CN111848970A - Europium-based metal organic framework material, preparation method thereof and application of europium-based metal organic framework material as proton conducting material - Google Patents
Europium-based metal organic framework material, preparation method thereof and application of europium-based metal organic framework material as proton conducting material Download PDFInfo
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Abstract
The invention discloses a europium-based metal organic framework material, a preparation method thereof and application of the europium-based metal organic framework material as a proton conducting material. The molecular formula of the Eu (III) -MOFs is { [ Eu { [ III ]2(TTHA)(H2O)4]·9H2O}nWherein TTHA represents an anionic group formed by 6 protons of the ligand 1,3, 5-triazine-2, 4, 6-triamine-hexaacetic acid which are lost. The preparation method of the Eu (III) -MOFs comprises the following steps: h is to be6TTHA, 4' -bipyridine, Eu (NO)3)3·6H2And adding O into a water/acetonitrile mixed solvent, adjusting the pH value of a solution system to be acidic, and carrying out hydrothermal reaction to obtain the compound. The Eu (III) -MOFs has better proton conductivity in a wider temperature and relative humidity range, and the conductivity at 353K and 98 percent RH reaches 3.50 in a simple manner10‑3S·cm‑1Compared with most MOFs proton conductors reported in the prior art, the MOFs proton conductor can be widely applied to electrochemical devices, sensors, fuel cells and the like.
Description
Technical Field
The invention relates to a proton conducting material, in particular to a europium-based metal-organic framework proton conducting material, namely Eu (III) -MOFs, and specifically relates to Eu (III) -MOFs formed by assembling Eu (III) as a central metal ion and TTHA as an organic ligand, a preparation method of Eu (III) -MOFs and application of Eu (III) -MOFs as the proton conducting material, belonging to the technical field of fuel cells.
Background
With the rapid development of the world economy, the increasing global energy demand and the enormous consumption of non-renewable resources have brought about a serious energy crisis. Under such a background, the development of new energy has become an urgent problem to be solved. The proton exchange membrane fuel cell has the advantages of high energy conversion rate, no pollution in power generation, no noise and the like, and is expected to become a green and sustainable energy source, and the proton exchange material is the most central part of the proton exchange membrane fuel cell. Currently, commercially used conductive materials are based on perfluorosulfonic acids, which have a temperature of greater than 10 at 60-80 ℃ and 98% RH-2S·cm-1The proton conductivity of (1). However, perfluorosulfonic acid is expensive, complicated in manufacturing process, and cannot be used in a high-temperature environment, so that its application is limited. In recent years, a lot of research has been conducted to develop conductive materials having high activity and capable of being recycled for a long period of time, and various types of conductive materials, such as organic polymers, inorganic materials, Covalent Organic Frameworks (COFs), and the like, have been successively developed. Among them, metal organic framework compounds (MOFs), as a novel proton conductive material, have high crystallinity and tunability of structure and performance, and have a significant advantage in that they have precise structural information compared to other types of conductive materials, and thus, the proton conductive mechanism can be deeply studied from a molecular level. In addition, the MOFs material contains high concentration of acid groups and water molecules and continuous hydrogen bond networkThe network provides a carrier and a transmission channel for the transfer of protons. Among them, the organic acids Ln-MOFs have attracted a great deal of attention for the study of proton conductivity due to structural diversity, stable skeleton and unique properties.
Among the compounds which have been reported so far, La (H)5DTMP)·7H2O(σ＝8×10-3S·cm-1，24℃，98％RH)、(N2H5)[Nd2(ox)4(N2H5)]·4H2O(σ＝2.7×10-3S·cm-125 ℃, 100% RH) and [ Me2NH2][Eu(ox)2(H2O)]·3H2O(σ＝2.73×10-3S·cm-155 ℃, 95% RH) represents a better proton conduction result, but there is still a gap compared to MOFs materials with ultra-high proton conductivity, and these materials are mainly studied for proton conduction at low temperature, and their conductivity at higher temperature cannot be fully understood. In practical applications, low temperature conductive materials are receiving attention due to their portability, while high temperature conductive materials are more conducive to efficient hydrogen conversion. Therefore, the development of the Ln-MOFs conductive material which has high activity in a wide working temperature range and can be stably used has theoretical significance and practical application value. Reference documents: 【1】 R.m.p.colorrero, p.olivera-plastor, e.r.losilla, m.a.g.aranda, l.leon-Reina, m.papadaki, a.c.mckinlay, r.e.morris, k.d.demadis and a.cabeza, Dalton trans.2012, 41, 4045-; 【2】 Zhang, x.xie, h.li, j.gao, l.nie, y.pan, j.xie, d.tiana, w.liu, q.fan, h.su, l.huang and w.huang, adv.mater.,2017,29, 1701804; 【3】 X.wang, t.qin, s.s.bao, y.c.zhang, x.shen, l.m.zheng and d.r.zhu, j.mater.chem.a,2016,4, 16484-; 【4】 Yang, G.xu, Y.B.Dou, B.Wang, H.Zhang, H.Wu, W.ZHou, J.R.Li and B.L.Chen, nat.energy,2017,2, 877-membered ring 883; 【5】 S.r.kim, b.joarder, j.a.hurd, j.f.zhang, k.w.dawson, b.s.gelfand, n.e.wong and g.k.h.shimizu, j.am.chem.soc.,2018,140, 1077-; 【6】 S.m.elahi, s.chand, w.h.deng, a.pal and m.c.das, angelw.chem.int.edit, 2018,57, 6662-.
Disclosure of Invention
Aiming at the defects of the existing organic acid Ln-MOFs conductive material, the first purpose of the invention is to provide Eu (III) -MOFs which has proton conductivity higher than that of most MOFs materials in a wide working temperature range and can still maintain high conductivity in a high-temperature and high-relative-humidity environment, and the Eu (III) -MOFs can be widely applied to electrochemical devices, sensors, fuel cells and the like as a proton conductor.
The second purpose of the present invention is to provide a method for preparing eu (iii) -MOFs, which is a hydrothermal method for synthesizing eu (iii) -MOFs in one step, and has the advantages of simple operation, low cost and easy expanded production.
The third purpose of the present invention is to provide an application of eu (iii) -MOFs, which can maintain high proton conductivity in a wide temperature range and in a high temperature and high relative humidity environment, and can be widely applied to electrochemical devices, sensors, fuel cells, etc. as a proton conductor.
In order to achieve the above technical objects, the present invention provides eu (iii) -MOFs having the following chemical expression:
{[Eu2(TTHA)(H2O)4]·9H2O}n；
wherein, Eu2(TTHA)(H2O)4]·9H2O is one constituent unit of Eu (III) -MOFs, n represents polymerization number (n)>1)。
TTHA denotes the ligand 1,3, 5-triazine-2, 4, 6-triamine-hexaacetic acid (H)6TTHA) loses an anionic group formed by 6 protons in the synthesis of a metal organic framework compound, which has the structural formula:
eu (III) -MOFs of the invention belongs to a monoclinic system, a space group is C2/C, and unit cell parameters are as follows:
α＝90°，β＝91.265(4)°，γ＝90°，
Dcalc＝2.119g·cm-3，Z＝4，μ＝4.048mm-1，F(000)＝1984.0。
the crystallographic parameters, partial bond lengths and hydrogen bond configurations of the eu (iii) -MOFs are shown in tables 1, 2 and 3 below, respectively.
TABLE 1 crystallographic parameters of Eu (III) -MOFs
Table 2 partial bond lengths of Eu (III) -MOFs
Hydrogen bonding configuration of Eu (III) -MOFs shown in Table 3 (
,°)
The Eu (III) -MOFs of the invention is formed by Eu (III) central metal ions and TTHA3-The three-dimensional network structure formed by coordination contains a large amount of coordinated and uncoordinated water molecules, can be used as a proton carrier, and rich hydrogen bond networks are formed between the water molecules and carboxylic acid oxygen atoms and can be used as proton transmission channels, so that Eu (III) -MOFs has high proton conductivity and can be used as a proton conduction material.
The invention also provides a preparation method of Eu (III) -MOFs, which is implemented by reacting H6TTHA, 4' -bipyridine, Eu (NO)3)3·6H2And adding O into a water/acetonitrile mixed solvent, adjusting the pH value of a solution system to be acidic, and carrying out hydrothermal reaction to obtain the compound.
Preferred embodiment, H6TTHA, 4' -bipyridine and Eu (NO)3)2·6H2The mass ratio of O is 0.2-2: 0.15-2.5.
In a preferable scheme, the volume ratio of water to acetonitrile in the water/acetonitrile mixed solvent is 30-80: 10-30.
In the preferable scheme, the pH value of the solution system is adjusted to 0.5-5. The pH value is adjusted by dilute hydrochloric acid, and the concentration of the dilute hydrochloric acid is 1-6 mol/L.
In a preferred embodiment, the hydrothermal reaction conditions are: keeping the temperature at 100-160 ℃ for 24-72 h.
In a preferred embodiment, the Eu (III) -MOFs are colorless needle crystals.
The preparation method of Eu (III) -MOFs comprises the following specific operations: h is to be60.2-2 g of TTHA, 0.15-2.5 g of 4, 4' -bipyridine, Eu (NO)3)3·6H2Adding 0.15-2.5 g of O into a mixed solution of 30-80 mL of deionized water and 10-30 mL of acetonitrile, adjusting the pH value to 0.5-5 by using a hydrochloric acid solution with the concentration of 1-6 mol/L, then adding the mixture into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining in an autoclave, standing at a constant temperature of 100-160 ℃ for 24-72 hours, cooling, separating out colorless needle crystals, and washing the crystals with deionized water for multiple times to obtain Eu (III) -MOFs.
The invention also provides application of Eu (III) -MOFs as a proton conducting material.
The Eu- (III) -MOFs as the proton conduction material can be applied in different relative humidity and wide temperature range, and shows excellent proton conduction performance.
Preferably, the proton conductivity of the Eu (III) -MOFs is 1.34 x 10 under the conditions of 293-353K and 98% RH-4S·cm-1～3.50×10-3S·cm-1Within the range. The proton conductivity increases with increasing temperature.
Preferably, the proton conductivity of the Eu (III) -MOFs at 60% -98% RH and 298K is 1.42 × 10-5S·cm-1～1.63×10-4S·cm-1In the meantime. Proton conductivity increases with increasing relative humidity. The method shows that under the condition of high relative humidity, more adsorbed water molecules are taken as carriers and participate in the construction of hydrogen bond channels, so that the concentration and the transmission efficiency of proton carriers are improved.
Preferably, the Eu (III) -MOFs reaches a maximum of 3.50X 10 at 353K and 98% RH-3S·cm-1Higher than the conduction value of most MOFs reported at present. The conductive material still keeps a very high conduction value under high temperature and high relative humidity, and is a potential proton conductor.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
the Eu (III) -MOFs provided by the invention is formed by Eu (III) central metal ions and TTHA3-The three-dimensional network structure formed by coordination contains a large amount of coordinated and uncoordinated water molecules in the crystal structure, can be used as a proton carrier, and rich hydrogen bond networks are formed between the water molecules and carboxylic acid oxygen atoms and can be used as proton transmission channels, so that Eu (III) -MOFs has high proton conductivity. Eu (III) -MOFs have excellent proton conduction effect in a wide working temperature range, can keep a very high conduction value at high temperature and high relative humidity, and can be applied to various extreme working environments for a long time.
The preparation method of Eu (III) -MOFs provided by the invention is simple to operate, can be completed in one step through hydrothermal reaction, is low in cost, and is beneficial to industrial production.
Drawings
FIG. 1 is ligand H6Structural formula of TTHA.
FIG. 2 is a three-dimensional network structure of Eu (III) -MOFs obtained in example 1 of the present invention.
FIG. 3 is a graph showing the impedance of Eu (III) -MOFs at 293 to 313K and 98% RH according to example 1 of the present invention.
FIG. 4 is an impedance spectrum of Eu (III) -MOFs at 318-353K and 98% RH obtained in example 1 of the present invention.
FIG. 5 is a graph showing the proton conductivity with temperature of Eu (III) -MOFs obtained in example 1 according to the present invention.
FIG. 6 is a graph showing impedance profiles of Eu (III) -MOFs at different relative humidities, obtained in example 1 according to the present invention.
FIG. 7 is a graph showing the proton conductivity of Eu (III) -MOFs obtained in example 1 according to the present invention as a function of relative humidity.
FIG. 8 is an Arrhenius spectrum obtained in example 1 of the present invention for Eu (III) -MOFs at 293-353K and 98% RH.
Detailed Description
In order to better explain the technical solutions and advantages of the present invention, the following detailed description of the present invention is provided with reference to the embodiments. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as those skilled in the art will be able to make insubstantial modifications and variations of this invention in light of the above teachings, and will nevertheless fall within the scope of this invention.
Example 1
0.4g H6TTHA, 0.8g of 4, 4' -bipyridine, 0.6g of Eu (NO)3)3·6H2Adding O into a mixed solution of 40mL of deionized water and 20mL of acetonitrile, adjusting the pH value to 2 by using a 3mol/L hydrochloric acid solution, then adding the solution into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining into a high-pressure kettle, standing the autoclave at the constant temperature of 140 ℃ for 48 hours, cooling the product to obtain colorless needle crystals, and washing the crystals with deionized water for multiple times to obtain Eu (III) -MOFs. The molecular formula of the Eu (III) -MOFs is C15H38Eu2N6O25Elemental analysis data, theoretical value: c, 17.9; h, 3.81; and N, 8.35%. The experimental value is C, 17.55; h, 4.17; n,8.68 percent.
Example 2
0.4g H6TTHA, 0.8g of 4, 4' -bipyridine, 0.6g of Eu (NO)3)3·6H2Adding O into a mixed solution of 40mL of deionized water and 20mL of acetonitrile, adjusting the pH value to 2 by using a 3mol/L hydrochloric acid solution, then adding the solution into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining into a high-pressure kettle, standing the autoclave at a constant temperature of 100 ℃ for 72 hours, cooling the solution to obtain colorless needle crystals, and washing the crystals for multiple times by using the deionized water to obtain Eu (III) -MOFs.
Example 3
0.4g H6TTHA, 0.8g of 4, 4' -bipyridine, 0.6g of Eu (NO)3)3·6H2Adding O into a mixed solution of 40mL of deionized water and 20mL of acetonitrile, adjusting the pH value to 0.5 by using a 3mol/L hydrochloric acid solution, then adding the solution into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining into a high-pressure kettle, standing the polytetrafluoroethylene lining at a constant temperature of 140 ℃ for 48 hours, cooling the polytetrafluoroethylene lining to obtain colorless needle crystals, and washing the crystals for multiple times by using the deionized water to obtain Eu (III) -MOFs.
Example 4
0.2g H6TTHA, 0.4g of 4, 4' -bipyridine, 0.3g of Eu (NO)3)3·6H2Adding O into a mixed solution of 40mL of deionized water and 20mL of acetonitrile, adjusting the pH value to 2 by using a 3mol/L hydrochloric acid solution, then adding the solution into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining into an autoclave, standing the autoclave at the constant temperature of 140 ℃ for 48 hours, cooling the polytetrafluoroethylene lining to obtain colorless needle crystals, and washing the crystals for multiple times by using the deionized water to obtain Eu (III) -MOFs.
Example 5
0.2g H6TTHA, 0.4g of 4, 4' -bipyridine, 0.3g of Eu (NO)3)3·6H2Adding O into a mixed solution of 40mL of deionized water and 20mL of acetonitrile, adjusting the pH value to 0.5 by using a 3mol/L hydrochloric acid solution, then adding the solution into a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining into a high-pressure kettle, standing the autoclave at a constant temperature of 120 ℃ for 24 hours, cooling the polytetrafluoroethylene lining to obtain colorless needle crystals, and washing the crystals for multiple times by using the deionized water to obtain Eu (III) -MOFs.
Analyzing the single crystal structure of Eu (III) -MOFs prepared in embodiments 1-5 of the invention, collecting single crystal diffraction data by using a Bruker Smart CCD diffractometer, and monochromating Mo/k alpha rays by using a graphite monochromator
Scanning, the following results were obtained: in examples 1 to 5, single crystal diffraction peaks of Eu (III) -MOFs were the same, which indicates that the same crystalline compound was obtained by the above-described preparation methods 1 to 5. Analyzing the crystal structure of the Eu (III) -MOFs, wherein the crystal structure is monoclinic, the space group is C2/C, and the unit cell parameters are as follows:
α＝90°，β＝91.265(4)°，γ＝90°，
Dcalc＝2.119g·cm-3，Z＝4，μ＝4.048mm-1f (000) ═ 1984.0. The crystal structure of the eu (iii) -MOFs was mapped using Diamond software, resulting in a three-dimensional network structure as shown in fig. 2.
To examine the proton conductivity of Eu (III) -MOFs prepared according to the present invention, approximately 50mg of Eu (III) -MOFs prepared according to the present invention in example 1 was fabricated into a wafer having a diameter of approximately 10mm and a thickness of 0.5 mm. The wafer was then placed between porous carbon electrodes (Sigracet, GDL 10BB, no Pt). Impedance data were collected by an HP4284A impedance analyzer with a frequency range of 20Hz to 1MHz and an applied voltage of 0.2V. The temperature test range of the Eu (III) -MOFs is 293-353K, and the relative humidity range is 60% -98% RH. And recording the numerical value after the value to be tested is stable, and processing the data by using a winDETA program package.
Application example 1
Impedance maps of Eu (III) -MOFs prepared in example 1 of the present invention at 98% RH and 293-353K are shown in FIGS. 3 and 4. The proton conductivity properties show that the conductivity values of the Eu (III) -MOFs gradually increase with increasing temperature due to the thermal activation mechanism and reach a maximum value of 3.50X 10 at 353K3S·cm-1As shown in fig. 5.
Application example 2
Impedance diagram of Eu (III) -MOFs prepared in embodiment 1 of the invention at 298K and 60% -98% RHThe spectra are shown in FIG. 6. The proton conduction performance of the Eu (III) -MOFs is tested, and the conduction value of the Eu (III) -MOFs is 1.42 multiplied by 10 at 60 percent RH along with the increase of relative humidity-5S·cm-11.63X 10 at 98% RH-4S·cm-1. At 98% RH, part of the arc in the low frequency region of the impedance spectrum disappears, indicating that the proton conduction type is H+It also shows that the high humidity environment is more favorable for the transfer of protons. The conductivity curves of the Eu (III) -MOFs are shown in FIG. 7.
Application example 3
The activation energy (Ea) of Eu (III) -MOFs prepared in example 1 of the present invention in the temperature range of 98% RH and 293-353K is represented by Arrhenius equation [ sigma-sigma ]0exp(-Ea/kBT)]And (4) calculating. The Ea value of the Eu (III) -MOFs is 0.44eV obtained by linear fitting of ln (sigma T) vs 1000/T, and an Arrhenius map is shown in FIG. 8, which illustrates that the proton transfer of the Eu (III) -MOFs follows a transport mechanism. The water molecule is used as a proton carrier, the protons are continuously transmitted to the next proton carrier, and then the protons are received to further transport the protons on the hydrogen bonding channel and complete the transmission.
The Eu- (III) -MOFs prepared by the invention has excellent proton conduction performance in a wide working temperature range, can still keep the stability of the structure in a high-temperature and high-relative-humidity environment, can clearly understand the path and mechanism of proton transmission from the atomic scale, can be used as a potential proton conduction material to meet the use of different environments, and has very high practical application value.
Claims (9)
1. Eu (III) -MOFs, characterized in that: having the following chemical expression:
{[Eu2(TTHA)(H2O)4]·9H2O}n；
wherein the content of the first and second substances,
the structural formula of ligand TTHA is:
2. eu (iii) -MOFs according to claim 1, characterized in that: eu (III) -MOFs belongs to monoclinic system, space group is C2/C, unit cell parameters:
α＝90°，β＝91.265(4)°，γ＝90°，
Dcalc＝2.119g·cm-3，Z＝4，μ＝4.048mm-1，F(000)＝1984.0。
3. process for the preparation of eu (iii) -MOFs according to claim 1 or 2, characterized by: h is to be6TTHA, 4' -bipyridine, Eu (NO)3)3·6H2And adding O into a water/acetonitrile mixed solvent, adjusting the pH value of a solution system to be acidic, and carrying out hydrothermal reaction to obtain the compound.
4. Process for the preparation of Eu (III) -MOFs according to claim 3, characterized in that: h6TTHA, 4' -bipyridine and Eu (NO)3)2·6H2The mass ratio of O is 0.2-2: 0.15-2.5.
5. Process for the preparation of Eu (III) -MOFs according to claim 3, characterized in that: the volume ratio of water to acetonitrile in the water/acetonitrile mixed solvent is 30-80: 10-30.
6. Process for the preparation of Eu (III) -MOFs according to claim 3, characterized in that: and adjusting the pH value of the solution system to 0.5-5.
7. Process for the preparation of Eu (III) -MOFs according to claim 3, characterized in that: the conditions of the hydrothermal reaction are as follows: keeping the temperature at 100-160 ℃ for 24-72 h.
8. Use of eu (iii) -MOFs according to claim 1 or 2, characterized by: the material is applied as a proton conducting material.
9. Use of eu (iii) -MOFs according to claim 8, characterized in that: the Eu (III) -MOFs is in the range of 293-353K and 60% -98% relative humidity, and the proton conductivity is 1.42 multiplied by 10-5S·cm-1～3.53×10-3S·cm-1In the meantime.
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| CN112915968A (en) * | 2021-01-25 | 2021-06-08 | 肇庆市武大环境技术研究院 | Application of europium-based metal organic framework material as water vapor adsorption material |
| CN115521273A (en) * | 2022-11-28 | 2022-12-27 | 广东工业大学 | Pz-2COOH-SO 2 Ligand, preparation method and application thereof |
| CN115521273B (en) * | 2022-11-28 | 2023-04-07 | 广东工业大学 | Pz-2COOH-SO 2 Ligand, preparation method and application thereof |
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