Ligand-engineered Cu-based halide perovskite for highly efficient near-infrared photocatalytic CO2 reduction

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 352, P. 124048 - 124048

Published: April 21, 2024

Language: Английский

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Manipulating the Spin State of Spinel Octahedral Sites via a π–π Type Orbital Coupling to Boost Water Oxidation

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(37)

Published: June 24, 2024

Spin state is often regarded as the crucial valve to release reactivity of energy-related catalysts, yet it also challenging precisely manipulate, especially for active center ions occupied at specific geometric sites. Herein, a π-π type orbital coupling 3d (Co)-2p (O)-4f (Ce) was employed regulate spin octahedral cobalt sites (Co

Language: Английский

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Establishment of Gas–Liquid–Solid Interface on Multilevel Porous Cu₂O for Potential-Driven Selective CO₂ Electroreduction toward C₁ or C₂ Products

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 20, 2025

Copper-based catalysts demonstrate distinctive multicarbon product activity in the CO2 electroreduction reaction (CO2RR); however, their low selectivity presents significant challenges for practical applications. Herein, we have developed a multilevel porous spherical Cu2O structure, wherein mesopores are enriched with catalytic active sites and effectively stabilize Cu+, while macropores facilitate formation of "gas–liquid–solid" three-phase interface, thereby creating microenvironment an increasing water concentration gradient from interior to exterior. Potential-driven phase engineering protonation synergistically optimize pathway, facilitating switch between CO C2H4. At current density 100 mA cm–2, faradaic efficiency (FE) reaches impressive 96.97%. When increases 1000 FEC2H4 attains 53.05%. Experiments theoretical calculations indicate that at lower potentials, pure diminishes adsorption *CO intermediates, weak inhibits hydrogen evolution reactions, promoting production. Conversely, more negative Cu0/Cu+ interface strong generate locally elevated concentrations *COOH which enhance C–C coupling deep hydrogenation, ultimately improving toward C2+ products. This study provides novel insights into rational design copper-based customizable

Language: Английский

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Ultrathin Palladium-loaded Cuprous oxide stabilises Copper(I) to facilitate electrochemical carbon dioxide reduction reaction

Journal of Colloid and Interface Science, Journal Year: 2025, Volume and Issue: 685, P. 537 - 545

Published: Jan. 20, 2025

Language: Английский

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Advances in rare earth catalysts for small molecule electrosynthesis☆

Journal of Rare Earths, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 1, 2025

Language: Английский

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Electronic metal-support interaction modulates Cu electronic structures for CO2 electroreduction to desired products

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 25, 2025

In this work, the Cu single-atom catalysts (SACs) supported by metal-oxides (Al2O3-CuSAC, CeO2-CuSAC, and TiO2-CuSAC) are used as theoretical models to explore correlations between electronic structures CO2RR performances. For these catalysts, metal-support interaction (EMSI) induced charge transfer sites supports subtly modulates structure form different highest occupied-orbital. The occupied 3dyz orbital of Al2O3-CuSAC enhances adsorption strength CO weakens C-O bonds through 3dyz-π* electron back-donation. This reduces energy barrier for C-C coupling, thereby promoting multicarbon formation on Al2O3-CuSAC. 3dz2 TiO2-CuSAC accelerates H2O activation, lowers reaction forming CH4. over activated H2O, in turn, intensifies competing hydrogen evolution (HER), which hinders high-selectivity production CH4 TiO2-CuSAC. CeO2-CuSAC with 3dx2-y2 promotes CO2 activation its localized state inhibits coupling. moderate water activity facilitates *CO deep hydrogenation without excessively activating HER. Hence, exhibits Faradaic efficiency 70.3% at 400 mA cm−2. Rational regulation control electroreduction pathways is challenging. Here, authors report modulating single-sites via interaction, enabling switchable selectivity multicarbons methane.

Language: Английский

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Stabilizing Oxidation State of Cu via Ce Doping into La₂CuO₄ for Enhanced Electroreduction of CO₂ to Multicarbon Products

Small Methods, Journal Year: 2025, Volume and Issue: unknown

Published: March 4, 2025

Stabilizing oxidation state of Cu (Cuδ+, δ > 0) sites is the key-enabling issue for electrocatalytic carbon dioxide (CO2) reduction reaction (eCO2RR) to multicarbon (C2+) products. The present study addresses this challenge by introducing cerium (Ce) doping into La2CuO4. Ce facilitates f-d orbital coupling between 4f and 3d orbitals, suppressing electron enrichment around atoms transferring electrons from orbitals via a Cu-O-Ce chain. These changes modulate electronic structure Cu, reduce distance neighboring atoms, optimize binding energy surface-adsorbed CO (*CO), lower barrier *CO dimerization. As result, La1.95Ce0.05CuO4 catalyst achieves Faradaic efficiency up 81% C2+ products maintains high stability over 50 h operation. This work highlights unique role in stabilizing Cuδ+ hence enhancing C-C coupling, providing pathway designing efficient catalysts eCO2RR.

Language: Английский

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Core–shell structures of Cu₂O constructed by carbon quantum dots as high-performance zinc-ion battery cathodes

Journal of Materials Chemistry A, Journal Year: 2023, Volume and Issue: 11(45), P. 24823 - 24835

Published: Jan. 1, 2023

Core–shell structure of Cu 2 O constructed by carbon quantum dots exhibited high discharge specific capacity and excellent rate performance. And the conversion-type zinc storage mechanism was confirmed in situ XRD Raman technology.

Language: Английский

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Ce⁴⁺-Doped CuO Mesoporous Nanosheets for CO₂ Electroreduction to C₂H₆ with High Selectivity under a Wide Potential Window in a Flow Cell

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(8), P. 2969 - 2977

Published: Feb. 13, 2024

CO2 electrocatalytic reduction (CO2ER) to multiple carbonous products is a valuably sustainable way obtain fuels and chemicals. However, its practical application still hindered by low selectivity activity under large current density. A flow cell enables CO2ER operate at high densities mitigating the mass transport limitation issue. Here, we report Ce4+-doped CuO mesoporous nanosheets affording toward C2H6 in cell. Ce4+ doping induces oxygen vacancies modulates electron distribution of CuO, which enhances adsorption intensity coverage *CO intermediate for further C–C coupling finally produce C2H6. Moreover, can well protect Cu2+ species from being reduced during CO2ER, guarantees stability generation. As result, optimal Ce0.03Cu0.97O0.83 exhibits partial 55.3 ± 1.6–235.5 4.3 mA cm–2 with Faradaic efficiencies over 50% ethane wide potential window −0.5 −0.9 V This work clarifies that nanostructure doped lanthanide metal ions modulate reaction pathway

Language: Английский

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Molten-Salt Electrochemical-Assisted Synthesis of the CeO₂-O_V@GC Composite-Supported Pt Clusters with a Pt–O–Ce Structure for the Oxygen Reduction Reaction

Nano Letters, Journal Year: 2024, Volume and Issue: 24(23), P. 6957 - 6964

Published: May 28, 2024

Highly active and robust Pt-based electrocatalysts for an oxygen reduction reaction (ORR) are of crucial significance the development proton exchange membrane fuel cells (PEMFCs). Herein, high-loading well-dispersive Pt clusters on graphitic carbon-supported CeO2 with abundant vacancies (PtAC/CeO2-OV@GC) were successfully fabricated by a molten-salt electrochemical-assisted method. The bonding highly electronegative O induces charge redistribution through Pt–O–Ce structure, thus reducing adsorption energies oxygen-containing species. Such PtAC/CeO2-OV@GC electrocatalyst exhibits greatly enhanced ORR performance mass activity 0.41 ± 0.02 A·mg–1Pt at 0.9 V versus reversible hydrogen electrode, which is 2.7 times value commercial Pt/C catalyst shows negligible decay after 20000 cycles accelerated degradation tests. It anticipated that this work will provide enlightening guidance controllable synthesis rational design high-performance PEMFCs.

Language: Английский

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