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ACS Nano · 2025 · IF 16

Self-Optimized Interfacial Co–O–Ru Motifs of Hollow Nanotube Composites Trigger Interfacial Lattice Oxygen Participation and Diffusion

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.

CAS / MDL: 25249-54-1 9003-39-8
研究领域: 材料科学 · 电化学 · 纳米科技
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Water · 2025 ·Vol. 17 ·期 14 ·2161 · IF 3

Cu–Co–O-Codoped Graphite Carbon Nitride as an Efficient Peroxymonosulfate Activator for Sulfamethoxazole Degradation: Characterization, Performance, and Mechanism

Qiliang Xiao,Jun Nan

This study presents the development of a novel Cu–Co–O-codoped graphitic carbon nitride (g-C3N4) catalyst for efficient peroxymonosulfate (PMS) activation to degrade sulfamethoxazole (SMX) in aqueous environments. The synthesized Cu–Co–O-g-C3N4catalyst demonstrated exceptional catalytic performance, achieving 90% SMX removal within 10 min—significantly outperforming pristine g-C3N4(14%) and O-doped g-C3N4(22%)—with a reaction rate constant of 0.63 min−1. The superior activity was attributed to the synergistic effects of Cu-Co bimetallic doping and oxygen incorporation, which enhanced the active sites, stabilized metal ions, and minimized leaching. Mechanistic studies revealed a dual-pathway degradation process: (1) a radical pathway dominated by sulfate radicals (SO4•−) and (2) a non-radical pathway driven by singlet oxygen (1O2), with the latter identified as the dominant species through quenching experiments. The catalyst exhibited broad pH adaptability and optimal performance at neutral to alkaline conditions. Characterization techniques (XRD, FTIR, XPS) confirmed successful doping and revealed that oxygen incorporation modified the electronic structure of g-C3N4, improving charge carrier separation. This work provides a sustainable strategy for antibiotic removal, addressing key challenges in advanced oxidation processes (AOPs), and highlights the potential of multi-heteroatom-doped carbon nitride catalysts for water purification.

研究领域: 环境科学 · 催化 · 水处理 · 材料科学 · 化学工程
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Inorganic Chemistry Frontiers · 2024 · IF 6.1

Promoting Electrocatalytic Water Oxidation via crafting Co-O-W bridge bonds on Amorphous core/shell NiCo-ZIF@POM catalyst

Tianhao Yu,peng gao,Hong Du,ling dong

The oxygen evolution reaction (OER) requires the development of a strong and efficient electrocatalyst due to its slow mechanism and high overpotential. Hence, we assembled POM and NiCo-ZIF-67 to obtain the amorphous hollow core-shell material NiCo-ZIF-67@POM (donated as NiCo-ZIF@POM) with high catalytic activity. NiCo-ZIF@POM (1:3) presents a low overpotential (η≈150 mV@10 mA cm-2), a small Tafel slope (100 mV dec-1), and great stability for OER in 1 M KOH solution. Theoretical calculations indicate that the excellent activity of NiCo-ZIF@POM might be attributed to the charge rearrangement due to the interaction between Co and W. In addition, the low electronegativity of P and the high oxidation state of W in POM could accelerate the rapid OH- transfer and induce the intermediates to adsorb on the Co-O-W bridge bond conformation, which improves the performance of the catalytic OER. This study provides a new idea for the secondary assembly of POM and MOF materials.

研究领域: 材料科学 · 电化学
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FIBERS AND POLYMERS · 2013 ·Vol. 14 ·期 1 ·8-15 · IF 0.912

Characterization and electrochemical properties of poly(aniline-co-o-methoxyaniline)/multi-walled carbon nanotubes composites synthesized by solid-state method

Xu Feng,Jamal Ruxangul,Ubul Aminam,Shao Weiwei,Abdiryim Tursun

The composites of copolymers of aniline (An) and o -methoxyaniline (OMA) with multi-walled carbon nanotubes, named as copolymers/MWNT, (poly(An-co-OMA)/MWNT) were prepared by solid-state synthesis method at room temperature. The homopolymers/MWNT composites were synthesized for comparison. The structure and morphology of these composites were characterized by FT-IR spectroscopy, UV-Vis absorption spectroscopy, X-ray diffraction (XRD) and TEM. The electrochemical performances of the composites were investigated by galvanostatic charge-discharge, cyclic voltammetry (CV) and cycle life measurements. The results from FT-IR and UV-Vis spectra showed that different molar ratio of [An]/[OMA] in reaction system has great influence on the oxidation degree, conjugation length and doping level of the copolymers in these composites. The presence of MWNT in the composites was confirmed from the characteristic peaks of MWNT in XRD patterns and the enwrapped MWNT in TEM images. The TEM images further indicates that the MWNT uniformly distributed and enwrapped with polymer in the case of composite from molar ratio of [An]/[OMA]=1:1. The results also showed that the morphology, crystallinity and solubility of composites were highly affected by the incorporation of OMA unit copolymer chain. The results from electrochemical performances suggested that the molar ratio of [An]/[OMA]=3:1 in reaction system can make the obtained composites displayed a higher specific capacitance, good rate ability and cycling stability.

研究领域: 材料科学 · 电化学
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CHEMICAL ENGINEERING JOURNAL · 2026 · IF 12.5

Co-O-Ce sites on defect-engineered Co0.05Ce0.95O2-δ solid solutions drive the direct conversion of CO2 to dimethyl carbonate

Yunhui Xia,Bingyan Liu,Mingyuan Zhang,Guohui Cai,Mengjia Zhang,Jianghui Lin,Ling Li

Co-doped CeO 2 creates synergistic Co-O-Ce interfaces and oxygen vacancies. • Distinct CH 3 OH and CO 2 activation sites alleviate competitive adsorption. • Achieves high DMC yield of 16.5 mmol·g −1 ·h −1 under 2 MPa CO 2 and 140 °C. • Excellent stability demonstrated over five consecutive reaction cycles. • In situ IR confirms cooperative mechanism at Co-O-Ce active centers and O V . The direct conversion of carbon dioxide (CO 2 ) and methanol (CH 3 OH) into dimethyl carbonate (DMC) represents a highly attractive route for sustainable chemical synthesis and carbon utilization. However, when operating without dehydrating agents (typically used to shift the thermodynamic equilibrium), the process faces a fundamental challenge on conventional CeO 2 -based catalysts: the competitive adsorption of CO 2 and CH 3 OH for similar active sites, which ultimately limits reaction efficiency. To address this challenge, an innovative strategy was developed through the design of defect-engineered Co 0.05 Ce 0.95 O 2-δ solid solutions. Comprehensive characterization using Raman spectroscopy, XPS, XANES and EXAFS spectra, and AC-TEM confirmed the successful incorporation of Co into the CeO 2 lattice. The incorporation of Co generated abundant oxygen vacancies (O V ) and unique Co-associated interfacial sites (Co-O-Ce). These sites collectively enhanced the catalyst's acidity and basicity and helped alleviate competitive adsorption. Specifically, Co-O-Ce sites are proposed to favor CH 3 OH adsorption and activation, while O V and adjacent Ce ions facilitate CO 2 adsorption and polarization. This cooperative interaction substantially enhances the reaction efficiency, enabling the catalyst to achieve a high DMC formation rate of 16.5 mmol·g −1 ·h −1 under mild conditions (140 °C, 2 MPa), which surpasses that of most reported CeO 2 -based catalysts under comparable conditions. Moreover, the catalyst exhibited outstanding stability over five consecutive cycles. The reaction mechanism, involving the synergistic function of the Co-O-Ce interface sites, was further validated by in situ infrared spectroscopy. Beyond providing a highly efficient and stable catalyst, this work offers fundamental insights into active site engineering for promoting cooperative activation in CO 2 conversion reactions. Download: Download high-res image (339KB) Download: Download full-size image

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JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY · 2024 · IF 11.2

Lattice oxygen-mediated Co–O–Fe formation in Co-MOF via Fe doping and ligand design for efficient oxygen evolution

Tao Zhao,Dazhong Zhong,Qiang Fang,Xin Zhao,Runxin Du,Genyan Hao,Guang Liu,Jinping Li,Qiang Zhao

The rational design of metal-organic frameworks (MOFs) provides potential opportunities for improving energy conversion efficiency. However, developing efficient MOF-based electrocatalysts remains highly challenging. Herein, a strategy involving strain engineering is developed to promote the electrocatalytic performance of MOFs by optimizing electronic configuration and improving the active site. As expected, the optimized CoFe–BDC NO 2 exhibits a low overpotential of 292 mV at 10 mA cm –2 and a small Tafel slope of 31.6 mV dec –1 as oxygen evolution reaction (OER) electrocatalyst. Notably, when CoFe–BDC NO 2 is prepared on Nickel foam (NF), the overpotential is only 345 mV at 1 A cm –2 , which ensures efficient water oxidation properties. Integrating CoFe–BDC NO 2 /NF anode in membrane electrode assembly (MEA) for overall water splitting and CO 2 reduction reaction (CO 2 RR) tests, the results show that the cell voltages of CoFe–BDC NO 2 /NF are 3.14 and 3.09 V at 300 mA cm –2 (25 °C), respectively, indicating that MOFs have various practical application prospects. The research of the structure-performance relationship reveals the lattice oxygen oxidation mechanism (LOM) where the Co-O-Fe bond is formed during the OER process by changing the electronic environment and coordination structure of CoFe–BDC NO 2 , and with high valence Co as active center, which provides a deep understanding of the structure design of MOFs and their structural transformation during OER.

研究领域: 材料科学 · 电化学 · 能源转换
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ACS Nano · 2024 · IF 15.8

Regulating Second-Shell Coordination in Cobalt Single-Atom Catalysts toward Highly Selective Hydrogenation

Yunxia Duan,Yongming Xia,Yuxuan Ling,Shijie Zhou,Xuehui Liu,Yinghui Lan,Xiong Yin,Yusen Yang,Xiaoying Yan,Minghui Liang,Song Hong,Lipeng Zhang,Leyu Wang

Manipulating the local coordination environment of central metal atoms in single-atom catalysts (SACs) is a powerful strategy to exploit efficient SACs with optimal electronic structures for various applications. Herein, Co-SACs featured by Co single atoms with coordinating S atoms in the second shell dispersed in a nitrogen-doped carbon matrix have been developed toward the selective hydrogenation of halo-nitrobenzene. The location of the S atom in the model Co-SAC is verified through synchrotron-based X-ray absorption spectroscopy and theoretical calculations. The resultant Co-SACs containing second-coordination shell S atoms demonstrate excellent activity and outstanding durability for selective hydrogenation, superior to most precious metal-based catalysts. In situ characterizations and theoretical results verify that high activity and selectivity are attributed to the advantageous formation of the Co–O bond between p-chloronitrobenzene and Co atom at Co1N4–S moieties and the lower free energy and energy barriers of the reaction. Our findings unveil the correlation between the performance and second-shell coordination atom of SACs.

CAS / MDL: 126213-50-1 67-56-1
研究领域: 催化 · 材料科学 · 化学工程 · 物理化学
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Nature Communications · 2019 ·Vol. 10 ·期 1 ·1-8 · IF 11.878

Screening highly active perovskites for hydrogen-evolving reaction via unifying ionic electronegativity descriptor

Guan Daqin,Zhou Jing,Huang Yu-Cheng,Dong Chung-Li,Wang Jian-Qiang,Zhou Wei,Shao Zongping

Facile and reliable screening of cost-effective, high-performance and scalable electrocatalysts is key for energy conversion technologies such as water splitting. ABO 3- δ perovskites, with rich constitutions and structures, have never been designed via activity descriptors for critical hydrogen evolution reaction (HER). Here, we apply coordination rationales to introduce A-site ionic electronegativity (AIE) as an efficient unifying descriptor to predict the HER activities of 13 cobalt-based perovskites. Compared with A-site structural or thermodynamic parameter, AIE endows the HER activity with the best volcano trend. (Gd 0.5 La 0.5 )BaCo 2 O 5.5+ δ predicted from an AIE value of ~2.33 exceeds the state-of-the-art Pt/C catalyst in electrode activity and stability. X-ray absorption and computational studies reveal that the peak HER activities at a moderate AIE value of ~2.33 can be associated with the optimal electronic states of active B-sites via inductive effect in perovskite structure (~200 nm depth), including Co valence, Co-O bond covalency, band gap and O 2 p -band position.

研究领域: 材料科学 · 电化学 · 催化 · 能量转换
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NEW JOURNAL OF CHEMISTRY · 2025 · IF 2.5

Enhancement of the catalytic performance of Co3O4 towards butyl acetate oxidation by weakening the Co-O bond and promoting oxygen activation

Wenjing Kong,Xueyun Zhong,Ying Yan,Yun Xing,Lei Liu,Chuan Yu,Leneng Yang,Xiaofei Song,Mingli Fu

With the widespread use of waterborne coatings, the treatment of volatile organic compounds (VOCs), which is also easy to produce odor pollution, has become the major concern of the air pollution control in coating industry. Since the deep oxidation of the butyl acetate (BA) molecule requires the involvement of a large amount of reactive oxygen species, the catalytic oxidation of BA was promoted by weakening the Co-O bond strength on the cobalt oxide surface. In this study, we adopted a simple sacrificial template approach to fabricate a series of specifically shaped and uniform Co3O4 catalysts for the catalytic oxidation of BA. The flake CM71-C catalyst showed the most excellent catalytic properties of BA (T50 = 197 °C, T90 = 215 °C). According to the characterization results, flake CM71-C has the largest specific surface area and the weakest Co-O bond, which is more conducive to redox and oxygen activation capabilities of catalyst. The results of In-situ DRIFTS studies showed that the surface reactive oxygen species were continuously recharged during the reaction due to the higher oxygen activation capacity, which accelerated the rapid decomposition of carboxylate, a key reactive intermediate species in the deep oxidation of BA. This study provides a practical and effective way to gain insight into the role of oxygen vacancies in the preparation of efficient catalysts with specific morphology for VOCs oxidation.

CAS / MDL: 1308-06-1
研究领域: 环境科学 · 催化化学
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LANGMUIR · 2024 · IF 3.7

Cation Chain Length of Nonhalogenated Ionic Liquids Matters in Enhancing SERS of Cytochrome c on Zr–Al–Co–O Nanotube Arrays

Mian Gong,Yihui Dong,Minghai Zhu,Fengxiang Qin,Tianchi Wang,Faiz Ullah Shah,Rong An

Surface-enhanced Raman scattering (SERS) is a remarkably powerful analytical technique enabling trace-level detection of biological molecules. The interaction of a probe molecule with the SERS substrate shows important distinctions in the SERS spectra, providing inherent fingerprint information on the probe molecule. Herein, nonhalogenated phosphonium-based ionic liquids (ILs) containing cations with varying chain lengths were used as trace additives to amplify the interaction between the cytochrome c (Cyt c) and Zr–Al–Co–O (ZACO) nanotube arrays, strengthening the SERS signals. An increased enhancement factor (EF) by 2.5–41.2 times compared with the system without ILs was achieved. The improvement of the SERS sensitivity with the introduction of these ILs is strongly dependent on the cation chain length, in which the increasing magnitude of EF is more pronounced in the system with a longer alkyl chain length on the cation. Comparing the interaction forces measured by Cyt c-grafted atomic force microscopy (AFM) probes on ZACO substrates with those predicted by the extended Derjaguin–Landau–Verwey–Overbeek (XDLVO) theory, the van der Waals forces became increasingly dominant as the chain length of the cations increased, associated with stronger Cyt c–ZACO XDLVO interaction forces. The major contributing component, van der Waals force, stems from the longer cation chains of the IL, which act as a bridge to connect Cyt c and the ZACO substrate, promoting the anchoring of the Cyt c molecules onto the substrate, thereby benefiting SERS enhancement.

CAS / MDL: 7778-77-0 10039-32-4
研究领域: 分析化学 · 生物物理学
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INORGANIC CHEMISTRY · 2024 · IF 4.3

Improving the Electrocatalytic Activity of a Core/Shell NiCo–ZIF@PBA Catalyst by Co–O–Fe Bridge Bonds for Water Oxidation

Tianhao Yu,Peng Gao,Yu Wang,Maidina Muhetaer,Hong Du

In response to the limitations of slow reaction kinetics and elevated overpotentials in the OER, a novel core–shell structured electrocatalyst, termed NiCo–ZIF-67@Fe–Co–Ni-PBA or NiCo–ZIF@PBA, has been developed. This material demonstrates exceptional catalytic performance, exhibiting a minimal overpotential of approximately 188 mV at 10 mA cm–2, alongside a Tafel slope of 109 mV dec–1. Its robust stability in a 1 M KOH solution during the OER operations is noteworthy. Theoretical insights from DFT calculations reveal that a Co–O–Fe bridging configuration within NiCo–ZIF@PBA lowers the energy barrier for the reaction to 1.79 eV, a significant reduction from 2.67 eV observed with NiCo–ZIF-67. The improvement in electrochemical performance is primarily due to the emergence of Co3+ ions, which results from the efficient charge transfer occurring at the interface of the PBA and NiCo–ZIF core–shell structure. These findings suggest a promising strategy for designing advanced core–shell materials for electrocatalytic applications.

研究领域: 材料科学 · 电化学
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JOURNAL OF ALLOYS AND COMPOUNDS · 2021 · IF 5.316

Rational construction of MOF-derived Zn-Co-O/NiCo-LDH core/shell nanosheet arrays on nickel foam for high-performance supercapacitors

Manlin Zhu,Wangfeng Cai,Hongbo Wang,Leqiu He,Yan Wang

A morphologically adjustable metal-organic framework (MOF) template and a unique hierarchical structure show improved electrochemical performance of electrode materials for supercapacitors . Herein, Zn/Co-MOF-derived zinc-cobalt oxide/nickel cobalt layered double hydroxides (Zn-Co-O/NiCo-LDH) hierarchical core/shell nanostructures on nickel foam (NF) were synthesized by simple methods and exhibited high specific capacitance. The results showed that both the reasonable morphology of the MOF-templated continuous nanosheet network and synergy between transition bimetallic oxides and transition bimetallic hydroxide played an important role in improving the electrochemical properties . Hence, the as-prepared Zn-Co-O/NiCo-LDH battery-type electrode exhibited excellent specific capacitance of 2275.2 F/g at 1 A/g and remarkable cycling stability of 82.4% capacitance retention after 5000 cycles. Moreover, the as-prepared Zn-Co-O/NiCo-LDH was used as the positive electrode to assemble a hybrid supercapacitor (HSC) device, which attained a distinguished energy density of 44.5 W h/kg at a power density of 800 W/kg and satisfactory stability (71.5% retention after 5000 cycles). It was concluded that MOF-templated core/shell heterostructures in electrode materials have broad prospects and great potential for energy storage.

研究领域: 材料科学 · 能源存储
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