CN114540876B - Sulfonated polybenzimidazole-based electrocatalyst for oxygen evolution reaction and preparation method thereof - Google Patents

Sulfonated polybenzimidazole-based electrocatalyst for oxygen evolution reaction and preparation method thereof Download PDF

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CN114540876B
CN114540876B CN202210380414.6A CN202210380414A CN114540876B CN 114540876 B CN114540876 B CN 114540876B CN 202210380414 A CN202210380414 A CN 202210380414A CN 114540876 B CN114540876 B CN 114540876B
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spbi
sulfonated polybenzimidazole
oxygen evolution
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electrocatalyst
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CN114540876A (en
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王刚
杨帅
卢明霞
白红娟
王飞飞
陈孝东
华冰艳
陈军航
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Henan University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

The invention relates to the field of preparation and research of oxygen evolution reaction electrocatalysts, and provides a sulfonated polybenzimidazole electrocatalyst for oxygen evolution reaction and a preparation method thereof. The electrocatalyst for oxygen evolution reaction is prepared by a dipping-annealing combination method by taking sulfonated polybenzimidazole as a carrier. The beneficial effects of the invention are as follows: the raw materials are low in cost, nontoxic and harmless; the reaction temperature is stable and easy to control. An OER electrocatalyst in the form of nanoparticles is prepared, the graphite structure present in such nanoparticles optimising OER conductivity. And after annealing treatment, pyrrole-N metal coordination sites are generated, and Co-N coordination bonds are formed through strong interaction of Co and sPBI, so that the structural stability of the nano particles is improved. Simultaneously generate pyridine-N species, can accelerate O 2 And reduces OER overpotential. Finally, crystal defects are generated after annealing treatment, more active sites are exposed, and the adsorption capacity of the intermediate is improved, so that the electrocatalyst has quite large OER activity.

Description

Sulfonated polybenzimidazole-based electrocatalyst for oxygen evolution reaction and preparation method thereof
Technical Field
The invention relates to an electrocatalyst for oxygen evolution reaction and a preparation method thereof, in particular to a sulfonated polybenzimidazole-based electrocatalyst and a preparation method thereof.
Background
Clean, high energy density hydrogen energy is an important direction of green energy development today, while environmental friendly electrolyzed water systems are important hydrogen production technologies. Oxygen Evolution Reaction (OER) is one of the half reactions of electrolyzed water and is also the rate controlling step of electrolyzed water. During OER, with the formation of O-O bonds, electron transfer slows down the overall kinetics of hydrolysis. Thus, the research is higherThe efficient, more advanced electrocatalysts have a profound effect on the development of the promoted water electrolysis. Currently, ruO 2 And IrO 2 Electrocatalysts of such noble metals are widely reported for their excellent OER properties, but their high cost limits their widespread commercialization. Therefore, low cost transition metals have become an important point of research in recent years, and complexes containing various transition metals also provide directions for preparing OER electrocatalysts.
Sulfonated polybenzimidazoles (sPBI) are a class of high performance polymers with high thermal stability, oxidation resistance, and good mechanical properties, which are commonly used to make proton exchange membranes. In addition, the polymer has-SO 3 H may enable sPBI to have good conductivity; while the N species of sPBI may generate lone pair electrons. This allows sPBI to act as an electrocatalyst matrix material, but it requires anchoring of a suitable metal ligand to exert excellent electrocatalytic properties.
Aiming at the problems, the OER electrocatalyst with low cost and high performance and the preparation method thereof are provided.
Disclosure of Invention
The invention aims to provide a sulfonated polybenzimidazole OER electrocatalyst and a preparation method thereof. Firstly, sPBI is synthesized by a direct polycondensation method, and the repeating unit structure is shown as follows:
wherein sPBI can be respectively soaked in HCl solution and Li 2 CO 3 Solution, na 2 CO 3 Solution, K 2 CO 3 Solution and Mg 2 CO 3 X is carried out in solution 1 Hydrogen, lithium, sodium, potassium or magnesium, respectively.
X 2 The structure is produced by corresponding aromatic dicarboxylic acid, and the sPBI structure contains one or more than one X according to the selected aromatic dicarboxylic acid monomers 2 The following figures list different X 2 Structure and corresponding aromatic dicarboxylic acid monomerThe invention is described with reference to sulfonated polybenzimidazole containing structural units of flexible ether linkages, i.e., the aromatic dicarboxylic acid monomer of choice is 4, 4-dicarboxydiphenyl ether.
Secondly, the sPBI and cobalt acetate powder are subjected to a water immersion method and a thermal annealing treatment to obtain the OER electrocatalyst with nano-particle morphology.
The preparation method of the OER electrocatalyst provided by the invention comprises the following preparation steps:
(1) Preparation of sPBI: polymerizing 3, 3' -Diaminobenzidine (DAB), 4-dicarboxydiphenyl ether (PE) and 3, 3' -sodium disulfonate-4, 4' -dicarboxydiphenyl (SCBP) by adopting a direct polycondensation method, filtering, salting, washing with water, and finally drying in vacuum to obtain sPBI.
(2) Preparation of precursor (Co/sPBI Pre): grinding sPBI obtained in (1) into powder and adding to ultrasonic treated Co (OAc) 2 And (3) in the solution, evaporating by using water, and drying in vacuum to obtain Co/sPBI Pre.
(3) Preparation of nanoparticle catalysts (Co/sPBI NPs): the Co/sPBI Pre obtained in (2) is expressed in N 2 And (5) annealing treatment is carried out by a tube furnace in atmosphere, so that the Co/sPBI NPs are obtained.
Preferably, in step (1), the concentration of the SCBP material is 60%; the solution used for salt leaching is 5 wt% Na 2 CO 3 The soaking time of the solution is 24 h; the vacuum drying temperature was 100℃and the drying time was 36 h.
Preferably, in the step (2), the mass percentages of Co element to sPBI are respectively 0.2, 0.4 and 0.6.
Preferably, in the step (2), the power value of the ultrasonic treatment is 1500W, and the ultrasonic treatment is carried out for 15 min at 90% energy output value; the hydrothermal evaporation temperature is 60 ℃; the vacuum drying temperature was 80℃and the drying time was 24 h.
Preferably, in the step (3), the annealing temperature is 800 ℃, 850 ℃ and 900 ℃, the annealing time is 3 h, and the heating rate is 6 ℃/min.
Compared with the prior art, the preparation method of the OER electrocatalyst provided by the invention has the following steps:
(1) The OER electrocatalyst provided by the invention has the advantages of low raw material cost, no toxicity and no harm, and is easy to obtain; the reaction temperature is stable, the reaction is mild, and the control is easy.
(2) The method provided by the invention produces the OER electrocatalyst in the form of nano particles, and the microcrystalline graphite structure existing in the nano particles optimizes OER conductivity.
According to the preparation method of the OER electrocatalyst, pyrrole-N metal coordination sites are generated after annealing treatment, and Co-N coordination bonds can be formed through strong interaction of Co and sPBI, so that the structural stability of the nano-particles can be improved; in addition, the annealing process also generates pyridine-N species, which can accelerate O 2 Reducing OER overpotential; finally, crystal defects can be generated after annealing treatment, more active sites can be exposed due to the existence of the crystal defects, electron transfer is accelerated, and the adsorption capacity of an intermediate is improved, so that the electrocatalyst has quite large OER activity.
Drawings
The chemical structure of sPBI synthesized by the invention is that 1 H NMR was confirmed; the crystal structures of sPBI and Co/sPBI Pre were analyzed by XRD; the morphology of Co/sPBI NPs was characterized by SEM.
FIG. 1 shows sPBI obtained in example one 1 H NMR spectrum;
FIG. 2 is an XRD spectrum of sPBI and Co/sPBI Pre prepared in examples one and two;
FIG. 3 is an SEM image of Co/sPBI NPs produced in example III.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Embodiment one:
1) Preparation of sPBI: preparation of sPBI by polycondensation reaction 10 g phosphorus pentoxide (P) 2 O 5 ) And 30 g polyphosphoric acid (PPA) to a mechanical stirrer and N 2 100 mL port in a three neck round bottom bottle. The mixture was then stirred at 175℃until P 2 O 5 Completely dissolved and then cooled to about 25 ℃. Then, 4 mmol DAB was put into a bottle and stirred at 80℃and 120℃for 1 h, respectively. After cooling, 2.4 mmol SCBP and 1.6 mmol PE were placed in the mixture. The mixture was then stirred at 120 ℃, 150 ℃, 170 ℃ and 190 ℃ respectively 12 h. After a slight cooling, the mixture was poured into deionized water to give a brown filamentous product. The product was washed with deionized water to remove the remaining acid and then dried over 5 wt% Na 2 CO 3 Soaking 24 h in the solution. The soaked product was then suction filtered and washed to neutral pH. Finally, the neutral pH product was dried in vacuo at 100 ℃ 36 h. Sulfonated polybenzimidazole was prepared and named sPBI.
The sulfonated polybenzimidazole (sPBI) is synthesized by polycondensation of SCBP, DAB and PE in PPA by direct polycondensation. As shown in fig. 1, the H atoms in sPBI match well with all signal peaks. Meanwhile, the signal peaks (H7, H7') of H of benzimidazole ring show different chemical shifts at 13.50 and 13.60 ppm under different chemical environments of sulfonated and non-sulfonated. H1, H8 and H9 all have sharp peaks and the intensity is highest, mainly related to the high H atom content. The chemical shift of H4, H4', H5', H6' is between 7.87 and 7.63 ppm, which is similar to H atom shift in other reported sPBI. 1 H NMR spectra confirmed the chemical structure of sPBI, which was successfully prepared.
In addition, in the case of the optical fiber,
embodiment two:
1) Preparation of precursor (0.2 Co/sPBI Pre): 150 mL deionized water and 180.2 mg Co (OAc) 2 Added to a 300 mL beaker and sonicated at 1500W power value, 90% energy output value for 15 min until a homogeneous solution is formed.Subsequently, 300 s mg s pbi was added to the solution, followed by magnetic stirring at 60 ℃ until the water was completely evaporated. Finally, the product was dried under vacuum at 80 ℃ 24 h. A precursor was prepared and designated 0.2. 0.2 Co/sPBI Pre.
2) Preparation of precursor (0.4 Co/sPBI Pre): 150 mL deionized water and 360.5 mg Co (OAc) 2 Added to a 300 mL beaker and sonicated at 1500W power value, 90% energy output value for 15 min until a homogeneous solution is formed. Subsequently, 300 s mg s pbi was added to the solution, followed by magnetic stirring at 60 ℃ until the moisture was completely evaporated. Finally, the product was dried under vacuum at 80 ℃ 24 h. A precursor was prepared and designated 0.4. 0.4 Co/sPBI Pre.
3) Preparation of precursor (0.6 Co/sPBI Pre): 150 mL deionized water and 540.7 mg Co (OAc) 2 Added to a 300 mL beaker and sonicated at 1500W power value, 90% energy output value for 15 min until a homogeneous solution is formed. Subsequently, 300 s mg s pbi was added to the solution, followed by magnetic stirring at 60 ℃ until the water was completely evaporated. Finally, the product was dried under vacuum at 80 ℃ 24 h. A precursor was prepared and designated 0.6. 0.6 Co/sPBI Pre.
All prepared precursors are different in that Co element accounts for 20%,40% and 60% of sPBI in mass percent, respectively, of sPBI in 0.2 Co/sPBI Pre,0.4 Co/sPBI Pre and 0.6 Co/sPBI Pre. From fig. 2, it can be seen that the sPBI has a broad peak with lower crystallinity at 24.5 °, due to the periodic parallelism of the sPBI polymer backbone, indicating that the sPBI has an amorphous structure. Similarly, co/sPBI Pre also had a broad diffraction peak at 24.5℃indicating good preservation of sPBI polymer chains by immersion, co 2+ Provides good conditions for adsorption. At the same time due to Co 2+ The characteristic diffraction peak intensity of Co/sPBI Pre is reduced compared with sPBI by adding sPBI main chain. Notably, no other crystalline phases were detected in the Co/sPBI precursor, indicating Co 2+ Co/sPBI Pre has been successfully prepared, having been fully incorporated into the sPBI backbone.
Embodiment III:
1) Nanoparticle catalysts (0)Preparation of 2 Co/sPBI NPs-850 ℃): at N 2 In the atmosphere, 150 mg of 0.2 Co/sPBI Pre was placed in a tube furnace, the air tightness was checked, and after the temperature was programmed to 850℃at a temperature-rising rate of 6℃per minute, 3 h was baked. A nanoparticle catalyst was prepared and designated 0.2 Co/sPBI NPs-850 ℃.
2) Preparation of nanoparticle catalyst (0.4 Co/sPBI NPs-850 ℃): at N 2 In the atmosphere, 150 mg of 0.4 Co/sPBI Pre was placed in a tube furnace, the air tightness was checked, and after the temperature was programmed to 850℃at a temperature-rising rate of 6℃per minute, 3 h was baked. A nanoparticle catalyst was prepared and designated 0.4. 0.4 Co/sPBI NPs-850 ℃.
3) Preparation of nanoparticle catalyst (0.6 Co/sPBI NPs-850 ℃): at N 2 In the atmosphere, 150 mg of 0.6 Co/sPBI Pre was placed in a tube furnace, the air tightness was checked, and after the temperature was programmed to 850℃at a temperature-rising rate of 6℃per minute, 3 h was baked. A nanoparticle catalyst was prepared and designated 0.6 Co/sPBI NPs-850 ℃.
The invention also prepares 0.2 Co/sPBI NPs-900 ℃ and 0.4 Co/sPBI NPs-900 ℃ and 0.6 Co/sPBI NPs-900 ℃ at an annealing temperature of 900 ℃, and specific steps are not described any more, and all the prepared nano-catalysts are different in the annealing temperature. As shown in FIG. 3 (a and d represent 0.2 Co/sPBI NPs-850 ℃ and 0.2 Co/sPBI NPs-900 ℃, b and c represent 0.4 Co/sPBI NPs-850 ℃ and 0.4 Co/sPBI NPs-900 ℃, c and f represent 0.6 Co/sPBI NPs-850 ℃ and 0.6 Co/sPBI NPs-900 ℃), SEM images of all Co/sPBI NPs showed similar morphology and structure, i.e., the nanoplatelet structure of sPBI was completely covered by Co/sPBI NPs nanoparticles, indicating Co 2+ The Co/sPBI NPs are successfully prepared by well anchoring on the sPBI surface to form the required nanoparticle structure.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (5)

1. A sulfonated polybenzimidazole-based electrocatalyst for oxygen evolution reaction, characterized in that: the sulfonated polybenzimidazole containing a repeated structural unit is used as a matrix, transition metal is used as a ligand, and transition metal ions are anchored on the surface of a polymer matrix through effective pi-pi accumulation of benzene rings and strong hydrogen bonding;
；
X 1 hydrogen, lithium, sodium, potassium or magnesium ions;
X 2 the structure of (2) is as follows:
；
the repeating structural unit of the sulfonated polybenzimidazole contains one or more X 2 Structure is as follows.
2. The preparation method of the sulfonated polybenzimidazole-based electrocatalyst for oxygen evolution reaction is characterized by adopting a direct polycondensation method and an immersion-annealing treatment, and comprises the following specific steps:
(1) Preparing sulfonated polybenzimidazole, polymerizing 3, 3 '-diaminobenzidine, 4' -dicarboxyl diphenyl ether and 3, 3 '-sodium disulfonate-4, 4' -dicarboxyl biphenyl, filtering, salting, washing with water, and finally vacuum drying to obtain sulfonated polybenzimidazole sPBI;
(2) Preparation of the precursor sPBI was ground to a powder and then added to sonicated Co (OAc) 2 In the solution, carrying out hydrothermal evaporation and vacuum drying to obtain a precursor Co/sPBI Pre;
(3) The preparation method of the nanoparticle catalyst comprises the steps of putting Co/sPBI Pre in N 2 And annealing treatment is carried out by a tube furnace under atmosphere, so that the nano-particle catalyst Co/sPBI NPs is obtained.
3. The method for preparing the sulfonated polybenzimidazole based electrocatalyst for oxygen evolution reaction according to claim 2, wherein: the concentration of 3, 3' -disulfonic acid sodium salt-4, 4' -dicarboxybiphenyl material is 60% of the concentration of 3, 3' -diaminobenzidine material; the solution used for the salt leaching is Na with the concentration of 5 wt percent 2 CO 3 The soaking time of the solution is 24 h; the vacuum drying temperature was 100℃and the drying time was 36 h.
4. The method for preparing the sulfonated polybenzimidazole based electrocatalyst for oxygen evolution reaction according to claim 2, wherein: the mass percentages of Co element to sPBI are respectively 0.2, 0.4 and 0.6; the power value of the ultrasonic treatment is 1500W, and the ultrasonic treatment is carried out for 15 min under the energy output value of 90%; the hydrothermal evaporation temperature is 60 ℃; the vacuum drying temperature was 80℃and the drying time was 24 h.
5. The method for preparing the sulfonated polybenzimidazole based electrocatalyst for oxygen evolution reaction according to claim 2, wherein: the annealing temperature is 800 ℃, 850 ℃ and 900 ℃, the annealing time is 3 h, and the heating rate is 6 ℃/min.
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JP2003327826A (en) * 2002-05-08 2003-11-19 Toyobo Co Ltd Composition containing acidic group-containing polybenzimidazole-based compound and acidic group- containing polymer, ion-conductive film, adhesive, composite material and fuel cell
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