Fe-Nx Active Sites Research Articles

Joule heating synthesis for single-atomic Fe sites on porous carbon spheres and armchair-type edge defect engineering dominated oxygen reduction reaction performance

Single-atom catalysts (SACs) embedded in heteroatom-doped carbon are the most promising oxygen reduction reaction (ORR) electrocatalysts. However, the expeditious and facile synthesis of high-performance SACs with Fe-Nx active sites and identifying the role of edge-type defect at the atomic level in carbon support are essential but remain challenging. Herein, Joule heating is applied to anchor Fe single atoms on newly defect rich porous carbon spheres (Fe-N-DCSs) in milliseconds. Fe-N-DCSs achieves exceptional ORR performance, with a half-wave potential (E1/2) of 0.90 V and E1/2 lost of only 20 mV after 30,000 cycles in 0.1 M KOH, and superior Zn-air batteries performances. Density functional theory calculations establish that armchair-type edge defects decorated Fe-N4 active sites boost the desorption of OH* and diminish the ORR overpotential. This work not only provides a speedy route for the fabrication of SACs but also presents new insights into the excellent ORR activity.

Decomposition of tetracycline with peroxymonosulfate activated by an ordered hierarchical pores Fe-N/C catalyst rich in FeNx sites: Insights into singlet oxygen mechanism

FeNx sites show significant superiority in the degradation of antibiotic contaminants, but there are difficulties in successfully constructing highly dispersed FeNx sites. In this work, Fe-N/C catalysts doped with hierarchical ordered pores structure and FeNx active sites were prepared by metal node exchange strategy. Among them, Fe-N/C-2 had more excite species for peroxymonosulfate (PMS) owing to the synergy between Fe and N coordination, which achieved 89.36 % tetracycline (TC) removal rate within 20 min, and its reaction kinetic (k = 0.245 min−1) is 7.66 times more than original PMS system. Moreover, the material exhibited excellent activation performance in a variety of complex water environments, such as the coexistence of multiple anions, strong acids and alkalis (pH = 2.90 ∼ 10.73), and natural organic matter interference. Chemical bond detection confirmed the successful formation of FeNx sites, free radical trapping experiments showed that FeNx was the main catalytic site, and 1O2 was the main active component. Furthermore, the reaction principle of the FeNx site catalyzing the production of 1O2 from PMS was revealed in detail through mechanism exploration. Next, the probable pathways of TC decomposition were elaborated in terms of the intermediates identified by Liquid Chromatograph Mass Spectrometer (LC-MS). This study emphasized the significant potential of synthesizing Fe-N/C catalysts with activated FeNx sites, elucidated mechanism of FeNx in PMS activation, and confirmed its feasibility in TC degradation.

Construction of 2D porous g-C3N4 by steam reforming with the introduction of Fe clusters forming Fe-Nx to enhance photo-Fenton catalytic activity

In this study, the Fe clusters were anchored onto 2D porous g-C3N4 nanosheets to synthesize Photo-Fenton catalysts Fe-CNS with highly and uniformly dispersed Fe-Nx active sites via a supramolecular thermal polymerization and subsequent impregnation strategy. The obtained Fe-CNS composites exhibited excellent Photo-Fenton catalytic activity and stability even under high pH and anion conditions, suggesting Fe clusters doping into 2D porous g-C3N4 nanosheets host through Fe-Nx coordination structures enhanced the separation efficiency of light-generated charge carriers, promoted Fe3+/Fe2+ redox cycle, accelerated the activation of H2O2 and improved the stability of Fe species and leading to a remarkable Photo-Fenton synergistic effect. Among these Fe-CNS composites, Fe-CNS with doping amount of 7 % Fe species shows superior Photo-Fenton activity for the elimination of Tetracycline (TC), and the corresponding k value is 0.04729 min−1, which is 25.4 times superior to that of photocatalytic oxidation TC of bulk g-C3N4, indicating that the strategy on changing Fe doping amount yielded opportunity to optimize Photo-Fenton combined action between Fe clusters and g-C3N4 nanosheets host. The degradation mechanism of TC using Fe-CNS composites in the Photo-Fenton system has been further elucidated by considering that the embedded Fe clusters in the N-rich 2D g-C3N4 nanosheets form abundant Fe-Nx active sites.

Microenvironment Tailoring of NiCo Alloys Coupled with FePc as Efficient Bifunctional Catalysts for High-Rate Zn-Air Batteries.

The practical application of Zn-air batteries require exploring cost-effective and durable bifunctional electrocatalysts. However, the simultaneous preparation of catalysts with bifunctional activities for oxygen reduction reaction (ORR) and oxygen precipitation reaction (OER) remains challenging. Herein, we synthesized a novel hybrid catalyst (FePc/NiCo/CNT), which couples NiCo alloy with FePc through electrostatic interaction. The interaction between FePc and NiCo alloy can enhance the intrinsic catalytic activity of the active site Fe-N4 and prevent the electrolyte corrosion of the metal alloy, ultimately improving the stability of the catalyst by the microenvironment-tailoring strategy. The resultant FePc/NiCo/CNT catalyst exhibits outstanding oxygen reduction reaction (ORR) activity with a half-wave potential of 0.88 V, which is attributed to the abundant Fe-Nx active sites. Furthermore, the electron interactions between NiCo/CNT and FePc accelerate electron transfer and enhance the activation of oxygen intermediates, consequently boosting the OER activity with an overpotential of 260 mV at 10 mA cm-2. The Zn-air batteries assembled with FePc/NiCo/CNT show a high power density of 175.1 mW cm-2 and excellent cycling stability for up to 430 h at 20 mA cm-2. The preparation of oxygen electrode catalysts for renewable clean energy devices can be made more convenient with this directly engineered strategy for ORR and OER active centers.

Fe, N Co-doped amine-functionalized MIL 101(Al)-derived mesoporous carbon-based catalysts as high-performance ORR cathode material for Zn-Air battery

The investigation of effective non-noble metal carbon catalysts for oxygen reduction reactions is of great significance importance in Zn-air batteries. Among them, carbon-based materials obtained from metal-organic frameworks (MOFs) demonstrate outstanding catalytic activity in ORR. However, most MOFs-derived catalysts are microporous, which results in poor mass transfer and low utilization of FeNX active sites. In this study, amine-functionalized MIL 101(Al) (NH2-MIL-101) precursors with mesoporous cage structure are synthesized. N-doped carbon carriers with mesoporou structures are prepared at various pyrolysis temperatures. Subsequently, the carbon materials are doped with Fe(phen)32+ complexes and pyrolyzed once more to fabricate highly efficient Fe-Phen-MIL101 catalyst with abundant FeN active sites. The obtained catalyst has a half-wave potential of 0.86 V, which is higher than that of the commercial Pt/C of 0.82 V. Notably, the assembled liquid Zn-air battery (ZAB) exhibits high power density of 120.6 mW cm−2, specific capacity of 725.17 mAh gZn−1, and remarkable cycling stability.

A Simple Approach for Modulating the Active Site in Fe-Based Electrocatalysts

Proton Exchange Membrane Fuel Cells (PEMFCs) have garnered attention as a next-generation, environmentally friendly energy solution to address issues like the climate crisis and depletion of fossil fuels resulting from excessive usage. Nevertheless, the commercialization of PEMFCs faces challenges due to the use of expensive platinum catalysts for the Oxygen Reduction Reaction (ORR). In contrast, Anion Exchange Membrane Fuel Cells (AEMFCs) offer advantages by utilizing cost-effective non-platinum catalysts, making ongoing research on non-platinum catalysts for AEMFCs essential. Numerous studies have been conducted to develop M-N-C catalysts in nanoparticle units using transition metals such as Fe, Co, and Ni for AEMFCs. Notably, Fe-based catalysts with FeNx active sites are considered representative candidates for AEMFCs. Moreover, recent research aims to advance Fe catalysts by incorporating single-atom active sites to enhance mass transfer and improve reaction efficiency at the atomic level.We have developed a straightforward method for synthesizing an Fe catalyst. The catalyst, synthesized through a redox reaction between aniline and a metal ion, followed by pyrolysis, exhibited remarkable durability and activity for the Oxygen Reduction Reaction (ORR). Notably, it possesses an active FeNx site crucial for ORR. Furthermore, by simply altering the solvent during the synthesis process, we observed a variation in the Fe-to-N ratio. Particularly noteworthy was the synthesis of Fe4N, which demonstrated activity for the Oxygen Evolution Reaction (OER). This synthesis method allows for the controlled manipulation of the catalyst's chemistry by varying the solvent, resulting in the production of Fe-based catalysts with either FeNx or Fe4N active sites, active for ORR and OER, respectively. To understand the catalyst's characteristics based on the solvent used during synthesis, we conducted a comprehensive characterization using techniques such as Thermogravimetric Analysis (TGA), X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM). The electrochemical activity was investigated through a half-cell test, and efforts were made to interpret the results based on the catalyst's properties.

High performance bagasse based iron–nitrogen-carbon catalyst for oxygen reduction reaction

The design and synthesis of highly stable and low-cost for the oxygen reduction reactions (ORR) catalysts to replace non-noble metal catalysts is crucial for their applications in fuel cells. In this work, bagasse activated carbon (BAC) was used as the carbon source to prepare the high specific area and multi-porous carbon. The BAC@FeN catalysts derived from BAC, FeCl2 and melamine were prepared by pre-activation treatment and high-temperature pyrolysis. The BAC@FeN-900–30 catalyst encapsulated with Fe3C and Fe3O4 exhibited an outstanding catalytic activity (Eonset = 1.01 V and E1/2 = 0.87 V) and superior operational stability of 90.50 % compared to Pt/C (20 wt%) catalyst. The results demonstrated that iron, carbon and nitrogen piggybacked BAC could generate abundant Fe-Nx active sites, which greatly improved the catalytic activity of ORR and had a broad application prospect in energy conversion.

FeNC@nitrogen doped porous carbon leaf-carbon nanotube hybrids for oxygen reduction reaction

A series of nitrogen doped porous carbon leaf-carbon nanotubes incorporated FeNx electrocatalysts (FeNC@NCL-CNT) are prepared by pyrolysis of Fe doped leaf-like Zn-zeolitic imidazolate framework (FeZn-ZIF-L) with different Fe contents. Among the catalysts, FeNC@NCL-CNT-3 exhibits the highest ORR activity in alkaline solution with onset potential (Eonset) of 0.95 V, half-wave potential (E1/2) of 0.81 V, and limiting diffusion current density of 6.14 mA cm−2. The Eonset and E1/2 of FeNC@NCL-CNT-3 are positively shifted by ca. 20 and 6 mV, respectively compared with Pt/C. The self-generated CNT caused by Fe catalysis improves the electronic conductivity and enlarges the average pore size of the catalyst from 1.77 to 8.12 nm. The highest density of pyridine-N and Fe-Nx active sites (50.7 %) and the largest electrochemically active surface area (ECSA, 1075 cm2) also contribute to its superior activity. The Tafel slope of FeNC@NCL-CNT-3 is 75.4 mV dec-1, which is close to that of Pt/C. Fe-NCL/CNT-3 shows excellent long-term stability (99.4 % retention) and superior methanol tolerance. It catalyzes ORR through 4e- path.

Rapid Synthesis and Microenvironment Optimization of Hierarchical Porous Fe─N─C Catalysts for Enhanced ORR in Microbial Fuel Cells.

Here, an approach to produce a hierarchical porous Fe-N-C@TABOH catalyst with densely accessible high intrinsic active FeNx sites is proposed. The method involves a single-step pyrolysis of Zn/Fe-zeolitic imidazolate framework (Zn/Fe-ZIF-H) with tetrabutylammonium hydroxide (TABOH) micelles, which is obtained by utilizing TABOH as a structural template and electronic mediator at room temperature for a brief duration of 16min. Notably, the yield of Zn/Fe-ZIF-H is 3.5 times that of Zn/Fe-ZIF-N prepared by conventional method. Results indicate that in addition to expediting synthesis and increasing yield of the Zn/Fe-ZIF-H, the TABOH induces a hierarchical porous structure and fosters the formation of more and higher intrinsic active FeNx moieties in Fex-N-C@TABOH, showing that TABOH is a multifunctional template. Crucially, the increased mesoporosity/external surface area and optimized microenvironment of Fe-N-C@TABOH significantly enhance ORR activity by facilitating the formation of high intrinsic active FeNx sites, increasing accessible FeNx sites, and reducing mass transfer resistance. Through structure tailoring and microenvironment optimization, the resulting Fe-N-C@TABOH exhibits superior ORR performance. DFT calculation further validates that the synergistic effect of these two factors leads to low ORR barrier and optimized *OH adsorption energy. This study underscores the importance of structure and electronic engineering in the development of highly active ORR catalysts.

Fe-Phenanthroline derived FeNx coordinated chitosan effectively activates peroxymonosulfate to degrade tetracycline through both radical and non-radical pathways

Fe-Nx sites can activate peroxymonosulfate (PMS) in advanced oxidation processes (AOPs) to produce various reactive oxygen species, and have great potential for removing tetracycline (TC), but their formation and catalytic mechanism are rarely studied. Herein, the Fe/N-C catalyst was prepared by crosslinking chitosan (CS) using a coordination complex of Fe2+ and phenanthroline as the precursor for FeNx. The results of crystal structure, lattice constant, chemical state of N element and structural analysis have demonstrated the successful construction of FeNx sites. The degradation experiments confirmed that the removal efficiency of tetracycline reached up to 90.7 % within 15 min, with a degradation rate of up to 0.184 min−1. Moreover, the material has exhibited excellent performance in complex water environments and within a broad pH range (pH = 2.30 ∼ 9.88). Mechanism analysis proves that the active substances in the system are 1O2, •O2−, SO4•−, •OH and FeIV = O, of which 1O2 played the principal role. The FeNx structure is the primary active site, where the redox cycle between Fe2+ and Fe3+, electron transport between pyridinic N, electron-deficient C and PMS produces active components. In addition, based on the various intermediate products detected, two possible TC degradation pathways are reasonably speculated. In this study, the highly active FeNx sites were successfully constructed, and elucidated their activation mechanism towards PMS, which proved the broad prospect of Fe/N-C materials in pollutant degradation.

Enzymolytic lignin derived Fe–N codoped porous carbon materials as catalysts for oxygen reduction reactions

Numerous active sites and hierarchical pore structures are important for improving catalytic performance for the oxygen reduction reaction (ORR). In this work, a series of iron-nitrogen-doped porous carbon materials (Fe–N–C) with ORR catalytic activity were prepared by a one-step pyrolysis method using enzymolytic lignin as the raw material, soy protein isolate and iron chloride as dopants. The results showed that the samples with the best performance have abundant Fe-Nx active sites and mesoporous structures. At the same time, the electrocatalytic results indicate that the half-wave potential of catalyst was 0.84 V, which reached 96.55% of commercial Pt/C catalysts (E1/2 = 0.86 V), it still preserves an initial current density of 92%, after 10,000 s of circulation, which is much better than Pt/C (86%). Due to the low cost, high activity and stable ORR property, the prepared non-precious metal electrocatalyst will play an important role in the applications of fuel cells.

Coordinately unsaturated single Fe-atoms with N vacancies and enhanced sp3 carbon defects in Fe-N(sp2)-C structural units for suppression of cancer cell metabolism and electrochemical oxygen evolution.

Installing coordinately unsaturated Fe-N-C structural units on polymer-composite-derived N-doped carbon offers highly active Fe-Nx sites for the electrochemical oxygen evolution reaction (OER) and reactive oxygen species (ROS) generation in tumor cells. An NH4Cl-driven high-temperature etching method was employed for the formation of FeSA950NC with coordinately unsaturated single Fe-atoms in an Fe-N(sp2)-C structural unit together with N vacancies (VN) and sp3 defects. The carbonization of Fe-phen@ZIF-8 at 800 °C for 30 min under argon, followed by grinding Fe-ZIF-8@RF-urea with NH4Cl at 950 °C for 2 hours, resulted in sp3 carbon defects and VN sites with coordination unsaturation in Fe-Nx due to NH4Cl decomposition to NH3 and HCl, which produced substantial internal stress for etching the carbon matrix. FeSA950NC was used to treat both A549 lung cancer cells and NIH3T3 mouse fibroblast cells to determine its potential as an efficient tumor therapeutic strategy using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and ROS assays. Additionally, FeSA950NC provided high stability and excellent OER activity through the Fe-N(sp2)-C structural unit on pyridinic nitrogen by delivering at a minimum overpotential of 300 mV, which is much lower than that of structurally similar Fe-atom sites. The significantly stronger ROS and OER activities of FeSA950NC suggested the role of VN and sp3-carbon defects with coordinately unsaturated Fe-N2 sites in improving its catalytic performance.

Operando x-Ray Absorption Spectroscopy Investigation of Secondary Metal Doping into Iron-Nitrogen-Carbon Catalysts for Oxygen Electroreduction

Oxygen reduction reaction (ORR) plays a key role in the development of fuel cell technology, and great efforts have been made to reduce the amount of platinum, required to speed up this sluggish reaction, or, even more desirable, to use efficient electrocatalysts based on earth-abundant metals. To date, numerous single-atom catalysts in the form of metal-doped carbon-nitrogen materials (MNC) have proved to be a promising alternative to ORR Pt-based materials. [1-3]In this study we employed advanced spectroscopic techniques, namely Mössbauer spectroscopy and operando X-ray absorption (XAS) spectroscopy, to understand the structural and electronic factors underlying an increase in the catalytic turn over frequency (TOF) of bimetallic FeSnNC and FeCoNC catalysts, relative to the parent FeNC materials. In particular, 57Fe Mössbauer spectroscopy identified a larger ratio of D1/D2 species in both bimetallic catalysts, supporting a larger ratio of Fe(III)-Nx/Fe(II)-Nx sites. The combination of extended X-ray absorption fine structure (EXAFS) modeling, and the analysis of operando X-ray absorption near-edge spectroscopy (XANES) spectra revealed a disordered carbon structure around FeNx active sites, and variations in the iron oxidation state that can be linked to the enhanced intrinsic catalytic reactivity (TOF). This talk is therefore intended to draw attention to the potential of the XAS technique, especially when applied to in-situ/operando studies in the field of electrocatalysis. References F. Luo, A. Roy, L. Silvioli, D.A. Cullen, A. Zitolo, M.T. Sougrati, I.C. Oguz, T. Mineva, D. Teschner, S. Wagner, J. Wen, F. Dionigi, U.I. Kramm, J. Rossmeisl, F. Jaouen and P. Strasser. P-block single-metal-site tin/nitrogen-doped carbon fuel cell cathode catalyst for oxygen reduction reaction. Nature Materials 2020, 19, 1215-1223A. Zitolo, N. Ranjbar, T. Mineva, J. Li, Q. Jia, S. Stamatin, G.F. Harrington, S.M. Lyth, P. Krtil, S. Mukerjee, E. Fonda, F. Jaouen. Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction. Nature Communications 2017, 8(1), 957A. Zitolo, V. Goellner, V. Armel, M. T. Sougrati, T. Mineva, L. Stievano, E. Fonda, F. Jaouen. Identification of catalytic sites for oxygen reduction in iron and nitrogen doped graphene materials. Nature Materials 2015, 14, 937-942

Fe-N-C Oxygen Reduction Catalysts Via Chemical Vapor Deposition in Fluidized Bed Reactor

Metal nitrogen carbon catalysts (MNC) are an attractive substitute for platinum-based catalysts in the oxygen reduction reaction (ORR) in PEM fuel cells. However, state-of-the-art MNC catalysts still suffer from low activity and instability. Li et al. [1] demonstrated the use of zinc imidazolate frameworks (ZIF-8) in chemical vapor deposition (CVD) to form active sites without unwanted particle formation or additional treatment steps. In this method, gaseous iron chloride exchanges the zinc in the precatalyst to form active sites.In this work, we introduce a vertical fluidized bed reactor (FBR) for high-scale synthesis of FeNC via CVD, allowing for uniform dispersion of the precatalyst and better zinc-iron exchange. Furthermore, we investigated the influence of differently sized ZIF-8 on the CVD and the formation of the FeNC catalyst.The final catalysts were characterized for their electrochemical activity in a rotating ring disc setup, their site density via CO-chemisorption, and their respective turnover frequency. The physicochemical characterization includes the analysis of surface area and pore structure via nitrogen physisorption, SEM, and TEM, as well as surface structure and compositional analysis via elemental analysis, ICP-OES, and XPS.The exchange of Zn was in the range of 90%, resulting in an iron content of 3.8 wt% with only the formation of desired Fe-Nx active sites. STEM-EDX imaging shows an even distribution of iron and nitrogen in the catalyst, with mean particle sizes of 110 nm. In rotating disc electrode experiments with 0.5 M sulfuric acid, mass activities of 0.23 A/g at 0.9 V vs RHE were achieved.Commercially nano-scaled ZIF-8 with mean particle sizes of 500 nm, synthesized particles with mean sizes of 110 nm were tested, compared to the commercial ZIF-8 Basolite Z1200 with mean particle sizes of 4.9 µm. We could show improved activity in RRDE of the nano-scaled ZIF-8 materials compared to the macro-scaled Basolite.Applying this highly scalable synthesis method for MNC catalysts could be a viable way to achieve high-performance catalysts for ORR.[1] Li Jiao, Jingkun Li, Lynne Larochelle Richard, Qiang Sun, Thomas Stracensky, et al.. Chemical vapour deposition of Fe–N–C oxygen reduction catalysts with full utilization of dense Fe–N4 sites. Nature Materials, 2021, 20, pp.1385-1391.

The chemical state of iron species influence on the performance of Fe–N–C bifunctional electrocatalyst for Zn–air batteries

Fe–N–C materials have emerged as promising alternatives to precious metals for oxygen reduction reaction/oxygen evolution reaction (ORR/OER). In this study, a strategy is presented to investigate the influence of different chemical states of iron species in Fe–N–C materials on their electrocatalytic performance. Three Fe–N–C catalysts, containing either zero-valent Fe or Fe3O4 nanoparticles, are synthesized using acid pickling, high-speed centrifugation and ultrasound-assisted hydrothermal methods, respectively. The findings manifest that the chemical state of iron significantly affects the electrocatalytic activity of Fe–NX active sites, namely zero-valent Fe enhancing Fe–NX activity while Fe3O4 weakening its activity. Notably, the Fe@FeNC catalyst containing only zero-valent iron, demonstrates the only 0.621 V potential difference between the ORR half-wave potential and the OER potential at 10 mA cm−2. Furthermore, the rechargeable Zn–air battery assembled with Fe@FeNC as the air cathode exhibits a remarkable peak power density of 179.0 mW cm−2, excellent cycling stability over 210 h (with a cycle frequency of one every 10 min), and the minimal voltage gap of 0.710 V. These results reveal the significance of different chemical states of metal-based nanoparticles in Fe–NX activity of Fe–N–C catalysts and offer insights into the rational design of electrocatalysts with exceptional activity and versatile applications.

Identification of the optimal doping position of hetero-atoms in chalcogen-doped Fe–N–C catalysts for oxygen reduction reaction

The excellent oxygen reduction reaction (ORR) activity of Fe–N–C catalysts in acidic media makes them potential for low-cost proton exchange membrane fuel cells. In recent years, it has been shown that heteroatoms (B, O, S, P, Cl, F, etc.) can be used as electron-withdrawing groups to modulate the planar structure and electron distribution of the Fe–Nx active sites to achieve simultaneous improvement of catalytic activity and stability. However, the optimal location of the heteroatoms remains unclear. Here, taking chalcogen heteroatoms (S and Se) as an example, we control the doping positions and investigate their effect on the ORR performance of the Fe–N–C catalysts. The first coordination shell of the iron single atom is identified as the optimal doping position. The optimized catalyst Fe–N3S1/NC and Fe–N3Se1/NC demonstrate improved activity and stability in both half cells and fuel cells. This work provides insights into the enhancement mechanism of heteroatom doping of single-atom catalysts.

ZIF-8-derived Fe-C catalysts: Relationship between structure and catalytic activity toward the oxygen reduction reaction

The oxygen reduction reaction (ORR) activity of carbonized ZIF-8 (CZ) and its Fe-doped derivatives, CZ-A (doped with ammonium iron (II) sulphate) and CZ-B (doped with iron (II) acetate), were examined in both acidic (0.5 M H2SO4) and basic (0.1 M KOH) electrolytes using a rotating disk electrode setup. These data show that the ORR activity of the Fe-doped catalysts is higher than that of pure CZ, with a higher activity in basic than acidic electrolyte. Extensive materials characterization highlights important differences in the sample crystallinity, morphology, porosity, and chemical composition as a function of the deployed precursor. The performance of the prepared catalysts is also impacted by the Fe precursor selection, highlighting the importance of such synthetic parameters in controlling the density and identify of Fe-Nx active sites. These results demonstrate the potential application of Fe-doped carbonized ZIF-8 catalysts for the ORR in basic electrolyte and offer important knowledge for the future design of non-precious metal fuel cell electrocatalysts.

EDA/PANI derived FeNxC with Fe-Nx active sites as room temperature hydrogen storage material

FeNxC is explored as an efficient and cost-effective hydrogen storage material. Fe/Ethylenediamine (EDA) complex formed initially is protected by (Polyaniline) PANI polymer that gets converted to FeNxC through two-step pyrolysis process. In the first pyrolysis, (Iron sulfide) FeS particles are formed, which get converted to Fe3O4 nanoparticles in second pyrolysis. Fe-Nx active sites get exposed in micro/mesoporous carbon matrix after oxide removal through acid wash. Hydrogen adsorption studies are conducted at 25–100 °C temperature, 5–30 bar pressure. The maximum hydrogen storage capacity is observed as 2.83 wt% at 26 bar, 25 °C for the two-step calcined, acid-washed FeNxC-900–800 A, which possesses large surface area of 995 m2/g, pore volume of 0.711 cm3/g when compared to FeNxC-900–800 and FeNxC-900. The adsorption mechanism, spillover occurring at covalently bonded Fe-Nx active sites and subsequent migration, diffusion to get physisorbed within porous carbon surface, leads to the enhancement in the hydrogen adsorption.

Bionic Fe-N-C catalyst with abundant exposed Fe-Nx sites and enhanced mass transfer properties for efficient oxygen reduction

Transition metal and nitrogen co-doped carbon electrocatalysts are promising candidates to replace the precious metal platinum (Pt) in oxygen reduction reactions (ORR). Unfortunately, the electrochemical performance of existing electrocatalysts is restricted due to limited accessibility of active sites. Inspired by jellyfish tentacles, we design an efficient ORR micro-reactor called Fe-Nx/HC@NWs. It features abundant exposed Fe-Nx active sites dispersed on nitrogen-doped cubic carbon cages, which have a hierarchically porous and hairy structure. The accessible, atomically dispersed Fe-Nx sites and the elaborate substrate architecture synergize to provide the catalyst withremarkable ORR catalytic activity, extraordinary long-term stability, and favorable methanol tolerance in an alkaline electrolyte; overall, its performance is comparable to that of commercial carbon-supported Pt. Our synthesis is facile and controllable, paving a new avenue toward advanced non-precious metal-based electrocatalysts for energy storage and conversion.

An electrochemical sensor based on FeCo bimetallic single-atom nanozyme for sensitive detection of H2O2

Efficient catalytic decomposition of H2O2 is accompanied by electron transfer through Fe-Nx active sites of hemin in the human body. Inspired by this reaction process, the Fe SAs/Co CNs were successfully synthesized by combined Co atomic sites with nitrogen-carbon doped Fe single-atom active sites (SAs). The synergy between transition metals not only reduces agglomeration during synthesis but also improves its own electrical conductivity due to the interaction between Fe and Co that promotes the formation of graphite surface. Crucially, the synergistic effect of the Co site significantly enhanced the peroxidase activity of the Fe SAs and the reaction rate of the Fenton-like reaction, resulting in an efficient detection of H2O2. Catalytic kinetic calculations and enzymatic kinetic calculations were used to verify the electron transfer rate and catalytic performance of their constructed electrochemical sensing interfaces. The results showed that Fe SAs/Co CNs@GCE showed better detection performance than Fe SAs CNs@GCE. It was applied successfully to detect H2O2 released from cells in real-time as well. The linear detection range of Fe SAs/Co CNs@GCE for H2O2 was 1–16664 μM, and the detection limit was as low as 0.25 μM. Furthermore, an electrochemical sensing chip was constructed using Fe SAs/Co CNs@SPE and the prepared microfluidic channel. The constructed portable FeSAs/Co CNs@SPE had a linear range of 1–400 μM and a detection limit of 0.36 μM and achieved the recovery detection of H2O2 in serum. The electrochemical sensing interfaces constructed based on Fe SAs/Co CNs all have efficient catalytic performance and excellent real-time hydrogen peroxide detection performance, which have practical application potential for human oxidative stress level detection. And it provides a novel approach to the trace detection of bioactive small molecules.