Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), School of Chemistry and Materials Science, Hefei Science Center (CAS), and National Synchrotron Radiation Laboratory, University of Science and Technology of China , Hefei, Anhui 230026, P. R. China.
J Am Chem Soc. 2016 Jul 20;138(28):8928-35. doi: 10.1021/jacs.6b04629. Epub 2016 Jul 11.
Modern development of chemical manufacturing requires a substantial reduction in energy consumption and catalyst cost. Sunlight-driven chemical transformation by metal oxides holds great promise for this goal; however, it remains a grand challenge to efficiently couple solar energy into many catalytic reactions. Here we report that defect engineering on oxide catalyst can serve as a versatile approach to bridge light harvesting with surface reactions by ensuring species chemisorption. The chemisorption not only spatially enables the transfer of photoexcited electrons to reaction species, but also alters the form of active species to lower the photon energy requirement for reactions. In a proof of concept, oxygen molecules are activated into superoxide radicals on defect-rich tungsten oxide through visible-near-infrared illumination to trigger organic aerobic couplings of amines to corresponding imines. The excellent efficiency and durability for such a highly important process in chemical transformation can otherwise be virtually impossible to attain by counterpart materials.
现代化学制造的发展需要大量减少能源消耗和催化剂成本。金属氧化物的阳光驱动的化学转化为实现这一目标带来了巨大的希望;然而,将太阳能有效地耦合到许多催化反应中仍然是一个巨大的挑战。在这里,我们报告说,氧化物催化剂的缺陷工程可以作为一种通用的方法,通过确保物种化学吸附来桥接光捕获和表面反应。化学吸附不仅在空间上将光激发电子转移到反应物种,而且还改变活性物种的形式,以降低反应的光子能量要求。在一个概念验证中,通过可见光-近红外光照射,富含缺陷的氧化钨将氧分子激活成超氧自由基,从而引发胺与相应亚胺的有氧偶联。对于化学转化中如此重要的过程,这种卓越的效率和耐久性是用其他对比材料几乎不可能实现的。