JOURNAL OF THE ELECTROCHEMICAL SOCIETY
·
2024
·Vol. 171
·期 9
·096505
·
IF 3.1
Zhefei Zhao,Linlin Zhang,Minghao Chen,Ruopeng Yu,Xuyao Yao,Yinghua Xu,Youqun Chu,Xinbiao Mao,Huajun Zheng
Electrochemical selective dechlorination can be regarded as one of the most promising strategies for generating high-valued chemicals. In the electrochemical dechlorination process of 2-chloro-5-trichloromethylpyridine (TCMP), except the anticipated dechlorination products involving 2-chloro-5-dichloromethylpyridine (DCMP), 2-chloro-5-chloromethylpyridine (CCMP), and 2-chloro-5-methylpyridine (CMP), some unexpected oxygen-incorporated products (6-chloronicotinic acid (CNA) and 6-chloronicotinoyl methyl ester (MCN)) can be obtained. Consequently, understanding the electrochemical dechlorination behavior of TCMP is crucial. Our research revealed that the activated Ag electrodes in halide ion solution exhibit enhanced electrochemical activities for electrochemical dechlorination of TCMP, compared with the pure Ag owing to the increased active specific surface areas and charge transfer. Second, oxygen participation in the reaction is a necessary condition for the formation of oxygen-incorporated products. A 100% selectivity of oxygen-incorporated products can be obtained at the potential of −0.6 V vs Ag/AgCl. Conversely, insufficient oxygen may lead to the potential becoming the determining condition that affects the reaction pathways. A more negative potential (−1.2 V vs Ag/AgCl) is conducive to the formation of dechlorination products with 94.2% conversion and 100% selectivity. This study, for the first time, elucidates the electrocatalyst, atmosphere, and potential-dependent activity and selectivity for the two dechlorination pathways of TCMP.
研究领域:
环境科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Nano
·
2025
·
IF 16
Haijuan Zhang,Hengyue Xu,Jie Chen,Daqin Guan,Zhiwei Hu,Xiaomin Xu,Zezhou Lin,Hainan Sun,Xiao Sun,Jiayi Tang,Chih-Wen Pao,Chien-Te Chen,Wei Zhou,Chunchang Wang,Youmin Guo,Zongping Shao
Lattice oxygen participation mechanism (LOM) can break the conventional adsorption scaling limitations to boost electrocatalysis performance and has been utilized to design promising single-phase oxides that generally show favorable bulk oxygen-ion diffusion capability. In pure-phase materials, bulk oxygen vacancies could act as oxygen-ion diffusion channels, implying rich bulk oxygen vacancies at the interfaces of hybrid-phase composites may further boost LOM. Here, by designing hybrid Co2.5Ru0.5Ox hollow nanotubes with rich two-phase interfaces, we report a phenomenon of interfacial LOM. Such hollow nanotubes (∼10 nm wall thickness), composed of spinel Co3O4-x-rutile RuO2-x interfaces, exhibiting a low overpotential of 430 mV and a long-term stability of 1000 h at 500 mA cm–2 for oxygen-evolving reaction (OER) in near-industrial alkaline solutions (6 M KOH). The constructed anion exchange membrane electrolyzer requires only 1.82 V to achieve a 1 A cm–2. Interfacial Co/Ru atomic interactions trigger Co–O–Ru motifs to undergo self-optimization during OER through oxidizing Co/Ru ions and narrowing bond length to create short synergetic active sites, while interfacial oxygen vacancies act as ion-diffusion pathways. Combined mechanism experiments and computations unravel the exceptional interfacial LOM processes. Additionally, the hollow nanotube structure promotes OH– adsorption, serving as a beneficial driving force for interfacial LOM.
研究领域:
材料科学
·
电化学
·
纳米科技
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Lina Tang,Tingting Fan,Zhou Chen,Jianling Tian,Hongquan Guo,Meilan Peng,Fan Zuo,Xianzhu Fu,Meng Li,Yunfei Bu,Yang Luo,Jianhui Li,Yifei Sun
Lattice oxygen-mediated mechanism (LOM) on perovskite oxides for oxygen evolution reaction (OER) process has revealed kinetic superiority over conventional adsorbate evolution mechanism (AEM). However, feasibly enhancing the participation of lattice oxygen is still challenging. Here we designed a perovskite cobaltate (La 0.6 Sr 0.4 Co 0.8 Fe 0.1 Mn 0.1 O 3-δ , LSCFM) nanofiber, and discovered that the co-incorporation of Fe/Mn elements significantly intensifies the involvement of lattice oxygen for OER. Compared with its mono-dopant (Fe or Mn only) counterparts, the LSCFM gives rise to higher surface oxygen vacancies (V o ) concentration and faster oxygen ion diffusion coefficient, endowing a small overpotential of 343 mV at 10 mA cm −2 and low Tafel slope of 63 mV dec −1 . The strongest pH-dependent activity and metal–oxygen covalency are further unveiled on LSCFM by experimental and theoretical approaches, evidencing that the promoted OER kinetics on LSCFM predominantly stems from the formation of reactive lattice oxygen site.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Chem
·
2023
·
IF 23.5
Na Yao,Hongnan Jia,Juan Zhu,Zhaoping Shi,Hengjiang Cong,Junjie Ge,Wei Luo
The development of highly efficient and stable electrocatalysts toward the acidic oxygen evolution reaction (OER) is essential for the practical application of proton-exchange membrane water electrolyzers. Although Ru oxides possess remarkable initial activity toward the acidic OER due to the kinetically favorable lattice oxygen oxidation mechanism pathway, the soluble high-valence oxygen-vacancy intermediate (∗Vo-RuO 4 2− ) may accelerate the dissolution of Ru species, leading to dramatically decreased activity and unsatisfied long-term stability. Here, we developed a robust metal-organic framework anchored strategy by stabilizing atomically isolated Ru oxide on UiO-67-bpydc with strong coordinating pyridine ligands. Theory calculations and experimental results including in situ Raman, X-ray absorption spectroscopy, and 18 O-labeled differential electrochemical mass spectrometry reveal that the Ru–N bonds between Ru oxide and UiO-67-bpydc could not only accelerate the participation of lattice oxygen during the OER process but also stabilize the soluble ∗Vo-RuO 4 2− intermediate, which contribute to the enhanced OER performance and long-term stability of up to 115 h.
研究领域:
电催化
·
材料化学
·
能源科学
·
无机化学
·
物理化学
✓ 已验证
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2025
·
IF 8.3
Mingxin Cai,Qinghua Ye,Ziru Wang,Peilei He
Electrochemical water splitting for hydrogen production is currently constrained by the sluggish kinetics of the anodic oxygen evolution reaction (OER). NiFe-based catalysts have emerged as promising alternatives to precious metal OER catalysts due to their low cost and relatively high electrocatalytic activity. However, NiFe-based catalysts prepared by conventional synthesis methods suffer from a low density of exposed active sites and ambiguous structures. Herein, we report a straightforward solution-thermal strategy for constructing two-dimensional sub-1 nm nanosheets (SNSs) through the self-assembly of an iron-substituted polyoxometalate (FeMo 6 ) cluster with Ni 3 S 2 . The Ni 3 S 2 –FeMo 6 SNSs exhibit excellent electrocatalytic performance in 1 M KOH, achieving an overpotential of only 342 mV at a current density of 100 mA cm −2 and maintaining stability for 100 h at 10 mA cm −2 . The synergistic effect between Fe and Ni 3 S 2 effectively modulates the electronic structure of the catalyst, accelerating the formation of the active NiOOH phase. Furthermore, Fe incorporation actively enhances hydroxyl groups adsorption on the catalyst surface and facilitates lattice oxygen participation in the reaction. This work clarifies the role of Fe in NiFe-based electrocatalysts, providing new perspectives for developing facile-to-synthesize and high-performance electrocatalysts.
研究领域:
电化学
·
纳米材料
·
催化
·
能量转换
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）