Mesoporous Carbon Nitride Research Articles

Modulating Schottky barriers and active sites of Ag-Ni bi-metallic cluster on mesoporous carbon nitride for enhanced photocatalytic hydrogen evolution

The advancement of photocatalysis relies on the development of novel hetero-structured materials with unique architectures. In this study, we successfully synthesized a hetero-structured g-C3N4 (GCN) material with a distinctive surface-interface modification. To further enhance its photocatalytic performance, we optimized the Ag and Ni concentration to maximize the visible light absorption and catalytic active sites for hydrogen evolution reactions. By using systematic physicochemical characterizations and density functional theory (DFT) calculations, we elucidated the pivotal role of graphitic carbon nitride (g-C3N4) in facilitating the formation of an efficient charge transfer channel and promoting the effective generation and separation of photo-generated carriers. From the DFT calculations, we also demonstrated that the Ag and Ni nanoparticles provide more efficient visible light absorption and active sites than Ni nanoparticles for water splitting and hydrogen evolution and In-situ TEM exploration. Furthermore, the hetero microstructure consisting of thin g-C3N4 nano scrolls has a crucial role in shortening the migration distance of the carriers, effectively suppressing carrier recombination. Consequently, these extraordinary characteristics resulted in a superior solar light-driven photocatalytic H2 evolution rate of 2507 μmol.h-1.g−1, surpassing the rate achieved by g-C3N4 heterostructures by a remarkable 18.6-folds. Moreover, the apparent quantum efficiency of this hetero-structured material reached an exceptional value of 1.6 % under a 1.5 G air mass filter.

Nanoarchitectonics of vanadium nanoparticles decorated mesoporous carbon nitride in photocatalytic systems: A study on ethylbenzene oxidation reaction

In this work, we have described the synthesis of vanadium (V) nanoparticles (NPs) anchored on mesoporous graphitic carbon nitride (V@mpg-C3N4) and their uses in photocatalytic ethylbenzene oxidation to the respective acetophenones. The mpg-C3N4 serves as the support for the decoration of V NPs, through a simple impregnation method. Various advanced techniques, such as XRD, UV–vis spectrometry, HRTEM, HAADF-STEM, AC-STEM, elemental mapping, and BET surface area analysis, were employed for the characterization of V@mpg-C3N4. The detailed characterization studies reveal that the V@mpg-C3N4 catalyst has a medium band gap (2.78 eV), a high surface area (76.7 m2g−1), and a mesoporous nature. The V@mpg-C3N4 photocatalysts demonstrated excellent performance in the light-assisted oxidation of ethylbenzene, achieving over 99 % conversion and selectivity for acetophenone in an environmentally friendly solvent (water) using a domestic light source (50 W white light). This developed synthesis strategy will be useful for synthesizing various noble and non-noble metal-based catalysts and their applications in organic transformation and environmental remediation.

Efficient selective cleavage of C−C bonds in lignin under visible light enabled by the Fe-doped mesoporous graphitic carbon nitride photocatalyst

To obtain high-valued aromatic products, it is paramount to cleave the Cα−Cβ bonds in lignin under mild conditions selectively. Nevertheless, this task remains daunting due to the formidable dissociation energies and steric hindrance associated with these bonds. Herein, a facile, efficient and cost-effective strategy for selectively breaking the Cα−Cβ bond in lignin with visible-light irradiation and room temperature is proposed, facilitated by the utilization of the ferric-doped mesoporous graphitic carbon nitride (Fe/mpg-CN) photocatalyst. Collective contributed by the reduced band gap and photoluminescence, combined with intensified visible-light absorption and enhanced photocurrent, the effectiveness in photocatalytic activity of Fe/mpg-CN is offered. Specifically, a high conversion rate (98 %) of the lignin model compound (2-phenoxy-1-phenylethanol), coupled with an excellent selectivity of 98 % in cleaving the Cα−Cβ bonds is achieved by Fe/mpg-CN. Photogenerated holes are indicated as the main active species through comprehensive mechanistic investigations. Additionally, the successful photocatalytic depolymerization of the complex dimer model compound (conversion rate ∼ 96 %) and pine kraft lignin further corroborate the satisfying photocatalytic activity and selectivity of Fe/mpg-CN. This study introduces a promising and viable strategy for the selective breaking of lignin through photocatalysis, offering significant implications for the sustainable production of valuable aromatic compounds.

Simple synthesis of 2D/3D mpg-C3N4/ZnO nanocages with built-in driven Z-scheme heterostructures: Photocatalytic degradation of tetracycline antibiotics and lifting the limitation of the complex water environment

Tetracycline antibiotics have attracted attention due to their difficulty in being degraded by the natural environment. In this work, 2D/3D mesoporous graphitic carbon nitride (mpg-C3N4)/ zinc oxide (ZnO) hollow nanocage (MCNZH) complexes with Z-scheme heterostructure were prepared for the photocatalytic degradation of tetracycline antibiotics. The catalysts were characterized by SEM, TEM, BET, XRD, FT-IR, EIS, etc. The degradation of tetracycline hydrochloride (40 mg L–1) by MCNZH (1.2 g L–1) can reach 92.08 %. Further, the energy band structure of the catalysts were calculated and the possible degradation mechanism was proposed. The results showed that ·OH– and ·O2– were the main active species, and the internal electric field suppressed the compounding of photogenerated carriers. The catalysts exhibited broad-spectrum degradation of tetracycline antibiotics. Practical sample spiking experiments on soil and river water confirmed its practicability, which provide great significance for the application of the photocatalytic technology in the practical environmental purification.

High-performance pseudo-capacitance supercapacitor with highly mesoporous fluorine doped polymeric carbon nitride nanosheets as electrode material

In this study, graphitic carbon nitride (GCN) material obtained from urea was hydrothermally doped with fluorine atoms (F-doped GCN). The resulting F-doped GCN material was designed as an electrode material for supercapacitors. Characterization of these samples was carried out by XRD, EDS, SEM, nitrogen adsorption and FTIR analyses. EDS and FTIR analyses confirmed the doping of fluorine atoms onto GCN. Nitrogen adsorption analyses supported the formation of a significant mesoporous structure with fluoride doping on GCN. The specific capacitance values of the GCN and F-doped GCN supercapacitors were calculated as 39.75 F/g and 305.72 F/g at a frequency of 0.01 Hz. A significant increase of about 7-fold in capacitance value was obtained by fluorine doping on GCN. Cycling trials of the F-doped GCN supercapacitor for up to 1000 cycles at a current density of 0.4 A/g maintain an efficiency of 86.72 %. For the supercapacitor designed from F-doped GCN material, the maximum energy density and power density were calculated as 4.26 Wh/kg and 1792 Wh/kg, respectively.

Control interfacial charge transfer behavior by creating surface defects on structure unit of heterojunction to drive carrier separation for enhancing photocatalytic CO2 reduction

Controlling interfacial charge transfer behavior of heterojunction is an arduous issue to efficiently drive separation of photogenerated carriers for improving the photocatalytic activity. Herein, the interface charge transfer behavior is effectively controlled by fabricating an unparalleled VO-NiWO4/PCN heterojunction that is prepared by encapsulating NiWO4 nanoparticles rich in surface oxygen vacancies (VO-NiWO4) in the mesoporous polymeric carbon nitride (PCN) nanosheets. Experimental and theoretical investigations show that, differing with the traditional p-n junction, the direction of built-in electric field between p-type NiWO4 and n-type PCN is reversed interestingly. The strongly codirectional built-in electric field is also produced between the surface defect region and inside of VO-NiWO4 besides in the space charge region, the dual drive effect of which forcefully propels interface charge transfer through triggering Z-Scheme mechanism, thus significantly improving the separation efficiency of photogenerated carriers. Moreover, the unique mesoporous encapsulation structure of VO-NiWO4/PCN heterostructure can not only afford the confinement effect to improve the reaction kinetics and specificity in the CO2 reduction to CO, but also significantly reduce mass transfer resistance of molecular diffusion towards the reaction sites. Therefore, the VO-NiWO4/PCN heterostructure demonstrates the preeminent activity, stability and reusability for photocatalytic CO2 reduction to CO reaction. The average evolution rate of CO over the optimal 10 %-VO-NiWO4/PCN composite reaches around 2.5 and 1.8 times higher than that of individual PCN and VO-NiWO4, respectively. This work contributes a fresh design approach of interface structure in the heterojunction to control charge transfer behaviors and thus improve the photocatalytic performance.

Efficient removal of Rhodamine-B dye using sulfonated/un-sulfonated three-dimensional mesoporous carbon nitride prepared from KIT-6 template: kinetics, modelling, thermodynamic analysis

Mesoporous carbon nitride (MCN-K) was prepared using mesoporous KIT-6 material as a template and ethylenediamine and carbon tetrachloride as N and C sources, respectively. The synthesized MCN-K was treated with sulfuric acid under different experimental conditions, thus obtaining sulfonated MCN-KS adsorbents. The effects of initial solution pH, initial dye concentration, adsorbent amount, and temperature on Rhodamine-B (Rh-B) dye removal were investigated. The XRD, FT-IR, and N2 adsorption–desorption analyses confirmed that the mesoporous carbon nitride structure was successfully synthesized. The high nitrogen content (C/N molar ratio: 4.0) of the MCN-K sample was confirmed by (carbon, hydrogen, nitrogen and sulfur) CHNS elemental analysis. The XPS analysis was used to characterize the chemical states of the C, N and S atoms in the MCN-K and MCN-KS sorbents. It was found that there was not much difference between the removal percentages (93.13–89.92%) obtained in the pH range (4–12) studied. This result was attributed to the zwitter-ion form of Rh-B. The exothermic nature of the adsorption process of Rh-B on the MCN-K sorbent was determined by adsorption experiments performed at different temperatures. Adsorption capacities obtained from the Langmuir model were 185.2–104.2 mg/g in the studied temperature range. The kinetic behavior of the adsorption process was explained by the pseudo-second-order kinetic model in terms of both correlation coefficients (R2 > 0.91) and qe (35.59–190.26 mg/g) values. When the percentages of dye removal of the un-sulfonated and sulfonated samples were compared, it was found that sulfonation increased the adsorption rate considerably but did not contribute positively to the dye removal percentage.

Harnessing photocatalytic activity of mesoporous graphitic carbon nitride decorated by copper single-atom catalysts for oxidative dehydrogenation of N-heterocycles

This work describes the application of Cu single-atom catalysts (SACs) for photocatalytic oxidative dehydrogenation of N-heterocyclic amines to the respective N-heteroaromatics through environmentally benign and sustainable pathways. The mesoporous graphitic carbon nitride (mpg-C3N4), prepared by the one-step pyrolysis method, possesses a lightweight material with a high surface area (95 m2 g−1) and an average pore diameter (3.6 nm). A simple microwave-assisted preparation method was employed to decorate Cu single-atom over mpg-C3N4 support. The Cu single-atom decorated on mpg-C3N4 support (Cu@mpg-C3N4) is characterized by various characterization techniques, including XRD, UV–visible spectrophotometry, HRTEM, HAADF-STEM with elemental mapping, AC-STEM, ICP-OES, XANES, EXAFS, and BET surface area. These characterization studies confirmed that the Cu@mpg-C3N4 catalyst exhibited high surface area, mesoporous nature, medium band gap, and low metal loading. The as-synthesized and well-characterized Cu@mpg-C3N4 single-atom photocatalyst is then evaluated for its efficacy in converting N-heterocycles into corresponding N-heteroaromatic compounds with excellent conversion and selectivity (>99 %). This transformation is achieved using water as a green solvent and a 30 W white light as a visible light source, demonstrating the catalyst's potential for sustainable and environmentally benign reactions.

Efficient and selective cleavage of lignin C–C bonds under visible light facilitated by the Zn(II)-doped mesoporous graphitic carbon nitride photocatalyst

Despite the promise of photocatalysis for extracting aromatic compounds from renewable lignin feedstocks, the selective cleavage of Cα–Cβ bonds in lignin under mild conditions poses a persistent challenge, primarily due to their elevated dissociation energies and steric hindrance. Herein, an efficient photocatalytic strategy for selectively breaking the Cα–Cβ bonds of lignin with visible-light irradiation and room temperature is proposed, facilitated by the Zn(II)-doped porous graphitic carbon nitride (Zn/CN) photocatalyst. Reduced energy band gap and photoluminescence, along with intensified visible-light absorption and enhanced photocurrent of Zn/CN, contribute to its efficacy in photocatalytic activity. Consequently, the lignin model compound (2-phenoxy-1-phenylethanol) achieves a conversion rate of 99 %, demonstrating a notable selectivity of 97 % in specifically breaking the Cα–Cβ bonds. Mechanistic investigations identify that photogenerated holes play a pivotal role during the photocatalytic conversion. Additionally, the activity and selectivity of Zn/CN photocatalyst are further confirmed by the successful photocatalytic conversion of pine kraft lignin, yielding high-value chemicals such as benzoic acid and vanillin. This research proposes an economical, efficient, and facile method for utilizing renewable lignin feedstocks under photocatalysis, thus advancing the production of high-value aromatic compounds.

Palladium‐Silver Alloys Deposited on Different Carriers for Dehydrogenation of Formic Acid

AbstractHydrogen (H2) is recognized as a clean energy carrier with great potential for the future energy systems. Given the existing challenges in direct H2 storage and delivery, the current option for utilizing hydrogen energy is to produce hydrogen from its storage carriers on‐site, and the development of a highly active, highly selective, and highly stable catalyst for H2 production is an important part of this. Herein, PdAg alloy was deposited on mesoporous carbon nitride (mpg‐C3N4) as a catalyst for the dehydrogenation of the formic acid (FA). The synergistic effect of Pd and Ag metals for catalysis was explored. The role of the supports on the catalytic performance was also demonstrated by depositing PdAg alloy on several carriers of Silica@Resorcinol‐Formaldehyde Spheres, Carbon Flower Particles and SBA‐15. Pd1Ag1/2/mpg‐C3N4 showed a considerable activity during FA dehydrogenation with a turnover frequency (TOF) value of 887 h−1 at 333 K, demonstrating that carbon nitride as a carrier has a significant enhancement on the catalytic hydrogen production from formic acid.

Metal-Free C60-Doped Mesoporous Carbon Nitride Drives Red-Light Photocatalysis.

The pursuit of novel strategies for synthesizing high-performance nanostructures of graphitic carbon nitride (g-C3N4) has garnered increasing scholarly attention in the field of photocatalysis. Herein, we have successfully designed a metal-free photocatalyst by integrating mesoporous carbon nitride (mpg-C3N4) and C60 through a straightforward and innovative method, marking the first instance of such an achievement. Under red light, the C60/mpg-C3N4 composite exhibited a significantly accelerated rhodamine B (RhB) photodecomposition rate, surpassing bulk g-C3N4 by more than 25.8 times and outperforming pure mpg-C3N4 by 7.8 times. The synergistic effect of C60 and the mesoporous structure significantly enhanced the photocatalytic performance of g-C3N4 by adjusting its electronic structure, broadening the light absorption range, increasing the active sites, and reducing the recombination of photogenerated carriers. This work presents a promising avenue for harnessing a metal-free, stable, efficient photocatalyst driven by red light, with potential for enhancing solar energy utilization in environmental remediation.

Ionic copolymer-modified hexagonal carbon nitride tube as a high-performance catalyst for regioselective synthesis of hexahydroquinoline frameworks

The conventional structure of carbon nitride materials presents limitations, especially in the catalysis field, attributed to a restricted number of active sites and a low surface area. To address these challenges, we developed a unique design for a mesoporous carbon nitride tube (CNT), which was constructed by incorporating the ionic imidazole-epichlorohydrin copolymer ([IMEP][Cl]) as a template in the fabrication process. The self-assembly behavior of [IMEP][Cl] influences the formation of the melamine-cyanuric acid aggregate (as precursors) through electrostatic forces and polarity, potentially resulting in the creation of a thin-wall CNT with unique pore morphology. Synthesized three-dimensional hollow CNT demonstrated key factors of a high-performance catalyst in terms of high thermal stability (up to 550 °C), good specific surface area (108 m²/g), and significant recoverability (seven runs without a significant decrease in reaction yield). The CNT architecture was employed as a heterogeneous catalyst, and its catalytic efficiency was investigated in the regioselective synthesis of hexahydroquinoline ring systems. Based on the obtained results, CNT shows super-fast synthesis (5 min) of different pharmaceutical quinoline frameworks with exceptional yields (94–98 %) under ultrasound agitations. For the first time, an effective synthesis method is introduced for constructing hollow carbon nitride tubes, utilizing an ionic polymer (produced via chemical crosslinking rather than radical chain polymerization) as a template. This work offers a new viewpoint on improving the catalytic capability of traditional graphitic carbon nitrides through the utilization of ionic copolymers, presenting potential advancements for various technological applications.

Facile synthesis of SiOx/C as high-performance anodes for lithium-ion batteries

Despite its high capacity (∼2615 mAh·g−1), silicon oxide (SiOx) suffers from low electrical conductivity and volume expansion during cycling, leading to capacity fading. In this work, a SiOx/C composite was synthesized by magnesium thermal reduction using co-assembled mesoporous SiO2 and graphitic carbon nitride (g-C3N4) as precursors. The SiOx/C composite displays a sheet-like nanostructure with highly dispersed SiOx. The presence of carbon enhances the conductivity and structural stability of the composite, leading to a low charge resistance (94.0 Ω), fast lithium diffusion (DLi+ = 5.15 × 10−14 cm2·s−1), and excellent cycling capability (863 mAh·g−1 after 160 cycles).

Qualitative and quantitative analysis of electrons donated by pollutants in electron transfer-based oxidation system: Electrochemical measurement and theoretical calculations

In order to gain a profound understanding of the fate of pollutants in advanced oxidation processes (AOPs), this study analyzed the electron contribution of pollutants qualitatively and quantitatively which rarely reported before. The rich electron transfer system was constructed by mesoporous carbon nitride (MCN) coupling with persulfate (PS) driven by visible light and the sulfanilamide antibiotics (SULs) were used as target contaminants. Firstly, the qualitative analysis of electron transfer in the system was confirmed systematically. The electron flow direction tested by i-t curves indicated that PS absorbed electrons, while SULs released electrons. The flow rate of electrons was also accelerated after the addition of SULs. The fitting curve between the kinetics and the peak potential difference tested by CV curve showed that the larger potential difference, the slower rate of oxidative degradation. Secondly, the quantification of electron transfer was achieved through theoretical calculations to simulate the interactions of the ‘catalyst-oxidant-antibiotic’ system. After the addition of SULs, the adsorption energy of the ‘catalyst-oxidant-antibiotic’ system was enhanced and the bond length of the peroxide bond was stretched. Notably, the electron transfer analysis results showed that the charge of SULs was around 0.032–0.056e, indicating that SULs pollutants played the role of electron contributors in the system. The oxidative degradation pathway included the direct cracking of S-N bond, shedding of marginal groups, ring-opening and hydroxyl addition reaction. This study clarified the electronic contribution of SULs in the oxidation system, providing necessary theoretical supplement for the analysis of the transformation of pollutants in AOPs.

Diatomite supported bagel-like hydroxylated mesoporous carbon nitride towards the adsorption desulfurization application

The carbon nitride (g-C3N4) nanosheets was apt to occur the donor-acceptor (D-A) interaction with the sulfides via the influence of the electronic structure of C atoms in the ring. Accordingly, we implemented an environmental- friendly approach to raise the electropositivity of the C atoms of N atoms in the ring of g-C3N4 through the hydroxylation treatment of hydrogen peroxide(H2O2), and afterwards constructed a bagel-like morphology composite ((HO)x/g-C3N4@DE) by virtue of the calcined combination of hydroxylated mesoporous g-C3N4 and diatomite (DE). The characterization results showed that the substantial mesoporous structure was produced in the formation of (HO)x/g-C3N4@DE composite. The adsorption desulfurization experiments showed that the bagel-like hydroxylated mesoporous (HO)x/g-C3N4@DE had the optimum adsorption capacity of up to 42.2 mg/g for thiophene (TH) and 30.8 mg/g for benzothiophene (BT), respectively. Moreover, the adsorption capacities of the hydroxylated mesoporous (HO)x/g-C3N4@DE were dramatically higher than the individual (HO)x/g-C3N4 (18.92 mg/g for TH and 15.64 mg/g for BT), suggesting that the occurrence of the secondary stacked mesopores in the formation of the (HO)x/g-C3N4 on the surface and macro-porous structure of DE affected the adsorption capacity. Lastly, the adsorption mechanism of the hydroxylated mesoporous (HO)x/g-C3N4@DE was proposed.

Preparation of a new composite based on multilayer fullerene with mesoporous carbon nitride and its application in the extraction of tacrolimus and everolimus from plasma prior to LC-MS/MS analysis.

The development of new and efficient adsorbents for dispersive solid-phase extraction method, particularly prior to chromatography analysis, is increasing. In particular, this method is recommended for use before biological sample analysis. In this work, a new composite was prepared from mesoporous carbon nitrides and carbon nano-onions and was utilized for the extraction of tacrolimus and everolimus from plasma samples prior to high-performance liquid chromatography-tandem mass spectrometry analysis. To achieve this aim, first, mesoporous carbon nitrides and carbon nano-onions were synthesized separately and mixed at optimized proportions. Subsequently, a suitable amount of the prepared composite (5 mg) was added to 2 mL of sample solution containing the analytes under vortexing. Next, the extracted analytes were eluted using acetonitrile. The approach was linear within the ranges of 1.0-500 and 0.51-500 ng mL-1 for tacrolimus and everolimus, respectively. Sensitive limits of detection (0.31 and 0.15 ng mL-1 for tacrolimus and everolimus, respectively), acceptable relative standard deviations (intra- and inter-day precisions of ≤5.6% and high extraction recoveries of 71.0% and 83.0% for tacrolimus and everolimus, respectively) were obtained. The results showed that the method can be successfully applied in the simultaneous extraction of the studied analytes from plasma.

Template-assisted synthesis of 3D ordered mesoporous graphitic carbon nitride decorated with gold nanoparticles for dopamine sensing

Three-dimensional mesoporous graphitic carbon nitride (Au/3Dom CN) decorated with a gold nanoparticle composite was successfully prepared via a template-assisted method using Au–SiO2 nanospheres as sacrificial agents.

C(sp2)–S cross-coupling reactions with nickel, visible light, and mesoporous graphitic carbon nitride

Operationally simple photo-nickel C(sp2)–S cross-coupling with a reusable heterogeneous photocatalyst.

Evaluation of the adsorption and degradation performance of lanthanum-modified mesoporous carbon nitride composite materials for tetracycline wastewater treatment

Lanthanum-modified mesoporous graphite nitride carbon composites (La-g-C3N4) were synthesized using a thermal shrinkage polymerization method. The La30-g-C3N4 sample exhibited rapid and efficient degradation, along with excellent adsorption capacity for both TC and AF.

Elucidating the conformation effects within adsorption of natural organic matter on mesoporous graphitic carbon

The conformation effects were frequently reported to affect the adsorption of natural organic matter (NOM), but such a specific mechanism is poorly understood. To address this knowledge gap, based on the adsorption of NOM on mesoporous graphitic carbon nitride (MCN) prepared via a novel pseudo-templating method, the conformation effects were elucidated. The results showed that MCNs nano-architectures with uniform mesopores were successfully fabricated and showed prominent adsorption capacity. The maximum adsorption amounts of MCN-0.5 for fulvic acid (FA) and leonardite humic acid (HA) were 73.61 mgC g−1 and 135.57 mgC g−1, respectively. The adsorptive affinities of components for HA and Elliott soil HA (ESHA) were related to structural condensation; the components with the more coiled conformation exhibited higher affinities because of occupying less active sites and weakening the electrostatic repulsion. Such conformation effects were further established with respect to NOM types and components, as well as solution chemistry. HA and ESHA suffered from variations from the coiled to linear conformations as pH increased, but not the other four types of NOM tested, and particularly the humic-like and territorial humic-like components were critical in such conformational variations. The adsorption of HA and ESHA was affected by pH via both the conformation effects and the interaction mechanism. By contrast, the conformation of six types of NOM was not affected by the common cations (Na+, K+, Mg2+, Ca2+), and these cations impacted NOM adsorption only through the conventional interactions.