Structural and Reactivity Effects of Secondary Metal Doping into Iron-Nitrogen-Carbon Catalysts for Oxygen Electroreduction.

While improved activity was recently reported for bimetallic iron-metal-nitrogen-carbon (FeMNC) catalysts for the oxygen reduction reaction (ORR) in acid medium, the nature of active sites and interactions between the two metals are poorly understood. Here, FeSnNC and FeCoNC catalysts were structurally and catalytically compared to their parent FeNC and SnNC catalysts. While CO cryo-chemisorption revealed a twice lower site density of M-Nx sites for FeSnNC and FeCoNC relative to FeNC and SnNC, the mass activity of both bimetallic catalysts is 50-100% higher than that of FeNC due to a larger turnover frequency in the bimetallic catalysts. Electron microscopy and X-ray absorption spectroscopy identified the coexistence of Fe-Nx and Sn-Nx or Co-Nx sites, while no evidence was found for binuclear Fe-M-Nx sites. 57Fe Mössbauer spectroscopy revealed that the bimetallic catalysts feature a higher D1/D2 ratio of the spectral signatures assigned to two distinct Fe-Nx sites, relative to the FeNC parent catalyst. Thus, the addition of the secondary metal favored the formation of D1 sites, associated with the higher turnover frequency.

Chemical Kinetic Method for Active-Site Quantification in Fe-N-C Catalysts and Correlation with Molecular Probe and Spectroscopic Site-Counting Methods.

Mononuclear Fe ions ligated by nitrogen (FeNx) dispersed on nitrogen-doped carbon (Fe-N-C) serve as active centers for electrocatalytic O2 reduction and thermocatalytic aerobic oxidations. Despite their promise as replacements for precious metals in a variety of practical applications, such as fuel cells, the discovery of new Fe-N-C catalysts has relied primarily on empirical approaches. In this context, the development of quantitative structure-reactivity relationships and benchmarking of catalysts prepared by different synthetic routes and by different laboratories would be facilitated by the broader adoption of methods to quantify atomically dispersed FeNx active centers. In this study, we develop a kinetic probe reaction method that uses the aerobic oxidation of a model hydroquinone substrate to quantify the density of FeNx centers in Fe-N-C catalysts. The kinetic method is compared with low-temperature Mössbauer spectroscopy, CO pulse chemisorption, and electrochemical reductive stripping of NO derived from NO2- on a suite of Fe-N-C catalysts prepared by diverse routes and featuring either the exclusive presence of Fe as FeNx sites or the coexistence of aggregated Fe species in addition to FeNx. The FeNx site densities derived from the kinetic method correlate well with those obtained from CO pulse chemisorption and Mössbauer spectroscopy. The broad survey of Fe-N-C materials also reveals the presence of outliers and challenges associated with each site quantification approach. The kinetic method developed here does not require pretreatments that may alter active-site distributions or specialized equipment beyond reaction vessels and standard analytical instrumentation.

Chemical vapour deposition of Fe-N-C oxygen reduction catalysts with full utilization of dense Fe-N4 sites.

Replacing scarce and expensive platinum (Pt) with metal-nitrogen-carbon (M-N-C) catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells has largely been impeded by the low oxygen reduction reaction activity of M-N-C due to low active site density and site utilization. Herein, we overcome these limits by implementing chemical vapour deposition to synthesize Fe-N-C by flowing iron chloride vapour over a Zn-N-C substrate at 750 °C, leading to high-temperature trans-metalation of Zn-N4 sites into Fe-N4 sites. Characterization by multiple techniques shows that all Fe-N4 sites formed via this approach are gas-phase and electrochemically accessible. As a result, the Fe-N-C catalyst has an active site density of 1.92 × 1020 sites per gram with 100% site utilization. This catalyst delivers an unprecedented oxygen reduction reaction activity of 33 mA cm-2 at 0.90 V (iR-corrected; i, current; R, resistance) in a H2-O2 proton exchange membrane fuel cell at 1.0 bar and 80 °C.

P-block single-metal-site tin/nitrogen-doped carbon fuel cell cathode catalyst for oxygen reduction reaction.

This contribution reports the discovery and analysis of a p-block Sn-based catalyst for the electroreduction of molecular oxygen in acidic conditions at fuel cell cathodes; the catalyst is free of platinum-group metals and contains single-metal-atom actives sites coordinated by nitrogen. The prepared SnNC catalysts meet and exceed state-of-the-art FeNC catalysts in terms of intrinsic catalytic turn-over frequency and hydrogen-air fuel cell power density. The SnNC-NH3 catalysts displayed a 40-50% higher current density than FeNC-NH3 at cell voltages below 0.7 V. Additional benefits include a highly favourable selectivity for the four-electron reduction pathway and a Fenton-inactive character of Sn. A range of analytical techniques combined with density functional theory calculations indicate that stannic Sn(IV)Nx single-metal sites with moderate oxygen chemisorption properties and low pyridinic N coordination numbers act as catalytically active moieties. The superior proton-exchange membrane fuel cell performance of SnNC cathode catalysts under realistic, hydrogen-air fuel cell conditions, particularly after NH3 activation treatment, makes them a promising alternative to today's state-of-the-art Fe-based catalysts.

Impact of Solution Chemistry on Growth and Structural Features of Mo-Substituted Spinel Iron Oxides.

The effect of crystallizing solution chemistry on the chemistry of subsequently as-grown materials was investigated for Mo-substituted iron oxides prepared by thermally activated co-precipitation. In the presence of Mo ions, we find that varying the oxidation state of the iron precursor from Fe(II) to Fe(III) causes a progressive loss of atomic long-range order with the stabilization of 2-4 nm particles for the sample prepared with Fe(III). The oxidation state of the Fe precursor also affects the distribution of Fe and Mo cations within the spinel structure. Increasing the Fe precursor oxidation state gives decreased Fe-ion occupation and increased Mo-ion occupation of tetrahedral sites, as revealed by the extended X-ray absorption fine structure. The stabilization of Mo within tetrahedral sites appears to be unexpected, considering the octahedral preferred coordination number of Mo(VI). The analysis of the atomic structure of the sample prepared with Fe(III) indicates a local ordering of vacancies and that the occupation of tetrahedral sites by Mo induces a contraction of the interatomic distances within the polyhedra as compared to Fe atoms. Moreover, the occupancy of Mo into the thermodynamic site preference of a Mo dopant in Fe2O3 assessed by density functional theory calculations points to a stronger preference for Mo substitution at octahedral sites. Hence, we suggest that the synthetized compound is thermodynamically metastable, that is, kinetically trapped. Such a state is suggested to be a consequence of the tetrahedral site occupation by Mo ions. The population of these sites, known to be reactive sites enabling particle growth, is concomitant with the stabilization of very small particles. We confirmed our hypothesis by using a blank experiment without Mo ions, further supporting the impact of tetrahedral Mo ions on the growth of iron oxide nanoparticles. Our findings provide new insights into the relationships between the Fe-chemistry of the crystallizing solution and the structural features of the as-grown Mo-substituted Fe-oxide materials.

Evolution Pathway from Iron Compounds to Fe1(II)-N4 Sites through Gas-Phase Iron during Pyrolysis.

Pyrolysis is indispensable for synthesizing highly active Fe-N-C catalysts for the oxygen reduction reaction (ORR) in acid, but how Fe, N, and C precursors transform to ORR-active sites during pyrolysis remains unclear. This knowledge gap obscures the connections between the input precursors and the output products, clouding the pathway toward Fe-N-C catalyst improvement. Herein, we unravel the evolution pathway of precursors to ORR-active catalyst comprised exclusively of single-atom Fe1(II)-N4 sites via in-temperature X-ray absorption spectroscopy. The Fe precursor transforms to Fe oxides below 300 °C and then to tetrahedral Fe1(II)-O4 via a crystal-to-melt-like transformation below 600 °C. The Fe1(II)-O4 releases a single Fe atom that diffuses into the N-doped carbon defect forming Fe1(II)-N4 above 600 °C. This vapor-phase single Fe atom transport mechanism is verified by synthesizing Fe1(II)-N4 sites via "noncontact pyrolysis" wherein the Fe precursor is not in physical contact with the N and C precursors during pyrolysis.

Quantum-Chemical Study of the FeNCN Conversion-Reaction Mechanism in Lithium- and Sodium-Ion Batteries.

We report a computational study on 3d transition-metal (Cr, Mn, Fe, and Co) carbodiimides in Li- and Na-ion batteries. The obtained cell voltages semi-quantitatively fit the experiments, highlighting the practicality of PBE+U as an approach for modeling the conversion-reaction mechanism of the FeNCN archetype with lithium and sodium. Also, the calculated voltage profiles agree satisfactorily with experiment both for full (Li-ion battery) and partial (Na-ion battery) discharge, even though experimental atomistic knowledge is missing up to now. Moreover, we rationalize the structural preference of intermediate ternaries and their characteristic lowering in the voltage profile using chemical-bonding and Mulliken-charge analysis. The formation of such ternary intermediates for the lithiation of FeNCN and the contribution of at least one ternary intermediate is also confirmed experimentally. This theoretical approach, aided by experimental findings, supports the atomistic exploration of electrode materials governed by conversion reactions.

Understanding Fundamentals and Reaction Mechanisms of Electrode Materials for Na-Ion Batteries.

Development of efficient, affordable, and sustainable energy storage technologies has become an area of interest due to the worsening environmental issues and rising technological dependence on Li-ion batteries. Na-ion batteries (NIBs) have been receiving intensive research efforts during the last few years. Owing to their potentially low cost and relatively high energy density, NIBs are promising energy storage devices, especially for stationary applications. A fundamental understanding of electrode properties during electrochemical reactions is important for the development of low cost, high-energy density, and long shelf life NIBs. This Review aims to summarize and discuss reaction mechanisms of the major types of NIB electrode materials reported. By appreciating how the material works and the fundamental flaws it possesses, it is hoped that this Review will assist readers in coming up with innovative solutions for designing better materials for NIBs.

Unraveling the Nature of Sites Active toward Hydrogen Peroxide Reduction in Fe-N-C Catalysts.

Fe-N-C catalysts with high O2 reduction performance are crucial for displacing Pt in low-temperature fuel cells. However, insufficient understanding of which reaction steps are catalyzed by what sites limits their progress. The nature of sites were investigated that are active toward H2 O2 reduction, a key intermediate during indirect O2 reduction and a source of deactivation in fuel cells. Catalysts comprising different relative contents of FeNx Cy moieties and Fe particles encapsulated in N-doped carbon layers (0-100 %) show that both types of sites are active, although moderately, toward H2 O2 reduction. In contrast, N-doped carbons free of Fe and Fe particles exposed to the electrolyte are inactive. When catalyzing the ORR, FeNx Cy moieties are more selective than Fe particles encapsulated in N-doped carbon. These novel insights offer rational approaches for more selective and therefore more durable Fe-N-C catalysts.

Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials.

While platinum has hitherto been the element of choice for catalysing oxygen electroreduction in acidic polymer fuel cells, tremendous progress has been reported for pyrolysed Fe-N-C materials. However, the structure of their active sites has remained elusive, delaying further advance. Here, we synthesized Fe-N-C materials quasi-free of crystallographic iron structures after argon or ammonia pyrolysis. These materials exhibit nearly identical Mössbauer spectra and identical X-ray absorption near-edge spectroscopy (XANES) spectra, revealing the same Fe-centred moieties. However, the much higher activity and basicity of NH3-pyrolysed Fe-N-C materials demonstrates that the turnover frequency of Fe-centred moieties depends on the physico-chemical properties of the support. Following a thorough XANES analysis, the detailed structures of two FeN4 porphyrinic architectures with different O2 adsorption modes were then identified. These porphyrinic moieties are not easily integrated in graphene sheets, in contrast with Fe-centred moieties assumed hitherto for pyrolysed Fe-N-C materials. These new insights open the path to bottom-up synthesis approaches and studies on site-support interactions.

Synthesis, Structure, and Electrochemical Properties of Na3MB5O10 (M = Fe, Co) Containing M2+ in Tetrahedral Coordination.

In the search for new cathode materials for sodium ion batteries, the exploration of polyanionic compounds has led to attractive candidates in terms of high redox potential and cycling stability. Herein we report the synthesis of the two new sodium transition-metal pentaborates Na3MB5O10 (M = Fe, Co), where Na3FeB5O10 represents the first sodium iron borate reported at present. By means of synchrotron X-ray diffraction, we reveal a layered structure consisting of pentaborate B5O10 groups connected through M2+ in tetrahedral coordination, providing possible three-dimensional Na-ion migration pathways. Inspired by these structural features, we examined the electrochemical performances versus sodium and showed that Na3FeB5O10 is active at an average potential of 2.5 V vs Na+/Na0, correlated to the Fe3+/Fe2+ redox couple as deduced from ex situ Mössbauer measurements. This contrasts with the case for Na3CoB5O10, which is electrochemically inactive. Moreover, we show that their electrochemical performances are kinetically limited, as deduced by complementary ac/dc conductivity measurements, hence confirming once again the complexity in designing high-performance borate-based electrodes.

Understanding the roles of anionic redox and oxygen release during electrochemical cycling of lithium-rich layered Li4FeSbO6.

Li-rich oxides continue to be of immense interest as potential next generation Li-ion battery positive electrodes, and yet the role of oxygen during cycling is still poorly understood. Here, the complex electrochemical behavior of Li4FeSbO6 materials is studied thoroughly with a variety of methods. Herein, we show that oxygen release occurs at a distinct voltage plateau from the peroxo/superoxo formation making this material ideal for revealing new aspects of oxygen redox processes in Li-rich oxides. Moreover, we directly demonstrate the limited reversibility of the oxygenated species (O2(n-); n = 1, 2, 3) for the first time. We also find that during charge to 4.2 V iron is oxidized from +3 to an unusual +4 state with the concomitant formation of oxygenated species. Upon further charge to 5.0 V, an oxygen release process associated with the reduction of iron +4 to +3 is present, indicative of the reductive coupling mechanism between oxygen and metals previously reported. Thus, in full state of charge, lithium removal is fully compensated by oxygen only, as the iron and antimony are both very close to their pristine states. Besides, this charging step results in complex phase transformations that are ultimately destructive to the crystallinity of the material. Such findings again demonstrate the vital importance of fully understanding the behavior of oxygen in such systems. The consequences of these new aspects of the electrochemical behavior of lithium-rich oxides are discussed in detail.

An oxysulfate Fe2O(SO4)2 electrode for sustainable Li-based batteries.

High-performing Fe-based electrodes for Li-based batteries are eagerly pursued because of the abundance and environmental benignity of iron, with especially great interest in polyanionic compounds because of their flexibility in tuning the Fe(3+)/Fe(2+) redox potential. We report herein the synthesis and structure of a new Fe-based oxysulfate phase, Fe2O(SO4)2, made at low temperature from abundant elements, which electrochemically reacts with nearly 1.6 Li atoms at an average voltage of 3.0 V versus Li(+)/Li, leading to a sustained reversible capacity of ≈125 mAh/g. The Li insertion-deinsertion process, the first ever reported in any oxysulfate, entails complex phase transformations associated with the position of iron within the FeO6 octahedra. This finding opens a new path worth exploring in the quest for new positive electrode materials.

Engineered magnetic core-shell SiO2/Fe microspheres and "medusa-like" microspheres of SiO2/iron oxide/carbon nanofibers or nanotubes.

Iron oxide (IO) thin coatings of controlled thickness on SiO2 microspheres of narrow size distribution were prepared by decomposition at 160 °C of triiron dodecacarbonyl onto silica microspheres dispersed in diethylene glycol diethyl ether free of surfactant or stabilizer. The dried washed SiO2/IO core-shell microspheres were annealed at different temperatures and time periods under inert (Ar) or reducing (H2) atmosphere. The effect of temperature on the chemical composition, morphology, crystallinity, and magnetic properties of the IO and the elemental Fe nanoparticles type coatings onto the SiO2 core microspheres has been elucidated. "Medusa-like" SiO2/IO/carbon nanofibers and tubes particles were prepared by CVD of ethylene on the surface of the SiO2/IO microspheres at different temperatures. The morphology change of the grafted carbon nanofibers and tubes as a function of the CVD temperature was also elucidated.

Degradation of Fe/N/C catalysts upon high polarization in acid medium.

A comprehensive study of the degradation of a highly active Fe/N/C catalyst in acid medium is reported. An accelerated aging protocol was applied in the temperature range of 20 to 80 °C. From fundamental rotating-disc electrode studies and polymer electrolyte membrane fuel cell investigations combined with identical-location electron microscopy and Mößbauer spectroscopy at various stages of degradation, important insights into the structural and chemical changes of the catalyst were obtained. Most importantly, the degradation is strongly enhanced at elevated temperature, which is correlated to (i) increased carbon-corrosion rate and (ii) parallel non-preferential dissolution of the FeNx-based active sites. The degradation not only leads to a decreased ORR kinetics over time but also induces significant charge- and mass-transport resistances due to the collapse of the electrode structure.

Capacitive-Controlled Prussian White with a Nickel Iron Hexacyanoferrate Composite Cathode for Rapid Sodium Diffusion.

Prussian blue analogues receive tremendous attention owing to their spacious three-dimensional skeleton, high theoretical specific capacity, facile synthesis procedure, and high cost-effectiveness as among the most promising candidates for cathode materials in sodium-ion batteries (SIBs). Nonetheless, the practical specific capacity, especially under high current, is particularly frail due to the sluggish ion diffusion. In this study, the strategy of Ni substitution and formation of water-coordinated Fe is applied to lower the crystal field energy and elevate the active low-spin (LS) Fe content, which leads to a capacitive sodium storage mechanism, resulting in a substantial specific capacity under high current density. The delivered specific capacity of PW-325@2NiFe-55 is 95 mAh g-1 at 50 C, which is 72.5% capacity retention of the one at 0.5 C. Also, it maintains 80.2% of its initial specific capacity after 500 cycles at 5 C. Furthermore, a hypothesis of a joint diffusion-controlled and capacitive mechanism for high-spin (HS) Fe and a mere capacitive mechanism for LS Fe is put forward and verified through potentiastatic tests, operando 57Fe Mössbauer spectroscopy, and ex situ XRD, which provides a new horizon to enhance the electrochemical performance for SIBs.

Lithium and cobalt extraction from LiCoO2 assisted by p(VBPDA-co-FDA) copolymers in supercritical CO2.

Supercritical CO2 (scCO2) extraction assisted by complexing copolymers is a promising process to recover valuable metals from lithium-ion batteries (LIBs). CO2, in addition to being non-toxic, abundant and non-flammable, allows an easy separation of metal-complexes from the extraction medium by depressurization, limiting the wastewater production. In this study, CO2-philic gradient copolymers bearing phosphonic diacid complexing groups (poly(vinylbenzylphosphonic diacid-co-1,1,2,2-tetrahydroperfluorodecylacrylate), p(VBPDA-co-FDA)) were synthesized for the extraction of lithium and cobalt from LiCoO2 cathode material. Notably, the copolymer was able to play the triple role of leaching agent, complexing agent and surfactant. The proof of concept for leaching, complexation and extraction was achieved, using two different extraction systems. A first extraction system used aqueous hydrogen peroxide as reducing agent while it was replaced by ethanol in the second extraction system. The scCO2 extraction conditions such as extraction time, temperature, functional copolymer concentration, and the presence of additives were optimized to improve the metals extraction from LiCoO2 cathode material, leading to an extraction efficiency of Li and Co up to ca. 75 % at 60 °C and 250 bar.

K2Fe(C2O4)2: An Oxalate Cathode for Li/Na-Ion Batteries Exhibiting a Combination of Multielectron Cation and Anion Redox.

The development of multielectron redox-active cathode materials is a top priority for achieving high energy density with long cycle life in the next-generation secondary battery applications. Triggering anion redox activity is regarded as a promising strategy to enhance the energy density of polyanionic cathodes for Li/Na-ion batteries. Herein, K2Fe(C2O4)2 is shown to be a promising new cathode material that combines metal redox activity with oxalate anion (C2O4 2-) redox. This compound reveals specific discharge capacities of 116 and 60 mAh g-1 for sodium-ion batterie (NIB) and lithium-ion batterie (LIB) cathode applications, respectively, at a rate of 10 mA g-1, with excellent cycling stability. The experimental results are complemented by density functional theory (DFT) calculations of the average atomic charges.

Unveiling redox mechanism at the iron centers in the mechanochemically activated conversion of CO2 in the presence of olivine.

The transformation of olivine during the conversion of CO2 to light hydrocarbons activated by mechanochemical treatments at different impact frequencies was studied by a combination of several complementary characterization methods including X-ray diffraction, Raman and 57Fe Mössbauer spectroscopy. Several olivine samples were studied as a function of the milling time, indicating the gradual transformation of FeII-containing olivine into new FeIII-containing weathering products including iron oxides, magnesium iron carbonates and silicates. The results presented here complement those of a previous study on the weathering process of olivine promoted by mechanochemical activation, by demonstrating the role of the redox activity of the iron species during the activation process. These additional spectroscopic results allow us to thoroughly understand the complex weathering mechanism and to correlate it with the efficiency of the CO2 conversion and storage properties of mechanochemically activated olivine. Supplementary Information: The online version contains supplementary material available at 10.1007/s10853-022-06962-x.