APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
IF 20.2
Yuan Qin,Zihao Ou,Chaozhong Guo,Yao Liu,Rong Jin,Chuanlan Xu,Haifeng Chen,Yujun Si,Honglin Li
Regulating the electronic structure by phosphor-doping is a preferred strategy to boost the performance of carbon-based catalysts for oxygen reduction reaction (ORR). Here, a porous Fe, P, N-codoped carbon catalyst (PCF-FeTz-900) is designed by a phytic acid-assisted thermal etching strategy, in which P atoms are first doped into the carbon matrix to form a stable P C bond, and then FeN 4 sites are produced from Fe-2,4,6-Tris(2-pyridyl)-s-triazine complex (Fe-TPTz). Theoretical calculations suggest that the electrons are transferred from the doped P atom to the neighboring FeN 4 sites, which facilitates the ORR at the Fe sites by reducing the energy barrier and the adsorption energy of intermediates. Additionally, the P-doped FeN 4 (FeN 4 P) structure manifests a lower free energy difference than that of FeN 4 and the d -band center of Fe is also lowered, which further ensures its higher ORR catalytic ability. As a result, the PCF-FeTz-900 catalyst exhibits superior ORR activity and stability in alkaline electrolyte, and the assembled primary zinc-air battery shows greater performances compared to the commercial Pt/C catalyst. This work can provide an effective pathway for modulating the performance of doped-carbon materials in energy conversion devices.
研究领域:
材料科学
·
电化学
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DOI
高影响因子
Nano Materials Science
·
2026
·
IF 20.5
Weicheng Tang,Xiaoyu Guo,Yuting Chen,Zhenyu Xiao,Yunmei Du,Jun Xing,Zexing Wu,Lei Wang,Kang Liu
The catalytic performance of single-atom catalysts primarily depends on their coordination environment. To date, research on the catalytic regulation of SACs has predominantly concentrated on the first and second coordination structures of the central atom. In this study, we demonstrate that regulating the nitrogen-mediated non-coordinated microenvironment beyond the second coordination sphere of SACs is also crucial for optimizing catalytic performance. A dual metal-organic framework precursor, ZIF-L@ZIF-8/Fc, was constructed using the “MOF@MOF” strategy, wherein ferrocene was in situ anchored within the cages of ZIF-L@ZIF-8. Notably, a ligand exchange strategy was adopted, where the 1,2,4-triazole-3,5-diamine ligand underwent ligand exchange with the dimethylimidazole ligand in the ZIF-L@ZIF-8/Fc precursor, and the e-Fe SA /CSNC catalyst rich in Fe-N 4 active sites was formed through pyrolysis. Density functional theory confirmed that the ligand exchange strategy optimized the non-coordinated microenvironment of the Fe-N 4 active sites. Consequently, the e-Fe SA /CSNC catalyst exhibits excellent performance across the entire pH range, with half-wave potentials of 0.95 V, 0.81 V, and 0.83 V in alkaline, acidic, and neutral media, respectively. Furthermore, the e-Fe SA /CSNC-based zinc-air battery and quasi-solid-state zinc-air battery show long-term cycling stability, during which the intrinsic morphology of ZIF-L is maintained, exhibiting excellent overall performance.
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高影响因子
ACS Catalysis
·
2026
·
IF 13.6
Xiong Zhang,Jian Zhao,Changqi Heng,Yiyang Lei,Minyan Yu,Zhonghua Xiang,Michael Y. Hu,Jiyong Zhao,Esen Ercan Alp,Xuning Li,Yanqiang Huang
Iron-nitrogen-carbon (FeNC) catalysts are considered among the most promising alternative to Pt catalysts in acidic oxygen reduction reaction (ORR), yet the geometric and electronic structures of the true active site under reaction conditions have not been clearly elucidated. Herein, we synthesized a representative FeNC catalyst by pyrolyzing Fe3+ absorbed on ZIF-8-derived N-doped carbon at a mild temperature under the H2/Ar atmosphere, where a formation mechanism of FeN4 sites through a Zn-mediated Fe nanoparticle atomization process was proposed. The resulting FeNC-750 catalyst shows high acidic ORR activity with a half-wave potential of 0.838 V and a peak power density of 1 W cm-2 in proton-exchange membrane fuel cell (PEMFC). By using operando57Fe Mössbauer spectroscopy on FeNC-750, it was revealed that the pyrrolic N-coordinated high-spin Fe2+N4 sites, which are in situ generated from high-spin Fe3+N4 during ORR, are identified as catalytic active states. Density functional theory calculations further verified that, compared to the pyridinic N-coordinated low-spin Fe2+N4, the pyrrolic N-coordinated high-spin Fe2+ exhibits optimized adsorption energy for reaction intermediates, thereby lowering the energy barrier of the rate-determining step (RDS) and facilitating OH* desorption. This work provides both experimental and theoretical evidence of the true active site in the FeNC during acidic ORR, offering significant insights for the rational design of high-performance materials for acidic fuel cells.
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高影响因子
Frontiers of Environmental Science & Engineering
·
2025
·Vol. 19
·期 12
·1-17
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IF 6.4
Wei Biao,Liu Daoqing,Peng Ran,Zhou Yi,Li Qianwei,Zhao Huazhang
The remediation of nitroaromatic-contaminated water systems remains a critical environmental challenge, creating the urgent need for cost-effective, non-precious metal catalysts to increase wastewater biodegradability. In this study, we present an Fe/N-functionalized three-dimensional porous carbon (Fe–N–C) catalyst synthesized via a straightforward pyrolysis approach that enables efficient nitrobenzene (NB) degradation via electrochemical and chemical reduction pathways. The high-temperature pyrolysis process facilitates the iron-catalyzed reconstruction of the carbon matrix, resulting in a hierarchically porous structure with increased graphitization and uniformly distributed macrocyclic Fe–N 4 coordination sites. These structural features give the Fe–N–C catalyst exceptional electron transfer kinetics, catalytic activity, and pH adaptability, surpassing conventional graphite (GR) and nitrogen-doped carbons (NPCs) in NB reduction. Systematic evaluation of the electrochemical reduction performance revealed that the Fe–N–C electrode achieved the highest NB removal efficiency. To further assess the versatility of the catalyst, a functionalized Fe–N–C/zero-valent iron (ZVI) composite was engineered by integrating Fe–N–C as a catalytic layer onto the reductant ZVI. Compared with ZVI alone, this composite markedly increased the NB reduction efficiency. These findings provide valuable insights into the electrochemical reduction process of Fe–N–C and new directions for the rational design of efficient nitrobenzene reduction systems.
研究领域:
环境科学
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材料科学
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电化学
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催化
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水处理
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高影响因子
Journal of Materials Chemistry A
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2021
·Vol. 9
·期 26
·14793-14805
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IF 12.732
Yuan Gao,Xiaoguang Duan,Bin Li,Qianqian Jia,Yang Li,Xiaobin Fan,Fengbao Zhang,Guoliang Zhang,Shaobin Wang,Wenchao Peng
Persulfate-based advanced oxidation processes are promising technologies to solve water pollution. In this work, single iron atoms are anchored on three-dimensional N-doped carbon nanosheets by a chemical vapor deposition (CVD) method with ferrocene-loaded CaO as the hard template. The high surface density of Fe–N4 sites and abundant interconnected meso–macro pores are highly favorable for activating peroxymonosulfate (PMS) to produce superoxide radicals (O2˙−), giving rise to ultrahigh activity and excellent stability for pollutant degradation. Experiment and density functional theory (DFT) calculations reveal that Fe–N4 is the main active site, on which electrons transfer from C to Fe via the C–N–Fe bond to secure the low-valence state of Fe species for the redox process. This work proposes a new strategy for developing highly active single-atom materials by CVD and reveals mechanisms of PMS activation on single-atom activators.
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高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2021
·Vol. 31
·期 13
·2007877
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IF 18.808
Feng Chen,Xi-Lin Wu,Chenyang Shi,Hongjun Lin,Jianrong Chen,Yanpeng Shi,Shaobin Wang,Xiaoguang Duan
Heterogeneous Fenton-like reactions (HFLR) are promising alternative strategies to address the inherent limitations of the classic Fenton systems. Herein, a facile and scale-up approach for the synthesis of transition metal single-atom sites (SA-TM, TM = Cr, Mn, Fe, Co, Cu) coordinated onto pyrrolic N-rich g-C 3 N 4 (PN-g-C 3 N 4 ) scaffold is developed. The regulated pyrrolic N-rich SA-TM catalytic sites exhibit excellent performances for HFLR. As a model of SA-TM/PN-g-C 3 N 4 , SA-Cr/PN-g-C 3 N 4 is efficient for the catalytic oxidation of bisphenol A via HFLR under visible light with outstanding cyclic stability and wide effective pH range (3.0–11.0). The synergy of photocatalysis and single-atom catalysis leads to accelerated production and separation of charge carriers as well as the cycling of Cr 3+ /Cr 2+ couple, consequently boosting the performance in HFLR. Theoretical calculations indicate that the Cr(II)-N 4 sites with the metalloporphyrin-like structure are more reactive than the doped Cr(II) sites in the g-C 3 N 4 matrix, which act as the peroxidase-mimicking nanozyme for efficient and homolytic cleavage of peroxide O O in H 2 O 2 . This study expands the family of the iron-free Fenton-like systems and provides new strategies to the rational design and precise regulation of on-demand multifunctional single-atom catalysts for advanced water remediation.
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高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2019
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IF 6.361
Liang Dong,Jianbing Zang,Weiping Wang,Xin Liu,Yan Zhang,Jing Su,Yanhui Wang,Xiumei Han,Jinsheng Li
The metal (Fe/Co), nitrogen co-doped carbon represent an important class of oxygen reduction reaction (ORR), which can be obtained via the thermal treatment of transition-metal macrocycles (TMMs). However, the N 4 -chelate complex with metal atom (M-N 4 ) moieties as major activity site for ORR are easily destroyed to form inorganic metal species during simple pyrolysis of TMMs. In this report, polyacrylonitrile (PAN) nanofibers were prepared by electrospinning containing a small amount of hemin (chloroprotoporphyrin IX iron(III), TMMs). The electrospun nanofibers were converted into Fe, N co-doped carbon nanofibers (Fe- N -CNFs) through preoxidized and thermal treatment. The PAN macromolecules can prevent hemin from aggregation during the process of pyrolysis. The Fe elemental mapping demonstrated that Fe species probably existed in a single atom state. The Fe K-edge X-ray absorption fine structure spectrum of Fe- N -CNFs proved that the Fe-N 4 moieties have been successfully reserved. The X-ray photoelectron spectra of Fe- N -CNFs indicated that the amount of Fe-N 4 moieties increased with the increased percent of hemin. Therefore, the Fe- N -CNFs exhibited the higher catalytic activity for ORR compared with Pt electrocatalysts . Furthermore, the Fe1- N -CNFs displayed higher stability and methanol tolerance than Pt/C.
研究领域:
材料科学
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电化学
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纳米技术
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催化
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产品关联
DOI
PubMed
高影响因子
APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Yuxiang Mao,Jun Cheng,Hao Guo,Lei Qian,Jiacan Tu,Weijuan Yang
To enhance catalytic acid-base sites in ZIFs and efficiently promote conversion of microalgal lipids, a bifunctional catalyst with single-atom Fe-N 4 sites and Fe nanoparticles (NPs) was synthesized by pyrolyzing Fe-doped ZIF-8. Compared with ZIF precursors, Fe nanoparticles and coordinated Fe ions in Fe-N 4 sites enhanced Lewis acidity, while increased uncoordinated N atoms enhanced Lewis basicity. Therefore, the acidity of Fe-NC increased from 0.473 to 1.845 mmol/g, while basicity increased from 0.172 to 0.439 mmol/g. DFT calculations showed that the adsorption energies of acetic acid on the Fe–N 4 and Fe NP were −0.536 eV and −0.397 eV, respectively, exceeding that (-0.190 eV) on the Zn–N 4 site. The energy barriers for rate-determining steps over the Fe-N 4 and Fe NP were + 0.32 eV and + 0.21 eV, respectively, which were lower than that (+1.01 eV) over the Zn-N 4 site. The maximum biodiesel yield reached 98.3% over Fe-NC catalyst, higher than that (84.5%) over ZIF-8 catalyst.
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高影响因子
ADVANCED MATERIALS
·
2021
·Vol. 34
·期 5
·2105410
·
IF 30.849
Leping Yang,Xu Zhang,Lingxiao Yu,Jianhua Hou,Zhen Zhou,Ruitao Lv
Noble-metal-free, durable, and high-efficiency electrocatalysts for oxygen reduction and evolution reaction (ORR/OER) are vital for rechargeable Zn–air batteries (ZABs). Herein, a flexible and free-standing carbon fiber membrane immobilized with atomically dispersed Fe–N 4 /C catalysts (Fe/SNCFs-NH 3 ) is synthesized and used as air cathode for ZABs. The intertwined fibers with hierarchical nanopores facilitate the gas transportation, electrolyte infiltration and electron transfer. The large specific surface area exposes a high concentration of Fe–N 4 /C sites embedded in the carbon matrix. Modulation of local atomic configurations by sulfur doping in Fe/SNCFs-NH 3 catalyst leads to excellent ORR and enhanced OER activities. The as-synthesized Fe/SNCFs-NH 3 catalyst demonstrates a positive half-wave potential of 0.89 V and a small Tafel slope of 70.82 mV dec –1 , outperforming the commercial Pt/C (0.86 V/94.74 mV dec –1 ) and most reported M–N x /C (M = Fe, Co, Ni) catalysts. Experimental characterizations and theoretical calculations uncover the crucial role of S doping in regulating ORR and OER activities. The liquid-state ZABs with Fe/SNCFs-NH 3 catalyst as air cathode deliver a large peak power density of 255.84 mW cm –2 and long-term cycle durability over 1000 h. Solid-state ZAB shows stable cycling at various flat/bent/flat states, demonstrating great prospects in flexible electronic device applications.
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DOI
PubMed
高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
·
2024
·
IF 10.8
Zhe Li,Yunshuo Wu,Haiqiang Wang,Zhongbiao Wu,Xuanhao Wu
Nitrous oxide (N2O) is a potent greenhouse gas with a high global warming potential, emphasizing the critical need to develop efficient elimination methods. Electrocatalytic N2O reduction reaction (N2ORR) stands out as a promising approach, offering room temperature conversion of N2O to N2 without the production of NOx byproducts. In this study, we present the synthesis of a copper-based single-atom catalyst featuring atomic Cu on nitrogen-doped carbon black (Cu1–NCB). Attributed to the highly dispersed single-atom Cu sites and the effective suppression of the hydrogen evolution reaction, Cu1–NCB demonstrated an optimal N2 faradaic efficiency (82.1%) and yield rate (3.53 mmol h–1 mgmetal–1) at −0.2 and −0.5 V vs RHE, respectively, outperforming previously reported N2ORR electrocatalysts. Further, a gas diffusion electrode cell was employed to improve mass transfer and achieved a 28.6% conversion rate of 30% N2O with only a 14 s residence time, demonstrating the potential for practical application. Density functional theory calculations identified Cu–N4 as the crucial active site for N2ORR, highlighting the significance of the unsaturated coordination and metal–support electronic structure. O-terminal adsorption of N2O was favored, and the dissociative adsorption (*ON2 → *O + N2) was the rate-determining step. These findings reveal the broad prospects of N2O decomposition via electrocatalysis.
研究领域:
环境科学
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催化
·
电化学
·
材料科学
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产品关联
DOI
PubMed
高影响因子
CHINESE CHEMICAL LETTERS
·
2025
·
IF 8.9
Ying Li,Zelin Wu,Xiaoyu Liu,Bingkun Huang,Jing Zhang,Yanbiao Shi,Chuan-Shu He,Zhaokun Xiong,Xingxing An,Bo Lai
Extensive research has been devoted to single-atom activation of persulfates in recent years. However, mechanistic understanding of the distinct interactions between different persulfates ( i.e. , peroxymonosulfate (PMS) and peroxydisulfate (PDS)) and the coordination environments of single-atom catalysts (SACs) remains critical for advancing their practical applications. Herein, we developed a Fe-N 4 SAC exhibiting dual activation capabilities for both PMS and PDS. Intriguingly, experimental results revealed divergent activation mechanisms: PMS activation was predominantly mediated via single-site reactions generating singlet oxygen ( 1 O 2 ), whereas PDS activation proceeded through both dual-site and single-site pathways involving concurrent 1 O 2 generation and electron transfer processes. Density functional theory calculations further demonstrated that the geometric alignment between the inter-site distances of Fe-N 4 centers and the molecular dimensions of PDS serves as the key determinant for enabling the electron transfer pathway. This fundamental structure-reactivity correlation suggests that the intrinsic molecular-scale differences between PMS and PDS govern their distinct interaction mechanisms with Fe-N 4 SACs. Finally, the scale-up experiments realized nearly complete sulfamethoxazole degradation during 120 h continuous operation without obvious decline in both the Fe-N 4 /PMS and Fe-N 4 /PDS systems. This work provides fundamental insights into molecular-scale effects on persulfate activation mechanisms, establishing new design principles for SACs optimization in advanced oxidation processes.
研究领域:
催化
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环境化学
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材料科学
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物理化学
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水处理技术
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产品关联
DOI
高影响因子
Journal of Energy Chemistry
·
2026
·
IF 15.6
Zihan Wang,Tianqi Song,Xue Wang,Yanlong Ren,Yanli Zeng,Jingyuan Ma,Mingxing Wu,Jianing Guo
Covalent organic polymers (COPs) are regarded as prospective catalysts toward the oxygen reduction reaction (ORR) owing to their tailorable skeleton structures and precisely identifiable catalytic sites. Nevertheless, their intrinsically low conductivity and insufficiently exposed active sites constitute critical bottlenecks that greatly restrict ORR catalytic performance and cycling durability in practical applications. Herein, we propose a structural engineering strategy to construct high-efficiency and durable composite electrocatalysts (COP@HPC) with well-defined Fe-N 4 active sites, which is achieved by integrating a fully π-conjugated iron-phthalocyanine-based COP with a three-dimensional hierarchically porous carbon substrate via strong π-π interactions. The interconnected conductive network can effectively accelerate electron transfer and mass transport kinetics, while the conjugated COP offers atomically dispersed Fe-N 4 active sites with tunable electronic properties. Consequently, COP@HPC composite catalyst delivers outstanding electrocatalytic performance toward ORR with a high half-wave potential ( E 1/2 ) of 0.92 V, which is superior to that of the composite supported on a dense carbon substrate. In-situ Raman and density functional theory (DFT) calculations confirm the dynamic evolution of ORR intermediates on π-π modulated Fe-N 4 sites, verifying that strong interfacial coupling optimizes intermediate adsorption energy and reduces the rate-determining step energy barrier. When integrated into a liquid zinc-air battery, COP@HPC displays an excellent power density of 227 mW cm −2 and retains stable cycling for over 1000 h (1538 cycles). This work establishes a universal structural engineering methodology for developing high-efficiency single-atom electrocatalysts. A π-π assembly non-pyrolysis strategy is developed to synthesize COP@HPC single-atom electrocatalysts with well-defined Fe-N 4 sites. The 3D porous conductive matrix facilitates electron/mass transfer, while interlayer π-π interactions lower the ORR rate-determining barrier. Download: Download high-res image (189KB) Download: Download full-size image
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高影响因子
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