Carbon Nitride Hybrid Research Articles

Fabrication of graphitic carbon nitride functionalized P–CoFe2O4 for the removal of tetracycline under visible light: Optimization, degradation pathways and mechanism evaluation

In this study, nano-sized CoFe2O4 composites were prepared through co-precipitation process. Then the phosphorus-doped strong magnetic graphitic carbon nitride hybrids composites (P–CoFe2O4@GCN) was stemmed from the CoFe2O4 composites via the thermal polymerization method. The TEM results show that the CoFe2O4 nanoparticles have been successfully embedded into the graphitic carbon nitride (GCN). The BET specific surface area of P–CoFe2O4@GCN-1 could reach 36.91 m2/g, which was 5.38 times higher than that of GCN. Thus, it provided sufficient reaction active sites to enhance the photocatalytic activity for tetracycline (TC) decomposition. The results from the photocatalytic experiments showed that the degradation efficiency of TC by P–CoFe2O4@GCN-1 could reach 96.2% within 60 min, which is 3.19 times higher than that of GCN. The h+, O2•- and •OH radicals detected by the electron spin resonance (ESR) were responsible for the TC decomposition in the photocatalytic reaction system. Persulfate (PS) can further activate the hybrid mixture system, and the fitting model predicted by the response surface methodology (RSM) indicated that the maximum tetracycline removal could reach 99.6% within 30 min. In addition, the degradation intermediates of TC were detected by HPLC-MS and the photodegradation mechanism was discussed.

Enhanced xylene sensing performance using Ag-V2O5 loaded mesoporous graphitic carbon nitride.

A 3-dimensional ordered cubic mesoporous Ag-V2O5 loaded graphitic carbon nitride (mpg-CN) hybrid was fabricated via a facile nanocasting technique using mesoporous silica as the hard template and its sensing response towards xylene gas was investigated in detail. The physicochemical properties of the as prepared nanocomposite were estimated by transmission electron microscopy (TEM), X-ray diffraction (XRD), scanning electron microscopy (SEM), elemental dispersive X-ray spectroscopy (EDX) and BET surface area analysis. The hybridized Ag-V2O5/mpg-CN nanocomposite prepared by template inversion of KIT-6 silica showed temperature reliant response towards the detection of common VOCs (xylene, formaldehyde, 2-propanol and benzene) usually found in our indoor environment. Sensing response values of 4.9 for 50 ppm and 12.7 for 500 ppm were reported for xylene gas at an operating temperature of 40 °C. Besides, average response/recovery times of 6.1/4.1 s (xylene), 7.7/5.1 s (formaldehyde), 8.7/6.6 s (2-propanol) and 9.5/8.4 s (benzene) were recorded for Ag-V2O5/mpg-CN, which demonstrated the potential of utilizing the as-prepared sensor in commercial real-time sensing applications.

In-situ photovoltage transients assisted catalytic study on H2O2 photoproduction over organic molecules modified carbon nitride photocatalyst

Artificial photocatalysis holds great promise for the production of cheap and clean H2O2. Therefore, it is emerging interest to develop metal-free photocatalysts due to their adjustable band gap, wide spectral response range and cheap. Here, we demonstrated the high efficient H2O2 photoproduction of 833 μmol g−1 h−1 (18.41 μmol m-2 h−1) with terephthalic acid modified carbon nitride (PTA0.6/CN) hybrids as catalysts, which was 13.6 times (20.92 times) higher than that of pristine carbon nitride. The apparent quantum efficiency (QE) is up to 0.67 % (at λ =420 nm). Notably, with the assistance of in-situ transient photovoltage (TPV) analysis, the catalytic mechanism, catalytic kinetics and optimized reaction conditions were determined in this alluring approach. These in-situ TPV tests and analysis offered a thermodynamic-kinetic model, which showed the great capability to directly extract the half reaction rate, electron transfer number and catalytic activities without carrying out complex parallel, contrast and optimal experiments. This study not only provides a new model system for exploring photoelectric interface, thermodynamic and kinetic properties of catalysts, but also opens up opportunities for the design of next-generation high-performance photocatalysts.

Carbon-Graphitic Carbon Nitride Hybrids for Heterogeneous Photocatalysis.

Polymeric graphitic carbon nitride (g-C3 N4 ) and various carbon materials have experienced a renaissance as viable alternates in photocatalysis due to their captivating metal-free features, favorable photoelectric properties, and economic adaptabilities. Although numerous efforts have focused on the integration of both materials with optimized photocatalytic performance in recent years, the direct parameters for this emerging enhancement are not fully summarized yet. Fully understanding the synergistic effects between g-C3 N4 and carbon materials on photocatalytic action is vital to further development of metal-free semiconductors in future studies. Here, recent advances of carbon/g-C3 N4 hybrids on various photocatalytic applications are reviewed. The dominant governing factors by inducing carbon into g-C3 N4 photocatalysts with involving photocatalytic mechanism are highlighted. Five typical carbon-induced enhancement effects are mainly discussed here, i.e., local electric modification, band structure tailoring, multiple charge carrier activation, chemical group functionalization, and abundant surface-modified engineering. Photocatalytic performance of carbon-induced g-C3 N4 photocatalysts for addressing directly both the renewable energy storage and environmental remediation is also summarized. Finally, perspectives and ongoing challenges encountered in the development of metal-free carbon-induced g-C3 N4 photocatalysts are presented.

Organic Aluminum Hypophosphite/Graphitic Carbon Nitride Hybrids as Halogen-Free Flame Retardants for Polyamide 6.

The novel organic aluminum hypophosphite (ALCPA) and its hybrid (CNALCPA) with graphitic carbon nitride (g-C3N4) were successfully synthesized and applied as halogen-free flame retardants in polyamide 6 (PA6). Their structures, morphology, thermal stability, and fire properties were characterized. Results showed that both ALCPA and CNALCPA had good flame retardancy. PA6/CNALCPA composites achieved a high limited-oxygen-index (LOI) value of 38.3% and a V-0 rating for UL94 at 20 wt % loading, while PA6/ALCPA composites could reach a V-1 rating for UL94. The flame-retardant mechanism was also studied. On the one hand, the incorporation of g-C3N4 produced more gas-phase products, which indicated a gas-phase mechanism. On the other hand, g-C3N4 could catalyze the thermal degradation of ALCPA and PA6 to form a compact char layer that was evidence for a solid-phase mechanism. The tensile test of the PA6 composites also displayed good mechanical properties.

In-situ hard template synthesis of mesoporous carbon/graphite carbon nitride (C/CN-T-x) composites with high photocatalytic activities under visible light irridation

Carbon/graphite carbon nitride (C/CN-T-x) hybrid composites with high photocatalytic activities under visible light irradiation were synthesized by an in-situ hard template method using the partially formaldehyde-modified dicyandiamide (PFMD) and tetraethyl orthosilicate (TEOS) as the precursors and template, respectively. The structures of the as-prepared composites were characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), elemental analysis, nitrogen adsorption-desorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), photoluminescence (PL) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The composite prepared under the optimal conditions exhibits the large surface area of 174 m2･g−1 and high photocatalytic activity for the degradation of methylene blue (MB) under visible light irradiation. The significant improvement in photocatalytic activity of the composite, as compared with the pure graphite carbon nitride (CN), is attributed to the large surface area, strong dye adsorption ability and enhanced separation efficiency of photogenerated electron-hole pairs.

New effects of TiO2 nanotube/g-C3N4 hybrids on the corrosion protection performance of epoxy coatings

In this research, the effects of visible-light-driven titanium dioxide (TiO2) nanotube/graphitic carbon nitride (g-C3N4) hybrids on the corrosion protection performance of epoxy coatings both in the dark and under visible-light irradiation are studied. For this, TiO2 nanotube/g-C3N4 hybrids and 3-(aminopropyl)triethoxysilane functionalized hybrids were synthesized and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscopy coupled with energy dispersive X-ray spectroscopy mapping, N2 adsorption/desorption technique, and UV–Vis spectroscopy. TiO2 nanotubes containing 30 wt% g-C3N4 (H30%) showed the highest photocatalytic performance due to the simultaneous effects of high surface area and band-gap structure; however, the photocatalytic activity decreased after the silane functionalization of H30%. Then, epoxy coatings containing H30% and silane functionalized H30% in different amounts (0.1, 0.3, and 0.5 wt%) were prepared, and their corrosion resistance was investigated by electrochemical impedance spectroscopy in NaCl solution. The results revealed that the epoxy coatings containing 0.3 wt% hybrids have higher corrosion resistance than that of the neat coating, and silane-functionalized nanofillers more effectively enhance the corrosion resistance. However, when these nanocomposite coatings are irradiated with visible light, their corrosion protection performance remarkably reduces owing to the degradation of organic matrix by the oxidizing radicals formed on the photocatalytic hybrid surface.

Significantly Strengthening Epoxy by Incorporating Carbon Nanotubes/Graphitic Carbon Nitride Hybrid Nanofillers

AbstractNovel hybrid nanofillers consist of carbon nanotubes (CNTs) and graphitic carbon nitride (g‐C3N4) are prepared for the enhanced mechanical properties of epoxy by improving the dispersion of CNTs. 2D planar structure, large surface area, and plentiful of surface reactive groups of g‐C3N4 efficiently resist the microcrack propagation, impede the thermal transfer, and provide chemical bonding with epoxy chains. The well‐dispersed CNTs by anchoring on g‐C3N4 surface promotes the efficient transfers of stress, and supply the stronger mechanical interlocking for interfacial bonding. The significantly enhanced mechanical properties of epoxy containing hybrid nanofillers are based on the synergistic effects between CNTs and g‐C3N4. Compared with neat epoxy, the tensile strength, tensile modulus, and storage modulus of epoxy containing 0.5 wt% hybrid nanofillers (CNTs: g‐C3N4 = 1: 9, w/w) below glass transition temperature (Tg) are increased by 37.65%, 29.36%, and 32.92%, respectively. Meanwhile, the Tg, onset decomposition temperature and char residue are also obviously raised.

Enhancement on the tribological properties of poly(phthalazinone ether sulfone ketone) by carbon nanotube‐supported graphitic carbon nitride hybrid

AbstractA novel hybrid of carbon nanotube‐supported graphitic carbon nitride (g‐C3N4/CNT) was firstly fabricated via facile calcination method, and then filled into poly (phthalazinone ether sulfone ketone) (PPESK) to prepare self‐lubricating composite film. The microstructure and chemical composition of g‐C3N4/CNT hybrid were characterized, and its enhancement on the tribological properties of PPESK was investigated by comparing to pure PPESK and its composite films with g‐C3N4 or CNT only. Results showed that g‐C3N4 was in situ attached to CNT surface uniformly, which favored for improving the physical and chemical interfacial interaction between fillers and PPESK. Besides, by the incorporation of g‐C3N4/CNT, the hardness and elastic modulus of PPESK were improved by 15.05% and 41.75%, respectively. More importantly, PPESK‐g‐C3N4/CNT composite film showed the best tribological property among PPESK composite films. Its friction coefficient and wear rates were 65.5% and 84.1% lower than those of pure PPESK, as a result of good dispersion and interfacial action, as well as synergism between CNT and g‐C3N4. Based on the worn surface analysis, the enhancement mechanism of g‐C3N4/CNT was proposed.

Black Phosphorus and Carbon Nitride Hybrid Photocatalysts for Photoredox Reactions

AbstractThe development of metal‐free photocatalysts with high efficiency, stability, and broadband solar absorption is a major challenge to realize green and sustainable chemical development. Recently, metal‐free nanohybrids (BP/CN) composed of black phosphorus (BP) and polymeric carbon nitride (CN) are emerged as photocatalytic hybrids with broadband light‐harvesting capabilities and higher photocatalytic performance. Herein, the latest progress of BP/CN hybrids for multifarious photoredox reactions is summarized. The different heterojunction types of BP/CN hybrid photocatalysts, including type I, type II, and multicomponent heterojunctions, are illustrated. Furthermore, the relevant applications of BP/CN hybrid photocatalysts for photocatalytic water splitting, CO2 photoreduction, N2 fixation, H2O2 production, pollutant decomposition, and bacterial inactivation are discussed. An overview of the challenge in this area and the directions for the future is presented.

Ratiometric Fluorescent Paper-Based Sensor Based on CdTe Quantum Dots and Graphite Carbon Nitride Hybrid for Visual and Rapid Determination of Cu2+ in Drinks.

A simple and effective ratiometric fluorescence sensor of CdTe QDs/GCNNs for on-site and rapid analysis of Cu2+ has been established by mixing physically CdTe QDs and graphite carbon nitride (GCNNs). Two emissions peaks of CdTe QDs at 572nm and GCNNs at 436nm are both excitated at 340nm. Under a UV lamp, fluorescent of traffic yellow CdTe QDs is linearly quenched by Cu2+ (as the detection signal), while blue GCNNs remains unchanged (as the reference), resulting in a distinguishable color change gradually from pink yellow to blue. The limit of detection (LOD) of this new sensor for Cu2+ is as low as 0.47ngmL-1 with 1.4 % RSD. The established method has been successfully applied to detection of Cu2+ in various drinks with satisfactory results. Moreover, a paper-based sensor, which has been prepared by soaking cellulose acetate membrane in CdTe QDs/GCNNs sensor solution, has a wide semiquantitative detection range for Cu2+ (0.01~5.0μgmL-1 ). It has realized successfully on-site and rapid determination of Cu2+ in red wine without any pretreatment procedure and is of great promotion and application value in determination of Cu2+ in liquid samples.

Highly sensitive smartphone-integrated colorimetric glucose sensor based on MnFe2O4 – graphitic carbon nitride hybrid nanostructure

An extremely sensitive colorimetric glucose sensor was fabricated using a novel hybrid nanostructure comprised of manganese ferrite oxide– graphitic carbon nitride (MnFe2O4/g-C3N4). A neural network-based glucose analytical smartphone application can be used to easily monitor the glucose concentration with a high accuracy by only taking images with the smartphone camera. The as-synthesized MnFe2O4/g-C3N4 exhibited a very high affinity toward 3,3′,5,5′-tetramethylbenzidine (TMB) and H2O2, as calculated via Michaelis-Menten kinetics. The glucose sensors using as-synthesized MnFe2O4/g-C3N4 exhibit a wide linear range and very low detection limits of 20.5 nM for H2O2 and 17.3 nM for glucose, which are one of the lowest values ever reported.The instrumental analysis with XPS, XRD, and TEM revealed that MnFe2O4/g-C3N4 had a highly crystalline structure of MnFe2O4 and g-C3N4 with abundant oxygen vacancies and well-developed hybrid structures, which might result in excellent catalytic activity and glucose sensitivity.

In-situ formation of oxygen-vacancy-rich NiCo2O4/nitrogen-deficient graphitic carbon nitride hybrids for high-performance supercapacitors

Rational designing of a facile synthetic protocol for synchronously generating NiCo2O4 and conductive carbon is a great challenging for high-performance supercapacitors. Herein, a one-pot and scalable approach has been developed to in-situ construct oxygen-vacancy-rich NiCo2O4/nitrogen-deficient graphitic carbon nitride (Ov-NiCo2O4/ND-g-C3N4) hybrids. The in-depth investigations reveal that there is an intriguing interaction between NiCo2O4 and g-C3N4, which unexpectedly enables the generating of Ov-NiCo2O4 and transforming of g-C3N4 into ND-g-C3N4 structures. Moreover, the g-C3N4 plays the skeleton and template role to form the foam-like structure. Benefiting from abundant active species and improved electrical conductivity, the resultant Ov-NiCo2O4/ND-g-C3N4 exhibits an unrivalled specific capacitance of 1998 F g−1 (equalling 277.5 mAh g−1) at a current density of 2 A g−1 and excellent rate capability (78.66% capacity retention at 20 A g−1). Besides, the assembled Ov-NiCo2O4/ND-g-C3N4//activated carbon asymmetric supercapacitors deliver a maximum energy density of 70.22 Wh kg−1 at a power density of 800 W kg−1, and a remarkable cycling stability with 95.22% retention even after 5000 cycles, outstripping most of reported NiCo2O4-based supercapacitors. Thus, this work sheds light on the developing of advanced pseudocapacitive materials for electrochemical energy storage.

Peroxymonosulfate enhancing visible light photocatalytic degradation of bezafibrate by Pd/g-C3N4 catalysts: The role of sulfate radicals and hydroxyl radicals

For efficient usage of visible light, Pd loading graphitic carbon nitride (Pd/g-C3N4) hybrids were synthesized and peroxymonosulfate (PMS) was accompanied to improve the photoactivities of Pd/g-C3N4. The photocatalytic system consisting of Pd/g-C3N4, PMS and visible light (Pd/g-C3N4-PMS-Vis) exhibited higher bezafibrate (BZF) removal efficiency than Pd/g-C3N4-PMS, Pd/g-C3N4-Vis, g-C3N4-PMS, g-C3N4-Vis, and g-C3N4-PMS-Vis systems, which can be ascribed to the electron transfer from Pd/g-C3N4 to PMS. Density functional theory (DFT) calculation proved that the chemical bond interaction forming between Pd and g-C3N4 inspired the electron excitation, separation and transportation. Meanwhile, Pd particles with local surface plasma resonance (LSPR) phenomenon could also enhance the visible light adsorption. Notably, the photocurrent response of Pd/g-C3N4 was significantly improved with PMS, demonstrating the photoinduced electrons on Pd/g-C3N4 are capable to immigrate to PMS. The added PMS can perform as electron acceptors, thus favoring the quantum efficiency of photoinduced charge carriers to form SO4−. The BZF degradation mechanism was clarified by the addition of different scavengers and the major reaction active species were hydroxyl radicals (OH) and sulfate radical (SO4−). Four possible pathways in the degradation of BZF were also put forward via LC-MS/MS analysis (R-oxy substituent, oxidation dichlorination, OH-addition and oxidation deaminization). In the 2%Pd/g-C3N4-PMS-Vis system, an obvious decrease of genetic toxicity was observed because of the high removal efficiency and final low concentration of BZF. The results of this research underlined great prospective of Pd/g-C3N4 catalysts and provided a potential approach to photocatalytically remedy the polluted water by micropollutants.

Consciously Constructing the Robust NiS/g-C3N4 Hybrids for Enhanced Photocatalytic Hydrogen Evolution

Selective growth of cocatalyst on the surface of photocatalyst has been attracted considerable attention due to their efficient charges transfer property. In this study, the robust NiS modified graphitic carbon nitride (g-C3N4) hybrids were successfully synthesized by a facile surface photochemical deposition process. The structure and composition characterization results revealed that the NiS is highly dispersed loading on the surface of g-C3N4 nanosheets, and the NiS/g-C3N4 hybrids possess large surface areas and excellent optical properties. Under the visible light illumination, the NiS/g-C3N4 hybrids with 1.0% weight content of NiS cocatalyst exhibits the highest hydrogen evolution rate of 1346.1 μmol h−1 g−1 with an apparent quantum efficiency (AQE) of 7.67%. On the basis of photoluminescence (PL) spectra and photoelectrochemical methodology, the photocatalytic hydrogen evolution mechanism was proposed. The results demonstrated that the excellent activity arises from the strong electronic coupling, highly efficient charges separation and migration. This work demonstrates a facile photochemical deposition method to consciously construct the robust two-dimensional (2D) hybrids, so as to realize accurate deposition of cocatalyst and efficient migration of photo-generated carriers.

Electroless-hydrothermal construction of nickel bridged nickel sulfide@mesoporous carbon nitride hybrids for highly efficient noble metal-free photocatalytic H2 production

Metallic Ni bridged NiS@mesoporous carbon nitride hybrids were for the first time fabricated through a one-pot electroless-assisted hydrothermal method. The intimate Ni bridge between the interface of mesoporous carbon nitride and NiS was confirmed by HRTEM and in-depth XPS analysis using an Ar+-cluster sputtering gun and a possible mechanism was put forward to elucidate the formation process of the unique structure. Without adding any noble metals as cocatalysts, the optimized catalyst 10% NiS/m-CN-160-12 showed a H2 evolution rate of 1419 μmol·g−1·h−1, which is about 34 and 14 fold higher than that of bare mesoporous carbon nitride and NiS, respectively. The dramatically enhanced photocatalytic performance was mainly ascribed to the synergistic effect of NiS cocatalyst loading and the formation of metallic Ni between the interface of mesoporous carbon nitride and NiS, which served as a charge-transfer bridge to facilitate the transfer and separation of photo-induced electron-hole pairs.

A h-BCN for Electrochemical Sensor of Dopamine and Uric Acid

A hexagonal boron carbon nitride hybrid (h-BCN) is developed by in situ high-temperature solid-state reaction and subsequent chemical reduction with hydrazine. The XRD and TEM results show that the h-BCN features interlayered structures with two characteristic d-spacing of 0.33 and 0.21 nm. The obtained h-BCN exhibits significant electrochemical sensor for dopamine and uric acid. The cyclic voltammetric and amperometric experiments revealed a good linear relationship between current densities and concentrations of dopamine (DA) of 10-300 μM and uric acid (UA) of 10-500 μM, with high sensitivities of 0.14 μA/μM and 0.32 μA/μM and detection limits of 5 μM and 2 μM, respectively.

Preparation of vanadium-substituted polyoxometalate doped carbon nitride hybrid materials POM/g-C3N4 and their photocatalytic oxidation performance

A series of vanadium-substituted Keggin-type polyoxometalate ((NH4)4 [PMo11VO40]) doped carbon nitride (POM/g-C3N4) hybrid materials were prepared by using green dipping method and characterized by FTIR, XRD, and DRS. Their photocatalytic oxidation performance was investigated by degradation of different dye pollutants under visible light irradiation. In different composition, POM/g-C3N4 (1:3) exhibited the best photocatalytic activity compared with POM, g-C3N4, POM/g-C3N4 (1:1) and POM/g-C3N4 (1:5). The synergistic effect of POM and g-C3N4 in the hybrid facilitated its high photocatalytic capability.

Construction of covalent bonding oxygen-doped carbon nitride/graphitic carbon nitride Z-scheme heterojunction for enhanced visible-light-driven H2 evolution

Photocatalytic water splitting for hydrogen production is a brilliant method for utilization of solar energy. Herein, a series of covalent bonding oxygen-doped carbon nitride/graphitic carbon nitride hybrids (O-CN/CN) have been synthesized via solvothermal treatment using cyanuric chloride, cyanuric acid (derived from hydrolysis of cyanuric chloride) and urea-derived graphitic carbon nitride as precursors. In O-CN/CN hybrids, guest O-CN was covalently bonded with incomplete polycondensation –NHx derived from the host CN surface as verified by XRD, FT-IR, XPS and solid-state 13C MAS NMR spectra. With assistance of Pt co-catalyst, the most efficient O-CN/CN-3 photocatalyst showed the highest H2 generation rate at 6.97 mmol g−1h−1 under visible light irradiation (λ > 420 nm) by 12.4 times as that of pristine CN (0.56 mmol g−1h−1). Moreover, the apparent quantum yield (AQY) was estimated as 21.4% at 425 nm irradiation for O-CN/CN-3. The improved photocatalytic performance was ascribed to the extended visible light absorption, the inhibited photo-induced charge carrier recombination and rapid charge carriers transfer that were confirmed by UV–vis diffuse reflectance spectra, photoluminescence spectra, transient photocurrent responses, electrochemical impedance spectroscopy and time-resolved photoluminescence. Moreover, the photocatalytic activity displayed unnoticeable deactivation within five recycles, further verifying that O-CN/CN hybrids were stable for visible-light-driven H2 evolution. This present work promotes new insights into Z-scheme heterojunction engineering for graphitic carbon nitride.

Doping reduced graphene oxide and graphitic carbon nitride hybrid for dual functionality: High performance supercapacitance and hydrogen evolution reaction

A high efficiency hybrid electrocatalyst (Co3O4-rGO-gC3N4) was developed via a facile method of doping cobalt oxide (Co3O4) on reduced graphene oxide (rGO) supported by graphitic carbon nitride (GCN, g-C3N4). The synthesized composite was tested for supercapacitance and hydrogen evolution reaction (HER) activity. The results demonstrate excellent supercapacitance properties based on tests with two electrode configurations to produce capacitance of 675 F g-1 at a current density of 1 A g−1. The electrode showed excellent capacitance retention ability (85.4%), cycling stability (93%), high energy density (28.3 W h kg−1) and power density (0.8 kW kg−1). The composite exhibited excellent electrocatalytic activity for hydrogen evolution reaction (HER) with a Tafel slope of 65 mV.dec−1, a low onset overpotential of 75 mV and an overpotential of −180 mV at a current density of 10 mA cm−2. The performance of the doped hybrid was found to be superior to those reported for other metallic and non-metallic materials.