Polymeric Carbon Research Articles

Sn Nanoclusters Confined in COP‐Derived Carbon for Catalytic Oxygen Reduction Reaction

AbstractThe development of catalysts composed of single atoms is crucial for enhancing the performance of oxygen reduction reaction (ORR). However, the unsatisfactory intrinsic activity of these catalysts still poses a major challenge, limiting their overall effectiveness. One approach to addressing this challenge is the introduction of metal clusters, which can form a synergistic effect with the single atoms, ultimately improving their performance. In this study, core‐shell structured carbon polymer is constructed with Zn atoms and Sn nanoclusters by directly subjecting pyrolysis of the covalent organic polymer (COP) and metal organic framework (MOF) (COP@MOF). The thin COP shell serves a dual purpose: it prevents the collapse and aggregation of zeolitic imidazolate framework‐8 (ZIF‐8) and promotes the formation of mesopores, facilitating mass transport and enhancing the graphitization degree to improve conductivity. The resulting Sn‐COP@MOF800 exhibits promising catalytic performance in the ORR, demonstrating a half‐wave potential of 0.81 V and current density of 5.56 mA cm−2 in 0.1 m KOH, which is comparable to that of Pt/C. This study provides new ideas for exploring the application of metal single atoms and metal nanoclusters in ORR catalysis through synergistic effects.

Recent Advances in Biomedical Nanotechnology Related to Natural Products.

Natural product processing via nanotechnology has opened the door to innovative and significant applications in medical fields. On one hand, plants-derived bioactive ingredients such as phenols, pentacyclic triterpenes and flavonoids exhibit significant pharmacological activities, on another hand, most of them are hydrophobic in nature, posing challenges to their use. To overcome this issue, nanoencapsulation technology is employed to encapsulate these lipophilic compounds and enhance their bioavailability. In this regard, various nano-sized vehicles, including degradable functional polymer organic compounds, mesoporous silicon or carbon materials, offer superior stability and retention for bioactive ingredients against decomposition and loss during delivery as well as sustained release. On the other hand, some naturally occurring polymers, lipids and even microorganisms, which constitute a significant portion of Earth's biomass, show promising potential for biomedical applications as well. Through nano-processing, these natural products can be developed into nano-delivery systems with desirable characteristics for encapsulation a wide range of bioactive components and therapeutic agents, facilitating in vivo drug transport. Beyond the presentation of the most recent nanoencapsulation and nano-processing advancements with formulations mainly based on natural products, this review emphasizes the importance of their physicochemical properties at the nanoscale and their potential in disease therapy.

Recent advances in photoresponsive printing inks for security encoding applications

AbstractCounterfeiting of banknotes, important documents, and branded goods continues to be a major worldwide problem for governments, businesses, and consumers. This problem has serious financial, security, and health implications. Due to their stability for printing on various substrates, the photochromic anticounterfeiting inks have received important interest. There have been various photochromic agents, such as polymer nanoparticles, quantum and carbon dots, and organic and inorganic fluorophores and luminophores, which have been broadly used for antiforging applications. In comparison to organic agents, inorganic photochromic materials have better stability under reversible/long‐term light illumination. Recently, the remarkable optical characteristics and chemical stability of photoluminescent and photochromic agents have led to their extensive usage anticounterfeiting products. There have been also several strategies to tackle the rising problem of counterfeiting. Both of solvent‐based and water‐based inks have been developed for security encoding purposes. Additionally, the printing methods, including screen printing, labeling, stamping, inkjet printing, and handwriting, that have been used to apply anticounterfeiting inks onto various surfaces are discussed. The limitations of photoluminescent and photochromic agents and the potential for their future preparation to combat counterfeiting were discussed. This review would benefit academic researchers and industrial developers who are interested in the area of security printing.

Flexible Electrochemical Supercapacitors: A Review

Flexible supercapacitors (FSCs), especially wearable ones, have become a hotspot of research because of their advantages such as energy density, high specific capacitance, good mechanical properties, decent stability, and eco-friendliness. The storage mechanism in FSCs is either a faradaic mechanism in pseudocapacitors (PCs) or a non-faradaic mechanism as in double-layer supercapacitors (ELSCs). This review summarized the research progress for manufacturing electrodes from various types of materials, whereas carbon, metal oxides, or conductive polymers are utilized as electrodes. An overview of what researchers have performed in changing the original shape of materials and combining them to obtain flexible electrodes with good electrochemical performances. The review includes the presence of different types of electrolytes in the FSCs structure. Perspectives on the direction of future development of research in the field of FSCs are also discussed.

Features of the Use of Electrically Conductive Knitted Wire Meshes and Perforated Foils When Creating Lightning-Protection Systems for Polymer Carbon Composite Structures (Review, Part II)

Features of the Use of Electrically Conductive Knitted Wire Meshes and Perforated Foils When Creating Lightning-Protection Systems for Polymer Carbon Composite Structures (Review, Part II)

Synthesis Bi2O3/gC3N4 heterostructures: Investigation structural, morphological and photocatalytic activity towards methylene blue and rhodamine B

Waste from various dyes as a result of industrial development is an important source of pollutants for water resources; These wastes are frequently carcinogenic, mutagenic and toxic to aquatic life, so treating wastewater is vitally important. Photocatalytic purification is a popular method because it can break down dye molecules and change them into non-toxic, small and harmless species. Moreover, utilizing the power of sunlight, this technology holds significant promise for enabling environmentally friendly, sustainable, and economically viable technologies. The non-toxic polymeric photocatalyst graphitic carbon nitride (gC3N4) is an n-type semiconductor. Its facile and economical synthesis, effective band structure, and stability make it a popular option for photocatalytic investigations. It is crucial to develop nanocomposites to boost the capacity of materials for photocatalysis. The objective of this study is to fabricate nanocomposites of graphitic carbon nitride from thiourea, incorporating varying ratios of bismuth oxide through thermal condensation. The aim is to employ these composites for the catalytic degradation of Methylene Blue (MB) and Rhodamine B (Rh B) dyes. The synthesized samples' morphological and structural characteristics were studied. Their photocatalytic activity against methylene blue and rhodamine B dyes has also been reported. The Bi2O3/gC3N4 heterostructured samples were prepared considering bismuth nitrate and thiourea at weight ratios of 0.125:10, 0.25:10, and 0.5:10. In the study, the Bi2O3/gC3N4 heterostructured sample with the lowest bismuth doping rate was seen to have the highest photocatalytic degradation efficiency. A remarkable degradation rate, reaching 98.83 % within 70 min for MB and 98.59 % within 60 min for RhB dye was observed. The enhanced photocatalytic activities of the synthesized composite can be attributed to the synergistic effect of the heterostructure developed between graphitic carbon nitride and bismuth oxide. As a result, this study has shown promise that Bi2O3/gC3N4 composite photocatalysts can be an effective material for removing dyes.

Single Dispersion of Fe(H2O)2-Based Polyoxometalate on Polymeric Carbon Nitride for Biomimetic CH4 Photooxidation.

Direct methane conversion to value-added oxygenates under mild conditions with in-depth mechanism investigation has attracted wide interest. Inspired by methane monooxygenase, the K9Na2Fe(H2O)2{[γ-SiW9O34Fe(H2O)]}2·25H2O polyoxometalate (Fe-POM) with well-defined Fe(H2O)2 sites is synthesized to clarify the key role of Fe species and their microenvironment toward CH4 photooxidation. The Fe-POM can efficiently drive the conversion of CH4 to HCOOH with a yield of 1570.0µmol gPOM -1 and 95.8% selectivity at ambient conditions, much superior to that of [Fe(H2O)SiW11O39]5- with Fe(H2O) active site, [Fe2SiW10O38(OH)]2 14- and [P8W48O184Fe16(OH)28(H2O)4]20- with multinuclear Fe-OH-Fe active sites. Single-dispersion of Fe-POM on polymeric carbon nitride (PCN) is facilely achieved to provide single-cluster functionalized PCN with well-defined Fe(H2O)2 site, the HCOOH yield can be improved to 5981.3µmol gPOM -1. Systemic investigations demonstrate that the (WO)4-Fe(H2O)2 can supply Fe═O active center for C-H activation via forming (WO)4-Fea-Ot···CH4 intermediate, similar to that for CH4 oxidation in the monooxygenase. This work highlights a promising and facile strategy for single dispersion of ≈1-2 Å metal center with precise coordination microenvironment by uniformly anchoring nanoscale molecular clusters, which provides a well-defined model for in-depth mechanism research.

Suitably Incorporated Hydrophobic, Redox-Active Drug in Poly Lactic Acid-Graphene Nanoplatelet Composite Generates 3D-Printed Medicinal Patch for Electrostimulatory Therapeutics.

Polymer carbon composites have been reported for improved mechanical, thermal and electrical properties to provide reduced side effect by 3D printing personalized biomedical drug delivery devices. But control on homogeneity in loading and release of dopants like carbon allotropes and drugs, respectively, in the bulk and on the surface has always been a challenge. Herein, we are reporting a methodological cascade to achieve a model, customizable, 3D printed, homogeneously layered and electrically stimulatory, PLA-Graphene nanoplatelet (hl-PLGR) based drug delivery device, called 3D-est-MediPatch. The medicinal patch has been prepared by 3D-printing a Nic-hl-PLGR composite obtained by incorporating a redox active model drug, niclosamide (Nic) in hl-PLGR. The composite of Nic-hl-PLGR was characterized in three sequentially complex forms─composite film, hot melt extruded (HME) filament, and 3D printed (3DP) patches to understand the effect of filament extrusion and 3D-printing processes on Nic-hl-PLGR composite and overall drug incorporation efficiency and control. The incorporation of graphene was found to improve the homogeneity of the drug, and the hot melt extrusion improved the dispersion of drug and graphene fillers in the composite. The electroresponsive drug release from the Nic-hl-PLGR composite was found to be controllably accelerated compared to the drug release by diffusion, in simulated buffer condition. The released drug concentration was found to reach within the IC50 range for malignant melanoma cell (A375) and showed in vitro selectively, with reduced effects in noncancerous, fibroblast cells (NIH3T3). Further, the feasibility of application for this system was assessed in generating personalized 3D-est-MediPatch for skin, liver and spleen tissues in ex-vivo scenario. It showed excellent feasibility and efficacy of the 3D-est-MediPatch in controlled and personalized release of drugs during electrostimulation. Thus, a model platform, 3D-est-MediPatch, could be achieved by suitably incorporating a hydrophobic, redox-active drug (niclosamide) in poly lactic acid-graphene nanoplatelet composite for electrostimulatory therapeutics with reduced side effects.

Tailored Polymeric Carbon Nitride Coupled with Bi2O3 for Constructing Z‐Scheme Heterojunction with Enhanced Photocatalytic Activity

AbstractThe great demand for visible‐light‐induced catalysts with high photocatalytic performance has stimulated extensive interest in constructing g‐C3N4‐based Z‐Scheme heterojunctions. In this research work, the g‐C3N4/Bi2O3 Z‐Scheme heterojunction by precipitation‐hydrothermal method was constructed, and characterized by various techniques. The g‐C3N4/Bi2O3‐1 composite exhibited a transient photocurrent response approximately 7 and 5 times higher than that of bare g‐C3N4 and Bi2O3, respectively, and showed higher visible photocatalytic activity with 99.8 % degradation of methylene blue (MB) within 75 min. Meanwhile, the pH effect on the photocatalytic degradation of MB was investigated. Radicals trapping experiments showed that •OH free radical played a predominant role for the degradation of MB, EPR analysis confirmed the presence of superoxide radicals, which combined with the band structure of the composites, confirmed the Z‐Scheme of the heterojunction. A possible mechanism for photocatalytic degradation of MB dyes in g‐C3N4/Bi2O3‐1 composites was also proposed. This study provided a new avenue for the development of novel g‐C3N4‐based Z‐Scheme heterojunction materials with prospective applications in the fields of energy and environment.

Construction of carbon and nitride double vacancy defects on ultrathin porous g-C3N4 nanosheets assisted by freeze-drying for enhanced photocatalysis

Graphitic carbon nitride based photocatalysts have been found extensive application in the degradation of antibiotics and organic pollutants. However, the insufficient of surface active sites and the low efficiency of photogenerated charge carriers separation hinder the development. Herein, ultrathin porous polymer carbon nitride nanosheets (PCNS-F) with carbon and nitride double vacancy defects were successfully fabricated. The facile freeze-drying step, following solvent-thermal treatment and preceding the thermal etching process, stands as a critical step for triggering vacancy generation and adjusting the carbon/nitride ratio. The optimized PCNS-F photocatalyst exhibits an ultrathin structure featuring a substantial abundance of defects in a porous state, resulting in exceptional structural characteristics (183.3 m² g-1, 0.84 cm³ g-1). Surface defect sites increase, and the efficient separation and transfer of photo-generated charge carriers are promoted with the introduction of a suitable vacancy density. PCNS-F demonstrated outstanding photocatalytic degradation performances for tetracycline (81.7 %) and methylene blue (97.7 %) under visible light irradiation for 2 h, which are 10 and 7.2 times higher than those of bulk g-C3N4. The active species of ∙O2- was confirmed to play a major role in the photodegradation process. This work provides a mild approach for engineering carbon and nitride double vacancy defects on g-C3N4 nanosheets, accompanied by tuning carbon/nitride ratio, to effectively eliminate pollutants and cleanse the environment.’

Diastereoselective dearomatization of indoles via photocatalytic hydroboration on hydramine-functionalized carbon nitride.

A protocol for trans-hydroboration of indole derivatives using heterogeneous photocatalysis with NHC-borane has been developed, addressing a persistent challenge in organic synthesis. The protocol, leveraging high crystalline vacancy-engineered polymeric carbon nitride as a catalyst, enables diastereoselective synthesis, expanding substrate scope and complementing existing methods. The approach emphasizes eco-friendliness, cost-effectiveness, and scalability, making it suitable for industrial applications, particularly in renewable energy contexts. The catalyst's superior performance, attributed to its rich carbon-vacancies and well-ordered structure, surpasses more expensive homogeneous alternatives, enhancing viability for large-scale use. This innovation holds promise for synthesizing bioactive compounds and materials relevant to medicinal chemistry and beyond.

Pd(II) coordination molecule modified g-C3N4 for boosting photocatalytic hydrogen production

The photocatalytic H2 production activity of polymer carbon nitride (g-C3N4) is limited by the rapid recombination of photoelectron-hole pairs and slow surface reduction dynamic process. Here, a supramolecular complex (named R-TAP-Pd(II)) was fabricated via self-assembly of (R)-N-(1-phenylethyl)-4-(4-(pyridin-2-yl)-1H-1,2,3-triazol-1-yl)benzamide (R-TAP) with Pd(II) and used to modify g-C3N4. In the R-TAP-Pd(II)@g-C3N4 composite photocatalyst, the spin polarization of R-TAP-Pd(II) can promote charge transfer and inhibit photogenerated carrier recombination, as confirmed by spectral tests and photoelectrochemical performance tests. Electrochemical tests and in situ X-ray photoelectron spectroscopy (XPS) tests proved that the Pd(II) ion in the R-TAP-Pd(II) molecule can serve as active sites to accelerate H2 production. The R-TAP-Pd(II)@g-C3N4 presented a photocatalytic H2 generation rate of 1085 μmol g−1 h−1 when exposed to visible light, which was a about 278-fold increase compared with g-C3N4. This work finds a new approach to boost the photocatalytic efficiency of g-C3N4 via supramolecular self-assembly.

Polymeric Carbon Nitride Tubular Sponges with Edge Functionalized Phosphonic Groups for Photocatalysis

Polymeric Carbon Nitride Tubular Sponges with Edge Functionalized Phosphonic Groups for Photocatalysis

A direct polymeric carbon nitride/tungsten oxide Z-scheme heterostructure for efficient photocatalytic hydrogen generation via reforming of plastics into value-added chemicals

A direct polymeric carbon nitride/tungsten oxide Z-scheme heterostructure for efficient photocatalytic hydrogen generation via reforming of plastics into value-added chemicals

Metal atom-induced microenvironment regulation in polymeric carbon nitride for photocatalytic hydrogen evolution

Metal atom-induced microenvironment regulation in polymeric carbon nitride for photocatalytic hydrogen evolution

Enhancing the Activity of a Carbon Nitride Photocatalyst by Constructing a Triazine-Heptazine Homojunction.

Establishing homojunctions at the molecular level between different but physicochemically similar phases belonging to the same family of materials is an effective approach to promoting the photocatalytic activity of polymeric carbon nitride (CN) materials. Here, we prepared a CN material with a uniform distribution of homojunctions by combining two synthetic strategies: supramolecular assemblies as the precursor and molten salt as the medium. We designed porous CN rods with triazine-heptazine homojunctions (THCNs) using a melem supramolecular aggregate (Me) and melamine as the precursors and a KCl/LiBr salt mixture as the liquid reaction medium. The triazine/heptazine ratio is controlled by varying the relative amounts of the chosen precursors, and the molten salt treatment enhances the structural order of the interplanar packing units for the THCN skeleton, leading to rapid charge migration. The resulting built-in electric field induced by the triazine-heptazine homojunction enhances photogenerated charge separation; the optimal THCN catalyst exhibits an excellent H2 evolution rate via photocatalytic water splitting, which is ∼24 times as high as that of reference bulk CN, with long-term stability.

Ionic liquid catalyzed low-temperature hydrothermal carbonization of sewage sludge to produce hydrochar with low heavy metal content and positive energy recovery

An ionic liquid (IL, [DMAPA]HSO4) was prepared to facilitate the removal of heavy metals by hydrothermal carbonization (HTC) in sewage sludge (SS) and to obtain a positive energy recovery (ER, (Energyoutput/Energyinput − 1) > 0). The results found that the removal efficiencies of the Fe, Mn, Zn, Co, and Cd from SS exceeded 75 % with positive ER (6 %) at 20 wt% IL dosage (IL:SS). IL promoted the HTC reactions of proteins and polysaccharides to produce fixed carbon and small molecule polymers. The process mainly relies on IL to catalyze the dehydration and graphitization of SS and to destroy the heavy metal binding sites such as carboxyl and hydroxyl groups. Additionally, IL aids in constructing the macropore structures in hydrochar, thereby facilitating the release of heavy metals and water during the HTC process. This discovery holds promise for removing heavy metals from SS by one-pot HTC processes with positive energy recovery.

Sensitizer created defective metal organic framework as a new platform for boosting visible-light photocatalysis of g-C3N4

We developed herein for the first time a sensitizer created defective MOF (SCD-MOF), simultaneously possessing sensitizers and defects as visible-light harvester and electron trapper, respectively, which can synergistically improve the visible-light photocatalysis of polymeric graphitic carbon nitride (g-C3N4). Based on this discovery, the resulting 5.0 wt% FeTCPP⊂UiO-66@g-C3N4 shows a significant 6.6 and 3.9 times improvement in catalytic efficiency compared with its parent materials of FeTCPP⊂UiO-66 and g-C3N4 in degrading organic pollutants. Moreover, it shows a 10.4 times enhancement in catalytic efficiency compared with commercial TiO2 (P25). Mechanism studies suggest that sensitizer molecules and defects in SCD-MOF can synergistically improve photocatalytic efficiency because of broadening the visible-light response and strengthening the charge carrier separation. This work illustrates a remarkably triple synergetic effect among visible-light harvester, electron/hole separator, and semiconductor and thus established SCD-MOF as a class of new platform to greatly improve the visible-light photocatalytic performance of conventional semiconductors.

Understanding the effect of multiple configurations in polymeric carbon nitride for efficient solar-driven hydrogen peroxide photosynthesis

A oxygen and potassium co-doped polymeric carbon nitride (O/K-PCNs) was simply constructed by an acid gas cutting strategy for photocatalytic H2O2 generation. The effect of each accompanied configurations on photosynthesis of H2O2 was systematically analyzed. The C–O–C structure formed by O doping is capable of decreasing K ions incorporated energy barrier, thus remarkably improving the content of crucial K active sites. Dual heteroatom sites synergistically enhance O2 adsorption and surface ORR by a bridge K–O–O–C model. Moreover, the accompanied cyano defect and poly(heptazine imide) is responsible for improving in-plane and interlayer carriers separation, respectively. The optimal O/K-PCNs exhibits 60-fold higher photocatalytic H2O2 production rate than pure PCN. A positive correlation between the H2O2 production rate and the K heteratoms content was established. This work clarifies role of multiple configurations in PCN, especially O-containing groups, providing a new insight for design heteroatoms-doped materials for solar energy conversion.

Temperature-dependent excitonic emission characteristics of highly crystallized carbon nitride nanosheets

Highly-crystallized carbon nitride (HCCN) nanosheets exhibit significant potential for advancements in the field of photoelectric conversion. However, to fully exploit their potential, a thorough understanding of the fundamental excitonic photophysical processes is crucial. Here, the temperature-dependent excitonic photoluminescence (PL) of HCCN nanosheets and amorphous polymeric carbon nitride (PCN) is investigated using steady-state and time-resolved PL spectroscopy. The exciton binding energy of HCCN is determined to be 109.26 meV, lower than that of PCN (207.39 meV), which is attributed to the ordered stacking structure of HCCN with a weaker Coulomb interaction between electrons and holes. As the temperature increases, a noticeable reduction in PL lifetime is observed on both the HCCN and PCN, which is ascribed to the thermal activation of carrier trapping by the enhanced electron–phonon coupling effect. The thermal activation energy of HCCN is determined to be 102.9 meV, close to the value of PCN, due to their same band structures. Through wavelength-dependent PL dynamics analysis, we have identified the PL emission of HCCN as deriving from the transitions: σ*–LP, π*–π, and π*–LP, where the π*–LP transition dominants the emission because of the high excited state density of the LP state. These results demonstrate the impact of high-crystallinity on the excitonic emission of HCCN materials, thereby expanding their potential applications in the field of photoelectric conversion.