Oxygen Reduction Activity Research Articles

Unveiling enhanced oxygen reduction activity in PtCo bimetallic solid solutions through controlled crystal strain

Unveiling enhanced oxygen reduction activity in PtCo bimetallic solid solutions through controlled crystal strain

Fine Engineering of d-Orbital Vacancies of ZnN4 via High-Shell Metal and Nonmetal Single-Atoms for Efficient and Poisoning-Resistant ORR.

Atomically dispersed metal-nitrogen-carbon (M-N-C) materials are active oxygen reduction reaction (ORR) catalysts. Among M-N-C catalysts, ZnN4 single-atom catalysts (SACs) due to a nearly full 3d10 electronic configuration insufficiently activate oxygen and display low ORR activity. To finely engineer d-orbital vacancies of ZnN4, we combine high-shell metal and nonmetal SAs as electronic regulators that are ZnN4Cl and carbon vacancy-hosted -Cl motifs, which show complementary electron-withdrawing capacities versus the ZnN4. Under that, the ZnN4 exhibits significantly enhanced ORR activity with a half-wave potential (E1/2) of 0.912 VRHE relative to the unmodified ZnN4 (E1/2 = 0.822 VRHE) and simultaneously robust durability (negligible activity loss after 10,000 potential cycles). Particularly, the engineered ZnN4 possesses high resistance to SCN- poisoning, which is rarely achieved among M-N-C SACs. Our works show that combining high-shell metal and nonmetal SAs can finely engineer d-orbital vacancies of metal centers to an optimal state, thereby intrinsically enhancing their catalytic performance.

High-entropy perovskite (Pr1/6Nd1/6Sm1/6Ba1/6Sr1/6)6/7(Mn1/6Co)6/7O3-δ as a highly active and CO2 durable cathode for solid oxide fuel cells

Solid oxide fuel cells (SOFCs) are environmentally friendly energy conversion devices that convert the chemical energy in fuels directly into electrical power. The development of high-catalytic activity and durability cathode materials is crucial for the commercialization of SOFCs. Herein, a novel A-site deficient high-entropy perovskite oxide (Pr1/6Nd1/6Sm1/6Ba1/6Sr1/6)6/7(Mn1/6Co)6/7O3-δ (PNSBSMC) was designed. The strong disorder effect associated with entropy increase in high-entropy perovskite oxide is anticipated to accelerate oxygen reduction reaction (ORR) kinetics. PNSBSMC demonstrates excellent catalytic activity for oxygen reduction, primarily due to the entropy-driven enhancement that promotes oxygen adsorption, dissociation, and charge transfer dynamics. The increase in entropy not only significantly mitigates the thermal expansion of PNSBSMC but also provides additional pathways for ionic/electronic transport. At 800 °C, the PNSBSMC-based single cell achieved a remarkable peak power density of 1.41 W cm−2, representing an 88.0 % improvement over the single-phase PBC. Additionally, PNSBSMC demonstrates superior performance stability and CO2 tolerance. These findings suggest that high-entropy PNSBSMC perovskite holds significant potential as an effective cathode for SOFCs. This study offers new insights for the future development of high-stability, high-activity SOFC cathode materials.

Suppression of Pt Nanocluster Aggregation and Enhanced Oxygen Reduction Activity by Heteroatom Doping of Carbon Nanotubes

Suppression of Pt Nanocluster Aggregation and Enhanced Oxygen Reduction Activity by Heteroatom Doping of Carbon Nanotubes

Cobalt Nitride-Implanted PtCo Intermetallic Nanocatalysts for Ultrahigh Fuel Cell Cathode Performance.

Stable and active oxygen reduction electrocatalysts are essential for practical fuel cells. Herein, we report a novel class of highly ordered platinum-cobalt (Pt-Co) alloys embedded with cobalt nitride. The intermetallic core-shell catalyst demonstrates an initial mass activity of 0.88 A mgPt-1 at 0.9 V with 71% retention after 30,000 potential cycles of an aggressive square-wave accelerated durability test and loses only 9% of its electrochemical surface area, far exceeding the US Department of Energy 2025 targets, with unprecedented stability and only a minimal voltage loss under practical fuel cell operating conditions. We discover that regulating the atomic ordering in the core results in an optimal lattice configuration that accelerates the oxygen reduction kinetics. The presence of cobalt nitride decorated within PtCo superlattices guarantees a larger barrier to Co dissolution, leading to the excellent endurance of the electrocatalysts. This work brings up a transformative structural engineering strategy for rationally designing high-performing Pt-based catalysts with a unique atomic configuration for broad practical uses in energy conversion technology.

Harnessing the Synergistic Interplay between Atomic-Scale Vacancies and Ligand Effect to Optimize the Oxygen Reduction Activity and Tolerance Performance.

Defect engineering is an effective strategy for regulating the electrocatalysis of nanomaterials, yet it is seldom considered for modulating Pt-based electrocatalysts for the oxygen reduction reaction (ORR). In this study, we designed Ni-doped vacancy-rich Pt nanoparticles anchored on nitrogen-doped graphene (Vac-NiPt NPs/NG) with a low Pt loading of 3.5 wt . % and a Ni/Pt ratio of 0.038 : 1. Physical characterizations confirmed the presence of abundant atomic-scale vacancies in the Pt NPs induces long-range lattice distortions, and the Ni dopant generates a ligand effect resulting in electronic transfer from Ni to Pt. Experimental results and theoretical calculations indicated that atomic-scale vacancies mainly contributed the tolerance performances towards CO and CH3OH, the ligand effect derived from a tiny of Ni dopant accelerated the transformation from *O to *OH species, thereby improved the ORR activity without compromising the tolerance capabilities. Benefiting from the synergistic interplay between atomic-scale vacancies and ligand effect, as-prepared Vac-NiPt NPs/NG exhibited improved ORR activity, sufficient tolerance capabilities, and excellent durability. This study offers a new avenue for modulating the electrocatalytic activity of metal-based nanomaterials.

Harnessing the Synergistic Interplay between Atomic‐Scale Vacancies and Ligand Effect to Optimize the Oxygen Reduction Activity and Tolerance Performance

AbstractDefect engineering is an effective strategy for regulating the electrocatalysis of nanomaterials, yet it is seldom considered for modulating Pt‐based electrocatalysts for the oxygen reduction reaction (ORR). In this study, we designed Ni‐doped vacancy‐rich Pt nanoparticles anchored on nitrogen‐doped graphene (Vac‐NiPt NPs/NG) with a low Pt loading of 3.5 wt . % and a Ni/Pt ratio of 0.038 : 1. Physical characterizations confirmed the presence of abundant atomic‐scale vacancies in the Pt NPs induces long‐range lattice distortions, and the Ni dopant generates a ligand effect resulting in electronic transfer from Ni to Pt. Experimental results and theoretical calculations indicated that atomic‐scale vacancies mainly contributed the tolerance performances towards CO and CH3OH, the ligand effect derived from a tiny of Ni dopant accelerated the transformation from *O to *OH species, thereby improved the ORR activity without compromising the tolerance capabilities. Benefiting from the synergistic interplay between atomic‐scale vacancies and ligand effect, as‐prepared Vac‐NiPt NPs/NG exhibited improved ORR activity, sufficient tolerance capabilities, and excellent durability. This study offers a new avenue for modulating the electrocatalytic activity of metal‐based nanomaterials.

Nickel-Nitrogen Doped MnO2 as Oxygen Reduction Reaction Catalyst for Aluminum Air Batteries.

Aluminum-air battery has the advantages of high energy density, low cost and environmental protection, and is considered as an ideal next-generation energy storage conversion system. However, the slow oxygen reduction reaction (ORR) in air cathode leads toitsunsatisfactory performance. Here, we report an electrode made of N and Ni co-doped MnO2nanotubes. In alkaline solution, Ni/N-MnO2has higher oxygen reduction activity than undoped MnO2, with an initial potential of 1.00 V and a half-wave potential of 0.75 V. This is because it has abundant defects, high specific surface area and sufficient Mn3+active sites, which promote the transfer of electrons and oxygen-containing intermediates.Density functional theory (DFT) calculations show that MnO2doped with N and Ni atoms reduces the reaction overpotential and improves the ORR kinetics. The peak power density and energy density of the Ni/N-MnO2air electrodeincreased by 34.03 mW·cm-2and 316.41 mWh·g-1, respectively. The results show that N and Ni co-doped MnO2nanotubes are a promising air electrode, which can provide some ideas for the research of aluminum-air batteries.

Carbon fiber with superhydrophilic interface as metal-free air electrode for all-solid-state Zn-air batteries

The burgeoning interest in all-solid-state Zn-air batteries as next-generation power sources for portable electronics is conspicuous. A pivotal aspect of their advancement lies in developing cost-effective, metal-free air electrodes with high-activity bifunctional oxygen electrocatalysts. This study introduces a superhydrophilic carbon fiber modified with oxygen functional groups (CF-O), achieved through a straightforward one-step activation treatment. Comparative analyses reveal that the CF-O electrode surpasses pristine CF in oxygen reduction and evolution reaction (OER and ORR) activity due to enhanced active sites and expedited ion transport. Notably, the OER/ORR performance depends on the type and quantity of oxygen functional groups. The optimal CF-O electrode displays an OER overpotential of 365.6 mV at 10 mA cm-2 and an ORR peak potential of 0.683 V. Utilizing the CF-O sample as the air electrode in all-solid-state Zn-air batteries yields an open-circuit voltage of 1.28 V and a peak volume power density of 82.8 mW cm-3. Furthermore, endurance testing reveals a charge/discharge voltage gap of 1.07 V at a current density of 1.0 mA cm-2 after 30 cycles. This facile and economical fabrication approach for metal-free air electrodes holds promise for advancing high-performance metal-air batteries compared to various existing techniques.

High activity of cobalt-atomically dispersed catalyst on mesoporous carbon for rechargeable Zn-air batteries via effective removal of the hard template

The use of oxygen from air in Zn-air batteries requires the smart design of materials with bifunctional activity for oxygen reduction and evolution reactions (ORR/OER), and with a porous structure to facilitate the diffusion of oxygen gas to active sites. Kit-6 template-assisted porous structures have been proposed to this end; however, traditional methods for the removal of Kit-6 templates are highly aggressive and environmentally harmful. In this study, we present the synthesis of a cobalt atomically dispersed catalyst (Co-ADC) with interlayer engineering using mesoporous Kit−6 templates, focusing on two removal strategies: sodium hydroxide (0.5, 1, and 2 M) and hydrofluoric acid (15, 30, and 45 %). Physicochemical results indicated that Co-ADC-containing nanoparticles were obtained using the proposed methodology, while the use of HF promoted the loss of cobalt in the catalyst. During the activity evaluation for the ORR, and it was found that 0.5 M NaOH and HF at 15 % displayed similar activity, which could be related to the effect of carbon material as co-catalyst, but the first enabled a close 4e− pathway, and thus, the Co-ADC presented a ΔEOER-ORR of 640 mV. This optimized ADC displayed improved functionality owing to diffusion improvements by the mesoporous structure, presenting a maximum power density of 130.6 mW cm−2 and 30 % higher specific activity than the Pt + IrO2/C reference material. Rechargeability was evaluated, yielding a ΔV = 0.87 V at 5.175 mA cm−2 with a round-trip efficiency of 57.5 %. Nonetheless, the optimized material presented higher rechargeability, displaying no significant round-trip changes after 100 cycles, while Pt + IrO2/C presented changes due to OER issues after only 48 cycles.

Lignin-derived Fe–N–C electrocatalyst with 3D porous structure for efficient oxygen reduction reaction

Developing low-cost, high-performance oxygen reduction reaction (ORR) catalysts is crucial for the commercialization of fuel cells and zinc-air batteries. Herein, we report a lignin-derived Fe/N co-doped 3D porous carbon electrocatalyst Fe-NLC-1 as an alternative to commercial Pt/C catalysts, which was synthesized by a green and facile in situ carbonization strategy. Fe-NLC-1 exhibits higher oxygen reduction activity with a half-wave potential (E1/2) of 0.90 V vs. RHE than commercial 20 wt% Pt/C (E1/2 = 0.85 V) in the alkaline conditions, as well as excellent methanol tolerance and stability. Furthermore, the Zn-air battery loaded with Fe-NLC-1 exhibits a maximum power density of 125 mW cm−2, an open circuit voltage of 1.477 V, and stable discharge performance, which are comparable or even better than the commercial Pt/C. This study highlights the potential of biomass-derived porous carbon materials for the development of high-performance ORR electrocatalysts.

Atomic-scale mechanistic study of oxygen reduction mechanism for B-site doped Pr(Ba,Sr)Co2O5+δ by density functional theory calculations

Pr(Ba,Sr)Co2O5+δ is a promising cathode material for solid oxide fuel cell (SOFC) due to its high oxygen ion transport capability and oxygen reduction activity. Density functional theory (DFT) calculations were performed to elucidate the oxygen reduction mechanism of B-site doped Pr(Ba,Sr)(Co,M)2O5+δ (M = Fe, Ni, Cu, and Zn) materials. First, we investigated the formation of O vacancies. The results indicate that Cu and Zn doping facilitate O vacancy formation, resulting in lower O vacancy formation energies. Furthermore, the interaction between oxygen and the (0 0 1) surfaces of B-site doped Pr(Ba,Sr)(Co,M)2O5+δ has been comprehensively discussed, involving both perfect and defective surfaces. The results demonstrate that the presence of O vacancies enhances the catalytic activity for oxygen reduction, by reducing the energy required for O2 dissociation. Zn-doped Pr(Ba,Sr)(Co,M)2O5+δ exhibits a low O vacancy formation energy, resulting in a stable adsorption configuration upon oxygen dissociation, indicating its potential as a cathode material for SOFC.

Electro-functionalized 2D nitrogen-carbon nanosheets decorated with symbiotic cobalt single-atoms/clusters

Two-dimensional (2D) materials loaded with single atoms and clusters are being set at the forefront of catalysis due to their distinctive geometric and electronic features. However, the usually-complicated synthesis procedures impede in-depth clarification of their catalytic mechanisms. To this end, herein we developed an efficient one-step dimension-reduction carbonization strategy, with which we successfully architected a highly-efficient catalyst for oxygen reduction reaction (ORR), featured with symbiotic cobalt single atoms and clusters decorated in two-dimensional (2D) ultra-thin (3.5 nm thickness) nitrogen-carbon nanosheets. The synergistic effects of the two components afford excellent oxygen reduction activity in alkaline media (E1/2=0.823 V vs. RHE) and thereof a high power density (146.61 mW cm−2) in an assembled Zn-air battery. As revealed by theoretical calculations, the cobalt clusters can regulate electrons surrounding those individual atoms and affect the adsorption of intermediate species. As a consequence, the derived active sites of single cobalt atoms lead to a significant improvement of the ORR performance. Thus, our work may fuel interests to delicate architecture of single atoms and clusters coexisting 2D support toward optimal electrocatalytic performance.

Stability enhancement of molybdenum modified rutile – carbon composite supported platinum electrocatalysts by reductive pretreatment: Surface characteristics and advanced electrocatalytic properties

Development of strong metal-support interaction (SMSI) and its influence on the catalytic performance of the Pt/Ti0.8Mo0.2O2-C system, a representative of the mixed oxide-carbon composite supported Pt electrocatalyst family, were investigated. Structural, surface chemical and electrochemical properties of the as-prepared Pt/Ti0.8Mo0.2O2-C catalyst and its counterparts reduced in the 150–450 °C temperature range were compared. TEM elemental mapping confirmed the widespread formation of Pt-oxide-C triple junctions in all catalysts. XPS revealed electronic interaction between the Pt particles and the oxide both in the as-prepared and the reduced catalysts, moreover, demonstrated that transport of Mo to the surface of Pt is initiated by reduction in the 150–250 °C range. Electrochemical measurements pointed out the durability of these Pt-bound Mo species, which also enhance the oxygen reduction activity of the catalyst. Based on the results of 10,000-cycle stability tests, reductive pretreatment between 250–350 °C is recommended for enhancing the properties of Pt/Ti0.8Mo0.2O2-C catalysts by SMSI.

Screening Transition-Metal-Incorporated β-AgVO3 for Augmented Oxygen Reduction Activity.

Exploring cost-effective alternatives to Pt-based catalysts for the oxygen reduction reaction (ORR) in fuel cells is crucial for their large-scale deployment in green energy applications. Silver vanadate (AgVO3) is a well-studied material for photocatalytic applications. Here, we investigate the electrocatalytic ORR activity of the thermodynamically stable β phase of AgVO3 through computational modeling based on DFT. It is found that β-AgVO3 exhibits weak catalytic activity for the ORR, with vanadium being the preferable active site. Incorporating single atoms of transition metals at surface-level vacancies in β-AgVO3 significantly modifies the ORR activity. We study the scaling of free energy changes for the ORR intermediates *OOH, *OH, and *O for various transition metals incorporated, which leads to an optimal overpotential for the system. The optimal overpotential thus obtained is remarkably lower than that of pristine β-AgVO3. For the transition metal atoms we consider here, Co-incorporated β-AgVO3 exhibits the best ORR catalytic activity due to its optimal binding of ORR species to the vanadium site. It is also observed that some of the transition metals considered like Re, Rh, Os, or Mn show weak activity, either due to strong or weak binding. Analysis of the electronic structure of the adsorbate-catalyst interface shows a strong correlation between optimal activity and evolution of midgap states in β-AgVO3, due to transition metal incorporation. Our study concludes that the ORR activity of a stable mixed transition metal oxide like β-AgVO3 can be enhanced with a minimal loading of transition metals, which could help in developing a novel series of ORR catalysts.

Degradation of phenol by metal-free electro-fenton using a carbonyl-modified activated carbon cathode: Promoting simultaneous H2O2 generation and activation

The low yield of hydrogen peroxide, narrow pH application range, and secondary pollution due to iron sludge precipitation are the major drawbacks of the electro-Fenton (EF) process. Metal-free electro-Fenton technology based on carbonaceous materials is a promising green pollutant degradation technology. Activated carbon cathodes enriched with carbonyl functional groups were prepared using a two-step annealing method for the degradation of phenol pollutants. The •OH in the activation process of H2O2 were identified using the EPR test technique. The action mechanism of carbonyl groups on H2O2 activation was investigated in conjunction with density functional theory (DFT) calculations. The EPR tests demonstrated that the modified activated carbon could promote the in-situ activation of H2O2 to •OH. And the results of material analysis and DFT showed that C=O could facilitate the activation of hydrogen peroxide through the electron transfer mechanism as an electron-donating group. Electrochemical tests showed that both the oxygen reduction activity and 2e−ORR selectivity of the modified activated carbons were significantly improved. Compared with the original activated carbon cathode and EF, the degradation efficiency of phenol in the ACNH-1000/GF cathode was increased by 58.10% and 45.61%, respectively. Compared with EF, ACNH-1000/GF metal-free electro-Fenton effectively expands the pH application range, and is proven to be less affected by solution initial pH, while avoiding secondary pollution. The metal-free electro-Fenton system can save more than a quarter of the cost of EF system. This study has a deep understanding of the reaction mechanism of the carbonyl modified activated carbon, and provides valuable insights for the design of metal-free catalysts, so as to promote its application in the degradation of organic pollutants.

Key Role of Density Functional Approximation in Predicting M–N–C Catalyst Activities for Oxygen Reduction

Key Role of Density Functional Approximation in Predicting M–N–C Catalyst Activities for Oxygen Reduction

Efficient generation of singlet oxygen (1O2) by CoP/Ni2P@NF for degradation of sulfamerazine through a heterogeneous electro-Fenton process at circumneutral pH

In electro-Fenton (EF), the development of a catalytic material with wide pH application range and high interference resistance is more suitable for practical wastewater treatment. In this study, the nanoneedle-shaped CoP/Ni2P heterostructure loaded onto a nickel foam substrate (CoP/Ni2P@NF) was successfully fabricated, which was used as a cathode material for heterogeneous electro-Fenton (Hetero-EF) to degrade sulfamerazine (SMR) at circumneutral pH. The SMR degradation efficiency within 90 min went to 100% and 87% at initial pH of 6.8 and 11, respectively. Experiments and theoretical calculations demonstrated that the heterostructure of CoP/Ni2P redistributed the interfacial charge and accelerated the electron transfer, resulting in different two-electron oxygen reduction (2e−ORR) selectivity and activity than CoP and Ni2P. The ion interference and complex water quality experiment exhibited that the degradation performance remained almost unchanged, showing better anti-interference ability and complex water quality applications. Through quenching experiments and EPR tests, it is confirmed that singlet oxygen (1O2) was the major reactive oxygen species (ROS) and 1O2 was converted from hydroxyl radical (·OH) adsorbed on the catalyst surface. This study provides an efficient catalyst for the application of Hetero-EF to remove organic compounds in complex water at circumneutral pH.

Origins of enhanced oxygen reduction activity of transition metal nitrides.

Transition metal nitride (TMN-) based materials have recently emerged as promising non-precious-metal-containing electrocatalysts for the oxygen reduction reaction (ORR) in alkaline media. However, the lack of fundamental understanding of the oxide surface has limited insights into structure-(re)activity relationships and rational catalyst design. Here we demonstrate how a well-defined TMN can dictate/control the as-formed oxide surface and the resulting ORR electrocatalytic activity. Structural characterization of MnN nanocuboids revealed that an electrocatalytically active Mn3O4 shell grew epitaxially on the MnN core, with an expansive strain along the [010] direction to the surface Mn3O4. The strained Mn3O4 shell on the MnN core exhibited an intrinsic activity that was over 300% higher than that of pure Mn3O4. A combined electrochemical and computational investigation indicated/suggested that the enhancement probably originates from a more hydroxylated oxide surface resulting from the expansive strain. This work establishes a clear and definitive atomistic picture of the nitride/oxide interface and provides a comprehensive mechanistic understanding of the structure-reactivity relationship in TMNs, critical for other catalytic interfaces for different electrochemical processes.

Phosphor-doping modulates the d-band center of Fe atoms in Fe-N4 catalytic sites to boost the activity of oxygen reduction

Regulating the electronic structure by phosphor-doping is a preferred strategy to boost the performance of carbon-based catalysts for oxygen reduction reaction (ORR). Here, a porous Fe, P, N-codoped carbon catalyst (PCF-FeTz-900) is designed by a phytic acid-assisted thermal etching strategy, in which P atoms are first doped into the carbon matrix to form a stable PC bond, and then FeN4 sites are produced from Fe-2,4,6-Tris(2-pyridyl)-s-triazine complex (Fe-TPTz). Theoretical calculations suggest that the electrons are transferred from the doped P atom to the neighboring FeN4 sites, which facilitates the ORR at the Fe sites by reducing the energy barrier and the adsorption energy of intermediates. Additionally, the P-doped FeN4 (FeN4P) structure manifests a lower free energy difference than that of FeN4 and the d-band center of Fe is also lowered, which further ensures its higher ORR catalytic ability. As a result, the PCF-FeTz-900 catalyst exhibits superior ORR activity and stability in alkaline electrolyte, and the assembled primary zinc-air battery shows greater performances compared to the commercial Pt/C catalyst. This work can provide an effective pathway for modulating the performance of doped-carbon materials in energy conversion devices.