RESUMEN
Transition metal-based nanoparticles (NPs) are emerging as potential alternatives to platinum for catalyzing the oxygen reduction reaction (ORR) in zinc-air batteries (ZAB). However, the simultaneous coexistence of single-atom moieties in the preparation of NPs is inevitable, and the structural complexity of catalysts poses a great challenge to identifying the true active site. Herein, by employing in situ and ex situ XAS analysis, we demonstrate the coexistence of single-atom moieties and iron phosphide NPs in the N, P co-doped porous carbon (in short, Fe-N4-Fe2P NPs/NPC), and identify that ORR predominantly proceeds via the atomic-dispersed Fe-N4 sites, while the presence of Fe2P NPs exerts an inhibitory effect by decreasing the site utilization and impeding mass transfer of reactants. The single-atom catalyst Fe-N4/NPC displays a half-wave potential of 0.873 V, surpassing both Fe-N4-Fe2P NPs/NPC (0.858 V) and commercial Pt/C (0.842 V) in alkaline condition. In addition, the ZAB based on Fe-N4/NPC achieves a peak power density of 140.3 mW cm-2, outperforming that of Pt/C-based ZAB (91.8 mW cm-2) and exhibits excellent long-term stability. This study provides insight into the identification of true active sites of supported ORR catalysts and offers an approach for developing highly efficient, nonprecious metal-based catalysts for high-energy-density metal-air batteries.
RESUMEN
The advanced oxygen reduction reaction (ORR) catalysts, integrating with well-dispersed single atom (SA) and atomic cluster (AC) sites, showcase potential in bolstering catalytic activity. However, the precise structural modulation and in-depth investigation of their catalytic mechanisms pose ongoing challenges. Herein, a proactive cluster lockdown strategy is introduced, relying on the confinement of trinuclear clusters with metal atom exchange in the covalent organic polymers, enabling the targeted synthesis of a series of multicomponent ensembles featuring FeCo (Fe or Co) dual-single-atom (DSA) and atomic cluster (AC) configurations (FeCo-DSA/AC) via thermal pyrolysis. The designed FeCo-DSA/AC surpasses Fe- and Co-derived counterparts by 18 mV and 49 mV in ORR half-wave potential, whilst exhibiting exemplary performance in Zn-air batteries. Comprehensive analysis and theoretical simulation elucidate the enhanced activity stems from adeptly orchestrating dz2-dxz and O 2p orbital hybridization proximate to the Fermi level, fine-tuning the antibonding states to expedite OH* desorption and OOH* formation, thereby augmenting catalytic activity. This work elucidates the synergistic potentiation of active sites in hybrid electrocatalysts, pioneering innovative targeted design strategies for single-atom-cluster electrocatalysts.
RESUMEN
Due to the slow dynamics of mass and charge transfer at Zn|electrolyte interface, the stable operation of Zn-air batteries (ZABs) is challenging, especially at low temperature. Herein, inspired by cell membrane, a hydrophilic-hydrophobic dual modulated Zn|electrolyte interface is constructed. This amphiphilic design enables the quasi-solid-state (QSS) ZABs to display a long-term cyclability of 180 h@50 mA cm-2 at 25 °C. Moreover, a record-long time of 173 h@4 mA cm-2 at -60 °C is also achieved, which is almost threefolds of untreated QSS ZABs. Control experiments and (in situ) characterization reveal that the growth of insulating ZnO passivation layers is largely inhibited by tuned hydrophilic-hydrophobic behavior. Thus, the enhanced transfer dynamic of Zn2+ at Zn|electrolyte interface from 25 to -60 °C is attained. As an extension, the QSS Al-air batteries (AABs) with bioinspired interface also show unprecedented discharge stability of 420 h@1 mA cm-2 at -40 °C, which is about two times of untreated QSS AABs. This bioinspired-hydrophilic-hydrophobic dual modulation strategy may provide a reference for energy transform and storage devices with broad temperature adaptability.
RESUMEN
Photo-assisted Zn-air batteries can accelerate the kinetics of oxygen reduction and oxygen evolution reactions (ORR/OER); however, challenges such as rapid charge carrier recombination and continuous electrolyte evaporation remain. Herein, for the first time, piezoelectric catalysis is introduced in a photo-assisted Zn-air battery to improve carrier separation capability and accelerate the ORR/OER kinetics of the photoelectric cathode. The designed microhelical catalyst exploits simple harmonic vibrations to regenerate the built-in electric field continuously. Specifically, in the presence of the low-frequency kinetic energy that occurs during water flow, the piezoelectric-photocoupling catalyst of poly(vinylidene fluoride-co-trifluoroethylene)@ferric oxide(Fe@P(V-T)) is periodically deformed, generating a constant reconfiguration of the built-in electric field that separates photogenerated electrons and holes continuously. Further, on exposure to microvibrations, the gap between the charge and discharge potentials of the Fe@P(V-T)-based photo-assisted Zn-air battery is reduced by 1.7 times compared to that without piezoelectric assistance, indicating that piezoelectric catalysis is highly effective for enhancing photocatalytic efficiency. This study provides a thorough understanding of coupling piezoelectric polarization and photo-assisted strategy in the field of energy storage and opens a fresh perspective for the investigation of multi-field coupling-assisted Zn-air batteries.
RESUMEN
Bimetallic atom catalysts exhibit ultra-high oxygen electrocatalytic activity by harnessing mutual promotion and synergistic effects between adjacent metal active centers, surpassing the performance of single metal atomic catalysts. Herein, FeNi atom pairs protected by hierarchical porous annular carbon grids (P-FeNi-NPC) are introduced using a mediator-assisted MOFs-derived strategy. The introduction of the multi-block copolymer P123 ensures the uniform confinement and dispersion of metal ions, followed by thermal decomposition to form a "planetary-ring-like" carbon framework that anchors the bimetallic atomic pairs in the active region. The homogeneous distribution of adjacent Fe-N4 and Ni-N4 active sites significantly enhances catalytic activity and stability. Leveraging unique electronic and geometric structures, the resulting P-FeNi-NPC catalyst demonstrates exceptional ORR and OER activities with an ΔE value of 0.705 (E1/2 = 0.845 V, Ej = 10 = 1.55 V). Theoretical calculations unveil that FeNi bimetallic sites loaded on nitrogen-doped carbon frameworks with specific curvature effectively modulate the energy of d-band centers, thus balancing the free energy of oxygen-containing intermediates. This study presents a novel and versatile approach for synthesizing advanced bifunctional catalysts, poised to drive the future development of Zn-air batteries.
RESUMEN
Single-atom catalysts show good oxygen reduction reaction (ORR) performance in metal-air battery. However, the symmetric electron distribution results in discontented adsorption energy of ORR intermediates and a lower ORR activity. Herein, Fe-Co dual-atom catalyst with FeN3-CoN3 configuration was prepared by encapsulating nitrogen-rich ion (triethylenediamine cobalt complex, [Co(en)3]3+) in Fe based MOF cage to greatly enhance ORR performance. Due to the confinement effect of the MOF cage, the encapsulated [Co(en)3]3+ is closer to Fe of MOF, thus easily generating FeN3-CoN3 sites. The FeN3-CoN3 sites can break the symmetric electron distribution of single-atom sites, optimizing adsorption energy of oxygen intermediate. Thus, FeCo-NC exhibits extraordinary ORR activity with a high half-wave potential of 0.915 V and 0.789 V in alkaline and acidic electrolyte, respectively, while it was 0.874 V and 0.79 V for Pt/C. The liquid and solid Zn-air batteries with FeCo-NC as cathode show higher peak power density and specific capacity. DFT results indicate that FeN3-CoN3 site can reduce the reaction energy barrier of the rate-determining step resulting in an excellent ORR performance.
RESUMEN
Zinc-air batteries (ZABs) have garnered considerable attention as a highly promising contender in the field of energy storage and conversion. Nevertheless, their performance is considerably impeded by the proliferation of dendrites on the Zinc anode and the slow kinetics of the redox reaction on the air cathode. Herein, taking Ag30%@LaCoO3 (Ag30%@LCO) heterojunction catalyst as the cathode, it is demonstrated that adding KI additives to the alkaline electrolyte can not only enhance the oxygen electrocatalytic reaction but also inhibit the formation of zinc anode dendrites, thereby achieving a comprehensive improvement in the performance of ZABs. Under the action of the KI additive, the optimized Ag30%@LCO catalyst shows a decreased overpotential from 460 to 220 mV at j = 10 mA cm-2, while the assembled ZAB shows reduced charging potential (1.8 V), and long cycle stability (180 h). Furthermore, the morphology characterization results indicate a reduction in dendrites on the Zn anode. Both experimental and calculated results indicate that the presence of I- as a reaction modifier alters the trajectory of the conventional oxygen evolution reaction, resulting in a more thermodynamically favorable pathway. The introduction of KI additives as electrolytes provides a straightforward approach to developing comprehensively improved ZABs.
RESUMEN
Flexible rechargeable Zn-air batteries (FZABs) exhibit high energy density, ultra-thin, lightweight, green, and safe features, and are considered as one of the ideal power sources for flexible wearable electronics. However, the slow and high overpotential oxygen reaction at the air cathode has become one of the key factors restricting the development of FZABs. The improvement of activity and stability of bifunctional catalysts has become a top priority. At the same time, FZABs should maintain the battery performance under different bending and twisting conditions, and the design of the overall structure of FZABs is also important. Based on the understanding of the three typical configurations and working principles of FZABs, this work highlights two common strategies for applying bifunctional catalysts to FZABs: 1) powder-based flexible air cathode and 2) flexible self-supported air cathode. It summarizes the recent advances in bifunctional oxygen electrocatalysts and explores the various types of catalyst structures as well as the related mechanistic understanding. Based on the latest catalyst research advances, this paper introduces and discusses various structure modulation strategies and expects to guide the synthesis and preparation of efficient bifunctional catalysts. Finally, the current status and challenges of bifunctional catalyst research in FZABs are summarized.
RESUMEN
In the quest to enhance Zn-air batteries (ZABs) for operating across a wide spectrum of temperatures, synthesizing robust oxygen electrocatalysts is paramount. Conventional strategies focusing on orbital hybridization of d-d and p-d aim to moderate the excessive interaction between the d-band of the transition metal active site and oxygen intermediate, yet often yield suboptimal performance. Herein, an innovative s-block metal modulation is reported to refine the electronic structure and catalytic behavior of CoâNC catalysts. Employing density functional theory (DFT) calculations, it is revealed that incorporating Mg markedly depresses the d-band center of Co sites, thereby fine-tuning the adsorption energy of the oxygen reduction reaction (ORR) intermediate. Consequently, the Mg-modified CoâNC catalyst (MgCoâNC) unveils remarkable intrinsic ORR activity with a significantly reduced activation energy (Ea) of 10.0 kJ mol-1, outstripping the performance of both CoâNC (17.6 kJ mol-1), benchmark Pt/C (15.9 kJ mol-1), and many recent reports. Moreover, ZABs outfitted with the finely tuned Mg0.1Co0.9âNC realize a formidable power density of 157.0 mW cm-2, paired with an extremely long cycle life of 1700 h, and an exceptionally minimal voltage gap decay rate of 0.006 mV h-1. Further, the Mg0.1Co0.9âNC-based flexible ZAB presents a mere 2% specific capacity degradation when the temperature fluctuates from 25 to -20 °C, underscoring its robustness and suitability for practical deployment in diverse environmental conditions.
RESUMEN
Single-atom catalysts (SACs), with precisely controlled metal atom distribution and adjustable coordination architecture, have gained intensive concerns as efficient oxygen reduction reaction (ORR) electrocatalysts in Zn-air batteries (ZAB). The attainment of a monodispersed state for metallic atoms anchored on the carbonaceous substrate remains the foremost research priority; however, the persistent challenges lie in the relatively weak metal-support interactions and the instability of captured single atom active sites. Furthermore, in order to achieve rapid transport of O2 and other reactive substances within the carbon matrix, manufacturing SACs based on multi-stage porous carbon substrates is highly anticipated. Here, we propose a methodology for the fabrication of carbon aerogels (CA)-supported SACs utilizing papermaking nanofibers, which incorporates advanced strategies for N-atom self-doping, defect/vacancy introduction, and single-atom interface engineering. Specifically, taking advantages of using green and energy-efficient feedstocks, combining with a direct pore-forming template volatilization and chemical vapor deposition approach, we successfully developed N-doped carbon aerogels immobilized with separated iron sites (Fe-SAC@N/CA-Cd). The obtained Fe-SAC@N/CA-Cd exhibited substantially large specific surface area (SBET = 1173 m2/g) and a multi-level pore structure, which can effectively mitigate the random aggregation of Fe atoms during pyrolysis. As a result, it demonstrated appreciable activity and stability in catalyzing the ORR progress (E1/2 = 0.88 V, Eonset = 0.96 V). Furthermore, the assembled liquid electrolyte-state Zn-air batteries (LES-ZAB) and all-solid-state Zn-air battery (ASS-ZAB) also provides encouraging performance, with a peak power density of 169 mW cm-2 for LES-ZAB and a maximum power density of 124 mW cm-2 for ASS-ZAB.
RESUMEN
The rational construction of highly active and robust non-precious metal oxygen reduction electrocatalysts is a vital factor to facilitate commercial applications of Zn-air batteries. In this study, a precise and stable heterostructure, comprised of a coupling of Co3Fe7 and Fe3C, was constructed through an interface engineering-induced strategy. The coordination polymerization of the resin with the bimetallic components was meticulously regulated to control the interfacial characteristics of the heterostructure. The synergistic interfacial effects of the heterostructure successfully facilitated electron coupling and rapid charge transfer. Consequently, the optimized CST-FeCo displayed superb oxygen reduction catalytic activity with a positive half-wave potential of 0.855 V vs. RHE. Furthermore, the CST-FeCo air electrode of the liquid zinc-air battery revealed a large specific capacity of 805.6 mAh gZn-1, corresponding to a remarkable peak power density of 162.7 mW cm-2, and a long charge/discharge cycle stability of 220 h, surpassing that of the commercial Pt/C catalyst.
RESUMEN
The development of a highly efficient, stable, and low-cost bifunctional catalyst is imperative for facilitating the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). However, significant challenges are involved in extending its applications to rechargeable zinc-air batteries. This study presents a bifunctional catalyst, Zr2ON2@NiFe layered double hydroxide (LDH), that was developed by utilizing a urea-glass route for synthesizing the Zr2ON2 precursor, followed by riveting NiFe LDH nanosheets using a hydrothermal method. Specifically, the vertical distribution of NiFe LDH on the Zr2ON2 surface ensures the maximization of the number of accessible active sites and interfacial catalysis of NiFe LDH. Notably, Zr2ON2@NiFe LDH demonstrates ORR and OER bifunctional electrocatalytic behavior and high stability owing to its heterostructure and composition. Furthermore, a rechargeable zinc-air battery using a Zr2ON2@NiFe LDH electrocatalyst as the air cathode demonstrated a high peak power density (172 mW cm-2) and galvanostatic charge-discharge cycle stability (5 mA cm-2 over 443 h). Thus, this study presents an efficient and cost-effective strategy for the design of bifunctional electrocatalysts.
RESUMEN
Based on experimental and computational evidence, phthalocyanine (Pc) compounds in the form of quaternary-bound metal-nitrogen (N) atoms are the most effective catalysts for oxygen reduction reaction (ORR). However, the heat treatment process used in their synthesis may compromise the ideal structure, causing the agglomeration of transition metals. To overcome this issue, a novel method is developed for synthesizing iron (Fe) single-atom catalysts with ideal structures supported by thermally exfoliated graphene oxide (GO). This is achieved through a short heat treatment of only 2.5 min involving FePc and N, N-dimethylformamide in the presence of GO. According to the synthesis mechanism revealed by this study, carbon monoxide acts as a strong linker between the single Fe atoms and graphene. It facilitates the formation of a structure containing oxygen species between FeN4 and graphene, which provides high activity and stability for the ORR. These catalysts possess an enormous number of active sites and exhibit enhanced activity toward the alkaline ORR. They demonstrate excellent performance when applied to real electrochemical devices, such as zinc-air batteries and anion exchange membrane fuel cells. It is expected that the instantaneous heat treatment method developed in this study will aid in the development of high-performing single-atom catalysts.
RESUMEN
Demetalation caused by the electrochemical dissolution of metallic Fe atoms is a major challenge for the practical application of FeâNâC catalysts. Herein, an efficient single metallic Mn active site is constructed to improve the strength of the FeâN bond, inhibiting the demetalation effect of FeâNâC. Mn acts as an electron donor inducing more delocalized electrons to reduce the oxidation state of Fe by increasing the electron density, thereby enhancing the FeâN bond and inhibiting the electrochemical dissolution of Fe. The oxygen reduction reaction pathway for the dissociation of FeâMn dual sites can overcome the high energy barriers to direct OâO bond dissociation and modulate the electronic states of FeâN4 sites. The resulting FeMnâNâC exhibits excellent ORR activity with a high half-wave potential of 0.92 V in alkaline electrolytes. FeMnâNâC as a cathode catalyst for Zn-air batteries has a cycle stability of 700 h at 25 °C and a long cycle stability of more than 210 h under extremely cold conditions at -40 °C. These findings contribute to the development of efficient and stable metal-nitrogen-carbon catalysts for various energy devices.
RESUMEN
Despite extensive research has been conducted on atomic dispersion catalysts for various reactions, altering the electronic structure of the central metal to enhance electrochemical reactivity remains a challenging task. Herein, the electrochemical reactivity was considerably enhanced by introducing heteroatomic B to adjust the d-band of single Fe center. In specific, the obtained FeSA-BNC catalyst demonstrated an outstanding ORR performance (E1/2 = 0.87 V) and exhibited greater long-term durability in alkaline media compared to Pt/C. The performance of FeSA-BNC in Zn-air battery was also higher than that of Pt/C. According to theoretical calculations, a downward shift in the d-band center of Fe was induced by introducing B, thereby improving the desorption of intermediates and facilitating the oxygen reduction reaction (ORR).
RESUMEN
Palladium hydride (PdHx) is one of the well-known electrocatalytic materials, yet its synthesis is still a challenge through an energy-efficient and straightforward method. Herein, we propose a new and facile cyanogel-assisted synthesis strategy for the preparation of PdH0.649 at a mild environment with NaBH4 as the hydrogen source. Unlike traditional inorganic Pd precursors, the unique Pd-CN-Pd bridge in Pdx[Pd(CN)4]y â aH2O cyanogel offers more favourable spatial sites for insertion of H atoms. The characteristic three-dimensional backbone of cyanogel also acts as a support scaffold resulting in the interconnected network structure of PdH0.649. Due to the incorporation of H atoms and interconnected network structure, the PdH0.649 achieves a high half-wave potential of 0.932â V, a high onset potential of 1.062â V, and a low activation energy, as well as a long-term lifetime for oxygen reduction reaction. Theoretical calculation demonstrates a downshift of the d-band centre of Pd in PdH0.649 owing to the dominant Pd-H incorporation that weakens the binding energies of the *OH intermediate species. Zn-air batteries (ZAB) based on PdH0.649 exhibits high power density, competitive open circuit voltage, and good stability, exceeding that of commercial Pt black. This work not only opens up a new avenue for the development of high-efficiency Pt-free catalysts but also provides an original approach and insight into the synthesis of PdHx.
RESUMEN
Nitrogen doping has been recognized as an important strategy to enhance the oxygen reduction reaction (ORR) activity of carbon-encapsulated transition metal catalysts (TM@C). However, previous reports on nitrogen doping have tended to result in a random distribution of nitrogen atoms, which leads to disordered electrostatic potential differences on the surface of carbon layers, limiting further control over the materials' electronic structure. Herein, a gradient nitrogen doping strategy to prepare nitrogen-deficient graphene and nitrogen-rich carbon nanotubes encapsulated cobalt nanoparticles catalysts (Co@CNTs@NG) is proposed. The unique gradient nitrogen doping leads to a gradual increase in the electrostatic potential of the carbon layer from the nitrogen-rich region to the nitrogen-deficient region, facilitating the directed electron transfer within these layers and ultimately optimizing the charge distribution of the material. Therefore, this strategy effectively regulates the density of state and work function of the material, further optimizing the adsorption of oxygen-containing intermediates and enhancing ORR activity. Theoretical and experimental results show that under controlled gradient nitrogen doping, Co@CNTs@NG exhibits significantly ORR performance (Eonset = 0.96 V, E1/2 = 0.86 V). At the same time, Co@CNTs@NG also displays excellent performance as a cathode material for Zn-air batteries, with peak power density of 132.65 mA cm-2 and open-circuit voltage (OCV) of 1.51 V. This work provides an effective gradient nitrogen doping strategy to optimize the ORR performance.
RESUMEN
Heterogeneous interface and defect engineering offer effective pathways to accelerate oxygen evolution reaction (OER) charge transfer kinetics and motivate optimal intrinsic catalytic activity. Herein, we report the lattice-matched NiO/NiFe2O4 heterostructure with ample oxygen vacancies (Vo-NiO/NiFe2O4) induced by a feasible hydrothermal followed by calcination and plasma-engraving assistant technique, which shows the unique porous microflower arrangement of intertwined nanosheets. Benefitting from the synergetic effects between lattice-matched heterointerface and oxygen vacancies induce the strong electronic coupling, optimized OH-/O2 diffusion pathway and ample active sites, thus-prepared Vo-NiO/NiFe2O4 presents a favorable OER performance with a low overpotential (261â mV @ 10â mA cm-2) and small Tafel slope (39.4â mV dec-1), even surpassing commercial RuO2 catalyst. Additionally, the two-electrode configuration water electrolyzer and rechargeable zinc-air battery assembled by Vo-NiO/NiFe2O4 catalyst show the potential practical application directions. This work provides an innovative avenue for strengthening OER performance toward water electrolysis and Zn-air batteries via the interface and vacancy engineering strategy.
RESUMEN
Cobalt-nitrogen-carbon (Co-N-C) catalysts with a CoN4 structure exhibit great potential for oxygen reduction reaction (ORR), but the imperfect adsorption energy toward oxygen species greatly limits their reduction efficiency and practical application potential. Here, F-coordinated Co-N-C catalysts with square-pyramidal CoN4-F1 configuration are successfully synthesized using F atoms to regulate the axial coordination of Co centers via hydrothermal and chemical vapor deposition methods. During the synthesis process, the geometry structure of the Co atom converts from six-coordinated Co-F6 to square-pyramidal CoN4-F1 in the coordinatively unsaturated state, which provides an open binding site for the O2. The introduction of axial F atoms into the CoN4 plane alters the local atomic environment around Co, significantly improving the ORR activity and Zn-air batteries performance. In situ spectroscopy proves that CoN4-F1 sites strongly combine with the OOH* intermediate and facilitate the splitting of O-O bond, making OOH* readily decompose into O* and OH* via a dissociative pathway. Theoretical calculations confirm that the axial F atom effectively reduces the electronic density of the Co centers and facilitates the desorption of the OH* intermediate, efficiently accelerating the overall ORR kinetics. This work advances a feasible synthesis mechanism of axial ligands and provides a route to construct efficient high-coordination catalysts.
RESUMEN
Lignin upgrading to various functional products is promising to realize high-value utilization of low-cost and renewable biomass waste, but is still in its infancy. Herein, using industry waste lignosulfonate as the biomass-based carbon source and urea as the dopant, we constructed a heteroatom-doped porous carbon nanosheet structure by a simple NaCl template-assisted pyrolytic strategy. Through the synergistic effect of the NaCl template and urea, the optimized lignin-derived porous carbon catalyst with high content of active nitrogen species and large specific surface area can be obtained. As a result, the fabricated catalysts exhibited excellent electrocatalytic oxygen reduction activity, as well as good methanol tolerance and stability, comparable to that of commercial Pt/C. Moreover, rechargeable Zn-air batteries assembled with this electrocatalyst have a peak power density of up to 150 mW cm-2 and prominent long-term cycling stability. This study offers an inexpensive and efficient way for the massive production of highly active metal-free catalysts from the plentiful, inexpensive and environmentally friendly lignin, offering a good direction for biomass waste recycling and utilization.