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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Neodymium‐Evoked Valence Electronic Modulation to Balance Reversible Oxygen Electrocatalysis

Advanced Energy Materials, Journal Year: 2022, Volume and Issue: 13(2)

Published: Nov. 23, 2022

Abstract Suffering from the competition adsorption between oxygen reduction reaction (ORR) and evolution (OER), development of high‐efficiency electrocatalysts with bifunctional properties still remains a challenge. Herein, novel effective neodymium‐evoked valence electronic perturbation strategy to improve balance reversible electrocatalysis metallic cobalt sites is proposed. To heighten coupling Nd Co, metal‐organic‐framework‐induced method chosen prepare target catalyst atomic Nd‐doped Co on an N‐doped carbon substrate. The as‐prepared presents excellent electrocatalytic low overpotential 288 mV at 10 mA cm −2 for OER high half‐wave potential 0.85 V ORR. robust stabilities both ORR are also proven. electrochemical in situ Raman spectra confirm surface dynamic change transformation intermediates by noting formation Co–OOH. Theoretical calculations verify that balanced owing strong 3d‐Nd 4f orbital effect below Fermi level. Moreover, practicability further demonstrated solid‐state rechargeable Zn‐Air batteries, which exhibit large power density long cycling life.

Language: Английский

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Improving the Oxygen Evolution Activity of Layered Double‐Hydroxide via Erbium‐Induced Electronic Engineering

Small, Journal Year: 2022, Volume and Issue: 19(5)

Published: Nov. 29, 2022

Layered double-hydroxide (LDH) has been considered an important class of electrocatalysts for the oxygen evolution reaction (OER), but adsorption-desorption behaviors intermediates on its surface still remain unsatisfactory. Apart from transition-metal doping to solve this electrocatalytic problem LDH, rare-earth (RE) species have sprung up as emerging dopants owing their unique 4f valence-electronic configurations. Herein, Er is chosen a RE model improve OER activity LDH via constructing nickel foam supported Er-doped NiFe-LDH catalyst (Er-NiFe-LDH@NF). The optimal Er-NiFe-LDH@NF exhibits low overpotential (191 mV at 10 mA cm-2 ), high turnover frequency (0.588 s-1 and activation energy (36.03 kJ mol-1 which are superior Er-free sample. Electrochemical in situ Raman spectra reveal facilitated transition Ni-OH into Ni-OOH promoted kinetics through effect. Theoretical calculations demonstrate that introduction facilitates spin crossover valence electrons by optimizing d band center NiFe-LDH, leads GO -GHO closer kinetic volcano balancing bonding strength *O *OH. Moreover, presents practicability electrochemical water-splitting devices with driving potential well-extended period.

Language: Английский

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Heterojunction Engineering of Multinary Metal Sulfide‐Based Photocatalysts for Efficient Photocatalytic Hydrogen Evolution

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(11)

Published: Dec. 2, 2023

Photocatalytic hydrogen evolution (PHE) via water splitting using semiconductor photocatalysts is an effective path to solve the current energy crisis and environmental pollution. Heterojunction photocatalysts, containing two or more semiconductors, exhibit better PHE rates than those with only one owing altered band alignment at interface stronger driving force for charge separation. Traditional binary metal sulfide (BMS)-based heterojunction such as CdS, MoS

Language: Английский

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Fluorination of Covalent Organic Framework Reinforcing the Confinement of Pd Nanoclusters Enhances Hydrogen Peroxide Photosynthesis

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(36), P. 19877 - 19884

Published: Aug. 16, 2023

Metal-isolated clusters (MICs) physically confined on photoactive materials are of great interest in the field photosynthesis hydrogen peroxide (H2O2). Despite recent important endeavors, weak confinement MICs reported photocatalytic systems leads to their low catalytic activity and stability. Herein, we report a new strategy fluorinated covalent organic frameworks (COFs) strongly confine Pd ICs for greatly boosting stability H2O2 photosynthesis. Both experimental theoretical results reveal that strong electronegative fluorine can increase metal–support interaction optimize d-band center ICs, thus significantly enhancing H2O2. An optimal TAPT-TFPA COFs@Pd photocatalyst delivers stable yield rate 2143 μmol h–1 g–1. Most importantly, as-made exhibit high over 100 h, which is best among materials.

Language: Английский

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Terbium-induced cobalt valence-band narrowing boosts electrocatalytic oxygen reduction

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(11), P. 5500 - 5512

Published: Jan. 1, 2023

Tb 2 O 3 endows Co 3d with a narrow band and appropriate location via 3d–O 2p–Tb 4f gradient orbital coupling to efficiently enhance the oxygen reduction reaction.

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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Lanthanide-regulating Ru-O covalency optimizes acidic oxygen evolution electrocatalysis

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 11, 2024

Abstract Precisely modulating the Ru-O covalency in RuO x for enhanced stability proton exchange membrane water electrolysis is highly desired. However, transition metals with d -valence electrons, which were doped into or alloyed , are inherently susceptible to influence of coordination environment, making it challenging modulate a precise and continuous manner. Here, we first deduce that introduction lanthanide gradually changing electronic configurations can continuously owing shielding effect 5 s /5 p orbitals. Theoretical calculations confirm durability Ln-RuO following volcanic trend as function covalency. Among various Er-RuO identified optimal catalyst possesses 35.5 times higher than 2 . Particularly, -based device requires only 1.837 V reach 3 A cm −2 shows long-term at 500 mA 100 h degradation rate mere 37 μV −1

Language: Английский

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Boosting CO₂ Electroreduction to C₂H₄ via Unconventional Hybridization: High-Order Ce⁴⁺ 4f and O 2p Interaction in Ce-Cu₂O for Stabilizing Cu⁺

ACS Nano, Journal Year: 2023, Volume and Issue: 17(14), P. 13974 - 13984

Published: July 6, 2023

Efficient conversion of carbon dioxide (CO2) into value-added materials and feedstocks, powered by renewable electricity, presents a promising strategy to reduce greenhouse gas emissions close the anthropogenic loop. Recently, there has been intense interest in Cu2O-based catalysts for CO2 reduction reaction (CO2RR), owing their capabilities enhancing C–C coupling. However, electrochemical instability Cu+ Cu2O leads its inevitable Cu0, resulting poor selectivity C2+ products. Herein, we propose an unconventional feasible stabilizing through construction Ce4+ 4f–O 2p–Cu+ 3d network structure Ce-Cu2O. Experimental results theoretical calculations confirm that orbital hybridization near Ef based on high-order 4f 2p can more effectively inhibit leaching lattice oxygen, thereby Ce-Cu2O, compared with traditional d–p hybridization. Compared pure Cu2O, Ce-Cu2O catalyst increased ratio C2H4/CO 1.69-fold during CO2RR at −1.3 V. Furthermore, situ ex spectroscopic techniques were utilized track oxidation valency copper under conditions time resolution, identifying well-maintained species catalyst. This work not only avenue design involving but also provides deep insights metal-oxidation-state-dependent catalysts.

Language: Английский

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