稳定糖异体化过渡状态中的 Entropy 主要作用
Michael J Cordon1, James W Harris1, Juan Carlos Vega-Vila1
1Charles D. Davidson School of Chemical Engineering , Purdue University , 480 Stadium Mall Drive , West Lafayette , Indiana 47907 , United States.
Journal of the American Chemical Society
|September 29, 2018
概括
疏水性焦化物微孔通过减少水干扰和稳定过渡状态来增强糖异构催化,导致与疏水性孔相比的转化率显著提高. 这提高了水溶液中的催化效率.
科学领域:
- 催化剂
- 材料科学
- 物理化学
背景情况:
- 石中的易斯酸位是水相糖异构的关键.
- 微孔极性的对催化活性和反应机制的影响尚不完全理解.
研究的目的:
- 为了阐明协同吸收水对葡萄糖异构反应的影响,在热质体内协调自由能景观.
- 澄清竞争性水吸附和过渡状态稳定在疏水性与疏水性微孔中的作用.
主要方法:
- 在现场减弱的全反射红外 (IR) 光谱和调制刺激光谱.
- 传输红外光谱和密度函数理论 (DFT) 的计算.
- 在Ti-Beta石上对水相葡萄糖异构的动态测量.
主要成果:
- 与水友性化化相比,水友性化具有较高的葡萄糖异构化周转率 (3-12倍).
- 水在性微孔中形成结网络,而不是恐水性.
- 疏水性限制降低了异构化过渡状态的吉布斯自由能量,并减少了水对活性部位的影响.
结论:
- 微孔极性通过调节水吸附和过渡状态稳定,显著影响酸催化糖异构.
- 通过最大限度地减少水干扰和稳定关键反应中间体,疏水性限制提高了催化性能.
- 量身定制齐奥利特微孔极性为优化液相催化过程提供了一个有前途的策略.
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