Unique PCoN Surface Bonding States Constructed on g‐C3N4 Nanosheets for Drastically Enhanced Photocatalytic Activity of H2 Evolution

Developing high‐efficiency and low‐cost photocatalysts by avoiding expensive noble metals, yet remarkably improving H₂ evolution performance, is a great challenge. Noble‐metal‐free catalysts containing Co(Fe)?N?C moieties have been widely reported in recent years for electrochemical oxygen reduction reaction and have also gained noticeable interest for organic transformation. However, to date, no prior studies are available in the literature about the activity of N‐coordinated metal centers for photocatalytic H₂ evolution. Herein, a new photocatalyst containing g‐C₃N₄ decorated with CoP nanodots constructed from low‐cost precursors is reported. It is for the first time revealed that the unique P(δ^?)?Co(δ⁺)?N(δ^?) surface bonding states lead to much superior H₂ evolution activity (96.2 µmol h^?1) compared to noble metal (Pt)‐decorated g‐C₃N₄ photocatalyst (32.3 µmol h^?1). The quantum efficiency of 12.4% at 420 nm is also much higher than the record values (≈2%) of other transition metal cocatalysts‐loaded g‐C₃N₄. It is believed that this work marks an important step toward developing high‐performance and low‐cost photocatalytic materials for H₂ evolution.     

Ag3PO4/BiPO4 p–n heterojunction nanocomposite prepared in room-temperature ionic liquid medium with improved photocatalytic activity

A visible-light-active Ag₃PO₄/BiPO₄ nanocomposite with a p–n heterojunction structure was fabricated via a co-precipitation hydrothermal process using 2-hydroxylethylammonium formate (RTIL) as a room-temperature ionic liquid. The resulting catalysts were characterized by various techniques. The photocatalytic activity of the photocatalysts was evaluated by the photodegradation of phthalocyanine Reactive Blue 21 (RB21) under both visible and UV light irradiations. The results reveal that the heterojunction composite prepared in RTIL noticeably exhibited an improvement in both efficiency and rate of RB21 photodegradation in comparison with pure Ag₃PO₄ and BiPO₄. The enhanced photocatalytic activity of Ag₃PO₄/BiPO₄ heterostructure prepared in RTIL is mainly ascribed to the internal electric field built at the heterojunction interface and efficient charge separation and transfer across the p–n junction. RTIL can also assist in decreasing the crystalline size, orderly distributing the particles, preventing the collapse of pore structures, and losing of composite surface area.     

g‐C3N4 Loading Black Phosphorus Quantum Dot for Efficient and Stable Photocatalytic H2 Generation under Visible Light

Black phosphorus (BP) is an interesting two‐dimensional material with low‐cost and abundant metal‐free properties and is used as one cocatalyst for photocatalytic H₂ production. However, the BP quantum dot (BPQD) is not studied. Herein, for the first time, BPQD is introduced as a hole‐migration cocatalyst of layered g‐C₃N₄ for visible‐light‐driven photocatalytic hydrogen generation. A high‐vacuum stirring method is developed for BPQD loading without the dissociation of BP. The layered BPQD is coupled on the layered g‐C₃N₄ surface to form a heterojunction structure. The 7% BPQD–C₃N₄ samples show similar time‐resolved photoluminescence curves as 0.5% Pt–C₃N₄. The optimum hydrogen rates of the modified sample (7% BPQD–C₃N₄) are 190, 133, 90, and 10.4 µmol h^?1 under simulated sunlight, LED‐405, LED‐420, and LED‐550 nm irradiation, respectively, which are 3.5, 3.6, and 3 times larger than that of the pristine g‐C₃N₄. Such low‐cost layered system not only optimizes the optical, electrical, and texture properties of the hybrid materials for photocatalytic water splitting to generate hydrogen but also provides ideas for designing novel or easily oxidized candidates by incorporating different available materials with given carriers.     

Unique P?Co?N Surface Bonding States Constructed on g‐C3N4 Nanosheets for Drastically Enhanced Photocatalytic Activity of H2 Evolution

Developing high‐efficiency and low‐cost photocatalysts by avoiding expensive noble metals, yet remarkably improving H₂ evolution performance, is a great challenge. Noble‐metal‐free catalysts containing Co(Fe)? N? C moieties have been widely reported in recent years for electrochemical oxygen reduction reaction and have also gained noticeable interest for organic transformation. However, to date, no prior studies are available in the literature about the activity of N‐coordinated metal centers for photocatalytic H₂ evolution. Herein, a new photocatalyst containing g‐C₃N₄ decorated with CoP nanodots constructed from low‐cost precursors is reported. It is for the first time revealed that the unique P(δ^?)? Co(δ⁺)? N(δ^?) surface bonding states lead to much superior H₂ evolution activity (96.2 µmol h^?1) compared to noble metal (Pt)‐decorated g‐C₃N₄ photocatalyst (32.3 µmol h^?1). The quantum efficiency of 12.4% at 420 nm is also much higher than the record values (≈2%) of other transition metal cocatalysts‐loaded g‐C₃N₄. It is believed that this work marks an important step toward developing high‐performance and low‐cost photocatalytic materials for H₂ evolution.     

Ice‐Assisted Synthesis of Black Phosphorus Nanosheets as a Metal‐Free Photocatalyst: 2D/2D Heterostructure for Broadband H2 Evolution

A 2D/2D heterojunction of black phosphorous (BP)/graphitic carbon nitride (g‐C₃N₄) is designed and synthesized for photocatalytic H₂ evolution. The ice‐assisted exfoliation method developed herein for preparing BP nanosheets from bulk BP, leads to high yield of few‐layer BP nanosheets (≈6 layers on average) with large lateral size at reduced duration and power for liquid exfoliation. The combination of BP with g‐C₃N₄ protects BP from oxidation and contributes to enhanced activity both under λ > 420 nm and λ > 475 nm light irradiation and to long‐term stability. The H₂ production rate of BP/g‐C₃N₄ (384.17 µmol g^?1 h^?1) is comparable to, and even surpasses that of the previously reported, precious metal‐loaded photocatalyst under λ > 420 nm light. The efficient charge transfer between BP and g‐C₃N₄ (likely due to formed N? P bonds) and broadened photon absorption (supported both experimentally and theoretically) contribute to the excellent photocatalytic performance. The possible mechanisms of H₂ evolution under various forms of light irradiation is unveiled. This work presents a novel, facile method to prepare 2D nanomaterials and provides a successful paradigm for the design of metal‐free photocatalysts with improved charge‐carrier dynamics for renewable energy conversion.     

Regeneration of novel visible-light-driven Ag/Ag3PO4@C3N4 hybrid materials and their high photocatalytic stability

Novel visible-light-driven Ag₃PO₄@C₃N₄PO₄ loaded with metal Ag were synthesised via an anion-exchange precipitation method and regenerated by H₂O₂ and NaNH₃HPO₄. The obtained Ag/Ag₃PO₄@C₃N₄ and regenerated Ag/Ag₃PO₄@C₃N₄ were characterised by XRD, XPS, SEM and UV–vis. The XRD and UV–vis results revealed that the crystal structure and light adsorption property of Ag/Ag₃PO₄@C₃N₄ were similar to that of regenerated Ag/Ag₃PO₄@C₃N₄. The XPS result showed that the metallic Ag⁰ deposited on the surface of Ag/Ag₃PO₄@C₃N₄ and regenerated Ag/Ag₃PO₄@C₃N₄. The Ag/Ag₃PO₄@C₃N₄ hybrids displayed remarkable photocatalytic activity and stability after regeneration. Compared with pure Ag₃PO₄ or C₃N₄, the Ag/Ag₃PO₄@C₃N₄ and regenerated Ag/Ag₃PO₄@C₃N₄ enhancement in the photodegradation rate towards methyl orange is observed over under visible light irradiation. The enhanced photocatalytic performance was attributed to the synergistic effect between Ag₃PO₄ and C₃N₄ and a small amount of Ag⁰ which suppresses the charge recombination during photocatalytic process. This work could provide new insights into the fabrication of high stability visible photocatalysts and facilitate their practical application in environment issues.     

Freestanding Graphitic Carbon Nitride Photonic Crystals for Enhanced Photocatalysis

Graphitic carbon nitride (g‐C₃N₄) has attracted tremendous attention in photocatalysis due to its extraordinary features, such as good thermal and chemical stability, metal‐free composition, and easy preparation. However, the photocatalytic performance of g‐C₃N₄ is still restricted by the limited surface area, inefficient visible light absorption, and high recombination rate of photoinduced charge carriers. Herein, a facile synthesis to produce freestanding g‐C₃N₄ photonic crystals (PCs) by crack‐free, highly ordered colloid crystals templating is reported. The PC structure succeeded from the silica opals induces bicontinuous framework, stronger optical absorption, and increase in the lifetime of photoexcited charge carriers compared to that of the bulk g‐C₃N₄, while the chemical structure remains similar to that of the bulk g‐C₃N₄. As such, the g‐C₃N₄ PCs have a much higher photodegradation kinetic of methyl orange and photocatalytic hydrogen production rate which is nearly nine times the rate of bulk g‐C₃N₄.     

Engineering the Photocatalytic Behaviors of g/C3N4‐Based Metal‐Free Materials for Degradation of a Representative Antibiotic

Graphitic carbon nitride (g/C₃N₄) is of promise as a highly efficient metal‐free photocatalyst, yet engineering the photocatalytic behaviours for efficiently and selectively degrading complicated molecules is still challenging. Herein, the photocatalytic behaviors of g/C₃N₄ are modified by tuning the energy band, optimizing the charge extraction, and decorating the cocatalyst. The combination shows a synergistic effect for boosting the photocatalytic degradation of a representative antibiotic, lincomycin, both in the degradation rate and the degree of decomposition. In comparison with the intrinsic g/C₃N₄, the structurally optimized photocatalyst shows a tenfold enhancement in degradation rate. Interestingly, various methods and experiments demonstrate the specific catalytic mechanisms for the multiple systems of g/C₃N₄‐based photocatalysts. In the degradation, the active species, including ·O₂^?, ·OH, and h⁺, have different contributions in the different photocatalysts. The intermediate, H₂O₂, plays an important role in the photocatalytic process, and the detailed functions and originations are clarified for the first time.     

Dual Functions of CO2 Molecular Activation and 4f Levels as Electron Transport Bridge in Dysprosium Single Atom Composite Photocatalysts with Enhanced Visible-Light Photoactivities

The effect of rare earth (RE) single atoms on photocatalytic activity is very complex due to its special electronic configuration, which leads to few reports on the RE single atoms. Here, Dy³⁺ single atom composite photocatalysts are successfully constructed based on both the special role of Dy³⁺ and the special advantages of CdS/g-C₃N₄ heterojunction in the field of photocatalysis. The results show that an efficient way of electron transfer is provided to promote charge separation, and the dual functions of CO₂ molecular activation of rare-earth single atom and 4f levels as electron transport bridge are fully exploited. It is exciting that under visible-light irradiation, the catalytic performance of CdS:Dy³⁺/g-C₃N₄ is ≈ 6.9 times higher than that of pure g-C₃N₄. The catalytic performance of CdS:Dy³⁺ and CdS:Dy³⁺/g-C₃N₄ are ≈ 7 and ≈ 13.7 times higher than those of pure CdS, respectively. Besides, not all RE ions are suitable for charge transfer bridges, which is not only related to the 4f levels of RE ions but also related to the bandgap structure of CdS and g-C₃N₄. The pattern of combining single-atom catalysis and heterojunction opens up new methods for enhancing photocatalytic activity.     

In Situ Bond Modulation of Graphitic Carbon Nitride to Construct p–n Homojunctions for Enhanced Photocatalytic Hydrogen Production

Graphitic carbon nitride (g‐C₃N₄) has recently emerged as an attractive photocatalyst for solar energy conversion. However, the photocatalytic activities of g‐C₃N₄ remain moderate because of the insufficient solar‐light absorption and the fast electron–hole recombination. Here, defect‐modified g‐C₃N₄ (DCN) photocatalysts, which are easily prepared under mild conditions and show much extended light absorption with band gaps decreased from 2.75 to 2.00 eV, are reported. More importantly, cyano terminal C?N groups, acting as electron acceptors, are introduced into the DCN sheet edge, which endows the DCN with both n‐ and p‐type conductivities, consequently giving rise to the generation of p–n homojunctions. This homojunction structure is demonstrated to be highly efficient in charge transfer and separation, and results in a fivefold enhanced photocatalytic H₂ evolution activity. The findings deepen the understanding on the defect‐related issues of g‐C₃N₄‐based materials. Additionally, the ability to build homojunction structures by the defect‐induced self‐functionalization presents a promising strategy to realize precise band engineering of g‐C₃N₄ and related polymer semiconductors for more efficient solar energy conversion applications.     

g-C3N4/Ag3PO4 composites with synergistic effect for increased photocatalytic activity under the visible light irradiation

The g-C₃N₄ was synthesized by a hydrothermal method and the g-C₃N₄/Ag₃PO₄ composites were prepared by a ordinary precipitation method. Microstructures, morphologies and optical properties of the as-prepared samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), UV–vis diffuse reflectance spectroscopy (DRS), transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS). The results showed that the Ag₃PO₄ nanoparticles were dispersed on the surface of the flake-like g-C₃N₄, and the heterojunction was formed on the interface. The g-C₃N₄/Ag₃PO₄ (2 wt%) photocatalyst presented the highest photocatalytic activity for organic dye methylene blue (MB) degradation, and its photocurrent intensity was approximately 2 times than that of the pure Ag₃PO₄. The g-C₃N₄/Ag₃PO₄ (2 wt%) photocatalyst also exhibited photocatalytic performance in the decomposition of colorless antibiotic ciprofloxacin (CIP). The capture experiment confirmed that holes acted as the main active species during the photocatalytic reaction.     

Graphene‐Like Carbon Nitride Nanosheets for Improved Photocatalytic Activities

“Graphitic” (g)‐C₃N₄ with a layered structure has the potential of forming graphene‐like nanosheets with unusual physicochemical properties due to weak van der Waals forces between layers. Herein is shown that g‐C₃N₄ nanosheets with a thickness of around 2 nm can be easily obtained by a simple top‐down strategy, namely, thermal oxidation etching of bulk g‐C₃N₄ in air. Compared to the bulk g‐C₃N₄, the highly anisotropic 2D‐nanosheets possess a high specific surface area of 306 m² g^?1, a larger bandgap (by 0.2 eV), improved electron transport ability along the in‐plane direction, and increased lifetime of photoexcited charge carriers because of the quantum confinement effect. As a consequence, the photocatalytic activities of g‐C₃N₄ nanosheets have been remarkably improved in terms of ?OH radical generation and photocatalytic hydrogen evolution.     

Effect of morphology on the photocatalytic activity of g-C3N4 photocatalysts under visible-light irradiation

Graphite-like carbon nitride (g-C₃N₄) photocatalysts with different morphologies have been synthesized using melamine as a precursor using a template-free wet chemical method. The as-prepared g-C₃N₄ nanorods, g-C₃N₄ microcones and porous g-C₃N₄ quadruple prisms were characterized by XRD, FESEM, FT-IR and UV–vis absorption spectrophotometer. These nanostructured g-C₃N₄ photocatalysts show better photocatalytic activity than bulk g-C₃N₄ under visible light irradiation in view of degrading Rhodamine B (RhB). The porous g-C₃N₄ quadruple prisms show the highest photocatalytic efficiency. We deduce that the surface area of the catalysts and their adsorption ability of target molecules play important roles in improving the photocatalytic activity of the g-C₃N₄ photocatalysts.     

Effective Prevention of Charge Trapping in Graphitic Carbon Nitride with Nanosized Red Phosphorus Modification for Superior Photo(electro)catalysis

The high occurrence of trapped unreactive charges due to chemical defects seriously affects the performance of g‐C₃N₄ in photocatalytic applications. This problem can be overcome by introducing ultrasmall red phosphorus (red P) crystals on g‐C₃N₄ sheets. The elemental red P atoms reduce the number of defects in the g‐C₃N₄ structure by forming new chemical bonds for much more effective charge separation. The product shows significantly enhanced photocatalytic activity toward hydrogen production. To the best of our knowledge, the hydrogen evolution rate obtained on this hybrid should be the highest among all P‐containing g‐C₃N₄ photocatalysts reported so far. The trapping and detrapping processes in this red P/g‐C₃N₄ system are thoroughly revealed by using time‐resolved transient absorption spectroscopy.     

Synthesis and characterization of g-C3N4/BiFeO3 composites with an enhanced visible light photocatalytic activity

The novel visible light-induced g-C₃N₄/BiFeO₃ composites were successfully synthesized by introducing BiFeO₃ into polymeric g-C₃N₄. The structures and optical properties of composites were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), field-emission transmission electron microscope (TEM), UV–vis diffuse reflection spectroscopy (DRS), respectively. For the degradation of Rhodamine B (RhB), the g-C₃N₄/BiFeO₃ composites exhibited significantly higher visible light photocatalytic activity than that of a single semiconductor. The optimal percentage of doped g-C₃N₄ was 50%. Both photooxidation and photoreduction processes follow first order kinetics. In addition, the stability of the prepared photocatalyst in the photocatalytic process was also investigated. The enhanced photocatalytic performance could be due to the high separation efficiency of the photogenerated electron–holes pairs. The possible photocatalytic mechanism of g-C₃N₄/BiFeO₃ was proposed to guide the further improvement of their photocatalytic activity.     

Incorporating Graphitic Carbon Nitride (g‐C3N4) Quantum Dots into Bulk‐Heterojunction Polymer Solar Cells Leads to Efficiency Enhancement

Graphitic carbon nitride (g‐C₃N₄) has been commonly used as photocatalyst with promising applications in visible‐light photocatalytic water‐splitting. Rare studies are reported in applying g‐C₃N₄ in polymer solar cells. Here g‐C₃N₄ is applied in bulk heterojunction (BHJ) polymer solar cells (PSCs) for the first time by doping solution‐processable g‐C₃N₄ quantum dots (C₃N₄ QDs) in the active layer, leading to a dramatic efficiency enhancement. Upon C₃N₄ QDs doping, power conversion efficiencies (PCEs) of the inverted BHJ‐PSC devices based on different active layers including poly(3‐hexylthiophene‐2,5‐diyl):[6,6]‐phenyl‐C61‐butyric acid methyl ester (P3HT:PC₆₁BM), poly(4,8‐bis‐alkyloxybenzo(l,2‐b:4,5‐b′)dithiophene‐2,6‐diylalt‐(alkyl thieno(3,4‐b)thiophene‐2‐carboxylate)‐2,6‐diyl):[6,6]‐phenyl C₇₁‐butyric acid methyl ester (PBDTTT‐C:PC₇₁BM), and poly[4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐co‐3‐fluorothieno [3,4‐b]thiophene‐2‐carboxylate] (PTB7‐Th):PC₇₁BM reach 4.23%, 6.36%, and 9.18%, which are enhanced by ≈17.5%, 11.6%, and 11.8%, respectively, compared to that of the reference (undoped) devices. The PCE enhancement of the C₃N₄ QDs doped BHJ‐PSC device is found to be primarily attributed to the increase of short‐circuit current (J_sc), and this is confirmed by external quantum efficiency (EQE) measurements. The effects of C₃N₄ QDs on the surface morphology, optical absorption and photoluminescence (PL) properties of the active layer film as well as the charge transport property of the device are investigated, revealing that the efficiency enhancement of the BHJ‐PSC devices upon C₃N₄ QDs doping is due to the conjunct effects including the improved interfacial contact between the active layer and the hole transport layer due to the increase of the roughness of the active layer film, the facilitated photoinduced electron transfer from the conducting polymer donor to fullerene acceptor, the improved conductivity of the active layer, and the improved charge (hole and electron) transport.     

Apparent Potential Difference Boosting Directional Electron Transfer for Full Solar Spectrum‐Irradiated Catalytic H2 Evolution

Directional charge transfer among nanolayers of graphitic carbon nitride (g‐C₃N₄) is still inefficient because of the interlayer electrostatic potential barrier, which tremendously restricts the utilization of charges in conversion of solar energy into fuel. Herein, an apparent potential among nanolayers is introduced to boost interlayer electron transfer by curving planar g‐C₃N₄ nanosheets into carbon nitride square tubes (C₃N₄Ts), and Ni₂P nanoparticles as electron acceptors are loaded on C₃N₄Ts (Ni₂P/C₃N₄Ts) for highly efficient H₂ evolution. Study results present H₂‐evolution efficiency over the constructed Ni₂P/C₃N₄Ts up to 19.25 mmol g^?1 h^?1 with a large number of visible H₂ bubbles, which is more than 1.9 and 2.6 times of that over g‐C₃N₄ supported 1 wt%Pt and 3 wt%Pd, respectively. Density functional theory (DFT) and characterizations reveal efficient directional transfer through C₃N₄T interlayer (001) to Ni₂P (111) is achieved under the apparent potential difference of C₃N₄Ts, which therefore ensures the high H₂‐evolution performance of Ni₂P/C₃N₄Ts. These results in the field of material engineering supply a novel strategy to boost directional charge transfer for solar energy conversion efficiency by introducing apparent potential difference.     

Smart Hybrids of Zn2GeO4 Nanoparticles and Ultrathin g‐C3N4 Layers: Synergistic Lithium Storage and Excellent Electrochemical Performance

Smart hybrids of Zn₂GeO₄ nanoparticles and ultrathin g‐C₃N₄ layers (Zn₂GeO₄/g‐C₃N₄ hybrids) are realized by a facile solution approach, where g‐C₃N₄ layers act as an effective substrate for the nucleation and subsequent in situ growth of Zn₂GeO₄ nanoparticles. A synergistic effect is demonstrated on the two building blocks of Zn₂GeO₄/g‐C₃N₄ hybrids for lithium storage: Zn₂GeO₄ nanoparticles contribute high capacity and serve as spacers to isolate the ultrathin g‐C₃N₄ layers from restacking, resulting in expanded interlayer and exposed vacancies with doubly bonded nitrogen for extra Li‐ion storage and diffusion pathway; 2D g‐C₃N₄ layers, in turn, minimize the strain of particles expansion and prevent the formation of unstable solid electrolyte interphase, leading to highly reversible lithium storage. Benefiting from the remarkable synergy, the Zn₂GeO₄/g‐C₃N₄ hybrids exhibit highly reversible capacity of 1370 mA h g^?1 at 200 mA g^?1 after 140 cycles and excellent rate capability of 950 mA h g^?1 at 2000 mA g^?1. The synergistic effect originating from the hybrids brings out excellent electrochemical performance, and thus casts new light on the development of high‐energy and high‐power anode materials.     

Boosting Performance of Non‐Fullerene Organic Solar Cells by 2D g‐C3N4 Doped PEDOT:PSS

The power‐conversion efficiency (PCE) of single‐junction organic solar cells (OSCs) has exceeded 16% thanks to the development of non‐fullerene acceptor materials and morphological optimization of active layer. In addition, interfacial engineering always plays a crucial role in further improving the performance of OSCs based on a well‐established active‐layer system. Doping of graphitic carbon nitride (g‐C₃N₄) into poly(3,4‐ethylene‐dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) as a hole transport layer (HTL) for PM6:Y6‐based OSCs is reported, boosting the PCE to almost 16.4%. After being added into the PEDOT:PSS, the g‐C₃N₄ as a Bronsted base can be protonated, weakening the shield effect of insulating PSS on conductive PEDOT, which enables exposures of more PEDOT chains on the surface of PEDOT:PSS core‐shell structure, and thus increasing the conductivity. Therefore, at the interface between g‐C₃N₄ doped HTL and PM6:Y6 layer, the charge transport is improved and the charge recombination is suppressed, leading to the increases of fill factor and short‐circuit current density of devices. This work demonstrates that doping g‐C₃N₄ into PEDOT:PSS is an efficient strategy to increase the conductivity of HTL, resulting in higher OSC performance.     

Composites Based on Core–Shell Structured HBCuPc@CNTs-Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> and Polyarylene Ether Nitriles with Excellent Dielectric and Mechanical Properties

Core–shell structured magnetic carbon nanotubes (CNTs-Fe₃O₄) coated with hyperbranched copper phthalocyanine (HBCuPc) (HBCuPc@CNTs-Fe₃O₄) hybrids were prepared by the solvent-thermal method. The results indicated that the HBCuPc molecules were decorated on the surface of CNTs-Fe₃O₄ through coordination behavior of phthalocyanines, and the CNTs-Fe₃O₄ core was completely coaxial wrapped by a functional intermediate HBCuPc shell. Then, polymer-based composites with a relatively high dielectric constant and low dielectric loss were fabricated by using core–shell structured HBCuPc@CNTs-Fe₃O₄ hybrids as fillers and polyarylene ether nitriles (PEN) as the polymer matrix. The cross-sectional scanning electron microscopy (SEM) images of composites showed that there is almost no agglomeration and internal delamination. In addition, the rheological analysis reveals that the core–shell structured HBCuPc@CNTs-Fe₃O₄ hybrids present better dispersion and stronger interface adhesion with the PEN matrix than CNTs-Fe₃O₄, thus resulting in significant improvement of the mechanical, thermal and dielectric properties of polymer-based composites.