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

Huang, Yanjun1; Dai, Hao2; Moonshiram, Dooshaye3; Li, Zhuofeng4; Luo, Zhi-Mei5; Zhang, Ji-Hong6; Yang, Wenxing4; Shen, Yong1; Wang, Jia-Wei1,5; Ouyang, Gangfeng1,7,8

2023-02-08

10.1039/d2ta08781b

Journal of Materials Chemistry A   Impact Factor & Quartile

2050-7488

2050-7496

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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English

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National Natural Science Foundation of China["21737006","22076222","22036003"] ; Natural Science Foundation of Guangdong Province[2021A1515010068] ; Guangdong Basic and Applied Basic Research Foundation["2020A1515110017","2021A1515012033"] ; Ramon y Cajal grant through Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Cientificas[RYC2020-029863-I] ; Spanish Ministerio de Ciencia, Innovacion y Universidades grant[PID2019-111086RA-I00]

Chemistry ; Energy & Fuels ; Materials Science

Chemistry, Physical ; Energy & Fuels ; Materials Science, Multidisciplinary

WOS:000922016400001

ROYAL SOC CHEMISTRY

Web of Science

1.Sun Yat sen Univ, Sch Chem, KLGHEI Environm & Energy Chem, Guangzhou 510275, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
3.Consejo Super Invest Cient CS ICMM, Inst Ciencia Mat Madrid, Sor Juana Ines Cruz 3, Madrid 28049, Spain
4.Westlake Univ, Ctr Artificial Photosynth Solar Fuels, Sch Sci, Dept Chem, 18 Shilongshan Rd, Hangzhou 310024, Peoples R China
5.Barcelona Inst Sci & Technol BIST, Inst Chem Res Catalonia ICIQ, Avinguda Paisos Catalans 16, Tarragona 43007, Spain
6.Tianjin Univ Technol, Sch Mat Sci & Engn, Inst New Energy Mat & Low Carbon Technol, Tianjin 300384, Peoples R China
7.Zhengzhou Univ, Chem Coll, Ctr Adv Anal & Gene Sequencing, Zhengzhou 450001, Peoples R China
8.China Natl Analyt Ctr Guangzhou, Guangdong Inst Anal, Guangdong Prov Key Lab Emergency Test Dangerous Ch, Guangzhou 510070, Peoples R China

Huang, Yanjun,Dai, Hao,Moonshiram, Dooshaye,et al. Impaired conjugation boosts CO2 electroreduction by Ni(ii) macrocyclic catalysts immobilized on carbon nanotubes[J]. Journal of Materials Chemistry A,2023,11(6).

Huang, Yanjun.,Dai, Hao.,Moonshiram, Dooshaye.,Li, Zhuofeng.,Luo, Zhi-Mei.,...&Ouyang, Gangfeng.(2023).Impaired conjugation boosts CO2 electroreduction by Ni(ii) macrocyclic catalysts immobilized on carbon nanotubes.Journal of Materials Chemistry A,11(6).

Huang, Yanjun,et al."Impaired conjugation boosts CO2 electroreduction by Ni(ii) macrocyclic catalysts immobilized on carbon nanotubes".Journal of Materials Chemistry A 11.6(2023).