Three-dimensional Porous Carbon Materials Research Articles

Co-crosslinking and anchoring strategy: One-step preparation of N-doped porous carbon for supercapacitors and zinc ion hybrid capacitors

Porous carbon has been widely used in aqueous capacitors due to its wide source, high stability, and controllable preparation. However, the two-step preparation strategy of carbonization and activation with complex operation and serious energy consumption severely limits its further application. In this paper, resorcinol/urea-furfural resin was successfully prepared by using cleaner and greener furfural as raw material and co-crosslinking with resorcinol and urea under the action of catalyst. It is noteworthy that during the curing process, KOH is uniformly anchored inside the resin, so the system only needs one-step high-temperature pyrolysis to obtain a N-doped ant-nest-like three-dimensional interconnected porous carbon material. Consequently, the porous carbon exhibited an impressive specific capacitance of 283F g−1. The assembled symmetrical device shows a capacitance retention of 92 % after 50 000 cycles, showing excellent cycle stability. In addition, the assembled zinc ion hybrid capacitor exhibits a capacitance of 138 mAh g−1 and an energy density of 111 Wh kg−1. The one-step carbonization-doping-activation strategy of this bottom-up in-situ anchoring activator will provide further insights into the hierarchical pore structure design of porous carbon and facilitate the simple and efficient preparation of carbon materials.

Potassium single-atoms anchoring on three-dimensional porous N-doped carbon material as sensing material for boosting electrochemical sensing of hydrogen peroxide.

For thefirst time potassium single-atoms (K SA) are explored as the sensing material to boost electrochemical sensing of hydrogen peroxide (H2O2). The N-doped carbon material with a three-dimensional porous structure (3D NG) was prepared using NaCl as the template, and K SA were anchored to the surface of 3D NG through high-temperature pyrolysis. The structure of K SA/3D NG was characterized by TEM, HAADF-STEM, XPS, and XRD. The results of electrochemical studies indicate that K SA play a crucial role in promoting the electrocatalytic reduction of H2O2, which not only optimized the adsorption strength for H2O2 but also improved the electron transfer rate, therefore improving the sensitivity for detecting H2O2. This study demonstrates the excellent electrocatalytic activity of K SA, which provides a promising sensing material for the detection of H2O2 andlays the foundation for the application of alkali metal single-atoms in the field of electrochemical sensing.

In situ loading of ZnO on hierarchical porous carbon derived from banana-peel waste to enrich mechanism for microwave absorption

Biomass has received widespread attention due to its easy availability, low cost, and environmental friendliness as an electromagnetic wave absorber candidate. Inspired by the natural porosity of biomass, the three-dimensional (3D) porous carbon materials derived from banana peels were prepared via coordination and pyrolysis carbonization. A conductive network of biomass-zinc complexes was constructed by introducing Zn2+ to coordinate with organic polymers. Hierarchical porous carbon/ZnO composites with a 3D skeleton network were obtained, which demonstrated outstanding electromagnetic wave absorption performance with an effective absorption bandwidth (EAB) of 6.72 GHz and the reflection loss (RL) of −44.18 dB. The banana peel-derived porous carbon (BPC) embedded with ZnO particles brings about conductive loss and interface polarization, further enriching the microwave loss mechanisms. This work offers a fresh idea for creating a green, sustainable, and high-value functional carbon-based composite material.

In Situ Laser-Induced 3D Porous Graphene within Transparent Polymers for Encapsulation-Free and Tunable Ultrabroadband Terahertz Absorption.

Three-dimensional (3D) porous carbon materials have great potential for fabricating flexible tunable broadband absorbers owing to their high electrical conductivity, strong dielectric loss, and unique microstructure. Herein, we introduce an innovative method for synthesizing 3D porous graphene that incorporates advanced tuning and encapsulation processes to augment its functional efficacy. Through the modulation of both thermal and nonthermal interactions between a femtosecond (fs) laser and a polydimethylsiloxane (PDMS) film, we have synergistically fine-tuned the surface morphology and lattice properties of 3D porous graphene. This approach enabled us to create a flexible terahertz (THz) absorber with customizable characteristics, boasting an impressive absorbance range of 80%-99% in the 0.4-1.0 THz spectrum, alongside a peak reflection loss (RL) of up to 35.6 dB. Furthermore, we have successfully demonstrated the production of photoinduced 3D porous graphene within a PDMS film, which serves as both a carbon precursor and protective layer. This simplifies the conventional packaging process. These devices exhibit a RL of up to 41.6 dB and an absorption bandwidth of 2.5 THz (0.6-3.1 THz). Our study presents a production methodology for high-performance, flexible THz absorbers, offering a straightforward and innovative solution for the rapid development of sophisticated, flexible THz absorbing materials.

Three-Dimensional Porous Carbon Material Derived from Moldy Rice Noodles for Highly Efficient Removal of Methylene Blue Dye

Three-Dimensional Porous Carbon Material Derived from Moldy Rice Noodles for Highly Efficient Removal of Methylene Blue Dye

Zinc sulfide quantum dots modified 3D Nitrogen-Doped framework carbon enhances the ion transport rate of potassium ion hybrid capacitors

The potassium-ion hybrid capacitor (PIHC) has garnered considerable attention due to its ability to leverage the advantages of both battery-type anodes and capacitor-type cathodes simultaneously. Nevertheless, the slow K+ transfer rate between the PIHC battery-type anode and capacitor-type cathode significantly impedes the overall performance. Herein, we have employed quantum-sized zinc sulfide (ZnS) immobilized within a three-dimensional N-doped porous carbon framework (ZnSQDS@3DNC) as a standalone anode. The corresponding three-dimensional N-doped porous carbon (3DNC) serves as the cathode, thereby constructing a PIHC device. The strong coupling between ZnS quantum dots and N-doped three-dimensional porous carbon material effectively enhances ion/electron transport, facilitating intercalation-conversion-exfoliation reactions and improving K+ transfer rates. The numerous active sites within the 3DNC significantly enhance the capacitance performance of the cathode, facilitating the reversible adsorption and desorption of FSI-. The values of DK+ have all been calculated to be within the range of 10-10 to 10-9 cm2 s−1, indicating the rapid diffusion capability of this ZnSQDs@3DNC structure. More impressively, the assembled PIHC device can achieve high energy densities of 179.9 Wh kg−1 at power densities of 200 W kg−1, with an ultralong cycling life over 10,000 cycles. This study serves to advance the development of metal-ion hybrid capacitors and provides direction for improving ion transport kinetics.

Polyacrylonitrile-sodium lignosulfonate -derived nitrogen-doped three-dimensional hierarchical porous carbon for supercapacitors

Modulation of pore structure and heteroatom doping are very important strategies to improve the electrochemical properties of carbon electrode materials. This report investigates the use of biomass-derived nitrogen-doped porous carbon materials to address the challenge of the specific capacitance and energy density in supercapacitors. Nitrogen-doped three-dimensional hierarchical porous carbon materials were prepared using a polyacrylonitrile/sodium lignosulfonate composite monolith as a precursor by thermally induced phase separation and subsequent carbonization/activation. This method precisely controls the structure and surface properties of porous carbon materials by regulating the structure of the precursor and situ doping of nitrogen, which is a valuable strategy for the controllable regulation of the pore structure for nitrogen-doped porous carbon materials. The resulting carbon material displayed excellent capacitance performance, exhibiting a high specific capacitance of 325.7F g -1 at a current density of 0.5 A/g, maintaining initial capacitance retention of 90.1 % at a current density of 5 A/g after 10,000 cycles. When investigated for practical applications, the assembled supercapacitor device had a higher energy density (9.88 W h kg- 1), which is higher than commercial carbon-based supercapacitors.

Efficient fenton-like catalysis enabled by single cobalt atoms anchored on expanded graphite: Remarkable intrinsic activity of Co-N4 sites and the enhanced mass transfer facilitated by gradient mesopore structure

The single-atom catalysts derived from traditional Zeolitic Imidazolate Framework (ZIF) materials are exclusively characterized by a micropore structure, which severely hampers both the mass transfer efficiency and the accessibility of metal sites during catalysis. Herein, by utilizing mesoporous expanded graphite (EG) and ZIF-67 as precursors, a novel single-atom cobalt catalyst anchored on three-dimensional porous carbon materials (ZIF-67-x@EG) has been developed. Experiments demonstrate that introducing cobalt atoms in the formed bulges of EG increases carrier concentration and significantly enhances carrier mobility. The resulting ZIF-67-1@EG catalyst exhibits remarkable efficiency in degrading levofloxacin (LEVO concentration = 48 mg/L), with a degradation rate constant (0.078 min−1) 3.25 times higher than EG@N (0.024 min−1). The Co amounts in all ZIF-67-x@EG catalysts positively correlated with the reaction rate constant (R2 = 0.995). The ZIF-67-1@EG, with a small amount of cobalt loading (2.29 at%), exhibited an exceptionally high turnover frequency (TOF) value for LEVO (0.49 min−1). The degradation process involves an electron transfer pathway (ETP) and the contribution of singlet oxygen (1O2). The toxicity of the intermediates was characterized by quantitative structure-activity relationship (QSAR) prognostication, and the toxicity was reduced post-reaction. PMS/Co-N4 (-0.37 eV) and PMS/pyridinic N (-0.39 eV) configurations exhibit lower adsorption energies than PMS/pyrrolic N (-0.32 eV) structure, indicating that PMS primarily binds to these sites in the ZIF-67-1@EG/PMS system.

Three-dimensional porous carbon materials as catalysts for upgrading coal pyrolysis volatiles to boost light tar

The large proportion of heavy components in volatiles from coal pyrolysis is liable to entrain dust and form coke, resulting in the difficulty of separating oil from dust, which thus causes the blocking of technical pipelines. Carbon-based catalysts (BC and BHC) and metal-modified carbon-based catalysts (Fe-BC, Ni-BC, Fe-BHC and Ni-BHC) were prepared for the upgrading of volatiles from coal pyrolysis. This three-dimensional interconnected macroporous carbon material is primarily derived from the pyrolysis of the blend of a biochar and a caking coal. The results show that the metal-modified carbon-based catalysts aid in activating small molecules, such as CH4, CO2, and H2O, increasing in-situ hydrogen donation while cracking polycyclic aromatics, macromolecular oxygen-containing compounds, and N, S-containing heterocyclic compounds. This thus increases the selective catalysis of benzene, naphthalene, biphenyl, and anthracene and improves tar quality. The unactivated Fe-BC and Ni-BC catalysts exhibit high selectivity for light oil with a boiling point below 170 °C. In contrast, the activated Fe-BHC and Ni-BHC catalysts have a stronger ability to crack heavy tar due to the synergistic effect of metal and carbon defect structures. However, the micropores within the catalysts prevent mass transfer of macromolecular compounds, drastically lowering the tar yield with coke formation. Overall, the unactivated metal modified catalyst with three-dimensional porous structure allows for the synergistic effect of dust removal and upgrading of volatiles while maintaining the tar yield, especially the Fe-BC catalyst with a lower price.

Electrochemical enzyme sensor based on gold-biomass carbon composite modified electrode

In this paper a three-dimensional biomass porous carbon material (WSBPC) was prepared via carbonization combining with KOH activation method by using waste walnut shells as raw materials. Then WSBPC was adopted as a modifier to construct an electrochemical sensing platform based on carbon ionic liquid electrode for sensitive detection of trichloroacetic acid (TCA) and potassium bromate (KBrO3), in which horseradish peroxidase (HRP) was used as the catalyst and Au nanoparticle was employed as signal amplifier. The detection ranges of the supposed sensing platform for testing TCA and KBrO3 were 10.0–1000.0 mM and 0.10–1.10 mM with the lower detection limits as 3.33 mM and 0.03 mM. Beside, this method was used to determine the KBrO3 content in tap water samples with satisfactory results.

3D Nitrogen-Doped Porous Carbon Supported Pt Catalyst for Electrocatalytic Oxidation of Glucose

Glucose fuel cells have attracted widespread attention in the biomedical field due to their ability to generate electrical energy continuously. The development of this technology has great potential in the application of powering implantable medical devices. However, the efficiency of the glucose oxidation reaction at the anode of the fuel cell is low, and a catalyst needs to be added to improve the reaction efficiency. Platinum (Pt) catalysts are prone to agglomerate during use, which limits the improvement of their properties such as catalytic activity and stability. To address this problem, in this paper, a three-dimensional ( 3D) N-doped porous carbon (NCZIF-8) material with a large specific surface area was prepared as a catalyst carrier using ZIF-8 as a precursor. Low loading rate of platinum (10 wt. %) was prepared (10% Pt/NCZIF-8) and used as catalysts for glucose oxidation reaction. The materials were structurally characterized by XRD, SEM, TEM, Raman and FT-IR, etc. The electrocatalytic properties of the materials were characterized using an electrochemical workstation. It was shown that the incorporation of NCZIF-8 carrier promotes the dispersion of Pt nanoparticles (NPs) and the utilization of the catalyst, which enhances the catalytic activity and stability of catalysts during electrocatalytic glucose oxidation. After 300 times cyclic voltammetry (CV) tests, the peak current density of 10% Pt/NCZIF-8 only decreased by 21. 12% and 8. 59% in the double-layer region and oxygen region, respectively, indicating the excellent stability of the catalyst. This kind of catalyst with low loading rate of precious metal has great potential for its practical application by improving catalyst utilization, which not only improves the catalytic efficiency but also reduces the material cost.

Hierarchically Porous Carbon Nanosheets from One-Step Carbonization of Zinc Gluconate for High-Performance Supercapacitors.

Supercapacitors, with high energy density, rapid charge-discharge capabilities, and long cycling ability, have gained favor among many researchers. However, the universality of high-performance carbon-based electrodes is often constrained by their complex fabrication methods. In this study, the common industrial materials, zinc gluconate and ammonium chloride, are uniformly mixed and subjected to a one-step carbonization strategy to prepare three-dimensional hierarchical porous carbon materials with high specific surface area and suitable nitrogen doping. The results show that a specific capacitance of 221 F g-1 is achieved at a current density of 1 A g-1. The assembled symmetrical supercapacitor achieves a high energy density of 17 Wh kg-1, and after 50,000 cycles at a current density of 50 A g-1, it retains 82% of its initial capacitance. Moreover, the operating voltage window of the symmetrical device can be easily expanded to 2.5 V when using Et4NBF4 as the electrolyte, resulting in a maximum energy density of up to 153 Wh kg-1, and retaining 85.03% of the initial specific capacitance after 10,000 cycles. This method, using common industrial materials as raw materials, provides ideas for the simple preparation of high-performance carbon materials and also provides a promising method for the large-scale production of highly porous carbons.

Graphene oxide mediated carbon foam/CNTs composites for highly efficient adsorption of methylene blue and mechanism insight

The preparation of high performance, low cost and recyclable adsorbents is very important to cope with the increasingly devastating water pollution. As a typical three-dimensional porous carbon material, carbon foam (CF) is expected to be a highly efficient adsorbent to wipe out organic dyes from wastewater. However, the uneven size distribution, and lack of adsorption sites signified by insufficient foaming process limit its wider application in the environmental field. Here, CF/carbon nanotubes/graphene oxide (CF/CNTs/GO) composites (adsorbents) were prepared by press-assisted foaming and carbonization methods using mesophase precursors of coal tar pitch and CNTs followed by impregnation of GO nanosheets. The results highlighted that the addition of CNTs facilitated improvement in pore distribution, porosities, and mechanical properties (20 MPa). After treating with GO nanosheets, the adsorption performances of CF/CNTs/GO adsorbents substantially improved due to the increased active sites in the CF/CNTs and the adsorption rate and capacity of methylene blue (MB) reached 73.1% and 146 mg/g respectively. Further, adsorption isotherms (Langmuir and Freundlich), thermodynamics, quasi-first order and quasi-second order kinetics and intraparticle diffusion models were employed to investigate the adsorption mechanism. This work provides a low-cost fabrication technique for the high-performance CF/CNTs/GO adsorbent and is expected to provide reference for application in the treatment of contaminated water.

3D Porous VOx/N-Doped Carbon Nanosheet Hybrids Derived from Cross-Linked Dicyandiamide-Chitosan Hydrogels for Superior Supercapacitor Electrode Materials.

Three-dimensional porous carbon materials with moderate heteroatom-doping have been extensively investigated as promising electrode materials for energy storage. In this study, we fabricated a 3D cross-linked chitosan-dicyandiamide-VOSO4 hydrogel using a polymerization process. After pyrolysis at high temperature, 3D porous VOx/N-doped carbon nanosheet hybrids (3D VNCN) were obtained. The unique 3D porous skeleton, abundant doping elements, and presence of VOx 3D VNCN pyrolyzed at 800 °C (3D VNCN-800) ensured excellent electrochemical performance. The 3D VNCN-800 electrode exhibits a maximum specific capacitance of 408.1 F·g-1 at 1 A·g-1 current density and an admirable cycling stability with 96.8% capacitance retention after 5000 cycles. Moreover, an assembled symmetrical supercapacitor based on the 3D VNCN-800 electrode delivers a maximum energy density of 15.6 Wh·Kg-1 at a power density of 600 W·Kg-1. Our study demonstrates a potential guideline for the fabrication of porous carbon materials with 3D structure and abundant heteroatom-doping.

Expanded graphite and thermally reduced graphene oxide filled with NiCo2O4 for improve microwave absorption

Three-dimensional porous carbon materials provide an effective way for electromagnetic wave absorbers that are lightweight and effective. We explore the effects of different three-dimensional porous expanded graphite (EG) and thermally reduced graphene oxide (TERGO) on wave absorption performance in this study. NiCo2O4-EG and NiCo2O4-TERGO three-dimensional wave-absorbing materials were prepared by an in situ self-assembly hydrothermal process. To address the problem of impedance mismatch and improve the attenuation capability, the microstructure of EG and TERGO were designed to control the conductivity loss and polarization loss. After heat treatment at 800 °C to form a regular honeycomb pore distribution, TERGO composites have moderate conductivity and conductive losses, as well as multiple polarization loss mechanisms. Consequently, the NiCo2O4-TERGO800 composite with a lower filling ratio displayed excellent microwave absorption, with the bandwidth of reflection loss ≤−10 dB coved 4.05 GHz. These findings provide valuable insights for fabrication and research of three-dimensional porous carbon material microwave absorbers.

Ultralight melamine foam derived metal nanoparticles encapsulated CNTs/porous carbon composite for electromagnetic absorption

Three-dimensional (3D) porous carbon materials have emerged as potential microwave absorption candidates due to their unique advantages of high specific surface area and high porosity. However, much less attention has been paid to enhance the performance by designing microstructures. In this work, metal nanoparticles encapsulated carbon nanotubes/carbonized melamine foam composites were successfully synthesized by a simple chemical and pyrolysis method. The microstructure and microwave absorption properties are investigated, and the magnetic/dielectric loss mechanism is studied furtherly. During the pyrolysis process, metal nanoparticles encapsulated carbon nanotubes in-situ growth on 3D porous carbon derived from melamine foam. The metal component and CNTs morphology could be regulated by changing the precursor concentration and that further tuning the absorption performance. Ascribed to multiple interface reflections, dielectric/magnetic loss, multiple polarization behavior and improved impedance matching, the CNTs/CF-3:0 composite achieves a strong reflection loss (− 75.4 dB at 5.2 GHz) and ultra-wide response bandwidth (4.1–18.0 GHz with RL value over − 10 dB). Such a 3D network framework realizes the low density. These results may generate interest and inspiration for the elaborate design and synthesis of submicron-scale structures of 3D porous carbon-based absorbing materials.

Customizing the structure and chemical composition of ultralight carbon foams for superior microwave absorption performance

Developing biomass-derived three-dimensional porous carbon materials (porous carbon foam, PCF) has become a common strategy to obtain lightweight and efficient electromagnetic microwave-absorbing materials. Without the introduction of a template and subsequent activation process, several ultra-lightweight honeycomb PCF samples were successfully prepared from dried ballonflower/yamakurage (DB) by simple calcination. In addition, the calcination temperature plays a decisive role in regulating the pore size, composition and microwave absorption properties of PCF samples. Furthermore, it is worth noting that different cutting directions also influenced the hole size of the PCF sample and the microwave absorption performances. Under the combined effects of multiple reflections and scattering of PCF porous structure, dipole polarization of abundant heterogeneous atoms and good conductive loss of carbon material, the vertical cutting sample PCF-900V exhibits optimal microwave absorption performances with the minimal reflection loss (RLmin) value of −46.95 dB at 1.46 mm thickness and the effective absorption bandwidth (EAB) value of 5.52 GHz at 1.72 mm matching thickness respectively, indicating its great potential for application as a promising lightweight and efficient microwave absorbing material.

Multielement Co-Doped Carbon Derived from Spent LIBs Boosts Potassium Storage

Sustainability issues with batteries include making sure that the materials can be recycled into electrodes once they are no longer needed and that they have enough power to charge all devices. Existing technologies for material recovery and selective extraction continue to be inefficient and unsustainable. Here, N/S co-doping porous carbon materials comprising transitional-metal nanoparticles are synthesized through microstructural reconstruction from the waste layered cathode materials. The resultant three-dimensional (3D) porous carbon materials have various distinct and desirable structural characteristics and function admirably in potassium-ion batteries. The internal particle distribution, the interconnected carbon layer network, and the open-packed structure of microcapsules all contribute to the electrochemical transfer process. The proposed strategy offers almost zero-emission and pollution-free environment and can be extended to various spent lithium-ion batteries (LIBs) containing Li, Ni, Co, Mn, and other metals. The research may provide the potential to extend the environmental frontier for the development of energy materials.

Three-dimensional honeycomb-like porous carbon embedded with Ge nanoparticles anode composites for ultrastable lithium storage

Designing a kind of electrode material with effective morphology and structural function is always a topical issue in the field of electrochemical energy storage. Herein, we report a simple and scalable NH4Cl/KOH etching method to construct the three-dimensional honeycomb-like porous carbon material derived from biomass sweet potato starch, then load Ge nanoparticles for the use as anode material. This three-dimensional honeycomb material contains uniform cavities with size of 3–6 µm, which can provide more space for the adsorption of Ge nanoparticles because of a higher specific surface area and an increased graphitization degree. This specific structure can maintain stability and mitigate the effect of volume expansion of Ge nanoparticles, while it can effectively improve the electronic conductivity and electrochemical activity of the Ge-BSPPC composite. Therein, the honeycomb porous Ge-BSPPC composite exhibits excellent discharge capacity and ultrastable lithium storage ability: the initial discharge capacity of 1257 mAh g−1, with the initial coulombic efficiency of 85.4%; the stable capacity after 100 cycles of 1025 mAh g−1, with the coulombic efficiency of 97.8%. This method provides a simple and cost-efficient approach for converting biomass into high-performance electrode materials.

Synthesis of CoP@B,N,P co-doped porous carbon by a supramolecular gel self-assembly method for lithium-sulfur battery separator modification.

Lithium-sulfur batteries (LSBs) are regarded as promising next-generation batteries due to their high abundance and high theoretical energy density. However, the commercial application of LSBs is hindered by the shuttle effect of soluble lithium polysulfides (LiPSs). Hence, we synthesised B, N, P co-doped three-dimensional hierarchical porous carbon materials, uniformly dispersed with CoP nanoparticles, and utilized them as the coating material for the PE separator. The catalytic and adsorption capacity of the composite material was significantly enhanced by CoP. Both experimental and theoretical calculations show that the LiPS adsorption capacity of the composite material is significantly enhanced after the introduction of B atoms. As a result, the assembled LSBs with the CoP@BNPC/PE separator show excellent long-term stability (940.8 mA h g-1 after 500 cycles at 1.0 C, and only a 0.026% decay rate per cycle) and superior rate performance (613.6 mA h g-1 at 5.0 C). Our work further proves that a modified separator is an effective strategy to promote the commercialization of LSBs.