Steering CO2 electrolysis selectivity by modulating the local reaction environment: An online DEMS approach for Cu electrodes

Yao, Ke; Zhang, Guiru; Ni, Baoxin; Guo, Liejin; Deng, Chengwei; Zhuang, Xiaodong; Zhao, C.Y.; Cai, Wen‐Bin; Jiang, Kun

doi:10.1016/j.esci.2023.100143

Cited by 22 publications

(10 citation statements)

References 63 publications

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“…The XPS analysis (Figure S4b) for the used catalyst reveals the presence of metallic Cu 0 species on its surface with the B.E. at 931.7 and 951.5 eV, respectively, − which is in an agreement with the XRD result. Moreover, the doublet peaks at 933.4 and 953.3 eV, together with the shakeup satellite peak in the range of 939–945 eV, can be attributed to Cu 2+ species, which was caused by the surface oxidation of metallic Cu in air.…”

Section: Results and Discussionsupporting

confidence: 78%

Nano-Cu Derived from a Copper Nitride Precatalyst for Reductive Coupling of Nitroaromatics to Azo Compounds

Du,

Duan,

Gao

et al. 2024

Inorg. Chem.

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The study of structural reconstruction is vital for the understanding of the real active sites in heterogeneous catalysis and guiding the improved catalyst design. Herein, we applied a copper nitride precatalyst in the nitroarene reductive coupling reaction and made a systematic investigation on the dynamic structural evolution behaviors and catalytic performance. This Cu3N precatalyst undergoes a rapid phase transition to nanostructured Cu with rich defective sites, which act as the actual catalytic sites for the coupling process. The nitride-derived defective Cu is very active and selective for azo formation, with 99.6% conversion of nitrobenzene and 97.1% selectivity to azobenzene obtained under mild reaction conditions. Density functional theory calculations suggest that the defective Cu sites play a role for the preferential adsorption of nitrosobenzene intermediates and significantly lowered the activation energy of the key coupling step. This work not only proposes a highly efficient noble-metal-free catalyst for nitroarenes coupling to valuable azo products but also may inspire more scientific interest in the study of the dynamic evolution of metal nitrides in different catalytic reactions.

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Section: Results and Discussionsupporting

confidence: 78%

Nano-Cu Derived from a Copper Nitride Precatalyst for Reductive Coupling of Nitroaromatics to Azo Compounds

Du,

Duan,

Gao

et al. 2024

Inorg. Chem.

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“…92 Advanced operando spectroscopy and microscopy characterization with sufficient temporal and spatial resolution would help in resolving the exact structures of catalysts and ligands in these systems. 42,[93][94][95][96][97] In addition to initial states and conditions, reaction microenvironments are also dynamic and closely associated with reaction rates. As the mass transport of reactive species (e.g., CO 2 , H 2 O, H + , OH À , carbonate, bicarbonate, cations, and intermediates) at the mesoscale in the reaction microenvironments significantly influences reaction kinetics, their concentration profiles at the electrode/electrolyte interface should be accurately determined via experimental measurements under reaction conditions and/or multiphysics simulations using reasonable reaction-diffusion models.…”

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Reaction microenvironment control in membrane electrode assemblies for CO₂ electrolysis

Yan,

Gao,

Velasco-Vélez

et al. 2024

EES. Catal.

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“…To affirm the 2e − pathway associated with the charging− discharging process, differential electrochemical mass spec-trometry (DEMS) was employed to monitor the O 2 consumption and evolution. 47 During the discharging process, ORR occurs and O 2 is consumed on the cathode, where the number of electrons transferred is calculated to be 2.11 e − /O 2 (Figure 5d). This suggests that peroxide species was formed, which can be confirmed by the XRD result and TEM images in Figure S45 with characteristic peaks and diffraction spots of ZnO 2 .…”

Section: Theoretical Prediction Of O-containing Groupsmentioning

confidence: 99%

Selective Oxidation of sp-Bonded Carbon in Graphdiyne/Carbon Nanotubes Heterostructures to Form Dominant Epoxy Groups for Two-Electron Oxygen Reduction

Lu,

Sun,

Wang

et al. 2024

ACS Nano

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Two-electron oxygen reduction reaction (2e– ORR) is of great significance to H2O2 production and reversible nonalkaline Zn-air batteries (ZABs). Multiple oxygen-containing sp2-bonded nanocarbons have been developed as electrocatalysts for 2e– ORR, but they still suffer from poor activity and stability due to the limited and mixed active sites at the edges as well as hydrophilic character. Herein, graphdiyne (GDY) with rich sp-C bonds is studied for enhanced 2e– ORR. First, computational studies show that GDY has a favorable formation energy for producing five-membered epoxy ring-dominated groups, which is selective toward the 2e– ORR pathway. Then based on the difference in chemical activity of sp-C bonds in GDY and sp2-C bonds in CNTs, we experimentally achieved conductive and hydrophobic carbon nanotubes (CNTs) covering O-modified GDY (CNTs/GDY-O) through a mild oxidation treatment combined with an in situ CNTs growth approach. Consequently, the CNTs/GDY-O exhibits an average Faraday efficiency of 91.8% toward H2O2 production and record stability over 330 h in neutral media. As a cathode electrocatalyst, it greatly extends the lifetime of 2e– nonalkaline ZABs at both room and subzero temperatures.

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Steering CO2 electrolysis selectivity by modulating the local reaction environment: An online DEMS approach for Cu electrodes

Cited by 22 publications

References 63 publications

Nano-Cu Derived from a Copper Nitride Precatalyst for Reductive Coupling of Nitroaromatics to Azo Compounds

Nano-Cu Derived from a Copper Nitride Precatalyst for Reductive Coupling of Nitroaromatics to Azo Compounds

Reaction microenvironment control in membrane electrode assemblies for CO₂ electrolysis

Selective Oxidation of sp-Bonded Carbon in Graphdiyne/Carbon Nanotubes Heterostructures to Form Dominant Epoxy Groups for Two-Electron Oxygen Reduction

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Steering CO2 electrolysis selectivity by modulating the local reaction environment: An online DEMS approach for Cu electrodes

Cited by 22 publications

References 63 publications

Nano-Cu Derived from a Copper Nitride Precatalyst for Reductive Coupling of Nitroaromatics to Azo Compounds

Nano-Cu Derived from a Copper Nitride Precatalyst for Reductive Coupling of Nitroaromatics to Azo Compounds

Reaction microenvironment control in membrane electrode assemblies for CO2 electrolysis

Selective Oxidation of sp-Bonded Carbon in Graphdiyne/Carbon Nanotubes Heterostructures to Form Dominant Epoxy Groups for Two-Electron Oxygen Reduction

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Reaction microenvironment control in membrane electrode assemblies for CO₂ electrolysis