Zn Sites Research Articles

Highly dispersed Zn-N, S co-doped carbon for highly efficient electrocatalytic oxygen reduction

Supportive atomic Zn electrocatalysts exhibit excellent stability for oxygen reduction reaction (ORR) due to their fully occupied d orbitals of Zn, but their catalytic activity is not satisfactory. Whereas heteroatom doping can anchor the Zn atoms to achieve higher Zn loading; and additionally serve as auxiliary sites to enhance the catalytic activity of Zn sites. Herein, we present a method for the synthesis of N, S co-doped carbon with highly dispersed Zn (named Zn-NSC). The ORR activity of the Zn-NSC catalysts is optimized by adjusting the pyrolysis temperature and the atomic structure of the dopant molecules. The optimized Zn-NSC demonstrates significantly enhanced ORR electrocatalytic activity, this is attributable to its highly co-doping of N and S heteroatoms that are adjacent to Zn atoms. Specifically, the Zn-NSC3 catalyst exhibits remarkable ORR characteristics with excellent onset voltage (0.97 V vs RHE) and half-wave potential (0.87 V vs RHE), surpassing those of Pt/C (0.97 V and 0.85 V, respectively). Additionally, the Zn-NSC3 can be utilized as efficient cathode for Al-air batteries, achieving a high power density of 119.4 mW cm−2 and satisfactory discharge stability. This work proposes an approach for synthesizing low-cost and efficient ORR electrocatalysts for Al-air battery applications.

Exploring the Performance Improvement for CO2 Chemical Fixation in Zn/ZnMg-MOFs.

A new 3D zinc-based metal-organic framework {[Zn7L2(DMF)3(H2O)(OH)2]·5DMF}n (1) (H6L = 5,5',5″-(methylsilanetriyl) triisophthalic acid) was constructed with an organosilicon-based linker, where H6L is a tetrahedral structure furnished with rich -COO- chelating sites for Zn(II) immobilization. Compound 1 exhibited two types of irregular one-dimensional channels and a three-dimensional skeleton with large specific surface area, making it a promising catalytic platform. Moreover, by incorporation of the second metal ion into the inorganic node of framework 1, isomorphic bimetallic MOF ZnMg-1 was successfully synthesized. ZnMg-1 demonstrated enhanced catalytic activity compared to 1 under identical conditions. Contrast experiments and theoretical calculations indicate that bimetallic active sites play a facilitating role in the chemical fixation of epoxides and CO2. It indicated that efficient chemical fixation of CO2 to cyclic carbonates was obtained over isomorphic MOF catalysts 1 and ZnMg-1.

Manipulating Zn Metal Texture with Guided Zincophilic Sites via Electrochemical Stripping for Dendrite-Free Zn Anodes.

Constructing a three-dimensional (3D) structure along with Zn (002) texture selective exposure is a promising strategy to tackle the issues faced by Zn metal anodes. Herein, for the first time, we proposed an electrochemical stripping strategy to achieve controlled modification of the texture and microstructure of zinc foils in one step, building a hierarchical structure with (002) texture preferred exposed Zn (SZ). The SZ with favorable zincophilic properties not only can reduce the concentration polarization at the interface but also allow Zn to grow horizontally on the edge of the (002) texture by guiding the adsorption sites for Zn2+. Moreover, the honeycomb-like structure is beneficial to rearrange the distribution of the Zn2+ flux as well as alleviating stress changes during cycling. Thus, the SZ||Cu cell exhibits excellent stability with a Coulombic efficiency of 99.76% over 1800 cycles. The SZ||NaV3O8·xH2O cell with inconspicuous self-discharge effect maintains a high areal capacity of 3.67 mA h cm-2 even after 700 cycles with a low N/P ratio of 3.6. This work achieves texture architecture and structure designing on Zn foils simultaneously by metallurgical electrochemical methods and opens up a potential strategy to implement the practicality of zinc metal anodes.

Accelerating the Phosphatase-like Activity of Uio-66-NH2 by Catalytically Inactive Metal Ions and Its Application for Improved Fluorescence Detection of Cardiac Troponin I.

Compared with natural enzymes, nanozymes usually exhibit much lower catalytic activities, which limit the sensitivities of nanozyme-based immunoassays. Herein, several metal ions without enzyme-like activities were engineered onto Uio-66-NH2 nanozyme through postsynthetic modification. The obtained Mn+@Uio-66-NH2 (Mn+ = Zn2+, Cd2+, Co2+, Ca2+and Ni2+) exhibited improved phosphatase-like catalytic activities. In particular, a 12-fold increase in the catalytic efficiency (kcat/Km) of Uio-66-NH2 was observed after the modification with Zn2+. Mechanism investigations indicate that both the amino groups and oxygen-containing functional groups in Uio-66-NH2 are the binding sites of Zn2+, and the modified Zn2+ ions on Uio-66-NH2 serve as the additional catalytic sites for improving the catalytic performance. Furthermore, the highly active Zn2+@Uio-66-NH2 was used as a nanozyme label to develop a fluorescence immunoassay method for the detection of cardiac troponin I (cTnI). Compared with pristine Uio-66-NH2, Zn2+@Uio-66-NH2 can widen the linear range by 1 order of magnitude (from 10 pg/mL-1 μg/mL to 1 pg/mL-1 μg/mL) and also lower the detection limit by 5 times (from 4.7 pg/mL to 0.9 pg/mL).

Li4 Zn(PO4 )2 :Mn2+ thermosensitive phosphor with dual luminescent centres for optical thermometry.

An optical thermometry strategy based on Mn2+ -doped dual-wavelength emission phosphor has been reported. Samples with different doping content were synthesized through a high-temperature solid-phase method under an air atmosphere. The electronic structure of Li4 Zn(PO4 )2 was calculated using density functional theory, revealing it to be a direct band gap material with an energy gap of 4.708 eV. Moreover, the emitting bands of Mn2+ at 530 and 640 nm can be simultaneously observed when using 417 nm as the exciting wavelength. This is due to the occupation of Mn2+ at the Zn2+ site and the interstitial site. Further analysis was conducted on the temperature-dependent emission characteristics of the sample in the range 293-483 K. Mn2+ has different responses to temperature at different doping sites in Li4 Zn(PO4 )2 . Based on the calculations using the fluorescence intensity ratio technique, the maximum relative sensitivity at a temperature of 483 K was determined to be 1.69% K-1 , while the absolute sensitivity was found to be 0.12% K-1 . The results showed that the Li4 Zn(PO4 )2 :Mn2+ phosphor has potential application in optical thermometry.

Atomically synergistic Zn-Cr catalyst for iso-stoichiometric co-conversion of ethane and CO2 to ethylene and CO

Developing atomically synergistic bifunctional catalysts relies on the creation of colocalized active atoms to facilitate distinct elementary steps in catalytic cycles. Herein, we show that the atomically-synergistic binuclear-site catalyst (ABC) consisting of Znδ+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{{{{\\rm{Zn}}}}}}^{\\delta+}$$\\end{document}-O-Cr6+ on zeolite SSZ-13 displays unique catalytic properties for iso-stoichiometric co-conversion of ethane and CO2. Ethylene selectivity and utilization of converted CO2 can reach 100 % and 99.0% under 500 °C at ethane conversion of 9.6%, respectively. In-situ/ex-situ spectroscopic studies and DFT calculations reveal atomic synergies between acidic Zn and redox Cr sites. Znδ+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{{{{\\rm{Zn}}}}}}^{\\delta+}$$\\end{document} (0<δ<2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$0 \\, < \\, \\delta \\, < \\, 2$$\\end{document}) sites facilitate β-C-H bond cleavage in ethane and the formation of Zn-Hδ- hydride, thereby the enhanced basicity promotes CO2 adsorption/activation and prevents ethane C-C bond scission. The redox Cr site accelerates CO2 dissociation by replenishing lattice oxygen and facilitates H2O formation/desorption. This study presents the advantages of the ABC concept, paving the way for the rational design of novel advanced catalysts.

In situ synthesis of ZIF-8 on lignosulfonate functionalized polyethyleneimine/carboxymethyl chitosan hybrid aerogels for efficient tetracycline removal

The alarming overuse of antibiotics poses a serious threat to the environmental security. Herein, a hybrid aerogel adsorbent, sodium lignosulfonate functionalized polyethyleneimine/carboxymethyl chitosan@ZIF-8 (CCSL@ZIF-8), was fabricated by introducing sodium lignosulfonate into polyethyleneimine/carboxymethyl chitosan (CSSL) and then in situ uniformly anchoring of ZIF-8 on CSSL aerogel. The incorporation of sodium lignosulfonate not only enhanced the mechanical properties of CCSL, but also provided a large number of chelating sites for Zn2+ and promoted the formation of ZIF-8. The sorption behavior and mechanism were studied by batch adsorption experiments and characterization analysis. The experimental results demonstrated that the maximum adsorption capacity of CCSL-1.0@ZIF-8 was 231.36 mg/g with a tetracycline (TC) concentration of 200 mg/L at 303 K, which was 7 times higher than that of CCSL-1.0 (30.73 mg/g). The absorption process followed the pseudo-second-order kinetic model and Freundlich isothermal model, and the process of adsorbing TC was dominated by multilayer chemisorption. The adsorption mechanism included pore filling, coordination bonds, hydrogen bonding, electrostatic interactions and π-π interactions. Moreover, the removal efficiency of TC by CCSL-1.0@ZIF-8 was maintained above 78 % after 6 cycles. Overall, this work presents a potential bio-based adsorbent for the effective removal of tetracycline from wastewater and provides a novel, facile, and green chemical technique for high-value utilization of lignin. Furthermore, the prepared biomass-based hybrid adsorbent has outstanding reusability and water stability, which has broad practical application prospects in antibiotic wastewater treatment.

Dual-Site Biomimetic Cu/Zn-MOF for Atopic Dermatitis Catalytic Therapy via Suppressing FcγR-Mediated Phagocytosis.

Atopic dermatitis (AD) is a prevalent chronic inflammatory skin disease that carries a significant global economic burden. Elevated levels of reactive oxygen species (ROS) have been recognized as contributing to AD exacerbation, making them a potential therapeutic target for AD treatment. Here, we introduce a dual-site biomimetic copper/zinc metal-organic framework (Cu/Zn-MOF) featuring four types of enzyme-like activities for AD treatment via suppressing the Fcγ receptor (FcγR)-mediated phagocytosis signal by mimicking the bimetallic sites of natural copper-zinc superoxide dismutase (CuZn-SOD). Interestingly, the neighboring Cu and Zn sites in both Cu/Zn-MOF and CuZn-SOD are at similar distances of ∼5.98 and ∼6.3 Å from each other, respectively, and additionally, both Cu and Zn sites are coordinated to nitrogen atoms in both structures, and the coordinating ligands to Cu and Zn are both imidazole rings. Cu/Zn-MOF exhibits remarkable SOD-like activity as well as its glutathione peroxidase (GPx)-, thiol peroxidase (TPx)-, and ascorbate peroxidase (APx)-like activities to continuously consume ROS and mitigate oxidative stress in keratinocytes. Animal experiments show that Cu/Zn-MOF outperforms halcinonide solution (a potent steroid medication) in terms of preventing mechanical injuries, reducing cutaneous water loss, and inhibiting inflammatory responses while presenting favorable biosafety. Mechanistically, Cu/Zn-MOF functions through an FcγR-mediated phagocytosis signal pathway, decreasing the continuous accumulation of ROS in AD and ultimately suppressing disease progression. These findings will provide an effective paradigm for AD therapy and contribute to the development of two-site bionics (TSB).

Boosted hydrogen evolution kinetics of heteroatom-doped carbons with isolated Zn as an accelerant

Carbon-based single-atom catalysts, a promising candidate in electrocatalysis, offer insights into electron-donating effects of metal center on adjacent atoms. Herein, we present a practical strategy to rationally design a model catalyst with a single zinc (Zn) atom coordinated with nitrogen and sulfur atoms in a multilevel carbon matrix. The Zn site exhibits an atomic interface configuration of ZnN4S1, where Zn's electron injection effect enables thermal-neutral hydrogen adsorption on neighboring atoms, pushing the activity boundaries of carbon electrocatalysts toward electrochemical hydrogen evolution to an unprecedented level. Experimental and theoretical analyses confirm the low-barrier Volmer-Tafel mechanism of proton reduction, while the multishell hollow structures facilitate the hydrogen evolution even at high current intensities. This work provides insights for understanding the actual active species during hydrogen evolution reaction and paves the way for designing high-performance electrocatalysts.

Melamine induced co-regulation of solvation structure and interface engineering to achieve dendrite-free Zn-ion hybrid capacitors

Aqueous zinc (Zn)-based energy storage devices have attracted great attention due to their inherent low cost, intrinsic safety, and environmental friendliness. However, the growth of Zn dendrite and side reactions from water decomposition have limited the lifespan of Zn-ion energy storage. Herein, a green and multifunctional melamine (M) molecules is proposed as electrolyte additive and incorporated into the ZnSO4 electrolyte to modulate the deposition/stripping environment of Zn2+ and stabilize the Zn anode. The results of experiments coupled with density-functional theory (DFT) calculations and molecular dynamics (MD) simulations show that M molecules are able to optimize the electrolyte environment and regulate the electrode-electrolyte surface. More specifically, the hydrophilic group (-NH2) in the M molecule can effectively break the electrolyte sheath structure and reconstruct the hydrogen bonding network, because the M molecule has a stronger binding energy compared to H2O. Meanwhile, the -N= groups in M can anchor Zn2+ and cooperate with them to form a dynamic electrostatic protective layer, change the electric field distribution around the Zn deposition layer, provide more nucleation sites for Zn2+ and promote the deposition of Zn along the (002) crystal plane, thus inhibiting the random growth of Zn dendrite and the occurrence of side reactions. Consequently, the Zn//Zn symmetric cell assembled with the ZnSO4+M electrolyte presents boost the stable lifespan over 1,100 hours at a current density of 2 mA cm−2, 1 mAh cm−2, and also up to 1900 stable cycles with almost 100 % Coulomb efficiency for Zn//Cu asymmetric cell.

Modifying Surface Termination by Bidentate Chelating Strategy Enables 13.77% Efficient Kesterite Solar Cells.

Surfaces display discontinuities in the kesterite-based polycrystalline films can produce large defect densities, including strained and dangling bonds. These physical defects tend to introduce electronic defects and surface states, which can greatly promote nonradiative recombination of electron-hole pairs and damage device performance. Here, an effective chelation strategy is reported to suppress these harmful physical defects related to unterminated Cu, Zn, and Sn sites by modifying the surface of Cu2ZnSn(S,Se)4 (CZTSSe) films with sodium diethyldithiocarbamate (NaDDTC). The conjoint theoretical calculations and experimental results reveal that the NaDDTC molecules can be coordinate to surface metal sites of CZTSSe films via robust bidentate chelating interactions, effectively reducing surface undercoordinated defects and passivating the electron trap states. Consequently, the solar cell efficiency of the NaDDTC-treated device is increased to as high as 13.77% under 100mW cm-2 illumination, with significant improvement in fill factor and open-circuit voltage. This surface chelation strategy provides strong surface termination and defect passivation for further development and application of kesterite-based photovoltaics.

Single Zn Atoms with Acetate‐Anion‐Enabled Asymmetric Coordination for Efficient H2O2 Photosynthesis

AbstractExploring unique single‐atom sites capable of efficiently reducing O2 to H2O2 while being inert to H2O2 decomposition under light conditions is significant for H2O2 photosynthesis, but it remains challenging. Herein, we report the facile design and fabrication of polymeric carbon nitride (CN) decorated with single‐Zn sites that have tailorable local coordination environments, which is enabled by utilizing different Zn salt anions. Specifically, the O atom from acetate (OAc) anion participates in the coordination of single‐Zn sites on CN, forming asymmetric Zn−N3O moiety on CN (denoted as CN/Zn−OAc), in contrast to the obtained Zn−N4 sites when sulfate (SO4) is adopted (CN/Zn−SO4). Both experimental and theoretical investigations demonstrate that the Zn−N3O moiety exhibits higher intrinsic activity for O2 reduction to H2O2 than the Zn−N4 moiety. This is attributed to the asymmetric N/O coordination, which promotes the adsorption of O2 and the formation of the key intermediate *OOH on Zn sites due to their modulated electronic structure. Moreover, it is inactive for H2O2 decomposition under both dark and light conditions. As a result, the optimized CN/Zn−OAc catalyst exhibits significantly improved photocatalytic H2O2 production activity under visible light irradiation.

Single Zn Atoms with Acetate-Anion-Enabled Asymmetric Coordination for Efficient H2 O2 Photosynthesis.

Exploring unique single-atom sites capable of efficiently reducing O2 to H2 O2 while being inert to H2 O2 decomposition under light conditions is significant for H2 O2 photosynthesis, but it remains challenging. Herein, we report the facile design and fabrication of polymeric carbon nitride (CN) decorated with single-Zn sites that have tailorable local coordination environments, which is enabled by utilizing different Zn salt anions. Specifically, the O atom from acetate (OAc) anion participates in the coordination of single-Zn sites on CN, forming asymmetric Zn-N3 O moiety on CN (denoted as CN/Zn-OAc), in contrast to the obtained Zn-N4 sites when sulfate (SO4 ) is adopted (CN/Zn-SO4 ). Both experimental and theoretical investigations demonstrate that the Zn-N3 O moiety exhibits higher intrinsic activity for O2 reduction to H2 O2 than the Zn-N4 moiety. This is attributed to the asymmetric N/O coordination, which promotes the adsorption of O2 and the formation of the key intermediate *OOH on Zn sites due to their modulated electronic structure. Moreover, it is inactive for H2 O2 decomposition under both dark and light conditions. As a result, the optimized CN/Zn-OAc catalyst exhibits significantly improved photocatalytic H2 O2 production activity under visible light irradiation.

Physical upcycling of spent artificial diamond accelerant into bifunctional oxygen electrocatalyst with dual-metal active sites for durable rechargeable Zn–air batteries

The low-cost and efficient bifunctional electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is critical for advanced rechargeable Zn–air batteries (ZABs). Herein, we designed and fabricated a bifunctional m-Fe2.04Ni0.66 @GCFs catalyst using a sustainable physical upcycling strategy involving spent artificial diamond accelerants. Experiments and theoretical calculations verified that dual-metal active-site synergy between *Fe2.04Ni0.66 @GC and Fe2.04 *Ni0.66 @GC enhances the rapid adsorption/desorption of *OOH/*OH species, thereby improving ORR/OER performance. In situ Raman technique confirmed that ORR/OER activities are dependent on the FeOOH, Fe(OH)2, and β-NiOOH intermediates formed during the reaction. Impressively, the m-Fe2.04Ni0.66 @GCFs catalyst exhibited outstanding ORR/OER activities with a small potential difference of only 0.73 V in alkaline media. The assembled rechargeable ZAB exhibited high peak power density (115.2 mW cm−2), large specific capacity (786.9 mA h g−1), and long-term charge-discharge cycling stability of more than 1200 cycles. These results not only contribute to the design of efficient bifunctional catalysts, but also provide a new approach to the high-value utilisation of waste catalyst resources.

Study the Structural, Electronic, Optical Properties of CZTS Compound after Doping Ba at Zn Site and Si at Sn Site Using Density Functional Theory (DFT)

Study the Structural, Electronic, Optical Properties of CZTS Compound after Doping Ba at Zn Site and Si at Sn Site Using Density Functional Theory (DFT)

Synergistic dual sites of Zn-Mg on hierarchical porous carbon as an advanced oxygen reduction electrocatalyst for Zn-air batteries.

The development of cost-effective and high-performance non-noble metal catalysts for the oxygen reduction reaction (ORR) holds substantial promise for real-world applications. Introducing a secondary metal to design bimetallic sites enables effective modulation of a metal-nitrogen-carbon (M-N-C) catalyst's electronic structure, providing new opportunities for enhancing ORR activity and stability. Here, we successfully synthesized an innovative hierarchical porous carbon material with dual sites of Zn and Mg (Zn/Mg-N-C) using polymeric ionic liquids (PILs) as precursors and SBA-15 as a template through a bottom-up approach. The hierarchical porous structure and optimized Zn-Mg bimetallic catalytic centers enable Zn/Mg-N-C to exhibit a half-wave potential of 0.89 V, excellent stability, and good methanol tolerance in 0.1 M KOH solution. Theoretical calculations indicated that the Zn-Mg bimetallic sites in Zn/Mg-N-C effectively lowered the ORR energy barrier. Furthermore, the Zn-air batteries assembled based on Zn/Mg-N-C demonstrated an outstanding peak power density (298.7 mW cm-2) and superior cycling stability. This work provides a method for designing and synthesizing bimetallic site catalysts for advanced catalysis.

Controllable construction of a 3D-honeycomb-like porous carbon network as a high-performance cathode for promoting Zn-ion storage capability.

Inheriting the energy storage mechanism of supercapacitors and rechargeable ion batteries, zinc ion capacitors (ZICs) greatly increase their energy density at high power without sacrificing their life span. However, sluggish kinetics and insufficient active sites for Zn2+ storage induced by the significant mismatch of charge carriers with limited pore size hinder the efficient Zn2+ storage and smooth application of carbonaceous cathode materials. Herein, a three-dimensional honeycomb-like porous carbon network (HPCN) was fabricated, which can reduce the diffusion barrier for fast kinetics, produce a high-density defect area, effectively increase active sites for charge storage, and generate a high nitrogen-doping content. Benefiting from these advantages, the optimized ZICs bring out a marvelous energy/power density (130 W h kg-1/11.7 kW kg-1) with an ultrahigh reliable cyclability of 97.8% after 50 000 cycles at a high current density of 5 A g-1. Importantly, systematic ex situ characterizations combined with theoretical calculations demonstrate that the outstanding Zn2+ storage capacity is attributed to the synergistic effect of physical co-adsorption of cations and reversible chemisorption. This work presents an attractive strategy for developing advanced carbon cathodes with suitable pores and accelerates the exploration of charge storage mechanisms, which may open a new avenue for practical supercapacitors.

Pauling-Type Adsorption of O2 Induced by Heteroatom Doped ZnIn2 S4 for Boosted Solar-Driven H2 O2 Production.

Breaking the trade-off between activity and selectivity has perennially been a formidable endeavor in the field of hydrogen peroxide (H2 O2 ) photosynthesis, especially the side-on configuration of oxygen (O2 ) on the catalyst surface will cause the cleavage of O-O bonds, which drastically hinders the H2 O2 production performance. Herein, we present an atomically heteroatom P doped ZnIn2 S4 catalyst with tunable oxygen adsorption configuration to accelerate the ORR kinetics essential for solar-driven H2 O2 production. Indeed, the spectroscopy characterizations (such as EXAFS and in situ FTIR) and DFT calculations reveal that heteroatom P doped ZnIn2 S4 at substitutional and interstitial sites, which not only optimizes the coordination environment of Zn active sites, but also facilitates electron transfer to the Zn sites and improves charge density, avoiding the breakage of O-O bonds and reducing the energy barriers to H2 O2 production. As a result, the oxygen adsorption configuration is regulated from side-on (Yeager-type) to end-on (Pauling-type), resulting in the accelerated ORR kinetics from 874.94 to 2107.66 μmol g-1 h-1 . This finding offers a new avenue toward strategic tailoring oxygen adsorption configuration by the rational design of doped photocatalyst.

Pauling‐Type Adsorption of O2Induced by Heteroatom Doped ZnIn2S4for Boosted Solar‐Driven H2O2Production

AbstractBreaking the trade‐off between activity and selectivity has perennially been a formidable endeavor in the field of hydrogen peroxide (H2O2) photosynthesis, especially the side‐on configuration of oxygen (O2) on the catalyst surface will cause the cleavage of O−O bonds, which drastically hinders the H2O2production performance. Herein, we present an atomically heteroatom P doped ZnIn2S4catalyst with tunable oxygen adsorption configuration to accelerate the ORR kinetics essential for solar‐driven H2O2production. Indeed, the spectroscopy characterizations (such as EXAFS and in situ FTIR) and DFT calculations reveal that heteroatom P doped ZnIn2S4at substitutional and interstitial sites, which not only optimizes the coordination environment of Zn active sites, but also facilitates electron transfer to the Zn sites and improves charge density, avoiding the breakage of O−O bonds and reducing the energy barriers to H2O2production. As a result, the oxygen adsorption configuration is regulated from side‐on (Yeager‐type) to end‐on (Pauling‐type), resulting in the accelerated ORR kinetics from 874.94 to 2107.66 μmol g−1 h−1. This finding offers a new avenue toward strategic tailoring oxygen adsorption configuration by the rational design of doped photocatalyst.

Mechanistic Insights of Zn‐Ion Storage in Synergistic Vanadium‐Based Composites

AbstractA novel composite material Na2V6O16·3H2O‐AlxV2O5 (NVO‐AVO) is designed and synthesized for the first time in aqueous zinc ion battery cathode. The electrochemical behavior is elucidated in detail using in situ and ex situ techniques. The NVO‐AVO is simple, inexpensive, and safe to fabricate and contributes to the synergistic effect of orthorhombic AlxV2O5 (AVO) and monoclinic Na2V6O16·3H2O (NVO), the NVO‐AVO composites have fast Zn2+ kinetics and exhibit good electrochemical properties. At 300 mA g−1, the specific capacity is as high as 392.5 mA h g−1, and even more excitingly, NVO‐AVO remains a specific capacity of 160.6 mA h g−1 even after 18 300 cycles at 5000 mA g−1, which is significantly better than the stability of both NVO and AVO. The distinctive V3O8 layered structure in Na2V6O16·3H2O facilitates the diffusion of Zn2+, and structural water located between the V3O8 layers facilitates rapid charge transfer by widening the gallery spacing and supposing more storage sites for Zn2+. In addition, AlxV2O5 forms [AlO6] octahedral units that enhance structural stability and play a crucial role in maintaining long‐term cycling stability. This work supports the theoretical basis and technical support for the development and extension studies of new vanadium‐based electrode materials.