CN111905736B - Cysteine functionalized modified iron oxyhydroxide, electrocatalyst, preparation methods and applications - Google Patents
Cysteine functionalized modified iron oxyhydroxide, electrocatalyst, preparation methods and applications Download PDFInfo
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- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical class [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 title claims abstract description 102
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 235000018417 cysteine Nutrition 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 8
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims abstract description 108
- 239000003054 catalyst Substances 0.000 claims abstract description 83
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 52
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000001301 oxygen Substances 0.000 claims abstract description 50
- 239000011259 mixed solution Substances 0.000 claims abstract description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000004201 L-cysteine Substances 0.000 claims abstract description 29
- 235000013878 L-cysteine Nutrition 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000004202 carbamide Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- 229920000557 Nafion® Polymers 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 16
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- -1 alcohol amine Chemical class 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000010494 dissociation reaction Methods 0.000 claims 1
- 230000005593 dissociations Effects 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 claims 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 abstract description 56
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 238000000354 decomposition reaction Methods 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 229910021607 Silver chloride Inorganic materials 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 238000013507 mapping Methods 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 8
- 238000001075 voltammogram Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N N,N-Diethylethanamine Substances CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000004832 voltammetry Methods 0.000 description 4
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical class [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 3
- 229910002588 FeOOH Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013112 stability test 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
- B01J23/745—Iron
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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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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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Abstract
The invention discloses cysteine functionalized modified iron oxyhydroxide, an electrocatalyst, a preparation method and application thereof, wherein the preparation method comprises the steps of mixing ferric nitrate and urea in deionized water according to the molar ratio of 1: 5 to obtain a first mixed solution; mixing the first mixed solution and the alcohol solution according to the volume ratio of 10-80: 1 to obtain a second mixed solution; mixing and stirring the second mixed solution and L-cysteine according to the concentration ratio of 25 mmol/L-125 mmol/L to obtain a third mixed solution; putting the third mixed solution into a high-pressure reaction kettle to prepare iron oxyhydroxide; adding the washed and dried iron oxyhydroxide into a Nafion solution for mixing, coating the mixture on foamed nickel after ultrasonic treatment, and naturally airing to obtain a cysteine functionalized modified iron oxyhydroxide catalyst; the preparation process is simple, and compared with unmodified iron oxyhydroxide, the prepared catalyst is applied to the electrocatalytic oxygen production reaction, the electrocatalytic performance is greatly improved and is far superior to commercial ruthenium dioxide, and the electrocatalytic oxygen evolution performance is good in stability and suitable for industrial application.
Description
Technical Field
The invention relates to the technical field of preparation of electrocatalytic materials, in particular to cysteine functionalized modified iron oxyhydroxide, an electrocatalyst, a preparation method and application.
Background
Environmental pollution and energy crisis impel people to find a new clean energy to replace fossil energy, and hydrogen energy is popular among people as a renewable clean energy with high energy density.
The electrocatalytic decomposition of water is a common technology for hydrogen production, however, the rate of Hydrogen Evolution Reaction (HER) by water electrolysis is limited by Oxygen Evolution Reaction (OER), so the key to improve the efficiency of the electrocatalyst for oxygen evolution reaction is to improve the hydrogen production by water electrolysis.
Catalysts with high performance oxygen evolution reactions have been reported to include ruthenium dioxide (RuO)2) And iron, cobalt, manganese, nickel-based nano materials and the like, but the electrocatalytic oxygen evolution performance of the catalysts is poor, and the requirements of industrial application cannot be met.
In view of the above-mentioned drawbacks, the inventors of the present invention have finally obtained the present invention through a long period of research and practice.
Disclosure of Invention
In order to solve the technical defects, the technical scheme adopted by the invention is to provide a preparation method of a cysteine functionalized modified hydroxyl oxidation ferroelectric catalyst, which comprises the following steps:
s1, uniformly mixing ferric nitrate and urea in deionized water according to the molar ratio of 1: 5 to obtain a first mixed solution;
s2, mixing the first mixed solution and the alcohol solution according to the volume ratio of 10-80: 1 to obtain a second mixed solution;
s3, mixing and stirring the second mixed solution and L-cysteine uniformly according to the concentration ratio of 25 mmol/L-125 mmol/L to obtain a third mixed solution;
s4, placing the third mixed solution in a high-pressure reaction kettle, and preparing cysteine functionalized modified iron oxyhydroxide by a hydrothermal method;
s5, adding the washed and dried cysteine functionalized modified iron oxyhydroxide into a Nafion solution to mix, wherein the concentration is 5mg/mL, uniformly coating the mixture on foamed nickel after ultrasonic treatment, and naturally airing to obtain the cysteine functionalized modified iron oxyhydroxide catalyst.
Preferably, in step S2, the alcohol solution is triethanolamine, ethanolamine, or diethanolamine.
Preferably, in the step S4, the hydrothermal reaction is performed at 120 ℃ for 12 hours.
Preferably, in the step S5, the cysteine-functionalized modified iron oxyhydroxide obtained is centrifugally filtered and washed with deionized water, and dried at 60 ℃ for 12 hours, wherein the mass concentration of the Nafion solution is 5%.
Preferably, the cysteine-functionalized modified iron oxyhydroxide is prepared by the steps S1 to S4 of the preparation method of the cysteine-functionalized modified iron oxyhydroxide catalyst.
Preferably, the electrocatalyst prepared by the preparation method of the cysteine functionalized and modified FeOOH catalyst comprises a foamed nickel substrate and a formed cysteine functionalized and modified FeOOH catalytic layer coated on the foamed nickel substrate.
Preferably, the application of the cysteine functionalized modified iron oxyhydroxide in the water decomposition oxygen analysis reaction is provided.
Preferably, the application of the electrocatalyst in the water decomposition oxygen analysis reaction is provided.
Compared with the prior art, the invention has the beneficial effects that: the cysteine functionalized modified hydroxyl iron oxide catalyst has a simple preparation process, and compared with unmodified hydroxyl iron oxide, the prepared catalyst applied to an electrocatalytic oxygen production reaction (OER) has the advantages that the electrocatalytic performance is greatly improved and is far superior to commercial ruthenium dioxide, the electrocatalytic oxygen evolution performance has good stability, and the catalyst is suitable for industrial application.
Drawings
FIG. 1 is a HRTEM image of cysteine functionalized modified iron oxyhydroxide prepared according to example one;
FIG. 2 is a mapping of the elements of cysteine functionalized modified iron oxyhydroxide prepared in example one;
FIG. 3 is a HRTEM image of iron oxyhydroxide prepared in example V;
FIG. 4 is a mapping of the elements of iron oxyhydroxide prepared in example five;
FIG. 5 is a HRTEM image of nitrogen-doped iron oxyhydroxide prepared in example six;
FIG. 6 is an elemental mapping plot of nitrogen-doped iron oxyhydroxide prepared according to example six;
FIG. 7 is a HRTEM image of a nitrogen, sulfur-doped iron oxyhydroxide prepared in example nine;
FIG. 8 is an elemental mapping plot of a nitrogen, sulfur-doped iron oxyhydroxide prepared in example nine;
FIG. 9 is a plot of electrocatalytic oxygen generation linear sweep voltammograms of cysteine functionally modified iron oxyhydroxide catalysts prepared from different molar amounts of L-cysteine and 2ml of triethanolamine prepared by examples one-four;
FIG. 10 is a plot of the electrocatalytic oxygen production linear sweep voltammograms of different volumes of triethanolamine-prepared iron oxyhydroxide catalysts prepared by the five to eight examples;
FIG. 11 is a linear sweep voltammogram of electrocatalytic oxygen production for iron oxyhydroxide catalysts prepared with different molar amounts of L-cysteine prepared in examples five and nine to twelve;
FIG. 12 is a linear sweep voltammogram of electrocatalytic oxygen production for iron oxyhydroxide catalysts prepared from different molar amounts of L-cysteine prepared in examples one-four;
FIG. 13 is a statistical plot of overpotential for Fe-urea-2mlTEOA-3mmolCys, Fe-urea-2mlTEOA, and Fe-urea at different current densities;
FIG. 14 is Fe-urea-2mlTEOA-3 mlTEOA, Fe-urea-2mlTEOA, Fe-urea-3 mlCys, Fe-urea and commercial RuO2Tafel plot of (1);
FIG. 15 is a graph showing the results of stability test of Fe-urea-2mlTEOA-3 mmolCys;
FIG. 16 is a plot of electrocatalytic oxygen generation linear voltammograms of Fe-urea-1mlMEA, Fe-urea-1mlDEA, Fe-urea-1mlTEOA, Fe-urea-1mlEDA, and Fe-urea-1 mlTEA.
Detailed Description
The above and further features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
The preparation method of the cysteine functionalized modified hydroxyl oxidation ferroelectric catalyst comprises the following steps:
s1, uniformly mixing ferric nitrate and urea in deionized water according to the molar ratio of 1: 5 to obtain a first mixed solution;
s2, mixing the first mixed solution and triethanolamine according to the volume ratio of 10-80: 1 to obtain a second mixed solution;
s3, mixing and stirring the second mixed solution and L-cysteine uniformly according to the concentration ratio of 25-125 mmol/L to obtain a third mixed solution;
s4, placing the third mixed solution in a high-pressure reaction kettle, and preparing cysteine functionalized modified iron oxyhydroxide by a hydrothermal method;
s5, adding the washed and dried cysteine functionalized modified iron oxyhydroxide into a Nafion solution to mix, wherein the concentration is 5mg/mL, uniformly coating the mixture on foamed nickel after ultrasonic treatment, and naturally airing to obtain the cysteine functionalized modified iron oxyhydroxide catalyst.
In step S2, the triethanolamine may be replaced by other alcohol amines, such as ethanolamine and diethanolamine.
In the step S4, the hydrothermal reaction is carried out at 120 ℃ for 12 h.
In the step S5, the cysteine-functionalized modified iron oxyhydroxide obtained is centrifugally filtered and washed with deionized water, and dried at 60 ℃ for 12 hours, wherein the mass concentration of the Nafion solution is 5%.
The catalyst comprises a foamed nickel substrate and a cysteine functionalized modified iron oxyhydroxide catalyst layer coated and molded on the foamed nickel substrate.
According to the preparation method of the cysteine functionalized modified iron oxyhydroxide catalyst, ferric nitrate, urea, triethanolamine and L-cysteine are added into deionized water to be mixed and stirred uniformly, the cysteine functionalized modified iron oxyhydroxide can be prepared by adopting a one-step hydrothermal method, the doping process is simple, and the cysteine functionalized modified iron oxyhydroxide is coated on foamed nickel to prepare the catalyst layer, so that the cysteine functionalized modified iron oxyhydroxide catalyst can be obtained.
The prepared cysteine functionalized modified iron oxyhydroxide catalyst has excellent catalytic performance when applied to electrochemical Oxygen Evolution Reaction (OER), and can catalyze the decomposition of water to generate oxygen at the current density of 20mA/cm2The overpotential in this case was 272 mV. Tafel slope of 61mV/dec, a significant improvement over the undoped iron oxyhydroxide catalyst. The cysteine-functionalized modified iron oxyhydroxide catalyst prepared by the method of the invention was subjected to an application of 20mA/cm2The electrocatalytic oxygen evolution performance of the catalyst is still stable after the current is 24 hours, so the cysteine functionalized modified hydroxyl oxidized ferroelectric catalyst has good industrial application prospect.
Example one
In this embodiment, the preparation method of the cysteine functionalized modified iron oxyhydroxide catalyst according to the present invention includes the following steps:
s1, uniformly mixing 2mmol of ferric nitrate and 10mmol of urea in 40ml of deionized water according to the molar ratio of 1: 5 to obtain a first mixed solution;
s2, mixing the first mixed solution and 2ml of triethanolamine according to the volume ratio of 20: 1 to obtain a second mixed solution;
s3, mixing and stirring the second mixed solution and 3mmol of L-cysteine uniformly to obtain a third mixed solution;
s4, placing the third mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, placing the high-pressure reaction kettle into a vacuum drying box, heating to 120 ℃, and preserving heat for 12 hours to obtain cysteine functionalized modified iron oxyhydroxide;
s5, adding 10mg of washed and dried cysteine functionalized modified iron oxyhydroxide into a mixed solution of 1.5ml of ethanol and 0.5ml of deionized water, adding 60 mu l of Nafion solution, ultrasonically mixing for 1h, then uniformly coating 20 mu l of the mixed solution on foamed nickel, and naturally airing to obtain the cysteine functionalized modified iron oxyhydroxide decomposition oxygen evolution catalyst which is marked as Fe-urea-2ml TEOA-3mmol Cys.
The prepared cysteine functionalized modified iron oxyhydroxide catalyst comprises a foamed nickel matrix and a catalyst layer, has the functions of both a catalyst and an electrode, is convenient to use, is used for electrolyzing water to prepare oxygen, and can simplify the process flow.
The TEM and element mapping of the cysteine-functionalized modified iron oxyhydroxide prepared in step S4 of this example are shown in fig. 1 and 2, respectively.
As can be seen from FIGS. 1 and 2, Fe-urea-2mlTEOA-3mmolCys has a hexagonal columnar structure, and Fe, C, N, S and O elements are uniformly distributed.
Applying 20mA/cm to Fe-urea-2mlTEOA-3mmolCys2The stability of Fe-urea-2mlTEOA-3mmolCys was tested at 24h current and the results are shown in FIG. 15. From the results in FIG. 15, it can be seen that 20mA/cm was applied to Fe-urea-2mlTEOA-3mmolCys2After the current is 24 hours, the electrocatalytic oxygen evolution performance of the catalyst still keeps stable, and the catalyst is suitable for industrial application.
Example two
This example prepared a cysteine functionalized modified iron oxyhydroxide catalyst, designated as Fe-urea-2ml TEOA-1mmol Cys, using 1mmol L-cysteine instead of 3mmol L-cysteine in one step S3 of the example.
Other embodiments are as in example one.
EXAMPLE III
This example prepared a cysteine functionalized modified iron oxyhydroxide catalyst, designated as Fe-urea-2ml TEOA-2mmol Cys, using 2mmol of L-cysteine instead of 3mmol of L-cysteine in one step S3 of the example.
Other embodiments are as in example one.
Example four
This example prepared a cysteine functionalized modified iron oxyhydroxide catalyst, designated as Fe-urea-2ml TEOA-4mmol Cys, using 4mmol L-cysteine instead of 3mmol L-cysteine in one step S3 of the example.
Other embodiments are as in example one.
The performance of the cysteine functionalized modified iron oxyhydroxide catalysts prepared in the first to fourth embodiments is tested for the oxygen production performance of the water by electrocatalytic decomposition by adopting a three-electrode system on an electrochemical workstation, and the specific process is as follows:
respectively taking Fe-urea-2mlTEOA-1mmolCys, Fe-urea-2mlTEOA-2mmolCys, Fe-urea-2mlTEOA-3mmolCys and Fe-urea-2mlTEOA-4mmolCys as working electrodes, a platinum sheet electrode as a counter electrode, an Ag/AgCl electrode as a reference electrode and 1mol/L potassium hydroxide solution as electrolyte, and testing the electrocatalytic oxygen generation linear sweep voltammetry curves of the nitrogen and sulfur doped iron oxyhydroxide catalyst prepared from different molar amounts of L-cysteine, wherein the electrocatalytic oxygen generation linear sweep voltammetry curves are shown in FIG. 9.
From the results in FIG. 9, it can be seen that the overpotential of the cysteine-functionalized modified iron oxyhydroxide catalyst prepared from 3mmol of L-cysteine is lower than that of the cysteine-functionalized modified iron oxyhydroxide catalyst prepared from other molar amounts of L-cysteine under the same current density condition, so that the electrocatalytic oxygen evolution performance of the cysteine-functionalized modified iron oxyhydroxide catalyst prepared from 3mmol of L-cysteine is better.
EXAMPLE five
This example provides a method of preparing an iron oxyhydroxide catalyst for comparison, comprising the steps of:
s1, uniformly mixing 2mmol of ferric nitrate and 10mmol of urea in 40ml of deionized water according to the molar ratio of 1: 5, pouring into a high-pressure reaction kettle with a polytetrafluoroethylene lining, putting into a vacuum drying oven, heating to 120 ℃, and preserving heat for 12 hours to obtain the ferric oxyhydroxide.
S2, adding 10mg of washed and dried iron oxyhydroxide into a mixed solution of 1.5ml of ethanol and 0.5ml of deionized water, adding 60ul of Nafion solution, carrying out ultrasonic mixing for 1h, then uniformly coating 20 mu l of the mixed solution on foamed nickel, and naturally airing to obtain the iron oxyhydroxide decomposition oxygen evolution catalyst which is recorded as Fe-urea.
The TEM and element mapping of the iron oxyhydroxide prepared in step S2 of this example are shown in fig. 3 and 4, respectively.
As can be seen from FIGS. 3 and 4, Fe-urea has a cubic granular structure, and Fe, C, N and O elements are uniformly distributed.
EXAMPLE six
This example provides a method for preparing a nitrogen-doped iron oxyhydroxide catalyst for comparison, comprising the steps of:
s1, uniformly mixing 2mmol of ferric nitrate and 10mmol of urea in 40ml of deionized water according to the molar ratio of 1: 5 to obtain a first mixed solution;
s2, mixing the first mixed solution and 2ml of triethanolamine according to the volume ratio of 20: 1 to obtain a second mixed solution;
s3, placing the second mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into a vacuum drying box, heating to 120 ℃, and preserving heat for 12 hours to obtain nitrogen-doped iron oxyhydroxide;
s4, adding 10mg of washed and dried nitrogen-doped iron oxyhydroxide into a mixed solution of 1.5ml of ethanol and 0.5ml of deionized water, adding 60ul of Nafion solution, carrying out ultrasonic mixing for 1h, then uniformly coating 20 mul of the mixed solution on foamed nickel, and naturally airing to obtain the nitrogen-doped iron oxyhydroxide water decomposition oxygen evolution catalyst which is marked as Fe-urea-2ml TEOA.
The TEM and element mapping of the nitrogen-doped iron oxyhydroxide prepared in step S3 of this example are shown in fig. 5 and 6, respectively.
As can be seen from FIGS. 5 and 6, Fe-urea-2ml TEOA has a fine granular structure, and Fe, C, N and O elements are uniformly distributed.
EXAMPLE seven
This example prepared a nitrogen doped iron oxyhydroxide catalyst, designated as Fe-urea-1ml TEOA, with 1ml of triethanolamine instead of 2ml of triethanolamine as in the six step S2 of the example.
Other embodiments are as in example six.
Example eight
This example prepared a nitrogen doped iron oxyhydroxide catalyst, designated as Fe-urea-3ml teoa, using 3ml of triethanolamine instead of 2ml of triethanolamine as in the six step S2 of the example.
Other embodiments are as in example six.
The oxygen production performance of the nitrogen-doped iron oxyhydroxide catalysts prepared in the fifth to eighth embodiments is tested by adopting a three-electrode system on an electrochemical workstation through electrocatalytic decomposition, and the specific process is as follows:
fe-urea, Fe-urea-1mlTEOA, Fe-urea-2mlTEOA and Fe-urea-3mlTEOA are respectively used as working electrodes, a platinum sheet electrode is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, 1mol/L potassium hydroxide solution is used as electrolyte, and the electrocatalytic oxygen production linear scanning voltammogram of the nitrogen-doped iron oxyhydroxide catalyst prepared by triethanolamine with different volumes is tested, and is shown in figure 10.
From the results of fig. 10, it can be seen that the overpotential of the nitrogen-doped iron oxyhydroxide catalyst prepared from 2ml of triethanolamine is lower than that of the nitrogen-doped iron oxyhydroxide catalyst prepared from other volumes of triethanolamine under the same current density condition, and thus the electrocatalytic oxygen evolution performance of the nitrogen-doped iron oxyhydroxide catalyst prepared from 2ml of triethanolamine is superior.
Example nine
This example provides a method for preparing a nitrogen and sulfur doped iron oxyhydroxide catalyst for comparison, comprising the steps of:
s1, uniformly mixing 2mmol of ferric nitrate and 10mmol of urea in 40ml of deionized water according to the molar ratio of 1: 5 to obtain a first mixed solution;
s2, mixing and stirring the first mixed solution and 3mmol of L-cysteine uniformly to obtain a second mixed solution;
s3, placing the second mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into a vacuum drying box, heating to 120 ℃, and preserving heat for 12 hours to obtain nitrogen and sulfur doped iron oxyhydroxide;
s4, adding 10mg of washed and dried nitrogen-doped iron oxyhydroxide into a mixed solution of 1.5ml of ethanol and 0.5ml of deionized water, adding 60ul of Nafion solution, carrying out ultrasonic mixing for 1h, then uniformly coating 20 mul of the mixed solution on foamed nickel, and naturally airing to obtain the nitrogen-sulfur-doped iron oxyhydroxide water decomposition oxygen evolution catalyst which is marked as Fe-urea-3 mmols Cys.
The TEM and element mapping of the nitrogen-doped iron oxyhydroxide prepared in step S3 of this example are shown in fig. 7 and 8, respectively.
As can be seen from FIGS. 7 and 8, Fe-urea-3mmolCys is an ultrathin nanosheet structure, and Fe, C, N, O and S elements are uniformly distributed.
Example ten
This example prepared a nitrogen, sulfur doped iron oxyhydroxide catalyst, designated as Fe-urea-1mmolCys, using 1mmol of L-cysteine instead of 3mmol of L-cysteine in step S2 of example nine.
Other embodiments are as in example nine.
EXAMPLE eleven
This example prepared a nitrogen, sulfur doped iron oxyhydroxide catalyst, designated as Fe-urea-2mmolCys, using 2mmol of L-cysteine instead of 3mmol of L-cysteine in step S2 of example nine.
Other embodiments are as in example nine.
Example twelve
This example prepared a nitrogen, sulfur doped iron oxyhydroxide catalyst, designated as Fe-urea-4mmolCys, using 4mmol of L-cysteine instead of 3mmol of L-cysteine in step S2 of example nine.
Other embodiments are as in example nine.
A three-electrode system is adopted on an electrochemical workstation to test the oxygen production performance of the nitrogen and sulfur doped iron oxyhydroxide catalyst prepared in the fifth embodiment and the ninth to twelfth embodiment by the electrocatalytic decomposition, and the specific process is as follows:
respectively taking Fe-urea, Fe-urea-1mmolCys, Fe-urea-2mmolCys, Fe-urea-3mmolCys and Fe-urea-4mmolCys as working electrodes, a platinum sheet electrode as a counter electrode, an Ag/AgCl electrode as a reference electrode and 1mol/L potassium hydroxide solution as electrolyte, and testing the electrocatalytic oxygen generation linear scanning voltammetry curve of the nitrogen and sulfur doped iron oxyhydroxide catalyst prepared from L-cysteine with different molar amounts, wherein the electrocatalytic oxygen generation linear scanning voltammetry curve is shown in figure 11.
From the results in FIG. 11, it is seen that the overpotential of the nitrogen-and sulfur-doped iron oxyhydroxide catalyst prepared from 3mmol of L-cysteine is lower than that of the nitrogen-and sulfur-doped iron oxyhydroxide catalyst prepared from other molar amounts of L-cysteine under the same current density condition, and therefore the electrocatalytic oxygen evolution performance of the nitrogen-and sulfur-doped iron oxyhydroxide catalyst prepared from 3mmol of L-cysteine is superior.
EXAMPLE thirteen
This example is for commercial RuO2The capability of the catalyst for electrically catalyzing and decomposing water to generate oxygen is tested and is matched with Fe-urea-2ml TEOA-3mmolCys, Fe-urea-2ml TEOA, Fe-urea-3mmolCys, Fe-urea were compared, respectively. The specific contents are as follows:
testing of commercial RuO using a three-electrode system on an electrochemical workstation2The capability of the catalyst for electrocatalytic decomposition of water to produce oxygen is specifically tested in the following process:
in commercial RuO2A working electrode, a platinum sheet electrode as a counter electrode, an Ag/AgCl electrode as a reference electrode and 1mol/L potassium hydroxide solution as electrolyte are used for testing the commercial RuO2The electrocatalytic oxygen production linear sweep voltammogram of (a) is shown in fig. 12.
From the results in FIG. 12, it can be seen that Fe-urea-2mlTEOA-3mmolCys, Fe-urea-2mlTEOA, Fe-urea-3mmolCys and commercial RuO were compared2The electrocatalytic oxygen production performance of Fe-urea-2mlTEOA-3mmolCys is found to be superior to that of Fe-urea and commercial RuO2And the electrocatalytic oxygen production performance of Fe-urea-2mlTEOA-3mmolCys is superior to that of Fe-urea-2mlTEOA and Fe-urea-3 mmolCys. Therefore, the nitrogen and sulfur doped iron oxyhydroxide has better electrocatalytic oxygen evolution performance than the undoped iron oxyhydroxide catalyst.
Example fourteen
This example tests the overpotentials and Tafel curves of Fe-urea-2mlTEOA-3mmolCys, Fe-urea-2mlTEOA, and Fe-urea at different current densities to compare the electrocatalytic decomposition of water to oxygen production capabilities of Fe-urea-2mlTEOA-3mmolCys, Fe-urea-2mlTEOA, and Fe-urea. The specific process is as follows:
fe-ura-2 mlTEOA-3mmolCys is taken as a working electrode, a platinum sheet electrode is taken as a counter electrode, an Ag/AgCl electrode is taken as a reference electrode, 1mol/L potassium hydroxide solution is taken as electrolyte, and the current density is respectively set to be 20mA/cm2、50mA/cm2、100mA/cm2And testing the overpotential of Fe-urea-2mlTEOA-3mmolCys under different current densities, wherein a statistical chart of the overpotential under different current densities is shown in FIG. 13.
Fe-urea-2ml TEOA is taken as a working electrode, a platinum sheet electrode is taken as a counter electrode, an Ag/AgCl electrode is taken as a reference electrode, 1mol/L potassium hydroxide solution is taken as electrolyte, and the current density is respectively set to be 20mA/cm2、50mA/cm2、100mA/cm2The overpotential of Fe-urea-2ml TEOA was tested at different current densities, and a statistical chart of the overpotential at different current densities is shown in FIG. 13.
Fe-urea is taken as a working electrode, a platinum sheet electrode is taken as a counter electrode, an Ag/AgCl electrode is taken as a reference electrode, 1mol/L potassium hydroxide solution is taken as electrolyte, and the current density is respectively set to be 20mA/cm2、50mA/cm2、100mA/cm2And testing overpotential of Fe-urea under different current densities, wherein a statistical chart of the overpotential under different current densities is shown in FIG. 13.
FIG. 14 is Fe-urea-2mlTEOA-3 mlTEOA, Fe-urea-2mlTEOA, Fe-urea-3 mlCys, Fe-urea and commercial RuO2Tafel curve of (1).
As is clear from the results in FIG. 13, the current densities were 20mA/cm, respectively2、50mA/cm2And 100mA/cm2When the over-potential is 272mV, 300mV and 318mV corresponding to Fe-urea-2mlTEOA-3mmolCys, 309mV, 331mV and 348mV corresponding to Fe-urea-2mlTEOA, 348mV, 375mV and 398mV corresponding to Fe-urea, respectively, the lower the over-potential is, the faster the reaction speed is, the less energy is consumed, and the better the oxygen evolution performance is, so the electrocatalytic oxygen evolution performance of the nitrogen and sulfur doped iron oxyhydroxide catalyst is superior to that of the undoped iron oxyhydroxide catalyst.
From the results in FIG. 14, it is clear that the Tafel slope of Fe-urea-2ml TEOA-3mmol Cys is 61mV/dec for commercial RuO2The gradient of the catalyst is 88mV/dec, the Tafel gradient represents the difficulty of electrochemical reaction, the smaller the gradient is, the more easily the electrochemical reaction is generated, therefore, the oxygen evolution performance of the nitrogen and sulfur doped iron oxyhydroxide catalyst is better than that of the commercial RuO2。
Example fifteen
This example prepared a nitrogen-doped iron oxyhydroxide catalyst, designated as Fe-urea-1mlMEA, using 1ml of ethanolamine instead of 1ml of triethanolamine as in example seven.
Other embodiments are as in example seven.
Example sixteen
This example prepared a nitrogen-doped iron oxyhydroxide catalyst, designated as Fe-urea-1mlDEA, using 1ml of diethanolamine instead of 1ml of triethanolamine as in example seven.
Other embodiments are as in example seven.
Example seventeen
This example prepared a nitrogen doped iron oxyhydroxide catalyst, designated as Fe-urea-1ml EDA, using 1ml of ethylenediamine instead of 1ml of triethanolamine as in example seven.
Other embodiments are as in example seven.
EXAMPLE eighteen
This example prepared a nitrogen-doped iron oxyhydroxide catalyst, designated as Fe-urea-1ml TEA, using 1ml of triethylamine instead of 1ml of triethanolamine as in example seven.
Other embodiments are as in example seven.
The performance of oxygen production by electrocatalytic decomposition of water by the nitrogen-doped iron oxyhydroxide catalyst prepared in the seventh and fifteenth to eighteen examples was tested by a three-electrode system on an electrochemical workstation, and the specific process was as follows:
respectively taking Fe-urea-1mlMEA, Fe-urea-1mlDEA, Fe-urea-1mlTEOA, Fe-urea-1mlEDA and Fe-urea-1mlTEA as working electrodes, taking a platinum sheet electrode as a counter electrode, taking an Ag/AgCl electrode as a reference electrode and taking 1mol/L potassium hydroxide solution as electrolyte, testing the electrocatalytic oxygen production linear scanning voltammetry curve of the nitrogen-doped iron oxyhydroxide catalyst prepared from different amines, wherein the electrocatalytic oxygen production linear scanning voltammetry curve is shown in figure 16. From the results in fig. 16, it can be seen that under the same current density condition, the overpotential of the nitrogen-doped iron oxyhydroxide catalyst prepared from 1m1 triethanolamine and 1ml diethanolamine is smaller than that of the nitrogen-doped iron oxyhydroxide catalyst prepared from other amine substances, so the functionally modified iron oxyhydroxide prepared with the assistance of the alcohol amine substances has excellent electrocatalytic oxygen evolution performance.
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. A preparation method of a cysteine functionalized modified hydroxyl oxidation ferroelectric catalyst is characterized by comprising the following steps:
s1, mixing ferric nitrate and urea according to a ratio of 1: 5 in deionized water to obtain a first mixed solution;
s2, mixing the first mixed solution and the alcohol amine solution according to the ratio of 10-80: 1 to obtain a second mixed solution;
s3, mixing and stirring the second mixed solution and L-cysteine according to the concentration ratio of 25 mmol/L-125 mmol/L to obtain a third mixed solution;
s4, placing the third mixed solution in a high-pressure reaction kettle, and preparing cysteine functionalized modified iron oxyhydroxide by a hydrothermal method;
s5, adding the washed and dried cysteine functionalized modified iron oxyhydroxide into a Nafion solution to mix, wherein the concentration is 5mg/mL, uniformly performing ultrasonic treatment, coating the mixture on foamed nickel, and naturally airing to obtain the cysteine functionalized modified iron oxyhydroxide catalyst;
in the step S2, the alcohol amine solution is triethanolamine, ethanolamine, or diethanolamine.
2. The method for preparing a cysteine-functionalized modified ferroelectric hydroxy oxide catalyst according to claim 1, wherein the hydrothermal reaction temperature in step S4 is 120 ℃ and the reaction time is 12 h.
3. The method according to claim 1, wherein in step S5, the obtained cysteine functionalized and modified iron oxyhydroxide is centrifugally filtered and washed with deionized water, and dried at 60 ℃ for 12h, and the mass concentration of the Nafion solution is 5%.
4. An electrocatalyst, prepared by the method of preparing a cysteine functionalized modified ferroelectric oxyhydroxide catalyst according to any one of claims 1 to 3, comprising a foamed nickel substrate and a shaped cysteine functionalized modified ferroelectric oxyhydroxide catalytic layer coated on the foamed nickel substrate.
5. Use of a cysteine functionalized modified iron oxyhydroxide prepared by the method for preparing a cysteine functionalized modified iron oxyhydroxide ferroelectric catalyst according to any one of claims 1 to 3 for water dissociation oxygen evolution reactions.
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