Decoupling Redox Hopping and Catalysis in Metal‐Organic Frameworks ‐based Electrocatalytic CO 2 Reduction
Decoupling Redox Hopping and Catalysis in Metal‐Organic Frameworks ‐based Electrocatalytic CO 2 Reduction
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基于金属有机框架的电催化 CO 2 还原中氧化还原跳跃和催化的解耦
DOI：
10.1002/anie.202219046
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Deria, Pravas
中科院分区：
文献类型：
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作者：
Li, Xinlin;Surendran Rajasree, Sreehari;Gude, Venkatesh;Maindan, Karan;Deria, Pravas
由催化连接体构建的传统MOF e-CRR在其多电子活化期间表现出动力学瓶颈。脱耦合催化和电荷传输可以解决这些问题。在这里，我们通过在氧化还原活性NU-1000 MOF中安装钴金属化酞菁和四苯基卟啉电催化剂，构建了两个MOF/e-CRR系统，CoPc@NU-1000和TPP（Co）@NU-1000。对于CoPc@NU‐1000，与TPP（Co）@NU‐1000相比，e-CRR响应CoI/0电位接近NU‐ 1000降低的电位。高效的电荷传输，由CoPC@NU-1000中较高的扩散（Dhop=4.1×10− 12 cm 2s −1）和较低的电荷传输电阻（=59.5 Ω）定义，导致FECO= 80%。 相比之下，NU-1000的TPP（Co）表现出较差的FECO= 24%（Dhop=1.4×10− 12 cm 2s − 1和=91.4 Ω）。 对于这样的解耦策略，仔细选择主体框架在与催化剂的潜在电化学性质配对以促进其活化的电荷递送方面是至关重要的。
Traditional MOF e‐CRR, constructed from catalytic linkers, manifest a kinetic bottleneck during their multi‐electron activation. Decoupling catalysis and charge transport can address such issues. Here, we build two MOF/e‐CRR systems, CoPc@NU‐1000 and TPP(Co)@NU‐1000, by installing cobalt metalated phthalocyanine and tetraphenylporphyrin electrocatalysts within the redox active NU‐1000 MOF. For CoPc@NU‐1000, the e‐CRR responsive CoI/0potential is close to that of NU‐1000 reduction compared to the TPP(Co)@NU‐1000. Efficient charge delivery, defined by a higher diffusion (Dhop=4.1×10−12cm2s−1) and low charge‐transport resistance ( =59.5 Ω) in CoPC@NU‐1000 led FECO=80 %. In contrast, TPP(Co)@NU‐1000 fared a poor FECO=24 % (Dhop=1.4×10−12cm2s−1and =91.4 Ω). For such a decoupling strategy, careful choice of the host framework is critical in pairing up with the underlying electrochemical properties of the catalysts to facilitate the charge delivery for its activation.