Advanced Energy Materials
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2025
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IF 26
Zongge Li,Wenjun Kang,Jingkai Lin,Rui Li,Konggang Qu,Suyuan Zeng,Lei Wang,Fanpeng Meng,Huayang Zhang,Haibo Li
The oxygen electrocatalytic activity of transition metal catalysts can be tuned by tailoring their microstructure to optimize electronic configuration. Here, a one-step Coordination-Selective Synthesis strategy is developed to integrate Co single-atom sites and Fe-based nanoparticles within the same matrix, enabling long-range electronic interactions that enhance Co-N 4 reactivity and improve oxygen reduction reaction performance. X-ray absorption spectroscopy confirmed that remote Fe-based nanoparticles modulate the electron distribution at Co-N 4 sites. Structural characterizations reveal that the optimal catalyst, Co 50% Fe 50% -NC, contains metallic Fe, Fe 3 O 4 , and Fe 4 N species. Electrochemical measurements show that it achieves onset and half-wave potentials of 0.984 and 0.927 V versus RHE, surpassing Co 100% -NC with only Co-N 4 sites. Additionally, it demonstrates efficient oxygen evolution reaction performance, achieving an overpotential of 298 mV at 20 mA cm −2 , comparable to RuO 2 . Density functional theory calculations reveal that Fe 4 N optimizes O-containing intermediate adsorption/desorption, lowering the theoretical overpotential. Zn-air batteries assembled with Co 50% Fe 50% -NC exhibited superior performance to Pt/C, highlighting its potential for bifunctional oxygen electrocatalysis. This study provides an approach for designing high-performance catalysts by utilizing synergistic interactions between atomic and nanoscale metal species.
研究领域:
材料科学
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电化学
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催化科学
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高影响因子
Journal of Materials Chemistry A
·
2020
·Vol. 8
·期 8
·4369-4375
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IF 11.301
Lulu Chen,Yelong Zhang,Lile Dong,Wenxiu Yang,Xiangjian Liu,Ling Long,Changyu Liu,Shaojun Dong,Jianbo Jia
Rational design of isolated metal atom doped carbon catalysts is essential for revealing the essence of high activity for the oxygen reduction reaction (ORR), which can promote the development of robust catalysts for clean energy conversion devices. Herein, we report a simple one-step strategy to prepare Fe and Co atomically supported on N-doped nanocarbon (FeCo-IA/NC) from metal–organic frameworks with excellent ORR activity. The isolated Fe–N4 and Co–N4 sites are characterized by atomic-resolution aberration-corrected scanning transmission electron microscopy and X-ray absorption fine structure spectroscopy. The electrochemical results and density functional theory calculations indicate that the synergetic effect between Fe–N4 and Co–N4 accounts for the enhanced ORR activity. Benefiting from the large BET surface area, microporous feature, and high content (85%) of pyridinic and graphitic N, the well-designed catalyst exhibits better ORR activity (half-wave potential of 0.88 V) and Zn–air battery performances (higher open circuit potential and power density) than commercial Pt/C. This work may lay a foundation for further exploring efficient non-precious metal-based catalysts for the ORR and developing clean energy conversion devices.
研究领域:
材料科学
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电化学
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催化科学
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高影响因子
Journal of Materials Chemistry A
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2024
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IF 10.7
Yuanzhe Zhao,Xiuheng Wang
Singlet oxygen (1O2) is an excellent active species for eliminating organic pollutants in single-atom catalyst (SAC) catalyzed peroxymonosulfate (PMS)-based Fenton-like systems. However, it is difficult to achieve high efficiency and selectivity in 1O2 generation as a result of the lack of effective SACs. In this work, a Co SAC (Co–N–C) containing highly uniform Co–N4 active sites with an ultralow-level Co loading of 0.34 wt% is fabricated, delivering boosted performance in tetracycline degradation with an extremely rapid rate of 0.573 min, which outperforms most advanced catalysts in reported studies. A vibrating-sample magnetometer is used to preliminarily determine the atomically dispersed Co sites in Co–N–C according to the obvious paramagnetic characteristics of Co–N–C, and this is in good agreement with the test results obtained by using an aberration-corrected high-angle annular dark-field scanning transmission electron microscope and synchrotron radiation facility. Electron spin resonance and free radical quenching experiments prove that Co–N–C facilitates PMS activation with the 1O2 generation of almost 100%. Mechanism analyses suggest that the Co–N4 site strengthens the adsorption of the terminal O of PMS, realizing enhanced electron transfer from Co–N–C to PMS, promoting the simultaneous and spontaneous cleavage of O–O and O–H bonds to produce O*, followed by a reaction with another O* to generate 1O2.
研究领域:
环境科学
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催化化学
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高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2026
·
IF 19.7
Qiankun Xu,Rui Wang
MOF-derived NiCo/NPC electrocatalyst was constructed with tailored M-N 4 coordination environments. • Ni incorporation regulated Co electronic structures for accelerated oxygen evolution reaction. • DFT calculations elucidated the electronic modulation mechanism and optimized OER energetics. The development of efficient, low-cost, and scalable oxygen evolution reaction (OER) catalysts is crucial for practical water electrolysis. Herein, a MOF-derived NiCo/NPC electrocatalyst containing predominantly atomically dispersed Co–N 4 /Ni–N 4 sites is prepared by controlled Ni incorporation into ZIF-67-derived porous carbon. The optimized 50% NiCo/NPC exhibits an overpotential of 207 mV at 10 m⋅A cm⁻ 2 , a Tafel slope of 51.6 mV⋅dec⁻ 1 , and stable operation for over 100 h, outperforming Co/NPC and commercial RuO 2 . Aberration-corrected HAADF-STEM directly visualizes atomically dispersed Co and Ni species, while synchrotron X-ray absorption spectroscopy confirms the Co–N 4 coordination environment and reveals that Ni incorporation modifies the electronic environment of the Co sites. Density functional theory calculations further show that Ni incorporation shifts the Co d -band center toward the Fermi level and lowers the energy barrier of the rate-determining step, accounting for the enhanced OER activity. In an anion exchange membrane water electrolyzer, the catalyst delivers current densities of 1000 and 4000 mA ⋅cm⁻ 2 at 2.02 and 2.46 V, respectively. This work provides an effective strategy for improving the OER performance of MOF-derived electrocatalysts through regulating the electronic structure of Co active sites. Download: Download high-res image (186KB) Download: Download full-size image Ni-doped ZIF-67 is converted via pyrolysis into morphology-retained Co–N 4 and Ni–N 4 single-atom active sites embedded in N-doped porous carbon (NiCo/NPC). Benefiting from the Ni-induced electronic modulation of Co active sites, together with the enhanced conductivity of the carbon framework, the catalyst achieves efficient and durable OER performance with a low overpotential.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
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2024
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IF 13.3
Fengliang Cao,Qingshan Zhao,Xiaojie Tan,Libo Wang,Yikun Zhao,Wei Deng,Linjie Zhi,Mingbo Wu
Optimizing the local environment of metal active centers bonded by nitrogen ligands (M−N 4 ) through additional axial coordination provides a promising approach to enhance the reaction kinetics of heterogeneous catalysis. However, achieving precise targeting and construction of efficient active sites remains a major challenge. In this study, under the guidance of density functional theory (DFT) calculations, we precisely position and engineer atomic Co–N 4 active sites with axial O coordination on porous carbon nanosheets (Co 1 /NOC) for boosted aromatic nitroreduction through a novel template-anchoring strategy. The resulting Co 1 /NOC catalyst exhibited unprecedented catalytic activities towards a series of functionalized nitroaromatics with a record overall turnover frequency (TOF) of 38022 h −1 under mild reaction conditions, 7.6- and 38 times higher than that of Co–N 4 sites (Co 1 /NC) and commercial Pd/C catalysts, respectively, standing ahead of the reported catalysts. Targeted DFT calculations reveal that axial oxygen coordination efficiently promotes the electronic delocalization of the Co center, which dramatically facilitates the formation and utilization of reactive H* species, enhances the selective adsorption of nitroaromatics, and accelerates the conversion of aromatic nitroreduction, eventually attaining exceptional catalytic performance. This work offers a new avenue for precisely tailoring the coordination environment of single-atom catalysts to achieve advanced catalytic performance in chemical transformations.
研究领域:
催化化学
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材料科学
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理论计算
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高影响因子
ELECTROCHIMICA ACTA
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2019
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IF 5.383
Bihua Hu,Weiwei Xie,Ruchun Li,Zhangweihao Pan,Shuqin Song,Yi Wang
Metal-N x -C based materials have emerged as one of the most promising electrocatalysts for electrochemical reduction of carbon dioxide (ERCD). Co-based macrocyclic compounds have shown unique performance, however, of which the relationship between the ligands structure surrounding Co–N 4 centers and reaction mechanism remains vague. To explore this issue, here, a series of Co-based macrocyclic compounds are elaborately chosen as model catalysts, including phthalocyanine cobalt (CoPc), cobalt (II) meso-Tetraphenylporphine (CoTp) and cobalt tetramethoxyphenylporphyrin (CoTop), which possess well-defined Co-N 4 coordinated centers but different ligands structure surrounding Co-N 4 . Electrochemical measurements show that CoPc possesses higher activity and selectivity for CO with Faradaic efficiency (FE) above 62% at −0.7 V ( vs. RHE) relative to those of CoTp and CoTop. Combining density functional theory (DFT) calculations, it can be further confirmed that CoPc is more favorable for ERCD to CO due to the rapid formation of key intermediate COOH* and the desorption of CO, demonstrating that the structure of ligands (phthalocyanine) surrounding Co-N 4 plays a crucial role in the high CO selectivity. It can be anticipated that an exclusive strategy will pave a new avenue for further understanding the ERCD mechanism of Co-N x -C catalysts.
研究领域:
材料科学
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电催化
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理论计算
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DOI
高影响因子
Journal of Bioresources and Bioproducts
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2026
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IF 19.9
Limin Zhou,Mengmeng Fan,Yanyan Liu,Shuling Liu,Guozheng Dong,Ao Wang,Jong-Min Lee,Kang Sun,Baojun Li
Single-atom catalysts (SACs) have advantages such as high atom utilization and well-defined active sites, and have been extensively studied in the field of oxygen electrocatalysis. However, current strategies for tuning the M-N 4 configurations predominantly focus on local coordination environments, which still makes it difficult to simultaneously optimize the balance of adsorption energies of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) intermediates. Herein, a Zn volatilization-induced pyrolysis strategy is developed to construct Co-N 4 sites coupled with Co nanoparticles on curved N-doped biomass-derived carbon (Co NPs + SA @NC). The intrinsic curvature and defect-rich structure induce lattice distortion and electronic polarization, significantly enhancing the metal-support interaction (MSI). This curvature-enhanced MSI triggers electronic reconstruction and symmetry breaking of Co-N 4 sites, narrowing the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap and facilitating electron transfer. Meanwhile, the influence of adjacent Co nanoparticles optimizes the electronic structure of Co-N 4 , improving the adsorption-desorption capacity of intermediates in the OER process. Therefore, the half-wave potential required to achieve ORR was 0.87 V, and the overpotential required to reach a current density of 10 mA/cm 2 is only 290 mV. A zinc-air battery (ZAB) based on Co NPs + SA @NC exhibited a high peak power density of 172 mW/cm 2 . This work highlights curvature-mediated MSI as an effective strategy for controlling single-atom configurations and advancing biomass-derived electrocatalysts.
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高影响因子
JACS Au
·
2024
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IF 8.5
Xixi Liu,Liang Huang,Yurong He,Peng Zhou,Xuedan Song,Zehui Zhang
It remains challenging to construct C═N bonds due to their facile hydrogenation. Herein, a single Co atom catalyst was discovered to be active for the selective construction of C═N bonds toward the synthesis of imines and N-heterocycles via reductive coupling of nitroarenes with various alcohols, including inert aliphatic ones. DFT calculations and experimental data revealed that the transfer hydrogenation proceeded via the intramolecular hydride transfer and the transfer of H from the α-Csp3-H bond to the nitro group was the rate-determining step. The single Co atoms served as a bridge to transfer the electrons from the catalyst to the adsorbed alcohol molecules, resulting in the activation of the α-Csp3-H bond. Unlike metal nanoparticles, the C═N bonds in imine products can be reserved due to the large steric hindrance from substituents on C and N. DFT calculation also confirmed that transfer hydrogenation of the C═N bonds in imines is thermodynamically unfavored with a much higher energy barrier compared with the transfer hydrogenation of the –NO2 group (1.47 vs 1.15 eV).
研究领域:
化学
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催化反应
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理论计算
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DOI
PubMed
高影响因子
Nanomaterials
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2026
·Vol. 16
·期 13
·813
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IF 4.8
Manman Zou,Xiaoling Zhuang,Qin Tian,Jili Yuan
Two-electron oxygen reduction reaction (2e−-ORR) represents a sustainable and energy-efficient approach for decentralized hydrogen peroxide (H2O2) production compared with the conventional anthraquinone process. Among various electrocatalysts, metal–nitrogen–carbon (M–N–C) materials have attracted extensive attention owing to their tunable electronic structures and favorable *OOH adsorption behavior. However, the uncontrolled pyrolysis process generally leads to structurally heterogeneous and ill-defined coordination environments, making it difficult to precisely regulate active sites and understand catalytic mechanisms. Herein, we report a single-atom catalyst (CoN@OCNT) featuring spatially confined pyridinic-N-coordinated Co single sites, synthesized by anchoring a well-defined hexapod terpyridine Co-precursor onto oxidized carbon nanotubes (OCNTs) to suppress metal aggregation during pyrolysis. Benefiting from the optimized coordination environment and enhanced mass/electron transfer, the CoN@OCNT catalyst exhibits nearly 100% H2O2selectivity over a wide potential window from −1.0 to 0.66 V versus RHE in neutral electrolyte. In situ FT-IR and Raman spectroscopy reveal a rapid *OOH-mediated reaction pathway during the 2e−-ORR process. Furthermore, membrane electrode assembly (MEA) testing demonstrates an H2O2production rate of 21.8 mol h−1gcat−1with stable operation over 80 h at 60 mA cm−2. Remarkably, at an industrially relevant current density of 300 mA cm−2, the catalyst achieves a record H2O2production rate of 70.3 mol h−1gcat−1and a salt-free H2O2concentration of 9.4 mM, highlighting its great potential for practical large-scale H2O2electrosynthesis in neutral media.
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PubMed
高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
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2022
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IF 11.357
Mengxue Yang,Zexi Hou,Xin Zhang,Baoyu Gao,Yanwei Li,Yanan Shang,Qinyan Yue,Xiaoguang Duan,Xing Xu
Single-atom catalysts (SACs)-based peroxymonosulfate (PMS) systems are highly selective to the type of organic pollutants while the mechanisms remain ambiguous. In this work, we carried out experimental and theoretical investigations to reveal the origins of selectivity of radical and nonradical pathways in a designated Co–N4–C/PMS system. Two typical pollutants [bisphenol A (BPA) and metronidazole (MNZ)] with different molecular structures were employed for comparison. We found that radical oxidation (SO4•– and HO•) and nonradical electron-transfer pathway (ETP) co-existed in the Co–N4–C/PMS system. Pollutants (e.g., MNZ) with a high redox potential were degraded primarily by free radicals rather than ETP, while the oxidization of low-redox pollutants (e.g., BPA) was dominated by ETP at the surface region of Co–N4–C which overwhelmed the contributions of radicals in the homogeneous phase. Intriguingly, the contributions of radical and nonradical pathways could be manipulated by the PMS loading, which simultaneously increased the radical population and elevated the oxidation potential of Co–N4–C-PMS* complexes in ETP. Findings from this work will unravel the mysterious selective behavior of the SACs/PMS systems in the oxidation of different micropollutants.
研究领域:
环境科学
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催化化学
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DOI
高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
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2026
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IF 11.3
Wei Wen,Chunying Wang,Xudong Chen,Jingyi Wang,Fei Wang,Kai Li,Yan Zhang,Yaobin Li,Changbin Zhang,Wenpo Shan
The development of high-efficiency non-noble-metal catalysts for HCHO removal is of great significance in indoor air purification. Zeolitic imidazolate frameworks (ZIFs) are characterized by large specific surface areas, well-defined porous structures, and tunable electronic properties, making them suitable for constructing single-atom catalysts with adjustable coordination environments. In this study, three Co-ZIF materials with distinct morphologies were synthesized and subsequently pyrolyzed, yielding cobalt-based catalysts with varied coordination structures. Among these catalysts, the Co–N–C(F) primarily features atomically dispersed Co species coordinated with four N atoms, forming Co-N4 active sites. Theoretical calculations indicate that the Co-N4 coordination structure exhibits enhanced oxygen activation compared to metallic cobalt sites, which is crucial for the degradation of intermediate products in the oxidation of HCHO. The Co–N–C (F) catalyst demonstrates superior activity in HCHO oxidation to even most noble metal catalysts. During a 710 h continuous test at 15 °C, the catalyst maintained 100% HCHO removal efficiency without observable deactivation. Simulation experiments further confirmed its practical applicability, with the catalyst module able to degrade 1 ppm of HCHO to <0.07 ppm within 2 h at room temperature. This work provides valuable insights for the development of commercial nonprecious metal catalysts for HCHO oxidation.
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PubMed
高影响因子
Journal of Environmental Chemical Engineering
·
2026
·Vol. 14
·期 5
·124130
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IF 7.5
Xiang Li,Yu Tian,Yalong Xu,Bo Liu,Shi Zhou,Wei Jiang,Chunbo Liu,Guangbo Che
Precisely designing catalyst structures through chemical strategies to achieve non-radical-mediated Fenton-like catalysis for the efficient removal of organic contaminants is of great significance. Herein, a heptazine-porphyrin organic polymer (HPOP) was synthesized via a nucleophilic substitution reaction. Subsequently, a heptazine-porphyrin organic polymer catalyst featuring Co-N 4 sites (HPOP-Co 20 ) was fabricated through a solvothermal method for efficient peroxymonosulfate (PMS) activation. The porphyrin core effectively anchored the Co-N 4 active sites, inducing the generation of singlet oxygen from PMS. The high conjugation of porphyrin and heptazine effectively enhances the charge transport capability of the catalyst. Upon coordination with Co single atoms, the charge distribution of the polymer was reconstructed, facilitating rapid electron transfer to PMS. Compared with the original HPOP, the reaction rate constant of HPOP-Co 20 activating PMS for degrading sulfamethoxazole (SMX) could reach 1.7018 min −1 , which is 92.99 times that of the HPOP/PMS system (0.0183 min −1 ). The non-radical-mediated characteristic enabled HPOP-Co 20 /PMS to achieve efficient degradation across various water bodies, pollutants, anions, and initial pH conditions. The results of phytotoxicity and continuous wastewater treatment experiments indicated that SMX toxicity decreased after degradation, highlighting the practical application potential of this system. This study introduces a controllable substrate structure and a Co-N 4 site catalyst that promote non-radical pathways and enhance its stability and environmental adaptability.
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高影响因子
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