PUBLICATIONS

2021
 

Highly Graphitized Fe-N-C Electrocatalysts Prepared from Chitosan Hydrogel Frameworks, G. Daniel, T. Kosmala, F. Brombin, M. Mazzucato, A. Facchin, M. C. Dalconi, D. Badocco, P. Pastore, G. Granozzi, and C. Durante, Catalysts 2021, 11(3), 390 - DOI 10.3390/catal11030390 - OPEN ACCESS

Abstract: The development of platinum group metal-free (PGM-free) electrocatalysts derived from cheap and environmentally friendly biomasses for oxygen reduction reaction (ORR) is a topic of relevant interest, particularly from the point of view of sustainability. Fe-nitrogen-doped carbon materials (Fe-N-C) have attracted particular interest as alternative to Pt-based materials, due to the high activity and selectivity of Fe-Nx active sites, the high availability and good tolerance to poisoning. Recently, many studies focused on developing synthetic strategies, which could transform N-containing biomasses into N-doped carbons. In this paper, chitosan was employed as a suitable N-containing biomass for preparing Fe-N-C catalyst in virtue of its high N content (7.1%) and unique chemical structure. Moreover, the major application of chitosan is based on its ability to strongly coordinate metal ions, a precondition for the formation of Fe-Nx active sites. The synthesis of Fe-N-C consists in a double step thermochemical conversion of a dried chitosan hydrogel. In acidic aqueous solution, the preparation of physical cross-linked hydrogel allows to obtain sophisticated organization, which assure an optimal mesoporosity before and after the pyrolysis. After the second thermal treatment at 900 °C, a highly graphitized material was obtained, which has been fully characterized in terms of textural, morphological and chemical properties. RRDE technique was used for understanding the activity and the selectivity of the material versus the ORR in 0.5 M H2SO4 electrolyte. Special attention was put in the determination of the active site density according to nitrite electrochemical reduction measurements. It was clearly established that the catalytic activity expressed as half wave potential linearly scales with the number of Fe-Nx sites. It was also established that the addition of the iron precursor after the first pyrolysis step leads to an increased activity due to both an increased number of active sites and of a hierarchical structure, which improves the access to active sites. At the same time, the increased graphitization degree, and a reduced density of pyrrolic nitrogen groups are helpful to increase the selectivity toward the 4e- ORR pathway.

Effect of induced Micro- and Meso-porosity on the formation and activity of Fe-N-C active sites for Oxygen Reduction Reaction, M. Mazzucato, G. Daniel, A. Mehmood, T. Kosmala, G. Granozzi, A. Kucernak, C. Durante, Applied Catalysis B: Environmental, Volume 291, 15 August 2021 , - DOI 10.1016/j.apcatb.2021.120068 - OPEN ACCESS

Abstract: Fe-N-C have emerged as one of the best non-PGM alternatives to Pt/C catalysts for the electrochemical reduction of O2 in fuel cells. In this work, we explore the effect of steam and CO2 treatments at high temperatures on the nanometric porous structure of a commercial carbon black. Using those support materials, we synthesize different Fe-N-C catalysts to achieve a better understanding on the role of micro- and mesopores of the support towards catalytic site formation and site activity. Different time and temperature of treatments result in an almost linear increment of surface area and microporous volume, which allows better nitrogen functionalization. Site density evaluation, performed using a recently described NO-stripping technique, showed an increase in site density and TOF which correlates well with the morphology variation. The percentage of active iron increases from 2.65 % to 14.74 % in activated catalysts confirming a better access of electrolyte to the iron sites.

Deactivation, reactivation and super-activation of Fe-N/C oxygen reduction electrocatalysts: gas sorption, physical and electrochemical investigation using NO and O2, P. Boldrin, D. Malko, A. Mehmood, U. I. Kramm, S. Paul, N. Weidler, A. Kucernak, Applied Catalysis B: Environmental, Volume 292, 5 September 2021, 120169, - DOI 10.1016/j.apcatb.2021.120169 - SPIRAL: https://spiral.imperial.ac.uk/handle/10044/1/87903

Abstract: We show that gaseous nitric oxide (NO) and oxygen (O2) are useful molecular probes to uncover complex surface processes in Fe-N/C catalysts. We unravel the difference between using gaseous NO in a temperature programmed desorption experiment and using NO (and progenitors) in an electrochemical experiment. Gas phase O2 adsorption is almost exclusively desorbed as CO2, and continued exposure to oxygen increases the amount of chemisorbed oxygen species on the surface. The oxidation state of the carbon surface is an important activity determining factor, and under normal “electrochemical” conditions many of the active sites are blocked. Only by treatment at 600 °C in Ar can we free those sites for oxygen adsorption, however under atmospheric storage, and especially during the oxygen reduction reaction (ORR), the surface quickly becomes deactivated with chemisorbed oxygen species and water. We demonstrate that the material can be super-activated by reductive electrochemical treatment, both in an electrochemical three electrode cell and in a fuel cell. The energy gained following the treatment is significantly larger than the energetic cost.

Impact of ionomer structuration on the performance of bio-inspired noble- metal-free fuel cell anodes, N. Coutard, T. Ngoc Huan, F. Valentino, R. T. Jane, S. Gentil, E. S. Andreiadis, A. Le Goff, T. Asset F. Maillard, B. Jousselme, A. Morozan, S. Lyonnard, V. Artero and P. Chenevier, Chem. Catalysis – Online 28 Janauary 2021, - DOI 10.1016/j.checat.2021.01.001 - HAL: https://hal-cnrs.archives-ouvertes.fr/hal-03126604 - OPEN ACCESS

Abstract: Molecular-engineered bio-inspired catalysts hold promise for the next generation of proton-exchange membrane fuel cells (PEMFCs). Yet, their implementation in catalytic layers with Nafionionomer faces nanocomposite formulation issues. Here, we use various DuBois nickel catalysts immobilized on carbon nanotubes to exemplify how self-assembly at the mesoscale affects H2 oxidation anode performance. We exploited the reversible activity of these catalysts together with potential-step chronoamperometry to locally produce H2 and probe mass transport within the catalytic layer. Small-angle neutron scattering studies serve to build amodel describing how the surface functionalization drives the structuration of the ionomer and affects the diffusion of protons and gas from and to catalytic centers. This study thus demonstrates that implementation of unconventional catalysts in catalytic layers requires the redesign of the whole system of materials. On the basis of such information, catalytic layer formulation was optimized, allowing order-of-magnitude performance enhancement of noble-metal-free PEMFCs.

Identification of Durable and Non-Durable FeNx Sites in Fe-N-C Materials for Proton Exchange Membrane Fuel Cells, J. Li M.-T. Sougrati, A. Zitolo, J. Ablett, I. C. Oguz, T. Mineva, I. Matanovic, P. Atanassov, A. di Cicco, K. Kumar, L. Dubau, F. Maillard, F. Jaouen, Nature Catalysis 2020 - DOI 10.1038/s41929-020-00545-2 ChemrXiv: 10.26434/chemrxiv.11842431.v1

Abstract: While Fe–N–C materials are a promising alternative to platinum for catalysing the oxygen reduction reaction in acidic polymer fuel cells, limited understanding of their operando degradation restricts rational approaches towards improved durability. Here we show that Fe–N–C catalysts initially comprising two distinct FeNx sites (S1 and S2) degrade via the transformation of S1 into iron oxides while the structure and number of S2 were unmodified. Structure–activity correlations drawn from end-of-test 57Fe Mössbauer spectroscopy reveal that both sites initially contribute to the oxygen reduction reaction activity but only S2 substantially contributes after 50 h of operation. From in situ 57Fe Mössbauer spectroscopy in inert gas coupled to calculations of the Mössbauer signature of FeNx moieties in different electronic states, we identify S1 to be a high-spin FeN4C12 moiety and S2 a low- or intermediate-spin FeN4C10 moiety. These insights lay the groundwork for rational approaches towards Fe–N–C cathodes with improved durability in acidic fuel cells.

2020
 

Upcycling of polyurethane into iron-nitrogen-carbon electrocatalysts active for oxygen reduction reaction, G. Daniel, T. Kosmala, M. C. Dalconi, L. Nodari, D. Badocco, P. Pastore, A. Lorenzetti, G. Granozzi, and C. Durante, Electrochimica Acta Volume 362, 1 December 2020, 137200 - DOI 10.1016/j.electacta.2020.137200

Abstract: World plastic production has increased since industrial-scale production began in the 1940s and while large amount of thermoplastic polymers can be effectively recycled and re-used, undifferentiated polymers or thermoset polymers cannot, and as a result, most of these raw materials end up in landfill or energy recovery in incinerators. The synthesis of carbon nanomaterials from conversion of waste polymers is an alternative, promising approach owing to the high added-value of these products. In particular, novel carbon materials, could translate into interesting and cheap material for the catalytic reduction of oxygen (ORR), a fundamental reaction for the production of H2O2 or in fuel cell and metal air batteries.
This paper presents the synthesis of iron-nitrogen-carbon (Fe-N-C) electrocatalysts starting from a mix of polyethylene (PE) and polyurethane (PU) by adding FeCl3 as an iron source for promoting Fe-Nx sites formation. The two polymers were mixed according to a solvent assisted process employing p-xylene or with a solvent free process using a Brabender plastograph. The blend of thermoplastic and thermoset polymers was converted into Fe-N-C materials in a two-step pyrolysis, where the temperature of second pyrolysis showed to sensitively affect the chemical and textural properties of the resulting material. Depending on the temperature, and initial PE content, the surface area ranges between 195 and 479 m2 g−1, with a preferential formation of micropores. XPS analysis confirmed that the employment of PU leads to the formation of nitrogen functional groups and Fe-Nx sites, while XRD investigation in heating chamber allowed to follow the formation Fe3C, Fe2O3, γ-Fe and α-Fe with temperature rises between 700–1000°C. The new Fe-N-C catalysts were characterized by linear sweep voltammetry at ring disk electrode showing interesting activity for the ORR in both acid and alkaline electrolyte and a selectivity for H2O2 which deeply depends on the type of electrolyte as well as on nitrogen content and on the surface area of the samples.

A comparative perspective of electrochemical and photochemical approaches for catalytic H2O2 production, Y. Sun, L. Han and P. Strasser, Chem. Soc. Rev., 2020, Advance Article, - DOI 10.1039/D0CS00257G - OPEN ACCESS

Abstract: Hydrogen peroxide (H2O2) has a wide range of important applications in various fields including chemical industry, environmental remediation, and sustainable energy conversion/storage. Nevertheless, the stark disconnect between today’s huge market demand and the historical unsustainability of the currently-used industrial anthraquinone-based production process is promoting extensive research on the development of efficient, energy-saving and sustainable methods for H2O2 production. Among several sustainable strategies, H2O2 production via electrochemical and photochemical routes has shown particular appeal, because only water, O2, and solar energy/electricity are involved during the whole process. In the past few years, considerable efforts have been devoted to the development of advanced electrocatalysts and photocatalysts for efficient and scalable H2O2 production with high efficiency and stability. In this review, we compare and contrast the two distinct yet inherently closely linked catalytic processes, before we detail recent advances in the design, preparation, and applications of different H2O2 catalyst systems from the viewpoint of electrochemical and photochemical approaches. We close with a balanced perspective on remaining future scientific and technical challenges and opportunities.

Establishing reactivity descriptors for platinum group metal (PGM)-free Fe–N–C catalysts for PEM fuel cells, M. Primbs, Y. Sun, A. Roy, D. Malko, As. Mehmood, M.-T. Sougrati, P.-Y. Blanchard, G. Granozzi, T. Kosmala, G. Daniel, P. Atanassov, J. Sharman, C. Durante, A. Kucernak, D. Jones, F. Jaouen and P. Strasser, Energy Environ. Sci., 2020, Advance Article, - DOI 10.1039/D0EE01013H - OPEN ACCESS

Abstract: We report a comprehensive analysis of the catalytic oxygen reduction reaction (ORR) reactivity of four of today's most active benchmark platinum group metal-free (PGM-free) iron/nitrogen doped carbon electrocatalysts (Fe–N–Cs). Our analysis reaches far beyond previous such attempts in linking kinetic performance metrics, such as electrocatalytic mass-based and surface area-based catalytic activity with previously elusive kinetic metrics such as the active metal site density (SD) and the catalytic turnover frequency (TOF). Kinetic ORR activities, SD and TOF values were evaluated using in situ electrochemical NO2 reduction as well as an ex situ gaseous CO cryo chemisorption. Experimental ex situ and in situ Fe surface site densities displayed remarkable quantitative congruence. Plots of SD versus TOF (“reactivity maps”) are utilized as new analytical tools to deconvolute ORR reactivities and thus enabling rational catalyst developments. A microporous catalyst showed large SD values paired with low TOF, while mesoporous catalysts displayed the opposite. Trends in Fe surface site density were linked to molecular nitrogen and Fe moieties (D1 and D2 from 57Fe Mössbauer spectroscopy), from which pore locations of catalytically active D1 and D2 sites were established. This cross-laboratory analysis, its employed experimental practices and analytical methodologies are expected to serve as a widely accepted reference for future, knowledge-based research into improved PGM-free fuel cell cathode catalysts.

Stable, Active and Methanol Tolerant PGM-free Surface in Acidic Medium: Electron Tunneling at Play in Pt/FeNC Hybrid Catalysts for Direct Methanol Fuel Cell Cathode, T. Kosmala, N. Bibent, M.-T. Sougrati, G. Drazic, S. Agnoli, F. Jaouen, and G. Granozzi, ACS Catal. Online June 10, 2020, - DOI 10.1021/acscatal.0c01288

Abstract: PGM-free catalysts have high initial activity for O2 reduction reaction, but suffer from low stability in acid medium in PEMFC and DMFC. Here, we shed light on the atomic-scale structure of hybrid Pt/FeNC catalysts (1-2 wt% of Pt), revealing by STEM and EDXS the presence of Pt@FeOx particles. The absence of exposed Pt on the surface is confirmed by the suppression of methanol oxidation reaction and CO stripping experiments. The promising application of such Pt/FeNC catalysts, comprising FeNx sites and Pt@FeOx particles, is demonstrated at the cathode of DMFC. To gain fundamental understanding on the stability in acid medium and on the intrinsic ORR activity of Pt@FeOx, we constructed model surfaces by depositing FeOx films with controlled thickness (from 1.0 to 6.4 nm), fully covering the Pt(111) surface, which resulted stable in acid medium in the potential range 0.45 – 1.05 V vs. RHE. The specific ORR activity of Fe2O3/Pt(111) increases exponentially with decreasing overlayer thickness, which is explained by the tunneling of Pt electrons through Fe2O3. This special phenomenon sheds light onto recently reported excellent durability of Pt/FeNC composites in PEMFC and identify a promising core@shell strategy leading to stable PGM-free surfaces in acid medium, and tolerant to methanol.

Noncovalent Integration of a Bioinspired Ni Catalyst to Graphene Acid for Reversible Electrocatalytic Hydrogen Oxidation, B. Reuillard, M. Blanco, L. Calvillo, N. Coutard, A. Ghedjatti, P. Chenevier, S. Agnoli, M. Otyepka, G. Granozzi and V. Artero, ACS Appl. Mater. Interfaces 2020 - DOI 10.1021/acsami.9b18922- OPEN ACCESS

Abstract: Efficient heterogeneous catalysis of hydrogen oxidation reaction (HOR) by platinum group metal (PGM)-free catalysts in proton-exchange membrane (PEM) fuel cells represents a significant challenge toward the development of a sustainable hydrogen economy. Here, we show that graphene acid (GA) can be used as an electrode scaffold for the noncovalent immobilization of a bioinspired nickel bis-diphosphine HOR catalyst. The highly functionalized structure of this material and optimization of the electrode-catalyst assembly sets new benchmark electrocatalytic performances for heterogeneous molecular HOR, with current densities above 30 mA cm–2 at 0.4 V versus reversible hydrogen electrode in acidic aqueous conditions and at room temperature. This study also shows the great potential of GA for catalyst loading improvement and porosity management within nanostructured electrodes toward achieving high current densities with a noble-metal free molecular catalyst.

2019
 

Accurate Evaluation of Active-Site Density (SD) and Turnover Frequency (TOF) of PGM-Free Metal−Nitrogen-Doped Carbon (MNC) Electrocatalysts using CO Cryo Adsorption, F. Luo, C. H. Choi, M. J.M. Primbs, W. Ju, S. Li, N. D. Leonard, A. Thomas, F. Jaouen and P. Strasser, ACS Catal. 2019, 9, 4841−4852 - DOI 10.1021/acscatal.9b00588 - HAL repository

Abstract: The number of catalytically active sites (site density, SD) and the catalytic turnover frequency (TOF) are critical for meaningful comparisons between catalytic materials and their rational improvement. SD and TOF numbers have remained elusive for PGM-free, metal/nitrogen-doped porous carbon electrocatalysts (MNC), in particular, FeNC materials that are now intensively investigated and widely utilized to catalyze the oxygen reduction reaction (ORR) in fuel cell cathodes. Here, we apply CO cryo sorption and desorption to evaluate SD and TOF numbers of a state-of-art FeNC ORR electrocatalyst with atomically dispersed coordinative FeNx (x ≤ 4) sites in acid and alkaline conditions. More specifically, we study the impact of thermal pretreatment conditions prior to assessing the number of sorption-active FeNx sites. We show that the pretreatment temperature sensitively affects the CO sorption uptake through a progressive thermal removal of airborne adsorbates, which, in turn, controls the resulting catalytic SD numbers. We correlate CO uptake with CO desorption and analyze the observed temperature-programmed desorption characteristics. The CO uptakes increased from 45 nmol·mg–1catalyst at 300 °C cleaning to 65 nmol·mg–1catalyst at 600 °C cleaning, where it leveled off. These values were converted into apparent SD values of 2.7 × 1019 to 3.8 × 1019 surface sites per gram catalyst. Because of similar ORR activity of the pristine catalyst and of the sample after 600 °C cleaning step, we conclude that the nature and number of surface FeNx sites remained largely unaffected up to 600 °C and that cleaning to less than 600 °C was insufficient to free the sites from previously adsorbed species, completely or partially impeding CO adsorption. Cleaning beyond that temperature, however, led to undesired chemical modifications of the FeNx moieties, resulting in higher TOF. In all, this study identifies and recommends a practical and useful protocol for the accurate evaluation of catalytic SD and TOF parameters of PGM-free ORR electrocatalyst, which enables a more rational future catalyst development and improvement.
PDF

Understanding Active Sites in Pyrolyzed Fe−N−C Catalysts for Fuel Cell Cathodes by Bridging Density Functional Theory Calculations and 57Fe Mössbauer Spectroscopy, T. Mineva, I. Matanovic, P. Atanassov, M.-T. Sougrati, L. Stievano, M. Clémancey, A. Kochem, J.-M. Latour, and F. Jaouen,  ACS Catalysis 2019 9 (10), 9359-9371 - DOI 10.1021/acscatal.9b02586 - HAL repository

Abstract: Pyrolyzed Fe–N–C materials are promising platinum-group-metal-free catalysts for proton-exchange membrane fuel cell cathodes. However, the detailed structure, oxidation, and spin states of their active sites are still undetermined. 57Fe Mössbauer spectroscopy has identified FeNx moieties as the most active sites, with their fingerprint being a doublet in low-temperature Mössbauer spectra. However, the interpretation of the doublets for such materials has lacked theoretical basis. Here, we applied density functional theory to calculate the quadrupole splitting energy of doublets (ΔEQS) for a range of FeNx structures in different oxidation and spin states. The calculated and experimental values are then compared for a reference Fe–N–C catalyst, whereas further information on the Fe oxidation and spin states was obtained from electron paramagnetic resonance, superconducting quantum interference device, and 57Fe Mössbauer spectroscopy under external magnetic field. The combined theoretical and experimental results identify the main presence of FeNx moieties in Fe(II) low-spin and Fe(III) high-spin states, whereas a minor fraction of sites could exist in the Fe(II) S = 1 state. From the analysis of the 57Fe Mössbauer spectrum under the external magnetic field and the comparison of calculated and measured ΔEQS values, we assign the experimental doublet D1 with a mean ΔEQS value of around 0.9 mm·s–1 to Fe(III)N4C12 moieties in high-spin state and the experimental doublet D2 with a mean ΔEQS value of around 2.3 mm·s–1 to Fe(II)N4C10 moieties in low and medium spin. These conclusions indicate that D1 corresponds to surface-exposed sites, whereas D2 may correspond either to bulk sites that are inaccessible to O2 or to surface sites that bind O2 weaker than D1.

 
2018
 

Toward Platinum Group Metal-Free Catalysts for Hydrogen/Air Proton-Exchange Membrane Fuel Cells, Jaouen, F.; Jones, D.; Coutard, N.; Artero, V.; Strasser, P.; Kucernak, A.  Johnson Matthey Technology Review, Volume 62, Number 2, 1 April 2018, pp. 231-255(25) - DOI 10.1595/205651318X6968288 - HAL repository - OPEN ACCESS

Abstract: The status, concepts and challenges toward catalysts free of platinum group metal (pgm) elements for proton-exchange membrane fuel cells (PEMFC) are reviewed. Due to the limited reserves of noble metals in the Earth’s crust, a major challenge for the worldwide development of PEMFC technology is to replace Pt with pgm-free catalysts with sufficient activity and stability. The priority target is the substitution of cathode catalysts (oxygen reduction) that account for more than 80% of pgms in current PEMFCs. Regarding hydrogen oxidation at the anode, ultralow Pt content electrodes have demonstrated good performance, but alternative non-pgm anode catalysts are desirable to increase fuel cell robustness, decrease the H2 purity requirements and ease the transition from H2 derived from natural gas to H2 produced from water and renewable energy sources.
PDF


We use cookies to improve our website and your experience when using it. Cookies used for the essential operation of this site have already been set. To find out more about the cookies we use and how to delete them, see our privacy policy. I accept cookies from this site. To find out more about the cookies we use and how to delete them, see our privacy policy.

  I accept cookies from this site.
EU Cookie Directive plugin by www.channeldigital.co.uk