Fe-Nx Sites Research Articles

High-performance fluoride removal by Fe/N co-doped microporous carbon: Mechanism of capacitive deionization with FeNx sites

Fluoride pollution is becoming increasingly serious with industrial growth. Controlling fluoride pollution have become important environmental issues of global concern. Transition metal nitrides are excellent CDI electrode materials due to their excellent conductivity and electrochemical stability. In this study, FeNx/C was synthesized as an electrode material for using the capacitive deionization (CDI) technique to achieve the effective removal of fluoride ions from wastewater. Its high specific surface area (463.278 mg/g) and high capacitance (44.29 F/g) were demonstrated and it had a high adsorption capacity of 158.33 mg/g. FeN3 and FeN4 were used as the main sites as capacitive deionization for removing fluoride from the water by chemisorption and hydrogen bonding. The higher adsorption energy by density functional calculation also indicated that the existence of Fe-N coordination bond effectively improved its electrosorption capacity. This study is beneficial to provide references and research ideas for removing fluoride in the CDI field.

Iron nanoparticles enhance the efficiency of single-atom Fenton-like catalyst by boosting Fe-NX activity

Single-atom catalysts (SACs) have been widely employed for the removal of organic contaminants via advanced oxidation processes (AOPs). The underlying principle involves central metal atoms that interact synergistically with surrounding atoms in specific ensembles to adsorb reactants and facilitate catalytic reactions. However, comprehensive studies exploring the ensemble effect of SACs in combination with metal nanoparticles relatively rare. In this study, we have synthesized a highly active iron single-atom catalyst (Fe@BC), which features both Fe-Nx coordination sites and iron nanoparticles. Fe@BC exhibits remarkable adsorption and degradation capabilities for bisphenol A across a wide pH range from 3.0 to 11.0. Scavenging experiments coupled with electron paramagnetic resonance analysis have revealed that •OH and O2•− are the key reactive oxygen species within the Fe@BC/PAA system, with •OH playing a crucial role in the removal of bisphenol A (BPA). Our comprehensive characterization analysis has validated the simultaneous presence of Fe nanoparticles and Fe-Nx sites, which are crucial for the catalyst's high activity. Furthermore, our experimental data highlight the importance of the synergistic effect between these two components. Density Functional Theory calculations have provided additional insights, showing that the presence of iron nanoparticles significantly boosts the Fe-Nx sites' activity. This enhancement is achieved by increasing adsorption energy, promoting electron transfer to peracetic acid (PAA), and decreasing the energy barrier for the formation of active species. These findings are vital for the strategic refinement of Fe single-atom catalysts for PAA-based advanced oxidation processes.

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.

Directional Construction of Low-Coordination Fe-N3 Coupled with Intrinsic Carbon Defects for High-Efficiency Oxygen Reduction.

Regulating the coordination environment of Fe-Nx sites is an efficient but challenging approach for promoting the intrinsic catalytic activity of single-atom Fe/N-codoped carbon (Fe-N-C) toward the oxygen reduction reaction (ORR). Herein, low-coordination Fe-N3 sites coupled with carbon vacancies (Fe-N3/CV) are directionally constructed in Fe-N-C via pyrolysis of a metal-organic framework (MOF) precursor with N3-Zn-O-Fe moieties, which are delicately prefabricated by chemically anchoring Fe3+ onto a H2O-etching induced linker-missing Zn-N3 site in the MOF precursor. The optimized Fe-N-C with the Fe-N3/CV sites displays a high ORR half-wave potential of 0.92 V (vs RHE), which is attributed to the optimized electronic structure and binding strengths of the active Fe center toward the ORR intermediates stemming from the synergy of the asymmetric configuration of Fe-N3 as well as the adjacent carbon vacancies. This work could be enlightening for the design and construction of high-activity coupling sites in metal and nitrogen-codoped carbon catalysts.

A rational construction of FexOy-N-ZSM-5 catalyst with graphene structures and FeNx sites for the selective catalytic oxidation of triethylamine

Stabilizing metal species at the atomic level and tuning their catalytic properties is a significant challenge. Herein, an N-doped FexOy-N-ZSM-5 catalyst with layered and chain-like graphene structures is reported. The catalyst can selectively catalyze the oxidation of triethylamine (TEA) with an efficiency of 99.7 % at 240 °C, and maintain an N2 yield of 97.6 % over the reaction temperature range of 240–360 °C. The results indicate that the layered graphene in the catalyst provide anchor sites for active Fe, while the abundant chain-like graphene act as connectors between ZSM-5 and the layered graphene, offering ample opportunities for TEA and its intermediates to contact the catalyst surface. This increases the number of active sites on the catalyst, thereby enhancing the catalytic performance of FexOy-N-ZSM-5. Notably, due to the interaction between FeOx and FeNx species, FexOy-N-ZSM-5 exhibits excellent thermal stability and water resistance, demonstrating promising potential for practical.

Coupling of Fe-Nx sites and Fe nanoparticles on nitrogen-doped porous carbon for boosting oxygen electroreduction in Zn-air batteries

Fe and nitrogen co-doped carbon (Fe-N-C) catalysts have emerged as attractive materials to substitute Pt-based catalysts for the oxygen reduction reaction (ORR) in Zn-air batteries (ZABs). However, the Fe-N-C catalysts with monotypic active component usually endow suboptimal catalytic performance and stability under both acid and alkaline medium. Herein, a nano ZnO template and two-step pyrolysis co-assisted strategy is proposed to achieve the coupling of Fe-Nx sites and metallic Fe nanoparticles in hierarchically porous N-doped carbon for ORR. The nano ZnO template contributes to the formation of meso/macropores structure, while the secondary pyrolysis is beneficial to the creation of more micropores. Besides the advanced hierarchical porosity, the combination of dispersed Fe-Nx sites and dominated metallic Fe nanoparticles is also conducive to boost ORR activity in both acid and alkaline solution. Impressively, the prepared Fe@FeHPNC-P2 electrocatalyst exhibits an excellent half-wave potentials (E1/2) of 0.88 V and 0.79 V in alkaline and acidic electrolyte, respectively. Meanwhile, the assembled liquid Zn-air battery using Fe@FeHPNC-P2 delivers a peak power density of 149.3 mW cm−2 and a maximum energy density of 957.1 Wh kgZn−1 along with long-term stability for 1000 cycles.

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.

Synergizing Fe2O3 Nanoparticles on Single Atom Fe-N-C for Nitrate Reduction to Ammonia at Industrial Current Densities.

The electrochemical reduction of nitrates (NO3 -) enables a pathway for the carbon neutral synthesis of ammonia (NH3), via the nitrate reduction reaction (NO3RR), which has been demonstrated at high selectivity. However, to make NH3 synthesis cost-competitive with current technologies, high NH3 partial current densities (jNH3) must be achieved to reduce the levelized cost of NH3. Here, the high NO3RR activity of Fe-based materials is leveraged to synthesize a novel active particle-active support system with Fe2O3 nanoparticles supported on atomically dispersed Fe-N-C. The optimized 3×Fe2O3/Fe-N-C catalyst demonstrates an ultrahigh NO3RR activity, reaching a maximum jNH3 of 1.95 A cm-2 at a Faradaic efficiency (FE) for NH3 of 100% and an NH3 yield rate over 9 mmol hr-1 cm-2. Operando XANES and post-mortem XPS reveal the importance of a pre-reduction activation step, reducing the surface Fe2O3 (Fe3+) to highly active Fe0 sites, which are maintained during electrolysis. Durability studies demonstrate the robustness of both the Fe2O3 particles and Fe-Nx sites at highly cathodic potentials, maintaining a current of -1.3 A cm-2 over 24 hours. This work exhibits an effective and durable active particle-active support system enhancing the performance of the NO3RR, enabling industrially relevant current densities and near 100% selectivity.

Size-dependent activity of Fe-N-doped mesoporous carbon nanoparticles towards oxygen reduction reaction

The rational design of Fe–N–C catalysts that possess easily accessible active sites and favorable mass transfer, which are usually determined by the structure of catalyst supports, is crucial for the oxygen reduction reaction (ORR). In this study, an oleic acid-assisted soft-templating approach is developed to synthesize size-controlled nitrogen-doped carbon nanoparticles (ranging from 130 nm to 60 nm and 35 nm, respectively) that feature spiral mesopores on their surface (SMCs). Next, atomically dispersed Fe–Nx sites are fabricated on the size-tunable SMCs (Fe1/SMC-x, where x represents the SMC size) and the size-dependent activity toward ORR is investigated. It is found that the catalytic performance of Fe1/SMCs is significantly influenced by the size of SMCs, where the Fe1/SMC-60 catalyst shows the highest ORR activity with a half-wave potential of 0.90 V vs. RHE in KOH electrolyte, indicating that the gas-liquid-solid three-phase interface on the Fe1/SMC-60 enhances the accessibility of Fe–Nx sites. In addition, when using Fe1/SMC-60 as the cathode catalyst in aqueous zinc-air batteries (ZABs), it delivers a higher open-circuit voltage (1.514 V), a greater power density (223 mW cm−2), and a larger specific capacity/energy than Pt/C-based counterparts. These results further highlight the potential of Fe1/SMC-60 for practical energy devices associated with ORR and the importance of size-controlled synthesis of SMCs.

Hybrid high-performance oxygen reduction reaction Fe–N–C electrocatalyst for anion exchange membrane fuel cells

Atomically dispersed active sites and hierarchical porosity in Fe–N–C catalyst materials are essential for efficient oxygen reduction reaction (ORR) electrocatalysis and effective mass transport, respectively. However, the majority of these catalysts fail to deliver outstanding electrocatalytic activity and stumble when used as cathode materials in fuel cells. Herein, we developed a catalyst with partially transformed metallic Fe into Fe-Nx sites embedded in the carbonaceous matrix, and its excellent electrocatalytic performance is attributed to the hybrid nanoparticles and built-in Fe-Nx site structures. The optimized Fe@Fe–N–C catalyst was tested for ORR performance both ex-situ using the rotating (ring)-disk electrode technique and in an anion exchange membrane fuel cell (AEMFC). The Fe@Fe–N–C electrocatalyst exhibited remarkably enhanced ORR activity in alkaline media with a half-wave potential of 0.822 V vs. reversible hydrogen electrode (RHE) and showed the maximum power density (Pmax) of 242 mW cm−2 in an AEMFC test, surpassing the peak power density obtained from the Pt/C cathode catalyst (Pmax = 220 mW cm−2) under H2–O2 conditions. Therefore, the study provides a promising prospect for designing improved, cost-effective, and noble metal-free electrocatalysts for achieving high performance in AEMFCs.

A gasification strategy to anchor Fe, Ni dual-sites on biomass-derived N, P co-doped porous carbon as an efficient bifunctional catalyst for Zn-air batteries

The fabrication of distinct sites on the carbonized substrate as bifunctional oxygen catalysts is pivotal for enhancing the practicality of Zn-air batteries, but remains a formidable challenge. Herein, a gas doping strategy is reported for anchoring Ni nanoparticles and further increasing FeNx sites on biomass-derived Fe, N, and P co-doped porous carbonized materials as highly efficient bifunctional electrocatalysts. The inherent porous structure and heteroatom of rattan tea provide a superior carrier for Fe and Ni-based active species. Notably, the as-prepared Ni@FeNPC/Fef shows unprecedented capability for oxygen reduction reaction and excellent catalytic activity for oxygen evolution reaction. In situ Raman spectroscopy studies shed light on the role of FeNx and heteroatom-doped carbon during the oxygen reduction reaction. Density functional theory calculations verify the catalytic mechanism on various active sites of Ni@FeNPC/Fef. Moreover, the Ni@FeNPC/Fef-based Zn-air battery maintains cyclic stability for over 400 h with negligible voltage degradation. This strategy endows a novel route for converting biomass into practical electrocatalysts for diverse energy-related systems.

Coupling iron-based zeolitic imidazolate Framework-8 and cellulose nanofiber for efficient peroxymonosulfate oxidation

The development of biocompatible Fenton-like catalysts with outstanding activities and stabilities, using low-cost sustainable bio-sourced materials, has garnered significant attention, yet remains a substantial challenge. In this study, we successfully constructed monodispersed iron anchored on a 3D porous N-doped carbon substrate (CNF@Fe-NC) via one-step annealing of Fe-based zeolitic imidazolate frameworks (ZIFs) and bacterial cellulose nanofibers (CNFs) as highly efficient peroxide-activation catalysts. Due to abundant micropores and mesopores in the interconnected CNF support and ZIFs, even after annealing, the obtained catalysts have a specific surface area of up to 739.4 m2/g. Owing to monodispersed Fe-Nx species and abundant nanofibrous structure, CNF@Fe-NC exhibited outstanding catalytic stability and superior activity for peroxymonosulfate (PMS) activation toward organic contaminant oxidation, outperforming the benchmark Fenton system. Surface Fe-Nx sites and CNF defects could adsorb negatively charged PMS to produce nonradical CNF@Fe-NC-PMS* complexes and high-valent iron oxo species (FeV = O), rather than radicals and 1O2, for eliminating pollutants. The strong iron − support electronic interaction and abundant π-conjugation in the CNF support facilitated the efficient adsorption and activation of PMS and the uniformly dispersed Fe species in CNF@Fe-NC improved atom-utilization efficiency. This study provides a clue to design biocompatible cellulosic-based Fenton-like catalysts for the removal of organic contaminants.

Hierarchical carbon with microporous core and mesoporous shell for efficient oxygen reduction application

We synthesize for the first time a novel carbon structure, i.e., “hierarchical core-shell carbon” (HCSC), featuring ordered microporous carbon core and mesoporous carbon shell. The preparation of HCSC is achieved through a two-step approach starting from the formation of hierarchical core-shell zeolite Y (HCSY) in a controllable etching, followed by a chemical vapor deposition using HCSY as the template. The ordered micropores in HCSC provide high specific area and abundant active sites, while the mesoporous shell enhances its efficient mass transfer, making HCSC promising potential as a catalyst support. As a demonstration, HCSC is doped with nitrogen and loaded with Fe single atom (Fe–N/HCSC) and used as an oxygen reduction reaction (ORR) electrocatalyst, exhibiting exceptional catalytic performance in 0.1 M KOH electrolyte, with an onset potential of 1.01 V and a half-wave potential of 0.915 V, significantly higher than those achieved by the commercial 20 wt% Pt/C catalyst. The superior catalytic activity of Fe–N/HCSC is attributed to the mesoporous carbon shell, improving mass transfer efficiency and enhances the accessibility of micropores, enabling the highly dispersed Fe-NX sites to fully utilize their catalytic activity. This study offers an effective solution to address the challenges associated with mass transfer in microporous materials.

Fe-Nx sites coupled with Fe3C on porous carbon from plastic wastes for oxygen reduction reaction.

Isolated Fe-Nx sites coupled with Fe3C nanoparticles co-embedded in N-doped porous carbon were fabricated using polyethylene terephthalate wastes as carbon sources. Benefiting from the synergistic effect between Fe-Nx sites and Fe3C, and the hierarchical porous structure, the catalyst exhibits outstanding ORR performance, realizing the concept of turning trash into treasure.

Dual single-atom sites coupled with graphene-encapsulated core–shell Fe–Cu nanoalloy for boosting the oxygen reduction reaction

The strategic integration of Cu–Nx sites and graphene-encapsulated Fe–Cu core–shell nanoalloys near Fe–Nx sites significantly enhances the performance of Fe single-atom catalysts for the oxygen reduction reaction.

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.

The N-anchoring effect in NH2-functionalized MOF-derived iron-carbon nanomaterials for oxygen reduction.

The incorporation of an iron source into NH2-MOF-5, followed by thermal decomposition, yields a porous metal-carbon catalyst (MOF5A-Fe@NC). This catalyst possesses significant N content, a high degree of graphitization, and abundant Fe-Nx sites, which contribute to enhanced oxygen reduction. Specifically, the obtained MOF5A-Fe@NC demonstrates a positive onset potential (0.972 V), a substantial limiting current density (4.815 mA cm-2), and a small Tafel slope (58.7 mV dec-1), and maintains a high current retention of 96.3% after 10 hours.

Mn Single-Atom Tuning Fe-N-C Catalyst Enables Highly Efficient and Durable Oxygen Electrocatalysis and Zinc-Air Batteries.

Fe-N-C catalyst is one of most promising candidates for oxygen electrocatalysis reaction in zinc-air batteries (ZABs), but achieving sustained high activity is still a challenging issue. Herein, we demonstrate that introducing Mn single atoms into Fe-N-C (Mn1@Fe-N-C/CNTs) enables the realization of highly efficient and durable oxygen electrocatalysis performance and application in ZABs. Multiple characterizations confirm that Mn1@Fe-N-C/CNTs is equipped with Mn-N2O2 and Fe-N4 sites and Fe nanoparticles. The Mn-N2O2 sites not only tune the electron structure of Fe-Nx sites to enhance intrinsic activity, but also scavenge the attack of radicals from Fe-Nx sites for improvement in ORR durability. As a result, Mn1@Fe-N-C/CNTs exhibits enhanced ORR performance to traditional Fe-N-C catalysts with high E1/2 of 0.89 V vs reversible hydrogen electrode (RHE) and maintains ORR activity after 15 000 CV. Impressively, Mn1@Fe-N-C/CNTs also presents excellent OER activity and the difference (ΔE) between E1/2 of ORR and OER potential at 10 mA cm-2 (Ej10) is only 0.59 V, outperforming most reported catalysts. In addition, the maintainable bifunctional activity of Mn1@Fe-N-C/CNTs is demonstrated in ZABs with almost unchanged cycle voltage efficiency up to 200 h. This work highlights the critical role of Mn single atoms in enhancing ORR activity and stability, promoting the development of advanced catalysts.

Heat-Treatment of a Fourteen Membered Macrocyclic Fe Complex for Electrocatalytic Oxygen Reduction

For the broad application of polymer electrolyte fuel cells (PEFCs), the development of non-precious-metal (NPM) catalysts for oxygen reduction is extremely important. To date, many NPM catalyst have been synthesized by pyrolyzing Fe-, N-, and C-containing precursors, but they suffer from the low density and uncertain chemical structure of their active sites. On the contrary, our research group has been studying a fourteen-membered macrocyclic Fe complex, which was inspired by the FeNx sites embed in graphene sheets (Fig. 1).In this study, a fourteen-membered macrocyclic Fe complex was loaded on a carbon support and then heat-treated, and found to be quite active as a non-precious metal oxygen reduction catalyst. The oxygen reduction current at 0.8 V (RHE) was 13.3 A gcat -1. The improvement is attributed to a high turnover frequency rather than the number of active sites. X-ray absorption spectroscopy and temperature programmed decomposition for the Fe complex suggested that the counter anions and the protons on the nitrogen atom in the ligand were eliminated by the heat-treatment. This change probably influenced the adsorption energy of the oxygen species during the oxygen reduction and resulted in the improved catalytic activity (Fig. 2). Simulation based-on the density functional theory well support this hypothesis. Figure 1