| Citation: |
Daqi Song, Wenjun Yang, Mutian Ma, Wei Hua, Zhangyi Zheng, Zhihe Wei, Muzi Chen, Jian Cheng, Jun Zhong, Zhao Deng, Yang Peng. Ligand-modulated Cu reconstruction to steer the hydride/hydroxyl pathway of electrocatalytic CO2 reduction[J]. Energy Lab, 2024, 2(3): 240010. doi: 10.54227/elab.20240010
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Ligand-modulated Cu reconstruction to steer the hydride/hydroxyl pathway of electrocatalytic CO2 reduction
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Abstract
Reconstructing metal-organic complexes effectively generates hybrid nanocatalysts for electrocatalytic CO2 reduction (eCO2R), but the role of metal-ligand interactions in shaping these hybrids and their influence on the electronic states of the reduced Cu species remain unclear. Herein, we impregnate Cu(II) acetate (Cu(OAc)2) into two Zirconium-based metal organic frameworks (MOFs) with different ligands to in situ construct Cu-based nanocatalysts for eCO2R. We show that Cu-ligand interactions crucially determine the transformation of Cu(OAc)2 during electrolysis, with biphenyl linkers forming agglomerated Cu2O particles and bipyridine linkers yielding highly dispersed Cu crystallites. This ligand-modulated Cu reconstruction diverges eCO2R towards C2 and C1 pathways, with agglomerated Cu2O particles producing C2+ products and smaller Cu crystallites achieving a maximum CH4 Faradaic efficiency (FE) of 60.3% ± 0.5% at 600 mA cm-2.
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References
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Daqi Song, Wenjun Yang, Mutian Ma, Wei Hua, Zhangyi Zheng, Zhihe Wei, Muzi Chen, Jian Cheng, Jun Zhong, Zhao Deng, Yang Peng. Ligand-modulated Cu reconstruction to steer the hydride/hydroxyl pathway of electrocatalytic CO2 reduction[J]. Energy Lab, 2024, 2(3): 240010. doi: 10.54227/elab.20240010
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Figure 1.
Schematic diagrams illustrating the synthesis and in situ reconstruction of UiO-67-Cu(OAc)2 (top) and UiO-bpy-Cu(OAc)2 (bottom). The lack of filler-host interaction in UiO-67-Cu(OAc)2 leads to the formation of Cu2O agglomerates upon reconstruction, while Cu(OAc)2 anchored through the bipyridine linkers of UiO-bpy turn into well-dispersed Cu crystallites.
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Figure 1.
Comparison of cyclic voltammograms for Cu(OAc)2·H2O and [Cu(bpy)2]Cl2 in 0.1 M TBABF4/MeCN (2 mM) under Ar atmosphere at a scan rate of 0.1 V s−1.
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Figure 2.
Structural characterizations on UiO-67-Cu(OAc)2 and UiO-bpy-Cu(OAc)2. a SEM, b and c TEM, and d EDX-mapping images of UiO-67-Cu(OAc)2. e SEM, f and g TEM, and h EDX-mapping images of UiO-bpy-Cu(OAc)2. i XRD patterns of the as-synthesized UiO-67, UiO-bpy, UiO-67-Cu(OAc)2, and UiO-bpy-Cu(OAc)2. j XPS N 1s spectra of UiO-bpy and UiO-bpy-Cu(OAc)2. k XPS Cu 2p3/2 spectra of UiO-67-Cu(OAc)2 and UiO-bpy-Cu(OAc)2. l XANES Cu k-edge and m the corresponding FT-EXAFS spectra of UiO-67-Cu(OAc)2 and UiO-bpy-Cu(OAc)2.
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Figure 3.
Electrocatalytic CO2 reduction performances of UiO-67-Cu(OAc)2 and UiO-bpy-Cu(OAc)2. a V-i plots acquired in 1 M KOH solution. FEs of H2, CO, CH4, and C2H4 on b UiO-67-Cu(OAc)2 and c UiO-bpy-Cu(OAc)2. Partial current densities of d CH4 and e C2H4 at different potentials. f Plots of the CH4/C2H4 ratios at various current densities.
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Figure 4.
Post-mortem characterization on UiO-67-Cu(OAc)2 and UiO-bpy-Cu(OAc)2 after eCO2R. Ex situ XRD patterns taken on a UiO-67-Cu(OAc)2 and b UiO-bpy-Cu(OAc)2 after different electrolysis time at 500 mA cm-2. c HRTEM and d HAADF-TEM mapping images of UiO-67-Cu(OAc)2 after eCO2R at 500 mA cm-2 for 2 h. e HRTEM and f HAADF-TEM mapping images of UiO-bpy-Cu(OAc)2 after eCO2R at 500 mA cm-2 for 2 h.
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Figure 5.
Mechanistic investigations into the eCO2R pathways on the reconstructed catalysts. In situ ATR-SEIRAS spectra recorded from OCP to −2.8 V vs. RHE to monitor the evolution of intermediates binding on a UiO-67-Cu(OAc)2 and b UiO-bpy-Cu(OAc)2 in an electrochemical spectroscopic cell. In situ Raman spectra taken from OCP to −1.20 V vs. RHE on c UiO-67-Cu(OAc)2 and d UiO-bpy-Cu(OAc)2 in a flow cell (left panel: 200-800 cm−1; right panel 950-
1150 cm−1; full spectra are given in Figure S32). e Proposed eCO2R mechanism on the hydroxyl-mediated pathway at the Cu2O surface (top) and hydride-mediated pathway at the Cu surface (bottom).
