Proton feeding from defect-rich carbon support to cobalt phthalocyanine for efficient CO2 electroreduction

doi:10.1016/S1872-2067(24)60061-6

Abstract

Abstract:

Electrocatalytic CO₂ reduction reaction (CO₂RR) holds significant promise for sustainable energy conversion, with cobalt phthalocyanine (CoPc) emerging as a notable catalyst due to its high CO selectivity. However, CoPc's efficacy is hindered by its limited ability to provide sufficient proton for the protonation process, particularly at industrial current densities. Herein, we introduce defect-engineered carbon nanotubes (d-CNT) to augment proton feeding for CO₂RR over CoPc, achieved by expediting water dissociation. Our kinetic measurements and in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy reveal d-CNT significantly enhances proton feeding, thereby facilitating CO₂ activation to *COOH in CoPc. Density functional theory calculations corroborate these findings, illustrating that d-CNT decreases the barrier to water dissociation. Consequently, the CoPc/d-CNT mixture demonstrates robust performance, achieving 500 mA cm^-2 for CO₂RR with CO selectivity exceeding 96%. Notably, CoPc/d-CNT remains stability for a duration of 20 h under a substantial current density of 150 mA cm^-2. The study broadens the scope of practical applications for molecular catalysts in CO₂RR, marking a significant step towards sustainable energy conversion.

Key words: Carbon defectCO₂ reduction reaction, Cobalt phthalocyanine, Proton feeding, Electrocatlysis

Ziwen Mei, Kejun Chen, Yao Tan, Qiuwen Liu, Qin Chen, Qiyou Wang, Xiqing Wang, Chao Cai, Kang Liu, Junwei Fu, Min Liu. Proton feeding from defect-rich carbon support to cobalt phthalocyanine for efficient CO₂ electroreduction[J]. Chinese Journal of Catalysis, 2024, 62: 190-197.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60061-6

https://www.cjcatal.com/EN/Y2024/V62/I7/190

Figures/Tables 5

Fig. 1. (a) Schematic diagram of the synthetic pathway about CoPc/d-CNT. (b) XPS survey of CNT, d-CNT, CoPc/CNT and CoPc/d-CNT. The inset shows the peaks of Co 2p3/2 and Co 2p1/2 in CNT, d-CNT, CoPc/CNT and CoPc/d-CNT. (c) High-resolution Co 2p XPS spectra of CoPc/CNT and CoPc/d-CNT. XANES spectra of Co K-edge (d) and EXAFS spectra of Co K-edge (e).

Fig. 2. (a,b) TEM images of CoPc/CNT and CoPc/d-CNT. (c) HAADF-STEM image and element mapping of CoPc/d-CNT. (d) XRD patterns of CNT, d-CNT, CoPc/CNT and CoPc/d-CNT. (e) Raman spectra of CNT, d-CNT, CoPc/CNT and CoPc/d-CNT.

Fig. 3. (a) LSV of CNT, d-CNT, CoPc/CNT and CoPc/d-CNT based on 0.5 mol L?1 CO2-saturated KHCO3 electrolyte in the H-cell. (b) KIE of CoPc/CNT and CoPc/d-CNT measured at -0.55 V (vs. RHE) in a 0.5 mol L?1 CO2-saturated KHCO3 electrolyte. In-situ ATR-SEIRAS of CoPc/d-CNT (c) and CoPc/CNT (d).

Fig. 4. (a,b) Theoretically computed model of d-CNT with *H2O and H3O+. (c,d) Theoretically computed model of CNT with *H2O and H3O+. (e) Reaction free energy of d-CNT (red) and CNT (green) from *H2O to H3O+.

Fig. 5. (a) LSV of CNT, d-CNT, CoPc/CNT and CoPc/d-CNT based on CO2 saturation in H-cell. (b) I-V curve of CoPc/CNT and CoPc/d-CNT in flow cell. (c) FECO of CoPc/CNT and CoPc/d-CNT. (d) Performance comparison chart. (e) Stability of CoPc/d-CNT at 150 mA cm?2 in flow cell.

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Proton feeding from defect-rich carbon support to cobalt phthalocyanine for efficient CO₂ electroreduction

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