采用XAFS,XRD和DTA方法研究了Ni-B和Ni-Ce-B超细非晶态合金在退火过程中的结构变化及其结构与催化性能的关系. 活性结果表明,在退火温度为623 K时,Ni-B和Ni-Ce-B样品的苯加氢催化反应转化率最高,分别为63%和81%, 0.3% Ce的掺入提高了Ni-Ce-B的催化活性. DTA结果表明,Ni-B超细非晶态合金在598和653 K有两个晶化峰,而Ni-Ce-B样品有5 48,603,696和801 K四个晶化峰. XAFS和XRD结果进一步说明,在573 K退火时,Ni-B样品晶化生成晶态Ni3B和纳米晶Ni,此时Ni-Ce-B仅有少量晶态Ni3B生成. 在673 K退火时, Ni -B样品中的Ni3B开始分解生成晶态Ni, 同时纳米晶Ni聚集并形成大颗粒晶态Ni, 而Ni-C e-B样品晶化生成晶态Ni3B和纳米晶Ni. 在773 K和更高的温度退火处理后,Ni-B样品中N i的局域环境结构与金属Ni箔基本一致,但Ni-Ce-B样品晶化生成的Ni晶格有较大畸变,同时Ni3B并未分解. 说明0.3%的Ce对提高Ni-Ce-B样品的稳定性有显著作用. 本文首次报道了Ni-B和Ni-Ce-B超细非晶态合金中苯加氢催化活性中心为纳米晶Ni和类似于金属Ni的 Ni-B非晶态合金.
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