Cu single-atom electrocatalyst on nitrogen-containing graphdiyne for CO2 electroreduction to CH4

doi:10.1016/S1872-2067(24)60106-3

Abstract

Abstract:

Developing Cu single-atom catalysts (SACs) with well-defined active sites is highly desirable for producing CH₄ in the electrochemical CO₂ reduction reaction and understanding the structure-property relationship. Herein, a new graphdiyne analogue with uniformly distributed N₂-bidentate (note that N₂-bidentate site = N^N-bidentate site; N₂ ≠ dinitrogen gas in this work) sites are synthesized. Due to the strong interaction between Cu and the N₂-bidentate site, a Cu SAC with isolated undercoordinated Cu-N₂ sites (Cu_1.0/N₂-GDY) is obtained, with the Cu loading of 1.0 wt%. Cu_1.0/N₂-GDY exhibits the highest Faradaic efficiency (FE) of 80.6% for CH₄ in electrocatalytic reduction of CO₂ at -0.96 V vs. RHE, and the partial current density of CH₄ is 160 mA cm^-2. The selectivity for CH₄ is maintained above 70% when the total current density is 100 to 300 mA cm^-2. More remarkably, the Cu_1.0/N₂-GDY achieves a mass activity of 53.2 A/mg_Cutoward CH₄ under -1.18 V vs. RHE. In situ electrochemical spectroscopic studies reveal that undercoordinated Cu-N₂ sites are more favorable in generating key *COOH and *CHO intermediate than Cu nanoparticle counterparts. This work provides an effective pathway to produce SACs with undercoordinated Metal-N₂ sites toward efficient electrocatalysis.

Key words: Carbon dioxide reduction, Electrocatalysis, Cu single-atom catalyst, N-containing graphdiyne, Methane

Hao Dai, Tao Song, Xian Yue, Shuting Wei, Fuzhi Li, Yanchao Xu, Siyan Shu, Ziang Cui, Cheng Wang, Jun Gu, Lele Duan. Cu single-atom electrocatalyst on nitrogen-containing graphdiyne for CO₂ electroreduction to CH₄[J]. Chinese Journal of Catalysis, 2024, 64: 123-132.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60106-3

https://www.cjcatal.com/EN/Y2024/V64/I9/123

Figures/Tables 6

Fig. 1. Cu SACs with different coordination structures for electrochemical CO2 reduction and the main products' maximum Faradaic efficiencies [6?-8,11,22].

Fig. 2. Synthetic schemes of HEQ (a), N2-GDY and Cu/N2-GDY (b).

Fig. 3. (a) Two possible binding sites (S1 and S2) for Cu atoms on N2-GDY. (b) Calculated binding energy of CuCl2, Cu on S1 and S2 sites. (c) TEM image of Cu1.0/N2-GDY. (d) TEM image of Cu0.6/TP-GDY. (e) Aberration-corrected HAADF-STEM image of Cu1.0/N2-GDY. The bright dots (circled in red) indicate isolated Cu atoms. (f) TEM image of Cu0.6/TP-GDY with Cu nanoparticles labeled by red circles. (g) EDS mapping images of Cu1.0/N2-GDY. (h) EDS mapping images of Cu0.6/TP-GDY with Cu nanoparticles labeled by red circles in the HAADF-STEM image.

Fig. 4. XPS spectra of Cu 2p (a) and Auger spectra (b) of Cu LMM for Cu1.0/N2-GDY and Cu0.6/TP-GDY. (c) XPS spectra of N 1s for Cu1.0/N2-GDY and N2-GDY. Normalized Cu K-edge XANES spectra (d) and Cu k3-weighted FT-EXAFS spectra (e) in R space for Cu foil, Cu1.0/N2-GDY, Cu0.6/TP-GDY, and Cu2O. (f) Fitting of the EXAFS spectrum for Cu1.0/N2-GDY.

Fig. 5. LSV curves (a), gaseous products at different current densities (b), partial current densities of CH4 (c) for Cu1.0/N2-GDY and Cu0.6 LSV curves (a), gaseous products at different current densities (b), partial current densities of CH4 (c) for Cu1.0/N2-GDY and Cu0.6/TP-GDY. FE of CH4 (d), mass activity of Cu (e) for CH4 production on Cu1.0/N2-GDY, Cu2.1/N2-GDY, and Cu4.6/N2-GDY at different potentials. (f) Comparison of Cu SACs with different coordination structures for CO2RR to CH4 (balls: structures in literature, star: Cu1.0/N2-GDY in this work).

Fig. 6. (a) In situ ATR-FTIR spectra of Cu1.0/N2-GDY, Cu0.6/TP-GDY, and Cu4.6/N2-GDY recorded at a potential range from -0.5 to -1.3 V. (b) Reaction path for CO2 electroreduction to CH4 on Cu1.0/N2-GDY.

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Cu single-atom electrocatalyst on nitrogen-containing graphdiyne for CO₂ electroreduction to CH₄

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