Oxygen Reduction Reaction Catalysts Research Articles

Optimized porous nanostructure of carbon fibers enabling excellent stability of Pt-based catalysts for oxygen reduction reaction

Facile synthesis of highly-dispersed Pt-based electrocatalysts on porous carbon supports with strong durability is extremely desirable for oxygen reduction reaction but remains challenging. The influence of pores in carbon supports on the stability and activity of catalysts is ambiguous and needs to be elucidated. Targeting this aim, herein, we prepared a series of carbon nanofibers with tunable pore diameter and specific surface area using the resorcinol-formaldehyde (RF) resins as a model system. Homogeneous composite precursors composed of RF resins and silica colloids were synthesized by the surfactant-assisted simultaneous polycondensation of RF resins and tetraethylorthosilicate (TEOS). The diameter of the pores induced by removal of silica could be controllable tailored through thermal treatment of the composite under various target temperatures. Pt3Co alloy nanoparticles loaded on the as-synthesized porous carbon nanofibers were prepared by an optimized wet-impregnation method. The experimental results indicated that the carbon nanofibers with pore size distribution focused on ∼1.27 nm and ∼2.34 nm provided the best stability without limiting current density decay, and negative shift of half-wave potential (E1/2) and mass activity (MA) loss of Pt after 20000 potential cycles are relatively mild. Conversely, negative shift of 21 mV, 15 mV and 22 mV in E1/2 and mass activity loss of 51.8%, 30.2% and 33.0% were observed for the Pt3Co nanoparticles supported on MC-60, MC-100 and MC-140 matrices which have pore size distribution focused on ∼2.73 nm, ∼2.73 nm as well as ∼4.66 nm, and ∼4.66 nm, respectively. This work demonstrates the importance of micropores and small mesopores for activity and long-term stability enhancement of carbon supported Pt-based electrocatalysts.

Thermochemical Activation of Wood with NaOH, KOH and H3PO4 for the Synthesis of Nitrogen-Doped Nanoporous Carbon for Oxygen Reduction Reaction

Carbonization of biomass residues followed by activation has great potential to become a safe process for the production of various carbon materials for various applications. Demand for commercial use of biomass-based carbon materials is growing rapidly in advanced technologies, including in the energy sector, as catalysts, batteries and capacitor electrodes. In this study, carbon materials were synthesized from hardwood using two carbonization methods, followed by activation with H3PO4, KOH and NaOH and doping with nitrogen. Their chemical composition, porous structure, thermal stability and structural order of samples were studied. It was shown that, despite the differences, the synthesized carbon materials are active catalysts for oxygen reduction reactions. Among the investigated carbon materials, NaOH-activated samples exhibited the lowest Tafel slope values, of −90.6 and −88.0 mV dec–1, which are very close to the values of commercial Pt/C at −86.6 mV dec–1.

Carbon‐Embedded Pt Alloy Cluster Catalysts for Proton Exchange Membrane Fuel Cells

AbstractMinimizing the use of platinum (Pt) in proton exchange membrane fuel cells (PEMFCs) is crucial for expanding the PEMFC market. The most straightforward approach would be to reduce the size of Pt particles. However, small Pt clusters, particularly those <2 nm in size, typically exhibit reduced activity for the oxygen reduction reaction (ORR) due to the overly strong adsorption of oxygen intermediates. Additionally, these small Pt clusters tend to degrade more quickly, resulting in lower durability. In this study, carbon‐embedded Pt alloy cluster catalysts (PtFe, PtCo, PtNi) that demonstrate high activity and durability in the PEMFC cathode are presented. Density functional theory calculations indicate that carbon atoms stably adsorb onto the Fe sites of PtFe clusters, making the neighboring Pt sites active for ORR with an optimal adsorption strength for oxygen intermediates. This research can pave the way for developing durable and efficient ORR catalysts while significantly reducing Pt usage in PEMFCs.

Single-atom Fe catalysts with pyrrolic-type FeN4 sites for efficient oxygen reduction reaction: Identifying the roles of different N species

Developing electrocatalysts with efficient cathode oxygen reduction reaction (ORR), for example, iron-based single-atom catalysts (Fe-SACs), has been deemed necessary to accelerate the commercialisation process of zinc (Zn)–air batteries. Nevertheless, determining how various nitrogen species and active metal centres coordinate on an atomic scale remains unclear and inadequately explained. Herein, we demonstrate a soft-template-aided technique using Fe-containing molecules (e.g. iron phthalocyanine [FePc], Fe-1,10-phenanthroline [Fe-Phen] and Fe-glucose) to enhance the performance of Fe-SACs in terms of ORR. In this technique, FePc molecules can be converted into atomically dispersed pyrrolic-type iron–nitrogen (FeN4) sites during a pyrolytic process. The resultant catalyst exhibits excellent ORR activity (half-wave potential = 0.90 V) in alkaline medium and standing battery performance when used in Zn–air batteries (peak power density = 197.3 mW cm−2 and specific capacity = 796.2 mAh g−1). As per the findings from control experiments and characterisation studies, electron transfer between the support and the active Fe centre amplifies the ORR performance. Theoretical calculations substantiate that Fe sites coordinated with pyrrolic N atoms govern the electronic configuration of the catalysis, reducing the free energy absorption of reaction intermediates and thus increasing its intrinsic ORR capability. Herein, we aim to offer a fresh perspective on the relation between coordination environments and catalytic activity in ORR catalysts.

Carbon Corrosion Induced by Surface Defects Accelerates Degradation of Platinum/Graphene Catalysts in Oxygen Reduction Reaction.

Graphene supported electrocatalysts have demonstrated remarkable catalytic performance for oxygen reduction reaction (ORR). However, their durability and cycling performance are greatly limited by Oswald ripening of platinum (Pt) and graphene support corrosion. Moreover, comprehensive studies on the mechanisms of catalysts degradation under 0.6-1.6V versus RHE (Reversible Hydrogen Electrode) is still lacking. Herein, degradation mechanisms triggered by different defects on graphene supports are investigated by two cycling protocols. In the start-up/shutdown cycling (1.0-1.6V vs.RHE), carbon oxidation reaction (COR) leads to shedding or swarm-like aggregation of Pt nanoparticles (NPs). Theoretical simulation results show that the expansion of vacancy defects promotes reaction kinetics of the decisive step in COR, reducing its reaction overpotential. While under the load cycling (0.6-1.0V vs.RHE), oxygen containing defects lead to an elevated content of Pt in its oxidation state which intensifies Oswald ripening of Pt. The presence of vacancy defects can enhance the transfer of electrons from graphene to the Pt surface, reducing the d-band center of Pt and making it more difficult for the oxidation state of platinum to form in the cycling. This work will provide comprehensive understanding on Pt/Graphene catalysts degradation mechanisms.

Enhanced corrosion protection of rebars in alkaline solutions by ferroporphyrin and the mechanisms of electron consumption and lattice reconstruction

Abstract Reinforced concretes are the primary materials in coastal and offshore engineering. In alkaline environment of concrete, the anodic process is passivation of rebars and the conjugated cathodic process is oxygen reduction reaction (ORR). It is proposed that a novel approach to enhance the passivation films through catalyzed ORR by iron meso-tetra(4-carboxyphenyl)porphine (FeTCPP). The ORR catalyst FeTCPP promotes the formation of passivation film, as it accelerates the consumption of abundant electrons generated and accumulated by the anodic formation of passivation films. The passivation films of rebars are highly defective Fe3O4 semiconductor. The dissolution of interstitial ferrous ions and lattice iron ions produces defects of O ion vacancies, Fe ion vacancies and interstitial Fe ions, and they further cause the formation and accumulation of Fe atom vacancies on the metal surface, leading to the collapse of the passivation films. The FeTCPP adsorbs on the surface of passivation films, hindering the dissolution of lattice iron ions and interstitial ferrous ions, thereby inhibiting the generation and accumulation of Fe atom vacancies and improving the integrity and protective ability of the passivation films.

Synthesis of biomass nitrogen-doped catalysts and their electrocatalytic performance in fuel cells

At present, biomass materials have the characteristics of low cost, stability, and relatively high activity, which is expected to replace platinum-based (Pt) materials as cathode catalysts. In this paper, Zn, Fe-N-C catalyst materials and Fe-N-C catalyst were composited by high-temperature calcination. Their crystal and morphological structures were featured by X-ray diffraction instruments (XRD) and scanning electron microscopy (SEM). Their activity and stability to oxygen reduction were tested by an electrochemical workstation, and it was found that Zn, Fe-N-C catalyst materials had the best performance. The investigation of this paper can furnish an effective method for oxygen reduction reaction catalysts.

NC Loaded PtM Alloy from M-NC with Ultralow Pt Loading for Oxygen Reduction Reaction

Abstract Developing low Pt or non-precious metal catalysts for oxygen reduction reaction (ORR) has becoming necessary in recent years. Herein, PtM alloy anchored on nitrogen-doped carbon (PtM/NC, M=Fe, Co) catalyst with ultralow Pt loading (~1 wt%) is prepared from the simple two-process pyrolysis, namely from C to M-NC then to PtM/NC. The as-prepared PtM/NC (M=Fe, Co) shows an excellent ORR catalytic performance with the peak potential and half-wave potential of 0.901 and 0.870 V for PtFe/NC, 0.868 and 0.845 V for Pt3Co/NC. The ORR on PtM/NC (M=Fe, Co) is a mainly direct 4-electron reaction pathway (3.75-3.90) in alkaline solution. Moreover, they possess good methanol tolerance and stability. Synergistic effect of Pt and M together with N species result in the excellent ORR catalytic activity of PtM/NC (M=Fe, Co). The negative shift of Pt binding energy caused by both lattice contraction and electron orbital coupling from M is beneficial for reducing the d-band center of Pt, weakening the oxygen binding energy and enhancing the ORR intrinsic activity of Pt. The strong interactions between NC and PtM alloy are beneficial for anchoring PtM nanoparticles, promoting the stability of catalyst. This work provides a new strategy for preparing ultralow Pt loading catalysts.

Theoretical insights on 3D transition metal anchored poly[5,10,15,20-tetra(4-ethynylphenyl)porphyrin]diyne as highly efficient bifunctional catalyst toward ORR and OER

Searching for highly active oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalysts is a challenging task in the development of clean energy devices. Herein, by using the poly[5,10,15,20-tetra(4-ethynyl-phenyl)porphyrin]diyne (TEPPD), we designed ORR and OER catalysts by anchoring 3d transition metal into TEPPD (TM@TEPPD, TM = Mn-Zn). Our study indicated that Fe@TEPPD is the best bifunctional catalyst for both ORR and OER. By proposing a proper descriptor, Ni-N3@TEPPD (Ni is only coordinated with three N atoms) is designed and also predicted to be a promising bifunctional catalyst. For Fe@TEPPD, ORR and OER become inactive when the acetylene bond in TEPPD is broken. The surface Pourbaix diagram indicated that on the surface of Fe@TEPPD, ORR and OER can be carried out at the whole pH region due to the high dissolution potential of Fe2+. For Ni-N3@TEPPD, however, the dissolution potential 0.71 V for Ni2+is low. Thus, for Ni-N3@TEPPD, ORR can be carried out only after pH>2.54, while OER is not likely at the whole pH region. This suggested that the conclusions from the free energy changes at URHE=0 and pH=0 could be different when different potentials and pH values are considered.

Bimetallic Center Metal–Organic Framework Catalysts for the Two-Electron Oxygen Reduction Reaction

Bimetallic Center Metal–Organic Framework Catalysts for the Two-Electron Oxygen Reduction Reaction

Interlayer Polymerization to Construct a Fully Conjugated Covalent Organic Framework as a Metal-Free Oxygen Reduction Reaction Catalyst for Anion Exchange Membrane Fuel Cells.

Two-dimensional (2D) covalent organic frameworks (COFs) have a multilayer skeleton with a periodic π-conjugated molecular array, which can facilitate charge carrier transport within a COF layer. However, the lack of an effective charge carrier transmission pathway between 2D COF layers greatly limits their applications in electrocatalysis. Herein, by employing a side-chain polymerization strategy to form polythiophene along the nanochannels, a conjugated bridge is constructed between the COF layers. The as-synthesized fully conjugated COF (PTh-COF) exhibits high oxygen reduction reaction (ORR) activity with narrowed energy band gaps. Correspondingly, PTh-COF is tested as a metal-free cathode catalyst for anion exchange membrane fuel cells (AEMFCs) which showed a maximum power density of 176mWcm-2 under a current density of 533mAcm-2. The density functional theory (DFT) calculation reveals that interlayer conjugated polythiophene optimizes the electron cloud distribution, which therefore enhances the ORR performance. This work not only provides new insight into the construction of a fully conjugated covalent organic framework but also promotes the development of new metal-free ORR catalysts.

A Non‐Macrocycle Thiolate‐Based Cobalt Catalyst for Selective O2 Reduction into H2O

AbstractThe reduction of dioxygen to produce selectively H2O2 or H2O is crucial in various fields. While platinum‐based materials excel in 4H+/4e− oxygen reduction reaction (ORR) catalysis, cost and resource limitations drive the search for cost‐effective and abundant transition metal catalysts. It is thus of great importance to understand how the selectivity and efficiency of 3d‐metal ORR catalysts can be tuned. In this context, we report on a Co complex supported by a bisthiolate N2S2‐donor ligand acting as a homogeneous ORR catalyst in acetonitrile solutions both in the presence of a one‐electron reducing agent (selectivity for H2O of 93 % and TOFi=3 000 h−1) and under electrochemically‐assisted conditions (0.81 V <η<1.10 V, selectivity for H2O between 85 % and 95 %). Interestingly, such a predominant 4H+/4e− pathway for Co‐based ORR catalysts is rare, highlighting the key role of the thiolate donor ligand. Besides, the selectivity of this Co catalyst under chemical ORR conditions is inverse with respect to the Mn and Fe catalysts supported by the same ligand, which evidences the impact of the nature of the metal ion on the ORR selectivity.

Innovative Strategy for Developing PEDOT Composite Scaffold for Reversible Oxygen Reduction Reaction.

Metal-air batteries are an emerging technology with great potential to satisfy the demand for energy in high-consumption applications. However, this technology is still in an early stage, facing significant challenges such as a low cycle life that currently limits its practical use. Poly(3,4-ethylenedioxythiophene) (PEDOT) conducting polymer has already demonstrated its efficiency as catalyst for oxygen reduction reaction (ORR) discharge as an alternative to traditional expensive and nonsustainable metal catalysts. Apart from that, in most electrochemical processes, three phenomena are needed: redox activity and electronic and ionic conduction. Material morphology is important to maximize the contact area and optimize the 3 mechanisms to obtain high-performance devices. In this work, porous scaffolds of PEDOT-organic ionic plastic crystal (OIPC) are prepared through vapor phase polymerization to be used as porous self-standing cathodes. The scaffolds, based on abundant elements, showed good thermal stability (200 °C), with potential ORR reversible electrocatalytic activity: 60% of Coulombic efficiency in aqueous medium after 200 cycles.

Metal–organic framework–derived trimetallic particles encapsulated by ultrathin nitrogen-doped carbon nanosheets on a network of nitrogen-doped carbon nanotubes as bifunctional catalysts for rechargeable zinc–air batteries

Economical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) bifunctional catalysts with high activity aimed at replacing precious metal catalysts for rechargeable zinc-air batteries (ZABs) must be developed. In this study, a multiple hierarchical-structural material is developed using a facile dielectric barrier discharge (DBD) plasma surface treatment, solvothermal reaction, and high-temperature carbonization strategy. This strategy allows for the construction of nanosheets using nitrogen-doped carbon (NC) material-encapsulated ternary CoNiFe alloy nanoparticles (NPs) on a network of NC nanotubes (NCNTs), denoted as CoNiFe–NC@p–NCNTs. Precisely, the presence of abundant CoNiFe alloy NPs and the formation of M–N–C active sites created by transition metals (cobalt, nickel, and iron) coupled with NC can provide superior OER/ORR bifunctional properties. Moreover, the prepared NC layers with a multilevel pore structure contribute to a larger specific surface area, exposing numerous active sites and enhancing the uniformity of electron and mass movement. The CoNiFe0.08–NC@p–NCNTs show remarkable dual functionality for electrochemical oxygen reactions (ORR half-wave potential of 0.811 V, limiting current density of 5.73 mA cm−2 measured with a rotating disk electrode at a rotation speed of 1600 rpm, and OER overpotential of 351 mV at 10 mA cm−2), which demonstrates similar ORR performance to 20 wt% Pt/C and better OER performance than the commercial RuO2. A liquid ZAB prepared using the proposed material has excellent bifunctionality with an open-circuit voltage of 1.450 V and long-term cycling stability of 230 h@10 mA cm−2.

Superior Catalytic Performance and Methanol Tolerance of Co@Mesoporous Graphene Nanocomposites toward Oxygen Reduction Reaction

AbstractThe global energy crisis and growing concerns about environmental pollution have spurred researchers to explore eco‐friendly methods of generating clean energy. Previous studies have often relied on noble metal catalysts to facilitate oxygen reduction reactions (ORR) in energy production reactions. However, their high cost has limited their widespread adoption, making the development of highly active and affordable ORR catalysts a significant challenge. In this study, a vacuum heat treatment technique was employed to fabricate a cobalt‐loaded mesoporous graphene (Co−Gs) nanocomposite. The inclusion of cobalt in graphene enhances the reaction, while the presence of mesoporous graphene provides a larger surface area to accommodate the active sites of Co. This synergistic effect promotes the improvement of catalytic performance. Additionally, the stability and methanol tolerance of Co−Gs nanocomposites is also superior than that of Pt−C. The excellent catalytic performance of the Co−Gs nanocomposite is attributed to a four‐electron pathway within the nanocomposite, as demonstrated by electrocatalytic kinetics investigations. Additionally, the interface interaction between the Co nanoparticles and Gs enhances the efficiency of electron transfer, effectively improving the catalytic performance. These findings highlight the potential of Co‐loaded graphene nanocomposites as highly efficient and cost‐effective electrocatalysts for clean energy application.

High-throughput screening of dual atom catalysts for oxygen reduction and evolution reactions and rechargeable zinc-air battery

We provide the rational design of dual atom catalysts (DACs) supported on nitrogen-doped graphene for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) through high-throughput computational screening of M1M2N6-DAC systems, where M1 and M2 represent Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, or Pt metals. We predict that FeRuN6-DAC at the summit of the volcano plot exhibits a low theoretical ORR overpotential (ηORR) of 0.24 V and a low theoretical OER overpotential (ηOER) of 0.19 V. The low ηORR and ηOER result from the catalytic performance of the Fe site being tuned to electronic properties that facilitate adsorption and desorption of the OH* intermediate. Inspired by these hybrid density functional theory (DFT) computational and machine learning (ML) results, we synthesized FeRuN6-DAC, FeN4-SAC, and RuN4-SAC and characterized them using X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), scanning transmission electron microscopy (STEM), and in-situ electron spin resonance (ESR). Our in-situ ESR spectroscopy signifies that the spin of the Fe active site increases with increasing applied potential due to the increase in the concentration of OH* intermediate on Fe. We verified experimentally the predicted catalytic performances, finding that FeRuN6-DAC leads to an experimental ORR overpotential of 0.29 V with a Tafel slope of 104 mVdec−1 and an OER overpotential of 0.27 V with a Tafel slope of 124 mVdec−1. The rechargeable Zinc-air battery setup was fabricated with FeRuN6-DAC in place of the cathode, showing a maximum power density of 0.45 W/cm2 at the current density of 0.44 A/cm2 and good stability after 120 cycles. According to our findings, we demonstrate that DFT-guided strategies are useful for designing advanced DACs applicable to ORR, OER, and Zinc-air battery applications.

Tailoring Zirconia Supported Intermetallic Platinum Alloy via Reactive Metal‐Support Interactions for High‐Performing Fuel Cells

Developing efficient and anti‐corrosive oxygen reduction reaction (ORR) catalysts is of great importance for the applications of proton exchange membrane fuel cells (PEMFCs). Herein, we report a novel approach to prepare metal oxides‐supported intermetallic Pt alloy nanoparticles (NPs) via the reactive metal‐support interaction (RMSI) as ORR catalysts, using Ni‐doped cubic ZrO2 (Ni/ZrO2) supported L10‐PtNi NPs as a proof of concept. Benefiting from the Ni migration during RMSI, the oxygen vacancy concentration in the support is increased, leading to an electron enrichment of Pt. The optimal L10‐PtNi‐Ni/ZrO2‐RMSI catalyst achieves remarkably low mass activity (MA) loss (17.8%) after 400,000 accelerated durability test cycles in a half‐cell and exceptional PEMFC performance (MA = 0.76 A mgPt−1 at 0.9 V, peak power density = 1.52/0.92 W cm−2 in H2‐O2/‐air, and 18.4% MA decay after 30,000 cycles), representing the best reported Pt‐based ORR catalysts without carbon supports. Density functional theory (DFT) calculations reveal that L10‐PtNi‐Ni/ZrO2‐RMSI requires a lower energetic barrier for ORR than L10‐PtNi‐Ni/ZrO2 (direct loading), which is ascribed to a decreased Bader charge transfer between Pt and *OH, and the improved stability of L10‐PtNi‐Ni/ZrO2‐RMSI compared to L10‐PtNi‐C can be contributed to the increased adhesion energy and Ni vacancy formation energy within the PtNi alloy.

Tailoring Zirconia Supported Intermetallic Platinum Alloy via Reactive Metal-Support Interactions for High-Performing Fuel Cells.

Developing efficient and anti-corrosive oxygen reduction reaction (ORR) catalysts is of great importance for the applications of proton exchange membrane fuel cells (PEMFCs). Herein, we report a novel approach to prepare metal oxides-supported intermetallic Pt alloy nanoparticles (NPs) via the reactive metal-support interaction (RMSI) as ORR catalysts, using Ni-doped cubic ZrO2 (Ni/ZrO2) supported L10-PtNi NPs as a proof of concept. Benefiting from the Ni migration during RMSI, the oxygen vacancy concentration in the support is increased, leading to an electron enrichment of Pt. The optimal L10-PtNi-Ni/ZrO2-RMSI catalyst achieves remarkably low mass activity (MA) loss (17.8%) after 400,000 accelerated durability test cycles in a half-cell and exceptional PEMFC performance (MA = 0.76 A mgPt-1at 0.9 V, peak power density = 1.52/0.92 W cm-2in H2-O2/-air, and 18.4% MA decayafter 30,000 cycles), representing the best reported Pt-based ORR catalysts without carbon supports. Density functional theory (DFT) calculations reveal that L10-PtNi-Ni/ZrO2-RMSI requires a lower energetic barrier for ORR than L10-PtNi-Ni/ZrO2 (direct loading), which is ascribed to a decreased Bader charge transfer between Pt and *OH, and the improved stability of L10-PtNi-Ni/ZrO2-RMSI compared to L10-PtNi-C can be contributed to the increased adhesion energy and Ni vacancy formation energy within the PtNi alloy.

Rational Design of Heteroatom-Doped Fe–N–C Single-Atom Catalysts for Oxygen Reduction Reaction via Simple Descriptor

Rational Design of Heteroatom-Doped Fe–N–C Single-Atom Catalysts for Oxygen Reduction Reaction via Simple Descriptor

Co-N-C axially coordination regulated H2O2 selectivity via water medicated recombination of solute •OH: A new route

The cobalt, earth abundant transition metal, embedded in nitrogen doped carbon material as single atom site (Co-N-C) has been manifested as promising electrochemical oxygen reduction reaction (ORR) catalyst, however the unsatisfying production selectivity has hampered its widespread applications. Herein, the H2O2 selectivity of Co-N-C catalyst has been tailored with Co axial functional groups. Thermodynamically, the selectivity is regulated due to the fine-tuning of the adsorption of the key reaction intermediates (ΔG*OOH), and five functional groups, including −O, –OH, –CN, −CH3 and −SO3, endow the Co-N-C catalyst with superior H2O2 selectivity. Importantly, we unravel a new water medicated recombination of solute •OH reaction pathway for H2O2 production, which was the result of dissociation of *HOOH in explicit water environment. That is, two •OH species reaction in the liquid environment which originated from the creaking of *OOH intermediates due to the weakened O-O bond by the interaction with surrounding water. This study provides foundational understanding for the ORR catalytic mechanism at the electrochemical interface and opens up new avenues for rational design of targeted high efficiency electrocatalysts.