Importing Antibonding‐Orbital Occupancy through Pd−O−Gd Bridge Promotes Electrocatalytic Oxygen Reduction

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(52)

Published: Nov. 9, 2023

The active-site density, intrinsic activity, and durability of Pd-based materials for oxygen reduction reaction (ORR) are critical to their application in industrial energy devices. This work constructs a series carbon-based rare-earth (RE) oxides (Gd2 O3 , Sm2 Eu2 CeO2 ) by using RE metal-organic frameworks tune the ORR performance Pd sites through Pd-REx Oy interface interaction. Taking Pd-Gd2 /C as representative, it is identified that strong coupling between Gd2 induces formation Pd-O-Gd bridge, which triggers charge redistribution . screened exhibits impressive with high onset potential (0.986 VRHE ), half-wave (0.877 excellent stability. Similar results also found Pd-Sm2 /C, Pd-Eu2 Pd-CeO2 catalysts. Theoretical analyses reveal promotes electron transfer antibonding-orbital occupancy Pd-*OH optimization *OH adsorption rate-determining step ORR. pH-dependent microkinetic modeling shows close theoretical optimal activity ORR, outperforming Pt under same conditions. By its ascendancy superior Zn-air battery an air cathode, implying practicability.

Language: Английский

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In-situ reconstructed Cu/Cu2O heterogeneous nanorods with oxygen vacancies for enhanced electrocatalytic nitrate reduction to ammonia

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 479, P. 147574 - 147574

Published: Nov. 20, 2023

Language: Английский

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Stabilizing the oxidation state of catalysts for effective electrochemical carbon dioxide conversion

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(12), P. 6295 - 6321

Published: Jan. 1, 2024

Developing sophisticated strategies to stabilize oxidative metal catalysts based on the correlation between dynamic oxidation state and product profile is favorable for efficient electrochemical CO 2 conversion.

Language: Английский

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Electronic Structure Design of Transition Metal-Based Catalysts for Electrochemical Carbon Dioxide Reduction

ACS Nano, Journal Year: 2024, Volume and Issue: 18(14), P. 9823 - 9851

Published: March 28, 2024

With the increasingly serious greenhouse effect, electrochemical carbon dioxide reduction reaction (CO2RR) has garnered widespread attention as it is capable of leveraging renewable energy to convert CO2 into value-added chemicals and fuels. However, performance CO2RR can hardly meet expectations because diverse intermediates complicated processes, necessitating exploitation highly efficient catalysts. In recent years, with advanced characterization technologies theoretical simulations, exploration catalytic mechanisms gradually deepened electronic structure catalysts their interactions intermediates, which serve a bridge facilitate deeper comprehension structure-performance relationships. Transition metal-based (TMCs), extensively applied in CO2RR, demonstrate substantial potential for further modulation, given abundance d electrons. Herein, we discuss representative feasible strategies modulate catalysts, including doping, vacancy, alloying, heterostructure, strain, phase engineering. These approaches profoundly alter inherent properties TMCs interaction thereby greatly affecting rate pathway CO2RR. It believed that rational design modulation fundamentally provide viable directions development toward conversion many other small molecules.

Language: Английский

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

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 1351 - 1362

Published: Jan. 11, 2024

Copper-based catalysts, hallmarked by their ideal C–C coupling energy facilitated the symbiotic presence of Cu+ and Cu0 active sites, are poised to revolutionize selective electrochemical reduction CO2 C2H4. Regrettably, these catalysts beleaguered unavoidable diminution during reaction process, resulting in suboptimal C2H4 yields. To circumvent this limitation, we have judiciously mitigated antibonding orbital occupancy O 2p 3d hybridization introducing Cu defects into Cu2O, thereby augmenting Cu–O bond strength stabilize sites further decipher stabilization mechanism Cu+. This structural refinement, illuminated meticulous DFT calculations, fosters a heightened free threshold for hydrogen evolution (HER), while orchestrating thermodynamically favorable milieu enhanced within Cu-deficient Cu2O (Cuv-Cu2O). Empirically, Cuv-Cu2O has outperformed its pure counterpart, exhibiting prominent C2H4/CO ratio 1.69 as opposed 1.01, without conceding significant ground production over an 8 h span at −1.3 V vs RHE. endeavor not only delineates critical influence on reveals deep about but also charts pioneering pathway realm advanced materials design.

Language: Английский

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Bottom‐up Growth of Convex Sphere with Adjustable Cu(0)/Cu(I) Interfaces for Effective C₂ Production from CO₂ Electroreduction

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(28)

Published: May 4, 2024

Abstract One challenge confronting the Cu 2 O catalysts in electrocatalysis of carbon dioxide reduction reaction (CO RR) is active Cu(I) species, resulting low selectivity and quick deactivation. In this study, we for first time introduce a bottom‐up growth convex sphere with adjustable Cu(0)/Cu(I) interfaces (Cu x @Cu spheres). Interestingly, are dynamically modulated by varying hydrothermal time, thus regulating conversion C 1 products. particular, 4 h treatment applied to 0.25 favorable interface results highest products (90.5 %). situ Fourier‐transform infrared spectroscopy measurements density functional theory calculations reveal that lowers energy barrier production ethylene ethanol while increasing coverage localized *CO adsorbate increased dimerization. This work establishes novel approach transforming state valence‐sensitive electrocatalysts into high‐value energy‐related engineering

Language: Английский

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Targeted C-O bond cleavage of *CH2CHO at copper active sites for efficient electrosynthesis of ethylene from CO2 reduction

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 351, P. 123992 - 123992

Published: April 24, 2024

Language: Английский

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Asymmetric Cu(I)─W Dual‐Atomic Sites Enable C─C Coupling for Selective Photocatalytic CO₂ Reduction to C₂H₄

Advanced Science, Journal Year: 2024, Volume and Issue: 11(28)

Published: April 26, 2024

Abstract Solar‐driven CO 2 reduction into value‐added C 2+ chemical fuels, such as H 4 , is promising in meeting the carbon‐neutral future, yet performance usually hindered by high energy barrier of C─C coupling process. Here, an efficient and stabilized Cu(I) single atoms‐modified W 18 O 49 nanowires (Cu 1 /W ) photocatalyst with asymmetric Cu─W dual sites reported for selective photocatalytic to . The interconversion between W(V) W(VI) ensures stability during Under light irradiation, optimal Cu (3.6‐Cu catalyst exhibits concurrent activity selectivity toward production, reaching a corresponding yield rate 4.9 µmol g −1 h 72.8%, respectively. Combined situ spectroscopies computational calculations reveal that atoms stabilize *CO intermediate, effectively reduce two neighboring intermediates, enabling highly generation from photoreduction. This work demonstrates leveraging atomically‐dispersed dual‐sites ‐to‐C conversion can provide new insight other targeted products through rational construction active coupling.

Language: Английский

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Engineering stable Cu+-Cu0 sites and oxygen defects in boron-doped copper oxide for electrocatalytic reduction of CO2 to C2+ products

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 484, P. 149710 - 149710

Published: Feb. 15, 2024

Language: Английский

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Rare earth nanomaterials in electrochemical reduction of carbon dioxide

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 516, P. 215983 - 215983

Published: May 28, 2024

Language: Английский

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