Stable Dioxin-Linked Metallophthalocyanine Covalent Organic Frameworks (COFs) as Photo-Coupled Electrocatalysts for CO2 Reduction
Stable Dioxin-Linked Metallophthalocyanine Covalent Organic Frameworks (COFs) as Photo-Coupled Electrocatalysts for CO2 Reduction
复制标题
稳定的二恶英连接的金属酞菁共价有机骨架（COF）作为二氧化碳还原的光耦合电催化剂
DOI：
10.1002/anie.202011722
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发表时间：
2021-01-04
影响因子：
16.6
通讯作者：
Lan, Ya-Qian
中科院分区：
文献类型：
--
作者：
Lu, Meng;Zhang, Mi;Lan, Ya-Qian
本工作在网状化学的指导下，合理设计了一系列结晶且稳定的二恶英连接的金属酞菁共价有机框架（COF; MPc-TFPN COF，M=Ni、Co、Zn）。作为一种新型的单活性中心催化剂，NiPc/CoPc-TFPNCOF具有优异的电催化还原CO2的活性和选择性（ECR; CO法拉第效率（FECO）=99.8（+/- 1.24）%/ 96.1（+/- 1.25）%）。更重要的是，当与光耦合时，与黑暗环境相比，NiPc-TPN COF的FECO和电流密度（j（CO））在所施加的电势范围（相对于RHE为-0.6至-1.2V）内得到进一步改善（j（CO）在-0.9V下从14.1增加至17.5A g（-1）; FECO达到高达约100 A g（-1））。在-0.8至-0.9 V时为100%）。并通过密度泛函理论（DFT）模拟和实验表征，对反应机理进行了深入的研究。本工作首次探索了COFs作为光耦合电催化剂提高ECR效率的应用，显示了将光敏COFs用于电催化领域的潜力。
In this work, we rationally designed a series of crystalline and stable dioxin-linked metallophthalocyanine covalent organic frameworks (COFs; MPc-TFPN COF, M=Ni, Co, Zn) under the guidance of reticular chemistry. As a novel single-site catalysts (SSCs), NiPc/CoPc-TFPN COF exhibited outstanding activity and selectivity for electrocatalytic CO2 reduction (ECR; Faradaic efficiency of CO (FECO)=99.8(+/- 1.24) %/ 96.1(+/- 1.25) % for NiPc/CoPc-TFPN COF). More importantly, when coupled with light, the FECO and current density (j(CO)) were further improved across the applied potential range (-0.6 to -1.2 V vs. RHE) compared to the dark environment for NiPc-TFPN COF (j(CO) increased from 14.1 to 17.5 A g(-1) at -0.9 V; FECO reached up to ca. 100 % at -0.8 to -0.9 V). Furthermore, an in-depth mechanism study was established by density functional theory (DFT) simulation and experimental characterization. For the first time, this work explored the application of COFs as photo-coupled electrocatalysts to improve ECR efficiency, which showed the potential of using light-sensitive COFs in the field of electrocatalysis.