Hierarchical porous sno2/zsm-5 methanol fuel cell anode catalyst and preparation method thereof
A crystallization and pore wall technology, applied in physical/chemical process catalysts, battery electrodes, molecular sieve catalysts, etc., can solve the problems of being unsuitable for large-scale commercial application and expensive, and achieve high methanol electrooxidation catalytic activity, high Effect of anti-CO poisoning properties
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[0035] The present invention also provides a kind of SnO that can be used as methanol fuel cell anode catalyst 2 The preparation method of / hierarchical pore (mesoporous) zeolite ZSM-5, described method comprises:
[0036] A) Hydrothermal synthesis of hierarchically porous (mesoporous) zeolite molecular sieves as a precursor;
[0037] B) Surface modification (such as using silane coupling agent) is used to make the surface of hierarchical porous (mesoporous) ZSM-5 negatively charged, and the Sn 4+ Uniformly grafted onto the surface of hierarchically porous (mesoporous) ZSM-5;
[0038] C) By titrating lye (NH 3 .H 2 O or NaOH) to form Sn(OH) 4 ;
[0039] D) While heat-treating at 400-700°C for 5-7 hours to crystallize the walls of the hierarchical pores (mesoporous) ZSM-5, the Sn(OH) 4 Thermal decomposition to form SnO 2 .
[0040] Zeolite materials have always been a research hotspot for domestic and foreign researchers. This type of heterogeneous catalyst occupies an i...
Embodiment 1
[0062] According to the above-mentioned technical scheme and process flow of the present invention, firstly, a multi-level porous (mesoporous) ZSM-5 zeolite precursor material is prepared. Weigh 0.3066g of aluminum isopropoxide and 15.624g of ethyl silicate and mix and add 45g of water and stir at room temperature, then dropwise add 10.98g of tetrapropylammonium hydroxide (TPAOH, 25wt%), 0.27g of NaOH and 45g of water The mixed solution was stirred at 40°C for 3h, then transferred to an oil bath at 100°C and continued to stir for 2d. The above reaction was carried out in a 250ml Duran bottle with good sealing performance. The above suspension was suction filtered, and the obtained powder was dried in an oven at 100°C to obtain a hierarchically porous (mesoporous) ZSM-5 zeolite;
[0063] After taking 0.5g of the above-mentioned zeolite molecular sieve powder and pulverizing it, add 100ml of water and 60g of ethanol to the mixed solution for ultrasonic dispersion, and then slowl...
Embodiment 2
[0067]According to technological process described (same as embodiment 1), take by weighing 0.3066g aluminum isopropoxide and 15.624g ethyl silicate mix and add 25g water to prepare hierarchical porous (mesoporous) ZSM-5 zeolite, other operations are implemented with Example 1, and electrostatically attracts Sn 4+ The resulting powder was calcined in a muffle furnace at 550°C for 7 hours to obtain SnO 2 / Hierarchical porous (mesoporous) ZSM-5 composite material; the specific surface area of the composite material is 371m 2 / g (Table 1), the shape is an irregular ellipsoid, the size is ~300nm, and the pore size is 10~50nm, such as figure 2 As shown in the SEM photos of B and D; and the material exhibits high catalytic activity for the electrochemical catalytic oxidation of CO, as shown in Figure 4A As shown, it has good anti-CO poisoning performance.
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