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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Pt Nanoparticle–Mn Single-Atom Pairs for Enhanced Oxygen Reduction

ACS Nano, Journal Year: 2024, Volume and Issue: 18(5), P. 4308 - 4319

Published: Jan. 23, 2024

The intrinsic roadblocks for designing promising Pt-based oxygen reduction reaction (ORR) catalysts emanate from the strong scaling relationship and activity–stability–cost trade-offs. Here, a carbon-supported Pt nanoparticle Mn single atom (PtNP–MnSA/C) as in situ constructed PtNP–MnSA pairs are demonstrated to be an efficient catalyst circumvent above seesaws with only ∼4 wt % loadings. Experimental theoretical investigations suggest that MnSA functions not "assist" sites cooperatively facilitate dissociation of O2 due electronic polarization, affording dissociative pathway reduced H2O2 production, but also structure "modulator" downshift d-band center sites, alleviating overbinding oxygen-containing intermediates. More importantly, serves "stabilizer" endow PtNP–MnSA/C excellent structural stability low Fenton-like reactivity, resisting fast demetalation metal sites. As result, PtNPs–MnSA/C shows ORR performance half-wave potential 0.93 V vs reversible hydrogen electrode high mass activity 1.77 A/mgPt at 0.9 acid media, which is 19 times higher than commercial Pt/C declines by 5% after 80,000 cycles. Specifically, reaches power density 1214 mW/cm2 2.87 A/cm2 H2–O2 fuel cell.

Language: Английский

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A sol–gel derived LaCoO₃ perovskite as an electrocatalyst for Al–air batteries

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(8), P. 3713 - 3721

Published: Jan. 1, 2024

In this work, we report the performance of LaCoO 3 perovskite oxide as a cathode catalyst for an Al–air battery.

Language: Английский

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Europium Oxide Evoked Multisite Synergism to Facilitate Water Dissociation for Alkaline Hydrogen Evolution

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: July 2, 2024

Abstract Exploring an efficient nonnoble metal catalyst for hydrogen evolution reaction (HER) is critical industrial alkaline water electrolysis. However, it remains a great challenge due to the additional energy required H─OH bond cleavage and lack of enough H 2 O adsorption sites most catalysts. Herein, integration oxophilic Eu 3 with NiCo alloy evoked multisite synergism facilitate dissociation HER proposed. The optimized ‐NiCo exhibits excellent activity low overpotential only 60 mV at 10 mA cm −2 good electrochemical stability, which superior that ‐free comparable benchmark Pt/C. key roles on enhanced performance are identified by in situ Raman spectroscopy theoretical calculations. It discovered strong oxophilicity facilitates breakage bonding while evoking electron redistribution /NiCo interface accelerating Volmer step HER. Furthermore, obtained as both anode cathode displays overall water‐splitting stability 1.0 M KOH solution. believed this study provides important inspiration design high‐performance electrocatalysts toward based rare‐earth materials.

Language: Английский

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Tailoring First Coordination Sphere of Dual‐Metal Atom Sites Boosts Oxygen Reduction and Evolution Activities

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(28)

Published: Feb. 24, 2024

Abstract It is important to tune the coordination configuration of dual‐atom catalyst (DAC), especially in first sphere, render high intrinsic catalytic activities for oxygen reduction/evolution reactions (ORR/OER). Herein, a type atomically dispersed and boron‐coordinated DAC structure, namely, FeN 4 B‐NiN B dual sites, reported. In this incorporation boron into sphere /NiN atomic sites regulates its geometry electronic structure by forming “Fe‐B‐N” “Ni‐B‐N” bridges. The exhibits much enhanced ORR OER property compared ‐NiN counterparts. Density functional theory calculations reveal that boron‐induced charge transfer asymmetric distributions central Fe/Ni atoms optimize adsorption desorption behavior ORR/OER intermediates reduce activation energy potential‐determining step. Zinc‐air batteries employing cathode exhibit maximum power density (236.9 mW cm −2 ) stable cyclability up 1100 h. result illustrates pivotal role first‐coordination DACs tuning electrochemical conversion storage activities.

Language: Английский

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Boosting ORR/OER bifunctional electrocatalysis by promoting electronic redistribution of Fe-N-C on CoFe-FeNC for ultra-long rechargeable Zn-air batteries

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 359, P. 124485 - 124485

Published: Aug. 8, 2024

Language: Английский

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Importing Atomic Rare‐Earth Sites to Activate Lattice Oxygen of Spinel Oxides for Electrocatalytic Oxygen Evolution

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 9, 2024

Abstract Spinel oxides have emerged as highly active catalysts for the oxygen evolution reaction (OER). Owing to covalency competition, OER process on spinel often follows an arduous adsorbate mechanism (AEM) pathway. Herein, we propose a novel rare‐earth sites substitution strategy tune lattice redox of and bypass AEM scaling relationship limitation. Taking NiCo 2 O 4 model, incorporation Ce into octahedral site induces formation Ce−O−M (M=Ni, Co) bridge, which triggers charge redistribution within . The developed Ce−NiCo exhibits remarkable activity with low overpotential, satisfactory electrochemical stability, good practicability in anion‐exchange membrane water electrolyzer. Theoretical analyses reveal that surface more favorable (LOM) pathway non‐concerted proton‐electron transfers compared pure , also verified by pH‐dependent behavior situ Raman analysis. 18 O‐labeled mass spectrometry provides direct evidence released during originates from We discover electron delocalization f states through favoring antibonding state occupation Ni−O bonding [Ce−O−Ni] unit site, thereby activating OER. This work new perspective designing offers significant insights rare‐earth‐enhanced LOM mechanism.

Language: Английский

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Atomic rare earths activate direct O-O coupling in manganese oxide towards electrocatalytic oxygen evolution

Nano Energy, Journal Year: 2024, Volume and Issue: 128, P. 109868 - 109868

Published: June 10, 2024

Language: Английский

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Oxophilic Tm‐Sites in MoS₂ Trigger Thermodynamic Spontaneous Water Dissociation for Enhanced Hydrogen Evolution

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: unknown

Published: June 11, 2024

Abstract 2D MoS 2 is acknowledged as a potential alternative to Pt‐based catalysts for hydrogen evolution reaction (HER) due its suitable * H adsorption energy. However, the weak water capacity of in an alkaline solution limits performance improvement toward HER. Herein, novel rare‐earth Tm single atoms decorated (Tm SAs‐MoS ) catalyst proposed, and key role SAs on enhanced HER identified. It verified that Tm‐site contributes asymmetric [Mo‐S‐Tm] unit site, which serves electron donor disturb electronic state accelerate accumulation at surrounding Mo‐S site. The obtained exhibits significantly improved activity with low overpotential 80 mV 10 mA cm −2 , robust stability good selectivity compared pure most ‐based catalysts. In situ Raman theoretical calculations prove oxophilic sites improves migration thermodynamic spontaneous dissociation interfacial O molecules during by Tm‐4f‐OH orbital overlap. Such [Tm‐S‐Mo] site allows optimal G *H location turn reaches apex volcano plot. This work expected open up new avenues design provide valuable understanding rare earth mechanisms.

Language: Английский

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Unraveling the Tandem Effect of Nitrogen Configuration Promoting Oxygen Reduction Reaction in Alkaline Seawater

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(24)

Published: April 10, 2024

Abstract Developing seawater‐based high‐performance oxygen reduction reaction (ORR) electrocatalysts is meaningful to renewable energy storage and conversion, the Fe‐based derivatives encapsulated by nitrogen (N) doped carbon are typical representative. Nevertheless, unrevealing mechanism of N configuration ORR activity chlorine resistance still a great challenge. In this work, feasible strategy developed prepare controllable pyridinic/pyrrolic‐N carbon‐coated (Fe x N‐NC). Drawing support from H 3 PO 4 blocking based in situ Fourier transform infrared spectroscopy (FTIR) test density‐functional theory (DFT) calculation, tandem effect pyridinic‐N pyrrolic‐N on proved. Additionally, low hydrogen peroxide (H 2 O ) yield 4e − pathway Fe N‐NC demonstrate that doping effectively reduces adsorption Cl , which consistent with DFT. The half‐wave potential (E 1/2 for reaches 0.874 V alkaline seawater, ZABs assembled as air cathode deliver remarkable power density (162 mW cm −2 ), along excellent long‐term durability (>400 h).

Language: Английский

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