Nano Research
·
2020
·Vol. 13
·期 8
·2079-2084
·
IF 8.183
Wang Hong-Hui,Lv Li-Bing,Zhang Shi-Nan,Su Hui,Zhai Guang-Yao,Lei Wei-Wei,Li Xin-Hao,Chen Jie-Sheng
The rational design of highly active and stable atomically dispersed M-X 4 (M = Fe, Co, Ni, etc., X = C, N) -based catalysts holds promises for wide application in almost all realms of catalysis. Despite great effort in the construction of specific M-X 4 centers, the possible effect of non-coordinated heteroatoms on the catalytic activity of metal centers has been rarely explored. Herein, we develop a new type of M-X 4 catalyst composed of Fe-N 4 centers and non-coordinated B heteroatoms (FeNC+B) and find the key role of non-coordinated B adjacent to Fe-N 4 centers in tailoring their electron density and final catalytic selectivity. The experimental and theoretical results demonstrated that non-coordinated boron atoms could decrease the electron density of Fe-N 4 centers to a suitable level and thus boost the selective production of nitriles from amine oxidation by depressing the formation of imines due to the flattened energy barrier of the reversible conversion of imines back to amines. As a reusable heterocatalyst, the state-of-the-art FeNC+B catalyst provides a turn-over frequency (TOF) value of 21.6 mol benzonitrile ·mol Fe −1 ·h −1 (100 °C), outpacing that of bench-marked nonnoble-metal-based homogeneous catalyst by a factor of 3.4.
研究领域:
催化化学
·
材料科学
·
理论化学
✓ 已验证
DOI
高影响因子
CARBON
·
2025
·
IF 11.6
Lianzhong Shen,Lin Wang,Zhouwei Li,Yu Ye,Qizhou Dai
Atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts are one of the more popular materials for electrochemical reduction of CO 2 to fuels and chemicals. Still, their Faraday efficiency and current density are generally low due to the single coordination environment and defect sites. Heteroatom doping has been demonstrated to increase the degree of defects in the material, improve the electron distribution at the single atomic sites, and enhance the catalytic performance. In this study, we prepared an S-doped single-atom catalyst called FeS@PC by a simple high-temperature pyrolysis method for efficient electroreduction of CO 2 to CO, with a maximum CO Faraday efficiency of 97.0% at -0.6 V vs. RHE potential. S atoms doped in the second-shell can change the electron distribution on the Fe-N 4 sites and accelerate the electron transfer during the electrochemical CO 2 reduction reaction (CO 2 RR). Through in situ ATR-FTIR characterization and kinetic experiments, it is found that the doped S can also promote the dissociation of H 2 O, provide sufficient protons for the conversion of CO 2 to *COOH, and promote the rate of CO conversion.
研究领域:
材料科学
·
催化化学
·
能源转换
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2022
·
IF 6.371
Meiling Fan,Peipei Liu,Yapeng Cheng,Haolin Tang,Bing Jin,Haining Zhang
Design and synthesis of earth-abundant elements-based electrocatalysts with sufficient activity and stability remain challenging for oxygen-involved electrochemical energy conversion and storage devices. In this work, catalyst with simultaneously engineered Fe-N 4 and Co-N 4 active sites and graphitic carbon multilayer-encapsulated FeCo alloy is developed by pyrolysis of metal salts doped G-g-C 3 N 4 . The obtained composite material exhibits promising catalytic activity and good stability for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolyte , as evidenced by the positive shift of half-wave potential by 44 mV compared to 20% Pt/C for ORR and the potential of 1.596 V at current density of 10 mAcm −2 for OER. In addition, the thus-assembled rechargeable zinc-air battery using the synthesized material as cathode delivers a maximum power density of 311.2 mWcm −2 with an open circuit potential of 1.51 V and a long-term cycling stability. DFT calculation results indicate that catalyst with composite active sites displays smaller energy barrier than that with single active site.
研究领域:
材料科学
·
电化学能源
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
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
·
电化学
·
能源存储与转换
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2025
·
IF 7.9
Lihui Xiao,Yaqiang Li,Peixia Yang,Qiang Lv,Xiangyu Lu,Hao Xu,Ruopeng Li,Huiling Zhang,Shengbo Yang,Anmin Liu,Dan Wang,Jinqiu Zhang,Maozhong An
Carbon nanotubes' (CNTs) preparation and formation mechanisms are of great interest. To improve their performance in the oxygen reduction reaction (ORR), a post-treatment to add active centers is required. This study presents a simple method using a molten-salt template to self-assemble bamboo-shaped CNTs (B-Fe-N-C) with highly stable Fe-N 4 (Fe-pyridinic-N 4 ) sites. By analyzing the evolution of high-temperature materials and the intermolecular bonding process, the formation mechanism of B-Fe-N-C follows a two-dimensional material synthesis--bonding--self-assembly--growth mechanism. Impressively, B-Fe-N-C exhibits superior ORR performance (a half-wave potential of 0.868 V) and stability (only 3 mV attenuation after 10000 cycles of accelerated durability test) in alkaline medium. Density functional theory calculations demonstrate that Fe-Pyridinic-N 4 sites can lower the energy barrier for ORR. Furthermore, Comsol multiphysics simulations confirm the significant enhancement of oxygen mass transfer by bamboo-shaped B-Fe-N-C. Therefore, B-Fe-N-C is employed in zinc-air batteries, resulting in nice discharge performance and high peak power density.
研究领域:
材料科学
·
电化学
·
理论计算
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Ziyi Wang,Xin Lian,Rongyan Yang,Xiaomeng Guo,Shengjie Wei,Jijie Zhang,Xian-He Bu
Introducing polarity in traditional metal-N4 catalytic sites and strengthening the adsorption of polar NO2* intermediate are advantageous for the deep reduction of nitrate into ammonia. Herein, the planar chlorination engineering strategy successfully introduced the C–Cl bonds adjacent to the Fe–N4 catalytic site with higher polarity, effectively boosting the catalytic activity for the nitrate reduction reaction (NO3RR). The maximal NH3 yield rate and the corresponding turnover frequency (TOF) value catalyzed by the Fe–N4/CNCl catalyst were 1.82 mg h–1 cm–2 and 245 h–1 at −0.83 V vs RHE, which were 3.4 times and 2.7 times those of the traditional Fe–N4/CN catalyst without polarity, respectively. The Fe–N4/CNCl catalyst also exhibited satisfactory stability during consecutive 15 cycles. The density functional theory (DFT) calculation revealed that the planar chlorination engineering of the Fe–N4 site with higher polarity strengthened the adsorption of polar NO2* intermediate, facilitated the deep reduction of nitrate into ammonia, lowered the energy barrier of rate-determining step (RDS) and thus improved the catalytic activity. This work exhibited the enormous advantage of a planar chlorination engineering strategy for enhancing the activity of electrocatalysis by introducing polarity in the traditional metal-N4 catalytic site.
研究领域:
材料科学
·
电催化
·
理论计算
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2021
·Vol. 9
·期 23
·13678-13687
·
IF 12.732
Dan Wang,Hao Xu,Peixia Yang,Xiangyu Lu,Jingyuan Ma,Ruopeng Li,Lihui Xiao,Jinqiu Zhang,Maozhong An
Compared to individual metal sites, e.g. Fe–N4 sites, the synergistic effect of dual-metal sites can further adjust the interaction of reactants or intermediates with active sites, which is beneficial for boosting the oxygen reduction reaction (ORR) in Zn–air batteries. However, developing a simple and direct method instead of complicated procedures and post-treatment to realize well-defined dual-metal sites is still a grand challenge. Herein, a facile one-step impregnation-pyrolysis route without any post-treatment is developed to controllably synthesize Fe and Co dual-metal sites embedded in hierarchical N-doped carbon from metal–organic frameworks. X-ray absorption spectra coupled with density functional theory calculations demonstrate that the Fe–N4 and Co–N4 dual sites can synergistically enhance the ORR activity. Impressively, the well-controlled FeCo–N–C catalyst exhibits excellent ORR performance, with half-wave potentials (E1/2) of 0.807 and 0.904 V in 0.1 M HClO4 and 0.1 M KOH, respectively. Benefiting from the highly active dual-metal sites and desired porous structure, FeCo–N–C serving as a cathode catalyst achieves an uplifting peak power density of 196.3 mW cm−2 and a remarkable specific capacity of 728.6 mA h gZn−1 at a discharge current density of 20 mA cm−2 in a practical liquid Zn–air battery. Besides this, such superb battery performance is demonstrated in an all-solid-state Zn–air battery.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
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
·
电化学
·
能源存储与转换
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Materials Chemistry A
·
2020
·Vol. 8
·期 8
·4369-4375
·
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
·
电化学
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2023
·
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
·
能源技术
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Lingzhe Meng,Shuwen Niu,Zhengyu Wei,Xue Qin,Faheem Naseem,Wei Wei
Iron phthalocyanine (FePc) with tetracoordinated Fe-N 4 site shows promising activity for catalyzing the oxygen reduction reaction (ORR) in alkaline media. However, the consecutive proton-coupled electron transfer (PCET) steps with water as the proton donor and low electronic conductivity of FePc raise the kinetic barriers for device application. Herein, a significant effect of polyoxometalates (POMs) on the ORR kinetics of Fe-N 4 sites via surface coordination of FePc is revealed. POM clusters modulate the interactive steric/electronic environment of Fe-N 4 , leading to a low barrier for H 2 O cleavage to produce protons along with a high electron transfer rate, thereby accelerating the PCET steps of FePc. With precisely controlled electron charge of POM clusters, the influence and mechanism of heteropoly blue in promoting PCET steps of FePc relative to heteropoly acid are elucidated, and noticeably enhanced ORR activity and reaction current are achieved. These findings highlight the potential of POMs as ligands to optimize dynamics of Fe-N 4 atomic sites toward efficient alkaline ORR.
研究领域:
化学
·
材料科学
·
催化
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2021
·Vol. 9
·期 26
·14793-14805
·
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.
研究领域:
环境科学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）