Restraining lattice oxygen of Cu<sub>2</sub>O by enhanced Cu–O hybridization for selective and stable production of ethylene with CO<sub>2</sub> electroreduction

Yao, Yebo; Zhou, Yunshan; Liu, Xia; Li, Yongjia; Wang, Dewei; Xin, Yue; Wang, Xiaoxuan; Zhao, Rui; Zhang, Huiying; Sun, Youxian; Yang, Zhiyu; Wei, Ying; Yan, Yi‐Ming

doi:10.1039/d2ta05565a

Cited by 27 publications

(15 citation statements)

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“…These peaks are indicative of the presence of Cu + /Cu 0 . The Cu LMM spectrum (Figure Ba) further confirms the coexistence of Cu 0 (567.9 eV) and Cu + (570.9 eV). − These results demonstrate that the Cu 2+ ions are successfully reduced to low-valence Cu and form Cu NCs under the protection of 2-MPD ligands. As shown in Figure Ab,Bb, several strong peaks can be observed around 935.2 and 955.3 eV, which correspond to the 2p orbitals of Cu 2+ ions.…”

Section: Resultsmentioning

confidence: 65%

Enhancing Fenton-like Degradation of Organic Pollutants at Neutral pH by Multivalent Cu NCs/HAp Nanocatalysts

Yang,

Zhang,

Jiang

et al. 2023

Langmuir

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Heterogeneous Fenton-like catalysis is a widely used method for the degradation of organic pollutants. However, it still has some limitations such as low activity in the neutral condition, low conversion rates of metals with different valence states, and potential secondary metal pollution. In this study, a Fenton-like nanocatalyst was first created by generating ultrasmall copper nanoclusters (Cu NCs) on the surface of hydroxyapatite (HAp) through a process of doping followed by modification. This resulted in the formation of a composite nanocatalyst known as Cu NCs/HAp. With the help of hydrogen peroxide (H 2 O 2 ), Cu NCs/HAp exhibits an outstanding Fenton-like catalytic performance by efficiently degrading organic dyes such as methylene blue under mild neutral conditions. The removal rate can reach over 83% within just 30 min, demonstrating ideal catalytic universality and stability. The improved Fentonlike catalytic performance of Cu NCs/HAp can be ascribed to the synergistic effect of the multivalent Cu species through two simultaneous reaction pathways. During route I, the embedded Cu NCs with a core−shell Cu 0 /Cu + structure can undergo sequential oxidation to form Cu 2+ , which continuously activates H 2 O 2 to generate hydroxyl radicals ( • OH) and singlet oxygen ( 1 O 2 ). In route II, Cu 2+ produced from route I and initially adsorbed on the surface of HAp can be reduced by H 2 O 2 , thus regenerating Cu + species for route I and achieving a closed-loop reaction. This work has confirmed that Cu NCs loaded on HAp may be an alternative Fenton-like catalyst for degradation of organic pollutants and environmental remediation, opening up new avenues for potential applications of other Cu NCs in future water pollution control.

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Section: Resultsmentioning

confidence: 65%

Enhancing Fenton-like Degradation of Organic Pollutants at Neutral pH by Multivalent Cu NCs/HAp Nanocatalysts

Yang,

Zhang,

Jiang

et al. 2023

Langmuir

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“…The stable Cu/Cu + interfaces are believed to be active catalytic sites for C 2 H 4 formation and the detailed mechanism can be found in previous reports. 50,51 Moreover, this prepared CuO-NF@Cu is more stable than those previously reported. This work provides a feasible procedure for preparing a stable Cu/Cu + interface-containing nanocatalyst and verifies its effectiveness in CO 2 RR and HMFOR.…”

Section: Cathodic Electrochemical Co 2 Reduction To Ethylenementioning

confidence: 67%

High efficiency coupled electrocatalytic CO₂ reduction to C₂H₄ with 5-hydroxymethylfurfural oxidation over Cu-based nanoflower electrocatalysts

Zhang¹,

Liu²,

Zhao³

et al. 2023

Green Chem.

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“…The amplification of O 2p and Cu + 3d orbital hybridization emerges as a potent mechanism to bolster the Cu−O bond, thereby stabilizing Cu + sites. 29,30,34,35 This hybridization yields a fully occupied bonding orbital at the low energy level, while also manifesting a partially occupied antibonding orbital at the high energy level. 36 Intriguingly, the antibonding orbital occupancy state at active sites is pivotal in modulating bonding strength.…”

Section: ■ Introductionmentioning

confidence: 99%

Deciphering the Stability Mechanism of Cu Active Sites in CO₂ Electroreduction via Suppression of Antibonding Orbital Occupancy in the O 2p-Cu 3d Hybridization

Sun,

Wang,

Zhang

et al. 2024

ACS Catal.

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Copper-based catalysts, hallmarked by their ideal C−C coupling energy facilitated by the symbiotic presence of Cu + and Cu 0 active sites, are poised to revolutionize the selective electrochemical reduction of CO 2 to C 2 H 4 . Regrettably, these catalysts are beleaguered by the unavoidable diminution of Cu + to Cu 0 during the reaction process, resulting in suboptimal C 2 H 4 yields. To circumvent this limitation, we have judiciously mitigated the antibonding orbital occupancy in the O 2p and Cu + 3d hybridization by introducing Cu defects into Cu 2 O, thereby augmenting the Cu−O bond strength to stabilize Cu + sites and further decipher the stabilization mechanism of Cu + . This structural refinement, illuminated by meticulous DFT calculations, fosters a heightened free energy threshold for the hydrogen evolution reaction (HER), while orchestrating a thermodynamically favorable milieu for enhanced C−C coupling within the Cu-deficient Cu 2 O (Cu v -Cu 2 O). Empirically, Cu v -Cu 2 O has outperformed its pure Cu 2 O counterpart, exhibiting a prominent C 2 H 4 /CO ratio of 1.69 as opposed to 1.01, without conceding significant ground in C 2 H 4 production over an 8 h span at −1.3 V vs RHE. This endeavor not only delineates the critical influence of antibonding orbital occupancy on bond strength and reveals the deep mechanism about Cu + sites but also charts a pioneering pathway in the realm of advanced materials design.

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Restraining lattice oxygen of Cu₂O by enhanced Cu–O hybridization for selective and stable production of ethylene with CO₂ electroreduction

Abstract: The development of highly selective and efficient catalysts for the electrochemical reduction of CO2 (CO2RR) to value-added chemical products is a promising pathway towards zero emissions and carbon neutrality. Cu2O...

Cited by 27 publications

References 50 publications

Enhancing Fenton-like Degradation of Organic Pollutants at Neutral pH by Multivalent Cu NCs/HAp Nanocatalysts

Enhancing Fenton-like Degradation of Organic Pollutants at Neutral pH by Multivalent Cu NCs/HAp Nanocatalysts

High efficiency coupled electrocatalytic CO₂ reduction to C₂H₄ with 5-hydroxymethylfurfural oxidation over Cu-based nanoflower electrocatalysts

Deciphering the Stability Mechanism of Cu Active Sites in CO₂ Electroreduction via Suppression of Antibonding Orbital Occupancy in the O 2p-Cu 3d Hybridization

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Restraining lattice oxygen of Cu2O by enhanced Cu–O hybridization for selective and stable production of ethylene with CO2 electroreduction

Abstract: The development of highly selective and efficient catalysts for the electrochemical reduction of CO2 (CO2RR) to value-added chemical products is a promising pathway towards zero emissions and carbon neutrality. Cu2O...

Cited by 27 publications

References 50 publications

Enhancing Fenton-like Degradation of Organic Pollutants at Neutral pH by Multivalent Cu NCs/HAp Nanocatalysts

Enhancing Fenton-like Degradation of Organic Pollutants at Neutral pH by Multivalent Cu NCs/HAp Nanocatalysts

High efficiency coupled electrocatalytic CO2 reduction to C2H4 with 5-hydroxymethylfurfural oxidation over Cu-based nanoflower electrocatalysts

Deciphering the Stability Mechanism of Cu Active Sites in CO2 Electroreduction via Suppression of Antibonding Orbital Occupancy in the O 2p-Cu 3d Hybridization

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Restraining lattice oxygen of Cu₂O by enhanced Cu–O hybridization for selective and stable production of ethylene with CO₂ electroreduction

High efficiency coupled electrocatalytic CO₂ reduction to C₂H₄ with 5-hydroxymethylfurfural oxidation over Cu-based nanoflower electrocatalysts

Deciphering the Stability Mechanism of Cu Active Sites in CO₂ Electroreduction via Suppression of Antibonding Orbital Occupancy in the O 2p-Cu 3d Hybridization