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
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.
研究领域:
催化化学
·
能源材料
·
生物技术
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Yanan Shang,Xinning Liu,Yanwei Li,Yue Gao,Baoyu Gao,Xing Xu,Qinyan Yue
The synthesis of a highly efficient and stable single atom catalyst (SAC) for peroxydisulfate (PDS) activation remains a challenge. Herein, a reconstructed iron single atom catalyst (Fe-SAC) with both abundant conjugated π-π sp 2 structured carbon and reactive Fe-N 4 sites was first reported to improve the decomposition of organics in PDS/SACs systems. Enhanced organics adsorption can be achieved by the conjugated π-π sp 2 structured carbon via π-π interaction to decrease the migration distance of reactive species to organic molecules. In addition, PDS tended to be attached onto the Fe-N 4 sites accompanied by the peroxymonosulfate (PMS) generation via S-O breakage of PDS, accelerating the generation of radicals. As a result, organics decomposition via PDS activation by reconstructed Fe-SAC was significantly higher (∼6 times) than the conventional Fe-SAC because of the synergistic effect of the resulting dual reaction sites. This work provides a new strategy to enhance the catalytic performances in PDS/SACs systems.
研究领域:
环境科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Chunfeng Shao,Lingmin Wu,Yinghua Wang,Konggang Qu,Hailiang Chu,Lixian Sun,Jianshan Ye,Baitao Li,Xiujun Wang
Single-atom catalysts (SACs) have sparked intense interest in heterogeneous catalysis lately, but insufficient accessibility of active sites restricts their further applications. Herein, a hydrangea-like carbon nanoparticle possessing highly open nanospaces and enhanced external surface area that fully exposes the catalytic sites is reported. By introducing mesoporous silica nanoparticles (MSNs), Fe-doping zeolitic imidazolate framework-8 (ZIF-8) precursors are assembled into a flower-like superstructure interlaced by porous nanosheets, which expand from inside out constructing an open and interconnected architecture. This unique structure can substantially liberate the densely dispersed but deeply buried Fe-N 4 sites inside carbon nanoparticles and accelerate mass transfer in the catalyst layer that increases active-site utilization. Furthermore, the physical and chemical properties of the assembled catalysts can be adjusted by the diameter (200, 300, and 500 nm) of MSNs. When the diameter was 500 nm, the optimal FeNC-F3 catalyst exhibited large specific surface area, maximum metal centers utilization, high oxygen reduction reaction efficiency, and excellent stability. The novel cathodic electrocatalyst achieved high power density of 0.32 mW cm −2 in microbial fuel cell and 288 mW cm −2 in Zn-air battery. This work established a realistic strategy for promoting the practical development of fuel cell catalysts.
研究领域:
材料科学
·
电化学
·
催化
·
能源存储与转换
✓ 已验证
产品关联
DOI
高影响因子
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
·
2024
·Vol. 27
·期 24
·e202400196
·
IF 2.2
Wenkang Mao,Jinjing Ju,Dan Li,Daishe Wu,Feigao Xu
Graphical Synopsis: A pyrrolic N-rich g-C 3 N 4 (PN-g-C 3 N 4 ) framework is synthesized with transition metal M (M=Fe, Co, Ni, Cu, Cr, and Mn) atomic sites coordinated onto it. M/PN-g-C 3 N 4 are constructed for peroxodisulfate activation. The synergy between photocatalysis and Fe/PN-g-C 3 N 4 catalyst results in increased generation and separation of charge carriers, along with the cyclic transformation of the Fe 3+ /Fe 2+ couple. Photocatalysis is an efficient technology for the degradation of pollutants. However, there is still much room for improvement in its degradation efficiency. In this study, a pyrrolic N-rich g-C 3 N 4 (PN-g-C 3 N 4 ) framework was synthesized with transition metal M (M=Fe, Co, Ni, Cu, Cr, and Mn) atomic sites coordinated onto it. Then, a series of single atomic metals M anchored to PN-g-C 3 N 4 (M/PN-g-C 3 N 4 ) are constructed for peroxodisulfate activation. Their order of catalytic activity follows Fe>Cr>Ni>Cu≈Co>Mn, in particular the degradation rates of the TCH for Fe-PN-g-C 3 N 4 are 3.74 times higher than that of undoped PN-g-C 3 N 4 . These carefully regulated pyrrolic N-rich Fe sites demonstrate outstanding performance in degrading organic pollutant. As an exemplary model, the Fe/PN-g-C 3 N 4 catalyst efficiently drives the catalytic oxidation of TCH through Fenton-like reaction under visible light, showcasing exceptional cycle stability and a broad effective pH range of 3.0–11.0. The synergy between photocatalysis and Fe doped catalysis results in increased generation and separation of charge carriers, along with the cyclic transformation of the Fe 3+ /Fe 2+ couple. This combination significantly enhances the Fenton-like performance, making it a highly effective process for pollutant degradation.
研究领域:
环境科学
·
催化
·
材料科学
·
化学工程
·
水处理技术
✓ 已验证
DOI
高影响因子
Journal of Materials Chemistry A
·
2019
·Vol. 7
·期 19
·11792-11801
·
IF 10.733
Xiang Ao,Wei Zhang,Zhishan Li,Lin Lv,Yunjun Ruan,Hong-Hui Wu,Wei-Hung Chiang,Chundong Wang,Meilin Liu,Xiao Cheng Zeng
The scarcity and weak durability of precious metal catalysts are among the biggest obstacles to achieving cost-effective electrocatalysts in fuel cells and metal–air batteries. Hence, it is imperative to develop low-cost non-precious metal catalysts with comparable oxygen reduction reaction (ORR) activity to precious metal catalysts. Herein, we report a highly effective strategy for the facile synthesis of Fe/N-functionalized 3D porous carbon networks. A major advantage of the newly designed catalyst is that ultrafine Fe4N nanoparticles are grown and uniformly mounted on the carbon framework upon pyrolysis treatment at 800 °C, and co-exist with numerous in situ formed Fe–N4 moieties in the carbon matrix, being evidenced by using X-ray absorption and photoelectron spectroscopy. The new electrocatalysts exhibit high ORR activity, comparable/superior to that of the state-of-the-art Fe/N–carbon based catalysts reported to date. Specifically, the catalysts show a half-wave potential of 0.890 V (vs. RHE) and a limited current density of 6.18 mA cm−2. By resorting to experimental measurements and density-functional theory (DFT) calculations, the synergistic effects between Fe–N4 moieties and the Fe4N support are identified for the first time, which play a key role in boosting the catalytic performance of the Fe/N-functionalized porous carbon networks.
研究领域:
材料科学
·
电化学
·
催化
·
能源材料
✓ 已验证
产品关联
DOI
高影响因子
Advanced Energy Materials
·
2023
·Vol. 13
·期 22
·2300325
·
IF 27.8
Zhen Zhang,Tianping Wang,Weiwen Wang,Xiangnan Wang,Xianglin Luo,Chong Cheng,Xikui Liu
Metallophthalocyanines (MPcs) hold great promise in the electrochemical reduction of oxygen; however, their practical applications in energy storage and conversion are still limited by their low stability and poor water oxidation activity. Herein, a novel stable 2D imide-linked metalphthalocyanine framework (denoted as FePc-PI) is reported, that has atomically dispersed Fe-N 4 sites deposited on the KB substrate via in situ growth, followed by incorporation of ultrafine nickel oxide nanoparticles (NiO x @FePc-PI/KB) to induce bifunctional electrocatalytic activities for the oxygen reduction reaction and oxygen evolution reaction. Benefitting from the robust aromatic backbone, the engineered catalytic centers, and the unique electronic structures owing to the interaction between the Fe-N 4 sites and NiO x species, the newly developed NiO x @FePc-PI/KB catalyst exhibits excellent reversible oxygen bifunctional activity ( E 1/2 = 0.926 V, η 10 = 285 mV), delivering a record-low overpotential difference (Δ E ) of 0.59 V, which far exceeds the noble-metal-based Pt/C+RuO 2 benchmark (Δ E = 0.77 V) and represents the highest level for reported bifunctional electrocatalysts. Furthermore, the rechargeable aqueous Zn-air batteries assembled with the NiO x @FePc-PI/KB catalyst deliver a high peak power density of 232.9 mW cm −2 and long-term cycling durability over 1400 cycles. Flexible all-solid-state Zn-air batteries exhibit stable cycling at various flat/bent/flat states, thus demonstrating their excellent prospects in realistic implementations.
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
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.
研究领域:
材料科学
·
电化学
·
能源存储
·
电池技术
·
催化
✓ 已验证
产品关联
DOI
PubMed
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 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
危险品化学品经营许可证（带存储）