Mechanistic Probes of Zeolitic Imidazolate Framework for Photocatalytic Application
Mechanistic Probes of Zeolitic Imidazolate Framework for Photocatalytic Application
复制标题
DOI：
10.1021/acscatal.7b02467
复制
发表时间：
2017-11
期刊：
影响因子：
12.9
通讯作者：
B. Pattengale;Sizhuo Yang;Sungsik Lee;Jier Huang
中科院分区：
文献类型：
--
作者：
B. Pattengale;Sizhuo Yang;Sungsik Lee;Jier Huang
在这项工作中，我们报告了一种沸石咪唑骨架（ZIF-67）具有显着的活性，在析氢反应（HER）：40 - 500 μmol H2/g的金属有机骨架（MOF）。据我们所知，这是任何MOF系统实现的最高活性。这一结果需要使用先进的光谱技术，包括时间分辨光学（OTA）和原位X射线吸收（XAS）光谱，评估ZIF-67在HER中的原子尺度机制功能。通过OTA结果与催化性能的相关性，我们证明光敏剂和ZIF-67之间的电子转移（ET）途径而不是能量转移（ENT）途径是控制HER活性效率的关键因素，因为经历ET途径的HER活性比经历ENT过程的HER活性高3个数量级。利用原位XAS，我们解开了关键中间物种的光谱特征，这可能是负责...
In this work, we report a zeolitic imidazolate framework (ZIF-67) with remarkable activity in the hydrogen evolution reaction (HER): 40 500 μmol H2/g of metal organic framework (MOF). This is, to the best of our knowledge, the highest activity achieved by any MOF system. This result necessitated assessment of the atomic-scale mechanistic function of ZIF-67 in HER, using advanced spectroscopy techniques, including time-resolved optical (OTA) and in situ X-ray-absorption (XAS) spectroscopy. Through the correlation of the OTA results with the catalytic performance, we demonstrated that the electron transfer (ET) pathway, rather than the energy transfer (ENT) pathway, between the photosensitizer and ZIF-67 is the key factor that controls the efficiency of HER activity, because HER activity that undergoes the ET pathway is 3 orders of magnitude higher than that which undergoes the ENT process. Using in situ XAS, we unraveled the spectral features for key intermediate species, which are likely responsible for t...