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Iron and nickel phthalocyanines along with different carbon supports, i. e., multi‐walled carbon nanotubes (MWCNT), graphene, carbide‐derived carbon, Vulcan carbon, and mesoporous carbon (MC, from Pajarito Powder, LLC), are used to prepare six bimetallic (Fe, Ni) N‐doped carbon‐based catalysts. The aim of this work is to investigate the electrocatalytic activity of bimetal phthalocyanine‐modified nanocarbon catalysts, e. g., the effect of carbon supports on the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), including the anion‐exchange membrane fuel cell (AEMFC) and rechargeable zinc‐air battery (RZAB) configuration. The catalysts exhibit excellent electrocatalytic activity as exemplified by their half‐wave potential (E1/2) for ORR and the potential at which the OER current density reaches 10 mA cm−2 (Ej=10), but the best performing catalysts are FeNiN−MC (E1/2=0.88 V, Ej=10=1.58 V) and FeNiN−MWCNT (E1/2=0.87 V, Ej=10=1.59 V). In AEMFC analyses, FeNiN−MWCNT cathode provides peak power density (Pmax) of 406 mW cm−2, slightly higher than that of FeNiN−MC (Pmax=386 mW cm−2). Both catalysts exhibit a good RZAB performance (Pmax of 85 mW cm−2 for FeNiN−MWCNT). The assembled RZABs run stably for 48 h without any significant loss of performance. [ABSTRACT FROM AUTHOR]

The development of non‐precious metal cathode catalysts for anion exchange membrane fuel cells (AEMFC) is beneficial for achieving a more affordable and sustainable H2 economy. Herein, we propose a polypyrrole, polythiophene, and multi‐walled carbon nanotube‐based composite material (PPy/PTh/MWCNT) for the electrocatalysis of oxygen reduction reaction (ORR) at the AEMFC cathode. The PPy/PTh/MWCNT catalyst has a tubular micro‐mesoporous structure with high specific surface area. The elemental composition of the catalyst's surface was studied by X‐ray photoelectron spectroscopy. In 0.1 M KOH solution, the ORR half‐wave potential is −0.16 V (SCE) and the electron transfer number is 4. In a single‐cell AEMFC, the PPy/PTh/MWCNT catalyst exhibited a maximum power density of 284 mW cm−2, which is 86 % of the value obtained using commercial Pt/C cathode catalyst under the same testing conditions. [ABSTRACT FROM AUTHOR]

Nitrogen and sulphur co-doped nanocarbon composites based on silicon carbide-derived carbon (SiCDC), carbon nanotubes (CNT) and/or mesoporous carbon (MPC) are prepared for oxygen reduction reaction (ORR) and anion-exchange membrane fuel cell (AEMFC) studies. Thiosemicarbazide is used as nitrogen and sulphur doping agent. The rotating ring-disc electrode (RRDE) measurements exhibit good electrocatalytic activity towards the ORR for all the prepared catalysts in alkaline solution. Obtained materials are rich in pyridinic-N and consist of thiophene-S, which could improve the ORR performance due to the synergistic effect of N and S. Textural properties, including specific surface area (SSA) and porosity parameters are different amongst the three studied N,S-doped nanocomposite materials, which also affect the outcome of AEMFC test results. In AEMFC testing using Aemion+ (AF2-HLE8-10-X, 10 μm) anion-exchange membrane, N,S-SiCDC/MPC (with SSA dft = 952 m2 g−1) shows the highest performance with the peak power density (P max) of 379 mW cm–2. This result is comparable with the performance of Pt/C catalyst in AEMFC (P max = 347 mW cm–2), making N,S-doped nanocomposite materials promising cathode catalyst for AEMFCs. [Display omitted] • Thiosemicarbazide is used as nitrogen and sulphur doping agent of carbon materials. • Textural properties are different amongst the three studied N,S-doped nanocomposites. • The N,S-doped nanocomposite materials exhibit similar ORR activity in alkaline media. • The best-performing cathode catalyst in AEMFC is N,S-SiCDC/MPC, P max = 379 mW cm−2. [ABSTRACT FROM AUTHOR]

[Display omitted] • Catalysts based on Fe and Co phthalocyanine co-doped electrospun carbon nanofibres. • The materials showed high electrocatalytic activity for ORR in alkaline solution. • The optimised catalyst material exhibited good performance in the AEMFC test. • High activity towards the ORR was mainly provided by the active centres of MN 4 type. The successful implementation of renewable energy transition assumes the introduction and widespread use of zero-emission and sustainable energy conversion devices. Anion-exchange membrane fuel cell (AEMFC) is one of the appliances that meets the prescribed criteria. In this study, Fe(II) phthalocyanine and Co(II) phthalocyanine co-doped polyacrylonitrile-based electrospun carbon nanofibre (CNF) catalysts were prepared via pyrolysis. The influence of carbonisation temperature, acid leaching conditions, presence of ionic liquid (IL) as porogen, and the metal phthalocyanine content were investigated. Physical characterisation revealed the nanofibrous structure, high specific surface area, presence of Co-N x , Fe-N x sites, and different N-species with high oxygen reduction reaction (ORR) activity. The catalyst material with the highest ORR performance, D-MN 4 -CNF-IL-A, showed a half-wave potential of 857 ± 6 mV vs. reversible hydrogen electrode in 0.1 M KOH and the maximum power density value of 231 mW cm−2 when applied as a cathode catalyst in the AEMFC. [ABSTRACT FROM AUTHOR]

Silver nanocatalyst (40 wt%) is deposited on commercial mesoporous carbon support material (Ag/C) using two different wet chemical methods, to obtain high electrochemically active surface area. The catalyst materials are characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, thermogravimetric analysis and are evaluated toward the oxygen reduction reaction (ORR) in alkaline media employing the rotating disk electrode method. It is worth noting that the Ag/C leads to oxygen reduction through a direct four-electron pathway in alkaline medium. The silver catalyst on mesoporous carbon exhibits relatively higher mass activity for ORR (38 A g−1) compared to that with Vulcan carbon (32 A g−1) at −0.2 V vs SCE at room temperature. Anion exchange membrane fuel cell shows maximum power density of 310 mW cm−2 with Ag/C cathode catalyst using H 2 and O 2 gases at 65% RH conditions at 65 °C. [Display omitted] • 40 wt% Ag/C catalysts were prepared onto novel mesoporous engineered carbon supports. • ORR on the synthesized Ag-based catalyst materials follows a four-electron pathway. • Mass activity for ORR on Ag/C catalysts surpassed that of Ag/VC. • Peak power density of 310 mW cm−2 with Ag/C cathode was obtained in AEMFC test. [ABSTRACT FROM AUTHOR]

This study presents the preparation of tridoped Fe, N, S carbon-based catalysts using ZIF-8 as the main carbon source and iron(II)acetate, 1,10-phenanthroline, ammonia gas and thiourea as precursors for Fe, N and S elements. Thiourea was mixed via planetary ball-milling with a Fe–N–C catalyst prepared by inert gas pyrolysis, and different pyrolysis conditions were applied thereafter. The main goal of the work is to synthesise active non-precious metal electrocatalysts for oxygen reduction reaction (ORR). High electrocatalytic ORR activity in alkaline media was observed for the two materials obtained after thiourea addition and subsequent pyrolysis. Physico-chemical characterisation revealed successful S- and N-doping for all three catalysts with enhanced porosity for the two materials that were subjected to additional pyrolysis after the thiourea addition. The sulphur doping was highest for the FeNSC3 material that was subjected to a second pyrolysis in N 2 and a third pyrolysis in NH 3 , compared to the FeNSC2 material that was subjected to a single pyrolysis in NH 3 flow after thiourea addition. The ORR activity of FeNSC2 with half-wave potential of 0.88 V was slightly higher than that of FeNSC3, and the former was selected for evaluation as a cathode catalyst in an anion-exchange membrane fuel cell. [Display omitted] [ABSTRACT FROM AUTHOR]

The use of Pt-based cathode catalyst materials hinders the widespread application of anion exchange membrane fuel cells (AEMFCs). Herein, we present a non-precious metal catalyst (NPMC) material based on pyrolysed Fe and Co co-doped electrospun carbon nanofibres (CNFs). The prepared materials are studied as oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalysts in alkaline and acidic environments. High activity towards the ORR in alkaline solution indicated the suitability of the prepared NPMCs for the application at the AEMFC cathode. In the AEMFC test, the membrane-electrode assembly bearing a cathode with the nanofibre-based catalyst prepared with the ionic liquid (IL) (Fe/Co/IL–CNF–800b) showed the maximum power density (P max) of 195 mW cm−2, which is 78% of the P max obtained with a commercial Pt/C cathode catalyst. Such high ORR electrocatalytic activity was attributed to the unique CNF structure, high micro-mesoporosity, different nature of nitrogen species and metal-N x active centres. [Display omitted] • Pyrolysed Fe and Co co-doped electrospun carbon nanofibre catalysts were prepared. • The materials were tested as ORR and OER catalysts in alkaline and acidic media. • Several materials were also employed as cathode catalysts in the AEMFC test. • The prepared nanofibre catalysts were found to have high activity towards the ORR. [ABSTRACT FROM AUTHOR]

[Display omitted] • Synthesis of melamine-phloroglucinol-formaldehyde (MPF) for N -doped porous carbon. • Catalyst materials possess hierarchical porous structure, high specific surface area. • MPF/M = Fe, Co catalysts show high ORR activity in 0.1 M KOH (E 1/2 up to 0.81 V) • M N C catalysts show excellent electrochemical stability for 10,000 potential cycles. • Excellent AEMFC performance (P max = 347, 324 mW cm−2) with MPF/Fe and MPF/Co catalysts. Delving into highly active and cost-efficient electrocatalysts for oxygen reduction reaction (ORR) is crucial for the large-scale application of polymer electrolyte fuel cells. Anion exchange membrane fuel cells (AEMFCs) are promising clean energy devices owing to their mild reaction conditions and the high probability of employing Pt-free catalysts for ORR. Developing the promising non-Pt ORR catalysts for AEMFC is still of great importance. Herein, we report the transition metal (Fe, Co, Mn, and Cu) impregnated melamine-phloroglucinol-formaldehyde (MPF) polymeric networks to derive metal-nitrogen-carbon (M N C) electrocatalysts via a robust synthesis route. The catalysts are screened through variable metal contents and different pyrolysis temperature optimizations by virtue of their ORR activity. The controlled synthesis method resulted to the prominent textural properties of the catalysts with efficient active centers to enhance the ORR performance. Amongst, iron-doped (MPF/Fe), and cobalt-doped (MPF/Co) catalysts are performing better in terms of half-wave potential (E 1/2) values of 0.81 and 0.80 V vs RHE which is attributed to the highly active M−N x sites and hierarchical porous structure of catalysts. Outstanding electrochemical stability in half-cell and high-power density in an AEMFC (up to 347 mW cm−2) made the present work drive to the development of highly efficient M N C catalysts for fuel cell applications. [ABSTRACT FROM AUTHOR]

• Ordered mesoporous carbon (OMC) with 7 nm pores made via green soft-templating route. • OMC, OMC/carbide-derived carbon and OMC/carbon nanotube composites act as supports. • 1,10-phenanthroline, Fe- and Co-acetates are used as doping agents in pyrolysis. • All CoFe-N-C catalysts show high ORR activity in alkaline media (E 1/2 = 0.84 V). • AEMFC performance depends on porous structure and CoFe-N-OMC/CNT is the best catalyst. Cobalt-, iron- and nitrogen-doped ordered mesoporous carbon (OMC)-based electrocatalysts are prepared, characterized, and used as cathode catalysts in anion-exchange membrane fuel cell (AEMFC). The OMC material is synthesized using a green and simple route via soft-template method and without the usage of harsh chemicals. To study the effect of porous structure of carbon support on the electrocatalytic properties, the OMC material is also mixed either with carbide-derived carbon (CDC) or carbon nanotubes (CNTs). Doping of carbon nanomaterials is done via high-temperature pyrolysis in the presence of cobalt and iron acetate as well as 1,10-phenanthroline. The physico-chemical characterization shows that the preparation of OMC and subsequent doping of nanocarbons has been successful, and the catalysts contain single-atom M-N x centres. The initial assessment employing the rotating disc electrode method indicates that all three doped catalyst materials exhibit very high electrocatalytic activity toward the oxygen reduction reaction (ORR) in alkaline media and good stability after 10,000 potential cycles. In AEMFC testing with AEMION+ anion exchange membrane, the prepared cathode catalysts show good performance with CoFe-N-OMC/CNT obtaining the highest peak power density of 336 mW cm–2. Slightly lower AEMFC performance observed for CoFe-N-OMC and CoFe-N-OMC/CDC cathodes indicates that it is influenced by the catalyst's porous structure. It can be concluded that the OMC-based materials are promising cathode catalysts for AEMFC application. [ABSTRACT FROM AUTHOR]

Transition metal- and nitrogen-doped mesoporous carbons are prepared, characterised, and used as oxygen reduction reaction (ORR) electrocatalysts in an anion exchange membrane fuel cell (AEMFC). Novel mesoporous carbon (MPC) based engineered catalyst support is doped using high-temperature pyrolysis in the presence of metal acetate(s) and 1,10-phenanthroline (nitrogen source). Three transition metals are used to prepare materials with the following metal compositions: Fe, Co, CoFe, FeMn, and CoMn. Physico-chemical characterisation shows the success of doping with similar morphology and textural properties of all materials. The rotating ring-disc electrode experiments in alkaline solution show that all five catalysts exhibit good electrocatalytic activity towards the ORR, with Fe-N-MPC, CoFe-N-MPC and FeMn-N-MPC being best-performing materials with excellent stability. The HO 2 – yield depends on the metal composition with Fe-N-MPC and FeMn-N-MPC giving the lowest percentage. The latter two are employed in the AEMFC and reach power densities of 473 and 474 mW cm–2, respectively. [Display omitted] • Mesoporous Engineered Catalyst Support (Pajarito Powder) as base for five catalysts. • 1,10-phenanthroline and Fe-, Co-, and/or Mn-acetates as doping agents in pyrolysis. • M-N-MPC catalysts show high ORR activity in alkaline media (E 1/2 up to 0.9 V). • RRDE experiments revealed low peroxide yield on Fe-containing catalysts. • Excellent AEMFC performance (P max =470 mW cm–2) of Fe-N-MPC and FeMn-N-MPC catalysts. [ABSTRACT FROM AUTHOR]

A new platinum group metal (PGM)-free proton exchange membrane fuel cell (PEMFC) cathode catalyst materials, synthesized using the VariPore™ method by Pajarito Powder, LLC, are characterized for their structure and activity. The physico-chemical analysis of the iron-nitrogen-carbon (Fe-N-C) electrocatalysts show mesoporous carbon material effectively doped with iron and nitrogen. The materials have an average pore size of 7–8 nm and high specific surface area. The Fe-N-C catalysts exhibit good oxygen reduction reaction (ORR) activity in 0.5 M H 2 SO 4 electrolyte with high half-wave potential and sustainable electrochemical stability over 10,000 repeated potential cycles with insignificant losses in their activities. As cathode catalysts in a PEMFC, the Fe-N-C materials deliver remarkably good fuel cell performance at low overpotential approaching that of the commercial Pt catalyst. The high ORR electrocatalytic activity of these Fe-N-C catalysts is credited to the synergy between nitrogen-moieties, specifically pyrrolic-N, pyridinic-N, and graphitic-N, and iron in addition to the high mesoporosity that facilitate an effective reaction path in boosting the electrocatalytic activity and stability. [Display omitted] • State-of-the-art commercial PGM-free catalysts for ORR were characterized and evaluated. • Was shown that active centres are atomically dispersed. • Performance of electrocatalysts was evaluated in industrially manufactured MEA form-factor. • The fuel cell performance is close to the state-of-the-art R&D PGM-free catalysts. [ABSTRACT FROM AUTHOR]

• Pd nanoparticles supported on mesoporous N-doped carbon are compared with Pd/Vulcan. • A characterisation of the catalysts by TEM, BET, XRD, XPS, EDX and Raman analysis. • These catalysts are used for oxygen reduction reaction in acid and alkaline media. • Excellent oxygen reduction reaction activity was observed for all Pd-based catalysts. • Pd catalyst on mesoporous carbon support outperformed Pd/Vulcan in an AEMFC test. In this work three mesoporous nitrogen-doped carbon support materials were evaluated for oxygen reduction reaction (ORR) in comparison to Vulcan carbon in 0.1 M KOH and 0.5 M H 2 SO 4 solutions. Palladium nanoparticles were synthesised using citrate method and the average particle size of 3.9 ± 0.6 nm was obtained, which was determined from transmission electron microscopy (TEM) images. Unique porosities of these mesoporous engineered catalyst supports (ECS) were evaluated using the BET method and all of the materials displayed similar microporosity, altrough mesopore distribution varied greatly between these materials. Three different loadings of the Pd catalyst were applied to the support materials (varying between 20-40 wt% of Pd) to evaluate the support ability to disperse a large amount of Pd. By comparing the 40 wt% Pd loaded ECS-003604 and Vulcan XC-72R it can be noted that the Vulcan carbon-supported Pd catalyst is more agglomerated. The agglomeration of this catalyst is also noticeable from cyclic voltammetry (CV) studies, where the PdO reduction peak shifts to more positive values as compared to the mesoporous Pd/C counterparts. The ORR kinetics were explored using the rotating disc electrode (RDE) method. In acidic media a Pd catalyst supported on a bimodal mesoporous ECS material showed highest specific activity for oxygen electroreduction, while in alkaline the activity difference is less noticeable between the Pd-based electrocatalyst materials. One of the mesoporous N-doped carbon supported Pd catalyst was also compared to Pd/Vulcan cathode in single-cell alkaline anion exchange membrane fuel cell and improved peak power density was observed. [ABSTRACT FROM AUTHOR]