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    柠檬酸调控Ni/La3Ce7Ox实现高效氨分解制氢过渡金属改性及失活作用机制研究

    Citric acid modified Ni/La3Ce7Ox to achieve efficient ammonia decomposition for hydrogen production: Mechanism of modification with transition metals and deactivation

    • 摘要: 为开发高效非贵金属氨分解制氢催化剂,探究了过渡金属(Co、Fe、Mn、Cu)掺杂与络合剂(柠檬酸、柠檬酸三铵)改性对Ni/La3Ce7Ox结构与催化性能的影响。研究结果表明:过渡金属掺杂引发催化剂晶粒尺寸生长、比表面积降低、氧空位减少,导致金属–载体相互作用弱化。柠檬酸改性则显著减小催化剂的晶粒尺寸、提高其低温还原性和氧缺陷浓度。催化性能测试表明:添加柠檬酸制备的Ni/La3Ce7Ox催化剂具有优异的催化活性和稳定性,其在气体空速为60000 mL/(g·h)和温度为550 ℃的条件下,氨分解转化率和氢气生成速率分别可达57.5%和39 mmol/(g·min),且在100 h循环测试中活性保持稳定。以上结果为低成本高效氨分解制氢催化剂的制备提供了参考。

       

      Abstract: In order to develop efficient non-precious metal catalysts for hydrogen production by ammonia decomposition, the effects of transition metal (Co, Fe, Mn, Cu) doping and chelating agent (citric acid, triammonium citrate) modification on the structure and properties of Ni/La3Ce7Ox were investigated. The results reveal that transition metal doping led to structural degradation of the catalyst, as indicated by increased grain size, reduced specific surface area, and decreased oxygen vacancies, which in turn lead to weakened metal-support interactions. Citric acid modification significantly optimizes the catalyst structure, reducing grain size, enhancing low-temperature reducibility, and increasing oxygen defect concentration. Performance testing demonstrates that the Ni/La3Ce7Ox catalyst, prepared via citric acid addition, exhibits excellent catalytic activity and stability. Under conditions of a gas hourly space velocity of 60000 mL/(g·h) and a temperature of 550 °C, the ammonia decomposition conversion and hydrogen production rate reach 57.5% and 39 mmol/(g·min), respectively. Moreover, the catalyst maintains stable activity over a 100 h cycling test. The above results provide valuable insights for the development of cost-effective and high-performance catalysts for ammonia decomposition to hydrogen production.

       

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