CHEMICAL ENGINEERING JOURNAL
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2023
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IF 15.1
Jili Yuan,Hao Yin,Xin Ge,Ronglan Pan,Caijuan Huang,Dechao Chen,Lin Hu,Haibo Xie
The coordination environment of transition metals in single-atom catalysts (SACs) is crucial for tuning the pathway of the electrocatalytic oxygen reduction reaction (ORR). However, it is significantly difficult to simultaneously and precisely control the first and second coordination structure near the metal active center. Herein, we report that the activated carbon black was used to anchor transition metals’ single atoms with a similar first and second coordination structure. As a result, Co-SACs exhibit an extraordinary performance for ORR to produce H 2 O 2 , where a current density of around ∼2.8 mA cm −2 at 0.1 V vs RHE by rotating ring-disk electrodes and a high yield rate of 110.2 mmol g metal −1 h −1 at the potential of 0.3 V vs RHE in a gas diffusion electrodes (GDEs) cell, with a high positive onset potential of 0.65 V vs RHE and a >80% selectivity of H 2 O 2 at the potential range from 0.25 to 0.65 V vs RHE, respectively. The combined experimental observations and theoretical calculations indicate that the catalytic active center lies in the Co-C 3 /O 1 moiety of the adjacent epoxy group. The possible position of the epoxy group in the second coordination sphere was further revealed. Moreover, Co-SACs were employed in an electrocatalytic GDEs cell for distributed generation of H 2 O 2 in the acidic media, and coupling Fe-SACs-based Fenton filter or electro-Fenton setup with the H 2 O 2 electrolytic generator delivers an efficient and distributable wastewater treatment system. Our study provides a promising and alternative route for on-site H 2 O 2 production coupling the practical application process.
研究领域:
催化化学
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环境科学
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材料科学
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2025
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IF 21.1
Bolong Zhao,Yuyu Wang,Min Xu,Duoning Zhao,Li Zhu,Liqiong Wang,Wenxin Ji,Yuanyuan Li,Guangsuo Yu,Yulong Ma,Yonggang Sun
Low-nuclearity cobalt-oxygen/nitrogen heterogeneous clusters (Co-O/N HCs) activated H 2 O 2 for non-radical oxidation of organic pollutants via unique oxygen atom transfer (OAT) and singlet oxygen ( 1 O 2 ) pathways. The novel Co-O/N HCs were synthesized using a ligand self-polymerization strategy. When applied to high-salinity wastewater, they efficiently degraded tetracycline via 100 % non-radical pathways over a wide pH range, with degradation rates greater than 0.1758 min −1 and no inhibition by Cl - . The confined cluster size (3–5 Co atomic units) and asymmetric nitrogen distribution modified the cobalt atoms' electronic structure, promoting two H 2 O 2 adsorption modes: bridge-adsorbed *O-O* mediated direct oxidation via OAT, while edge-adsorbed *OOH species selectively generated 1 O 2 . This work elucidates the active sites and mechanisms of H 2 O 2 activation, offering key insights for the design of advanced Fenton-like catalysts.
研究领域:
环境化学
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催化
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材料科学
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高级氧化技术
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水处理
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DOI
高影响因子
Small
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2024
·Vol. 20
·期 29
·2310087
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IF 13
Yunfeng Qiu,Yongxia Zhang,Miao Yu,Xinyi Li,Yanxia Wang,Zhuo Ma,Shaoqin Liu
Simultaneously improving electrochemical activity and stability is a long-term goal for water splitting. Herein, hierarchical N-doped carbon nanotubes on carbon nanowires derived from PPy are grown on carbon cloth, serving as a support for NiCo oxides/sulfides. The hierarchical electrodes annealed in N 2 or H 2 /N 2 display improved intrinsic activity and stability for hydrogen evolution reaction (HER) and glucose oxidation reaction. Compared with Pt/C||Ir/C in alkaline media, the glucose electrolysis assembled with electrodes exhibits a cell voltage of 1.38 V at 10 mA cm −2 , durability for >12 h at 50 mA cm −2 , and resistance to glucose/gluconic acid poisoning. In addition, electrocatalysts can also be applied in ethanol oxidation reactions. Systematic characterizations reveal the strong interactions between NiCo and N-doped carbon support-induced partial charge transfer at the interface and regulate the local electronic structure of active sites. Density functional theory calculations demonstrate that the synergistic effect between N-doped carbon supports, metallic NiCo, and NiCo oxides/sulfides optimize the adsorption energy of H 2 O and the H* free energy for HER. The energy barrier of the dehydrogenation of glucose effectively decreased. This work will attract attention to the role of metal-support interactions in enhancing the intrinsic activity and stability of electrocatalysts.
研究领域:
材料科学
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电催化
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能源转换与存储
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DOI
PubMed
高影响因子
Nature Communications
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2022
·Vol. 13
·期 1
·1-12
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IF 17.694
Wang Sihong,Jiang Qu,Ju Shenghong,Hsu Chia-Shuo,Chen Hao Ming,Zhang Di,Song Fang
Unraveling the precise location and nature of active sites is of paramount significance for the understanding of the catalytic mechanism and the rational design of efficient electrocatalysts. Here, we use well-defined crystalline cobalt oxyhydroxides CoOOH nanorods and nanosheets as model catalysts to investigate the geometric catalytic active sites. The morphology-dependent analysis reveals a ~50 times higher specific activity of CoOOH nanorods than that of CoOOH nanosheets. Furthermore, we disclose a linear correlation of catalytic activities with their lateral surface areas, suggesting that the active sites are exclusively located at lateral facets rather than basal facets. Theoretical calculations show that the coordinatively unsaturated cobalt sites of lateral facets upshift the O 2p -band center closer to the Fermi level, thereby enhancing the covalency of Co-O bonds to yield the reactivity. This work elucidates the geometrical catalytic active sites and enlightens the design strategy of surface engineering for efficient OER catalysts.
研究领域:
材料科学
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催化
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电化学
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DOI
PubMed
高影响因子
Small
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2025
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IF 12.1
Jiajie Xu,Tenghui Jin,Wei Qu,Kaizhou Huang,Zhiyu Liu,Ping Zhang,Jiaping Paul Chen
Development of high-performance photocatalysts for persulfate activation is often limited by rapid electron–hole recombination and insufficient quantum efficiency. To overcome the challenges, electronic metal–support interaction (EMSI) structure is designed. The innovative structure has several key benefits: recombination rates are significantly reduced, charge separation is enhanced, and content of active sites and intrinsic catalytic activity are increased. ZrO 2 /Co 3 O 4 bimetallic oxides featuring a synergistic Co─O─Zr EMSI coordination are synthesized via a sol-gel method. Strong EMSI effects markedly modulate and stabilize the Co 3d electronic structure, creating an electron-rich center on Co sites to promote persulfate activation, and an electron-deficient center on Zr sites to adsorb atrazine. The Gibbs free energy analysis reveals that Zr incorporation reduces the overpotential of oxygen evolution reaction, thereby facilitating electron transfer, promoting hole consumption and suppressing charge recombination. More importantly, it promotes the generation of reactive oxygen species—predominantly via a singlet oxygen ( 1 O 2 )-dominated non-radical mechanism. The optimized catalyst achieves 97.3% degradation of atrazine (a model compound) under visible light, outperforming commercial catalysts (e.g., 4.5-fold of Co 3 O 4 ). The work elucidates the cooperative mechanism of dual-site engineering and EMSI-mediated electron redistribution, providing a rational strategy for designing efficient photocatalysts toward sustainable advanced oxidation processes.
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DOI
PubMed
高影响因子
ACS Catalysis
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2024
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IF 11.3
Baoxin Ge,Pengyang Jiang,Biyi Chen,Caijin Huang
The orbital hybridization between metal and oxygen of perovskite catalysts can lower the overpotential and enhance the oxygen evolution reaction (OER) activity. This study combines density functional theory with experiments to clarify how Sr/Fe codoping modulates orbital hybridization and enhances OER catalytic activity of LaCoO3. The as-prepared La0.50Sr0.50Co0.75Fe0.25O3 shows remarkable performance with a low overpotential of 310 mV at 10 mA cm–2 current density and a 107.03 mV dec–1 Tafel slope, outperforming most state-of-the-art perovskite-based OER electrocatalysts. The experimental results confirm that Sr/Fe codoping enhances the expansion of Co–O–Co bond angles and strengthens the covalency of the Co–O bond in LaCoO3, leading to enhanced electrocatalytic activity. Moreover, increasing Sr doping reduces the distance between the Co 3d/O 2p center and the Fermi level, decreasing the energy difference between them and enhancing the degree of orbital hybridization between Co 3d and O 2p. As the degree of Co 3d/O 2p orbital hybridization increases, a higher charge transfer was found between the active center and intermediate product, OOH, reducing the energy barrier of the rate-determining step while lowering the overpotential. This study provides thorough insight into the rational design of OER catalysts based on orbital hybridization.
研究领域:
材料科学
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催化化学
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DOI
高影响因子
Engineering
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2025
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IF 11.6
Qian Hu,Shanli Wang,Kaixing Fu,Guangpeng Yang,Licong Xu,Wenbin Jiang,Minghua Wu,Wangyang Lu,Xiaomin Zhu,Jinming Luo
The singlet oxygen ( 1 O 2 )-driven nonradical oxidation pathway has shown great promise for the degradation of organic pollutants with high ionization potentials (IPs) in complex water matrices because of its longer half-life and stronger resistance to environmental interference. However, the symmetric configuration of the active sites (e.g., Fe–O–Fe) in heterogeneous catalysts largely restricts the efficacy of 1 O 2 generation during ozone activation. In this study, we constructed an asymmetric Co–O–Fe dual-site in bimetallic metal‒organic frameworks (MOFs) with enhanced electron delocalization to switch the ozone activation pathway from radical-dominant to nonradical-dominant. By combining experimental and theoretical analyses, we revealed that breaking the symmetry of iron sites with Co incorporation optimizes the local electronic structure, thereby facilitating ozone adsorption and reducing the O‒O bond scission energy barrier to produce 1 O 2 . As a result, the constructed asymmetric Co–O–Fe dual-site demonstrates impressive 6.6 and 2.0 fold increases in 1 O 2 selectivity and phenol degradation efficiency, surpassing the performance of the state-of-the-art ozonation catalysts. Furthermore, the Co–O–Fe dual-site/O 3 system could efficiently and stably remove diverse high-IP organic pollutants in complex water matrices, following a positive linear correlation ( R 2 > 0.97) between the kinetic rate constants and theoretical IP values, which further highlights the unique and critical role of 1 O 2 . This work advances the understanding and design of efficient dual-site catalysts for selective 1 O 2 generation and sustainable high-IP pollutant degradation.
研究领域:
环境化学
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催化科学
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材料科学
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水污染控制
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物理化学
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产品关联
DOI
高影响因子
JOURNAL OF THE ENERGY INSTITUTE
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2026
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IF 6.5
Yanni Liu,Dong Shen,Jun Liu,Yuqiong Zhao,Guojie Zhang
Dry reforming of methane (DRM) is a promising route for the simultaneous utilization of CH 4 and CO 2 to produce syngas, yet the development of efficient and stable catalysts for low-temperature DRM remains highly challenging. In this work, a series of Co/CeO 2 catalysts with morphology-controlled ceria supports were prepared to investigate the structure–performance relationship in DRM. Among them, the catalyst supported on CeO 2 nanorods (Co/CeO 2 -R) exhibited the best catalytic activity and stability at 600 °C. Structural characterization suggests that the CeO 2 -R support provides a higher surface area and defect density, which favors Co dispersion and the formation of Co-O-Ce interfacial structures. Raman, XPS, and H 2 -TPR results indicate that Co/CeO 2 -R possesses a higher concentration of oxygen vacancies and stronger interfacial interactions compared with other catalysts. CO 2 -TPD measurements further show enhanced CO 2 adsorption capacity, which is consistent with the increased density of defect sites. The results collectively suggest that the improved catalytic performance originates from the synergistic effect of Co dispersion, oxygen vacancies, and Co-O-Ce interfacial structures, which together promote CO 2 activation, oxygen transfer, and carbon removal. In situ DRIFTS results suggest a bifunctional reaction pathway, in which CH 4 activation is likely to occur on Co sites, while CO 2 is activated on defect-rich CeO 2 surfaces to form carbonate/formate species that may participate in carbon removal. Overall, this work establishes a structure-performance correlation between CeO 2 morphology and catalytic behavior, providing insights into the design of Co-based catalysts for low-temperature DRM.
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DOI
高影响因子
ELECTROCHIMICA ACTA
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2018
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IF 5.116
W.Q. Yang,Y.X. Hua,Q.B. Zhang,H. Lei,C.Y. Xu
The development of earth-abundant, low-cost, highly active, and durable bifunctional catalysts competent for efficient electrochemical water-splitting is intensively demanding and of vital importance to realize high-purity hydrogen production . Herein, we report that 3D quasi-amorphous pompon-like Co-O and Co-Se hybrid films grown on copper foil (Co-O@Co-Se/Cu) can be electrochemically synthesized from a choline chloride and urea mixed deep eutectic solvent , denoted as Reline, via a facile one-step electrochemical deposition approach. Benefiting from the induction effect of Se, the obtained Co-O@Co-Se/Cu hybrid electrode exhibits strongly enhanced catalytic activity. The optimal Co-O@Co-Se/Cu sample shows good activity and excellent durability for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in an alkaline solution with low overpotentials of 85 mV for HER and 340 mV for OER, respectively to reach a catalytic current of 10 mA cm −2 . The Co-Se component within the hybrid films is gradually converted into Co-O species during the course of the OER, which are responsible for the good OER performance. In addition, when performed as bifunctional catalysts in a two-electrode configured electrolyzer, the Co-O@Co-Se/Cu couple displays a water-splitting current of 10 mA cm -2 at 1.65 V with reasonable stability for long-term electrolysis over 100 h. This simple one-step electrochemical synthesis route operated in the Reline-based deep eutectic solvent is demonstrated as an efficient strategy to fabricate active non-noble-free electrocatalysts toward overall water splitting applications.
研究领域:
材料科学
·
能源化学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）