CN111875644B - Organic-inorganic hybrid polyacid-based crystalline electrocatalyst and preparation method thereof - Google Patents

Organic-inorganic hybrid polyacid-based crystalline electrocatalyst and preparation method thereof Download PDF

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CN111875644B
CN111875644B CN202010688999.9A CN202010688999A CN111875644B CN 111875644 B CN111875644 B CN 111875644B CN 202010688999 A CN202010688999 A CN 202010688999A CN 111875644 B CN111875644 B CN 111875644B
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赵海燕
任文强
刘佳铭
王利
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Abstract

An organic-inorganic hybrid polyacid-based crystalline electrocatalyst and a preparation method thereof belong to the technical field of catalytic materials. The chemical formula of the transition metal substituted organic-inorganic hybrid polyacid-based crystalline electrocatalyst used for solving the technical problem is as follows: [ Ni ]2(en)4(C2H3NO2)(H2O)][Ni(en)3][Ni(en)2][P2W18O62]·6H2And (O). The preparation method of the catalyst comprises the steps of firstly, preparing Na9[A‑α‑PW9O34]·7H2O,K12[α‑H2P2W12O48]·24H2O,Ni(CH3COO)2·4H2O, ethylenediamine and glycine are added to H in sequence2And O, stirring, putting into a stainless steel reaction kettle, sealing, heating in an oven, taking out after heating, naturally cooling to room temperature, filtering, washing with distilled water, and drying at room temperature to obtain the final product. The preparation method of the catalyst is simple, easy to operate, mild in reaction condition and low in cost.

Description

Organic-inorganic hybrid polyacid-based crystalline electrocatalyst and preparation method thereof
Technical Field
The invention relates to the field of catalytic materials, in particular to an organic-inorganic hybrid polyacid-based crystalline electrocatalyst and a preparation method thereof.
Background
Food safety is a civil problem and is also economically and politically associated. Currently, with the improvement of living standard of substances, people are strongly pursuing high quality of life. From the sense, the food can meet different taste requirements of people and the pursuit of color, aroma and taste, so that the food additive is widely used, can improve the color, aroma, taste and the like of the food, and can make outstanding contribution to the preservation and processing of the food. But at the same time, the safe use of the food additive plays an important role in the health of people, and the establishment of a quick and efficient method for measuring the food additive is also necessary.
Polyacid is called polyoxometallate, is a nano-scale inorganic metal oxygen cluster compound with rich composition, structure and various chemical properties, and has huge application prospects in the fields of catalysis, magnetism, medicaments and the like (coord. chem.rev.,2020,414,213260; ACS Catal.,2019,9, 10174; coord. chem.rev.,2019,391, 44; chem.eng.J.,2018,351,441). Due to the potential application prospect of the chemically modified electrode and the electrocatalytic property of polyacid, the polyacid is modified on the electrode to enable the electrode to have special functional properties, and the method is used for detecting the content of additives in food and medicines, and has attracted people's interest and research.
In recent years, more and more researchers are working on modifying polyacid and are expecting to obtain polyacid derivatives with more properties and good structures, wherein the synthesis of various inorganic-organic hybrid compounds based on polyacid is a research hotspot (energy chem,2019,1, 100021; coord. chem. rev.,2019,378,281), and the purpose is to realize the perfect combination of the advantages of each component through 'synergistic action' to prepare more polyacid-based functional materials with novel structures and excellent performance, and the polyacid-based functional materials are applied to numerous fields such as photoelectrocatalysis (coord. chem. rev.,2019,388,268; CrystEngComm,2019,21, 2641). Nowadays, flexible organic ligands are more and more favored to be used for constructing polyacid-based inorganic-organic hybrid materials of high-dimensional frameworks because the flexible organic ligands have more flexibility and coordination sites to help to construct new topological structures, and the flexible organic ligands have potential application values in the field of electrocatalysis (inorg. chem.,2020,59, 5149; chem electric chem,2018,5, 823).
Disclosure of Invention
Aiming at the defects, the invention provides an organic-inorganic hybrid polyacid-based crystalline electrocatalyst and a preparation method thereof, and the electrocatalyst prepared by the method has good catalytic effect.
The chemical formula of the transition metal substituted organic-inorganic hybrid polyacid-based crystalline electrocatalyst used for solving the technical problem is as follows: [ Ni ]2(en)4(C2H3NO2)(H2O)][Ni(en)3][Ni(en)2][P2W18O62]·6H2O, wherein en is ethylenediamine. The material belongs to a monoclinic system, P2(1)/n space group, and the unit cell parameters are as follows:
Figure BDA0002588645420000021
Figure BDA0002588645420000022
β＝100.521(2)°，Z＝4。
the invention also discloses a preparation method of the organic-inorganic hybrid polyacid-based crystalline electrocatalyst, which comprises the following steps:
(1) weighing the following raw materials in parts by weight: 8-13 parts of Na9[A-α-PW9O34]·7H2O, 38-40 parts of K12[α-H2P2W12O48]·24H2O, 45-50 parts of Ni (CH)3COO)2·4H2Adding H into O, ethylenediamine and 15-21 parts of glycine in sequence2And stirring for 90-180 minutes in the O solution.
(2) Putting the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle and heating the reaction kettle in an oven at the temperature of 110 ℃ and 125 ℃ for 96 to 130 hours.
(3) Taking out, naturally cooling to room temperature, filtering the product, washing with distilled water for 3-5 times, and drying at room temperature to obtain green columnar crystals.
Further, 1g of K12[α-H2P2W12O48]·24H20.38-0.64mL of ethylenediamine was added to O.
Further, 1g ofK12[α-H2P2W12O48]·24H20.38-0.53g of glycine was added to O.
Has the advantages that:
(1) the preparation method of the catalyst is simple, easy to operate, mild in reaction condition and low in cost.
(2) The catalyst has high-efficiency and stable electrocatalytic activity and has potential application prospect in the field of electrocatalysis.
Drawings
FIG. 1 is a schematic diagram of the structure of an asymmetric unit of a polyacid-based crystalline material.
FIG. 2 is a three-dimensional supramolecular structure diagram of a polyacid-based crystalline material.
FIG. 3 is an experimental and simulated X-ray powder diffraction pattern of a polyacid-based crystalline material.
FIG. 4 shows the concentration of the polyacid-based crystalline material at 0.5 mol.L-1Na2SO4/H2SO4(pH 2.68) sweep rate in solution 100 mV. s-1Cyclic-voltammogram of (c).
FIG. 5 shows the concentration of the polyacid-based crystalline material at 0.5 mol.L-1Na2SO4/H2SO4(pH 2.68) cycle-voltammograms in solution and at different sweep rates.
FIG. 6 shows the concentration of the polyacid-based crystalline material at 0.5 mol.L-1Na2SO4/H2SO4(pH 2.68) the sweep rate in solution was 100mV · s-1For IO of different concentrations3 -Cyclic-voltammogram of (c).
FIG. 7 shows the concentration of the polyacid-based crystalline material at 0.5 mol.L-1Na2SO4/H2SO4(pH 2.68) sweep rate in solution 100 mV. s-1For different concentrations of NO2 -Cyclic voltammogram of (a).
FIG. 8 shows the different concentrations of IO in the base electrode pair of the multi-acid-based crystalline material3 -And NO2 -A catalytic efficiency map.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Mixing Na9[A-α-PW9O34]·7H2O(0.1g),K12[α-H2P2W12O48]·24H2O(0.394g),Ni(CH3COO)2·4H2O (0.5g), ethylenediamine (0.20mL) and glycine (0.2g) were added sequentially to 10mLH2And O, stirring for 120 minutes, then putting the mixture into a 30mL stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, placing the reaction kettle in an oven at the temperature of 120 ℃, heating the reaction kettle for 120 hours, taking the reaction kettle out, naturally cooling the reaction kettle to the room temperature, filtering and washing the product with distilled water, and drying the product at the room temperature to obtain green columnar crystals.
Comparative example 1
The reaction time was shortened to 1 to 3 days, and other reaction conditions were not changed, and a product having the same structure as in example was not obtained.
Comparative example 2
Salt compounds of other transition elements Fe or Co are selected to replace Ni salt in the application, experiments are carried out according to the reaction conditions of the example 1, and products with the same structure as the example 1 are not obtained.
Comparative example 3
With Na10[A-α-SiW9O34]·19H2O or K8Na2[A-α-GeW9O34]·25H2O instead of Na9[A-α-PW9O34]·7H2O, and adjusting the reactant ratio range, a product having the same structure as in example 1 was not obtained.
Comparative example 4
The use of 1, 2-propanediamine, 1, 3-propanediamine and cyclohexylamine instead of ethylenediamine did not give a product of the same structure as in example 1.
Comparative example 5
The use of alanine and phenylalanine instead of glycine failed to provide a product of the same structure as in example 1.
Example 2
Mixing Na9[A-α-PW9O34]·7H2O(0.08g),K12[α-H2P2W12O48]·24H2O(0.38g),Ni(CH3COO)2·4H2O (0.45g), ethylenediamine (0.15mL) and glycine (0.15g) were added sequentially to 7mLH2And O, stirring for 90 minutes, then putting the mixture into a 30mL stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, heating the reaction kettle in an oven at 110 ℃ for 96 hours, taking the reaction kettle out, naturally cooling the reaction kettle to room temperature, filtering and washing the product with distilled water for 3 times, and drying the product at room temperature to obtain green columnar crystals.
Example 3
Mixing Na9[A-α-PW9O34]·7H2O(0.13g),K12[α-H2P2W12O48]·24H2O(0.40g),Ni(CH3COO)2·4H2O (0.47g), ethylenediamine (0.25mL) and glycine (0.20g) were added sequentially to 8mLH2And O, stirring for 160 minutes, then placing the mixture into a 30mL stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, placing the reaction kettle in an oven at 117 ℃ for heating for 130 hours, taking the reaction kettle out, naturally cooling the reaction kettle to room temperature, filtering and washing the product for 5 times by distilled water, and drying the product at room temperature to obtain green columnar crystals.
Example 4
Mixing Na9[A-α-PW9O34]·7H2O(0.08g),K12[α-H2P2W12O48]·24H2O(0.38g),Ni(CH3COO)2·4H2O (0.45g), ethylenediamine (0.22mL) and glycine (0.15g) were added sequentially to 7mLH2And O, stirring for 110 minutes, then putting the mixture into a 30mL stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, placing the reaction kettle in an oven at the temperature of 115 ℃ for heating for 125 hours, taking the reaction kettle out, naturally cooling the reaction kettle to room temperature, filtering and washing the product for 3 times by distilled water, and drying the product at the room temperature to obtain green columnar crystals.
The asymmetric molecular structural unit of the tested polyacid-based crystalline material comprises a binuclear [ Ni ]2(en)4(C2H3NO2)(H2O)]2+Cationic, saturated Wells-Dawson type [ P ]2W18O62]6-Cluster anionsA modified [ Ni1(en)3]2+Cation, one free [ Ni2(en)2]2+Cations and 6 free water molecules. Four crystallographically independent nickel ions are present in this compound, and their coordination patterns differ from each other: supported [ Ni1(en)3]2+Cation forming ON5With five nitrogen atoms from three ethylenediamine ligands and from [ P ]2W18O62]6-One oxygen coordination of the unit, free [ Ni2(en)2]2+In a square configuration, coordinating with four nitrogen atoms from two ethylenediamine ligands. In binuclear [ Ni ]2(en)4(C2H3NO2)(H2O)]2+Ni3 in cation2+And Ni42+All also exhibit a hexa-coordinated octahedral configuration, all coordinated to four nitrogen atoms from two ethylenediamine ligands, except Ni32+Wherein the other coordinating oxygen and nitrogen atoms are from glycine ligands, and Ni42+The other two coordinating oxygen atoms in (a) are from glycine ligands and water molecules, as shown in FIG. 1.
The nitrogen atoms of the nickel-organic cation and the oxygen atoms of the Dawson type cluster block are connected through abundant intramolecular and intermolecular hydrogen bonds to form an interesting three-dimensional supramolecular network structure as shown in fig. 2, and the distribution data of the hydrogen bonds existing in the network structure are shown in table 1:
TABLE 1 data sheet of hydrogen bonds present in polyacid-based crystalline materials
Figure BDA0002588645420000041
Figure BDA0002588645420000051
*Symmetry transformation used to generate equivalent atoms:a＝-x+1/2,y+1/2,-z+3/2；b＝x-1/2,-y+3/2,z-1/2；c＝x-1,y,z；d＝x+1/2,-y+3/2,z+1/2；e＝-x+1,-y+1,-z+1；f＝x-1/2,-y+1/2,z-1/2；g＝x+1/2,-y+1/2,z-1/2；h＝-x+1/2,y-1/2,-z+1/2.
The X-ray powder diffraction experimental pattern of the compound is substantially consistent with the theoretical pattern based on single crystal diffraction fitting, and the sample for property testing is proved to be pure, and the specific figure is shown in fig. 3.
The electrochemical and electrocatalytic performance of the compound is 0.5 mol.L-1Na2SO4/H2SO4(pH 2.68) the test was performed in solution. As shown in FIG. 4, the scan rate is 100m V · s over a voltage range of-1.0 to-0.2V-1When the compound exhibited three pairs of redox peaks I/I ', II/II' and III/III ', respectively-0.444 (I), -0.641(II) and-0.862 (III) V and-0.387 (I'), -0.589V (II '), and-0.803 (III') V, assigned as [ P2W18O62]6-W in cluster blockVIThe redox process of (2). When the scanning rate is from 50mV s-1Increase to 320mV · s-1The peak current intensity was linear with scan rate (R ═ 0.997), indicating that the redox process was surface controlled (fig. 5).
In addition, the electrocatalytic behavior of the compounds in solution was studied for iodate and nitrite, and FIGS. 6 and 7 show the compounds in solution with different concentrations of iodate and nitrite (1X 10, respectively)-3,3×10-3,5×10-3,7×10-3,9×10-3mol·L-1) The cyclic voltammogram of the electrolyte solution of (2), as is apparent from the figure, W in the compoundVIThe electron gain and loss on the-O skeleton play an obvious electrocatalysis role on nitrous acid and iodate ions.
By evaluating and comparing the Catalytic Activity (CAT) of the compounds on nitrite and iodate, respectively, with NO2 -By way of example, based on WVIThe reduction peak III' (-0.803V vs Ag/AgCl) of (A) was calculated, and the catalytic efficiency (CAT, CAT ═ I) was calculatedp(POM,substrate)-Ip(POM)]/Ip(POM)X 100%, where Ip (POM) and Ip (POM, NaNO)2) Respectively by addition of NO2 -Front and rear cathodic peak currents. When the concentration is 1X 10 respectively-3,3×10-3,5×10-3,7×10-3，9×10-3mol·L–1The corresponding catalytic efficiencies were 6.13%, 15.67%, 22.15%, 30.56% and 50.78%, respectively, for IO3Corresponding electrocatalytic efficiencies of 47.22%, 62.67%, 78.34%, 93.06% and 117.36% (FIG. 8), it can be seen that under the same conditions, the compound prepared in example 1 is responsible for IO3 –Catalytic activity of (2) to NO2 -The catalytic activity of (3) is high. In summary, the polyacid-based crystalline electrocatalyst is useful for IO3 –And NO2 –All show good electrocatalytic effect.
The process parameters and routes of the present invention are not limited to the specific embodiments listed above, which are only illustrative of the present invention and not limiting of the process parameters and routes described in the examples of the present invention. It will be appreciated by those skilled in the art that in practice modifications or equivalent arrangements can be made to the present invention in order to achieve the same technical result. As long as the application requirements are met, the invention is within the protection scope.

Claims (4)

1. An organic-inorganic hybrid polyacid-based crystalline electrocatalyst, characterized in that the chemical formula of the catalyst is: [ Ni ]2(en)4(C2H3NO2)(H2O)][Ni(en)3][Ni(en)2][P2W18O62]·6H2O, wherein en is ethylenediamine; the material belongs to a monoclinic system, P2(1)/n space group, and the unit cell parameters are as follows:
Figure FDA0003658172640000011
Figure FDA0003658172640000012
β＝100.521(2)°，Z＝4。
2. a method for preparing the organic-inorganic hybrid polyacid-based crystalline electrocatalyst according to claim 1, characterized in that the method comprises the following steps:
(1) weighing the following raw materials in parts by weight: 8-13 parts of Na9[A-α-PW9O34]·7H2O, 38-40 parts of K12[α-H2P2W12O48]·24H2O, 45-50 parts of Ni (CH)3COO)2·4H2Adding H into O, ethylenediamine and 15-21 parts of glycine in sequence2Stirring for 90-180 min in O, wherein the addition amount of the ethylenediamine is 1g of K12[α-H2P2W12O48]·24H2Adding 0.38-0.64mL of ethylenediamine into the O solution;
(2) putting the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the stainless steel reaction kettle and putting the stainless steel reaction kettle into an oven for heating, wherein the heating temperature is 110-;
(3) and taking out, naturally cooling to room temperature, filtering and washing a product with distilled water, and drying at room temperature to obtain green columnar crystals.
3. The method for preparing an organic-inorganic hybrid-type polyacid-based crystalline electrocatalyst according to claim 2, wherein H in step (1)2K with 1g of O12[α-H2P2W12O48]·24H20.38-0.53g of glycine was added to O.
4. The method for preparing an organic-inorganic hybrid-type polyacid-based crystalline electrocatalyst according to claim 2, wherein the washing number of the product in step (3) is 3-5.
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