LANGMUIR
·
2026
·Vol. 42
·期 31
·22973-22982
·
IF 4.4
Jia Xiaomeng,Dong Kaiyu,Zheng Zhe,Sheng Tian,Yuan Qiang
Nonprecious metal oxygen reduction
reaction (ORR) electrocatalysts
have garnered increasing attention owing to their extremely low cost
compared with Pt-based electrocatalysts. However, realizing the four-electron
pathway and developing highly antipoisoning nonprecious metal ORR
electrocatalysts are key challenges in practical energy devices. Herein,
atomic-level Fe doping was applied to Co@CoO core–shell nanoparticles
anchored in a porous carbon–nitrogen framework (denoted Fe–Co@CoO/NC)
derived from FeCoZn metal–organic frameworks. The Fe–Co@CoO/NC
exhibits a half-wave potential of 0.895 V in an alkaline medium, superior
to that of commercial Pt/C (0.842 V), and high in situ methanol and
CO tolerance. In situ spectroscopic characterizations and Rotating
Ring-Disc Electrode (RRDE) investigations reveal that four-electron
ORR is achieved using Fe–Co@CoO/NC through O–O bond
breaking in OOH* intermediate species. In addition, density functional
theory calculations show that compared with Pt, Fe–CoO effectively
suppresses H 2 O 2 generation and favors a more
advantageous four-electron reaction pathway. Fe–Co@CoO/NC as
a cathode material for direct methanol fuel cells (DMFCs) reaches
a peak power density of 113.7 mW·cm –2 , markedly
outperforming commercial Pt/C (72.0 mW·cm –2 ). This work provides an effective strategy for preparing high-efficiency
nonprecious metal four-electron ORR catalysts with intrinsic tolerance
to methanol and CO for DMFC devices.
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PubMed
高影响因子
ELECTROCHIMICA ACTA
·
2026
·
IF 5.8
Yutong Yang,Lijie Zhao,Ning Liu,Jianjiao Xin,Wanli Yang,Xinyou Zhang,Danfeng He,Fujiang Zhou,Hong Pan
La 3+ /Fe 2+ co-doping tailors U and W of CoO for bulk electronic optimization. • La 3+ -induced distortion reconstructs Lewis base sites to suppress shuttle effect. • Base sites show strong Li + adsorption and weaken S-S bonds via electron injection. • As supercapacitor cathode: 1405.6 F g −1 at 1 A g −1 , device energy 93.0 Wh kg −1 . • As Li-S sulfur host: 1161.6 mAh g −1 at 0.1 C, 62.1% retention after 100 cycles. This work develops La/Fe co-doped cobalt oxide (La/Fe-CoO) as a bifunctional electrode material to simultaneously enhance the electrochemical performance of supercapacitors and lithium-sulfur batteries, targeting the common bottlenecks of sluggish charge transport and poor surface reaction kinetics. The performance limitations of CoO arise primarily from its unfavorable electronic structure parameters: excessive Hubbard repulsion energy ( U ) and narrow band width ( W ), which severely restrict redox efficiency and electron conductivity. To address these issues, La 3+ and Fe 2+ co-doping is employed to achieve precise synergistic regulation of U and W . Fe 2+ doping constructs an extended “Co 3d -O 2p -Fe 3d ” orbital hybridization network that broadens W , optimizes charge transport pathways, and substantially improves intrinsic conductivity. Meanwhile, La 3+ reduces the effective Hubbard U through f-d orbital coupling, weakening intraorbital electron repulsion and lowering the reaction barrier. More importantly, the large ionic radius of La 3+ induces local lattice distortion, generating abundant electron-rich Lewis basic active sites on the material surface, which are distinctly different from the Lewis acidic sites commonly reported in the literature. Unlike acidic sites based on metal cations, these basic sites not only immobilize polysulfides by electrostatically adsorbing Li + ions, but also inject electrons into the S-S antibonding orbitals, exerting a redox catalytic effect that promotes S-S bond cleavage and accelerates polysulfide conversion kinetics, thereby effectively suppressing the shuttle effect in lithium-sulfur batteries. This work, through the synergistic design of bulk electronic structure ( U / W ) modulation and surface basic site reconstruction, offers a feasible strategy for developing high-performance bifunctional electrode materials for energy storage applications. Download: Download high-res image (412KB) Download: Download full-size image
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Yu Jiang,Jia Wang,Bo Liu,Wei Jiang,Tianyu Zhou,Yunchao Ma,Guangbo Che,Chunbo Liu
Herein, a N,S,O-doped Co/CoO/Co 9 S 8 @carbon hybrid (Co/CoO/Co 9 S 8 @NSOC) has been constructed by calcinating a Co-based metal–organic framework (Co-MOF) with 4,4-bipyridine and 2,5-thiophenedicarboxylic acid as linkers. Co/CoO/Co 9 S 8 @NSOC exhibited a high and recycled catalytic efficiency for peroxymonosulfate (PMS) activation to degrade sulfamethoxazole (SMX, 20 mg/L) with a reaction rate of 1.31 min −1 , which was 5.2 times than that of Co-MOF. The catalytic behavior should be attributed to the rich active sites, lamellar morphology, superhydrophilicity, and magnetism. Furthermore, the Co/CoO/Co 9 S 8 @NSOC was immobilized on a filter membrane (CMFM) to adapt to the flowing system, which could recycle 20 times without losing activity. To employ in a large-scale static environment, the Co/CoO/Co 9 S 8 @NSOC was loaded on the commercial sponge (CoSPG). In a 50 L water tank, the CoSPG realized to decompose 160 mg/L SMX solution with 37 h and had long-term stability over 10 days. Notably, the PMS cost of treating one ton of wastewater is only $0.34, indicating a huge industrial application value.
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高影响因子
Journal of Materials Chemistry A
·
2017
·Vol. 5
·期 12
·5865-5872
·
IF 8.867
X. X. Liu,J. B. Zang,L. Chen,L. B. Chen,X. Chen,P. Wu,S. Y. Zhou,Y. H. Wang
A novel electrochemical catalyst comprising CoO@Co nanoparticles with a core–shell structure immobilized on N-doped reduced graphene oxide (rGO) (CoO@Co/N-rGO) has been synthesized using a convenient and controllable technique — combining a rapid microwave-polyol method with a vacuum thermal treatment. Excellent features including the Co/N-doping effect, introduction of CoO@Co particles with a core–shell structure and good contact between the CoO@Co particles and N-doped graphene result in a highly multi-functional catalytic efficiency. The catalyst exhibits remarkable catalytic activity and superior stability towards the hydrogen evolution reaction, offering a low overpotential of 140 mV for 10 mA cm−2 in 0.5 M H2SO4 and 237 mV in 0.1 M KOH. The catalyst also shows excellent oxygen reduction reaction activity in 0.1 M KOH, a similar four-electron pathway, which is comparable to that of a commercial Pt/C catalyst, and superior stability. In addition, a good electrochemical performance towards the oxygen evolution reaction was observed for the catalyst, achieving a current density of 10 mA cm−2 with a small overpotential of 1.67 V in 0.1 M KOH, which is comparable to that of a commercial RuO2 catalyst. The unusual catalytic activities arise from the synergetic chemical coupling effects of metallic Co, cobalt oxides and Co/N-doped graphene. This study provides a new attractive multi-functional catalyst material for unitized regenerative fuel cells and overall water splitting technologies.
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高影响因子
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