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可重复使用的氧化催化,使用金属单甲基在坚固的金属有机框架中的物种
Honghan Fei1, JaeWook Shin, Ying Shirley Meng
1Department of Chemistry and Biochemistry and ‡Department of NanoEngineering, University of California, San Diego , La Jolla, California 92093, United States.
Journal of the American Chemical Society
|March 7, 2014
概括
研究人员使用后合成交换开发了新的金属有机框架 (MOF),以创建活跃的金属中心. 这些MOF催化剂有效氧化酒精,提供可回收和绿色化学溶液.
科学领域:
- 材料科学 材料科学 材料科学
- 催化剂是一种催化剂.
- 协调化学 协调化学
背景情况:
- 金属有机框架 (MOF) 为各种应用提供可调节的结构.
- 合成后的MOF功能化对于创建先进材料至关重要.
- 在MOF中实现孤立的活性金属位点仍然是一个合成挑战.
研究的目的:
- 为了开发强大的金属有机框架 (MOFs) 与隔离的金属单基分子.
- 为了比较MOF功能化后合成脱保护 (PSD) 和后合成交换 (PSE).
- 调查新型Cr金属化MOFs对酒精氧化的催化活性.
主要方法:
- 在基于Zr(IV的UIO MOF上利用了合成后交换 (PSE) 和合成后去保护 (PSD) 策略.
- 使用X射线吸收光谱学,X波段电子偏磁共振光谱学和 (57) Fe Mössbauer光谱学对金属化MOF进行了鉴定.
- 在酒精氧化反应中评估了Cr金属化MOF的催化性能.
主要成果:
- 通过PSE和PSD成功地在强大的MOF中实现了孤立的Fe-monocatecholato和Cr-monocatecholato物种.
- PSE被证明是一个比PSD更容易和更有效的功能化方法.
- 由此产生的基于Zr(IV) 的UiO MOF具有协调不和的活性金属中心.
- 金属化MOF在低金属负载 (0.5-1mol%) 的酒精氧化中表现出高活性和效率.
结论:
- 合成后的策略,特别是PSE,使得功能化MOFs与前所未有的金属单甲基物种的简单合成成为可能.
- 开发的Cr金属化MOF是高效的,可回收的催化剂,用于酒精氧化,与绿色化学原则保持一致.
- 这些发现为设计具有协调不和活性位点的先进MOF基催化剂提供了新的途径.
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