Oxygen Reduction Reaction Properties Research Articles

Reactivity and Durability of Covalent Organic Frameworks Derived Co‐Based Hybrid Bifunctional Electrocatalysts for Zinc‐Air Batteries

AbstractDeveloping bifunctional non‐precious metal electrocatalysts of superior reactivity and durability is essential. Herein, we report a class of phthalocyanine‐based covalent organic frameworks as self‐sacrificial precursors derived Co‐based hybrid electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The fabricated Co‐COFs/CNT‐700 catalysts displayed highly efficient ORR properties with a half‐potential of 0.83 V, while its half‐wave potential in alkaline solution at a current density of 10 mA cm−2 is 1.70 V in the OER test, reflecting exceptional OER activity. Moreover, zinc‐air batteries assembled with Co‐COFs/CNT‐700 catalysts exhibit a marginally higher power density (114 mW cm2) than traditional Pt/C−IrO2 batteries in an air atmosphere, along with an enhanced cycling stability (5.1 % potential loss after 65 h). This work may pave a facile and efficient approach for fabricating electrocatalytic materials with controllably introduced metals and heteroatoms.

Control Over Nitrogen Dopant Sites in Palladium Metallene for Manipulating Catalytic Activity and Stability in the Oxygen Reduction Reaction

AbstractDoping light elements in Pt‐group metals is an effective approach toward improving their catalytic properties for oxygen reduction reaction (ORR). However, it is challenging to control dopant sites and to establish the correlation between the doping site and the catalytic property. In this paper, this success is demonstrated in controlling N doping sites in Pd metallene to manipulate electrocatalytic properties toward ORR. A Pd metallene sample with N dopant predominantly located at the atomic vacancy site (V‐N‐Pd metallene) exhibits two times higher mass activity in ORR than a Pd metallene sample with N dopant mainly occupied the interstitial site (I‐N‐Pd metallene). However, the I‐N‐Pd metallene shows improved durability than the V‐N‐Pd metallene, with only a 4 mV decay in half‐wave potential after 20 000 cycles. Computational calculation results reveal that the significantly enhanced ORR activity of V‐N‐Pd metallene arises from the atomic vacancy‐doped N, which modulates the electronic structure of Pd metallene to weaken the adsorption energy of intermediate O* species. This work provides guidelines for manipulating catalytic properties by controlling the doping sites of light elements in metal nanostructures.

ORR properties of PtM (M = Fe and Ni) ordered alloys with the effect of small molecules of cyanamide

Ordered Pt alloy electrocatalysts have a special geometric structure and exhibit excellent oxygen reduction reaction (ORR) catalytic performance. Herein, we successfully prepared PtFe/PtNi ordered alloy catalysts by thermal annealing method under the protection of the encapsulated shell formed by pyrolysis of cyanamide molecules as well as the effect of the N element entering into the alloy system to cause defects, and kept the average particle size below 4 nm. The ordered structure enhances the electronic interactions, keeps more Pt0 valence states present and improves the ORR catalytic activity. Under acidic conditions, the PtFe ordered alloy catalyst had a mass activity of 0.752 A mgPt−1 and a specific activity of 1.138 mA cmPt−2, both of which were superior to the commercial Pt/C and disordered PtFe alloy. Importantly, the strong interaction between ordered Pt and Fe prevents the leaching of Fe and maintains high mass activity after a long period of circulation. DFT calculations show that the ordered PtFe alloy has a low reaction energy barrier, which is favorable for ORR.

Theoretical study of transition metal-oxygen doped carbon for oxygen reduction reaction

The transition metal doped carbon materials are currently one of the most promising electrocatalysts for the oxygen reduction reaction (ORR). In this work, the ORR properties of transition metal-oxygen doped carbon (TM-O4-C, TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni and Cu) had been systematically studied by density function theory (DFT). Since the adsorption strength of OH* on TM-O4-C species was relatively strong, the effect of OH* modification was further considered. The results showed that the OH* modification can improve the ORR performance on TM-O4-C species by adjusting the d-band center of TM atoms to optimize the adsorption strength of the intermediate. Upon OH* modification, Ni-O4-OH-C species showed the most promising ORR performance with the lowest overpotential of 0.39 V. This work would shed light on the rational design of highly efficient oxygen-containing transition metal doped carbon-based materials.

Enzymolytic lignin derived Fe–N codoped porous carbon materials as catalysts for oxygen reduction reactions

Numerous active sites and hierarchical pore structures are important for improving catalytic performance for the oxygen reduction reaction (ORR). In this work, a series of iron-nitrogen-doped porous carbon materials (Fe–N–C) with ORR catalytic activity were prepared by a one-step pyrolysis method using enzymolytic lignin as the raw material, soy protein isolate and iron chloride as dopants. The results showed that the samples with the best performance have abundant Fe-Nx active sites and mesoporous structures. At the same time, the electrocatalytic results indicate that the half-wave potential of catalyst was 0.84 V, which reached 96.55% of commercial Pt/C catalysts (E1/2 = 0.86 V), it still preserves an initial current density of 92%, after 10,000 s of circulation, which is much better than Pt/C (86%). Due to the low cost, high activity and stable ORR property, the prepared non-precious metal electrocatalyst will play an important role in the applications of fuel cells.

Strong Carbon Layer-Encapsulated Cobalt Tin Sulfide-Based Nanoporous Material as a Bifunctional Electrocatalyst for Zinc-Air Batteries.

Global demands for cost-effective, durable, highly active, and bifunctional catalysts for metal-air batteries are tremendously increasing in scientific research fields. In this work, a strategy for the rational fabrication of carbon layer-encapsulated cobalt tin sulfide nanopores (CoSnOH/S@C NPs) material as a bifunctional electrocatalyst for rechargeable zinc (Zn)-air batteries by a cost-effective and facile two-step hydrothermal method is reported. Moreover, the effect of metal elements on the morphology of CoSnOH nanodisks material via the hydrothermal method is investigated. Owing to its excellent nanostructure, exclusive porous network, and high specific surface area, the optimized CoSnOH/S@C NPs material reveals superior catalytic properties. The as-prepared CoSnOH/S@C NPs electrocatalyst reveals better properties of oxygen reduction reaction (half-wave potential of -0.88 V vs reversible hydrogen electrode) and oxygen evolution reaction (overpotential of 137mV at 10mAcm-2) when compared with commercial Pt/C and IrO2 catalyst materials. Most significantly, the CoSnO/S@C NPs-based Zn-air battery exhibits more excellent cycling stability than the Pt/C+IrO2 catalyst-based one. Consequently, the proposed material provides a new route for fabricating more active and stable multifunctional catalyst materials for energy conversion and storage systems.

High entropy La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3 with tailored eg occupancy and transition metal-oxygen bond properties for oxygen reduction reaction

Forming high entropy oxide provides a feasible approach to finding a balance among moderate eg occupancy, high transition metal-oxygen (TM-O) covalency, and lattice energy, which is essential to ensure efficient and durable oxygen reduction reaction (ORR) process for perovskite lanthanide-transition metal oxides (LaTMO3). However, due to the compositional complexity, clarifying the relevance among the high entropy components, eg occupancy, TM-O properties, and ORR performance still remains a challenge. Herein, adopting the B site entropy-driven strategy, a series of LaTMO3 (TM = Cr, Mn, Fe, Co, Ni) with tunable eg occupancy and TM-O bond properties are synthesized, and the correlations between high entropy elements, eg occupancy, TM-O properties, and ORR performances are revealed quantitively based on the crystal field theory and the Phillips–Van Vechten–Levine (P–V–L) valence bond theory. High entropy La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3 delivers a low overpotential of 493 mV (vs. 503 mV for LaMnO3) and a minuscule decline by only 1.7% (vs. 4.4% for LaMnO3) in half wave potential after 10,000 cycles, which can be associated with the tailored eg occupancy (1.06) and the significant enhancement in both TM-O covalency (4%) and lattice energy (691.75 kJ mol–1). This work not only demonstrates the prospects of high entropy LaTMO3 in the ORR field but also provides a new perspective for the quantitative analysis of the structure-activity relationship for high entropy oxide ORR catalysts.

Efficient and Stable Dual-Active-Site of Core-Shell NiFe-Layered Double Hydroxide Anchored on FeMnON-N-Doped Carbon Nanotubes as Bifunctional Oxygen Electrocatalysts for Zn-Air Batteries

The bifunctional air electrodes with numerous dual-active sites and low cost are desirable to modify the performance of Zn-air batteries (ZABs). Metal–oxygen-nitrogen–carbon substrate (M = Mn, Fe, Ni, etc.) and NiFe-layered double hydroxide (NiFe-LDH) nanosheets are excellent catalysts in the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) processes, respectively. Hereby, we investigate a bifunctional electrocatalytic substrate with a 3D core–shell hierarchical architecture by anchoring high OER-active NiFe-LDH on ORR-active FeMnZIF-8@gC3N4-derived FeMnON-N doped carbon nanotubes bamboo like (NiFe-LDH@FeMnON-NC). This nanocomposite has unique features such as robust synergistic effects, high conductivity, balance, and optimization of surface chemical valences of Fe, Mn, and Ni atoms to boost the bifunctional ORR and OER properties and stability in ZABs. The NiFe-LDH@FeMnON-NC nanocomposite not only exhibited superior OER electroactivity with a low onset overpotential of 235 mV (10 mA cm−2) but also had excellent ORR activity with a current density of −5.48 mA cm−2 and onset potential of 1.04 V, which is better than or comparable to those of commercial Pt/C and RuO2. Rechargeable ZABs constructed by bifunctional NiFe-LDH@FeMnON-NC have a peak power density (235.41 mW cm−2), open-circuit potential (OCV) (1.53 V), small discharge/charge band gap of 0.74 V and excellent discharge stability.

Manipulation of Electronic States of Pt Sites via d-Band Center Tuning for Enhanced Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells.

Expediting the torpid kinetics of the oxygen reduction reaction (ORR) at the cathode with minimal amounts of Pt under acidic conditions plays a significant role in the development of proton exchange membrane fuel cells (PEMFCs). Herein, a novel Pt-N-C system consisting of Pt single atoms and nanoparticles anchored onto the defective carbon nanofibers is proposed as a highly active ORR catalyst (denoted as Pt-N-C). Detailed characterizations together with theoretical simulations illustrate that the strong coupling effect between different Pt sites can enrich the electron density of Pt sites, modify the d-band electronic environments, and optimize the oxygen intermediate adsorption energies, ultimately leading to significantly enhanced ORR performance. Specifically, the as-designed Pt-N-C demonstrates exceptional ORR properties with a high half-wave potential of 0.84 V. Moreover, the mass activity of Pt-N-C reaches 193.8 mA gPt-1 at 0.9 V versus RHE, which is 8-fold greater than that of Pt/C, highlighting the enormously improved electrochemical properties. More impressively, when integrated into a membrane electrode assembly as cathode in an air-fed PEMFC, Pt-N-C achieved a higher maximum power density (655.1 mW cm-2) as compared to Pt/C-based batteries (376.25 mW cm-2), hinting at the practical application of Pt-N-C in PEMFCs.

Regulating electrocatalytic properties of oxygen reduction reaction via strong coupling effects between Co-NC sites and intermetallic Pt3Co

Developing the Pt-based intermetallic nanoparticles could accelerate the sluggish kinetic of oxygen reduction reaction, while it remains a great challenge to explore efficient synthesis strategies enhancing thermal stabilities and electrocatalytic properties. This work employed the metal-support coupling strategy to construct the Pt3Co/CoNC hierarchical nanostructure, where the well-dispersed atomically ordered Pt3Co nanoparticles were anchored on the Co-NC sites. Physical structure analysis combined with density functional theory calculations demonstrated the strong coupling effect between Pt and surrounding Co-NC sites, which could weaken the activation energy to break O-O bonds and enhance the intrinsic activity and stability of Pt. Hence, the Pt3Co/CoNC exhibited the optimized ORR activities with the half-wave potentials of 0.97 V in KOH solution and displayed the peak power density of 187 mW cm−2 as the cathode of Zn-air battery. This metal-support coupling strategy can be further generalized and improved to synthesize other Pt-based catalysts with efficient electrocatalytic properties.

Oxygen reduction mediated by tetrapyridylalkylamine Cu(II) complexes with diimines

Oxygen reduction reaction (ORR) is important in artificial energy conversion systems such as fuel cells. However, it is kinetically sluggish. It is thereby highly desirable to develop ORR catalysts to improve the efficiency of energy conversion. In this work, three copper(II) complexes based on the hexadentate tetrapyridylalkylamine N,N,N’,N’-tetrakis(2-pyridyl-methyl)-1,4-butanediamine (tpbn), namely [Cu2(tpbn)(CH3OH)4(ClO4)2](ClO4)2 (Cu-tpbn), [Cu2(tpbn)(bpy)2](ClO4)4.2CH3COCH3 (Cu-tpbn-bpy, bpy = 2,2′-bipyridine), and [Cu2(tpbn)(Me2bpy)2](ClO4)4.3CH3CN (Cu-tpbn-Me2bpy, Me2bpy = 4,4′-dimethyl-2,2′-bipyridine), were prepared and their catalytic properties for ORR studied. All three complexes were homogeneous electrocatalysts for ORR in neutral phosphate buffer solutions. The ORR mediated by Cu-tpbn-Me2bpy had the most positive onset potential of 0.461 V vs RHE. In the applied potential window of -0.19 – 0.50 V vs RHE, Cu-tpbn boosted the stepwise four-electron ORR to mainly produce H2O, whereas Cu-tpbn-bpy and Cu-tpbn-Me2bpy mediated the ORR to mainly generate H2O2. The rate constants for the ORR to H2O promoted by Cu-tpbn, Cu-tpbn-bpy and Cu-tpbn-Me2bpy were 1.2 × 103 s−1, 3.2 × 10 s−1 and 7.8 × 10 s−1, respectively. The foot-of-the-wave analysis showed that the turnover frequencies for the reduction of O2 to H2O2 mediated by Cu-tpbn, Cu-tpbn-bpy and Cu-tpbn-Me2bpy were 1.5 × 104 s−1, 7.5 × 10 s−1 and 2.7 × 102 s−1, respectively. Meanwhile, complexes Cu-tpbn-bpy and Cu-tpbn-Me2bpy were more stable than Cu-tpbn. This work unveiled that the catalytic activity and the product selectivity of the ORR were greatly associated with the denticity, the steric effect and the electronic property of the organic ligands.

ZnO-templated hollow amorphous carbon: oxygen adsorption and doping synergy for enhanced ORR catalysis.

In pursuit of highly active zinc-air battery (ZAB) catalysts, nitrogen doping has proven key to enhancing carbon-based non-metallic catalysts' performance in the oxygen reduction reaction (ORR). This study employed a novel method to synthesize variously sized ZnO materials coated with ZIF-8. Notably, smaller particle sizes correlated with reduced activation energy. ZnO-12, the smallest variant, fully carbonized at 800 °C, resulting in zinc ion evaporation and the formation of an amorphous carbon nano-hollow structure, ZIF8/ZnO-12. This material showcased remarkable ORR properties, with an onset potential of 0.9 V (vs. RHE) and a Tafel slope of 71.4 mV dec-1, surpassing the benchmark Pt/C catalyst and exhibiting excellent stability. Moreover, in ZAB tests, ZIF8/ZnO-12 achieved a specific capacity of 816 mA h g-1, outperforming Pt/C. DFT calculations indicate that under alkaline conditions, nitrogen-doped carbon materials containing adsorbed oxygen and doped oxygen exhibit lower catalytic activation energy for the ORR, which is beneficial for accelerating the ORR. This research provides valuable insights into designing more efficient carbon-based non-metallic catalysts for ZABs.

Component-controlled synthesis of PdxSny nanocrystals on carbon nanotubes as advanced electrocatalysts for oxygen reduction reaction.

Pd-based bimetallic or multimetallic nanocrystals are considered to be potential electrocatalysts for cathodic oxygen reduction reaction (ORR) in fuel cells. Although much advance has been made, the synthesis of component-controlled Pd-Sn alloy nanocrystals or corresponding nanohybrids is still challenging, and the electrocatalytic ORR properties are not fully explored. Herein, component-controlled synthesis of PdxSny nanocrystals (including Pd3Sn, Pd2Sn, Pd3Sn2, and PdSn) has been realized, which are in situ grown or deposited on pre-treated multi-walled carbon nanotubes (CNTs) to form well-coupled nanohybrids (NHs) by a facile one-pot non-hydrolytic system thermolysis method. In alkaline media, all the resultant PdxSny/CNTs NHs are effective at catalyzing ORR. Among them, the Pd3Sn/CNTs NHs exhibit the best catalytic activity with the half-wave potential of 0.85 V (vs. RHE), good cyclic stability, and excellent methanol-tolerant capability due to the suited Pd-Sn alloy component and its strong interaction or efficient electronic coupling with CNTs. This work is conducive to the advancement of Pd-based nanoalloy catalysts by combining component engineering and a hybridization strategy and promoting their application in clean energy devices.

Pt-surface stabilization by high-entropy alloys for enhancing oxygen reduction reaction property: Single-crystal model catalyst study

In this work, we study the oxygen reduction reaction (ORR) properties of Pt-containing 3d transition-metal high-entropy alloy (Pt-HEA) surfaces, focusing on the constituent alloying elements. The surface Pt and underlying Cr-Mn-Co-Ni(111) (Pt/Cr-Mn-Co-Ni(111)) stacked lattice layers, which are synthesized through the vacuum deposition of the underlying alloy and surface Pt stacking layers on Pt(111) substrate, exhibit high pristine ORR activity and structural stability under potential-cycle loading, compared to Pt/Cr-Co-Ni, Pt/Mn-Co-Ni, and Pt/Co-Ni(111) surfaces. The outperformed ORR properties are attributed to the effective suppression of the surface segregation of Cr. This study demonstrates that not only the “high-entropy” effect induced by increasing the numbers of constituent elements but also the “chemical affinity” of Pt and the individual HEA constituent elements determine the ORR performances of Pt-HEA.

Oxygen Reduction Reaction Properties of Dry-Process Synthesized Pt-Non PGM Transition Metal Multi-Component Alloys: Influence of Transition Metal Elements

Introduction Multi-component alloys (MCAs) have been attracted much attention in various engineering application fields. [1] By changing numbers of constituent elements (n) as well as their composition ratios (𝑥) of MCAs, the mixing-entropy (ΔSmix = −𝑅∑(𝑖=1→n) 𝑥𝑖 ln 𝑥𝑖) increases with increasing n, resulting in reduced Gibbs free-energy (ΔG = ΔH - TΔS) of the MCAs, which correlates with interesting bulk material’s properties. Furthermore, the MCAs surfaces possess specific chemical properties, for example, high thermodynamic and chemical stabilities, probably caused by the reduced ΔG, that are much different from those of binary alloys, e.g., Pt-Co or Pt-Ni. Therefore, the MCAs surfaces can be applied for novel nano-materials developments, including electrocatalytic materials. [2] Indeed, our previous study for single-crystal surfaces of the MCAs system of Pt and non-PGM Cr-Mn-Fe-Co-Ni (known as Cantor alloy [3]) demonstrates that enhanced oxygen reduction reaction (ORR) activity at a pristine state and, furthermore, electrochemical structural stability even through the potential cycle (PC)-loading. [4] Thermodynamical and chemical properties of the MCAs surfaces are, in general, a superposition of specific properties of the constituent elements and newly emerging properties that stemming from multi-component alloying. Therefore, catalytic influences of the multiple alloying-elements on ORR properties (activity and structural stability) of Pt-containing MCAs (referred to as Pt-MCAs) surfaces are much complicated, due mainly to the sluggish diffusion and segregation behaviors of the constituent elements. Thus, optimizing the constituent elements (kinds and n) and their composition ratios (𝑥) at the surface vicinity is surely essential for considering an application of the MCAs as practical ORR catalysts. In this study, we synthesized Pt-MCAs on Pt(111) substrate surface with various n and kinds of the constituent elements by controlling vacuum-deposition amounts of the elements and conducted fundamental investigations aimed for high performance cathode alloy catalyst’s developments of polymer electrolyte membrane fuel cells. Experimental In this study, we focused on equi-composition-ratio of the MCAs by picking up 2~5 elements of Cr, Mn, Fe, Co, and Ni as alloying elements of Pt. 10 monolayer (ML)-thick (1 ML = ca. 0.3 nm) MCAs layer was first deposited on the surface-cleaned Pt(111) substrate by using an arc-plasma deposition method at 300 K, and subsequently annealed in vacuum at 773 K for 30 min. Then, 4 ML-thick Pt layer was deposited on the MCAs layer at 300 K and post-annealed at 623 K in vacuum. The samples thus prepared are designated as Pt/MCAs/Pt(111). The atomic-level micro-structures and composition ratios of the surface-vicinity of resulting Pt/MCAs/Pt(111) were characterized by cross-sectional STEM-EDS and XPS. CVs and LSVs were conducted in N2-purged and O2-saturated 0.1 M HClO4 by using an RDE apparatus. ORR activity was evaluated from j k values estimated at 0.9 V vs. RHE by using Koutecky-Levich equation and structural stability (ORR durability) was discussed based upon the activity transitions during applying 5,000 potential cycles (PCs) of 0.6(3s)‐1.0(3s) V vs. RHE in O2 saturated 0.1 M HClO4 at room temperature. Results and Discussion The ORR activity trends under applying the PC loading (a), initial CVs (b), and XPS-estimated surface compositions of Pt/MCAs/Pt(111) are summarized in Fig. 1(a-c), where Cr-Mn-Fe-Co-Ni, Mn-Fe-Co-Ni, Cr-Fe-Co-Ni, and Fe-Co-Ni are adopted for the MCAs. Notably, the ORR activity of Cr containing Pt/Cr-Fe-Co-Ni/Pt(111) (green) decreased remarkably up to 2,000 PCs, compared to Cr-less Pt/Mn-Fe-Co-Ni/Pt(111) (red), Pt/Fe-Co-Ni/Pt(111) (yellow), and both Cr and Mn containing Pt/Cr-Mn-Fe-Co-Ni(Cantor alloy)/Pt(111) (blue). Furthermore, Pt/Cr-Fe-Co-Ni/Pt(111) exhibited increased electric double layer charge in the potential region of 0.4 to 0.6 V at the pristine state (b). Additionally, XPS-estimated relatively smaller and larger composition ratios of the Pt and Cr, respectively, among the tested Pt/MCAs/Pt(111) (c), suggesting that Cr of the MCAs preferentially diffuses and segregates at the surface-vicinity through the heat treatment process of the sample fabrication, which might cause severe decrease in ORR activity at the early stage of the PCs loading (up to 2,000 PCs). [5] At the meeting, correlations between the ORR properties and atomic-level microstructures of Pt/MCAs/Pt(111) surfaces will be discussed in detail. Acknowledgement This study was supported by new energy and industrial technology development organization (NEDO) of Japan, JST SPRING, Grant Number JPMJJSP2114 (Y.C.) and Grant-in-Aid for JSPS Fellows (Y.C.).

Boosting oxygen reduction via MnP nanoparticles encapsulated by N, P-doped carbon to Mn single atoms sites for Zn-air batteries

An electrocatalyst of single-atomic Mn sites with MnP nanoparticles (NPs) on N, P co-doped carbon substrate was constructed to enhance the catalytic activity of oxygen reduction reaction (ORR) through one-pot in situ doping-phosphatization strategy. The optimized MnSA-MnP-980℃ catalyst exhibits an excellent ORR activity in KOH electrolyte with a half-wave potential (E1/2) of 0.88 V (vs. RHE), and the ORR current density of MnSA-MnP-980℃ maintained 97.9 % for over 25000 s chronoamperometric i-t measurement. When using as the cathode, the MnSA-MnP-980℃ displays a peak power density of 51 mW cm−2 in Zinc-Air batteries, which observably outperformed commercial Pt/C (20 wt%). The X-ray photoelectron spectroscopy reveal that the doped P atoms with a strong electron-donating effectively enhances electron cloud density of Mn SAs sites, facilitating the adsorption of O2 molecules. Meanwhile, the introduction of MnP NPs can regulate the electronic structure of Mn SAs sites, making Mn SAs active sites exist in a low oxidation state and are less positively charged, which can supply electrons for ORR process to narrow the adsorption energy barrier of ORR intermediates. This work constructs novel active sites with excellent ORR properties and provides valuable reference for the development of practical application.

CoFe Alloys Dispersed on Se, N Co-Doped Graphitic Carbon as Efficient Bifunctional Catalysts for Zn-Air Batteries.

The development of a stable and efficient non-noble metal catalyst with both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is paramount to achieving the widespread application of Zn-air batteries (ZABs) but remains a great challenge. Herein, a novel Co3 Fe7 alloy nanoparticle dispersed on Se, N co-doped graphitic carbon (denoted as CoFe/Se@CN) was prepared through a facile hydrothermal and pyrolysis process. The synthesized CoFe/Se@CN exhibits outstanding ORR and OER properties with an ultralow potential gap of 0.625 V, which is mainly attributed to the abundant porous structure, the rich structural defects formed by doping Se atoms, and the strong synergistic effects between the CoFe alloys and graphitic carbon nanosheet. Furthermore, the ZAB fabricated by CoFe/Se@CN shows a high peak power density of 160 mW cm-2 and a large specific capacity of 802 mA h g-1 with favorable cycling stability, outperforming that of Pt/C+RuO2 . Our study offers a plausible strategy to explore bifunctional carbon-based materials with efficient electrocatalytic properties for rechargeable ZABs.

Nickel-iron layered double hydroxides interlinked by N-doped carbon network as bifunctional electrocatalysts for rechargeable zinc-air batteries

The rational design and fabrication of electrocatalysts with low cost and excellent bifunctional properties for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are desirable for high-efficiency rechargeable zinc-air batteries. Herein, we report the synthesis of NiFe LDHs nanoparticles interconnected by the one-dimensional N-doped carbon nanotubes (CNTs) and two-dimensional graphene nanosheets (NiFe-CNTs-rGO). The in-situ formed N-doped carbon and Fe-N-C active sites highly improve the ORR activity and the loading of NiFe LDHs nanoparticles promotes the OER. The integration of NiFe LDHs with intertwined CNTs and netlike rGO guarantees the good electrical conductivity of NiFe-CNTs-rGO. The unique composition and microstructure endow NiFe-CNTs-rGO with superior bifunctional activity toward ORR and OER. Moreover, the rechargeable zinc-air battery assembled with NiFe-CNTs-rGO electrocatalyst as air cathode shows a high capacity of 793 mA h g−1 and works stable for 100 h at 10 mA cm−2, outperforming commercial Pt/C and RuO2 mixture.

Electrochemical investigation of Pr6O11 infiltration into La0.8Sr0.2MnO3-δ-Ce0.9Gd0.1O1.95 cathodes for IT-SOFC

Infiltration through spray-pyrolysis deposition is a one-step and effective method for enhancing the electrode performance of solid oxide fuel cells (SOFCs) at intermediate temperatures. Among various infiltrated electrodes, Pr6O11 has shown promising electrocatalytic properties for oxygen reduction reaction (ORR), despite its relatively low electrical conductivity. This study focuses on obtaining Pr6O11-infiltrated cathodes using spray-pyrolysis deposition, with different porous backbone layers that exhibit electronic and/or ionic conductivity: La0.8Sr0.2MnO3-δ (LSM), Ce0.9Gd0.1O1.95 (CGO), and LSM-CGO composite. The electrochemical properties and the subprocesses involved in the ORR are investigated in symmetrical cells. It is observed that the polarization resistance (Rp) decreases when the backbone layer exhibits high ionic conductivity. At 650 °C, the Rp values are 0.03, 0.06 and 0.1 Ω cm2 for CGO, LSM-CGO and LSM backbones, respectively. The dependence of Rp contributions with pO2 reveals that the same electrochemical processes are involved regardless of the backbone composition, confirming a less resistive oxide-ion transport from the TPB into the electrolyte with the CGO backbone. In contrast, the CGO backbone exhibits higher series resistance (Rs) (44.5 Ω cm), attributed to an increased contribution of ohmic losses compared to the LSM backbone (39.8 Ω cm). This study provides valuable insights into the performance and optimization of Pr6O11-infiltrated cathodes with different backbone compositions for their implementation in SOFCs.

Experimental study platform for electrocatalysis of atomic-level controlled high-entropy alloy surfaces

High-entropy alloys (HEAs) have attracted considerable attention to improve performance of various electrocatalyst materials. A comprehensive understanding of the relationship between surface atomic-level structures and catalytic properties is essential to boost the development of novel catalysts. In this study, we propose an experimental study platform that enables the vacuum synthesis of atomic-level-controlled single-crystal high-entropy alloy surfaces and evaluates their catalytic properties. The platform provides essential information that is crucial for the microstructural fundamentals of electrocatalysis, i.e., the detailed relationship between multi-component alloy surface microstructures and their catalytic properties. Nanometre-thick epitaxially stacking layers of Pt and equi-atomic-ratio Cr-Mn-Fe-Co-Ni, the so-called Cantor alloy, were synthesised on low-index single-crystal Pt substrates (Pt/Cr-Mn-Fe-Co-Ni/Pt(hkl)) as a Pt-based single-crystal alloy surface model for oxygen reduction reaction (ORR) electrocatalysis. The usefulness of the platform was demonstrated by showing the outperforming oxygen reduction reaction properties of high-entropy alloy surfaces when compared to Pt-Co binary surfaces.