Single-atom Sites Research Articles

Cooperative dual single atom Ni/Cu catalyst for highly selective CO2-to-ethanol reduction

The electrochemical CO2-to-ethanol conversion bargains a promising approach to lowering CO2 emission while yielding valuable chemical products. Here, we report the NiCu-SACs/N-C catalysts with cooperative dual heteroactive sites that achieve by far the highest catalytic activity for yielding ethanol with the unprecedented Faradaic efficiency of 92.2 % at the potential of −0.6 V versus RHE. The catalyst exhibits the lowest onset potential of −0.4 V versus RHE to catalyze CO2-to-ethanol conversion. In-operando X-ray absorption spectroscopy provides an interesting observation of restructuring behavior of dynamically generated Cu clusters from atomically distributed Cu single-atoms and reversible structural changes or oxidation states of Cu sites while Ni sites remain unchanged during the catalytic reactions. Our experimental analysis and DFT computation suggest that CO produced on Cu-N4/Ni-N3 cooperative single atom sites undergoes C-C coupling, which is further reduced into ethanol. This strategy provides a new route to design selective and efficient catalysts for CO2-to-ethanol conversion.

Breaking scaling relation of single-atom site via energy storage-release effect from adjacent carbon vacancy for low-temperature-resistant Fenton-like catalysis

To realize efficient antibiotics degradation in low-temperature water, single-atom FeN4 sites are engineered near carbon vacancies in a porous catalyst (PCvFe1-5) via thermal-etching and pyrolysis. The high-specific-surface-area (2202.80 m2 g−1) carbon support and dispersive Fe atoms co-enrich sulfamethoxazole and peroxymonosulfate to enhance the reactant collision frequency. Carbon vacancies allow the catalyst to deform for storing the peroxymonosulfate adsorption energies at FeN4 sites, which are subsequently released to facilitate -SO4H desorption for rapid site regeneration. This breaks the scaling relation suffered by single-atom sites, thereby reducing the thermodynamic energy barrier. Consequently, a low-temperature-resistant Fenton-like system with ultralow activation energy of 9.06 kJ mol−1 is constructed for sulfamethoxazole degradation. The normalized kinetic rate constant at 2 ℃ exceeds that of reported catalysts working at 25/30 ℃ by 1–2 orders of magnitude. Moreover, due to the special site configuration, PCvFe1-5 degrades sulfamethoxazole via both long-range catalyst-mediated electron transfer and short-range direct collision oxidation.

One single-atom Mn doping strategy enabling two functions of oxygen reduction reaction and pseudocapacitive performance

Single-atom metal species as highly effective active sites are crucial for enhancing energy storage and conversion properties. However, achieving the simultaneous construction of single-atom sites and the regulation of matrix structures to enable their application in both energy storage and conversion remains a challenge. Here, we have successfully developed unique MnN2C2 active sites, atomically dispersed on N-doped mesoporous graphitic carbon sheets (MnSAs/NMC). This is accomplished through the strategic utilization of MnCl2 salt, which serves dual roles of a pore-forming agent and a template. The MnSAs/NMC catalyst demonstrates compelling electrocatalytic activity for the oxygen reduction reaction (ORR), with an impressive half-wave potential (E1/2 = 0.90 V), alongside superior capacitance reaching 444 F g-1 at 0.5 A g-1 for supercapacitors. Crucially, both experimental and theoretical simulations validate that the single-atom dispersed MnN2C2 optimizes the adsorption energy of reactants and intermediates in the ORR process and pseudocapacitive behavior, leading to excellent ORR activity and capacitive performance. Interestingly, MnSAs/NMC-based Zn-air batteries exhibit concurrently high-power density derived from capacitive property and high energy density enhanced by ORR process. This study presents a novel preparation method for single-atom catalysts, which paves the way for the commercial application of super energy storage and conversion devices.

Atomic-Level Asymmetric Tuning of the Co1-N3P1 Catalyst for Highly Efficient N-Alkylation of Amines with Alcohols.

Despite the extensive development of non-noble metals for the N-alkylation of amines with alcohols, the exploitation of catalysts with high selectivity, activity, and stability still faces challenges. The controllable modification of single-atom sites through asymmetric coordination with a second heteroatom offers new opportunities for enhancing the intrinsic activity of transition metal single-atom catalysts. Here, we prepared the asymmetric N/P hybrid coordination of single-atom Co1-N3P1 by absorbing the Co-P complex on ZIF-8 using a concise impregnation-pyrolysis process. The catalyst exhibits ultrahigh activity and selectivity in the N-alkylation of aniline and benzyl alcohol, achieving a turnover number (TON) value of 3480 and a turnover frequency (TOF) value of 174-h. The TON value is 1 order of magnitude higher than the reported catalysts and even 37-fold higher than that of the homogeneous catalyst CoCl2(PPh3)2. Furthermore, the catalyst maintains its high activity and selectivity even after 6 cycles of usage. Controlling experiments and isotope labeling experiments confirm that in the asymmetric Co1-N3P1 system, the N-alkylation of aniline with benzyl alcohol proceeds via a transfer hydrogenation mechanism involving the monohydride route. Theoretical calculations prove that the superior activity of asymmetric Co1-N3P1 is attributed to the higher d-band energy level of Co sites, which leads to a more stable four-membered ring transition state and a lower reaction energy barrier compared to symmetrical Co1-N4.

Engineering Single-Atom Sites with the Irving-Williams Series for the Simultaneous Co-photocatalytic CO2 Reduction and CH3CHO Oxidation.

The bonding effects between 3d transition-metal single sites and supports originate from crystal field stabilization energy (CFSE). The 3d transition-metal atoms of the spontaneous geometrical distortions, that is the Jahn-Teller effect, can alter CFSE, thereby leading to the Irving-Williams series. However, engineering single-atom sites (SASs) using the Irving-Williams series as an ideal guideline has not been reported to date. Herein, alkynyl-linked covalent phenanthroline frameworks (CPFs) with phenanthroline units are developed to anchor the desired 3d single metal ions from d5 to d10 (Mn2+, Fe3+, Co2+, Ni2+, Cu2+, and Zn2+). The Irving-Williams series was employed to accurately predict the bonding effects between 3d transition-metal atoms and phenanthroline units. To verify this, theoretical calculations and experimental results reveal that Cu-SASs/CPFs exhibits higher stability and faster charge-transfer efficiency, far surpassing other metal-SASs/CPFs. As expected, Cu-SASs/CPFs demonstrates a high photoreduction of CO2-to-CO activity (~30.3 μmol ⋅ g-1 ⋅ h-1) and an exceptional photooxidation of CH3CHO-to-CH3COOH activity (~24.7 μmol ⋅ g-1 ⋅ h-1). Interestingly, the generated *O2 - is derived from the process of CO2 reduction, thereby triggering a CH3CHO oxidation reaction. This work provides a novel design concept for designing SASs by the Irving-Williams to regulate the catalytic performances.

Engineering Single‐Atom Sites with the Irving–Williams Series for the Simultaneous Co‐photocatalytic CO2 Reduction and CH3CHO Oxidation

AbstractThe bonding effects between 3d transition‐metal single sites and supports originate from crystal field stabilization energy (CFSE). The 3d transition‐metal atoms of the spontaneous geometrical distortions, that is the Jahn–Teller effect, can alter CFSE, thereby leading to the Irving–Williams series. However, engineering single‐atom sites (SASs) using the Irving–Williams series as an ideal guideline has not been reported to date. Herein, alkynyl‐linked covalent phenanthroline frameworks (CPFs) with phenanthroline units are developed to anchor the desired 3d single metal ions from d5 to d10 (Mn2+, Fe3+, Co2+, Ni2+, Cu2+, and Zn2+). The Irving–Williams series was employed to accurately predict the bonding effects between 3d transition‐metal atoms and phenanthroline units. To verify this, theoretical calculations and experimental results reveal that Cu‐SASs/CPFs exhibits higher stability and faster charge‐transfer efficiency, far surpassing other metal‐SASs/CPFs. As expected, Cu‐SASs/CPFs demonstrates a high photoreduction of CO2‐to‐CO activity (~30.3 μmol ⋅ g−1 ⋅ h−1) and an exceptional photooxidation of CH3CHO‐to‐CH3COOH activity (~24.7 μmol ⋅ g−1 ⋅ h−1). Interestingly, the generated *O2− is derived from the process of CO2 reduction, thereby triggering a CH3CHO oxidation reaction. This work provides a novel design concept for designing SASs by the Irving–Williams to regulate the catalytic performances.

Single-Atom Catalysts through Pressure-Controlled Metal Diffusion.

Single-atom catalysts (SACs) open up new possibilities for advanced technologies. However, a major complication in preparing high-density single-atom sites is the aggregation of single atoms into clusters. This complication stems from the delicate balance between the diffusion and stabilization of metal atoms during pyrolysis. Here, we present pressure-controlled metal diffusion as a new concept for fabricating ultra-high-density SACs. Reducing the pressure inhibits aggregation substantially, resulting in almost three times higher single-atom loadings than those obtained at ambient pressure. Molecular dynamics and computational fluid dynamics simulations reveal the role of a metal hopping mechanism, maximizing the metal atom distribution through an increased probability of metal-ligand binding. The investigation of the active site density by electrocatalytic oxygen reduction validates the robustness of our approach. The first realization of Ullmann-type carbon-oxygen couplings catalyzed on single Cu sites demonstrates further options for efficient heterogeneous catalysis.

Introducing Hydrogen-Bonding Microenvironment in Close Proximity to Single-Atom Sites for Boosting Photocatalytic Hydrogen Production.

Inspired by enzymatic catalysis, it is crucial to construct hydrogen-bonding-rich microenvironment around catalytic sites; unfortunately, its precise construction and understanding how the distance between such microenvironment and catalytic sites affects the catalysis remain significantly challenging. In this work, a series of metal-organic framework (MOF)-based single-atom Ru1 catalysts, namely, Ru1/UiO-67-X (X = -H, -m-(NH2)2, -o-(NH2)2), have been synthesized, where the distance between the hydrogen-bonding microenvironment and Ru1 sites is modulated by altering the location of amino groups. The -NH2 group can form hydrogen bonds with H2O, constituting a unique microenvironment that causes an increased water concentration around the Ru1 sites. Remarkably, Ru1/UiO-67-o-(NH2)2 displays a superior photocatalytic hydrogen production rate, ∼4.6 and ∼146.6 times of Ru1/UiO-67-m-(NH2)2 and Ru1/UiO-67, respectively. Both experimental and computational results suggest that the close proximity of amino groups to the Ru1 sites in Ru1/UiO-67-o-(NH2)2 improves charge transfer and H2O dissociation, accounting for the promoted photocatalytic hydrogen production.

Efficient Electrosynthesis of Urea over Single-Atom Alloy with Electronic Metal Support Interaction.

Urea electrosynthesis from carbon dioxide (CO2) and nitrate (NO3 -) is an alternative approach to traditional energy-intensive urea synthesis technology. Herein, we report a CuAu single-atom alloy (SAA) with electronic metal support interaction (EMSI), achieving a high urea yield rate of 813.6 μg h-1 mgcat -1 at -0.94 V versus reversible hydrogen electrode (vs. RHE) and a Faradaic efficiency (FE) of 45.2 % at -0.74 V vs. RHE. In situ experiments and theoretical calculations demonstrated that single-atom Cu sites modulate the adsorption behavior of intermediate species. Bimetallic sites synergistically accelerate C-N bond formation through spontaneous coupling of *CO and *NO to form *ONCO as key intermediates. More importantly, electronic metal support interaction between CuAu SAA and CeO2 carrier further modulates electron structure and interfacial microenvironment, endowing electrocatalysts with superior activity and durability. This work constructs SAA electrocatalysts with EMSI effect to tailor C-N coupling at the atomic level, which can provide guidance for the development of C-N coupling systems.

Highly efficient recycling of polyester wastes to diols using Ru and Mo dual-atom catalyst

The chemical recycling of polyester wastes is of great significance for sustainable development, which also provides an opportunity to access various oxygen-containing chemicals, but generally suffers from low efficiency or separation difficulty. Herein, we report anatase TiO2 supported Ru and Mo dual-atom catalysts, which achieve transformation of various polyesters into corresponding diols in 100% selectivity via hydrolysis and subsequent hydrogenation in water under mild conditions (e.g., 160 °C, 4 MPa). Compelling evidence is provided for the coexistence of Ru single-atom and O-bridged Ru and Mo dual-atom sites within this kind of catalysts. It is verified that the Ru single-atom sites activate H2 for hydrogenation of carboxylic acid derived from polyester hydrolysis, and the O-bridged Ru and Mo dual-atom sites suppress hydrodeoxygenation of the resultant alcohols due to a high reaction energy barrier. Notably, this kind of dual-atom catalysts can be regenerated with high activity and stability. This work presents an effective way to reconstruct polyester wastes into valuable diols, which may have promising application potential.

Design of Atomically Dispersed CoN4 Sites and Co Clusters for Synergistically Enhanced Oxygen Reduction Electrocatalysis.

Constructing dual-site catalysts consisting of atomically dispersed metal single atoms and metal atomic clusters (MACs) is a promising approach to further boost the catalytic activity for oxygen reduction reaction (ORR). Herein, a porous CoSA-AC@SNC featuring the coexistence of Co single-atom sites (CoN4) and S-coordinated Co atomic clusters (SCo6) in S, N co-doped carbon substrate is successfully synthesized by using porphyrinic metal-organic framework (Co-TPyP MOF) as the precursor. The introduction of the sulfur source creates abundant microstructural defects to anchor Co metal clusters, thus modulating the electronic structure of its surrounding carbon substrate. The synergistic effect between the two types of active sites and structural advantages, in turn, results in high ORR performance of CoSA-AC@SNC with half-wave potential (E1/2) of 0.86V and Tafel slope of 50.17mVdec-1. Density functional theory (DFT) calculations also support the synergistic effect between CoN4 and SCo6 by detailing the catalytic mechanism for the improved ORR performance. The as-fabricated Zn-air battery (ZAB) using CoSA-AC@SNC demonstrates impressive peak power density of 174.1mWcm-2 and charge/discharge durability for 148h. This work provides a facile synthesis route for dual-site catalysts and can be extended to the development of other efficient atomically dispersed metal-based electrocatalysts.

Highly Selective Photocatalytic Synthesis of Acetic Acid at 0-25 °C.

Acetic acid (AA), a vital compound in chemical production and materials manufacturing, is conventionally synthesized by starting with coal or methane through multiple steps including high-temperature transformations. Here we present a new synthesis of AA from ethane through photocatalytic selective oxidation of ethane by H2O2 at 0-25 °C. The catalyst designed for this process comprises g-C3N4 with anchored Pd1 single-atom sites. In situ studies and computational simulation suggest the immobilized Pd1 atom becomes positively charged under photocatalytic condition. Under photoirradiation, the holes on the Pd1 single-atom of OH-Pd1 /g-C3N4 serves as a catalytic site for activating a C-H instead of C-C of C2H6 with a low activation barrier of 0.14 eV, through a concerted mechanism. Remarkably, the selectivity for synthesizing AA reaches 98.7 %, achieved under atmospheric pressure of ethane at 0 °C. By integrating photocatalysis with thermal catalysis, we introduce a highly selective, environmentally friendly, energy-efficient synthetic route for AA, starting from ethane, presenting a promising alternative for AA synthesis. This integration of photocatalysis in low-temperature oxidation demonstrates a new route of selective oxidation of light alkanes.

Boosting Electrochemical Nitrate Reduction at Low Concentrations Through Simultaneous Electronic States Regulation and Proton Provision.

Electrochemically converting nitrate (NO3 -) into ammonia (NH3) has emerged as an alternative strategy for NH3 production and effluent treatment. Nevertheless, the electroreduction of dilute NO3 - is still challenging due to the competitive adsorption between various aqueous species and NO3 -, and unfavorable water dissociation providing *H. Herein, a new tandem strategy is proposed to boost the electrochemical nitrate reduction reaction (NO3RR) performance of Cu nanoparticles supported on single Fe atoms dispersed N-doped carbon (Cu@Fe1-NC) at dilute NO3 - concentrations (≤100ppm NO3 --N). The optimized Cu@Fe1-NC presents a FENH3 of 97.7% at -0.4V versus RHE, and a significant NH3 yield of 1953.9mmolh-1gCu -1 at 100ppm NO3 --N, a record-high activity for dilute NO3RR. The metal/carbon heterojunctions in Cu@Fe1-NC enable a spontaneous electron transfer from Cu to carbon substrate, resulting in electron-deficient Cu. As a result, the electron-deficient Cu facilitates the adsorption of NO3 - compared with the pristine Cu. The adjacent atomic Fe sites efficiently promote water dissociation, providing abundant *H for the hydrogenation of *NOx e at Cu sites. The synergistic effects between Cu and single Fe atom sites simultaneously decrease the energy barrier for NO3 - adsorption and hydrogenation, thereby enhancing the overall activity of NO3 - reduction.

Efficient electrochemical reduction of nitrate to ammonia over metal-organic framework single-atom catalysts

The design and preparation of efficient catalysts for ammonia production under mild conditions is a desirable but highly challenging target. Here, we report a series of single-atom catalysts [M-SACs, M = Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Mo(II)] derived from UiO-66 containing structural defects and their application to electrochemical reduction of nitrate (NO3-) to ammonia (NH3). Cu-SAC and Fe-SAC exhibit remarkable yield rates for NH3 production of 30.0 and 29.0 mg h−1 cm−2, respectively, with a high Faradaic efficiency (FENH3) of over 96% at −1.0 V versus the reversible hydrogen electrode. Importantly, their catalytic performance can be retained in various simulated wastewaters. Complementary experiments confirmed the nature of single-atom sites within these catalysts and the binding domains of NO3- in UiO-66-Cu. In situ spectroscopic techniques, coupled with density functional theory calculations confirm the strong binding of NO3- and the formation of reaction intermediates, thus facilitating the catalytic conversion to NH3.

Unraveling the Synergistic Mechanism of Ir Species with Various Electron Densities over an Ir/ZSM-5 Catalyst Enables High-Efficiency NO Reduction by CO.

Selective catalytic reduction using CO as a reducing agent (CO-SCR) has exhibited its application potential in coal-fired, steel, and other industrial sectors. In comparison to NH3-SCR, CO-SCR can achieve synergistic control of CO and NO pollutants, making it a powerful denitrification technology that treats waste with waste. Unfortunately, the competitive adsorption of O2 and NO on CO-SCR catalysts inhibits efficient conversion of NOx under O2-containing conditions. In this work, we obtained two Ir sites with different electron densities, Ir1 single atoms in the oxidized Irδ+ state and Ir0 nanoparticles in the metallic state, by controlled pretreatment of the Ir/ZSM-5 catalyst with H2 at 200 °C. The coexistence of Ir1 single atoms and Ir0 nanoparticles on ZSM-5 creates a synergistic effect, which facilitates the reduction of NO through CO in the presence of O2, following the Langmuir-Hinshelwood mechanism. The ONNO dimer is formed on the Ir1 single atom sites and then spills over to the neighboring Ir0 nanoparticles for subsequent reduction to N2 by CO. Specifically, this tandem reaction enables 83% NO conversion and 100% CO conversion on an Ir-based catalyst at 250 °C under 3% O2.

Precise construction of RuPt dual single-atomic sites to optimize oxygen electrocatalytic behaviors for high-performance Zn-air batteries

The development of redox bifunctional electrocatalysts with high performance, low cost, and long lifetimes is essential for achieving clean energy goals. This study proposed an atom capture strategy for anchoring dual single atoms (DSAs) in a zinc–zeolitic imidazolate framework (Zn–ZIF), followed by calcination under an N2 atmosphere to synthesize ruthenium–platinum DSAs supported on a nitrogen-doped carbon substrate (RuPt DSAs-NC). Theoretical calculations showed that the degree of Ru 5dxz − *O 2px orbital hybridization was high when *O was adsorbed at the Ru site, indicating enhanced covalent hybridization of metal sites and oxygen ligands, which benefited the adsorption of intermediate species. The presence of the RuPtN6 active center optimized the absorption–desorption behavior of intermediates, improving the electrocatalytic performance of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). RuPt DSAs-NC exhibited a 0.87 V high half-wave potential and a 268 mV low overpotential at 10 mA cm−2 in an alkaline environment. Furthermore, rechargeable zinc–air batteries (ZABs) achieved a peak power density of 171 mW cm−2. The RuPt DSAs-NC demonstrated long-term cycling for up to 500 h with superior round-trip efficiency. This study provided an effective structural design strategy to construct DSAs active sites for enhanced electrocatalytic performance.

Universal Formation of Single Atoms from Molten Salt for Facilitating Selective CO2 Reduction.

Clarifying the formation mechanism of single-atom sites guides the design of emerging single-atom catalysts (SACs) and facilitates the identification of the active sites at atomic scale. Herein, a molten-salt atomization strategy is developed for synthesizing zinc (Zn) SACs with temperature universality from 400 to 1000/1100°C and an evolved coordination from Zn-N2Cl2 to Zn-N4. The electrochemical tests and in situ attenuated total reflectance-surface-enhanced infrared absorption spectroscopy confirm that the Zn-N4 atomic sites are active for electrochemical carbon dioxide (CO2) conversion to carbon monoxide (CO). In a strongly acidic medium (0.2m K2SO4, pH = 1), the Zn SAC formed at 1000°C (Zn1NC) containing Zn-N4 sites enables highly selective CO2 electroreduction to CO, with nearly 100% selectivity toward CO product in a wide current density range of 100-600mAcm-2. During a 50 h continuous electrolysis at the industrial current density of 200mAcm-2, Zn1NC achieves Faradaic efficiencies greater than 95% for CO product. The work presents a temperature-universal formation of single-atom sites, which provides a novel platform for unraveling the active sites in Zn SACs for CO2 electroreduction and extends the synthesis of SACs with controllable coordination sites.

Combination of Co Single Atom and MoS2 Antisite Defect for Efficient Electrocatalytic CO2 Methanation: A Rational Design at Electronic Scale

AbstractMethane, the simplest hydrocarbon, has a high energy density and is widely used as chemical feedstocks or fuels. Converting CO2 to methane through electrochemical reduction offers a promising strategy for managing the global carbon balance, but is a challenge due to the lack of effective electrocatalysts. Herein, the Co single atom catalyst supported by MoS2 antisite defect (Co‐MoS2) is designed from both the activity and selectivity aspects. By virtue of i) moderately electron‐deficient state (Coδ+) ensuring efficient CO2 activation and HER suppression; ii) the strong adsorption capability for intermediate enhancing selectivity; iii) the single atomic active site avoiding the formation of C2 products, Co‐MoS2 could selectively convert CO2 to CH4 with a limiting potential of −0.45 V vs. RHE, which outperforms most of the present catalysts, and is expected to be a promising substitution for Cu‐based catalysts.

Simultaneous sterilization and biosensing of pathogenic bacteria via copper phthalocyanine-based COF embedded with Cu-N4 single atomic sites and silver nanoparticles

The efficient inactivation and sensitive detection of waste water and food stuffs polluted by pathogenic bacteria are vital for ensuring food safety and protecting people’s healthy. Herein, a 2D copper phthalocyanine-based covalent-organic framework (COF) embraced with Cu-N4 single atomic sites and silver nanoparticles (denoted as CuPc-Dha-COF@AgNPs) was employed as a bifunctional bioplatform for the efficient sterilization via the multi-modal antibacterial mechanism and the sensitive detection of pathogenic bacteria via the photocatalytic oxidization of glutathione (GSH) using a photoelectrochemical (PEC) technique. Given the superior photothermal conversion efficiency, the high production efficiency of reactive oxygen species, the enhanced H2O2 self-supplying capability, and the controlled release of Ag+ ions under near-infrared light irradiation (808 nm and 1.0 W cm−2), 100 % bacteria were eliminated by CuPc-Dha-COF@AgNPs (200 μg mL−1) at 24 h. Furthermore, the CuPc-Dha-COF@AgNPs-based PEC biosensing platform exhibited highly selective determination ability toward GSH because of its superior mimetic enzyme performance caused by Cu-N4 single atomic sites, narrow bandgap, wide photoabsorption performance, and high separation of photoinduced electrons and holes. It thus showed an ultralow detection limit of 99 fM toward GSH within wide range from 1.0 pM to 1.0 nM, as well as high selectivity, good stability and reproducibility, and promising practicality. This work provides a new strategy for the sterilization and sensitive detection of pathogenic bacteria, simultaneously implementing and monitoring measures for the water system and food safety.

Asymmetric Zn-N4 atomic sites embedded hollow fibers as stable Zn anode for high-performance Zn-ion hybrid capacitor

Zn based electrochemical energy storage systems (EES) have attracted tremendous interests owing to their low cost and high intrinsic safety. Nevertheless, the uncontrolled growth of Zn dendrites and the side reactions of Zn metal anodes (ZMAs) severely restrict their applications. To address these issues, we design the asymmetric Zn-N4 atomic sites embedded hollow fibers (AS-IHF) as the flexible host for stable ZMAs. Through introducing different nitrogen resources in the synthesis, two kinds of coordination, i. e. Zn-N (pyridinic) and Zn-N (pyrrolic), are introduced in the Zn-N4 atomic module synchronously. The asymmetric Zn-N4 module with regulated micro-environment facilitates the superior zincophilic features and promotes the Zn adsorption. Meanwhile, the highly porous structure of the hollow fiber effectively reduces local current density, homogenize Zn ion flux, and alleviate structure stress. All the advantages endow the high efficiency and good stability for Zn plating/stripping. Both theoretical and experimental results demonstrate the high reversibility, low nucleation overpotential, and dendrite-free behavior of the AS-IHF@Zn anode, which afford the high stability in high-rate and long-term cycling. Moreover, the solid-state Zn-ion hybrid capacitor (ZIHC) based on AS-IHF@Zn anode shows the high flexibility, reliability, and superior long-term cycling capability in a wide-range of temperatures (−20–25 °C). Therefore, the present work not only gives a new strategy for modulating local environments of single atomic sites, but also propels the development of flexible power sources for diverse electronics.