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A cofacial metal–organic framework based photocathode for carbon dioxide reduction
Chemical Science ( IF 7.6 ) Pub Date : 2021-1-4 , DOI: 10.1039/d0sc04691d Bowen Ding 1 , Bun Chan 2 , Nicholas Proschogo 1 , Marcello B Solomon 1 , Cameron J Kepert 1 , Deanna M D'Alessandro 1
Chemical Science ( IF 7.6 ) Pub Date : 2021-1-4 , DOI: 10.1039/d0sc04691d Bowen Ding 1 , Bun Chan 2 , Nicholas Proschogo 1 , Marcello B Solomon 1 , Cameron J Kepert 1 , Deanna M D'Alessandro 1
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Innovative and robust photosensitisation materials play a cardinal role in advancing the combined effort towards efficient solar energy harvesting. Here, we demonstrate the photocathode functionality of a Metal–Organic Framework (MOF) featuring cofacial pairs of photo- and electro-active 1,4,5,8-naphthalenediimide (NDI) ligands, which was successfully applied to markedly reduce the overpotential required for CO2 reduction to CO by a well-known rhenium molecular electrocatalyst. Reduction of [Cd(DPNDI)(TDC)]n (DPNDI = N,N′-di(4-pyridyl)-1,4,5,8-naphthalenediimide, H2TDC = thiophene-2,5-dicarboxylic acid) to its mixed-valence state induces through-space Intervalence Charge Transfer (IVCT) within cofacial DPNDI units. Irradiation of the mixed-valence MOF in the visible region generates a DPNDI photoexcited radical monoanion state, which is stabilised as a persistent species by the inherent IVCT interactions and has been rationalised using Density Functional Theory (DFT). This photoexcited radical monoanion state was able to undergo charge transfer (CT) reduction of the rhenium molecular electrocatalyst to effect CO generation at a lower overpotential than that required by the discrete electrocatalyst itself. The exploitation of cofacial MOFs opens new directions for the design philosophy behind light harvesting materials.
中文翻译：
用于二氧化碳还原的共面金属有机框架光电阴极
创新且坚固的光敏材料在推动高效太阳能收集的共同努力中发挥着重要作用。在这里，我们展示了金属有机框架（MOF）的光电阴极功能，该框架具有光活性和电活性1,4,5,8-萘二亚胺（NDI）配体的共面对，该功能已成功应用于显着降低所需的过电势通过众所周知的铼分子电催化剂将CO 2还原为CO。 [Cd(DPNDI)(TDC)] n的还原（DPNDI = N , N '-二(4-吡啶基)-1,4,5,8-萘二亚胺，H 2 TDC = 噻吩-2,5-二甲酸）其混合价态会在共面 DPNDI 单元内引起跨空间间隔电荷转移 (IVCT)。在可见光区域照射混合价 MOF 会产生 DPNDI 光激发自由基单阴离子态，该态通过固有的 IVCT 相互作用稳定为持久物质，并使用密度泛函理论 (DFT) 进行了合理化。这种光激发自由基单阴离子状态能够经历铼分子电催化剂的电荷转移（CT）还原，从而在比离散电催化剂本身所需的过电势更低的过电势下产生CO。共面 MOF 的开发为光收集材料背后的设计理念开辟了新的方向。
更新日期：2021-01-25
中文翻译：
用于二氧化碳还原的共面金属有机框架光电阴极
创新且坚固的光敏材料在推动高效太阳能收集的共同努力中发挥着重要作用。在这里，我们展示了金属有机框架（MOF）的光电阴极功能，该框架具有光活性和电活性1,4,5,8-萘二亚胺（NDI）配体的共面对，该功能已成功应用于显着降低所需的过电势通过众所周知的铼分子电催化剂将CO 2还原为CO。 [Cd(DPNDI)(TDC)] n的还原（DPNDI = N , N '-二(4-吡啶基)-1,4,5,8-萘二亚胺，H 2 TDC = 噻吩-2,5-二甲酸）其混合价态会在共面 DPNDI 单元内引起跨空间间隔电荷转移 (IVCT)。在可见光区域照射混合价 MOF 会产生 DPNDI 光激发自由基单阴离子态，该态通过固有的 IVCT 相互作用稳定为持久物质，并使用密度泛函理论 (DFT) 进行了合理化。这种光激发自由基单阴离子状态能够经历铼分子电催化剂的电荷转移（CT）还原，从而在比离散电催化剂本身所需的过电势更低的过电势下产生CO。共面 MOF 的开发为光收集材料背后的设计理念开辟了新的方向。
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