CN115322387A - Method for preparing two-dimensional metal-organic framework electrocatalyst through double-regulator competitive coordination - Google Patents
Method for preparing two-dimensional metal-organic framework electrocatalyst through double-regulator competitive coordination Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 24
- 230000002860 competitive effect Effects 0.000 title claims abstract description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 42
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 22
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims abstract description 21
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 17
- -1 transition metal salt Chemical class 0.000 claims abstract description 15
- 239000013110 organic ligand Substances 0.000 claims abstract description 12
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000001632 sodium acetate Substances 0.000 claims abstract description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000004108 freeze drying Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 8
- 229960002089 ferrous chloride Drugs 0.000 claims description 7
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 239000012670 alkaline solution Substances 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 36
- 239000012973 diazabicyclooctane Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 19
- 238000001878 scanning electron micrograph Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000004502 linear sweep voltammetry Methods 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002135 nanosheet Substances 0.000 description 7
- 238000000527 sonication Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 238000003556 assay Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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Abstract
The invention discloses a method for preparing a two-dimensional metal-organic framework electrocatalyst by double-regulator competitive coordination. The method comprises the steps of dissolving terephthalic acid and triethylene diamine in N' N-dimethylformamide by ultrasonic waves to form an organic ligand solution, then uniformly mixing the organic ligand solution with a transition metal salt aqueous solution, adding sodium acetate and pyridine as regulators, and carrying out hydrothermal reaction to obtain the ultrathin two-dimensional MOFs electrocatalyst. The method is simple, and the two-dimensional MOFs electro-catalysts with different sizes can be obtained only by simply adjusting the dosage of pyridine and sodium acetate. The two-dimensional metal organic framework material electrocatalyst prepared by the invention can not be dissolved in alkaline solution, and has excellent electrocatalytic oxygen production performance and good cycle stability.
Description
Technical Field
The invention relates to a method for preparing a two-dimensional metal-organic framework electrocatalyst through double-regulator competitive coordination, belonging to the field of nano material preparation.
Background
The Metal Organic Framework (MOFs) compound is a porous coordination polymer with periodicity, which is self-assembled by taking metal ions as a connecting center and taking organic ligands as a bridging body. Because of the large specific surface area, rich pore channel structure, designable topological unit and flexible and adjustable composition, the MOFs has become one of the frontiers and hot spots of OER electrocatalyst research. Dimension tuning is a common strategy for performance optimization of MOFs-based electrocatalytic catalysts. Materials can be classified into zero-dimensional, one-dimensional, two-dimensional, and three-dimensional materials according to the direction and size of the dimension. Two-dimensional materials exhibit many peculiar properties because of their physical and chemical changes confined in two-dimensional planes, and are receiving continuous attention from researchers. For two-dimensional MOFs-based nanoplates: on one hand, the huge specific surface, high exposed metal active sites and the nanometer confinement effect of a two-dimensional material are combined; on the other hand, the structure morphology is adjustable, if the thickness of the two-dimensional MOFs-based nanosheet can be adjusted to be thin enough, the transport channel is shortened, and the quality transmission efficiency and the electron transfer efficiency are more excellent. However, the preparation method of two-dimensional MOFs-based nanosheets shows great difficulty. Common top-down peeling methods such as a mechanical peeling method, a liquid phase peeling method, an ion intercalation method and the like are difficult to damage the secondary bond acting force between layers, and meanwhile, a small amount of peeled two-dimensional nanosheets are easy to generate secondary agglomeration, so that the efficiency is low. In the existing reported growth method, due to the lack of growth driving force in the two-dimensional direction, the prepared two-dimensional MOFs-based nanosheet is difficult to realize the breakthrough of atomic scale. The nano plate is prepared by a hydrothermal method from bottom to top, but the material obtained by direct hydrothermal is thicker in thickness and larger in size, and is not beneficial to the exposure of a reaction active center in an electrocatalysis process. Document 1 (Chin. Chem. Lett.2020,31,2280). In addition, the existing two-dimensional MOFs nanosheets are difficult to keep stable in acid/alkaline solutions, and the application of the two-dimensional MOFs in the aspect of electrocatalytic decomposition of water to generate oxygen is greatly limited by the difficulties.
Disclosure of Invention
The invention aims to provide a method for preparing a two-dimensional metal-organic framework electrocatalyst by double-regulator competitive coordination.
The technical solution for realizing the purpose of the invention is as follows:
the method for preparing the two-dimensional metal-organic framework electrocatalyst by double regulator competitive coordination comprises the following steps:
and 2, uniformly mixing the organic ligand solution and the aqueous solution of the transition metal salt, adding sodium acetate and pyridine as regulators, carrying out hydrothermal reaction at 120 +/-10 ℃, centrifuging, washing with water, and freeze-drying after the reaction is finished to obtain the two-dimensional MOFs electrocatalyst.
Preferably, in the step 1, the ultrasonic treatment time is 1-2 min.
Preferably, in step 1, the molar ratio of BDC to DABCO is 2:1.
Preferably, in the step 1, in the organic ligand solution, the concentration of BDC is 0.01mol/L, and the concentration of DABCO is 0.005mol/L.
Preferably, in step 2, the transition metal salt is selected from one or two of nickel chloride hexahydrate, ferrous chloride tetrahydrate, cobalt nitrate hexahydrate and copper nitrate trihydrate.
Preferably, in step 2, the concentration of the aqueous solution of the transition metal salt is 0.004mol/L.
Preferably, in step 2, the molar weight of pyridine is 20 to 30 times that of terephthalic acid.
Preferably, in step 2, the molar amount of sodium acetate is 10 times that of terephthalic acid.
Preferably, in the step 2, the hydrothermal reaction time is 12 +/-2 h.
Preferably, in step 2, the freeze-drying time is 7-8 h.
Compared with the prior art, the invention has the advantages that:
(1) Pyridine coordinates to the amino groups on the MOFs, sodium acetate coordinates to the carboxylic acids on the MOFs, pyridine restricts growth in the horizontal direction of the material, and sodium acetate restricts growth in the vertical direction of the material.
(2) The preparation method of the catalyst is simple, and the two-dimensional metal organic framework material electro-catalysts with different sizes can be obtained only by simply adjusting the dosage of pyridine and sodium acetate.
(3) The obtained catalyst has uniform appearance, and all nanosheets have ultrathin thickness, thereby being beneficial to ion transmission and exposing active sites.
(4) The two-dimensional metal organic framework material electrocatalyst prepared by the invention can not be dissolved in alkaline solution, has excellent electrocatalytic oxygen production performance, and has current density reaching 10mA/cm 2 The required overpotential is only 269mV, tafel value is 100.7mv/dec, and the cycling stability is good.
Drawings
FIG. 1 is a schematic flow diagram of a process for preparing a two-dimensional metal-organic framework electrocatalyst according to the invention with dual mediator competitive coordination.
FIG. 2 is an FTIR spectrum of the Ni/Fe-BDC-DABCO-10-20 sample of example 1.
FIG. 3 is an SEM image of a Ni/Fe-BDC-DABCO-10-20 sample of example 1.
FIG. 4 is an XRD pattern of the Ni/Fe-BDC-DABCO-10-20 sample of example 1.
FIG. 5 is (a) a linear sweep voltammetry test and (b) a Tafel plot for the Ni/Fe-BDC-DABCO-10-20 sample of example 1.
FIG. 6 is a cycle test plot of the Ni/Fe-BDC-DABCO-10-20 sample of example 1.
FIG. 7 is an SEM image of a Ni/Fe-BDC-DABCO-10-30 sample of example 2.
FIG. 8 is an XRD pattern of the Ni/Fe-BDC-DABCO-10-30 sample of example 2.
FIG. 9 is (a) a linear sweep voltammetry test and (b) a Tafel plot for the Ni/Fe-BDC-DABCO-10-30 sample of example 2.
FIG. 10 is an SEM image of a Ni/Fe-BDC-DABCO-0-0 sample of comparative example 1.
FIG. 11 is an XRD pattern of the Ni/Fe-BDC-DABCO-0-0 sample of comparative example 1.
FIG. 12 is (a) a linear sweep voltammetry test and (b) a Tafel plot for the Ni/Fe-BDC-DABCO-0-0 sample of comparative example 1.
FIG. 13 is an SEM image of a Ni/Fe-BDC-DABCO-10-0 sample of comparative example 2.
FIG. 14 is an SEM image of a Ni/Fe-BDC-DABCO-0-20 sample of comparative example 3.
FIG. 15 is an SEM image of a Ni-BDC-DABCO sample of comparative example 4.
FIG. 16 is an XRD pattern of the Ni-BDC-DABCO sample of comparative example 4.
FIG. 17 is a plot of (a) the linear sweep voltammetry test and (b) the Tafel plot for the Ni-BDC-DABCO sample of comparative example 4.
FIG. 18 is an SEM image of a Co-BDC-DABCO sample of comparative example 5.
FIG. 19 is an XRD pattern of a sample of Co-BDC-DABCO of comparative example 5.
FIG. 20 is an SEM image of a Cu-BDC-DABCO sample of comparative example 6.
FIG. 21 is an XRD pattern of the Cu-BDC-DABCO sample of comparative example 6.
FIG. 22 is a plot of (a) the linear sweep voltammetry test and (b) the Tafel plot for the Cu-BDC-DABCO sample of comparative example 6.
Detailed Description
The invention is further illustrated by the following examples and figures.
Example 1
And 2, weighing 50mg (0.2 mmol) of nickel chloride hexahydrate and 8mg (0.04 mmol) of ferrous chloride tetrahydrate in a beaker, adding 10mL of water, and performing ultrasonic dissolution uniformly to obtain the transition metal salt solution. Uniformly mixing the organic ligand solution and the transition metal salt solution, adding 272mg (2 mmol, the dosage of which is 10 times of that of BDC) of sodium acetate trihydrate and 316mg (4 mmol, the dosage of which is 20 times of that of BDC) of pyridine serving as regulators while stirring, then placing the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12 hours at 120 ℃; and (4) centrifugally extracting the hydrothermal product, washing with water, and freeze-drying to obtain the two-dimensional MOFs electrocatalyst. The resulting product was named Ni/Fe-BDC-DABCO-10-20.
FIG. 2 shows Ni/FeIR spectrum of BDC-DABCO-10-20, characteristic IR absorption Peak 3590cm -1 (-OH)；3200-3400cm -1 (N-H)；3040cm -1 (-CH)；1560cm -1 (-COOH)；1370cm -1 (-CN)；1010cm -1 (-CO). FIG. 3 shows an SEM image of the product Ni/Fe-BDC-DABCO-10-20 as homogeneous nanosheets with rugosities. The XRD pattern shown in FIG. 4 indicates the formation of the product Ni/Fe-BDC-DABCO-10-20.
Weighing 2mg of Ni/Fe-BDC-DABCO-10-20 and 0.4mg of conductive carbon black, uniformly dispersing into 400 mu L of deionized water, 100 mu L of isopropanol and 20 mu L of nafion (5 wt%) dispersion liquid, and carrying out ultrasonic treatment on the mixed liquid for 40 minutes; then 15 mu L of dispersion liquid is measured by a liquid transfer gun and dripped on a glassy carbon electrode with the diameter of 5mm, and a layer of catalyst film is obtained after room temperature drying. The electrocatalytic test was performed in a three-electrode test involving a carbon rod as counter electrode, a mercury/mercury oxide electrode as reference electrode, and 1M potassium hydroxide solution as electrolyte.
FIG. 5 is a linear sweep voltammetry test (LSV) of OER of Ni/Fe-BDC-DABCO-10-20 (a), and Tafel plot (b), and it can be seen that the current density reached 10mA/cm 2 The required overpotential is only 269mV, which shows that Ni/Fe-BDC-DABCO-10-20 has good electrocatalytic activity, and the lower Tafel value is 100.7mV/dec, which proves that the catalyst has good dynamic performance.
The cycle profile of Ni/Fe-BDC-DABCO-10-20, as shown in FIG. 6.a, after 500 cycles of cycle testing at a current density of 10mA/cm 2 No obvious change is caused before the lower overpotential cycle, and as can be seen from 6.b, no obvious attenuation of catalytic performance is seen after cycle test for more than 12h, which indicates that Ni/Fe-BDC-DABCO-10-20 has good cycle stability.
Example 2
The reaction was carried out according to the procedure described in example 1, weighing 33.2mg (0.2 mmol) BDC and 11.2mg (0.1 mmol) DABCO into a beaker, adding 20mL LDMF, dissolving with ultrasound uniformly and recording as solution A. 50mg (0.2 mmol) of nickel chloride hexahydrate and 8mg (0.04 mmol) of ferrous chloride tetrahydrate are weighed into another beaker, 10mL of water is added, and the mixture is dissolved uniformly by ultrasonic sound and marked as solution B. Mixing the solution A and the solution B, adding 272mg (2 mmol, the dosage of which is 10 times of that of BDC) of sodium acetate trihydrate and 474mg (6 mmol, the dosage of which is 30 times of that of BDC) of pyridine serving as regulators while stirring, then placing the mixed solution in a polytetrafluoroethylene hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12 hours at 120 ℃; and centrifuging, washing and freeze-drying the hydrothermal product to obtain the two-dimensional MOFs electrocatalyst. The resulting product was named Ni/Fe-BDC-DABCO-10-30. FIG. 7 shows an SEM image of Ni/Fe-BDC-DABCO-10-30, which is a two-dimensional sheet material. The XRD pattern shown in FIG. 8 indicates the formation of the product Ni/Fe-BDC-DABCO-10-30.
FIG. 9 is a linear sweep voltammetry test (LSV) (a) of OER of Ni/Fe-BDC-DABCO-10-30, and a Tafel plot (b), and it can be seen that the current density reached 10mA/cm 2 The required overpotential is only 225mV, which shows that Ni/Fe-BDC-DABCO-10-30 has better electrocatalytic activity and a lower Tafel value of 149.4mV/dec, and proves that the catalyst has good dynamic performance.
Comparative example 1
The reaction was carried out according to the procedure in example 1 without addition of a regulator, and 33.2mg (0.2 mmol) of BDC and 11.2mg (0.1 mmol) of DABCO were weighed out in a beaker, and 20ml of DMF was added and dissolved by sonication to give a solution A. 50mg (0.2 mmol) of nickel chloride hexahydrate and 8mg (0.04 mmol) of ferrous chloride tetrahydrate are weighed into another beaker, 10mL of water is added, and the mixture is dissolved uniformly by ultrasonic waves and is marked as a solution B. Uniformly mixing the solution A and the solution B, placing the mixture in a polytetrafluoroethylene hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12 hours at 120 ℃; and centrifuging, washing and freeze-drying the hydrothermal product to obtain the two-dimensional MOFs electrocatalyst. The resulting product was named Ni/Fe-BDC-DABCO-0-0.
FIG. 10 shows an SEM image of Ni/Fe-BDC-DABCO-0-0, which is a two-dimensional sheet material. The XRD pattern shown in FIG. 11 indicates the formation of the product Ni/Fe-BDC-DABCO-0-0. The OER activity assay of Ni/Fe-BDC-DABCO-0-0 is presented in FIG. 12. The results show that when Ni/Fe-BDC-DABCO-0-0 is used as an OER catalyst, 10mA/cm is reached 2 The current density of (1) requires 298mV overpotential, and the Tafel value is 114mV/dec.
Comparative example 2
The reaction was carried out according to the procedure in example 1, using only sodium acetate as regulator, weighing 33.2mg (0.2 mmol) BDC,11.2mg (0.1 mmol) DABCO into a beaker, adding 20ml DMF, dissolving by sonication until homogeneous, and recording as solution A. 50mg (0.2 mmol) of nickel chloride hexahydrate and 8mg (0.04 mmol) of ferrous chloride tetrahydrate are weighed into another beaker, 10mL of water is added, and the mixture is dissolved uniformly by ultrasonic sound and marked as solution B. Uniformly mixing the solution A and the solution B, adding 272mg (2 mmol, the dosage is 10 times of BDC) of sodium acetate trihydrate as a regulator while stirring, then placing the mixed solution in a polytetrafluoroethylene hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12 hours at 120 ℃; (ii) a And centrifuging, washing and freeze-drying the hydrothermal product to obtain the two-dimensional MOFs electrocatalyst. The resulting product was named Ni/Fe-BDC-DABCO-10-0. FIG. 13 shows an SEM of Ni/Fe-BDC-DABCO-10-0, where it can be seen that a regular uniform morphology was not obtained with the addition of sodium acetate alone as a modifier.
Comparative example 3
The reaction was carried out according to the procedure in example 1 using only pyridine as a modifier, and 33.2mg (0.2 mmol) of BDC and 11.2mg (0.1 mmol) of DABCO were weighed out in a beaker, and 20ml of DMF was added and dissolved by sonication to obtain solution A. 50mg (0.2 mmol) of nickel chloride hexahydrate and 8mg (0.04 mmol) of ferrous chloride tetrahydrate are weighed into another beaker, 10mL of water is added, and the mixture is dissolved uniformly by ultrasonic sound and marked as solution B. Mixing the solution A and the solution B, adding 316mg (4 mmol, the dosage is 20 times of that of terephthalic acid) of pyridine as a regulator while stirring, then placing the mixed solution in a polytetrafluoroethylene hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12 hours at 120 ℃; and centrifuging, washing and freeze-drying the hydrothermal product to obtain the two-dimensional MOFs electrocatalyst. The resulting product was named Ni/Fe-BDC-DABCO-0-20. As can be seen from the SEM image of Ni/Fe-BDC-DABCO-0-20 shown in FIG. 14, the morphology was irregular and uneven when only pyridine was added as a modifier, and the target morphology could not be obtained when a single modifier was added, as is clear from the comparison example 2.
Comparative example 4
The reaction was carried out by referring to the procedure in example 1 with addition of only nickel chloride, and 33.2mg (0.2 mmol) of BDC and 11.2mg (0.1 mmol) of DABCO were weighed out in a beaker, and 20ml of DMF was added and dissolved by sonication to obtain a solution A. 50mg (0.2 mmol) of nickel chloride hexahydrate in another beaker, 10mL of water was added and dissolved by sonication until homogeneous, and the solution was recorded as solution B. Mixing solution AAdding 272mg (2 mmol, the dosage is 10 times of BDC) of sodium acetate trihydrate and 158mg (2 mmol, the dosage is 10 times of BDC) of pyridine serving as regulators into the solution B while stirring, then placing the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12 hours at 120 ℃; and centrifuging, washing and freeze-drying the hydrothermal product to obtain the two-dimensional MOFs electrocatalyst. The resulting product was named Ni-BDC-DABCO. FIG. 15 shows an SEM image of Ni-BDC-DABCO, which is a two-dimensional sheet material. The XRD pattern shown in FIG. 16 indicates the formation of the product Ni-BDC-DABCO. The OER activity assay for Ni-BDC-DABCO is presented in FIG. 17. The results show that when Ni-BDC-DABCO is used as an OER catalyst, 10mA/cm is reached 2 The current density of (2) needs an over-potential of 420mV, and the Tafel value is 233mV/dec. The electrocatalytic activity and kinetic performance are much lower than that of Ni-Fe-BDC-DABCO with two metals added.
Comparative example 5
After the reaction was carried out by referring to the procedure in example 1 by adding only cobalt nitrate, 33.2mg (0.2 mmol) of BDC and 11.2mg (0.1 mmol) of DABCO were weighed out in a beaker, and 20ml of DMF was added thereto and dissolved by sonication to obtain a solution A. 58.2mg (0.2 mmol) of cobalt nitrate hexahydrate is weighed into another beaker, 10mL of water is added, and the mixture is dissolved uniformly by ultrasonic sound and marked as solution B. Mixing the solution A and the solution B, adding 272mg (2 mmol, the dosage of which is 10 times of the BDC) of sodium acetate trihydrate and 158mg (2 mmol, the dosage of which is 10 times of the BDC) of pyridine serving as regulators while stirring, then placing the mixed solution into a polytetrafluoroethylene hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12 hours at 120 ℃; and centrifuging, washing and freeze-drying the hydrothermal product to obtain the two-dimensional MOFs electrocatalyst. The resulting product was named Co-BDC-DABCO. FIG. 18 shows an SEM image of Co-BDC-DABCO, which is a two-dimensional sheet material. The XRD pattern shown in FIG. 19 indicates the formation of the product Co-BDC-DABCO. The results after OER activity tests show that Co-BDC-DABCO has no OER activity.
Comparative example 6
The reaction was carried out by referring to the procedure in example 1 with addition of only copper nitrate, weighing 33.2mg (0.2 mmol) of BDC and 11.2mg (0.1 mmol) of DABCO in a beaker, adding 20ml of DMF, and dissolving by sonication until homogeneous, and recording as solution A. 46mg (0.2 mmol) of copper nitrate trihydrate are weighed into a separate beaker and added10mL of water, the solution is dissolved uniformly by ultrasonic, and is marked as a B solution. Mixing the solution A and the solution B, adding 272mg (2 mmol, the amount is 10 times of BDC) of sodium acetate trihydrate and 158mg (2 mmol, the amount is 10 times of BDC) of pyridine as regulators while stirring, then placing the mixed solution in a polytetrafluoroethylene hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12 hours at 120 ℃; and centrifuging, washing and freeze-drying the hydrothermal product to obtain the two-dimensional MOFs electrocatalyst. The resulting product was named Cu-BDC-DABCO. FIG. 20 shows an SEM image of Cu-BDC-DABCO, which is a two-dimensional slab-like material. The XRD pattern shown in FIG. 21 indicates the formation of the product Cu-BDC-DABCO. OER activity assay of Cu-BDC-DABCO is presented in FIG. 22. The results show that when Cu-BDC-DABCO is used as an OER catalyst, 10mA/cm is reached 2 The current density of (1) needs an over-potential of 432mV, and the Tafel value is 149mV/dec.
Claims (10)
1. The method for preparing the two-dimensional metal-organic framework electrocatalyst by double-regulator competitive coordination is characterized by comprising the following steps of:
step 1, ultrasonically dissolving terephthalic acid and triethylene diamine in N' N-dimethylformamide to obtain an organic ligand solution;
and 2, uniformly mixing the organic ligand solution and the aqueous solution of the transition metal salt, adding sodium acetate and pyridine as regulators, carrying out hydrothermal reaction at 120 +/-10 ℃, centrifuging, washing with water, and freeze-drying after the reaction is finished to obtain the two-dimensional MOFs electrocatalyst.
2. The method according to claim 1, wherein in step 1, the ultrasound time is 1-2 min.
3. The process of claim 1 wherein in step 1, the molar ratio of terephthalic acid to triethylene diamine is 2:1.
4. The method according to claim 1, wherein in the step 1, the concentration of the terephthalic acid in the organic ligand solution is 0.01mol/L, and the concentration of the triethylene diamine in the organic ligand solution is 0.005mol/L.
5. The method according to claim 1, wherein in step 2, the transition metal salt is selected from one or two of nickel chloride hexahydrate, ferrous chloride tetrahydrate, cobalt nitrate hexahydrate, and copper nitrate trihydrate.
6. The method according to claim 1, wherein the concentration of the aqueous solution of the transition metal salt in step 2 is 0.004mol/L.
7. The method of claim 1, wherein in step 2, the molar amount of pyridine is 20 to 30 times that of terephthalic acid.
8. The process of claim 1, wherein in step 2, the molar amount of sodium acetate is 10 times that of terephthalic acid.
9. The method according to claim 1, wherein in step 2, the hydrothermal reaction time is 12 ± 2h.
10. The method according to claim 1, wherein the freeze-drying time in step 2 is 7 to 8 hours.
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| WO2017128049A1 (en) * | 2016-01-26 | 2017-08-03 | Xia, Ling | Mofs as catalysts for ring opening polymerization |
| WO2018046930A1 (en) * | 2016-09-08 | 2018-03-15 | Universitetet I Oslo | Process for the preparation of zirconium based mofs. |
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