CHEMICAL ENGINEERING JOURNAL
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2022
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IF 16.744
Mengxue Yang,Ruixian Wu,Shengshuai Cao,Yanwei Li,Sisi Huo,Wei Wang,Zhen Hu,Xing Xu
Herein, we prepared two kinds of single-atom catalysts (SACs) with uniformed coordination structures (M−N 4 , M = Fe, and Cu) for evaluating the versatile pathways of peroxymonosulfate (PMS) activation by different metal sites. Fe-SAC exhibited a higher catalytic performance than that of Cu-SAC for chloroquine phosphate (CQP) oxidation. Results showed that the high-valent iron-oxo species accounted for 74.5 % for CQP oxidation in Fe-SAC/PMS system, while radicals (SO 4 •– and HO • ) dominated the CQP oxidation (58.3 %) in Cu-SAC/PMS system, which was associated to the different spin-state of the metal sites for PMS adsorption and breakage of O O in PMS as well as the intermediates in versatile pathways. The SACs were then fixed onto the catalytic filter for PMS activation , which showed stable and effective catalytic performance for versatile recalcitrant organics. Overall, this work not only provided the atomic-level knowledge on PMS activation, but also gave the potential applications of Fenton-like for water remediation.
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
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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DOI
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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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2026
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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
APPLIED CATALYSIS B-ENVIRONMENTAL
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2024
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IF 20.2
Lei Zhang,He Jiang,Min Tang,Ying Jiang,Bing Tang,Hao Tan,Yuan Kong,Haibo Hu
Construction of robust protective cover on delicate active sites is a frequently-used scheme to enhance the durability of air-cathode catalyst working in harsh environment, thus the lifespan of rechargeable Zinc-air batteries (ZABs). Paradoxically, this would degrade the activity due to the constricted accessibility of active sites to reactants. Herein, carbon nanotubes with abundant mesoporous defects and Fe-N 4 species were elaborately designed to be multifunctional protective armor to encapsulate Ni 3 Fe nano-alloys (Ni 3 Fe@CNTs/Fe-N 4 ) for bifunctional oxygen electrocatalyst . In/ex-situ spectroscopy analysis and theoretical calculations reveal that the constructed mesoporous carbon defects effectively facilitate the multiphase mass transfer and the oxygen evolution reaction kinetics via strong electrons coupling with packaged Ni 3 Fe nano-alloys. Meanwhile, the synchronously introduced Fe-N 4 moieties could serve as oxygen reduction active sites. Thus, the obtained Ni 3 Fe@CNTs/Fe-N 4 hybrid electrocatalyst simultaneously exhibits remarkable bifunctional catalytic activity (E 1/2 =0.86/E j=10 =1.59 V vs RHE) and durability over 450 h in the chronoamperometric test at 1.59 V, endowing the assembled Zn-air batteries (ZABs) with a high power density (150 mW cm −2 ) and lifespan (307 h), much better than that employing benchmark Pt/C+RuO 2 mixed catalyst. This work demonstrates an innovative design route for the multifunctional armor to concurrently enhance the durability, activity and robustness of air-cathode-catalyst for ZABs.
研究领域:
材料科学
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电化学
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能源存储与转换
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2022
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IF 16.744
Xiaoming Liu,Fengting He,Yangming Lu,Shuling Wang,Chaocheng Zhao,Shuaijun Wang,Xiaoguang Duan,Huayang Zhang,Xiaoli Zhao,Hongqi Sun,Jinqiang Zhang,Shaobin Wang
Single atom catalysts (SACs) are suggested to be ideal materials for catalysis and will exhibit the highest performance at the maximum single atom loading. However, their influences on the intrinsic structure and properties of a photocatalytic substrate should not be neglected. Herein, we proposed a facile and green approach for large scale synthesis of Ni-SA/g-C 3 N 4 catalysts with various contents of Ni-N 4 coordination. Experimental investigations and quantum chemical calculations disclosed that the Ni-N 4 and g-C 3 N 4 host are two active sites for photocatalysis and play different roles in photocatalysis. The promoting and suppressing effects of Ni-N 4 coordination on g-C 3 N 4 matrix at Ni-N 4 adjacency are also revealed. Maximum efficiency in photocatalytic water splitting and contaminant oxidation processes can only be realized at an optimized SA loading by the balance of the two effects. Extra loading of SA will make adjacent carbon nitride matrix lose semiconducting properties for generating hot carriers toward photocatalysis. This work reveals the intrinsic correlation between SAC structure and photocatalysis, shedding light on the fundamental understandings of structure-catalysis correlation and providing new insight into SACs.
研究领域:
材料科学
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化学工程
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环境科学
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DOI
高影响因子
ELECTROCHIMICA ACTA
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2022
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IF 7.336
Jing Yang,Hao Wu,Zhihao Wang,Meiting Lu,Shuang Liu,Zhiyu Ren,Zhimin Chen
Metallophthalocyanines (MPcs) with the especially active metal-N 4 catalytic sites have the great potential for the electrocatalytic CO 2 -to-CO conversion. However, the masking of metal-N 4 catalytic sites attributed to the strong π-π interaction and the difficulty in capturing CO 2 severely limits their catalytic efficiency. Herein, we designed a self-supported electrode that tetra-β-carboxy phthalocyanine cobalt(II) (TcPcCo) was anchored into polyaniline (PANI) chain in isolation using the carbon paper (CP) as a support. The PANI with unique porous structure provides large surface area, rapid electron transfer, and unimpeded pathways for CO 2 diffusion. More importantly, sufficient CO 2 captured by PANI can continuously spill over to metal-N 4 active sites and be reduced into CO. The synthesized electrode for CO 2 reduction reaction (CO 2 RR) could maintain a high CO Faraday efficiency of over 95% (maximum 99.3%) at an extraordinary wide potential range of 450 mV (from -0.50 V to -0.95 V vs. RHE), ranking foremost among the previously reported phthalocyanine-based electrocatalysts . Furthermore, relative to TcPcCo, the CO turnover frequency (TOF) of PANI-TcPcCo/CP significantly improves, especially at the more negative operating potential (about 7 ∼ 68 times). Theoretical calculations further reveal that the introduce of PANI optimizes the free energy barrier of CO 2 RR intermediate at Co-N 4 site, thus accommodating the*COOH formation, and also suppresses the competition of hydrogen evolution reaction. This work presents a new perspective on advancing the catalytic CO 2 RR capability of molecular materials by regulating the chemical environment surrounding a catalytically active site.
研究领域:
电化学
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材料科学
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催化反应
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DOI
高影响因子
LANGMUIR
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2025
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IF 3.9
Yingjin Ma,Qifeng Li,Xueqing Qiu,Zhixian Li
Single-atom nanozymes can accurately mimic the catalytic centers of enzymes at the atomic scale, showing high catalytic efficiency and selectivity. Inspired by the active center of natural laccase, we constructed a nitrogen-doped carbon-based single-atom nanozyme (Fe-NC) featuring planar Fe–N4 active sites using a zeolitic imidazolate framework (Fe/ZIF-8) as a precursor. The resulting Fe–NC showed high laccase-like activity toward phenolic substrates such as 2,4-dichlorophenol, with a catalytic efficiency 77 times higher than that of natural laccase. Furthermore, Fe–NC efficiently catalyzed the degradation of tetracycline hydrochloride (77.14%) under mild conditions, with an activity 13 times that of laccase. It also selectively and oxidatively depolymerized birch lignin into valuable aromatic monomers, including vanillin and vanillic acid. These findings highlight the key role of planar Fe–N4 coordination in improving bioinspired catalysis and reveal the great potential of single-atom nanozymes in biomass valorization.
研究领域:
纳米酶催化
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环境修复
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生物质转化
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材料化学
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仿生催化
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2025
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IF 9.7
Guitao Zhang,Kaicai Fan,Lingbo Zong,Fenghong Lu,Zumin Wang,Lei Wang
To achieve precise optimization of the geometric structure and control over spatial distribution of single atom active sites, we introduce an in situ polymer layer modification strategy. Through co-deposition of tannic acid (TA) and polyethyleneimine (PEI) on carbon nanotubes (CNTs), the polymer improves the dispersion and prevents the agglomeration of Fe atoms. Consequently, after controlled calcination, the geometrically distorted Fe-N 4 single atom active sites are constructed on the surface of the curved carbon support. The optimized distortion reduces the reaction energy barrier, optimizes the adsorption energy of oxygen intermediates, and leading to a remarkable improvement of oxygen reduction reaction (ORR) activity. As the result, the obtained single atom catalyst (SAC) Fe-NC@CNTs exhibits exceptional performance with a large onset potential ( E onset ) of 1.03 V and a half-wave potential ( E 1/2 ) of 0.91 V in 0.1 M KOH solution, surpassing the previously reported ORR electrocatalysts. Benefitting from these features, Fe-NC@CNTs-based rechargeable aqueous Zn-air battery (A-ZAB) delivers a higher power density of 209.5 mW cm −2 and can sustain stable changing/discharging for over 2000 h and experiences negligible charge–discharge potential gap fluctuation, being the most booming competitor among the reported electrocatalysts. Furthermore, quasi-solid-state Zn-air battery (QSS-ZAB) with Fe-NC@CNTs air cathode exhibits an impressive peak power density of 130.8 mW cm −2 , large round-trip efficiency of 82 %, and long cycling life of over 100 h. Our work reveals the relationship of strain-induced geometrical distortion and the structure activity relationship, offering a new way for the rational design of other highly efficient catalytic systems.
研究领域:
材料科学
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电化学
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能源存储与转换
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2023
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IF 9.9
Huimin Liu,Chen Wang,Xinbo Ai,Binquan Wang,Yingqi Bian,Geyu Wang,Yongfei Wang,Zhizhi Hu,Zhiqiang Zhang
Developing iron-based single-atom catalysts (Fe SACs) with low cost, high activity and stability is vital for commercialising sustainable energy technologies. However, accurately controlling and identifying structure–activity relationships of Fe SACs remains a significant challenge. Herein, we report Fe/N co-doped carbon nanofiber membranes with highly exposed Fe-N 4 sites (Fe/NCNFs), synthesized by electrospinning and pyrolysis . The three-dimensional (3D) hierarchical structure and atomically dispersed pyrrole-type Fe (III)-N 4 active sites provide the as-prepared catalyst with a positive half-wave potential of 0.87 V and an ultralow Tafel slope of 53 mV dec −1 . As an air cathode catalyst for liquid Zn − air batteries, it delivers a high open-circuit voltage (1.474 V), a large peak power density (190 mW cm −2 ) and a high durability of 2000 cycles at 5 mA cm −2 . As a self-standing air cathode, the as-assembled solid-state Zn − air batteries also show stable cycling with a small discharge/charge voltage gap of 0.65 V, indicating great prospects for developing portable zinc − air batteries.
研究领域:
材料科学
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能源技术
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电化学
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产品关联
DOI
PubMed
高影响因子
LANGMUIR
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2026
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IF 4.4
Chao Ge,Yunlan Gu,Bin He,Yanqing Wang,Yawen Tang,Tongfei Li
The advancement of catalysts that are both platinum-group-metal (PGM)-free and iron-free is essential for the oxygen reduction reaction (ORR), which is kinetically slow, particularly in anion-exchange membrane fuel cells (AEMFCs). One of the primary obstacles lies in achieving adequate activity and stability within the membrane electrode assembly (MEA) under real-world hydrogen-air operating conditions. Herein, an effective MnN4 site encased within N-doped carbon nanofibers (denoted as MnN4@N-CNFs) is designed for efficient ORR electrocatalysis. Benefiting from the electronic structure modulation of MnN4 moieties through strong interfacial coupling with the carbon matrix, and structural advantages of the 3D hierarchical porosity synergizing with N-doped carbon-MnN4 coordination systems, the as-resultant MnN4@N-CNFs demonstrate a high half-wave potential of 0.89 V, outstanding durability, and impressive methanol tolerance under alkaline environments, outperforming commercial Pt/C and a diversity of reported counterparts. Notably, the engineered catalyst demonstrates remarkable fuel cell performance with a peak power density of 222.0 mW cm–2 during practical AEMFC operation, while maintaining stable operation for over 15 h, representing a 3-fold enhancement over conventional Pt/C-based counterparts. This study establishes fundamental design principles for high-efficiency AEMFCs through atomic-level engineering of precisely coordinated metal–N–C active sites, providing a robust framework for next-generation electrocatalyst development.
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产品关联
DOI
PubMed
高影响因子
Journal of Energy Storage
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2026
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IF 10.7
Yang Wang,Jing Wang,Jiahuan Luo,Chuanhao Luo,Xu Deng,Ying Liu,Huihui Zhao,Jiayi Ren,Yubiao Xu,Shaojie Zhu,Wanting Shi,Zhenjun Liu,Hao Liu,Rui Hao,Ning Fu
Aqueous zinc‑iodine batteries (AZIBs) are considered promising candidates for large-scale energy storage owing to their high theoretical energy density and intrinsic safety. However, the practical performance is severely limited by sluggish I 2 redox kinetics and the shuttle effect of soluble polyiodide. In this work, a curvature engineering strategy is developed for Mn-N 4 single-atom sites, in which the introduction of C I bonds induces a surface-contracted structure, leading to the formation of a Mn-NC-I configuration. This structural modulation breaks the geometric symmetry of the Mn-N 4 sites and redistributes the local electronic density, enabling directional halogen-bond interactions with polyiodide. As a result, I 2 are effectively anchored, polyiodide shuttling is suppressed, and the I 3 − /I − conversion kinetics are significantly accelerated. Benefiting from enhanced I 2 confinement, and catalytically active Mn centers, the Mn-NC-I/I 2 cathode delivers a high reversible capacity of 148.4 mAh g −1 at 0.1 A g −1 , excellent rate capability, and an ultralow capacity decay rate of 0.0016% per cycle over 20,000 cycles at 10 A g −1 . This study elucidates the critical role of curvature engineering in regulating Mn-N 4 mediated I 2 redox chemistry and provides a viable design principle for high-performance single-atom catalysts in AZIBs.
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DOI
高影响因子
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