Defect Sites Research Articles

High temperature induced abundant closed nanopores for hard carbon as high-performance sodium-ion batteries anodes

Hard carbon (HC) stands out as the preeminent anode material for sodium-ion batteries (SIBs) which are deployed in expansive energy storage infrastructures. Herein, the large enough graphene nanosheets interlayer and abundant nanopores with a diameter of ∼2.1 nm induced by adjusting the pyrolysis temperature in the thermosetting phenolic resin-derived hard carbon matrix to augment the performance of the sodium ion storage. The presence of sufficiently large carbon interlayers has been proven to provide active sites for reversible adsorption, enabling effective storage of sodium ions in the high-voltage slope region, while also promoting rapid Na+ transport. Meanwhile, forming abundant closed nanopores with larger sizes helps sodium ion storage in the low-voltage plateau region. In the optimized samples, the formation of sufficient long graphene nanosheets with a perfect crystal lattice, which further shrinks to form enclosed nanopores, effectively reduces defective sites and specific surface area. Additionally, the appropriate content of C-O and C=O functional groups contributes to an exceptional initial Coulombic efficiency (ICE) of up to 93%. Simultaneously, the optimized sample HC-1500 contributes to a remarkable plateau capacity of 294 mAh g-1 during the charging process (high reversible capacity of 403 mAh g-1 at 0.1 C). Moreover, based on the microstructure evolution and Na storage behavior of hard carbon, an “adsorption (27%) – filling (73%)” sodium storage mechanism that the sodium storage as a quasi-metallic sodium state is demonstrated. Consequently, this study will offer valuable insights for the development of hard carbon anodes tailored for high-energy practical SIBs, while also advancing the understanding of sodium storage mechanisms.

Defective wood-based chainmail electrocatalysts boost performances of seawater-medium Zn-air batteries

A high-activity and stable bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalyst is critical for seawater-based Zn-air batteries (ZABs). Herein, we report a wood-derived chainmail electrocatalyst containing defective nitrogen-doped carbon nanotubes encapsulating cobalt nanoparticles (Co@D-NCNT/CW) to enhance the ORR/OER activity and stability in seawater medium. During the preparation process, the introduction and removal of Zn increased the defect sites and pyridine N content in the carbon material, modulating charge distribution and influencing the adsorption and activation processes. The highly ordered open channels in Co@D-NCNT/CW promoted mass transfer of reactants and accelerated gas diffusion. The resultant chainmail electrocatalyst exhibited impressive bifunctional ORR and OER activities with an ultra-low gap of 0.67 V in seawater-based alkaline electrolyte. The Co@D-NCNT/CW-assembled seawater-based rechargeable liquid ZABs demonstrated a maximum power density of 245.3 mW cm−2 and a long-term cycling performance over 500 h. The seawater-based all-solid-state ZABs achieved the maximum power density of 48.2 mW cm−2 and stabilized over 30 h. Density functional theory revealed that the presence of defects and pyridine nitrogen in Co@D-NCNT/CW modulated the electronic structure of Co, optimizing the binding affinity of the Co sites with intermediates and weakening Cl− adsorption. This work provides a new approach to preparing high-activity and stable ORR/OER electrocatalyst utilizing wood nanostructures, boosting the development of seawater-based ZABs.

Defect-rich N, S Co-doped porous carbon with hierarchical channel network for ultrafast capacitive deionization

Developing an eco-friendly and effective approach for preparing N, S co-doped hierarchical porous carbons (NSHPC) for capacitive deionization (CDI) is a huge task for desalination. Herein, NSHPCSKK with interconnected hierarchical pore structures, manufactured via self-activation/co-activation of sodium lignosulfonate (SLS) encapsulation using KNO3-KHCO3 activators, inducing N, S co-doping. Different from NSHPCS and NSHPCSK, NSHPCSKK exhibits the highest specific surface area (SBET, 2264.67 m2/g) and a unique hierarchical pore structure (mesoporous volume/pore volume (Vmeso/ Vpore), 0.65). Small-angle X-ray scattering (SAXS) and scanning electron microscopy (SEM) both reveal the complex interconnected pore structure of NSHPCSKK. Regional Raman imaging conjugated with XPS reveals the presence of extensively distributed N, S co-doped defect structures, providing NSHPCSKK with excellent wettability and electrochemical performance. DFT calculations indicate that the N, S co-doping at the defect sites depicts excellent adsorption capability. Eventually, NSHPCSKK acquired an impressive salt adsorption capacity (SAC) of 20.5 mg/g and the highest average salt adsorption rate (ASAR) of 12.1 mg/g/min, indicating its superior desalting performance. In-situ Raman spectroscopy confirms NSHPCSKK’s rapid ion regeneration mechanism. The research introduces a span-new NSHPC synthesis strategy for fabricating advanced NSHPC with rapid desalination response for upgrading CDI desalination.

Development of silk microfiber-reinforced bioink for muscle tissue engineering and in situ printing by a handheld 3D printer

Volumetric muscle loss (VML) presents a significant challenge in tissue engineering due to the irreparable nature of extensive muscle injuries. In this study, we propose a novel approach for VML treatment using a bioink composed of silk microfiber-reinforced silk fibroin (SF) hydrogel. The engineered scaffolds are predesigned to provide structural support and fiber alignment to promote tissue regeneration in situ. We also validated our custom-made handheld 3D printer performance and showcased its potential applications for in situ printing using robotics. The fiber contents of SF and gelatin ink were varied from 1 to 5 %. Silk fibroin microfibers reinforced ink offered increased viscosity of the gel, which enhanced the shape fidelity and mechanical strength of the bulk scaffold. The fiber-reinforced bioink also demonstrated better cell-biomaterial interaction upon printing. The handheld 3D printer enabled the precise and on-demand fabrication of scaffolds directly at the defect site, for personalized and minimally invasive treatment. This innovative approach holds promise for addressing the challenges associated with VML treatment and advancing the field of regenerative medicine.

Investigation on the creep mechanism of PA6 films based on quasi point defect theory

Polyamide 6 (PA6) films with significant α relaxation process was selected as the model system. The creep behavior and rheological mechanism during deformation in the amorphous regions of semi-crystalline polymers are systematically investigated by carrying out creep experiments. Based on the quasi point defect (QPD) theory, the complete physical process of PA6 film creep behavior from elasticity to viscoelasticity and viscoplasticity was analyzed and modeled from the perspective of structural heterogeneity. The results demonstrate that the creep deformation of PA6 film is a typical thermo-mechanical coupling and nonlinear mechanics process, and potential creep mechanisms corresponds to stress-induced local shear deformation enhancement and thermal activation-induced particle flow diffusion. The elastic-plastic transition involved in the creep deformation process of semi-crystalline polymer originates from the activation of quasi-point defective sites in the amorphous region, the expansion of sheared micro-domains and irreversible fusion. The generalized fractional Kelvin (GFK) model is proposed, and the physical meaning of parameters is explained by combining the quasi point defect theory and creep delay spectrum(L(τ)). Finally, the effectiveness of the GFK model and the QPD theory in studying the deformation behavior of PA6 films was validated by comparing experimental data with theoretical results, which theoretically reveals the structural evolution of PA6 film during creep process.

Thermomechanical and Structural Analysis of WO3 Array for Optimized Photoelectrochemical Chloride Oxidation Performance.

Understanding the crystal structure of WO3 is essential for optimizing its photoelectrochemical performance. This study comprehensively analyzes the structural characteristics of WO3 during synthesis and investigates their correlation with photoelectrochemical activity. Structural analysis, incorporating annealing procedure and WO3 thickness, identifies a blend of hexagonal, monoclinic, and orthorhombic phases within WO3 array. Specifically, detailed analysis reveals a predominance of monoclinic WO3 phase alongside the orthorhombic WO3 phase, both of which are commonly characterized by their monoclinic structure. Three-dimensional thermomechanical simulations using the finite element method reveal that thermal displacement in WO3 layers increases with thickness during the thermally induced synthesis process. These results highlight a direct correlation between WO3 thickness, thermal displacement, and phase transition, with thicker layers favoring the transformation from orthorhombic to monoclinic structures due to increased thermally induced deformation. The heightened monoclinic structure, which possesses lower symmetry than the orthorhombic structure, induces more defect sites, suggesting increased donor density. Notably, the monoclinic-dominated WO3 exhibits superior performance under UV-visible irradiation in 0.5 M NaCl. Furthermore, the WO3 array demonstrates over 85% Faradaic efficiency for chloride oxidation, indicating preferential selectivity over oxygen evolution reaction in 0.5 M NaCl. This study emphasizes the pivotal role of the crystal structure of WO3 in achieving efficient photoelectrochemical seawater splitting.

Functional Scaffolds for Bone Tissue Regeneration: A Comprehensive Review of Materials, Methods, and Future Directions.

Bone tissue regeneration is a rapidly evolving field aimed at the development of biocompatible materials and devices, such as scaffolds, to treat diseased and damaged osseous tissue. Functional scaffolds maintain structural integrity and provide mechanical support at the defect site during the healing process, while simultaneously enabling or improving regeneration through amplified cellular cues between the scaffold and native tissues. Ample research on functionalization has been conducted to improve scaffold-host tissue interaction, including fabrication techniques, biomaterial selection, scaffold surface modifications, integration of bioactive molecular additives, and post-processing modifications. Each of these methods plays a crucial role in enabling scaffolds to not only support but actively participate in the healing and regeneration process in bone and joint surgery. This review provides a state-of-the-art, comprehensive overview of the functionalization of scaffold-based strategies used in tissue engineering, specifically for bone regeneration. Critical issues and obstacles are highlighted, applications and advances are described, and future directions are identified.

Selective Photocatalytic Oxidation of 5‐Hydroxymethylfurfural using Ce doped TiO2: A Crucial Role of Defective Sites

AbstractTransforming platform compounds with conventional catalysts, such as homogeneous and heterogeneous, into valuable chemicals encounters challenges associated with entailing high temperature/pressure and reusability during the reaction. To address these challenges, photocatalysis is one of the promising approaches, especially with visible‐light‐driven photocatalysts for selective transformation. A series of cerium‐doped TiO2 (CexTiO2; x=0.5, 1, 3 and 5 wt %) are prepared via a simple coprecipitation method for the cocatalyst‐free selective oxidation of 5‐hydroxymethylfurfural (HMF) to 2,5‐diformylfuran (DFF) under visible light illumination. Introducing Ce into the network to TiO2 generates impurity energy levels, reduces the band gap, and extends the spectral response range. This also causes slight distortion to the surface structure, thereby originating defective sites and various surface oxygen species, confirmed by X‐ray photoelectron spectroscopy and electron paramagnetic resonance studies. The HMF adsorption studies infer that HMF forms a surface complex with CeTiO2, facilitating the formation of ligand‐to‐metal charge transfer complex (LMCT) under visible light (~420 nm), which efficiently catalyzes the conversion of HMF (54.4 %) to DFF with a selectivity of >99 %. In‐situ DRIFTS and surface passivation studies provide insight into the interaction between HMF and surface acidic/basic sites along with hydroxyl groups of CeTiO2, which subsequently convert selectively to DFF.

Biomimetic microgels for articular cartilage regeneration. A minipig knee model

The aim of this study is to explore, with an in vivo model, the regeneration of articular cartilage that can be obtained with a strategy that combines the stimulation of the subchondral bone with the implantation of a biomimetic microgel at the site of the cartilage defect. The microgel consists of an agglomerate of two types of microspheres: ones rigid, made of a biodegradable polyester, and the other ones composed of a polymeric network of gelatin and hyaluronic acid that encapsulate platelet-rich plasma (PRP) obtained from circulating autologous blood. A defect of 7 mm in diameter and full depth was performed in the in the articular cartilage at the trochlea of the animal knee, using a minipig model. Microdrilling was performed in the underlying bone and the defect was filled with the microgel in which the platelets it contains were previously activated with calcium chloride. The whole defect containing the microgel was covered with a synthetic membrane to avoid the release of microspheres. The results of the in vivo follow-up of the experiment, the histological analysis and the mechanical measurements of the regenerated tissue 9 months after implantation were compared with those of a group of animals in which only microdrilling was performed and the defect was covered with the membrane and with another group in which a clinical use commercial collagen mesh was implanted. The mean value of the elastic modulus of the newly formed tissue was not significantly different from that of the native tissue in the case of microgel implantation while its content of GAGs, was significantly better than in the other groups.

Explore synergistic catalytic ozonation by dual active sites of oxygen vacancies and defects in MgO/biochar for atrazine degradation

The design of highly efficient and sustainable catalytic materials is highly desirable for the development of advanced oxidation process (AOPs) used in water treatment. This study used waste litchi shells as precursors to prepare biochar (BC). The composite material (BC@MgO) was synthesized upon loading magnesium oxide (MgO) on BC and used for the heterogeneous catalytic ozonation (HCO) of atrazine (ATZ). BC@MgO exhibited an ATZ degradation rate of 92.8 % over 30 min under the optimal degradation conditions and maintained its good catalytic performance over four cycles, exhibiting excellent catalytic activity and stability. Characterization and experimental results revealed the synergistic effect of oxygen vacancies (OVs) and BC defects on the adsorption and decomposition of ozone molecules. The exposure of the surface magnesium ions was promoted in the presence of OVs on MgO, allowing water molecules to dissociate on the surface magnesium sites to form surface hydrated hydroxyl groups. Biochar defects accelerated the adsorption of ozone molecules by virtue of its higher surface energy. These active sites led to the substantial generation of reactive oxygen species (ROS), which possessed strong oxidizing ability and thereby participated in the degradation of ATZ. In addition, the possible degradation pathways and toxicity of ATZ were evaluated. Overall, this design provided a novel approach to the comprehensive utilization of waste lychee shells, as well as an efficient, stable, and green catalyst for the development of AOPs used in water treatment.

A multifunctional composite scaffold responds to microenvironment and guides osteogenesis for the repair of infected bone defects

Treating bone defect concomitant with microbial infection poses a formidable clinical challenge. Addressing this dilemma necessitates the implementation of biomaterials exhibiting dual capabilities in anti-bacteria and bone regeneration. Of particular significance is the altered microenvironment observed in infected bones, characterized by acidity, inflammation, and an abundance of reactive oxygen species (ROS). These conditions, while challenging, present an opportunity for therapeutic intervention in the context of contaminated bone defects. In this study, we developed an oriented composite scaffold containing copper-coated manganese dioxide (MnO2) nanoparticles loaded with parathyroid hormone (PMPC/Gelatin). The characteristics of these scaffolds were meticulously evaluated and confirmed the high sensitivity to H+, responsive drug release and ROS elimination. In vitro antibacterial analysis underscored the remarkable ability of PMPC/Gelatin scaffolds to substantially suppressed bacterial proliferation and colony formation. Furthermore, this nontoxic material demonstrated efficacy in mitigating ROS levels, thereby fostering osteogenic differentiation of bone marrow mesenchymal stem cells and enhancing angiogenic ability. Subsequently, the infected models of bone defects in rat skulls were established to investigate the effects of composite scaffolds on anti-bacteria and bone formation in vivo. The PMPC/Gelatin treatment exhibited excellent antibacterial activity, coupled with enhanced vascularization and osteogenesis at the defect sites. These compelling findings affirm that the PMPC/Gelatin composite scaffold represents a promising avenue for anti-bacteria and bone regeneration.

Defect-induced localization of information scrambling in 1D Kitaev model

We discuss one-dimensional(1D) spin compass model or 1D Kitaev model in the presence of local bond defects. Three types of local disorders concerning both bond-nature and bond-strength that occur on kitaev materials have been investigated. Using exact diagonalization, two-point spin-spin structural correlations and four-point Out-of-Time-Order Correlators(OTOC) have been computed for the defective spin chains. The proposed quantities give signatures of these defects in terms of their responses to location and strength of defects. A key observation is that the information scrambling in the OTOC space gets trapped at the defect site giving rise to the phenomena of localization of information scrambling thus making these correlators a suitable diagnostic tool to detect and characterize these defects.

Near-Infrared Carbon Dots With Antibacterial and Osteogenic Activities for Sonodynamic Therapy of Infected Bone Defects.

Repairing infected bone defects is hindered by the presence of stubborn bacterial infections and inadequate osteogenic activity. The incorporation of harmful antibiotics not only fosters the emergence of multidrug-resistant bacteria, but also diminishes the osteogenic properties of scaffold materials. In addition, it is essential to continuously monitor the degradation kinetics of scaffold materials at bone defect sites, yet the majority of bone repair materials lack imaging capability. To address these issues, this study reports for the first time the development of a single nanomaterial with triple functionality: efficient sonodynamic antibacterial activity, accelerated bone defect repair capability, and NIR imaging ability for visualized therapy of infected bone defects. Through rationally regulating the surface functional groups, the obtained multifunctional NIR carbon dots (NIR-CD) exhibit p-n junction-enhanced sonodynamic activity, narrow bandgap-facilitated NIR imaging capability, and negative charge-augmented osteogenic activity. The validation of NIR-CDs antibacterial and osteogenic activities in vivo is conducted by constructing 3D injectable hydrogels encapsulated by NIR-CDs (NIR-CD/GelMA). The implantation of multifunctional NIR-CD/GelMA hydrogel scaffolds in a model of MRSA-infected craniotomy defects results in almost complete restoration of the infected bone defects after 60 days. These findings will provide traceable, renewable, repairable and antibacterial candidate biomaterials for bone tissue engineering.

Chemistry of Formate and Water Ligands on Metal Oxide Cluster Nodes of Metal-Organic Framework hcp Hf-UiO-66: Keys to Understanding Reactivity of Paired μ2-OH and Defect Sites.

Many metal-organic frameworks (MOFs) incorporate nodes that are metal oxide clusters, and ligands that have been observed on these nodes include formates, acetates, water, hydroxyl groups, and others, all of which are potentially important in affecting reactivities for applications in separations, catalysis, and sensing. Formate is a common node ligand, arising from formic acid used as a modulator and from N,N-dimethylformamide used as a solvent in MOF syntheses. Yet only little work has been reported characterizing the reactivities of node formate ligands. Infrared spectra reported here show that formate bonds to two types of sites on the paired Hf6O8 nodes of hcp UiO-66, namely, defect and μ2-OH sites. Quantifying the number of formate ligands by 1H NMR spectroscopy of digested samples showed an almost equal number of formate ligands on the two sites, indicating the likelihood that they neighbor each other. These formate ligands interact with water molecules, reversibly switching their bonding from bidentate to monodentate. The formates on μ2-OH sites of hcp Hf-UiO-66 interact much more strongly with water than those on defect sites of the same node, and both interact more strongly than isolated defect sites of Hf-UiO-66. Correspondingly, the catalytic activities of hcp UiO-66 determined as turnover frequencies on each site are approximately twofold higher than those on UiO-66, bolstering the inference that methanol dehydration is catalyzed by a node defect site and a neighboring node μ2-OH site. The results show how MOFs, with their well-defined node structures, provide unprecedented opportunities to understand details of reactivities and catalysis on metal oxide clusters, in contrast to bulk metal oxide surfaces.

The Nature of Structural Defects in ZIF-8 Revealed with 1H and 31P MAS NMR and X-Ray Absorption Spectroscopy.

The metal-organic frameworks (MOFs) attract interest as potential catalysts whose catalytic properties are driven by defects. Several methods have been proposed for the defects-inducing synthesis of MOFs. However, the active species formed on the defective sites remain elusive and uncharacterized, as the spectroscopic fingerprints of these species are hidden by the regular structure signals. In this work, we have performed the synthesis of ZIF-8 MOF with defect-inducing procedures using fully deuterated 2-methylimidazolate ligands to enhance the defective sites' visibility. By combining 1H and 31P MAS NMR spectroscopy and X-ray absorption spectroscopy, we have found evidence for the presence of different structural hydroxyl Zn-OH groups in the ZIF-8 materials. It is demonstrated that the ZIF-8 defect sites are represented by Zn-OH hydroxyl groups with the signals at 0.3 and -0.7 ppm in the 1H MAS NMR spectrum. These species are of basic nature and may be responsible for the catalytic activity of the ZIF-8 material.

The nature of structural defects in ZIF‐8 revealed with 1H and 31P MAS NMR and X‐ray absorption spectroscopy

The metal‐organic frameworks (MOFs) attract interest as potential catalysts whose catalytic properties are driven by defects. Several methods have been proposed for the defects‐inducing synthesis of MOFs. However, the active species formed on the defective sites remain elusive and uncharacterized, as the spectroscopic fingerprints of these species are hidden by the regular structure signals. In this work, we have performed the synthesis of ZIF‐8 MOF with defect‐inducing procedures using fully deuterated 2‐methylimidazolate ligands to enhance the defective sites' visibility. By combining 1H and 31P MAS NMR spectroscopy and X‐ray absorption spectroscopy, we have found evidence for the presence of different structural hydroxyl Zn–OH groups in the ZIF‐8 materials. It is demonstrated that the ZIF‐8 defect sites are represented by Zn–OH hydroxyl groups with the signals at 0.3 and –0.7 ppm in 1H MAS NMR spectrum. These species are of basic nature and may be responsible for the catalytic activity of the ZIF‐8 material.

Regulation of surface oxygen functional groups in starch-derived hard carbon via pre-oxidation: A strategy for enhanced sodium storage performance

During the process of sodium storage in hard carbon anodes, the significance of surface oxygen functional groups cannot be overlooked. In this work, we utilize starch as raw material to synthesize hard carbon by the process of pre-oxidation and two-step carbonization. XPS analysis reveals that pre-oxidation bolsters the presence of CO bonds, thereby providing more active sites. TEM analysis reveals that hard carbon with pseudo-graphite and graphite-like structure is obtained at relatively high carbonization temperature (1400 °C), and the formation of closed pores results in lower specific surface area. The introduction of appropriate oxygen-containing groups in pre-oxidation process can facilitate the cross-linking of starch chains, promoting the increase of defect sites and the sodium storage performance of hard carbon. A series of samples are prepared at various pre-oxidation temperature. Among them, P200-HC obtained after pre-oxidation at 200 °C and carbonization at 1400 °C exhibits the highest reversible specific capacity of 342.7 mAh g−1 at current density of 0.1 C with an initial Coulombic efficiency of 71.1 %, and capacity retention of 87.3 % at current density of 1 C. The work presents a viable approach for the synthesis of hard carbon derived from starch, thereby expanding the design tactic of sodium-ion batteries with improved performance.

Efficient generation of 1O2 by activating peroxymonosulfate on graphitic carbon nanoribbons for water remediation

Few-layer graphitic carbon nanoribbons (GCN) with rich defective sites were prepared by pyrolysis at 800 oC in N2 of in situ-chelated Fe-polyaniline complexes synthesized via one-pot homogeneous Fenton-like oxidative polymerization of an acidic aniline solution. A minimal amount of iron (0.47 wt%) made a pivotal role in the nanoribbon growth and graphitization of GCN, and deposited highly dispersed iron species on GCN without post-synthesis acid leaching, which greatly simplified the synthesis procedure of GCN with improved yield. GCN exhibited high activity and stability for catalytic degradation of organic pollutants with peroxymonosulfate (PMS) mainly via non-radical pathways. The influences of various operating parameters on the catalytic performance of GCN were investigated. Scavenging tests, spin-trapping electron paramagnetic resonance spectra, electrochemical analyses, and theoretical calculations unveiled that 1O2 was the main reactive oxygen species generated from synergistic activation of PMS on GCN while GCN-mediated electron transfer made a minor contribution to organic degradation.

Floatable expanded perlite-loaded Z-scheme n-C3N5/Ag2CO3 core-shell structure with C-defects for enhanced adsorption and photodegradation of microcystin-LR: Insights into performance and mechanism

Efficient in-situ treatment of high concentrations microcystin-LR in surface waters is especially challenging. Herein, spherical floatable Z-scheme core-shell photocatalyst EP@n-C3N5/Ag2CO3 (EP@CNAC) with carbon defects was constructed using expanded perlite (EP) as floating carrier for efficient adsorption and degradation of microcystin-LR. The carbon defect sites and electron density distribution of C3N5 were investigated by DFT calculation. Benefited from synergistic effects of morphology and defect engineering, Z-scheme heterojunction, and floatability, the carrier migration kinetics and solar spectral responsiveness of EP@CNAC-3 were significantly enhanced, and 97 % of microcystin-LR was degraded within 16 min. The LC-MS, Fukui index, and electrostatic potential of microcystin-LR revealed that Adda side chain was cleaved by electrophilic attack of 1O2, while ring-opening reaction and decarboxylation were caused by nucleophilic attack of •O2- and strong oxidative properties of h+, respectively. These findings are expected to bring new insights into design of innovative floating photocatalysts and in-situ remediation mechanism of microcystin-LR.

Revealing an Extended Adsorption/Insertion-Filling Sodium Storage Mechanism in Petroleum Coke-Derived Amorphous Carbon.

Amorphous carbon holds great promise as anode material for sodium-ion batteries due to its cost-effectiveness and good performance. However, its sodium storage mechanism, particularly the insertion process and origin of plateau capacity, remains controversial. Here, an extended adsorption/insertion-filling sodium storage mechanism is proposed using petroleum coke-derived amorphous carbon as a multi-microcrystalline model. Combining in situ X-ray diffraction, in situ Raman, theoretical calculations, and neutron scattering, the effective storage form and location of sodium ions in amorphous carbon are revealed. The sodium adsorption at defect sites leads to a high-potential sloping capacity. The sodium insertion process occurs in both the pseudo-graphite phase (d002 > 0.370nm) and graphite-like phase (0.345 ≤ d002 < 0.370nm) rather than the graphite phase, contributing to low-potential sloping capacity. The sodium filling into accessible closed pores forms quasi-metallic sodium clusters, contributing to plateau capacity. The threshold of the effective interlayer spacing for sodium insertion is extended to 0.345nm, breaking the consensus of insertion interlayer threshold and enhancing understanding of closed pore filling. The extended adsorption/insertion-filling mechanism explains the sodium storage behavior of amorphous carbon with different microstructures, providing theoretical guidance for the rational design of high-performance amorphous carbon anodes.