Acid and Base Resistant Zirconium Polyphenolate-Metalloporphyrin Scaffolds for Efficient CO2 Photoreduction

Er-Xia Chen; Mei Qiu; Yong-Fan Zhang; Yong-Sheng Zhu; Li-Yang Liu; Ya-Yong Sun; Xianhui Bu; Jian Zhang; Qipu Lin

doi:10.1002/adma.201704388

Acid and Base Resistant Zirconium Polyphenolate-Metalloporphyrin Scaffolds for Efficient CO₂ Photoreduction

Adv Mater. 2018 Jan;30(2). doi: 10.1002/adma.201704388. Epub 2017 Nov 27.

Authors

Er-Xia Chen^{1

2}, Mei Qiu³, Yong-Fan Zhang⁴, Yong-Sheng Zhu¹, Li-Yang Liu¹, Ya-Yong Sun¹, Xianhui Bu⁵, Jian Zhang¹, Qipu Lin¹

Affiliations

¹ State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China.
² University of Chinese Academy of Sciences, Beijing, 100049, China.
³ College of Science, Jiangxi Agricultural University, Jiangxi, 330045, China.
⁴ College of Chemistry, Fuzhou University, Fuzhou, 350116, China.
⁵ Department of Chemistry and Biochemistry, California State University, Long Beach, CA, 90840, USA.

PMID: 29178432
DOI: 10.1002/adma.201704388

Abstract

A series of zirconium polyphenolate-decorated-(metallo)porphyrin metal-organic frameworks (MOFs), ZrPP-n (n = 1, 2), featuring infinite Zr^IV -oxo chains linked via polyphenolate groups on four peripheries of eclipse-arranged porphyrin macrocycles, are successfully constructed through a top-down process from simulation to synthesis. These are the unusual examples of Zr-MOFs (or MOFs in general) based on phenolic porphyrins, instead of commonly known carboxylate-based types. Representative ZrPP-1 not only exhibits strong acid resistance (pH = 1, HCl) but also remains intact even when immersed in saturated NaOH solution (≈20 m), an exceptionally large range of pH resistance among MOFs. The metallation at the porphyrin core gives rise to materials with enhanced sorption and catalytic properties. In particular, ZrPP-1-Co, with precise and uniform distribution of active centers, exhibits not only high CO₂ trapping capability (≈90 cm³ g^-1 at 1 atm, 273 K, among the highest in Zr-MOFs) but also high photocatalytic activity for reduction of CO₂ into CO (≈14 mmol g^-1 h^-1 ) and high selectivity over CH₄ (>96.4%) without any cocatalyst under visible-light irradiation (λ > 420 nm). Given the strong chemical resistance under extreme alkali conditions, these catalysts can be recycled without appreciable loss of activity. The possible mechanism for photocatalytic reduction of CO₂ -to-CO over ZrPP-1-Co is also proposed.

Keywords: acid-base-proof materials; carbon dioxide photoreduction; microporous frameworks; pyrogallic porphyrins; zirconium-phenolates.