Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low-Temperature Ionothermal Approach Towards Enhanced CO2 Electroreduction

Xian Suo; Fengtao Zhang; Zhenzhen Yang; Hao Chen; Tao Wang; Zongyu Wang; Takeshi Kobayashi; Chi Linh Do-Thanh; Dmitry Maltsev; Zhimin Liu; Sheng Dai

doi:10.1002/anie.202109342

Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low-Temperature Ionothermal Approach Towards Enhanced CO₂ Electroreduction

Xian Suo, Fengtao Zhang, Zhenzhen Yang, Hao Chen, Tao Wang, Zongyu Wang, Takeshi Kobayashi, Chi Linh Do-Thanh, Dmitry Maltsev, Zhimin Liu, Sheng Dai

Research output: Contribution to journal › Article › peer-review

46 Scopus citations

Abstract

Perfluorinated covalent triazine frameworks (F-CTFs) have shown unique features and attractive performance in separation and catalysis. However, state-of-the-art F-CTFs synthesized via the ZnCl₂-promoted procedure have quite low fluorine contents due to C−F bond cleavage induced by chloride (a Lewis base) and the harsh conditions deployed (400–700 °C). Fabricating F-CTFs with high fluorine contents (>30 wt %) remains challenging. Herein, we present a low-temperature ionothermal approach (275 °C) to prepare F-CTFs, which is achieved via polymerization of tetrafluoroterephthalonitrile (TFPN) over the Lewis superacids, e.g., zinc triflimide [Zn(NTf₂)₂] without side reactions. With low catalyst loading (equimolar), F-CTFs are afforded with high fluorine content (31 wt %), surface area up to 367 m² g⁻¹, and micropores around 1.1 nm. The highly hydrophobic F-CTF-1 exhibits good capability to boost electroreduction of CO₂ to CO, with faradaic efficiency of 95.7 % at −0.8 V and high current density (−141 mA cm⁻²) surpassing most of the metal-free electrocatalysts.

Original language	English
Pages (from-to)	25688-25694
Number of pages	7
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	49
DOIs	https://doi.org/10.1002/anie.202109342
State	Published - Dec 1 2021

Funding

The research was supported financially by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, US Department of Energy. Work at the Ames Laboratory (solid-state NMR) was supported by the Department of Energy-Basic Energy Sciences under Contract No. DE-AC02-07CH11358. The research was supported financially by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, US Department of Energy. Work at the Ames Laboratory (solid‐state NMR) was supported by the Department of Energy‐Basic Energy Sciences under Contract No. DE‐AC02‐07CH11358.

Funders	Funder number
Department of Energy-Basic Energy Sciences
Department of Energy‐Basic Energy Sciences	DE‐AC02‐07CH11358
U.S. Department of Energy
Basic Energy Sciences
Ames Laboratory
Chemical Sciences, Geosciences, and Biosciences Division

Keywords

CO electroreduction
Lewis superacid
covalent triazine framework
fluorinated
ionothermal procedure

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1002/anie.202109342

Cite this

Suo, X., Zhang, F., Yang, Z., Chen, H., Wang, T., Wang, Z., Kobayashi, T., Do-Thanh, C. L., Maltsev, D., Liu, Z., & Dai, S. (2021). Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low-Temperature Ionothermal Approach Towards Enhanced CO₂ Electroreduction. Angewandte Chemie - International Edition, 60(49), 25688-25694. https://doi.org/10.1002/anie.202109342

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title = "Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low-Temperature Ionothermal Approach Towards Enhanced CO2 Electroreduction",

abstract = "Perfluorinated covalent triazine frameworks (F-CTFs) have shown unique features and attractive performance in separation and catalysis. However, state-of-the-art F-CTFs synthesized via the ZnCl2-promoted procedure have quite low fluorine contents due to C−F bond cleavage induced by chloride (a Lewis base) and the harsh conditions deployed (400–700 °C). Fabricating F-CTFs with high fluorine contents (>30 wt %) remains challenging. Herein, we present a low-temperature ionothermal approach (275 °C) to prepare F-CTFs, which is achieved via polymerization of tetrafluoroterephthalonitrile (TFPN) over the Lewis superacids, e.g., zinc triflimide [Zn(NTf2)2] without side reactions. With low catalyst loading (equimolar), F-CTFs are afforded with high fluorine content (31 wt %), surface area up to 367 m2 g−1, and micropores around 1.1 nm. The highly hydrophobic F-CTF-1 exhibits good capability to boost electroreduction of CO2 to CO, with faradaic efficiency of 95.7 % at −0.8 V and high current density (−141 mA cm−2) surpassing most of the metal-free electrocatalysts.",

keywords = "CO electroreduction, Lewis superacid, covalent triazine framework, fluorinated, ionothermal procedure",

author = "Xian Suo and Fengtao Zhang and Zhenzhen Yang and Hao Chen and Tao Wang and Zongyu Wang and Takeshi Kobayashi and Do-Thanh, {Chi Linh} and Dmitry Maltsev and Zhimin Liu and Sheng Dai",

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Suo, X, Zhang, F, Yang, Z, Chen, H, Wang, T, Wang, Z, Kobayashi, T, Do-Thanh, CL, Maltsev, D, Liu, Z & Dai, S 2021, 'Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low-Temperature Ionothermal Approach Towards Enhanced CO₂ Electroreduction', Angewandte Chemie - International Edition, vol. 60, no. 49, pp. 25688-25694. https://doi.org/10.1002/anie.202109342

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T1 - Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low-Temperature Ionothermal Approach Towards Enhanced CO2 Electroreduction

AU - Suo, Xian

AU - Zhang, Fengtao

AU - Yang, Zhenzhen

AU - Chen, Hao

AU - Wang, Tao

AU - Wang, Zongyu

AU - Kobayashi, Takeshi

AU - Do-Thanh, Chi Linh

AU - Maltsev, Dmitry

AU - Liu, Zhimin

AU - Dai, Sheng

PY - 2021/12/1

Y1 - 2021/12/1

N2 - Perfluorinated covalent triazine frameworks (F-CTFs) have shown unique features and attractive performance in separation and catalysis. However, state-of-the-art F-CTFs synthesized via the ZnCl2-promoted procedure have quite low fluorine contents due to C−F bond cleavage induced by chloride (a Lewis base) and the harsh conditions deployed (400–700 °C). Fabricating F-CTFs with high fluorine contents (>30 wt %) remains challenging. Herein, we present a low-temperature ionothermal approach (275 °C) to prepare F-CTFs, which is achieved via polymerization of tetrafluoroterephthalonitrile (TFPN) over the Lewis superacids, e.g., zinc triflimide [Zn(NTf2)2] without side reactions. With low catalyst loading (equimolar), F-CTFs are afforded with high fluorine content (31 wt %), surface area up to 367 m2 g−1, and micropores around 1.1 nm. The highly hydrophobic F-CTF-1 exhibits good capability to boost electroreduction of CO2 to CO, with faradaic efficiency of 95.7 % at −0.8 V and high current density (−141 mA cm−2) surpassing most of the metal-free electrocatalysts.

AB - Perfluorinated covalent triazine frameworks (F-CTFs) have shown unique features and attractive performance in separation and catalysis. However, state-of-the-art F-CTFs synthesized via the ZnCl2-promoted procedure have quite low fluorine contents due to C−F bond cleavage induced by chloride (a Lewis base) and the harsh conditions deployed (400–700 °C). Fabricating F-CTFs with high fluorine contents (>30 wt %) remains challenging. Herein, we present a low-temperature ionothermal approach (275 °C) to prepare F-CTFs, which is achieved via polymerization of tetrafluoroterephthalonitrile (TFPN) over the Lewis superacids, e.g., zinc triflimide [Zn(NTf2)2] without side reactions. With low catalyst loading (equimolar), F-CTFs are afforded with high fluorine content (31 wt %), surface area up to 367 m2 g−1, and micropores around 1.1 nm. The highly hydrophobic F-CTF-1 exhibits good capability to boost electroreduction of CO2 to CO, with faradaic efficiency of 95.7 % at −0.8 V and high current density (−141 mA cm−2) surpassing most of the metal-free electrocatalysts.

KW - CO electroreduction

KW - Lewis superacid

KW - covalent triazine framework

KW - fluorinated

KW - ionothermal procedure

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