Spectroscopic evidence for origins of size and support effects on selectivity of Cu nanoparticle dehydrogenation catalysts.
Spectroscopic evidence for origins of size and support effects on selectivity of Cu nanoparticle dehydrogenation catalysts.
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DOI：
10.1039/c6cc08305f
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发表时间：
2017-01
影响因子：
4.9
通讯作者：
Megan E. Witzke;Paul J. Dietrich;Malek Y. S. Ibrahim;K. Al-Bardan;M. D. Triezenberg;David W. Flaherty
中科院分区：
文献类型：
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作者：
Megan E. Witzke;Paul J. Dietrich;Malek Y. S. Ibrahim;K. Al-Bardan;M. D. Triezenberg;David W. Flaherty
由生物衍生乙醇生产乙醛的选择性脱氢催化剂可以提高后续工艺的效率，例如通过金属氧化物进行C-C偶联以生产1-丁醇或1，3-丁二烯或氧化成乙酸。在这里，我们使用原位X-射线吸收光谱和稳态动力学实验，以确定Cuδ+在周边的负载Cu簇作为酯化和Cu 0表面的网站作为脱氢的网站的活性中心。脱氢和酯化选择性的Cu氧化态的原位测量的相关性表明，这种关系适用于在宽范围的直径（2-35 nm）和催化剂载体的Cu簇，并揭示，脱氢选择性可以通过操纵控制。
Selective dehydrogenation catalysts that produce acetaldehyde from bio-derived ethanol can increase the efficiency of subsequent processes such as C-C coupling over metal oxides to produce 1-butanol or 1,3-butadiene or oxidation to acetic acid. Here, we use in situ X-ray absorption spectroscopy and steady state kinetics experiments to identify Cuδ+ at the perimeter of supported Cu clusters as the active site for esterification and Cu0 surface sites as sites for dehydrogenation. Correlation of dehydrogenation and esterification selectivities to in situ measures of Cu oxidation states show that this relationship holds for Cu clusters over a wide-range of diameters (2-35 nm) and catalyst supports and reveals that dehydrogenation selectivities may be controlled by manipulating either.