Hierarchical Porous Architecture Research Articles

Heterogeneous Ni-Boride/Phosphide Anchored Amorphous B-C Layer for Overall Water Electrocatalysis.

The rational design of efficient and economical bifunctional electrocatalysts remained a challenge for overall water electrolysis. In this work, the Ni-boride/ phosphide particles anchored amorphous B-doped carbon layer with hierarchical porous characteristics in Ni foam (Ni3P/Ni3B/B-C/NF) was fabricated for overall water splitting. The Boroncarbide (B4C) power was filled and fixed in the NF interspace through the electroplating and electroless plating, and then annealed in vacuum high temperature. The amorphous B-C layer derived from the B4 C not only speeded up the electron transport, but also cooperate with Ni-boride/phosphide to enhance the electrocatalytic activity for HER and OER synergistically. Furthermore, the hierarchical porous architecture of Ni3P/Ni3B/B-C/NF increased space utilization to load more active materials. The self-supported Ni3P/Ni3B/B-C/NF electrode possessed a low overpotential of 212 and 280 mV to deliver 100 mA cm-2 for HER and OER, respectively, and high stability for 48 h. In particular, the electrolyzer constituted with the Ni3P/Ni3B/B-C/NF bifunctional electrocatalyst only required a voltage of 1.59 V at 50 mA cm-2 for water electrocatalysis under alkaline medium, and demonstrated long-term stability for 48 h. This study provides a new technical path for the development of bifunctional of transition metal borides to promote the application of hydrogen production from water splitting.

High-Energy Laser Protection Performance of Fibrous Felt-Reinforced Aerogels with Hierarchical Porous Architectures.

Continuous-wave lasers can cause irreversible damage to structured materials in a very short time. Modern high-energy laser protection materials are mainly constructed from ceramic, polymer, and metal constitutions. However, these materials are protected by sacrificing their structural integrity under the irradiation of high-energy lasers. In this contribution, we reported multilayer fibrous felt-reinforced aerogels that can sustain the continuous irradiation of a laser at a power density of 120 MW·m-2 without structural damage. It is found that the exceptional high-energy laser protection performance and the comparable mechanical properties of aerogel nanocomposites are attributed to the unique characteristics of hierarchical porous architectures. In comparison with various preparation methods and other aerogel materials, multilayer fibrous felt-reinforced aerogels exhibit the best performance in high-energy laser protection, arising from the gradual interception and the Raman-Rayleigh scattering cycles of a high-energy laser in the porous aerogels. Furthermore, a near-zero thermal expansion coefficient and extremely low thermal conductivity at high temperature allow the lightweight felt-reinforced aerogels to be applied in extreme conditions. The felt-reinforced aerogels reported herein offer an attractive material that can withstand complex thermomechanical stress and retain excellent insulation properties at extremely high temperature.

Catalytic Consequences of Hierarchical Pore Architectures within MFI and FAU Zeolites for Polyethylene Conversion

Catalytic Consequences of Hierarchical Pore Architectures within MFI and FAU Zeolites for Polyethylene Conversion

Porous carbon@carbon sponge for enhanced solar-driven seawater evaporation and wastewater remediation

Utilizing solar energy for interfacial solar steam generation and wastewater remediation is regarded as one of the sustainable approaches for alleviating clean water shortage. However, it is still a great challenge to comprehend all the requirements of efficient evaporation, salt resistance and wastewater treatment as well as low cost in one evaporator, thus hindering its large-scale practical application. Herein, in this work, an environmentally friendly and low-cost hierarchical porous architecture (APC@TMF) was prepared by assembling potassium citrate activated poplar catkin derived porous carbon (APC) into the porous structure of thermalized melamine formaldehyde resin sponge (TMF) by a simple dipping method. The APC@TMF integrates the advantages of APC and TMF, thus leading to good light absorption, low thermal conductivity, high hydrophilicity and fast water transport. As expected, APC@TMF exhibits a high evaporation flux of 2.28 kg m−2 h−1 with energy conversion efficiency of 96.3 % in seawater, which outperforms TMF, PVA/TMF, PVA/APC and recently reported evaporators. Beyond that, it demonstrates good performance for seawater desalination and wastewater remediation as well as high cost-effectiveness.

Spherical Binderless 4A/5A Zeolite Assemblies: Synthesis, Characterization, and Adsorbent Applications.

Zeolite microspheres have been successfully applied in commercial-scale separators such as oxygen concentrators. However, further enhancement of their applications is hampered by the post-synthetic shaping process that formulates the zeolite powder into packing-sized spherical bodies with various binders leading to active site blockage and suboptimal performance. Herein, binderless zeolite microspheres with a tunable broad size range from 2 µm to 500 µm have been developed with high crystallinity, sphericity over 92%, monodispersity with a coefficient of variation (CV) less than 5%, and hierarchical pore architecture. Combining precursor impregnation and steam-assisted crystallization (SAC), mesoporous silica microspheres with a wide size range could be successfully transformed into zeolite. For preserved size and spherical morphology, a judicious selection of the synthesis conditions is crucial to ensure a pure phase, high crystallinity, and hierarchical architecture. For the sub-2-µm zeolite microsphere, low-temperature prolonged aging was important so as to suppress external zeolization that led to a large, single macroporous crystal. For the large 500 µm sphere, ultrasound pretreatment and vacuum impregnation were crucial and facilitated spatially uniform gel matrix dispersion and homogenous crystallization. The obtained zeolite 5A microspheres exhibited excellent air separation performance, while the 4A microspheres displayed ammonium removal capabilities. This work provides a general strategy to overcome the existing limitations in fabricating binder-free technical bodies of zeolites for various applications.

Free‐Standing Multiscale Porous High Entropy NiFeCoZn Alloy as the Highly Active Bifunctional Electrocatalyst for Alkaline Water Splitting

Comprehensive SummaryIn the endeavor of searching for highly active and stable electrocatalysts toward overall water splitting, high‐entropy‐alloys have been the intense subjects owing to their advanced physicochemical property. The non‐noble metal free‐standing multiscale porous NiFeCoZn high‐entropy‐alloy is in situ constructed on the surface layer of NiZn intermetallic and Ni heterojunction over nickel foam (NiFeCoZn/NiZn‐Ni/NF) by one scalable dealloying protocal to fulfill the outstanding bifunctional electrocatalytic performances toward overall water splitting. Because of the high‐entropy effects and specific hierarchical porous architecture, the as‐made NiFeCoZn/NiZn‐Ni/ NF displays high intrinsic catalytic activities and durability toward both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline media. In particular, the in‐situ construction of bimodal porous NiFeCoZn high‐entropy‐alloy results in the small overpotentials (η1000 = 254/409 mV for HER and OER), low Tafel slopes, and exceptional long‐term catalytic durability for 400 h. Expressively, the electrolyzer constructed with NiFeCoZn/NiZn‐Ni/NF as both cathode and anode exhibits a low cell voltage of 1.72 V to deliver the current density of 500 mA·cm–2 for overall water splitting. This work not only provides a facile and scalable protocol for the preparation of self‐supporting high‐entropy‐alloy nanocatalysts but also enlightens the engineering of high performance bifunctional electrocatalysts toward water splitting.

Exploiting Natural Diatom Shells as an Affordable Polar Host for Sulfur in Li-S Batteries

<p>Given the high theoretical capacity (1,675 mAh g<sup>−1</sup>) and the inherent affordability and ubiquity of elemental sulfur, it stands out as a prominent cathode material for advanced lithium metal batteries. Traditionally, sulfur was sequestered within conductive porous carbons, rooted in the understanding that their inherent conductivity could offset sulfur’s non-conductive nature. This study, however, pivots toward a transformative approach by utilizing diatom shell (DS, diatomite)—a naturally abundant and economically viable siliceous mineral—as a sulfur host. This approach enabled the development of a sulfur-layered diatomite/S composite (DS/S) for cathodic applications. Even in the face of the insulating nature of both diatomite and sulfur, the DS/S composite displayed vigorous participation in the electrochemical conversion process. Furthermore, this composite substantially curbed the loss of soluble polysulfides and minimized structural wear during cycling. As a testament to its efficacy, our Li-S battery, integrating this composite, exhibited an excellent cycling performance: a specific capacity of 732 mAh g<sup>−1</sup> after 100 cycles and a robust 77% capacity retention. These findings challenge the erstwhile conviction of requiring a conductive host for sulfur. Owing to diatomite’s hierarchical porous architecture, eco-friendliness, and accessibility, the DS/S electrode boasts optimal sulfur utilization, elevated specific capacity, enhanced rate capabilities at intensified C rates, and steadfast cycling stability that underscore its vast commercial promise.</p>

Salt Effect Engineering Single Fe-N2P2-Cl Sites on Interlinked Porous Carbon Nanosheets for Superior Oxygen Reduction Reaction and Zn-Air Batteries.

Developing efficient metal-nitrogen-carbon (M-N-C) single-atom catalysts for oxygen reduction reaction (ORR) is significant for the widespread implementation of Zn-air batteries, while the synergic design of the matrix microstructure and coordination environment of metal centers remains challenges. Herein, a novel salt effect-induced strategy is proposed to engineer N and P coordinated atomically dispersed Fe atoms with extra-axial Cl on interlinked porous carbon nanosheets, achieving a superior single-atom Fe catalyst (denoted as Fe-NP-Cl-C) for ORR and Zn-air batteries. The hierarchical porous nanosheet architecture can provide rapid mass/electron transfer channels and facilitate the exposure of active sites. Experiments and density functional theory (DFT) calculations reveal the distinctive Fe-N2P2-Cl active sites afford significantly reduced energy barriers and promoted reaction kinetics for ORR. Consequently, the Fe-NP-Cl-C catalyst exhibits distinguished ORR performance with a half-wave potential (E1/2) of 0.92V and excellent stability. Remarkably, the assembled Zn-air battery based on Fe-NP-Cl-C delivers an extremely high peak power density of 260mWcm-2 and a large specific capacity of 812mAhg-1, outperforming the commercial Pt/C and most reported congeneric catalysts. This study offers a new perspective on structural optimization and coordination engineering of single-atom catalysts for efficient oxygen electrocatalysis and energy conversion devices.

From wasted polymers to N/O co-doped partially graphitic carbon with hierarchical porous architecture as a promising cathode for high performance Zn-ion hybrid supercapacitors

N/O co-doped graphitic hierarchical porous carbon is yielded from wasted polymers. A capacity of 257.9 mA h g−1 with an ultrahigh energy density of 226.5 W h kg−1 is delivered. Excellent energy storage ability is also obtained for wearable devices.

Super-assembled periodic mesoporous organosilica membranes with hierarchical channels for efficient glutathione sensing.

Bioinspired nanochannel-based sensors have elicited significant interest because of their excellent sensing performance, and robust mechanical and tunable chemical properties. However, the existing designs face limitations due to material constraints, which hamper broader application possibilities. Herein, a heteromembrane system composed of a periodic mesoporous organosilica (PMO) layer with three-dimensional (3D) network nanochannels is constructed for glutathione (GSH) detection. The unique hierarchical pore architecture provides a large surface area, abundant reaction sites and plentiful interconnected pathways for rapid ionic transport, contributing to efficient and sensitive detection. Moreover, the thioether groups in nanochannels can be selectively cleaved by GSH to generate hydrophilic thiol groups. Benefiting from the increased hydrophilic surface, the proposed sensor achieves efficient GSH detection with a detection limit of 1.2 μM by monitoring the transmembrane ionic current and shows good recovery ranges in fetal bovine serum sample detection. This work paves an avenue for designing and fabricating nanofluidic sensing systems for practical and biosensing applications.

Scalable synthesis of N, O co-doped hierarchical porous carbon for high energy density supercapacitors

Rational design of hierarchical porous architecture with abundant pseudocapacitive sites is highly desirable for carbon electrode materials. However, the lengthy production process and high economic input limit its broader application. Herein, we successfully prepared N, O co-doped hierarchical porous carbon (NOHC) through hydrothermal carbonization (HTC) of chitin biomass with the assist of NH4Cl and subsequent carbonization with NaNH2. The optimal NOHC600 exhibits a remarkable hierarchical porous structure and an ultrahigh specific surface area (SSA) of 2555 m2 g−1. Furthermore, it showcases a significant content of N, O co-doping, thereby providing abundant defects and additional active sites for ion adsorption. The aforementioned characteristics ensure outstanding capacitance performance of NOHC600. In the three-electrode system, NOHC600 exhibits a remarkable specific capacitance of up to 455 F g−1 at a current density of 0.5 A g-1. The symmetric supercapacitors (SCs) based on NOHC600 achieve an impressive energy density of 30.4 Wh kg−1 at a power density of 180 W kg−1. Moreover, the all-solid-state NOHC600 microsupercapacitors (MSCs) demonstrate an exceptional areal capacitance of 78.2 mF cm−2 and an areal energy density of up to 10.8 μWh cm−2. Accordingly, this facile and scalable strategy shows a great potential for producing high-heteroatom-doped porous carbon materials from chitin biomass, which can be applied in practical energy-related applications.

Coordination polymer and layered double hydroxide dual-precursors derived polymetallic phosphides confined in N-doped hierarchical porous carbon nanoflower as a highly efficient bifunctional electrocatalyst for overall water splitting

Controllable construction of proficient electrocatalyst with 3D hierarchical architecture to achieve low cost and high efficient overall water splitting is of great significance to the sustainable development. Hereby, trimetallic phosphides confined in N-doped carbon nanoflowers (CoNiP/CoNiFeP@NCNFs) were fabricated using CoNi coordination polymer nanoflowers/CoNiFe layered double hydroxide (CoNi CPNFs/CoNiFe LDH) as precursors followed by phosphorization. Benefiting from the unique 3D hierarchical porous architecture, preeminent conductivity, high specific surface area, efficient mass/charge transfer and synergic effect of various transition metals, the well-designed CoNiP/CoNiFeP@NCNFs exhibit extraordinary electrocatalytic performance for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline media. Particularly, this novel material can work as a bifunctional catalyst in an integrated water-splitting electrolyzer, which only requires a low voltage of 1.55 V to realize the current density of 10 mA cm−2 with admirable durability (at least 28 h). This work certified the foreground of composites assembled by 3D hierarchical porous carbon and polymetallic phosphides for overall water splitting. It also provided a novel proposal for the rational designing and constructing highly active electrocatalysts by using coordination polymer and LDH as dual-precursors.

Hierarchical CaMn2O4/C Network Framework toward Aqueous Zn Ion Hybrid Capacitors as Competitive Cathodes

Manganese-based materials have received more attention as cathodes for aqueous zinc ion hybrid capacitors (AZIHCs) due to their advantages such as abundant reserves, low cost, and large theoretical capacity. However, manganese-based materials have the disadvantage of poor electrical conductivity. Herein, a solid-phase method was used to synthesize a hierarchical carbon-coated calcium manganate (CaMn2O4/C) network framework as the cathode for AZIHCs. Thanks to the unique structural/componential merits including conductive carbon coating and hierarchical porous architecture, the achieved CaMn2O4/C cathode shows an exceptionally long life of close to 5000 cycles at 2.0 A g−1, with a reversible specific capacity of 195.6 mAh g−1. The assembled CaMn2O4/C-based AZIHCs also display excellent cycling stability with a capacity retention rate of 84.9% after 8000 cycles at 1.0 A g−1, and an energy density of 21.3 Wh kg−1 at an output power density of 180.0 W kg−1.

Mof-derived hierarchical Co3O4 assembled by porous nanocages towards toluene-sensing ability

Assembly of building blocks into porous hierarchical architecture can contribute the gas diffusion and gas–solid reaction. In this work, a novel hierarchical microstructure constructed with metal–organic framework (MOF)-derived Co3O4 porous nanocages was succeeded in synthesizing through a PVP-mediated wet-chemical and followed annealing route. This as-prepared Co3O4 sample integrate the structural merits of porous hierarchical surface, high specific surface area (69.6 m2/g), and rich contents of Co3+ and oxygen species (chemisorbed oxygen and oxygen vacancy). As a result, this as-prepared Co3O4 sensor possessed a clear response to toluene at the low working temperature (175 °C) in terms of the approving selectivity, high response value (Rg/Ra = 23 – 100 ppm), and real actual detection limit of 0.1 ppm. This paper provides a reliable way to design hierarchical structure over catalytic oxide (eg. Co3O4) for probing low reactive gas (eg. toluene).

Eco-friendly synthesis of chemically cross-linked chitosan/cellulose nanocrystal/CMK-3 aerogel based shape-stable phase change material with enhanced energy conversion and storage

Phase change materials (PCMs) have attracted numerous attention owing to their high energy storage density, cost-effective and operationally simple, however, the “solid-liquid” leakage and limited solar absorbance seriously hinder their widespread applications. Herein, an innovative chitosan/cellulose nanocrystal/CMK-3 (CS/CNC/CMK-3) aerogel based shape-stable PCM (SSPCM) was successfully synthesized, in which chemically cross-linked CS and CNC acted as three-dimensional supporting skeleton, CMK-3 endowed solar-to-thermal energy conversion ability and the impregnating polyethylene glycol (PEG) acted as the latent heat storage unit. The as-synthesized CS/CNC/CMK-3 aerogel/PEG (CCCA/PEG) showed ultrahigh melting/crystallization enthalpy of 178.5/171.1 J g−1 and excellent shape stability. The PEG was effectively embedded into the hierarchical porous architecture and the composite PCM could preserve its original shape without any leakage even compressed above the melting point of PEG. Meanwhile, the CCCA/PEG exhibited robust thermal reliability with an ultralow enthalpy fading rate of 0.030 ± 0.012 % per cycle over 100 thermal cycles. Intriguingly, the introduction of CMK-3 also significantly improved the solar-to-thermal energy conversion performance of CCCA/PEG, and a high solar-to-thermal conversion efficiency of 93.1 % could be realized. This work provided a potential strategy to design and synthesize high-performance sustainable SSPCM, which showed tremendous potential in the practical solar energy harvesting, conversion and storage applications.

Energy-Dense Zinc Ion Hybrid Supercapacitors with S, N Dual-Doped Porous Carbon Nanocube Based Cathodes.

Zinc ion hybrid supercapacitors (ZIHSCs) are truly promising as next-generation high-performance energy storage systems because they could offer high energy density like batteries while exhibiting high power output and long cycle life traits of supercapacitors. The key point of constructing a high-performance ZIHSC is to couple the Zn anode with an appropriate cathode material, which has high theoretical capacity, cost-effectiveness, and intrinsic safety features. In this work, we have demonstrated the potentiality of S, N co-doped porous carbon nanocubes (S, N-CNCs) as a cathode material for devising a ZIHSC with excellent energy density and cycle life. The S, N-CNCs are prepared from a zeolitic imidazolate framework (ZIF)-8 precursor via a simultaneous pyrolyzing-doping strategy in an inert atmosphere. Resultant CNCs are monodisperse with an average size of around 65 nm and porous in nature, with uniform N and S doping throughout the structure. Benefitted from such hierarchical porous architecture and the presence of abundant heteroatoms, the assembled ZIHSC with S, N-CNC as the cathode and Zn-foil as the anode in a ZnSO4 aqueous electrolyte could reach a specific capacity as high as 165.5 mA h g-1 (331 F g-1) at 1 A g-1, which corresponds to a satisfactory energy density of 148.9 W h kg-1 at the power density of 900 W kg-1. The ZIHSC has displayed a good cycle stability with more than 70% capacity retention after 10,000 charge-discharge cycles. Furthermore, to verify the practical feasibility of such a cathode material, an aqueous 3D Zn@Cu//S, N-CNC full-cell device is fabricated, which has demonstrated a satisfactory specific capacity (49.6 mAh g-1 at 0.25 A g-1) and an impressive energy density (42.2 Wh kg-1 with 212.2 W kg-1). Full ZIHSC devices are also found to be efficient in powering light-emitting diodes, further substantiating their feasibility in next-generation energy storage applications.

Combined contributions from multidimensional micropores and mesopores of hierarchical porous carbons for extraordinary Li-ion storage applications

Hierarchical porous carbons (HPCs) with optimized ultrafine micropores (<1 nm), large micropores (1–2 nm), small mesopores (2–5 nm) and large mesopores (>5 nm) are synthesized for a state-of-the-art Li-ion storage capacity. The HPCs are synthesized by direct carbonization of zinc citrate, while joint templating and activation effects of ZnO result in this hierarchical porous architecture and large specific area. The HPC obtained at 1200 °C (HPC-1200) displays the largest specific area (2245 m2 g−1) and pore volume (3.45 cm3 g−1) combined with an average pore size of 3.63 nm. This unique porous structure results in the highest specific capacity of 1850 mA h g−1 (Li5C6) at 0.1 A g−1, and superior rate performance and cycling stability. More significantly, mechanisms for this maximal capacity are investigated. It is found that mesopores are more effective to increase capacity, while micropores buffer Li-intercalation stress. Energy storage of HPC is surface-controlled with enhanced capacity achieved at enlarged surface area. In addition, the HPC-1200 exhibits excellent performance for assembly of full batteries with noticeable specific energy of 271.4 W h kg−1 achieved at 195.5 W kg−1, and the full battery is workable for energy-delivery when the specific power increases to 19 kW kg−1.

Overall upgrading Zn-ion storage capability by engineering N/O co-doped hydrophilic hierarchical porous carbon

The couple of supercapacitors' high power density and batteries' high energy density endows aqueous zinc-ion hybrid supercapacitors (ZIHSCs) a perspective candidate for next-generation energy storage devices. Biomass-derived hierarchical porous carbon with excellent wettability towards aqueous electrolyte is regarded as a promising cathode for ZIHSCs applications. Herein, a N/O co-doped hydrophilic carbon with hierarchical porous architecture is conversed from protein enriched recycled badminton feathers via a facile and scalable strategy. The resultant carbon presents hierarchical porous architecture with high surface area and mesopore-governed pore size distribution, rich dual-doping of N/O heteroatoms and good water wetting behavior. The all-round teamwork of these unique properties provides numerous interfacial active sites plus extra reversible redox reaction for high energy density, and speedy kinetics for high power density. Incredibly, as-assembled ZIHSC device displays an ultrahigh capacity of 225.3 mAh g−1 at 0.1 A g−1 with an appreciable capacity retention of 73.8 mAh g−1 even at a 1000-fold amplified current density, thereby delivering admirable energy and power densities of 201.4 Wh kg−1 and 83.6 kW kg−1. Most satisfyingly, an ultralong cycling life with no loss in capacity is achieved after 40,000 cycles even at 50 A g−1. Therefore, by taking advantage of its intrinsic component, the conversion of biomass waste to high performance carbon-based cathode material holds a broad prospect and practical significance.

Facile synthesis of hierarchical porous ZSM-5 zeolite with tunable mesostructure and its application in catalytic cracking of LDPE

ZSM-5 zeolites with hierarchical porosity have been an increasing attention due to their improvement in diffusion limitation issue. This work here reports that hierarchical porous ZSM-5 zeolites were synthesized using fumed silica and as-synthesized mesoporous silica nanoparticles (MSNs) as dual-silica source for the first time with the aid of silicate-1 seed. The effects of the amounts of silicate-1 seed and as-synthesized MSNs on crystallinity, morphology, mesoporous structure and acidity of the prepared ZSM-5 zeolites were systematically investigated by XRD, FT-IR, SEM, TEM, N2 adsorption-desorption and NH3-TPD techniques. The results showed that mesopores can be incorporated by introducing an appropriate amount of as-synthesized MSNs which also promote the crystallization of aluminosilicate at the same time. Moreover, the mesoporous structures of ZSM-5 zeolites can be flexibly regulated within a certain range via varying the dosage of as-synthesized MSNs. The obtained optimal sample Z-0.02–0.2 with high crystallinity and bi-modal mesopores centered at 2.1 nm and 3.4 nm exhibits significantly improved catalytic performance in LDPE cracking on a TG apparatus, compared with the conventional mono-modal microporous ZSM-5 zeolite. This approach constitutes a simple and low-cost pathway to synthesize ZSM-5 zeolites with controllable hierarchical porous architecture and might facilitate their industrial application.

Optimizing D-band center of tube brush-like CoZn13/Co/ZnO architecture with multiple-heterointerfaces enhancing ion/electron migration toward pseudocapacitive storage

The exploration of hierarchical heterostructures with heterointerfaces have proven indispensable for enhancing ion/electron migration of efficient energy storage. Herein, a fascinating design of CoZn13/Co/ZnO hierarchically porous nanostructures (CZCZ HPNs) with rich heterointerfaces concurrently encapsulated into N-doped carbon (NC), growing on three-dimensional Ni foam wrapped by N-doped graphene (denoted as CZCZ/NC HPNs) is showcased for pseudocapacitive storage. The ingeniously construction of CZCZ HPNs/NC features powerful built-in electric field (BIEF) introduced by well-defined heterointerface for boosting electronic/ionic transport dynamics, and unique porous hierarchical architectures for reinforcing the structural and electrochemical stability. Notably, combined with the differential charge density analysis, the BIEF in CZCZ/NC HPNs generated by two heterointerfaces of Co-ZnO and CoZn13-ZnO can offer additional driving forces for promoting electron transfer. The d band centers of different heterojunctions remarkably shift negatively in comparison with those of the monomers, indicative of lower electron/ion transfer energy barrier. Additionally, the CZCZ/NC HPNs as a positive electrode and porous γ-Fe2O3 nanorods wrapped by NC (γ-Fe2O3/NC) as a negative electrode are employed to assemble a soft-packed hybrid supercapacitor device with ultrahigh energy density of ∼107.2 Wh kg−1 at ∼399.9 W kg−1. This work highlights an in-depth fundamental understanding of underlying reaction mechanisms of the heterointerface and structures engineering in constructing other advanced electrodes in sustainable energy storage.