Zhang Bingqing, Xu Shaochen, He Da, Chen Rong, He Yumin, Fa Wenjun, Li Gonghu, Wang Dunwei
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
Department of Chemistry, University of New Hampshire, Durham, New Hampshire 03824, USA.
J Chem Phys. 2020 Aug 14;153(6):064703. doi: 10.1063/5.0016459.
(Photo)electrochemistry enables the synthesis of high-value fine chemicals and highly selective activation of molecules that are difficult to prepare using conventional chemical methods. In this work, light-driven NADH (reduced nicotinamide adenine dinucleotide) regeneration is achieved using a molecular Rh(III) mediator on Si photoelectrodes. This process is observed to be highly sensitive to the surface nature of Si photoelectrodes, exhibiting an overpotential reduction up to 600 mV on Si nanowires (SiNWs) as compared to planar Si. The use of a molecular mediator and SiNWs enables 100% selectivity toward NADH synthesis within a broad potential window. The origin of the striking difference is identified as the multifaceted nature of SiNWs.
（光）电化学能够合成高价值精细化学品，并对难以用传统化学方法制备的分子进行高选择性活化。在这项工作中，通过在硅光电极上使用分子铑（III）介质实现了光驱动的NADH（还原型烟酰胺腺嘌呤二核苷酸）再生。观察到该过程对硅光电极的表面性质高度敏感，与平面硅相比，在硅纳米线（SiNWs）上的过电位降低高达600 mV。分子介质和硅纳米线的使用在很宽的电位窗口内实现了对NADH合成的100%选择性。这种显著差异的根源被确定为硅纳米线的多面性质。
