Oxygen Reduction Reaction Pathway Research Articles

Recent Advances in Carbon-Based Single-Atom Catalysts for Electrochemical Oxygen Reduction to Hydrogen Peroxide in Acidic Media

Electrochemical oxygen reduction reaction (ORR) via the 2e− pathway in an acidic media shows great techno-economic potential for the production of hydrogen peroxide. Currently, carbon-based single-atom catalysts (C-SACs) have attracted extensive attention due to their tunable electronic structures, low cost, and sufficient stability in acidic media. This review summarizes recent advances in metal centers and their coordination environment in C-SACs for 2e−-ORR. Firstly, the reaction mechanism of 2e−-ORR on the active sites of C-SACs is systematically presented. Secondly, the structural regulation strategies for the active sites of 2e−-ORR are further summarized, including the metal active center, its species and configurations of nitrogen coordination or heteroatom coordination, and their near functional groups or substitute groups, which would provide available and proper ideas for developing superior acidic 2e−-ORR electrocatalysts of C-SACs. Finally, we propose the current challenges and future opportunities regarding the acidic 2e−-ORR pathway on C-SACs, which will eventually accelerate the development of the distributed H2O2 electrosynthesis process.

Bifunctional mechanism of oxygen evolution reaction and oxygen reduction reaction induced by surface reconstruction in Perovskite electrocatalysts

Elucidation of the relationship among crystal structure, material compositions, and electrocatalytic performance is beneficial to the design of electrocatalysts with high activity. Specially, for bifunctional electrocatalysts, there is a lack of the unified understanding of oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) mechanisms. Based on the first-principles calculations, LaCoO3 surface reconstructions with different OH coverage under OER/ORR condition are determined. Thereby, the different reaction pathways for OER and ORR with the cooperation of Co and O sites are revealed, under which Co and lattice O sites are activated dynamically, and an overpotential of 0.35 V for the OER and 0.44 V for the ORR are obtained. Furthermore, the octahedra lattice distortion-related bifunctional mechanism (DRBM) is proposed from electron structure analysis, and the bifunctional activity of different B-site doped LaCoO3 (LaCoMO3) are studied. Based on this mechanism, we find that OER, ORR, and their bifunctional activity of LaCoMO3 all exhibit a volcano trend as a function of the O-B-O bond angle formed by Co and lattice oxygen. Consequently, we predict that Mn, Cr, Fe, and Ti doped LaCoO3 electrocatalysts exhibit remarkable bifunctional activity, which is corroborated by the reported experimental results.

Second-Shell N Dopants Regulate Acidic O2 Reduction Pathways on Isolated Pt Sites.

Pt is a well-known benchmark catalyst in the acidic oxygen reduction reaction (ORR) that drives electrochemical O2-to-H2O conversion with maximum chemical energy-to-electricity efficiency. Once dispersing bulk Pt into isolated single atoms, however, the preferential ORR pathway remains a long-standing controversy due to their complex local coordination environment and diverse site density over substrates. Herein, using a set of carbon nanotube supported Pt-N-C single-atom catalysts, we demonstrate how the neighboring N dopants regulate the electronic structure of the Pt central atom and thus steer the ORR selectivity; that is, the O2-to-H2O2 conversion selectivity can be tailored from 10% to 85% at 0.3 V versus reversible hydrogen electrode. Moreover, via a comprehensive X-ray-radiated spectroscopy and shell-isolated nanoparticle-enhanced Raman spectroscopy analysis coupled with theoretical modeling, we reveal that a dominant pyridinic- and pyrrolic-N coordination within the first shell of Pt-N-C motifs favors the 4e- ORR, whereas the introduction of a second-shell graphitic-N dopant weakens *OOH binding on neighboring Pt sites and gives rise to a dominant 2e- ORR. These findings underscore the importance of the chemical environment effect for steering the electrochemical performance of single-atom catalysts.

Intrinsic Defect‐Rich Carbon‐Supported Iron Phthalocyanine as Beyond‐Pt Oxygen Reduction Catalysts for Zinc–Air Batteries

Molecular iron phthalocyanine (FePc) bearing a single‐atom Fe–N4 moiety is a high‐profile non‐platinum catalyst toward the oxygen reduction reaction (ORR), but its unsatisfactory activity and inadequate stability hinder the practical application. Herein, a novel strategy by hybridizing FePc with fullerene‐derived intrinsic defect‐rich carbon to improve its ORR activity and stability is reported. Via alkali‐assisted thermal pyrolysis, C60 molecules are disintegrated into tiny fragments that then restructure into pentagon‐ and edge‐rich carbon (FC). Utilizing FC as a support of FePc leads to a significantly improved ORR activity compared to other supports including reduced graphene oxide and carbon nanotube that hold distinct structural features. The optimized FePc/FC with a Fe loading of 3 wt% presents a half‐wave potential of 0.917 V, far beyond that of Pt/C (0.846 V), via selective four‐electron ORR pathway and excellent stability under accelerated stress test. The practical applicability of FePc/FC is also demonstrated as a high‐performing cathode catalyst of aqueous zinc–air batteries. It is, for the first time, explicitly disclosed that strong interactions between FePc molecules and intrinsic carbon defects (e.g., pentagons and edges) not only strengthen the anchoring effect of supported FePc but also enhance the intrinsic ORR activity of single‐atom Fe–N4 sites.

Interfacial engineering of high-performance Fe2P2O7-based electrocatalysts for alkaline exchange membrane fuel cells

Fuel cells promise high energy density and energy conversion efficiency but are plagued by the scarcity of platinum for facilitating the oxygen reduction reaction (ORR). Herein, a facile synthesis of a heterojunction electrocatalyst of ZIF-8 derived carbon (Z8C) supported Fe2P2O7 (Fe2P2O7@Z8C) is reported. The electrocatalyst exhibited higher half-wave potential than the state-of-the-art Pt/C catalyst by more than 33 mV and achieved a peak power density of 152.47 mW cm−2, outperforming the Pt/C-driven cell by ca. 14.5 mW cm−2 in alkaline membrane electrode assemblies under similar operating conditions. X-ray photoelectron and X-ray absorption spectroscopic studies suggested a spontaneous electron redistribution across the heterojunction interface in Fe2P2O7@Z8C. Density functional theory calculations indicated that the electron redistribution may remarkably promote the intrinsic activity of Fe2P2O7@Z8C toward the four-electron ORR pathway. These findings offer an indispensable strategy for rational design of highly efficient and durable non-noble electrocatalysts.

Mechanistic Insights into Surfactant-Modulated Electrode-Electrolyte Interface for Steering H2O2 Electrosynthesis.

Electrocatalytic reactions taking place at the electrified electrode-electrolyte interface involve processes of proton-coupled electron transfer. Interfacial protons are delivered to the electrode surface via a H2O-dominated hydrogen-bond network. Less efforts are made to regulate the interfacial proton transfer from the perspective of interfacial hydrogen-bond network. Here, we present quaternary ammonium salt cationic surfactants as electrolyte additives for enhancing the H2O2 selectivity of the oxygen reduction reaction (ORR). Through in situ vibrational spectroscopy and molecular dynamics calculation, it is revealed that the surfactants are irreversibly adsorbed on the electrode surface in response to a given bias potential range, leading to the weakening of the interfacial hydrogen-bond network. This decreases interfacial proton transfer kinetics, particularly at high bias potentials, thus suppressing the 4-electron ORR pathway and achieving a highly selective 2-electron pathway toward H2O2. These results highlight the opportunity for steering H2O-involved electrochemical reactions via modulating the interfacial hydrogen-bond network.

Ni-doped sites in yeast-derived catalysts for efficient electrochemical synthesis of hydrogen peroxide

The electrochemical synthesis of hydrogen peroxide (H2O2) via the 2-electron pathway of oxygen reduction reaction offers a green and on-site product. However, there remains an urgent need to develop cost-efficient electrocatalysts with H2O2 productivity that meets practical industrial-scale requirements. In this study, yeast-derived carbon material loaded with multiple Ni active sites achieved electrochemical synthesis of H2O2 at industrial current density. The precursor of heteroatom-doped carbon material was obtained through high-dispersed Ni(II) adsorption on yeast cells. By adjusting the pyrolysis temperature and Ni loading dosage, the carbon framework, pore structure, and Ni active sites within the obtained Ni/yeast were successfully regulated. Ni/yeast featured with highly active Ni single-atom sites, metallic Ni nanoparticles and Ni2P nanoparticles, enabling stable running for 10 h at 200 mA cm−2 in a flow cell. Ni/yeast exhibits remarkable H2O2 Faradaic efficiency of 94.6 % and a yield of 35.3 mol gcat−1h−1. The abundant pore structure and multiple Ni active sites within Ni/yeast provide promising avenues for manipulating heteroatom-doped carbon materials in H2O2 electrosynthesis.

Extended H-bonds/π-bonds networks for boosting electron transfer over polydopamine-covered nanocellulose/g-C3N4 toward efficient photocatalytic H2O2 production

Photocatalytic hydrogen peroxide production (PHP) from H2O and O2 is a promising solar-to-chemical conversion technology. However, conventional doping, heterojunction and defect engineering of catalyst modification for enhanced PHP process is unable to meet the highly requirements of efficient oxygen reduction reaction (ORR), while also damaging the intrinsic crystal structure of the catalysts. Herein, we demonstrate a rationally extended H-bonds/π-bonds intermolecular networks between carbon nitride (g-C3N4, CN) and carboxylated cellulose nanofibers (CNF) with a small quantity of polydopamine (PDA) for solar H2O2 production. Ultimately, CN/CNFP exhibits an extraordinary PHP of 130.7 μmol·L−1·h−1, surpassing CN/CNF (75.2 μmol·L−1·h−1) and pure CN (20.1 μmol·L−1·h−1). Experimental and density function theory (DFT) have validated that CNFP increases the adsorption capabilities of O2, enhancing the efficiency of photogenerated charge transfer and separation via multiple hydrogen bonding/π-π stacking with g-C3N4, thereby facilitating the superior PHP via a two-step single-electron ORR pathway. This work offered a viable route to modulate directed transfer of photogenerated charges with multiple intermolecular interactions and presented an encouraging strategy to obtain high-efficient PHP.

Oxygen Reduction Pathway for Spinel Metal Oxides in Alkaline Media: An Experimentally Supported Ab Initio Study.

Precious-metal-free spinel oxide electrocatalysts are promising candidates for catalyzing the oxygen reduction reaction (ORR) in alkaline fuel cells. In this theory-driven study, we use joint density functional theory (JDFT) in tandem with supporting electrochemical measurements to identify a novel theoretical pathway for the ORR on cubic Co3O4 nanoparticle electrocatalysts, which aligns more closely with experimental results than previous models. The new pathway employs the cracked adsorbates *(OH)(O) and *(OH)(OH), which, through hydrogen bonding, induce spectator surface *H. This results in an onset potential closely matching experimental values, in stark contrast to the traditional ORR pathway, which keeps adsorbates intact and overestimates the onset potential by 0.7 V. Finally, we introduce electrochemical strain spectroscopy (ESS), a groundbreaking strain analysis technique. ESS combines ab initio calculations with experimental measurements to validate the proposed reaction pathways and pinpoint rate-limiting steps.

Dual-axial engineering on atomically dispersed catalysts for ultrastable oxygen reduction in acidic and alkaline solutions

Atomically dispersed catalysts are a promising alternative to platinum group metal catalysts for catalyzing the oxygen reduction reaction (ORR), while limited durability during the electrocatalytic process severely restricts their practical application. Here, we report an atomically dispersed Co-doped carbon-nitrogen bilayer catalyst with unique dual-axial Co-C bonds (denoted as Co/DACN) by a smart phenyl-carbon-induced strategy, realizing highly efficient electrocatalytic ORR in both alkaline and acidic media. The corresponding half-wave potential for ORR is up to 0.85 and 0.77 V (vs. reversible hydrogen electrode (RHE)) in 0.5 M H2SO4 and 0.1 M KOH, respectively, representing the best ORR activity among all non-noble metal catalysts reported to date. Impressively, the Zn-air battery (ZAB) equipped with Co/DACN cathode achieves outstanding durability after 1,688 h operation at 10 mA cm-2 with a high current density (154.2 mA cm-2) and a peak power density (210.1 mW cm-2). Density functional theory calculations reveal that the unique dual-axial cross-linking Co-C bonds of Co/DACN significantly enhance the stability during ORR and also facilitate the 4e- ORR pathway by forming a joint electron pool due to the improved interlayer electron mobility. We believe that axial engineering opens a broad avenue to develop high-performance heterogeneous electrocatalysts for advanced energy conversion and storage.

Highly efficient photosynthesis of hydrogen peroxide by a stable Zr(IV)-based MOF with a diamino-functionalized ligand.

Metal-organic frameworks (MOFs) have emerged as a promising class of materials for solar-driven hydrogen peroxide (H2O2) generation due to their porosity, large surface area and designable molecular building blocks; however, producing H2O2 from oxygen and water without sacrificial agents remains a major challenge. Herein, we have constructed two UiO-67-type MOFs, UiO-67-NH2 and UiO-67-(NH2)2, by a solvothermal method using 2-amino-4,4'-biphenyldicarboxylic acid and 2,2'-diamino-4,4'-biphenyldicarboxylic acid as ligands, respectively. A variety of photochemical measurements have shown that the introduction of diamino groups into UiO-67-(NH2)2 not only enhances its absorption ability for visible light, but also facilitates the separation of photogenerated electron/hole pairs. Consequently, compared to monoamino-functionalized UiO-67-NH2, UiO-67-(NH2)2 exhibits a 5.5 times higher H2O2 production rate in pure water for 1 h. A two-step one-electron oxygen reduction reaction pathway for photocatalytic H2O2 production was suggested based on a series of control experiments and active species trapping tests by electron paramagnetic resonance spectra. This work provides new insights into the regulation of functionalized MOF ligands at the molecular level and a catalytic mechanism towards MOF-based photocatalysts for H2O2 production with high activity.

Investigating the Role of Fe‐Pyrrolic N4 Configuration in the Oxygen Reduction Reaction via Covalently Bound Porphyrin Functionalized Carbon Nanotubes

AbstractAtomically dispersed iron–nitrogen–carbon catalysts are promised, low‐cost, and high‐performance electrocatalysts for the Oxygen Reduction Reaction (ORR) in fuel cells. However, most Fe–N–C materials are produced via pyrolysis at a high temperature and it is difficult to characterise the precise Fe–N configurations. This can lead to confusion surrounding the best chemical and coordination environment for Fe and understanding the subsequent ORR mechanisms. In this work, Fe porphyrin is used to produce a specific Fe–N environment, therefore allowing the role and activity of this environment to be studied. Carbon nanotubes (CNTs) are covalently functionalized with iron 5,10,15,20‐triphenylporphyrin (FeTPP) motifs via aryl diazonium methodology, enabling the exact role of only the Fe‐Pyrrolic N4 configuration of FeTPP in ORR to be studied and better understood. Upon covalent functionalization, a high electrochemical active site density of 1.12 × 1015 sites cm−2, approximately six‐fold more than that of noncovalently functionalized samples with 12.7% electrochemical active site. The heightened active site density and superior electrochemical active site utilization (12.7%) lead to the more favorable 4‐electron pathway for the ORR. Furthermore, a preliminary discussion regarding the selectivity of the ORR pathway is initiated.

New Materials for Alkaline Fuel Cells from Electroplating Industries Waste Solution Oxygen Reduction Reaction Catalyzed by Pd on Carbon Nanotubes, Graphene and Carbon Black

Issues concerning the energy sector are the focus of international discussions; the progressive depletion of fossil reserves and the increase in energy demand have led to the rise in fuel and electricity prices. In this context, fuel cells are promising candidates for a sustainable future. Oxygen Reduction Reaction (ORR) is the bottle-neck strategic reaction ruling the fuel cell efficiency process. This reaction allows the release of chemical energy in the form of electricity without producing any waste. However, the slow kinetics of ORR require highly effective electrocatalysts for proper boosting. It is well known that best available catalysts, in terms of raw bulk elements, belong to the so-called platinum group metals (PGMs). PGMs are very expensive, hence lowering the PGM content of ORR catalysts is among the most prevalent research focuses [1,2].We propose two different ways to obtain carbon-based ORR catalyst with a low continent of PMGs. The first approach involves the use of Single-Ion catalysts designed by carbon nanotubes functionalized with palladium(II) complexes show [3]. The second approach is totally innovative and aims at recovering precious metals to reduce industrial waste and promote the development of a circular economy. Large quantities of wastewater are produced in electroplating industries. This wastewater not only has to be properly processed before it is released into the environment, but also contains metals like palladium [4]. Using carbon materials and an electroless deposition, palladium can be recovered from the wastewater of the electroplating industry. We focus on carbon black (CB) and two different types of graphene-type materials named as (G4) and (G7). It was found that CB and G4 can recover up to 97% palladium. In this way we obtained hybrid materials containing palladium that could be promising candidates for use as catalysts for the ORR in alkaline fuel cells.New catalysts were treated by preparing a nafion polymeric dispersion and tested with electroanalytical techniques. Rotating ring-disk electrode (RRDE) experiments were performed to investigate the catalytic pathway of ORR and asses the number of exchanged electrons per oxygen molecule. Results confirm that tested materials promote the four-electron reaction pathway and reduce the formation of hydrogen peroxide. These approaches provide the basis for further developments to improve the efficiency of future low-cost catalysts for alkaline fuel cells.[1] Passaponti, M.; Lari, L.; Bonechi, M.; Bruni, F.; Giurlani, W.; Sciortino, G.; Rosi, L.; Fabbri, L.; Vizza, M.; Lazarov, V.K.; et al. Optimisation Study of Co Deposition on Chars from MAP of Waste Tyres as Green Electrodes in ORR for Alkaline Fuel Cells. Energies 2020, 13, 5646, doi:10.3390/en13215646.[2] Bonechi, M.; Giurlani, W.; Vizza, M.; Savastano, M.; Stefani, A.; Bianchi, A.; Fontanesi, C.; Innocenti, M. On the Oxygen Reduction Reaction Mechanism Catalyzed by Pd Complexes on 2D Carbon. A Theoretical Study. Catalysts 2021, 11, 764, doi:10.3390/catal11070764.[3] Savastano, M.; Passaponti, M.; Giurlani, W.; Lari, L.; Calisi, N.; Delgado-Pinar, E.; Serrano, E.S.; Garcia-España, E.; Innocenti, M.; Lazarov, V.K.; et al. Linear, Tripodal, Macrocyclic: Ligand Geometry and ORR Activity of Supported Pd(II) Complexes. Inorganica Chim. Acta 2021, 518, 120250, doi:10.1016/j.ica.2021.120250.[4] De Beni, E.; Giurlani, W.; Fabbri, L.; Emanuele, R.; Santini, S.; Sarti, C.; Martellini, T.; Piciollo, E.; Cincinelli, A.; Innocenti, M. Graphene-Based Nanomaterials in the Electroplating Industry: A Suitable Choice for Heavy Metal Removal from Wastewater. Chemosphere 2022, 292, 133448, doi:10.1016/j.chemosphere.2021.133448.

A New Catalyst System for the Oxygen Reduction Reaction (ORR) at Fuel Cell Cathodes: P-Block Precious Group Metal-Free Tin and Nitrogen-Doped Carbon (SnNC) Catalyst

The sluggish kinetics of the Oxygen Reduction Reaction (ORR) and the consequently large amount of platinum catalyst required for cathode material in Proton Exchange Membrane Fuel Cell (PEMFC) is today’s primary hurdle for commercializing fuel cell technology in automotive application.1 A class of carbon-doped with metal and nitrogen electrocatalysts (labelled MNC) is promising substitute for platinum-group metals (PGMs) in oxygen reduction reaction (ORR) in PEMFC.2 Particular attention was placed on a specific family of MNC catalysts derived from 3d transition metal precursors with FeNC and CoNC being the most promising for PEMFC applications requiring high power density.3-5 In the present contribution, we report on a new MNC catalyst system, different by its chemical nature from all others catalysts previously reported as ORR-active in acidic medium. The highlights of this work are the successful design and synthesis of SnNC as a non-noble metal catalyst for the first time, and the finding that SnNC hosts Sn-based active sites that can achieve the same turnover frequency as Fe-based active sites in FeNC, and much higher turnover frequency than Co-based active sites in CoNC. FeNC and CoNC materials have, until now, been the state-of-art PGM-free catalysts for ORR in acidic medium. The present SnNC material shows also high and similar selectivity for the four-electron ORR pathway as FeNC, much higher than CoNC materials. The prepared SnNC catalysts meet and exceed the FeNC catalysts in terms of 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. Added benefits include a Fenton-inactive character of Sn. Among other techniques, density functional theory and 119Sn Mössbauer spectroscopy were used in combination to investigate SnNC, providing for the first time insights on the structure of its active sites, their rate-determining step for ORR and selectivity for the four-electron reduction pathway. References Holton, O. T.; Stevenson, J. W., The Role of Platinum in Proton Exchange Membrane Fuel Cells. Platinum Metals Review 2013, 57 (4), 259-271.Luo, F.; Wagner, S.; Ju, W.; Primbs, M.; Li, S.; Wang, H.; Kramm, U. I.; Strasser, P., Kinetic Diagnostics and Synthetic Design of Platinum Group Metal-Free Electrocatalysts for the Oxygen Reduction Reaction Using Reactivity Maps and Site Utilization Descriptors. Journal of the American Chemical Society 2022, 144 (30), 13487-13498.Zitolo, A.; Ranjbar-Sahraie, N.; Mineva, T.; Li, J.; Jia, Q.; Stamatin, S.; Harrington, G. F.; Lyth, S. M.; Krtil, P.; Mukerjee, S.; Fonda, E.; Jaouen, F., Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction. Nature Communications 2017, 8 (1), 957.Zitolo, A.; Goellner, V.; Armel, V.; Sougrati, M.-T.; Mineva, T.; Stievano, L.; Fonda, E.; Jaouen, F., Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials. Nature materials 2015, 14 (9), 937-942.Luo, F.; Roy, A.; Silvioli, L.; Cullen, D. A.; Zitolo, A.; Sougrati, M. T.; Oguz, I. C.; Mineva, T.; Teschner, D.; Wagner, S.; Wen, J.; Dionigi, F.; Kramm, U. I.; Rossmeisl, J.; Jaouen, F.; Strasser, P., P-block single-metal-site tin/nitrogen-doped carbon fuel cell cathode catalyst for oxygen reduction reaction. Nature materials 2020, 19 (11), 1215-1223.

Design strategies towards transition metal single atom catalysts for the oxygen reduction reaction – A review

The electrochemical oxygen reduction reaction (ORR) is pivotal in energy conversion <i>via</i> a 4e⁻ ORR pathway and green hydrogen peroxide production <i>via</i> 2e⁻ ORR pathway. Transition metal single atom catalysts (TM SACs) have attracted intense attention in recent years for ORR due to their high activity and near maximum metal atom utilization. The future development of TM SACs for ORR requires improved understanding of reaction pathways, since currently the true origin of activity remains contentious owing to the lack of qualitative/quantitative information about active sites. Knowledge-guided design is imperative for the optimization of TM SACs performance in terms of activity and selectivity. This review focuses on the latest progress in the design of TM SACs for ORR, placing particular attention on efforts to elucidate reaction mechanisms. Experimental evidence based on <i>in-situ/operando</i> characterization measurements, along with theoretical predictions, are summarized to deepen understanding of the structure-performance relationships at both atomic and molecular level. Finally, some perspectives are offered relating to the fundamental science needed for TM SACs to find practical application in energy storage and conversion devices. We hope this review will inspire the development of new synthetic routes towards high-performance ORR electrocatalysts for the energy sector.

Reduced graphene oxide-supported palladium oxide-MOx for improving the performance of air-cathode microbial fuel cells: Influence of the Sn, Ce, Zn, and Fe precursors

Over the past few decades, microbial fuel cells (MFCs) have attracted significant interest within the realm of renewable energy technologies owing to their capability to generate electricity from low-grade substrates. However, their commercialization and scaling-up are impeded by significant obstacles, including high capital costs, limited durability, and sluggish oxygen reduction reaction (ORR). Here, we demonstrate an environmentally-friendly approach for developing highly efficient electrocatalysts consisting of palladium oxide (PdO) and different transition metal oxides (i.e., tin (IV) oxide (SnO2), ceric oxide (CeO2), iron (III) oxide (Fe2O3), and zinc oxide (ZnO)) embedded within reduced graphene oxide (rGO) framework for improving the efficiency of ORR in neutral medium and MFCs. Among the as-prepared electrocatalysts, the PdO–SnO2/rGO possesses the highest ORR electrochemical catalytic activity in a neutral medium (pH ∼ 7.2) following a four-electron ORR pathway, with a current density slightly lower than that of benchmark Pt/C electrocatalyst. The assessment of MFC performance is conducted by employing activated sludge as the inoculum and glucose as the sole electron donor in the anode chamber of single-chamber, air-cathode MFCs. Consistent with electrochemical performance, the maximum power output of an MFC equipped with PdO–SnO2/rGO as an air cathode is significantly higher than other tested MFCs, reaching 84.6 ± 2.8 mW m−2, which represents ∼ 91 % of the power output of an MFC with Pt/C air cathode. Our results reveal that the incorporation of PdO into transition metal reduced graphene oxide framework has the potential to facilitate their long-term application as air cathodes in MFCs that possess easy fabrication, relatively affordable cost, and outstanding electrochemical catalytic oxygen reduction capability, for enhancing electricity generation from wastewater.

Rational Design of Oxygen Species Adsorption on Nonnoble Metal Catalysts for Two‐Electron Oxygen Reduction

AbstractMolecular oxygen can be electrochemically reduced to water via the 4e− transfer pathway or hydrogen peroxide via a 2e− pathway, which holds significant relevance within energy conversion and chemical synthesis. The specific oxygen reduction reaction (ORR) pathways intricately hinge upon the adsorption configuration and state of oxygen species. Precisely steering the adsorption state of oxygen species at the active sites serves as a crucial guiding principle for the design and preparation of ORR catalysts. This review succinctly summarizes the strategies employed to regulate the adsorption state of oxygen species on nonnoble metal catalyst surfaces, encompassing insights into the adsorption mechanism and state regulation of oxygen intermediates, with a particular focus on the 2e− ORR pathway to produce H2O2. Moreover, the persistent challenges that remain in the realm of non‐noble metal oxygen catalysts are pointed out and the prospects for their future development are meticulously evaluated.

Modulating Coordination of Iron Atom Clusters on N,P,S Triply-Doped Hollow Carbon Support towards Enhanced Electrocatalytic Oxygen Reduction.

Constructing atom-clusters (ACs) with in situ modulation of coordination environment and simultaneously hollowing carbon support are critical yet challenging for improving electrocatalytic efficiency of atomically dispersed catalysts (ADCs). Herein, a general diffusion-controlled strategy based on spatial confining and Kirkendall effect is proposed to construct metallic ACs in N,P,S triply-doped hollow carbon matrix (MACs /NPS-HC, M=Mn, Fe, Co, Ni, Cu). Thereinto, FeACs /NPS-HC with the best catalytic activity for oxygen reduction reaction (ORR) is thoroughly investigated. Unlike the benchmark sample of symmetrical N-surrounded iron single-atoms in N-doped carbon (FeSAs /N-C), FeACs /NPS-HC comprises bi-/tri-atomic Fe centers with engineered S/N coordination. Theoretical calculation reveals that proper Fe gathering and coordination modulation could mildly delocalize the electron distribution and optimize the free energy pathways of ORR. In addition, the triple doping and hollow structure of carbon matrix could further regulate the local environment and allow sufficient exposure of active sites, resulting in more enhanced ORR kinetics on FeACs /NPS-HC. The zinc-air battery assembled with FeACs /NPS-HC as cathodic catalyst exhibits all-round superiority to Pt/C and most Fe-based ADCs. This work provides an exemplary method for establishing atomic-cluster catalysts with engineered S-dominated coordination and hollowed carbon matrix, which paves a new avenue for the fabrication and optimization of advanced ADCs.

Modulating Coordination of Iron Atom Clusters on N,P,S Triply‐Doped Hollow Carbon Support towards Enhanced Electrocatalytic Oxygen Reduction

AbstractConstructing atom‐clusters (ACs) with in situ modulation of coordination environment and simultaneously hollowing carbon support are critical yet challenging for improving electrocatalytic efficiency of atomically dispersed catalysts (ADCs). Herein, a general diffusion‐controlled strategy based on spatial confining and Kirkendall effect is proposed to construct metallic ACs in N,P,S triply‐doped hollow carbon matrix (MACs/NPS−HC, M=Mn, Fe, Co, Ni, Cu). Thereinto, FeACs/NPS−HC with the best catalytic activity for oxygen reduction reaction (ORR) is thoroughly investigated. Unlike the benchmark sample of symmetrical N‐surrounded iron single‐atoms in N‐doped carbon (FeSAs/N−C), FeACs/NPS−HC comprises bi‐/tri‐atomic Fe centers with engineered S/N coordination. Theoretical calculation reveals that proper Fe gathering and coordination modulation could mildly delocalize the electron distribution and optimize the free energy pathways of ORR. In addition, the triple doping and hollow structure of carbon matrix could further regulate the local environment and allow sufficient exposure of active sites, resulting in more enhanced ORR kinetics on FeACs/NPS−HC. The zinc‐air battery assembled with FeACs/NPS−HC as cathodic catalyst exhibits all‐round superiority to Pt/C and most Fe‐based ADCs. This work provides an exemplary method for establishing atomic‐cluster catalysts with engineered S‐dominated coordination and hollowed carbon matrix, which paves a new avenue for the fabrication and optimization of advanced ADCs.

Understanding the Pathway Switch of the Oxygen Reduction Reaction from Single- to Double-/Triple-Atom Catalysts: A Dual Channel for Electron Acceptance-Backdonation.

Recently, a lot of attention has been dedicated to double- or triple-atom catalysts (DACs/TACs) as promising alternatives to platinum-based catalysts for the oxygen reduction reaction (ORR) in fuel cell applications. However, the ORR activity of DACs/TACs is usually theoretically understood or predicted using the single-site association pathway (O2 → OOH* → O* → OH* → H2O) proposed from Pt-based alloy and single-atom catalysts (SACs). Here, we investigate the ORR process on a series of graphene-supported Fe-Co DACs/TACs by means of first-principles calculation and an electrode microkinetic model. We propose that a dual channel for electron acceptance-backdonation on adjacent metal sites of DACs/TACs efficiently promotes O-O bond breakage compared with SACs, which makes ORR switch to proceed through dual-site dissociation pathways (O2 → O* + OH* → 2OH* → OH* → H2O) from the traditional single-site association pathway. Following this revised ORR network, a complete reaction phase diagram of DACs/TACs is established, where the preferential ORR pathways and activity can be described by a three-dimensional volcano plot spanned by the adsorption free energies of ΔG(O*) and ΔG(OH*). Besides, the kinetics preferability of dual-site dissociation pathways is also appropriate for other graphene- or oxide-supported DACs/TACs. The contribution of dual-site dissociation pathways, rather than the traditional single-site association pathway, makes the theoretical ORR activity of DACs/TACs in better agreement with available experiments, rationalizing the superior kinetic behavior of DACs/TACs to that of SACs. This work reveals the origin of ORR pathway switching from SACs to DACs/TACs, which broadens the ideas and lays the theoretical foundation for the rational design of DACs/TACs and may also be heuristic for other reactions catalyzed by DACs/TACs.