Enhanced Oxygen Reduction Reaction Research Articles

Unveiling the potential of a g-C3N4/BiOBr/Bi2O2CO3 ternary heterojunction photocatalyst for rechargeable zinc-air battery: Visible-light-driven photo-assisted charging for bifunctional ORR and OER at the air cathode

Advancements in solar-driven energy storage technology have been achieved for rechargeable zinc-air batteries (RZABs), facilitating accelerated kinetic responses in both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). In this study, we successfully synthesized a novel g-C3N4/BiOBr/Bi2O2CO3 ternary heterojunction through a facile hydrothermal process, demonstrating its efficacy as a bifunctional photocatalyst. Upon exposure to LED irradiation, this heterojunction triggers an effective separation of the photogenerated electron-hole pairs, resulting in enhanced oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) performance by 46.19 % and 65.69 % respectively, compared to non-LED conditions. Interestingly, the reduction in the potential gap under LED irradiation (0.06 V), correlating with a significant 2.71 % increase in round-trip efficiency (RTE), is observed. In addition, the optimized band alignment derived from g-C3N4/BiOBr/Bi2O2CO3 ternary heterojunction for photo-assisted charging rechargeable zinc-air batteries is proposed. Insightfully, photo-enhanced charging in RZABs mechanism during the charge/discharge process through in-situ X-ray absorption spectroscopy (XAS) is monitored, confirming the large interaction between O2 adsorption and Bi 6d orbitals of g-C3N4/BiOBr/Bi2O2CO3 in the presence of LED. In conclusion, our innovative g-C3N4/BiOBr/Bi2O2CO3 ternary heterojunction underscores the significant role that visible-light-driven photocatalysts can play in enhancing the efficiency of rechargeable zinc-air batteries.

Engineering atomically dispersed dual Pt–Ni sites on nitrogen-doped carbon with spherical core-shell structure for enhanced oxygen reduction activity towards microbial fuel cell

Inspired by the development of efficient, durable electrocatalytic functional materials to address the issues of kinetic retardation and mass transport to enhance oxygen reduction reaction (ORR), one strategy is proposed for core-shell structural nitrogen-doped carbon with atomically dispersed binary platinum-nickel (Pt–Ni) atoms (N–C@Pt–Ni/N–C) with controlled bimetallic sites and adjusted electronic coordination environment. Practical application of experimental and simulated theoretical calculation results show the coordination microenvironment optimization for active site can promote the charge rearrangement of Pt–Ni sites, thus regulating the free energy of the reaction intermediates of oxygen-containing species. The N–C@Pt–Ni/N–C reveals astounding catalytic capacity during ORR, leading to a large power density (1472.6 ± 50.6 mW m−2) and long-term reliability (OCP by the current loss with 0.1 mA) in the actual microbial fuel cells. This work not only reveals controllable preparation of functional materials with binary isolated atomic dispersion, but also presents more perspective of electronic structure optimal performance enhancement relationship at the atomic-sized active sites.

Highly Dispersed Mn-Doped Ceria Supported on N-Doped Carbon Nanotubes for Enhanced Oxygen Reduction Reaction.

The weak adsorption of oxygen on transition metal oxide catalysts limits the improvement of their electrocatalytic oxygen reduction reaction (ORR) performance. Herein, a dopamine-assisted method is developed to prepare Mn-doped ceria supported on nitrogen-doped carbon nanotubes (Mn-Ce-NCNTs). The morphology, dispersion of Mn-doped ceria, composition, and oxygen vacancies of the as-prepared catalysts were analyzed using various technologies. The results show that Mn-doped ceria was formed and highly dispersed on NCNTs, on which oxygen vacancies are abundant. The as-prepared Mn-Ce-NCNTs exhibit a high ORR performance, on which the average electron transfer number is 3.86 and the current density is 24.4% higher than that of commercial 20 wt % Pt/C. The peak power density of Mn-Ce-NCNTs is 68.1 mW cm-2 at the current density of 138.9 mA cm-2 for a Zn-air battery, which is close to that of 20 wt % Pt/C (69.4 mW cm-2 at 106.1 mA cm-2). Density functional theory (DFT) calculations show that the oxygen vacancy formation energies of Mn-doped CeO2(111) and pure CeO2(111) are -0.55 and 2.14 eV, respectively. Meanwhile, compared with undoped CeO2(111) (-0.02 eV), Mn-doped CeO2(111) easily adsorbs oxygen with the oxygen adsorption energy of only -0.68 eV. This work provides insights into the synergetic effect of Mn-doped ceria for facilitating oxygen adsorption and enhancing ORR performance.

In-situ immobilization strategy for single-atom iron sites to enhance oxygen reduction reaction in Zn–air batteries and microbial fuel cells

A straightforward and environmentally friendly approach was utilized to synthesize single-atomic Fe–N–C catalyst. In-situ immobilization of Fe3+ during the formation of polydopamine (PDA) and ZIF-8 in aqueous solution effectively prevent metal agglomeration. The mutual promotion of PDA and aqueous solution constructed the hybrid-level porous hollow structure in P–FeNC. This method extends the solution scope from organic solution system to water solution, thus providing fascinating opportunities for investigating metal-N-C catalyst by in-situ mixing various metal salt precursor and dopamine. The optimal P–FeNC catalyst demonstrates superlative oxygen reduction reaction (ORR) performance, with the half-wave potentials (E1/2) of 0.886 V, 0.79 V, and 0.72 V in 0.1 M KOH, 0.5 M H2SO4, and 0.05 M PBS solutions, which exceeded commercial 20 wt% Pt/C. The combinatorial impacts of highly dense FeN4 active sites and interconnected hierarchical mesopores/macropores are presumed to underpin the observed enhancement in ORR performance. Further evaluations show that the power densities of P–FeNC equipped zinc-air battery (ZAB) and microbial fuel cell (MFC) are 460 mW/cm2 and 3083 ± 10 mW/m2, respectively. This study confirms the feasibility to design the innovative single-atom catalyst in aqueous solution and provides constructive ideas to employ the high-performance P–FeNC electrocatalyst in ZABs and MFCs.

Asymmetrical anchor way of manganese atoms on carbon domain edge for enhanced oxygen reduction reaction

Single atomic catalysts (SACs), especially the catalysts featured by well-developed M-N4 moieties, show excellent catalytic activity and spark enormous attention. However, the highly symmetric active sites may result in some degenerate electronic states for the d orbitals of the center metal atom, which suffer from the unsatisfactory adsorption-desorption behaviors during reaction. Herein, we develop an asymmetric anchor site by two types of nitrogen (sp-N and pyridinic N) created in the inherent edge-rich carbon domain of hydrogen-substituted graphdiyne (HsGDY), where atomic catalyst like manganese atoms can be asymmetrically anchored on the one side of hexagon carbon rings. The abundant elegant hexagon carbon rings on HsGDY not only facilitate the creation of edge sites, but also provide available space for the coordination of terminal ligands (OH) with Mn atoms. The as-synthesized Mn-N-HsGDY exhibits excellent ORR activity and an impressive long-term cyclability for over 3800 cycles in a rechargeable Zn-air battery.

Strong Interaction between Titanium Carbonitride Embedded in Mesoporous Carbon Nanofibers and Pt Enables Durable Oxygen Reduction.

Platinum (Pt) supported on high surface area carbon has been the most widely used electrocatalyst in proton exchange membrane fuel cell (PEMFC). However, conventional carbon supports are susceptible to corrosion at high potentials, leading to severe degradation of electrochemical performance. In this work, titanium carbonitride embedded in mesoporous carbon nanofibers (m-TiCN NFs) are reported as a promising alternative to address this issue. Benefiting from the interpenetrating conductive pathways inside the one-dimensional (1D) nanostructures and the embedded TiCN nanoparticles (NPs), m-TiCN NFs exhibit excellent stability at high potentials and interact strongly with Pt NPs. Subsequently, m-TiCN NFs-supported Pt NPs deliver remarkably enhanced oxygen reduction reaction (ORR) activity and durability, with negligible activity decay and less than 5% loss of electrochemical surface area（ECSA） after 50000 cycles. Moreover, the fuel cell assembled by this catalyst delivers a maximum power density of 1.22W cm-2 and merely 3% loss after 30000 cycles of accelerated durability tests under U.S. Department of Energy (DOE) protocols. The improved ORR activity and durability are attributed to the superior corrosion resistance of the m-TiCN NF support and the strong interaction between Pt and m-TiCN NFs.

Regulating the Local Microenvironment of an Fe−N4 Single-Atom Catalyst for Enhanced Oxygen Reduction Reaction

Regulating the Local Microenvironment of an Fe−N₄ Single-Atom Catalyst for Enhanced Oxygen Reduction Reaction

Enhancing oxygen reduction reaction performance through eco-friendly chitosan gel-assisted molten salt strategy: Small NiCo alloy nanoparticles decorated with high-loading single Fe-NX

We developed an effective and eco-friendly strategy using chitosan gel-molten salt to achieve high loading (2.23 At. %) of single Fe-NX as assistive active sites. These sites were combined with small NiCo alloy NPs distributed on porous carbon aerogels to boost the ORR performance. The FeSAs-NiCo alloy@N-C sphere exhibits exceptional mass activity and specific activity of 3.705 A.mg−1 and 8.79 mA.cm−2(ECSA), respectively, at 0.85 V versus RHE. It has a superior onset potential of 1.08 V versus RHE, surpassing that of its nanoparticle Fe counterpart and NiCo alloy@N-C sphere. The significant improvement in ORR performance of the FeSAs-NiCo alloy@N-C sphere could be attributed to the positive effects of increased lattice strain due to the single atoms of Fe-NX hybridized with small NiCo alloy NPs. The chitosan gel-assisted molten salt strategy and assistive active sites of Fe-NX hybridized with NiCo alloy NPs regulate the electronic properties of the FeSAs-NiCo alloy@N-C sphere, both geometrically via lattice strain mismatch and electronically through shifting of the d-band center. This could influence the binding energies for oxygen and/or oxygen reduction intermediate adsorption/desorption. The additional improvement in the ORR performance of the FeSAs-NiCo alloy@N-C sphere also benefits from having a lower electrochemical activation energy.

Orienting Electron Fillings in d Orbitals of Cobalt Single Atoms for Effective Zinc–Air Battery at a Subzero Temperature

AbstractThe missions in extreme environments such as the moon, the Arctic/Antarctic, and the plateau require the operation of batteries at low temperatures even below the freezing point of water. Herein, it is reported that compressively stressed Co single atoms exhibit enhanced oxygen reduction reaction (ORR) activity and enable the effective operation of zinc–air battery at a subzero temperature. The compressive strain is generated by depositing Co single atoms on highly arced carbon layers with ultra‐small curvature radii ≈2 nm. The locally compressive strain on Co single atoms redistributes the electron fillings in d orbitals with different spatial orientations, thereby strengthening the adsorption of active intermediates and enhancing the activity toward ORR. As expected, compressively stressed Co single atoms outperform Co single atoms on a flat support without strain in terms of kinetic current density (31.09 mA cm−2 vs 0.35 mA cm−2) at 0.85 V during ORR. The integration of the catalyst into a Zn–air battery generates a superior power density of 54.8 mW cm−2 than the commercial Pt/C counterpart (24.1 mW cm−2) at −40 °C.

Self-Assembly Strategy for Constructing Porous Boron and Nitrogen Co-Doped Carbon as an Efficient ORR Electrocatalyst toward Zinc-Air Battery.

Carbon nanomaterials doped with N and B could activate nearby carbon atoms to promote charge polarization through the synergistic coupling effect between N and B atoms, thus facilitating adsorption of O2 and weakening O-O bond to enhance oxygen reduction reaction. Herein, a simple and controllable self-assembly strategy is applied to synthesize porous B, N co-doped carbon-based catalysts (BCN-P), which employs the macrocyclic molecule cucurbit[7]uril (CB7) as nitrogen source, and 3D aromatic-like closo-[B12H12]2- as boron source. In addition, polystyrene microspheres are added to help introduce porous structure to expose more active sites. Benefitting from porous structures and the synergistic coupling effect between N and B atoms, BCN-P has a high onset potential (Eonset=0.846 V) and half-wave potential (E1/2=0.74 V) in alkaline media. The zinc-air battery assembled with BCN-P shows high operating voltage (1.42 V), peak power density (128.7 mW cm-2) and stable charge/discharge cycles, which is even comparable with Pt/C.

Thermally Stable Silver Cathode Covered by Samaria-Doped Ceria for Low-Temperature Solid Oxide Fuel Cells.

Samaria-doped ceria (SDC) overlayers were deposited on Ag cathodes by sputtering. The SDC sputtering time was varied to investigate the properties of the Ag-SDC overlayer cathode-coated fuel cells depending on the thickness of the SDC overlayers. Among the fabricated fuel cells, Ag with a 10-nm-thick SDC overlayer (Ag-SDC10) cathode-coated fuel cell exhibited the highest peak power density of 6.587 mW/cm2 at 450 °C, showing higher performance than a pristine Pt-coated fuel cell. Moreover, electrochemical impedance spectroscopy revealed that the Ag-SDC10 cathode-coated fuel cell significantly mitigated polarization loss originating from enhanced oxygen reduction reaction kinetics compared to the pristine Ag-coated fuel cell.

Bimetallic iron complex constructed clusters and single atoms neighboring structure to enhance oxygen reduction reaction performance

Electrocatalysts are useful in lowering the energy barrier in oxygen reduction reaction (ORR). In this study, a catalyst with neighboring Fe single-atom and cluster is created by adsorbing a bimetallic Fe complex onto N-doped carbon and then pyrolyzing it. The resulting catalyst has good performance and a half-wave potential of 0.89 V. When used in Zn-air batteries, the voltage drops by only 8.13 % after 145 h of cycling. Theoretical studies show that electrons transfer from neighboring clusters to single atoms and the catalyst has a lower d-band center. These reduce intermediate desorption energy, hence improving ORR performance. This work demonstrates the capacity to adjust the catalytic properties through the interaction of diverse metal structures, which helps to design more efficient catalysts.

Synergistic Effect of Electrocatalyst for Enhanced Oxygen Reduction Reaction: Low Pt-Loaded CuPt Alloy Nanoparticles Supported on N-Doped Hierarchical Porous Carbon.

It is challenging to synthesize oxygen reduction reaction (ORR) electrocatalysts that are highly efficient, affordable, and stable for use in proton exchange membrane fuel cells. To address this challenge, we developed a low platinum-loading (only 6.68% wt) ORR catalyst (PtCu1-NC), comprising CuPt nanoparticles (average size: 1.51 nm) supported on the N-doped carbon substrates. PtCu1-NC possesses a high specific surface area of 662 m2 g-1 and a hierarchical porous structure, facilitating efficient mass transfer. The synergistic effect from introduced copper and the electron effect from nitrogen modify the electronic structure of platinum, effectively accelerating the ORR reaction and enhancing stability. Density functional theory calculations demonstrate the catalytic mechanism and further verify the synergistic effect. Electrochemical assessments indicate that PtCu1-NC exhibits specific activity and mass activity 5.3 and 5.6 times higher, respectively, than commercial Pt/C. The half-wave potential is 27 mV more positive than that of commercial Pt/C. The electrochemical active surface area value is 104.3 m2 g-1, surpassing that of Pt/C. Approximately 78% of current is retained after 10,000 s chronoamperometry measurement. These results highlight the effectiveness of alloying in improving the catalyst performance.

Simultaneously Engineering the First and Second Coordination Shells of Single Iron Catalysts for Enhanced Oxygen Reduction.

The atomically dispersed Fe-N4 active site presents enormous potential for various renewable energy conversions. Despite its already remarkable catalytic performance, the local atomic microenvironment of each Fe atom can be regulated to further enhance its efficiency. Herein, a novel conceptual strategy that utilizes a simple salt-template polymerization method to simultaneously adjust the first coordination shell (Fe-N3 S1 ) and second coordination shell (C-S-C, a structure similar to thiophene) of Fe-N4 isolated atoms is proposed. Theoretical studies suggest that this approach can redistribute charge density in the MN4 moiety, lowering the d-band center of the metal site. This weakens the binding of oxygenated intermediates, enhancing oxygen reduction reaction (ORR) activity when compared to only implementing coordination shell regulation. Based on the above discovery, a single Fe atom electrocatalyst with the optimal Fe-N3 S1 -S active moiety incorporated in nitrogen, sulfur co-doped graphene (Fe-SAc/NSG) is designed and synthesized. The Fe-SAc/NSG catalyst exhibits excellent alkaline ORR activity, exceeding benchmark Pt/C and most Fe-SAc ORR electrocatalysts, as well as superior stability in Zn-air battery. This work aims to pave the way for creating highly active single metal atom catalysts through the localized regulation of their atomic structure.

Lattice Strained Induced Spin Regulation in Co−N/S Coordination‐Framework Enhanced Oxygen Reduction Reaction

AbstractOxygen reduction reaction (ORR) is the bottleneck of metal‐air batteries and fuel cells. Strain regulation can change the geometry and adjust the surface charge distribution of catalysts, which is a powerful strategy to optimize the ORR activity. The introduction of controlled strain to the material is still difficult to achieve. Herein, we present a temperature‐pressure‐induced strategy to achieve the controlled lattice strain for metal coordination polymers. Through the systematic study of the strain effect on ORR performance, the relationship between geometric and electronic effects is further understood and confirmed. The strained Co‐DABDT (DABDT=2,5‐diaminobenzene‐1,4‐dithiol) with 2 % lattice compression exhibits a superior half‐wave potential of 0.81 V. Theoretical analysis reveals that the lattice strain changes spin‐charge densities around S atoms for Co‐DABDT, and then regulates the hydrogen bond interaction with intermediates to promote the ORR catalytic process. This work helps to understand the catalytic mechanism from the atomic level.

Lattice Strained Induced Spin Regulation in Co-N/S Coordination-Framework Enhanced Oxygen Reduction Reaction.

Oxygen reduction reaction (ORR) is the bottleneck of metal-air batteries and fuel cells. Strain regulation can change the geometry and adjust the surface charge distribution of catalysts, which is a powerful strategy to optimize the ORR activity. The introduction of controlled strain to the material is still difficult to achieve. Herein, we present a temperature-pressure-induced strategy to achieve the controlled lattice strain for metal coordination polymers. Through the systematic study of the strain effect on ORR performance, the relationship between geometric and electronic effects is further understood and confirmed. The strained Co-DABDT (DABDT=2,5-diaminobenzene-1,4-dithiol) with 2 % lattice compression exhibits a superior half-wave potential of 0.81 V. Theoretical analysis reveals that the lattice strain changes spin-charge densities around S atoms for Co-DABDT, and then regulates the hydrogen bond interaction with intermediates to promote the ORR catalytic process. This work helps to understand the catalytic mechanism from the atomic level.

Local tetragonal distortion of Pt alloy catalysts for enhanced oxygen reduction reaction efficiency

AbstractPlatinum‐based alloy nanoparticles are the most attractive catalysts for the oxygen reduction reaction at present, but an in‐depth understanding of the relationship between their short‐range structural information and catalytic performance is still lacking. Herein, we present a synthetic strategy that uses transition‐metal oxide‐assisted thermal diffusion. PtCo/C catalysts with localized tetragonal distortion were obtained by controlling the thermal diffusion process of transition‐metal elements. This localized structural distortion induced a significant strain effect on the nanoparticle surface, which further shortened the length of the Pt–Pt bond, improved the electronic state of the Pt surface, and enhanced the performance of the catalyst. PtCo/C catalysts with special short‐range structures achieved excellent mass activity (2.27 A mgPt−1) and specific activity (3.34 A cm−2). In addition, the localized tetragonal distortion‐induced surface compression of the Pt skin improved the stability of the catalyst. The mass activity decreased by only 13% after 30,000 cycles. Enhanced catalyst activity and excellent durability have also been demonstrated in the proton exchange membrane fuel cell configuration. This study provides valuable insights into the development of advanced Pt‐based nanocatalysts and paves the way for reducing noble‐metal loading and increasing the catalytic activity and catalyst stability.

In situ modulating coordination fields of single-atom cobalt catalyst for enhanced oxygen reduction reaction

Single-atom catalysts, especially those with metal−N4 moieties, hold great promise for facilitating the oxygen reduction reaction. However, the symmetrical distribution of electrons within the metal−N4 moiety results in unsatisfactory adsorption strength of intermediates, thereby limiting their performance improvements. Herein, we present atomically coordination-regulated Co single-atom catalysts that comprise a symmetry-broken Cl−Co−N4 moiety, which serves to break the symmetrical electron distribution. In situ characterizations reveal the dynamic evolution of the symmetry-broken Cl−Co−N4 moiety into a coordination-reduced Cl−Co−N2 structure, effectively optimizing the 3d electron filling of Co sites toward a reduced d-band electron occupancy (d5.8 → d5.28) under reaction conditions for a fast four-electron oxygen reduction reaction process. As a result, the coordination-regulated Co single-atom catalysts deliver a large half-potential of 0.93 V and a mass activity of 5480 A gmetal−1. Importantly, a Zn-air battery using the coordination-regulated Co single-atom catalysts as the cathode also exhibits a large power density and excellent stability.

Enhanced Electrocatalytic Oxygen Reduction Reaction of TiO2 Nanotubes by Combining Surface Oxygen Vacancy Engineering and Zr Doping.

This work examines the cooperative effect between Zr doping and oxygen vacancy engineering in anodized TiO2 nanotubes (TNTs) for enhanced oxygen reduction reactions (ORRs). Zr dopant and annealing conditions significantly affected the electrocatalytic characteristics of grown TNTs. Zr doping results in Zr4+ substituted for Ti4+ species, which indirectly creates oxygen vacancy donors that enhance charge transfer kinetics and reduce carrier recombination in TNT bulk. Moreover, oxygen vacancies promote the creation of unsaturated Ti3+(Zr3+) sites at the surface, which also boosts the ORR interfacial process. Annealing at reductive atmospheres (e.g., H2, vacuum) resulted in a larger increase in oxygen vacancies, which greatly enhanced the ORR activity. In comparison to bare TNTs, Zr doping and vacuum treatment (Zr:TNT-Vac) significantly improved the conductivity and activity of ORRs in alkaline media. The finding also provides selective hydrogen peroxide production by the electrochemical reduction of oxygen.

Atomically dispersed Fe-N-C catalyst with densely exposed Fe-N4 active sites for enhanced oxygen reduction reaction

Atomically dispersed Fe-N-C catalysts are a promising alternative to platinum group metal (PGM) catalysts for oxygen reduction reaction (ORR). However, attaining efficient ORR activity and superior stability in Fe-N-C catalysts is still crucial yet challenging. Herein, we report a rational SiO2-mediated two-step pyrolysis strategy for stabilizing densely exposed Fe-N4 active sites on hierarchically porous carbon (HP-Fe-N-C/2). Benefiting from the high density of accessible Fe-N4 sites and the high graphitization degree of carbon support, the obtained HP-Fe-N-C/2 catalyst demonstrates outstanding activity and stability for ORR in both alkaline and acidic media. When used as the cathode catalyst, the assembled Zn-air battery shows a high peak power density of 217 mW cm−2 and ultra-long cycling stability for 1342 h without noticeable degradation. As a PGM-free cathode in proton exchange membrane fuel cells, it delivers a maximum output power density of 0.66 W cm−2.