ChemElectroChem
·
2020
·Vol. 7
·期 14
·3116-3122
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IF 4.154
Sheng Song,Xiaoming Zhang,Xinlong Xu,Chuchu Wu,Huanqiao Li,Zhangxun Xia,Shansheng Yu,Suli Wang,Gongquan Sun
Graphical Strat talks : The density of FeN x active sites is increased by co-doping with trace Cu atoms. The as-prepared 20Fe10Cu-NC electrocatalyst exhibits outstanding oxygen reduction reaction performance in both alkaline and acid conditions. Iron-nitrogen-doped carbon (Fe-NC) is an ideal candidate to replace Pt-based oxygen reduction reaction (ORR) electrocatalysts due to its low cost and comparably high intrinsic activity. To further enhance the ORR performance of Fe-NC electrocatalysts, efforts have been focused on two main methods. One is to enhance the intrinsic activity of FeN x sites through electronic and geometric regulation, and the other is to increase the density of active sites by introducing high-nitrogen-containing precursors or co-doping methods. Herein, we report a strategy to further increase the Fe loading through the introduction of a trace amount of Cu atoms. Significant enhancement of the electrocatalytic ORR property is observed in the as-prepared Fe and Cu co-doped electrocatalyst with superior half-wave potential (E 1/2 ) in both alkaline and acid electrolyte. Experimental and theoretical study reveals that the introduction of a trace amount of Cu atoms is beneficial for the formation of FeN 4 sites, owing to the reduced formation energy. This work opens up a wide avenue to further increase the Fe loading in Fe-NC electrocatalysts through bimetal co-doping method.
研究领域:
材料科学
·
电化学
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DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2023
·
IF 6.2
Bin Hu,Yongqing Yang,Wei Cao,Xixi Wang,Chuan Zhou,Yiyang Mao,Lei Ge,Ran Ran,Wei Zhou
The high cost and unfavorable catalytic performance for oxygen reduction reaction (ORR) is one of the crucial obstacles that impede widely commercialization of proton-exchange membrane fuel cells (PEMFCs). Herein, we provide a novel, mass-producible ORR catalyst made of low-loading (10 wt%) Pt nanoparticles bound to patchy nitrogen-doped carbon (PNC) with uniformly dispersed FeN 4 sites (Pt/FeN 4 -PNC). The derived catalyst exhibits significantly improved catalytic activity and stability, obtaining a promising mass activity (MA) of 0.94 A mg pt −1 at 0.9 V (vs. RHE) with a negligible decay after 30,000 cycles accelerated durability test (ADT). In the fuel-cell assessment (under H 2 -Air conditions at 80 ℃), the Pt/FeN 4 -PNC and Pt/FeN 4 -PNC-10 g (scaled-up production) achieved peak power densities of 1.13 W cm −2 and 1.14 W cm −2 , respectively, and retained 88.5 % and 88.1 % of the initial values after 30,000 voltage cycles (0.60–0.95 V). The patchy structure of PNC substrate guarantees fast electron routes and resistance to corrosion. With the FeN 4 active sites in the PNC substrate, the oxygen molecules are concurrently reduced on the surfaces of the carbon substrate and Pt nanoparticles, thereby causing the ORR reaction zone on the catalyst layer to expand.
研究领域:
材料科学
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能源科学
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催化化学
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DOI
高影响因子
MOLECULES
·
2024
·Vol. 29
·期 23
·5561
·
IF 4.2
Yuxuan Liu,Yufan Tan,Keyi Zhang,Tianqi Guo,Yao Zhu,Ting Cao,Haiyang Lv,Junpeng Zhu,Ze Gao,Su Zhang,Zheng Liu,Juzhe Liu
The catalyst is the pivotal component in CO2electroreduction systems for converting CO2into valuable products. Carbon-based single-atom materials (CSAMs) have emerged as promising catalyst candidates due to their low cost and high atomic utilization efficiency. The rational design of the morphology and microstructure of such materials is desirable but poses a challenge. Here, we employed different Mg(OH)2templates to guide the fabrication of two kinds of amorphous nitrogen-doped carbon nanosheet-supported Fe single atoms (FeSNC) with rough and flat surface structures. In comparison to flat FeSNC with saturated FeN4sites, the rough FeSNC (R-FeSNC) exhibited unsaturated FeN4−xsites and contracted Fe-N bond length. The featured structure endowed R-FeSNC with superior capacity of catalyzing CO2reduction reaction, achieving an exceptional CO selectivity with Faradaic efficiency of 93% at a potential of −0.66 V vs. RHE. This study offers valuable insights into the design of CSAMs and provides a perspective for gaining a deeper understanding of their activity origins.
研究领域:
材料科学
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催化化学
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能源化学
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DOI
PubMed
高影响因子
Small
·
2026
·
IF 11.8
Hang Zhang,Yinuo Wu,Zhen Zhang,Ying Hou,Peizhi Liu,Ting Liao,Bingshe Xu,Yanhui Song,Haixia Zhang,Junjie Guo,Ziqi Sun
M-N-C single-atom catalysts have been demonstrated to be a promising class of non-noble-metal based catalysts, but their activity is largely constrained by the symmetrical electronic density distribution of the M-N 4 moieties. Herein, a ZIF-8 derived Fe/Fe dual-center catalyst (FeN 4 /FeO 5 @NC) is constructed by introducing a O-FeO 4 configuration adjacent to the Fe-N 4 sites to form asymmetric dumbbell-shaped FeN 4 -O-FeO 4 active sites, resulting in improved intrinsic activity of Fe─N─C catalyst. The dumbbell FeN 4 -O-FeO 4 dual-center catalyst features an electron transfer pathway of “FeN 4 → bridged O → FeO 4 ”, which breaks the symmetry of the electronic density distribution of the Fe moiety and regulates the position of the d-band center, increasing the electron transfer efficiency, reducing the desorption energy barrier of the rate-determining step, and enhancing the activation ability of O 2 molecules. The obtained FeN 4 -O-FeO 4 dual-center catalyst exhibits excellent ORR performance in a pH-universal range. The liquid-state Zn-air battery (ZAB) with this FeN 4 -O-FeO 4 dual-center catalyst delivers an outstanding open circuit voltage of 1.502 V and a peak power density of 246 mW cm −2 , superior to the Pt/C-cathode ZAB. This work represents an exploration of ways to improve the ORR performance of Fe─N─C catalysts and provides a paradigm for rationally designing low-cost, highly catalytic, and stable non-noble metal catalysts.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Xue Wang,Zijia Shang,Zihan Wang,Ziyu Guo,Xuan Li,Jingyuan Ma,Keqiang Ding,Jianing Guo,Mingxing Wu
Elaborate designed active sites and reasonable regulation of their electronic structure to develop efficient electrocatalysts are essential yet challenging for promoting the practical applications of zinc-air batteries. Instead of randomly fabricating metal‑nitrogen moieties on a carbon matrix by pyrolysis, an efficient composite electrocatalyst (Fe-COP/Co@HCF) is constructed in this study through π-π interaction between the well-designed π conjugated iron-covalent organic polymers (Fe-COP) with the atomically Fe N 4 centers and hollow carbon nanofibers supported by Co nanoparticles (Co@HCF) with high electrical conductivity and mass transfer capability. Additionally, the optimized Fe-COP/Co@HCF exhibits an outstanding electrocatalytic activity with a half-wave potential of 0.90 V (vs. RHE), attributed to the synergistic effect and intrinsic activity of the Fe N 4 moiety, as well as the unique hollow porous structure of carbon nanofibers. Density functional theory calculations demonstrate a significant electron rearrangement occurs around Fe centers, accompanied by the d-band center upshift, which effectively reduces the energy barrier for oxygen intermediate adsorption and accelerates the ORR kinetics. Notably, the liquid zinc-air battery assembled with Fe-COP/Co@HCF catalyst as a cathode achieves a peak power density of 204 mW cm −2 with extremely long-term stability (>2300 h). This work provides a feasible method for precisely designing active sites of electrocatalysts.
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高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2026
·
IF 9.6
Chenhong Liu,Xiaoli Yang,Kai Zhu,Wenbo Shi,Jialiang Pan,Qing Zhang,Zhengyu Bai,Lin Yang
Constructed a Fe 3 C nanoparticle/Fe single-atom composite catalyst and elucidated its proton-feeding mechanism. • Clarified the role of interfacial water and proposed a novel catalyst design strategy. • Synergy of mesopore-rich substrate and electronic modulation boosts intrinsic activity. • Fe 3 C@Fe/NC exhibits outstanding electrochemical performance and stability. The oxygen reduction reaction (ORR) is crucial for sustainable power generation, yet its sluggish kinetics, mainly caused by insufficient proton supply and excessive intermediates adsorption, severely limit the overall efficiency. An important ongoing challenge is to regulate both factors to significantly enhance ORR. Herein, a dual-effect catalyst, Fe 3 C@Fe/NC, was designed and synthesized via a systematic two-step Fe 3+ doping strategy to achieve closely adjacent multiple active sites. This catalyst features activated interfacial water to provide sufficient protons and optimized intermediate adsorption energy. Structural characterization revealed uniformly distributed FeN 4 sites alongside adjacent Fe 3 C nanoparticles interwoven by carbon nanotubes. In-situ spectroscopic techniques and theoretical calculations demonstrated that Fe 3 C nanoparticles can activate interfacial water, enhancing dynamic active hydrogen donation to neighboring FeN 4 sites, thereby accelerating the proton-coupled electron transfer (PCET) kinetics. Simultaneously, the regulated electronic structure around FeN 4 sites offers appropriate intermediate adsorption energy, further boosting ORR activity and durability. The Fe 3 C@Fe/NC catalyst exhibits a remarkable half-wave potential of 0.904 V, a higher power density of 221.3 mW cm −2 and excellent durability with 1250 h operation at 5 mA cm −2 in zinc-air battery test. This work establishes a proximal proton-donation strategy to overcome the alkaline ORR bottleneck. The Fe 3 C sites not only modulate the local microenvironment of the FeN 4 sites, more importantly, in-situ infrared spectroscopy and theoretical calculations reveal that the Fe 3 C sites can activate interfacial water and promote water dissociation, thereby supplying protons to the FeN 4 sites to accelerate the proton-coupled electron transfer process. Download: Download high-res image (52KB) Download: Download full-size image
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PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2026
·
IF 9.7
Dan Wang,Yankun Wei,Xiaosong Li,Jinxiang Chou,Yukai Chen,Xiaojiao Du,Wenchang Wang,Naotoshi Mitsuzaki,Zhidong Chen
The construction of edge-hosted Fe N sites presents a promising way to boost catalytic performance of typical Fe N sites for the oxygen reduction reaction (ORR). However, the controllable synthesis of densely accessible edge-hosted Fe N sites remains challenging. Herein, an oxalate anion-assisted strategy is developed for precise preparation of densely edge-hosted Fe N 4 atomic sites for ORR. The strong coordination between oxalate anions and Fe 3+ ions facilitates the formation of dense edge-hosted Fe N 4 atomic sites. The subsequent decomposition of oxalate anions creates a hierarchically porous structure. Remarkably, the obtained e -FeNC exhibits improved ORR activity in acidic (0.79 V) and alkaline (0.89 V) electrolytes, a higher site density (SD), and an enhanced turnover frequency (TOF, 3.71 s −1 ). Density functional theory calculations reveal that edge FeNC sites exhibit a lower energy barrier for ORR than center FeNC sites. The downward shift of the d-band center weakens the adsorption of ORR intermediates, accounting for the high intrinsic activity of edge FeNC sites. Additionally, the assembled Zn-air battery displays a high specific capacity of 781 mAh g −1 , a large energy density of 999 Wh kg Zn −1 , and outstanding cycling performance over 550 h with minimal voltage gap of 0.84 V.
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高影响因子
Catalysts
·
2026
·Vol. 16
·期 5
·462
·
IF 4.5
Danyang Zhu,Baolong Liu,Yiping Mo,Qiao Zhang,Yuhan Ma,Wenqi Dai,Wangyang Lu
Effective regulation of the adsorption strength of oxygen reduction reaction (ORR) intermediates on active sites is the key to enhancing their catalytic performance. This study proposes an axial coordination modulation strategy by successfully anchoring the dioxin-linked FePcF16-based covalent organic frameworks (COFs) onto amino-functionalized multi-walled carbon nanotubes (NH2-MWCNTs), constructing a FePcF16-COF/NH2-MWCNT hybrid catalyst. Experimental results demonstrate that the catalyst exhibits outstanding ORR activity (E1/2= 0.901 V; JL= 5.133 mA cm−2), outperforming commercial 20% Pt/C and most reported Fe-based non-precious metal catalysts. Furthermore, the robust dioxin-linked COF skeleton endows the catalyst with excellent electrochemical stability. A zinc–air battery using this catalyst as the cathode also demonstrates superior power density and cycling performance. This work provides a new strategy for designing highly efficient ORR catalysts through axial coordination environment engineering.
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高影响因子
CHINESE JOURNAL OF CATALYSIS
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2024
·
IF 15.7
Yuan Jiang,Ji Yang,Mu-Lin Li,Xue-Jia Wang,Na Yang,Wei-Ping Chen,Jin-Chao Dong,Jian-Feng Li
ABSTRACT Metal-nitrogen-carbon single-atom catalysts (M-N-C SACs) have emerged as a highly promising material for ammonia synthesis from electrocatalytic nitrate reduction due to their isolated metal site and capacity to prevent the N–N coupling. However, understanding the structure-activity relationship at molecular level remains challenging because of the inhomogeneous M N x structure presented in current synthesized M-N-C catalysts. In this study, we utilized metal phthalocyanine ( M Pc) as a model platform catalyst containing a uniform and well-defined M N 4 center to unravel their intrinsic activity tendency toward ammonia synthesis from nitrate reduction, both experimentally and theoretically. Our experimental results exhibit a significant activity difference for ammonia production in the order of FeN 4 > CuN 4 > NiN 4 > MnN 4 > CoN 4 > ZnN 4 , and among which the FeN 4 site delivers much higher faradic efficiency and the highest turnover frequency of 83.3% and 4395.2 h –1 at –1.0 V vs . RHE, respectively. Density-functional theory calculations indicates that, compared to CoN 4 and MnN 4 , the FeN 4 site not only has appropriate adsorption strength for NO x intermediate species, but also has certain inhibitory effects on hydrogen evolution reaction process. These findings provide systematic and reliable guidance for catalyst synthesis toward nitrate reduction to NH 3 from both the experimental and computational perspectives.
研究领域:
催化
·
电化学
·
材料科学
·
理论化学
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Mengxia Shen,Jiale Qi,Kun Gao,Chao Duan,Jun Liu,Qingqing Liu,Hao Yang,Yonghao Ni
Fe-N x C single-atom catalysts have been immensely explored as the most promising ORR catalysts for replacing noble metals. Nevertheless, how to precisely introduce Fe atoms to optimize their spatial distribution and coordination environment in carbonaceous matrices while constructing the hierarchical porous structures to facilitate the mass transport process and ensure the accessibility of Fe-N x sites remain significant challenges. Here, we propose a strategy to prepare porous N -doped carbon aerogels anchored with single atomic Fe sites (Fe-SA@PNC) as highly efficient ORR electrocatalysts via directional freeze-casting and chemical vapor deposition. Fe-SA@PNC exhibit remarkable ORR activity and stability due to the highly stable honeycomb morphology and hierarchical pore structure, as well as the atomically dispersed Fe-N 4 sites in the carbon support. Furthermore, the practical application of Fe-SA@PNC catalysts as cathode materials in Zn-air batteries was demonstrated with encouraging performance. This study provides a promising approach for constructing high-efficiency ORR single-atom catalysts.
研究领域:
材料科学
·
电化学
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DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2022
·
IF 9.965
Xinyi Li,Jingjing Liu,Qinghai Cai,Ziwang Kan,Song Liu,Jingxiang Zhao
Modulating the microenvironment of single-metal active sites holds excellent promises for developing highly efficiently oxygen electrocatalysts. Herein, by combining theoretical predictions and experiments, we reported a general strategy to engineer the electronic properties of iron-nitrogen-carbon (FeN 4 /C) catalysts via the incorporation of the boron (B) atom for achieving improved catalytic activity in oxygen electrocatalysis. Our theoretical results revealed that B modulation effectively tunes the d-band center of the iron (Fe) active site to optimize its adsorption strength with oxygenated species, greatly enhancing oxygen reduction reaction (ORR) and oxygen evolution reactions (OER) activity. Our experimental measurements then confirmed the above theoretical predictions: the as-synthesized B-doped FeN 4 /C (Fe-N 4 -B) material can perform as an eligible bifunctional catalyst for ORR and OER in alkaline media, and its catalytic activity even outperforms the commercial noble metal benchmarks. The present findings provide a promising strategy to further design the advanced catalysts for a wide range of electrochemical applications.
研究领域:
材料科学
·
电化学
·
催化
✓ 已验证
DOI
PubMed
高影响因子
ENVIRONMENTAL RESEARCH
·
2024
·
IF 7.7
Wenfei Ding,Zhaoyi Mo,Jia Qi,Mengying Wang,Junyu Zou,Kuo Wang,Daxiang Gong,Yongju Zhao,Hong Miao,Zhongquan Zhao
Cr(Ⅵ) residues in livestock and poultry wastewater are a rising concern for human health and biotic environments. For the removal of Cr(Ⅵ), its simultaneous reduction and adsorption represents a sustainable and efficient strategy. Herein, iron nodes on covalently bonded two-dimensional phthalocyanine organic polymer (PcOP-Fe) nanosheets with space-separated dual-active sites are developed for the simultaneous detection and removal of Cr(VI) from wastewater. In the FeN 4 structure of PcOP-Fe nanosheets, Fe acts as an electron capture center, effectively facilitating the accumulation of photogenerated electrons and transferring them to Cr(VI), thereby achieving its photocatalytic reduction. Meanwhile, pyrrolic nitrogen provides excellent adsorption sites, enabling the adsorption of Cr(III) or Cr(0). Fe accumulates the photogenerated electrons from pyrrole N and transfer them to Cr(Ⅵ). The formation of N-Cr(Ⅲ) bonds causes a space-separation between Cr(Ⅵ) and Cr(III). In addition, PcOP-Fe can be used for a Cr(Ⅵ) detection agent. The photoluminescence intensity decreases linearly with increasing Cr(Ⅵ) concentration from 80 μM to 2 mM, with a limit of detection of 0.18 μM. The PcOP-Fe nanosheets exhibit good Cr(Ⅵ) detection and reduction performance in livestock and poultry wastewater, suggesting their suitability for practical sensing applications. Thus, the PcOP-Fe nanosheets with space-separated dual-active sites are promising for the simultaneous detection and removal of Cr(Ⅵ) in water treatment processes.
研究领域:
环境科学
·
材料科学
·
化学
·
水处理
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PubMed
高影响因子
危险品化学品经营许可证（带存储）