial curve, which shows that the catalyst prepared by the present invention can be used for the full water electrolysis experiment and has good stability.
Example 2
A preparation method of a nickel-iron bimetal hydroxide/foamed nickel catalyst based on an iron trichloride/urea eutectic solvent comprises the following steps:
(1) synthesis of eutectic solvent: mixing ferric trichloride hexahydrate and urea in a molar ratio of 1:1, then heating for 30min at 60 ℃ in an oil bath to obtain reddish brown liquid with high viscosity, and cooling to room temperature to obtain the successfully synthesized ferric trichloride hexahydrate/urea eutectic solvent.
(2) Pretreatment of foamed nickel: cutting foamed nickel into 0.5 x 0.5cm2The subsequent processing steps and conditions were as described in example 1, to obtain pure nickel foam.
(3) Preparation of NiFe-LDH/foamed nickel catalyst: and (2) soaking the pure foamed nickel in the eutectic solvent obtained in the step (1) to react for 10s at 40 ℃. And then taking out the foamed nickel (the surface of the foamed nickel is loaded with NiFe-LDH), washing the foamed nickel for 3 times respectively by using ethanol and water, and drying the foamed nickel for 12 hours in vacuum at room temperature to obtain the NiFe-LDH/foamed nickel catalyst.
Example 3
A preparation method of a nickel-iron bimetal hydroxide/foamed nickel catalyst based on an iron trichloride/urea eutectic solvent comprises the following steps:
(1) synthesis of eutectic solvent: mixing ferric trichloride hexahydrate and urea in a molar ratio of 3:1, then heating for 30min at 60 ℃ in an oil bath to obtain reddish brown liquid with high viscosity, and cooling to room temperature to obtain the successfully synthesized ferric trichloride hexahydrate/urea eutectic solvent.
(2) Pretreatment of foamed nickel: cutting foamed nickel into 2 x 2cm2The subsequent processing steps and conditions were as described in example 1, to obtain pure nickel foam.
(3) Preparation of NiFe-LDH/foamed nickel catalyst: and (2) soaking the pure foamed nickel in the eutectic solvent obtained in the step (1) to react for 40s at the temperature of 80 ℃. And then taking out the foamed nickel (the surface of the foamed nickel is loaded with NiFe-LDH), washing the foamed nickel for 3 times respectively by using ethanol and water, and drying the foamed nickel for 12 hours in vacuum at room temperature to obtain the NiFe-LDH/foamed nickel catalyst.
Example 4
A preparation method of a nickel-iron bimetal hydroxide/foamed nickel catalyst based on an iron trichloride/urea eutectic solvent comprises the following steps:
(1) synthesis of eutectic solvent: mixing ferric trichloride hexahydrate and urea in a molar ratio of 1:2, then heating for 30min at 60 ℃ in an oil bath to obtain reddish brown liquid with high viscosity, and cooling to room temperature to obtain the successfully synthesized ferric trichloride hexahydrate/urea eutectic solvent.
(2) Pretreatment of foamed nickel: cutting foamed nickel into 1 x 1cm2The subsequent processing steps and conditions were as described in example 1, to obtain pure nickel foam.
(3) Preparation of NiFe-LDH/foamed nickel catalyst: and (2) soaking the pure foamed nickel in the eutectic solvent obtained in the step (1) to react for 30s at 60 ℃. And then taking out the foamed nickel (the surface of the foamed nickel is loaded with NiFe-LDH), washing the foamed nickel for 3 times respectively by using ethanol and water, and drying the foamed nickel for 12 hours in vacuum at room temperature to obtain the NiFe-LDH/foamed nickel catalyst.
Comparative example 1
A preparation method of a nickel-iron bimetal hydroxide/foamed nickel catalyst comprises the following steps:
(1) ferric chloride hexahydrate is dissolved in water, and then the mixture is heated for 30min at 60 ℃ in an oil bath to obtain a mixed solution (the volume of the mixed solution is the same as that of the eutectic solvent obtained in example 1, and the mass of the ferric chloride hexahydrate is the same as that of example 1).
(2) The nickel foam was pretreated as described in example 1 to obtain pure nickel foam.
(3) Preparation of NiFe-LDH/foamed nickel catalyst: and (2) soaking the pure foamed nickel in the mixed solution obtained in the step (1) to react for 30s at 60 ℃. And then taking out the foamed nickel (the surface of the foamed nickel is loaded with the ferronickel double metal hydroxide), washing the foamed nickel for 3 times respectively by using ethanol and water, and drying the foamed nickel for 12 hours in vacuum at room temperature to obtain the ferronickel double metal hydroxide/foamed nickel catalyst (NiFe-LDH _ W/NF for short).
The powder loaded on the surface of the foamed nickel in the catalyst of the comparative example is taken, and the X-ray powder diffraction pattern of the powder is shown in figure 1. As can be seen from FIG. 1, the powder supported on the surface of the nickel foam was NiFe-LDH, but there was a peak of nickel in addition to the peak of NiFe-LDH, and it was shown that nickel was derived from nickel foam, indicating that the skeleton of nickel foam was destroyed.
The scanning electron micrograph of NiFe-LDH in the catalyst prepared in this comparative example is shown in FIG. 2 b. As shown in FIG. 2b, the microstructure of the NiFe-LDH loaded on the surface of the foamed nickel is a nano-sheet structure, and the structure is not uniform.
The catalyst obtained in the comparative example was used in the oxidation of urea according to the method of example 1 of the present invention; as can be seen from FIG. 3a, the current density was 10mA/cm2The required potential is 1.37V, which is higher than that of the catalyst in the embodiment 1, and the catalyst prepared by using the eutectic solvent has better performance of electrocatalytic oxidation of urea.
The catalyst obtained in the comparative example is applied to oxygen evolution by electrolyzing water according to the method of the invention in the example 1; as can be seen from FIG. 3b, the current density was 10mA/cm2The required potential is 1.41V, which is higher than that of the catalyst in the embodiment 1, and the catalyst prepared by using the eutectic solvent has better performance of oxygen evolution in water electrolysis by electrocatalysis.
From the above comparative experiments, it can be seen that the electrocatalytic performance of the catalyst obtained in example 1 of the present invention is better than that of the catalyst obtained in comparative example 1, which illustrates the superiority of the low co-solvent, which is advantageous for preparing a catalyst with high catalytic activity.
Comparative example 2
The nickel foam is pretreated according to the method of the step (2) in the example 1, and pure nickel foam (NF for short) is obtained.
The NF obtained in the comparative example was applied to urea oxidation and electrolytic water oxygen evolution by the method of the invention example 1. As can be seen from FIGS. 3a and 3b, the electrocatalytic performance of pure nickel foam is negligible regardless of whether urea is oxidized or electrolyzed water is used for oxygen evolution. The catalytic active component in the catalyst prepared by the invention is the nickel-iron bimetal hydroxide, wherein the foamed nickel mainly plays the role of a carrier, and the nickel-iron bimetal hydroxide can effectively reduce the potential and has higher electrocatalytic activity.
Claims (9)
1. A nickel-iron bimetal hydroxide/foamed nickel catalyst based on an iron trichloride/urea eutectic solvent is characterized in that the nickel-iron bimetal hydroxide in the catalyst is a catalytic active component, foamed nickel is a carrier, and the nickel-iron bimetal hydroxide is loaded on the surface of the foamed nickel; the microscopic morphology of the ferronickel bimetal hydroxide is a nano flower-shaped structure formed by nano sheets, wherein the diameter of the nano flower is 0.8-1.2 mu m, and the thickness of the nano sheets is 11-14 nm;
the preparation method of the nickel-iron bimetal hydroxide/foamed nickel catalyst based on the ferric trichloride/urea eutectic solvent comprises the following steps:
(1) mixing ferric trichloride hexahydrate and urea, and heating at 40-100 ℃ for 10min-1h to obtain a eutectic solvent; the molar ratio of ferric trichloride hexahydrate to urea is 1:3-3: 1;
(2) soaking pure foam nickel into the eutectic solvent obtained in the step (1) to react for 10s-1min at the temperature of 40-100 ℃; then washing and drying to obtain the nickel-iron bimetal hydroxide/foamed nickel catalyst.
2. The nickel iron double hydroxide/nickel foam catalyst based on an iron trichloride/urea eutectic solvent according to claim 1, characterized in that the molar ratio of iron trichloride hexahydrate and urea in step (1) is 2: 1.
3. The nickel iron double hydroxide/foamed nickel catalyst based on an iron trichloride/urea eutectic solvent according to claim 1, characterized in that the heating temperature in step (1) is 60 ℃ and the heating time is 30 min.
4. The nickel-iron double hydroxide/nickel foam catalyst based on the eutectic solvent of ferric trichloride/urea according to claim 1, wherein the pure nickel foam in step (2) is prepared by the following method: and putting the foamed nickel in 0.5-3mol/L hydrochloric acid for ultrasonic treatment for 5-20min, putting in water for ultrasonic treatment for 5-15min, putting in ethanol for ultrasonic treatment for 5-15min, and vacuum drying at room temperature.
5. The ferronickel double hydroxide/nickel foam catalyst based on an iron trichloride/urea eutectic solvent according to claim 4, characterized in that the nickel foam is 0.5 x 0.5cm in size2-2*2cm2Square of (2).
6. The ferronickel double metal hydroxide/nickel foam catalyst based on an iron trichloride/urea eutectic solvent according to claim 4, characterized in that the molar concentration of the hydrochloric acid is 1mol/L and the ultrasonic time in hydrochloric acid is 10 min; ultrasonic treatment in water for 10 min; the ultrasonic treatment time in ethanol is 10 min; the drying time in vacuum at room temperature was 12 h.
7. The nickel iron double hydroxide/foamed nickel catalyst based on an iron trichloride/urea eutectic solvent according to claim 1, characterized in that the reaction temperature in step (2) is 60 ℃ and the reaction time is 30 s.
8. The nickel iron double hydroxide/nickel foam catalyst based on an iron trichloride/urea eutectic solvent according to claim 1, characterized in that the washing in step (2) is 3 times each with ethanol and water; the drying was carried out at room temperature under vacuum for 12 h.
9. The use of a nickel-iron double hydroxide/nickel foam catalyst based on an iron trichloride/urea eutectic solvent according to claim 1 for the electrocatalytic electrolysis of urea or of water.
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