Nitrogen, sulfur co-doped carbon-supported non-noble metal oxygen reduction catalyst and preparation method
A non-precious metal, nitrogen-doped carbon technology, which is applied in chemical instruments and methods, physical/chemical process catalysts, chemical/physical processes, etc., can solve the problems of difficult control of the process conditions in the preparation process, unfavorable catalyst industrialization, and complex catalyst preparation methods and other problems, to achieve excellent stability and methanol resistance, good ORR catalytic activity, and facilitate the effect of diffusion transfer
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[0064] Synthesis of tripyrrole-[1,3,5]-triazine (TPT):
[0065] Add 6.78g (0.10mol) of pyrrole and 80mL of anhydrous tetrahydrofuran into a 250mL single-necked round-bottomed flask, add KOH (8.86g, 0.15mol) into the above system under ice-cooling, rise to room temperature for 3 hours, and divide Add 5.59g (0.03mol) of cyanuric chloride in batches, and continue stirring at room temperature for 18h. After the reaction was completed, the reaction system was poured into a 250mL ice-water bath to settle, filtered, washed with deionized water three times (200mL×3), and then dried in a vacuum oven at 80°C for 24h. The obtained crude product was recrystallized with 15 mL of acetone and ethanol mixed solvent (acetone: ethanol ratio of 4:1), filtered, washed with ethanol, and the obtained off-white solid was vacuum-dried at room temperature to constant weight, 4.64 g, yield 56%, melting point: 210 ° C .
Embodiment 1
[0067] (1) Synthesis (P(TPT+Tp)): 55g (0.2mol) tripyrrole-[1,3,5]-triazine (TPT), 50.5g (0.6mol) thiophene (Tp) were dissolved in 2000mL nitric acid Add 18.26g (0.24mol) of dimethoxymethane and 32.28g (0.24mol) of anhydrous aluminum trichloride to benzene, stir at 45°C for 5h, then rise to 80°C and stir for 19h; after the reaction is complete, pour Settled in 10L methanol, filtered, washed with water (1000mL×2), and dried for later use; the infrared spectrum of polymer P (TPT+Tp) was as follows figure 1 shown.
[0068] The partial structure (i.e. repeating unit) of the polymer is as follows:
[0069] where n=1;
[0070] (2) Add 2.5g (P(TPT+Tp)) and 0.7g ferric chloride into 300mL ethanol, ultrasonically disperse the whole system for 180min, evaporate the ethanol to dryness, and dry in a vacuum oven at 80°C 4h;
[0071] (3) Gained 3.2g powdery solid in N2 Heat treatment at 900°C for 1 h in the atmosphere to obtain 0.9 g of nitrogen-doped carbon material;
[0072] (4) The...
Embodiment 2
[0081] (1) Synthesis (P(TPT+Tp)): 55g (0.2mol) tripyrrole-[1,3,5]-triazine (TPT), 50.5g (0.6mol) thiophene (Tp) were dissolved in 2000mL nitric acid Add 24g (0.24mol) dichloroethane and 32.28g (0.24mol) anhydrous aluminum trichloride to benzene, stir at 45°C for 5h, then rise to 80°C and stir for 19h; after the reaction is complete, pour 10L methanol Settling in medium, filtering, washing with water (1000mL×2), drying for later use; the infrared spectrum of polymer P (TPT+Tp) is as follows figure 1 shown;
[0082] (2) Add 2.5g (P(TPT+Tp)) and 0.7g ferric chloride into 300mL ethanol, ultrasonically disperse the whole system for 180min, evaporate the ethanol to dryness, and dry in a vacuum oven at 80°C 4h, obtain primary mixture;
[0083] (3) Gained 3.2g powdery solid in N 2 Heat treatment at 800°C for 1 hour in the atmosphere to obtain 0.95g of nitrogen-doped carbon material;
[0084] (4) The obtained nitrogen-doped carbon material was washed with 2000mL 0.5M dilute sulfuri...
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