CN111393662A - Polyacid-based metal organic complex for electrocatalytic hydrogen evolution electrode material under alkaline condition and application thereof - Google Patents
Polyacid-based metal organic complex for electrocatalytic hydrogen evolution electrode material under alkaline condition and application thereof Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 52
- 239000001257 hydrogen Substances 0.000 title claims abstract description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000007772 electrode material Substances 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910020628 SiW12O40 Inorganic materials 0.000 claims abstract description 17
- 229910001868 water Inorganic materials 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 12
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- JQGKKTUHZXGATO-UHFFFAOYSA-O N1=CC(=CC=C1)[N+]=1NN=NC=1 Chemical compound N1=CC(=CC=C1)[N+]=1NN=NC=1 JQGKKTUHZXGATO-UHFFFAOYSA-O 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- -1 3-pyridine tetrazole Chemical class 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
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- 238000002447 crystallographic data Methods 0.000 description 3
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- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
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- 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
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- 150000003536 tetrazoles Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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Abstract
A polyacid-based metal organic complex used for electrocatalytic hydrogen evolution electrode material under alkaline conditions has the following molecular formula: { Cu2(3‑bptz)3(H2O)4[SiW12O40]}·2H2O; the synthesis steps are as follows: adding CuCl2N, N' -bis (3-pyridyltetrazolium) -1,2 ethane and Na3SiW12O40Dissolving in deionized water, stirring with HCl solution for 30 min, adding into high pressure reactor, performing hydrothermal reaction at 120 deg.C, maintaining the temperature for 4 days, cooling to obtain green blocky crystal, alternately cleaning with deionized water and ethanol, and adding into a reactorAnd naturally airing at room temperature to obtain the product. The advantages are that: the electrode material has simple manufacturing process and low cost, and can be an electrode material with low equipment loss and high hydrogen evolution catalytic activity.
Description
Technical Field
The invention belongs to the field of electrocatalytic hydrogen evolution, and particularly relates to a polyacid-based metal organic complex for an electrocatalytic hydrogen evolution electrode material under an alkaline condition and application thereof.
Background
With the increasing demand for energy and the increasing problem of environmental pollution, the search for new energy sources to replace fossil fuels has become a major issue for all people. Hydrogen has been widely regarded as the most promising clean energy source in all countries of the world. At present, the hydrogen production method mainly takes industrial hydrogen production as a main raw material, takes petroleum, coal and natural gas as raw materials, and reacts with water vapor at high temperature to produce hydrogen. However, this method requires combustion of fossil fuel, and releases a large amount of carbon dioxide, which causes a series of environmental problems such as greenhouse effect.
The hydrogen is separated out by electrocatalysis water splitting as one of industrial hydrogen production modes, the hydrogen production by renewable energy sources is almost pollution-free, and the prepared hydrogen is quite clean. The electrocatalytic hydrogen splitting and hydrogen evolution is a recognized ideal hydrogen production method. The research on the mechanism of hydrogen evolution reaction can help us to improve the yield of hydrogen, including changing the reaction condition or adding a catalyst to lead the reaction to move to the required direction. Therefore, the selection of a proper electrode material to increase the control step rate has great significance for obtaining a catalytic hydrogen evolution electrode with high activity.
At present, an effective method for realizing large-scale hydrogen production by electrolyzing water and reducing electrolysis energy consumption is to reduce the cathode evolution potential of hydrogen and promote the reaction kinetics of the hydrogen evolution process. On the other hand, an acidic aqueous electrolyte is a commonly used catalytic reaction medium at present, but a preparation environment with an excessively low pH value has a certain loss to equipment, so that the acidic aqueous electrolyte is a preparation environment with a better application prospect in an alkaline electrolyte environment, but hydronium ions in the acidic electrolyte are lacked in the alkaline electrolyte, water molecules adsorbed on the surface of a material need to be directly cracked, extra energy is needed, and the electrocatalytic hydrogen evolution activity of a polyacid-based material needs to be further improved, so that an electrode material which can achieve both low equipment loss and high hydrogen evolution catalytic activity in the alkaline condition needs to be designed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a polyacid-based metal organic complex for an electrocatalytic hydrogen evolution electrode material under an alkaline condition and application thereof, wherein the electrode material is simple in manufacturing process and low in cost, and can be an electrode material with low equipment loss and high hydrogen evolution catalytic activity.
The technical scheme of the invention is as follows:
a polyacid-based metal organic complex used for electrocatalytic hydrogen evolution electrode material under alkaline conditions has the following molecular formula:
{Cu2(3-bptz)3(H2O)4[SiW12O40]}·2H2O；
wherein, the 3-bptz is N, N' -bis (3-pyridine tetrazole) -1,2 ethane.
Further, the specific synthesis steps of the complex are as follows:
adding CuCl2N, N' -bis (3-pyridyltetrazolium) -1,2 ethane and Na3SiW12O40Dissolving in deionized water to obtain CuCl2The molar ratio of the N, N' -bis (3-pyridyltetrazolium) -1,2 ethane to the Na is 47:503SiW12O40The molar ratio of the N, N' -bis (3-pyridyltetrazolium) -1,2 ethane is 1:1, the pH value is adjusted to 4.85 by using HCl solution, the mixture is stirred for 30 minutes, the mixture is poured into a high-pressure reaction kettle to perform hydrothermal reaction at 120 ℃, the hydrothermal reaction is performed for 4 days under the hydrothermal condition, the temperature is reduced to obtain green blocky crystals, the blocky crystals are alternately cleaned by using deionized water and ethanol and naturally dried at room temperature to obtain a { Cu product2(3-bptz)3(H2O)4[SiW12O40]}·2H2O。
The concentration of the HCl solution is 1 mol/L when the pH is adjusted.
An application of a polyacid-based metal organic complex used for an electrocatalytic hydrogen evolution electrode material under an alkaline condition in preparing the electrocatalytic hydrogen evolution electrode material under the alkaline condition.
The application of a polyacid-based metal organic complex used for an electrocatalytic hydrogen evolution electrode material under an alkaline condition in preparing the electrocatalytic hydrogen evolution electrode material under the alkaline condition comprises the following steps:
0.005g of graphite powder, 0.01g of { Cu }2(3-bptz)3(H2O)4[SiW12O40]}·2H2O and 0.005g of PVDF as a solid were mixed together and ground in a mortar for 2 hours, then 0.1m L of N-methylpyrrolidone was added to prepare a paste, and the mixture was applied to an area of 1cm2Drying the carbon cloth in a vacuum drying oven for 6 hours to obtain the polyacid-based metal organic complex-based electrode material.
According to the invention, polyacid anions, metal ions and organic ligands are selected as construction units by a hydrothermal method to obtain the polyacid-based metal-organic complex, and the complex is directly loaded on a current collector to obtain the electrode material capable of stably and efficiently evolving hydrogen under an alkaline condition, and the electrode material has the beneficial effects that:
1. the invention selects polyacid anions, organic ligands and metal ions, and prepares a novel polyacid-based complex, { Cu2(3-bptz)3(H2O)4[SiW12O40]}·2H2O, the complex has a two-dimensional structure.
2. According to the invention, a flexible bipyridine tetrazole ligand is selected, the ligand can provide more coordination points, the flexible conformation of the ligand can meet the coordination requirement of a central metal, a better space expansion space is provided, the ligand is provided with tetrazole and pyridine groups and has more coordination points, a two-dimensional layer structure is induced to be formed, polyacid can be clamped between two-dimensional layers in the form of a template agent, and the polyacid has high negative charges and a layered structure of a complex, so that the reaction kinetics and the catalytic sites can be fully promoted, and the reaction activity of the catalyst is promoted.
3. The coordination polymer can be directly prepared into an electrode without any post-treatment, and has the advantages of light weight, batch preparation and the like.
Drawings
FIG. 1 is a crystal structure diagram of a polyacid-based metal organic complex of the present invention; in the figure, (a) a coordination pattern of a central metal, (b) a one-dimensional chain structure of a complex, (c) a two-dimensional layer structure of a complex;
FIG. 2 is an infrared image of a polyacid-based metal organic complex of the present invention;
FIG. 3 is a diffraction pattern of X-ray powder of the polyacid-based metal-organic complex of the present invention and immersed in a 0.1 mol/L KOH solution;
FIG. 4 is a linear voltammogram at 1 mol/L KOH of a working electrode made from polyacid based metal-organic complex of the present invention;
FIG. 5 is a Tafel plot of a working electrode made with polyacid-based metal-organic complexes in accordance with the present invention;
FIG. 6 is a constant potential curve of hydrogen evolution at potential of a working electrode made of polyacid-based metal organic complex of the present invention.
Detailed Description
The present invention will be described in more detail below with reference to examples.
Examples
(1) Synthesis of polyacid-based metal organic complexes
The molecular formula of the complex is as follows: { Cu2(3-bptz)3(H2O)4[SiW12O40]}·2H2O; wherein, the 3-bptz is N, N' -bis (3-pyridine tetrazole) -1,2 ethane, and the structural formula is as follows:
the specific synthesis steps are as follows:
adding CuCl20.47mmol of N, N' -bis (3-pyridyltetrazolium) -1,2 ethane 0.05mmol and Na3SiW12O40Dissolving 0.05mmol in 20m L deionized water, adjusting pH to 4.85 with 1 mol/L HCl solution, stirring at room temperature for 30 min, transferring into inner liner of polytetrafluoroethylene high-temperature reaction kettle, loading into high-pressure reaction kettle, performing hydrothermal reaction at 120 deg.C for 4 days, cooling to obtain green blocky crystal, and removing deionized waterAlternately cleaning with water and ethanol, and naturally airing at room temperature to obtain the polyacid-based metal organic complex { Cu }2(3-bptz)3(H2O)4[SiW12O40]}·2H2O。
(2) Preparation of electrode Material (1-CC) based on polyacid-based Complex
0.005g of graphite powder, 0.01g of { Cu }2(3-bptz)3(H2O)4[SiW12O40]}·2H2O and 0.005g of PVDF as a solid were mixed together and stirred in a mortar for 2 hours, then 0.1m L of N-methylpyrrolidone was dropped to the mixture to prepare a paste, and the mixture was applied to an area of 1cm2Drying on carbon cloth in a vacuum drying oven for 6 hours to obtain polyacid-based metal organic complex-based electrode material for coating on 1cm2On the carbon cloth.
The prepared coordination polymer sample is subjected to single crystal X-ray diffraction, and the obtained crystal structure data of the complex is analyzed, so that the structure of the complex is that a central metal and a 3-bptzp organic ligand are coordinated with each other to form a two-dimensional layer structure, and polyacid anions are clamped between adjacent two-dimensional layers in the form of a template, as shown in figure 1.
Infrared Spectrum (IR) the measurement range was 400-4000 cm using Varian-640 and Shimadzu FT-IR 8400 infrared spectrometers–1From FIG. 2, a characteristic absorption peak of the polyacid, which is an organic ligand, was found by KBr pellet.
The complete powder diffraction data were collected on a Rigaku Ultima IV powder X-ray diffractometer operating at 40mA and 40 kV. Copper target X-rays were used. Scanning was fixed and the receiving slit was 0.1mm wide. Density data collection uses a 2 theta/theta scan pattern with a scan range of 5 deg. to 50 deg., a scan speed of 5 deg./s, and a span of 0.02 deg./time. Data fitting Using the program Cerius2, single crystal structure powder diffraction Spectroscopy simulated transformation was tested on an Ultima IVX-ray powder diffractometer using Mercury 1.4.1X-ray powder diffraction (PXRD). The infrared and XRD characterization (figures 2 and 3) proves the purity and high crystallinity of the material composition, and the XRD curve of the material after being soaked in 0.1M KOH solution for 6 hours is consistent with that of a newly prepared sample, which shows that the material has higher stability under alkaline conditions.
The crystal structure determination is that single crystals with proper size are selected by a microscope, diffraction data are collected by a Bruker SMART APEXII diffractometer (graphite monochromator, Mo-Ka) at room temperature, the diffraction data in a scanning mode are absorbed and corrected by an SADABS program, data reduction and structure analysis are completed by SAINT and SHE L XT L programs respectively, a least square method is used for determining all non-hydrogen atom coordinates, a theoretical hydrogenation method is used for obtaining hydrogen atom positions, a least square method is used for refining the crystal structure, and partial parameters of the collection of the data of the crystal diffraction points and the refining of the structure are shown in Table 1:
electrocatalytic hydrogen evolution performance of coordination polymers
The polyacid-based metal organic complex electrode material obtained in the embodiment of the invention is coated on 1cm2Connecting a platinum wire on the back of the carbon cloth, using 0.1M KOH as a test electrolyte, a mercury oxide electrode as a reference electrode, a platinum electrode as an auxiliary electrode and a Bio-logic, SP-150 electrochemical instrument as an electrochemical test in a three-electrode system, wherein the electrochemical test comprises linear voltammetry, Tafel curve and constant potential curve, and the potential value obtained by the test is represented by the formula ERHE＝ EHgO+0.2438+0.059pH. for the standard hydrogen potential.
Different potentials corresponding to reaction current are observed by testing a linear voltammetry curve of the electrode, and the obtained hydrogen evolution overpotential value is lower, which indicates that the catalytic activity of the hydrogen evolution overpotential is better. The reaction kinetics of the material can be obtained by analyzing the slope of the tafel curve, and the lower the slope, the faster the speed of the whole reaction process is. In order to prove the reaction stability of the material, the electrode is kept under the reaction potential all the time, the catalytic hydrogen evolution is continuously carried out, the maintenance effect of the reaction activity is judged by the current value without change, and the use maintenance rate of the material is explained.
Through tests, the current of the hydrogen evolution reaction can reach 10mA cm-2When the hydrogen evolution overpotential is 34mV, the reaction current reaches 50mA cm-2The overpotential was 74mV (FIG. 4). Then, taking the overpotential as the vertical axis and taking the logarithm of the corresponding current value as the horizontal axis, correspondingly making a tafel curve, and selecting a curve near the hydrogen evolution overpotential, wherein the slope of the part of the tafel curve is 79mVdec-1(FIG. 5). The catalytic hydrogen evolution was continued for 10 hours at an overpotential of 74mV, and the reaction current was maintained at 99% or more (FIG. 6).
The result shows that the polyacid-based ligand-based adsorption material designed and prepared by the invention induces the formation of a two-dimensional layered structure by virtue of the multidentate coordination sites and the flexible conformation of the flexible tetrazolopyridine ligand, so that the polyacid is clamped between two-dimensional layers in the form of a template agent. The layered structure promotes the migration speed of the reaction intermediate in the material, promotes the reaction activity and the dynamics in the electrocatalytic hydrogen evolution process, and further improves the utilization rate and the application value of the electrocatalytic hydrogen evolution material.
The above description is only exemplary of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A polyacid-based metal organic complex used for electrocatalytic hydrogen evolution electrode material under alkaline conditions has the following molecular formula:
{Cu2(3-bptz)3(H2O)4[SiW12O40]}·2H2O；
wherein, the 3-bptz is N, N' -bis (3-pyridine tetrazole) -1,2 ethane.
2. The polyacid-based metal-organic complex for electrocatalytic hydrogen evolution electrode material under basic conditions, as set forth in claim 1, characterized by:
the complex comprises the following specific synthetic steps:
adding CuCl2N, N' -bis (3-pyridyltetrazolium) -1,2 ethane and Na3SiW12O40Dissolving in deionized water to obtain CuCl2The molar ratio of the N, N' -bis (3-pyridyltetrazolium) -1,2 ethane to the Na is 47:503SiW12O40The molar ratio of the N, N' -bis (3-pyridyltetrazolium) -1,2 ethane is 1:1, the pH value is adjusted to 4.85 by using HCl solution, the mixture is stirred for 30 minutes, the mixture is poured into a high-pressure reaction kettle to perform hydrothermal reaction at 120 ℃, the hydrothermal reaction is performed for 4 days under the hydrothermal condition, the temperature is reduced to obtain green blocky crystals, the blocky crystals are alternately cleaned by using deionized water and ethanol and naturally dried at room temperature to obtain a { Cu product2(3-bptz)3(H2O)4[SiW12O40]}·2H2O。
3. The polyacid-based metal organic complex for electrocatalytic hydrogen evolution electrode material under alkaline conditions as set forth in claim 2, wherein the concentration of HCl solution is 1 mol/L when the pH is adjusted.
4. Use of the polyacid-based metal organic complex for electrocatalytic hydrogen evolution electrode material under alkaline conditions, as defined in claim 1, for the preparation of an electrocatalytic hydrogen evolution electrode material under alkaline conditions.
5. Use of the polyacid-based metal organic complex for electrocatalytic hydrogen evolution electrode material under alkaline conditions according to claim 4 for the preparation of an electrocatalytic hydrogen evolution electrode material under alkaline conditions, prepared as follows:
0.005g of graphite powder, 0.01g of { Cu }2(3-bptz)3(H2O)4[SiW12O40]}·2H2O and 0.005g of PVDF solid were mixed together, andgrinding in a mortar for 2 hours, adding 0.1m L N methylpyrrolidone, making the mixture into paste, and spreading the mixture on a 1cm area2Drying the carbon cloth in a vacuum drying oven for 6 hours to obtain the polyacid-based metal organic complex-based electrode material.
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