Reinforcing CoO Covalency via Ce(4f)─O(2p)─Co(3d) Gradient Orbital Coupling for High‐Efficiency Oxygen Evolution

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(30)

Published: April 18, 2023

Rare-earth (RE)-based transition metal oxides (TMO) are emerging as a frontier toward the oxygen evolution reaction (OER), yet knowledge regarding their electrocatalytic mechanism and active sites is very limited. In this work, atomically dispersed Ce on CoO successfully designed synthesized by an effective plasma (P)-assisted strategy model (P-Ce SAs@CoO) to investigate origin of OER performance in RE-TMO systems. The P-Ce SAs@CoO exhibits favorable with overpotential only 261 mV at 10 mA cm-2 robust electrochemical stability, superior individual CoO. X-ray absorption spectroscopy situ Raman reveal that Ce-induced electron redistribution inhibits CoO bond breakage CoOCe unit site. Theoretical analysis demonstrates gradient orbital coupling reinforces covalency Ce(4f)─O(2p)─Co(3d) site optimized Co-3d-eg occupancy, which can balance adsorption strength intermediates turn reach apex theoretical maximum, excellent agreement experimental observations. It believed establishment Ce-CoO set basis for mechanistic understanding structural design high-performance catalysts.

Language: Английский

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Ce‐Induced Differentiated Regulation of Co Sites via Gradient Orbital Coupling for Bifunctional Water‐Splitting Reactions

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(30)

Published: June 22, 2023

Abstract Rare‐earth (RE) elements have emerged as crucial promoters to regulate the electrocatalysis of transition metals (TM), but knowledge about RE‐enhanced mechanism TM in is limited. Herein, an array‐like Ce‐CoP catalyst constructed explore origin and distinction Ce‐induced enhanced Co sites both hydrogen evolution reaction (HER) oxygen (OER). Compared with individual CoP, developed exhibits superior bifunctional electrocatalytic activity overpotentials 81 240 mV at 10 mA cm −2 , respectively for HER OER, excellent stability. Theoretical calculations show that unique 4 f valence electron structure Ce endows differentiated regulation OER through f‐p‐d gradient orbital coupling. In HER, retained Ce‐4 state induces spin parallelism surrounding sites, promoting adsorption *H intermediates. While band acts sacrificing protect from overoxidation Ce‐O‐Co chain optimized Co‐3 d state, providing additional coupling These findings provide new insights into comprehending present valuable design guidelines development efficient multi‐functional electrocatalysts.

Language: Английский

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Hierarchical porous NiFe-P@NC as an efficient electrocatalyst for alkaline hydrogen production and seawater electrolysis at high current density

Inorganic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(5), P. 1493 - 1500

Published: Jan. 1, 2023

The TNiFe-P@NC presented excellent HER performance with an overpotential of 40 mV at 10 mA cm −2 and stability in KOH solution. An assembled NiFe-P@NC||NiFe-P@NC electrolyzer could drive 100/500 alkaline seawater electrolyte 1.77/1.93 V.

Language: Английский

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Rare earth-based nanomaterials in electrocatalysis

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 489, P. 215204 - 215204

Published: May 3, 2023

Language: Английский

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Joule heating synthesis of NiFe alloy/MoO2 and in-situ transformed (Ni,Fe)OOH/MoO2 heterostructure as effective complementary electrocatalysts for overall splitting in alkaline seawater

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 340, P. 123277 - 123277

Published: Sept. 7, 2023

Language: Английский

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Low-Pt supported on MOF-derived Ni(OH)2 with highly-efficiently electrocatalytic seawater splitting at high current density

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 331, P. 122703 - 122703

Published: March 31, 2023

Language: Английский

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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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Rare earth oxide based electrocatalysts: synthesis, properties and applications

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(2), P. 714 - 763

Published: Dec. 18, 2023

The synthesis, properties and applications of rare earth oxide based electrocatalysts in electrocatalysis reactions.

Language: Английский

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LDH-based nanomaterials for photocatalytic applications: A comprehensive review on the role of bi/trivalent cations, anions, morphology, defect engineering, memory effect, and heterojunction formation

Journal of Energy Chemistry, Journal Year: 2023, Volume and Issue: 84, P. 242 - 276

Published: May 25, 2023

Language: Английский

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Realizing efficient oxygen evolution at low overpotential via dopant-induced interfacial coupling enhancement effect

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 336, P. 122928 - 122928

Published: May 29, 2023

Language: Английский

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