Systematic Density Functional Theory Calculations Research Articles

Electroreductive C[sbnd]O coupling of benzaldehyde over SACs Au–NiMn2O4 spinel synergetic composites

Electroreductive CO coupling provides a prospective strategy for biomass derivative upgrading via reducing the number of oxygen-containing functional groups and increasing their molecular weight. However, exploring superior electrocatalysts with effective reactivity and high selectivity for target products are still a challenge. In this work, single atom Au surface derived NiMn2O4 (SACs Au−NiMn2O4) spinel synergetic composites were fabricated by a versatile adsorption-deposition method and applied in electroreductive self-coupling of benzaldehyde to dibenzyl ether. The SACs Au–NiMn2O4 spinel synergetic composites enhanced electroreductive coupling of benzaldehyde, significantly improved the yield and selectivity of dibenzyl ether. Systematic characterizations and density functional theory calculation revealed that atomically dispersed Au occupied surface Ni2+ vacancies, which played a dominated role in CO coupling of benzaldehyde. Detailed calculation results showed that benzaldehyde preferred to adsorb on Ni octa-hedral sites of NiMn2O4 spinel synergetic structure, single atom Au surficial derivation over NiMn2O4 further reduced the adsorption energy (Eads) of benzaldehyde on SACs Au−NiMn2O4, thus the CO coupling of benzaldehyde to dibenzyl ether was promoted. Moreover, single atom Au surficial derivation lowered the energy barrier of rate-determining step, facilitated the formation of dibenzyl ether species. Our work also paves an avenue for rational design single atom materials using spinel as support.

On native point defects in ZnSe

Aiming at a fundamental understanding of the defect chemistry of pure ZnSe for optical and quantum applications, systematic density functional theory calculations with hybrid exchange-correlation functionals were performed to build an accurate database of native defects in ZnSe, including isolated defects and first nearest-neighbor defect–defect complexes. From the defect formation energies, zinc vacancy is found to be the most prevalent defect as the Fermi level approaches the conduction band edge, while zinc interstitial in the selenium tetrahedron and selenium vacancy become the most prevalent defects as the Fermi level approaches the valence band maximum. The divacancy complex, consisting of first nearest-neighboring zinc and selenium vacancies, is also found to have a favorable binding energy across the entire bandgap. Its formation energy is, however, always higher than either the isolated zinc or selenium vacancy, meaning it will never be the predominant defect in equilibrium. Finally, a point defect with extended spin coherence in Fluorine-implanted ZnSe was recently discovered, and it was found to exhibit a broad emission peak centered at 2.28 eV. The identity of this defect was determined to be either zinc vacancy or its associated complex according to the electron paramagnetic resonance measurements. Explicit simulations of the optical signatures of all zinc vacancy-related native defects were conducted here, showing that both zinc vacancy and divacancy are the most likely native defect contributors to that peak.

2D KBr/Graphene Heterostructures-Influence on Work Function and Friction.

The intercalation of graphene is an effective approach to modify the electronic properties of two-dimensional heterostructures for attractive phenomena and applications. In this work, we characterize the growth and surface properties of ionic KBr layers altered by graphene using ultra-high vacuum atomic force microscopy at room temperature. We observed a strong rippling of the KBr islands on Ir(111), which is induced by a specific layer reconstruction but disappears when graphene is introduced in between. The latter causes a consistent change in both the work function and the frictional forces measured by Kelvin probe force microscopy and frictional force microscopy, respectively. Systematic density functional theory calculations of the different systems show that the change in work function is induced by the formation of a surface dipole moment while the friction force is dominated by adhesion forces.

Large magneto-optical effect and magnetic anisotropy energy in two-dimensional metallic ferromagnet Fe3GeTe2

The recent discovery of long-range magnetic orders in atomically thin semiconductors ${\mathrm{Cr}}_{2}{\mathrm{Ge}}_{2}{\mathrm{Te}}_{6}$ and $\mathrm{Cr}{\mathrm{I}}_{3}$ as well as metal ${\mathrm{Fe}}_{3}\mathrm{Ge}{\mathrm{Te}}_{2}$ has opened up exciting opportunities for fundamental physics of two-dimensional (2D) magnetism and also for technological applications based on 2D magnetic materials. To exploit these 2D metallic magnets, the mechanisms that control their physical properties should be well understood. In this paper, based on systematic first-principles density functional theory calculations, we study the magnetic anisotropy energy (MAE) and magneto-optical (MO) effects of ferromagnetic multilayers [mono-, bi-, tri-, tetra-, and pentalayer] and bulk ${\mathrm{Fe}}_{3}\mathrm{Ge}{\mathrm{Te}}_{2}$ as well as their connections with the underlying electronic structures of the materials. Firstly, all the considered ${\mathrm{Fe}}_{3}\mathrm{Ge}{\mathrm{Te}}_{2}$ structures are found to prefer the out-of-plane magnetization and have gigantic MAEs of $\ensuremath{\sim}3.0$ meV/f.u. This gigantic perpendicular anisotropy results from the large magnetocrystalline anisotropy energy (MCE), which is ten times larger than the competing magnetic dipolar anisotropy energy. The giant MCEs are attributed to the large Te ${p}_{x,y}$ orbital density of states near the Fermi level and also to the topological nodal point just below the Fermi level at the K points in the Brillouin zone. Secondly, 2D and bulk ${\mathrm{Fe}}_{3}\mathrm{Ge}{\mathrm{Te}}_{2}$ also exhibit strong MO effects with their Kerr and Faraday rotation angles being $\ensuremath{\sim}1.{0}^{\ensuremath{\circ}}$ and $\ensuremath{\sim}100 \mathrm{deg}/\ensuremath{\mu}\mathrm{m}$ in the visible-light frequency region, respectively. The strong MO Kerr and Faraday effects are found to result from the large MO conductivity (or strong magnetic circular dichroism) in these ferromagnetic materials. In particular, the calculated MO conductivity spectra are one order of magnitude larger than that of ${\mathrm{Y}}_{3}{\mathrm{Fe}}_{5}{\mathrm{O}}_{12}$. The calculated MO conductivity spectra are analysed in terms of the dipole-allowed optical transitions at high symmetry $\mathrm{\ensuremath{\Gamma}}$, K, and ${\mathrm{K}}^{\ensuremath{'}}$ points, which further indicate that atomically thin ${\mathrm{Fe}}_{3}\mathrm{Ge}{\mathrm{Te}}_{2}$ films with odd layer-number might exhibit anomalous ferrovalley Hall effect. All these interesting findings thus suggest that 2D and bulk ferromagnetic ${\mathrm{Fe}}_{3}\mathrm{Ge}{\mathrm{Te}}_{2}$ are promising materials for high-density MO and spintronic nanodevices.

Urchin-like Nb2O5 hollow microspheres enabling efficient and selective photocatalytic C–C bond cleavage in lignin models under ambient conditions

Selective cleavage of robust C−C bonds to harvest value-added aromatic oxygenates is an intriguing but challenging task in lignin depolymerization. Photocatalysis is a promising technology with the advantages of mild reaction conditions and strong sustainability. Herein, we show a novel urchin-like Nb2O5 hollow microsphere (U-Nb2O5 HM), prepared by one-pot hydrothermal method, are highly active and selective for Cα−Cβ bond cleavage of lignin β-O-4 model compounds under mild conditions, achieving 94% substrate conversion and 96% C−C bond cleavage selectivity. Systematic experimental studies and density functional theory (DFT) calculations revealed that the superior performance of U-Nb2O5 HMs arises from more exposed active sites, more efficient free charge separation and the active (001) facet, which facilitates the activation of Cβ−H bond of lignin models and generate key Cβ radical intermediates by photogenerated holes, further inducing the Cα−Cβ bond cleavage to produce aromatic oxygenates. This work could provide some suggestions for the fabrication of hierarchical photocatalysts in the lignin depolymerization system.

Oxygen Vacancy Engineering of Molybdenum Oxide Nanobelts by Fe Ion Intercalation for Aerobic Oxidative Desulfurization

Aerobic oxidative desulfurization (AODS) represents a sustainable way to deeply desulfurize transportation fuels through a high-performance catalyst to convert thiophenes into sulfones in an efficient way. Here, we report that iron (Fe) intercalated molybdenum oxides (MoOx) nanobelts can be a durable and robust catalyst for AODS, catalyzing the reaction efficiently at 80 °C with air as a sustainable oxygen source. By combining systematic characterization, kinetic analysis, and density functional theory calculation, we demonstrate that the guest Fe ions could precisely modulate the electronic structure of Mo sites, leading to a significant increase in surface oxygen vacancy density. An optimized doping amount enables our catalyst with excellent catalytic performance via thorough conversion of various sulfides. The catalyst maintained almost unchanged activity in repeated uses, qualifying it as a candidate for the sustainable AODS of fuel. We anticipate that the strategy demonstrated here will provide practical guidance on the rational design and optimization of Mo-based catalysts to promote aerobic oxidation reactions.

A Theory-Guided X-ray Absorption Spectroscopy Approach for Identifying Active Sites in Atomically Dispersed Transition-Metal Catalysts.

Atomically dispersed supported metal catalysts offer new properties and the benefits of maximized metal accessibility and utilization. The characterization of these materials, however, remains challenging. Using atomically dispersed platinum supported on crystalline MgO (chosen for its well-defined bonding sites) as a prototypical example, we demonstrate how systematic density functional theory calculations for assessing all the potentially stable platinum sites, combined with automated analysis of extended X-ray absorption fine structure (EXAFS) spectra, leads to unbiased identification of isolated, surface-enveloped platinum cations as the catalytic species for CO oxidation. The catalyst has been characterized by atomic-resolution imaging and EXAFS and high-energy resolution fluorescence detection X-ray absorption near edge spectroscopy. The proposed platinum sites are in agreement with experiment. This theory-guided workflow leads to rigorously determined structural models and provides a more detailed picture of the structure of the catalytically active site than what is currently possible with conventional EXAFS analyses. As this approach is efficient and agnostic to the metal, support, and catalytic reaction, we posit that it will be of broad interest to the materials characterization and catalysis communities.

Resolving the Intricate Mechanism and Selectivity of Syngas Conversion on Reduced ZnCr2Ox: A Quantitative Study from DFT and Microkinetic Simulations

By combining reduced oxide and zeolite (e.g., ZnCrOx/MSAPO), bifunctional catalysts achieve outstanding olefin selectivity for syngas conversion via a relay process (CO + H2 → IM → olefin) and are one of the hottest catalytic systems. However, the reaction mechanism on the reduced ZnCrOx as well as the intermediate (IM = ketene versus methanol) entering the zeolite are under heated debate owing to the complexity of this system. Herein, we perform systematic density functional theory (DFT) calculations and microkinetic simulations to inspect the possible elementary steps on the highly reduced ZnCr2O4(110) surface, which quantitatively unveils the favored reaction pathways for CO activation and conversion. We find that CO tends to adsorb at the two-coordinate O vacancy sites (VO 2C) and reacts with H at VO 2C to form CHO, while the disproportionation reaction and the direct C–O cleavage are less favored. Importantly, the conversion of CHO plays a vital role in product selectivity; the dissociation of CHO is identified to proceed easily and constitutes a major route responsible for the formation of CH4 and CH2CO, through the following pathway: CHO → CH + O; CH + H → CH2; CH2 + CO → CH2CO; or CH2 + 2H → CH4. Alternatively, CHO could undergo hydrogenation to give CH2O and CH3O intermediates, eventually leading to the formation of CH3OH and CH4. The kinetic analyses on such a complex reaction network disclose that CH4 is the dominant product, while both CH2CO and CH3OH (i.e., two experimentally controversial intermediates) exist in minority with CH2CO being relatively more readily formed. More interestingly, the kinetic model illustrates that the selectivity for CH2CO and the formation of triggered light olefins can be significantly improved over CH4 if a reaction channel converts CH2CO to light olefins when zeolite is added, providing insight into the bifunctionality of the oxide/zeolite system. Also, we demonstrate that high VO 2C coverage is a prerequisite for high activity of CO activation, and the reason for high selectivity of CO2 and low selectivity of H2O is identified to the easier removal of the lattice oxygen by CO to generate CO2 than by H2 to generate H2O. The understanding derived from this work could lay a solid theoretical foundation for comprehending the oxides for the syngas conversion mechanism.

Catalytic oxidation of NO to NO2 on pure and doped AunPt3-n (n=0–3) clusters: A DFT perspective

A systematic density functional theory (DFT) calculations are performed on pure as well as doped Au3 trimer clusters to study the catalytic oxidation of NO to NO2 using the M06L functional combined with a def2QZVPP basis set. Adsorption energies and Bader charges of adsorbed NO and O2 on the AunPt3-n clusters have been calculated to observe the stability of the adsorbed species. Results show that the adsorption of both NO and O2 on the bimetallic clusters is stronger on the Pt site than that of Au site. Owing to the high adsorption energy of both the reactants, we further propose a reaction mechanism of NO oxidation over AunPt3-n (n = 0–3) clusters following the Langmuir-Hinshelwood (L-H) mechanism. The rate constants of NO2 production at each step of the reaction mechanism are determined using the Transition State Theory (TST). Energetic span model is also used to determine the efficient catalytic system among the four clusters. This study offers a new insight into the fundamental effect of doping Pt on Au3 and conveys an understanding for the NO oxidation mechanism at the molecular level which in turn will help in building efficient catalysts for large-scale processes.

Dual-doped carbon hollow nanospheres achieve boosted pseudocapacitive energy storage for aqueous zinc ion hybrid capacitors

Rechargeable aqueous zinc ion hybrid capacitors (ZHCs) have attracted increasing attention for energy storage devices due to low cost, high safety and environmental friendliness. However, it suffers from low energy/power density and poor cycling stability due to the lack of suitable electrode materials, especially the promising cathode candidates with satisfactory capacity and excellent cycling stability. Herein, we developed dual-doped carbon hollow nanospheres (PN-CHoNS) through a dual-functional template induced strategy combined with the subsequent carbonization treatment, which can act as potential cathode materials. Impressively, when employed to assemble the ZHCs, the device can deliver an exceptional energy density of 116.0 Wh kg−1 at a power density of 141 W kg−1 and an extremely high power density of 21660 W kg−1 under a decent energy density of 36.1 Wh kg−1, as well as ultra-long cycling stability up to 12000 cycles. Moreover, the systematic characterization and density functional theory calculation decipher that dual-doping could promote the chemical absorption/desorption kinetics of Zn ions to boost the electrochemical charge storage of carbon. This work can not only provide a rational strategy to construct advanced carbon-based electrode materials, but also deepen the fundamental understanding of the charge storage mechanism of heteroatom-doped carbonaceous materials.

Predicted Electrocatalyst Properties on Metal Insulator MoTe2 for Hydrogen Evolution Reaction and Oxygen Reduction Reaction Application in Fuel Cells

Systematic spin-polarized density functional theory (DFT) calculations were executed to study the catalytic performance of the topological insulator MoTe2 (2H, 1T, and 1T′) phase. Topological insul...

High-throughput search for magnetic topological materials using spin-orbit spillage, machine learning, and experiments

Magnetic topological insulators and semi-metals have a variety of properties that make them attractive for applications including spintronics and quantum computation, but very few high-quality candidate materials are known. In this work, we use systematic high-throughput density functional theory calculations to identify magnetic topological materials from 40000 three-dimensional materials in the JARVIS-DFT database (https://jarvis.nist.gov/jarvisdft). First, we screen materials with net magnetic moment > 0.5 {\mu}B and spin-orbit spillage > 0.25, resulting in 25 insulating and 564 metallic candidates. The spillage acts as a signature of spin-orbit induced band-inversion. Then, we carry out calculations of Wannier charge centers, Chern numbers, anomalous Hall conductivities, surface bandstructures, and Fermi-surfaces to determine interesting topological characteristics of the screened compounds. We also train machine learning models for predicting the spillage, bandgaps, and magnetic moments of new compounds, to further accelerate the screening process. We experimentally synthesize and characterize a few candidate materials to support our theoretical predictions.

Photodegradation of organic water pollutants under visible light using anatase F, N co-doped TiO2/SiO2 nanocomposite: Semi-pilot plant experiment and density functional theory calculations

Visible-light driven photocatalysts are of great importance in wastewater treatment. In this work, fluorine and nitrogen co-doped titanium dioxide/silica nanocomposite (F–N–TiO2/SiO2) was synthetized using a sol-gel approach. The as-developed nanocomposite was well characterized using different techniques. In particular, an anatase structure with high surface area (345.69 m2/g) and a band gap of 2.97 eV were observed for the as-synthesized nanocomposite, which makes it a potential candidate for photocatalytic applications under visible light. A systematic density functional theory calculation was performed to get more insight into the effect of dopant atoms on the band gap of TiO2 nanoparticles. To enhance the reusability of the photocatalyst in semi-pilot scale, the as-developed nanocomposite was immobilized onto the glass beads by coupling dip-coating and heat attachment methods. A semi-pilot scale custom-designed fixed-bed photoreactor was used to evaluate the photocatalytic performance of the as-developed nanocomposite under both visible and solar irradiations. A mixture of three azo dyes (i.e., basic red 29, basic blue 41 and basic yellow 51) was used as the model industrial wastewater. The analysis of the wastewater showed that the complete removal of the pollutants under visible light and sunlight can occurred at pH of 3 and flow rate of 280 mL/min. The durability results demonstrated the successful degradation of the pollutants for five cycles. The results of this study show how careful controlling the operational parameters as well as using a highly photocatalytic nanomaterial can lead to successful decontamination of organic water pollutants. This approach might open up new windows to the future applications of photocatalytic nanomaterials for wastewater treatment.

Atomistic insight into hydrogen trapping at MC/BCC-Fe phase boundaries: The role of local atomic environment

A physical understanding of hydrogen trapping at microstructural defects such as grain boundaries (GBs) and phase boundaries (PBs) is vitally important for the design of hydrogen embrittlement (HE) resistant metals. As compared with GBs, the mechanism of hydrogen trapping at PBs is rather unclear due to the complex atomic environment at PBs. We perform systematic density functional theory (DFT) calculations to reveal the physical origin of hydrogen trapping at a variety of PBs between body centered cubic (BCC)-Fe and NaCl-type carbides (MCs). It is found that hydrogen trapping energetics at MC/BCC-Fe PBs depend not only on local volume dilation of the hydrogen trapping sites, but also on their local atomic environment. An array of descriptors such as lattice strain, geometric volume, and charge density, which has been proven to effectively predict hydrogen trapping at GBs, fail to quantify hydrogen trapping at MC/BCC-Fe PBs. We analyzed the electronic interactions at PBs and found that they are closely related to hydrogen binding energies, and the Bader volume of hydrogen is a universal descriptor for assessing hydrogen trapping energetics at PBs. This study provides new insight into hydrogen trapping at microstructural defects from atomic and electronic scales, and is aimed to advance the future design of hydrogen traps and HE resistant metals.

Activating PtSe2 monolayer for hydrogen evolution reaction by defect engineering and Pd doping

Platinum diselenide (PtSe2) has been successfully fabricated with a hope of catalytic applications. However, the active sites of pristine PtSe2 are only located at the edges while the sites in basal plane are largely inactive. To change such situation, in this study we introduce Pd dopant and vacancies to activate the basal plane for hydrogen evolution reaction (HER). Based on systematic density functional theory calculations, we find that Pd doping reduces the band gap and enhances the catalytic ability, and the divacancy sites (VSe2 and VPt2) in pristine PtSe2 monolayer and the monovacancy sites (VSe, VPd) as well as the divacancy sites (VPt2, VPdPt) in PdPtSe4 monolayer significantly improve the catalytic activities comparable to that of Pt(111). A band-center model is applied to better understand the difference in HER activities, where the chemical bond energies of H (ΔG1) show an approximately linear relationship with the energy of d/p level of Pt/Se. The strategy proposed here would be applicable to other two-dimensional materials.

Carbon quantum dots functionalized g-C3N4 nanosheets as enhanced visible-light photocatalysts for water splitting

Graphitic carbon nitride (g-C3N4) is a representative photocatalyst, but the photocatalytic activity is often limited because of the easy recombination and slow migration of photogenerated charges. Herein, we have successfully prepared carbon quantum dots (CQDs) functionalized g-C3N4 (CCN) by a simple thermal polymerization method. Besides, the CQDs serving as a photosensitizer can enlarge the absorption range of visible light of the composite material. As a result, under the irradiation of visible light, the optimized CCN showed superior catalytic activity with a high H2 production rate of 2321 μmol·g−1·h−1, which was almost about 7.4 times higher than that of bulk g-C3N4. Based on the systematic characterization and density functional theory (DFT) calculation, it was proved that the efficiencies of the separation and transfer of photogenerated charges were enhanced by the micro-regional heterostructure of CQDs and g-C3N4.

Origin of direct and indirect bandgap in B-X(X = Sb, Bi): A first principle study

In the quest of the origin of direct and indirect nature of bandgap of zinc-blende (ZB) phase Boron Antimonide and Bismuth (BSb, BBi), a systematic density functional theory (DFT) calculation is carried out, considering the full-potential linearized augmented plane wave (FPLAPW) basis sets in the Modified Becke-Johnson (mBJ) exchange correlation (XC) potential. Including the Generalized Gradient Approximation Perdew-Burke-Ernzerh (PBEsol) XC functional, a fully relaxed and optimized lattice constants, (5.23, and 5.52 Å) are obtained for BSb and BBi respectively. The optimized lattice constant serves as a basis for the calculation of optoelectronic properties like electronic density of state (DOS), band diagram, and optical absorption coefficient. The BSb offers a wider direct (Γ-Γ) bandgap of 2.804 eV compared to the indirect (Γ-X) one of 0.997 eV, while BBi exhibits a narrower direct (Γ-Γ) bandgap of 422 meV compared to the indirect (Γ-X) one of 1.046 eV. The computed total and partial DOS (TDOS, PDOS) brings out the better insight for foundation of indirect and direct nature of bandgap in BSb and BBi respectively. The calculated optical absorption spectra is in consistent with this direct and indirect nature of bandgap of BSb and BBi. Consequently, BSb become a promising contender for photovoltaic applications and BBi for IR application.

Self-consistent assessment of Li+ ion cathodes: Theory vs. experiments

A self-consistent DFT framework without fitting parameters has been carried out to make assessments for the well-recognized cathode materials for lithium ion batteries. It offers a dependable framework for theoretical assessment of cathode materials. Transition metal oxide cathodes such as layered LiCoO 2 , spinel LiMn 2 O 4 and olivine LiFePO 4 have been commercialized for several decades and widely used in the rechargeable Li-ion batteries (LIBs). While great theoretical efforts have been made using the density functional theory (DFT) method, leading to insightful understanding covering materials stability and functional properties, the lack of consistency in choices of functionals and/or convergence criteria makes it somewhat difficult to compare results. It is therefore highly useful to assess these established systems towards self-consistency, thus offering a reliable working basis for theoretical formulation of novel cathodes. Here in this work, we have carried out systematic DFT calculations on the basis of recently established framework covering both thermodynamic stability, functional properties and associated mechanisms. Efforts have been made in self-consistent selection of exchange–correlation (XC) functionals in terms of dependable accuracy with affordable computational cost, which is essential for high-throughput first-principles calculations. The outcome of the current work on three established cathode systems is in very good agreement with experimental data, and the methodology is to provide a solid basis for designing novel cathode materials without using costing non-local exchange–correlation functionals for structure-energy calculations.

The Interstitial Carbon–Dioxygen Center in Irradiated Silicon

We investigated, experimentally as well as theoretically, defect structures in electron irradiated Czochralski-grown silicon (Cz-Si) containing carbon. Infrared spectroscopy (IR) studies observed a band at 1020 cm−1 arisen in the spectra around 300 °C. Its growth occurs concomitantly with the decay out of the well-known vacancy-oxygen (VO) defect, with a Local Vibrational Mode (LVM) at 830 cm−1 and carbon interstitial-oxygen interstitial (CiOi) defect with a LVM at 862 cm−1, in silicon (Si). The main purpose of this work is to establish the origin of the 1020 cm−1 band. One potential candidate is the carbon interstitial-dioxygen (CiO2i) defect since it is expected to form upon annealing out of the CiOi pair. To this end, systematic density functional theory (DFT) calculations were used to predict the lowest energy structure of the (CiO2i) defect in Si. Thereafter, we employed the dipole–dipole interaction method to calculate the vibrational frequencies of the structure. We found that CiO2i defect has an LVM at ~1006 cm−1, a value very close to our experimental one. The analysis and study of the results lead us to tentatively correlate the 1020 cm−1 band with the CiO2i defect.

Hierarchical Multicavity Nitrogen-Doped Carbon Nanospheres as Efficient Polyselenide Reservoir for Fast and Long-Life Sodium-Selenium Batteries.

Sodium-selenium (Na-Se) battery has been emerging as one of the most prospective energy storage systems owing to their high volumetric energy density and cost effectiveness. Nevertheless, the shuttle effect of sodium polyselenide (NaPSe) and sluggish electrochemical reaction kinetics present the main bottlenecks for its practical implementation. Herein, a new Se host of 3D nitrogen-doped hierarchical multicavity carbon nanospheres (3DNHMCs) is designed and synthesized via a facile self-sacrifice templating strategy. The 3D NHMCs are verified to hold a favorable structure of a hollow macropore core and numerous micro/mesopores hollow shell for hosting Se, which can not only maximize Se utilization and alleviate the volumetric expansion but also promote the electrical/ionic conductivity and electrolyte infiltration. Moreover, the abundant self-functionalized surfaces as an efficient NaPSe scavenger via robust physical-chemical dual blocking effects demonstrate high-efficiency in situ anchoring-diffusion-conversion of NaPSe, rendering rapid reaction kinetics and remarkable suppressive shuttle effect, as evidenced by systematic experimental analysis and density functional theory calculations. As a result, the high-Se-loading 3D NHMCs/Se cathode exhibits an ultrahigh volumetric capacity (863mAhcm-3 ) and rate capability (377mAhg-1 at 20 C) and unexceptionable stability over 2000 cycles at 2 C.