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Gangfeng Ouyang thanks the National Natural Science Foundation of China (21737006, 22076222 and 22036003). Yong Shen acknowledges the Natural Science Foundation of Guangdong Province (2021A1515010068). Jia-Wei Wang acknowledges Prof. Antoni Llobet (ICIQ, present supervisor of Dr Jia-Wei Wang and Zhi-Mei Luo) for providing scholar resources during manuscript preparation as well as the financial support from Guangdong Basic and Applied Basic Research Foundation (2020A1515110017 and 2021A1515012033). Dooshaye Moonshiram acknowledges funding from the Ramon y Cajal grant RYC2020-029863-I through the Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Cientificas and the Spanish Ministerio de Ciencia, Innovacion y Universidades grant (PID2019-111086RA-I00). We also thank Dr Gautier Landrot for help with synchrotron measurements at the SAMBA beamline at SOLEIL.

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Impaired conjugation boosts CO2 electroreduction by Ni(ii) macrocyclic catalysts immobilized on carbon nanotubes

Publicado en:Journal Of Materials Chemistry a. 11 (6): 2969-2978 - 2023-02-08 11(6), DOI: 10.1039/d2ta08781b

Autores: Huang, YJ; Dai, H; Moonshiram, D; Li, ZF; Luo, ZM; Zhang, JH; Yang, WX; Shen, Y; Wang, JW; Ouyang, GF

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Resumen

Metal complexes hybridized with conductive supports are desirable as high-performance catalysts for CO2 electroreduction, while the delicate molecular design to improve both the intrinsic activity of complex and the molecule-support interactions still remains challenging. We here employ a conjugation-tuning strategy by comparison between Ni(ii) octabutoxyphthalocyanine and Ni(ii) octabutoxynaphthalocyanine on multi-walled carbon nanotubes (NiPc-B@CNT and NiNc-B@CNT) in aqueous electrocatalytic CO2 reduction, respectively. In contrast to the conventional promotive effects from extended conjugation, the impaired conjugation in the Ni(ii) macrocycles unusually boosts both activity and molecule-support affinity. These merits can be attributed to the favored electronic effects and the higher flexibility of long alkyl chains both arising from the absent extended benzene ring in NiPc-B. Consequently, NiPc-B@CNT exhibits much higher faradaic efficiencies for CO production (FECO >= 94% among -0.79 to -1.09 V vs. RHE) than NiNc-B@CNT (FECO < 20%) in an H-cell configuration. The use of a gas-diffusion electrode further raises the electrocatalytic performances of NiPc-B@CNT under 1 atm CO2 (FECO asymptotic to 100% at -0.15 A cm(-2)) or simulated flue gas (10% CO2, FECO &asymptotic to 80% at -0.1 A cm(-2)), respectively.

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