Single-Atom Metal Anchored Zr6-Cluster-Porphyrin Framework Hollow Nanocapsules with Ultrahigh Active-Center Density for Electrocatalytic CO2 Reduction

Wenjun Zhang; Yuren Xia; Shuangming Chen; Yi Hu; Songyuan Yang; Zuoxiu Tie; Zhong Jin

doi:10.1021/acs.nanolett.2c00547

Single-Atom Metal Anchored Zr₆-Cluster-Porphyrin Framework Hollow Nanocapsules with Ultrahigh Active-Center Density for Electrocatalytic CO₂ Reduction

Nano Lett. 2022 Apr 27;22(8):3340-3348. doi: 10.1021/acs.nanolett.2c00547. Epub 2022 Apr 12.

Authors

Wenjun Zhang^{1

2}, Yuren Xia^{1

3}, Shuangming Chen⁴, Yi Hu^{1

3}, Songyuan Yang^{1

3}, Zuoxiu Tie^{1

3}, Zhong Jin^{1

3}

Affiliations

¹ MOE Key Laboratory of Mesoscopic Chemistry, MOE Key Laboratory of High Performance Polymer Materials and Technology, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu 210023, China.
² Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Jiangsu Province Key Laboratory of Green Biomass-based Fuels and Chemicals, College of Chemical Engineering, Nanjing Forestry University, Nanjing, Jiangsu 210037, China.
³ Suzhou Tierui New Energy Technology Co. Ltd., Suzhou, Jiangsu 215228, China.
⁴ National Synchrotron Radiation Laboratory CAS Center for Excellence in Nanoscience, University of Science and Technology of China Hefei, Hefei, Anhui 230029, China.

PMID: 35412833
DOI: 10.1021/acs.nanolett.2c00547

Abstract

Designing earth-abundant electrocatalysts toward highly efficient CO₂ reduction has significant importance to decrease the global emission of greenhouse gas. Herein, we propose an efficient strategy to anchor non-noble metal single atoms on Zr₆-cluster-porphyrin framework hollow nanocapsules with well-defined and abundant metal-N₄ porphyrin sites for efficient electrochemical CO₂ reduction. Among different transition metal single atoms (Mn, Fe, Co, Ni, and Cu), Co single-atom anchored Zr₆-cluster-porphyrin framework hollow nanocapsules demonstrated the highest activity and selectivity for CO production. The rich Co-N₄ active centers and hierarchical porous structure contribute to enhanced CO₂ adsorption capability and moderate binding strength of reaction intermediates, thus facilitating *CO desorption and CO₂-to-CO conversion. The Co-anchored nanocapsules maintain high efficiency and well-preserved stability during long-term electrocatalysis tests. Moreover, the Co-anchored nanocapsules exhibit a remarkable solar-to-CO energy conversion efficiency of 12.5% in an integrated solar-driven CO₂ reduction/O₂ evolution electrolysis system when powered by a custom large-area [Cs_0.05(FA_0.85MA_0.15)_0.95]Pb_0.9(I_0.85Br_0.15)₃-based perovskite solar cell.

Keywords: Co−N4 sites; active-center density; electrochemical CO2 reduction; porous coordination network; single-atom anchoring.