Nitrogen Vacancies Research Articles

Dual Active Sites with Charge‐asymmetry in Organic Semiconductors Promoting C−C Coupling for Highly Efficient CO2 Photoreduction to Ethanol

AbstractSelective CO2 photoreduction into high‐energy‐density and high‐value‐added C2 products is an ideal strategy to achieve carbon neutrality and energy shortage, but it is still highly challenging due to the large energy barrier of the C−C coupling step and severe exciton annihilation in photocatalysts. Herein, strong and localized charge polarization is successfully induced on the surface of melon‐based organic semiconductors by creating dual active sites with a large charge asymmetry. Confirmed by multiscale characterization and theoretical simulations, such asymmetric charge distribution, originated from the oxygen dopants and nitrogen vacancies over melon‐based organic semiconductors, reduces exciton binding energy and boosts exciton dissociation. The as‐formed charge polarization sites not only donate electrons to CO2 molecules but also accelerate the coupling of asymmetric *CO*CO intermediates for CO2 photoreduction into ethanol by lowering the energy barrier of this process. Consequently, an exceptionally high selectivity of up to 97 % for C2H5OH and C2H5OH yield of 0.80 mmol g−1 h−1 have been achieved on this dual active sites organic semiconductor. This work, with its potential applicability to a variety of non‐metal multi‐site catalysts, represents a versatile strategy for the development of advanced catalysts tailored for CO2 photoreduction reactions.

Engineering Dual-Defective 0D/2D VN-CNQDs/VBi-Bi4O5Br2 S-Scheme Heterostructure for Boosting CO2 Photoreduction in Air.

The direct photocatalytic reduction of CO2 in air is the future trend of photocatalyst application. Herein, the 0D carbon nitride quantum dots with nitrogen vacancies (VN-CNQDs) and 2D bismuth-deficient Bi4O5Br2 (VBi-Bi4O5Br2) are integrated by hydrothermal method. The S-scheme heterostructure of VN-CNQDs/VBi-Bi4O5Br2 composite promotes the separation rate of photogenerated carriers and enhances the redox capacity. The dual defects provide a large number of adsorption and catalytic sites that enhance the ability to capture and reduce CO2. The synergistic effect of S-scheme heterostructure and defect engineering enables the efficiency of CO2 photoreduction to CO with VN-CNQDs/VBi-Bi4O5Br2 to reach 16.89µmolg-1h-1 in air and 55.69µmolg-1h-1 in VCO2: VAir = 3:1 condition, which is 17 and 21 times higher than that of Bi4O5Br2, respectively. The dual-defective VN-CNQDs/VBi-Bi4O5Br2 exhibits more lower energy barrier for forming *CO2, *COOH, and *CO and is easier to release CO gas. And it exhibits excellent cycling stability for photocatalytic CO2 reduction to CO. The photocatalytic reduction mechanism of CO2 to CO in the VN-CNQDs/VBi-Bi4O5Br2 S-scheme heterostructure is further analyzed. This work provides new perspectives for the design of the photocatalysts with defect engineering for efficient photoconversion at low CO2 concentrations.

Cover Feature: Combining Nitrogen Doping and Vacancies for Tunable Resonant States in Graphite (ChemPhysChem 21/2024)

Cover Feature: Combining Nitrogen Doping and Vacancies for Tunable Resonant States in Graphite (ChemPhysChem 21/2024)

Alkali-decorated carbon nitride enhances the removal of enrofloxacin by ferrihydrite-H2O2 system: Mechanistic insights and degradation pathways

Antibiotic pollution affects water quality. Based on the ferrihydrite-H2O2 (Fh-H2O2) photo-Fenton system, alkali-decorated carbon nitride was introduced, and KC3N4/Fh, with ·OH and ·O2− as the primary reactive oxygen species, was synthesized for the degradation of veterinary antibiotic enrofloxacin in water. The modification with KOH induced the formation of cyano groups and nitrogen vacancies in KC3N4/Fh. The presence of cyano groups altered the original charge distribution and energy band structure of the material, thereby establishing an internal electric field. Directed driving of nitrogen vacancies accelerated the transfer of photogenerated charges from the conduction band of KC3N4 to the surface of Fh, facilitating the cycle process of Fe(III) and Fe(II). Meanwhile, the nitrogen vacancies significantly enhanced the adsorption capacity of KC3N4/Fh for H2O2 and accelerated the reaction between the generated Fe(II) and H2O2 to produce ·OH, which subsequently led to the efficient degradation and mineralization of enrofloxacin. The results demonstrated that the degradation rate of enrofloxacin by KC3N4/Fh reached 95.96 % within 30 min, highlighting its high efficiency and stability. Furthermore, KC3N4/Fh exhibited effective degradation of actual effluent under sunlight. This work proposes a novel approach to creating a Fh-H2O2-based photo-Fenton system for the efficient antibiotic degradation.

Investigation of the leakage mechanism in solar-blind AlGaN p-i-n photodetector at high reverse bias

The leakage mechanism of solar-blind AlGaN p-i-n photodetectors has been investigated. By studying the temperature-dependent I–V curves, we determined that Poole–Frenkel emission is the main source of the leakage current, and the corresponding trap energy level is 0.61 eV. Cathodoluminescence measurement demonstrates that the leakage current of the device may be related to the deep-level traps in the p-AlGaN layer. An analysis of deep-level transient spectroscopy testing results for p-AlGaN suggests that nitrogen vacancies formed during the epitaxial growth of high Al-content p-AlGaN act as electron traps. The trap potential energy decreases at high reverse bias voltage, making trapped electrons easier to escape, which increases the leakage current.

Novel carbon nitride for efficient degradation of organic pollutants and value-added recycled plastics: synergistic effects of nitrogen vacancies and Fe

The introduction of nitrogen vacancies (VN) and iron (Fe) single atoms sites significantly enhances the visible light absorption and charge transfer ability of carbon nitride (CN) catalysts. This paper presents the successful synthesis of a VN-rich, Fe single atoms incorporated CN, a catalyst that demonstrates exceptional degradation performance and cycling stability. The 2-mercaptobenzothiazole (MBT) removal rate by 20Fe-CN reached 99.51% within just 11min under visible light, and the catalyst maintained superior photocatalytic performance upon repeated use. Additionally, the 20Fe-CN/Photo/High-temperature system effectively converted polystyrene (PS) to benzoic acid (BA), achieving a BA yield of 19.73% after 48hours. Under visible light irradiation, the VN sites captured electrons and facilitated their rapid transfer to neighboring Fe sites, enhancing the photocatalytic redox processes. This study also identified ·O2- as the primary active species in the photocatalytic process. This research supports the development of diverse single-atom modified carbon nitride photocatalysts, holding significant potential for wastewater treatment and plastic resource recycling, and providing valuable insights for future photocatalysts in environmental remediation.

Design of dual-defective polymeric carbon nitride with compact interlayer stacking for boosting photocatalytic H2O2 production: Insight of various configurations

Polymeric carbon nitride (PCN) is an environmentally friendly photocatalyst for solar-driven H2O2 production, but the activity of original PCN is still not satisfactory. The main limitation is the sluggish exciton dissociation leading to slow generation and conversion of superoxide radical (•O2−) intermediate. Herein, the PCN with dual defect sites and compact interlayer is rationally designed for H2O2 photosynthesis with an ultrahigh rate of 3930.9 μmol g−1h−1 and rapid •O2− yield rate of 1.92 min−1. The enhanced activity is attributed to effective exciton dissociation during interlayer and intralayer process. Moreover, nitrogen vacancies change the oxygen adsorption configuration (formation of C − O − O − C bridge mode), thus promoting O2 adsorption and activation. A well-matched linear relationship was established between the concentration of nitrogen vacancies and •O2−/H2O2 production. This work not only provides in-depth insights for the photocatalytic H2O2 generation mechanism, but also offers a new paradigm for designing efficient PCN-based photocatalysts for energy conversion.

Hydrogen- assisted synthesis of defective triazine/heptazine homostructured nanosheets for efficient CO2photoreduction.

Homostructure construction has been demonstrated to be an effective way for boosting the photocatalytic activity of polymeric carbon nitride. However, the contribution of the intrinsic activity of molecular fragments in the catalytic performance of homostructured carbon nitride is yet to be explored. In this paper, a facile hydrogen-assisted strategy was used to synthesize triazine/heptazine intermolecular homojunctions (g-C3N4(MU-H)) with an ultrathin and defective structure, via the co-pyrolysis of melamine and urea precursors. Experimental characterizations and theoretical calculations revealed the copolymerization of triazine- and heptazine-based carbon nitride generated a homostructured interface with a large build-in electric field for efficient separation of photogenerated carriers. Due to the synergestic effect between the homostructured interface and nitrogen vacancies, as-synethesized g-C3N4(MU-H) exhibited an outstanding activity for photocatalytic CO2 reduction, with a CO yield rate of 14.45 μmol h-1, which was 23.5 and 3.64 times higher than those of bulk g-C3N4 and g-C3N4(M-H) synthesized from a single precursor, respectively. This study provides a new avenue for optimizing the charge separation efficiency of CO2 photoreduction catalysts by constructing intramolecular homojunction.

Engineering Dual Carbon and Nitrogen Vacancies in g-C3N4 for Enhanced Photodegradation of Tetracycline Hydrochloride.

Ultrathin g-C3N4 nanosheets with specific nitrogen vacancies and combined carbon and nitrogen dual vacancies were created by annealing g-C3N4 under different atmospheric conditions. The nanosheets with dual vacancies showed significant improvements in the photodegradation of tetracycline hydrochloride (TC-HCl) compared with both the pristine g-C3N4 and its nitrogen-deficient version. Various techniques, such as Raman spectroscopy, electron spin resonance (ESR), X-ray photoelectron spectroscopy, wavelength-dependent studies, electrochemical methods, and photoluminescence measurements, were used to identify vacancy defects, revealing that performance enhancement was particularly notable under visible light. Density functional theory calculations indicated that dual vacancies introduced a shallow defect state above the valence band, enhancing visible light absorption and reducing electron-hole pair recombination. Conversely, nitrogen vacancies alone formed a deep defect state, which extended light absorption but potentially trapped photoelectrons, limiting their contribution to photoreactions. Radical-scavenging experiments and ESR spin-trap spectra identified the superoxide radical (·O2-) as the primary reactive oxygen species responsible for TC-HCl degradation. A comprehensive degradation pathway for TC-HCl was proposed using liquid chromatography-mass spectrometry data. This research highlights a strategic approach to boost TC-HCl photodegradation by engineering the vacancies in g-C3N4.

Temperature dependence of the low-frequency noise in AlGaN/GaN fin field effect transistors

Low-frequency (LF) noise measurements are compared for Schottky-gate AlGaN/GaN heterostructure planar and fin field-effect transistors (FinFETs) as functions of gate voltage and measuring temperature. The noise of each device type is consistent with a carrier number fluctuation model. Similar effective defect-energy Eo distributions are derived for each of the two device architectures from measurements of excess drain-voltage noise-power spectral density vs temperature from 80 to 380 K. Defect- and/or impurity-related peaks are observed in the inferred energy distributions for Eo < 0.2 eV, Eo ≈ 0.45 eV, and Eo > 0.6 eV. Significant contributions to the LF noise are inferred for nitrogen vacancies and ON and FeGa impurity complexes. Ga dangling bonds at fin interfaces with gate metal are likely candidates for enhanced noise observed in FinFETs, relative to planar devices. Reducing the concentrations of these defects and impurity complexes should reduce the LF noise and enhance the performance, reliability, and radiation tolerance of GaN-based high electron mobility transistors.

Dual Active Sites with Charge-asymmetry in Organic Semiconductors Promoting C-C Coupling for Highly Efficient CO2 Photoreduction to Ethanol.

Selective CO2 photoreduction into high-energy-density and high-value-added C2 products is an ideal strategy to achieve carbon neutrality and energy shortage, but it is still highly challenging due to the large energy barrier of the C-C coupling step and severe exciton annihilation in photocatalysts. Herein, strong and localized charge polarization is successfully induced on the surface of melon-based organic semiconductors by creating dual active sites with a large charge asymmetry. Confirmed by multiscale characterization and theoretical simulations, such asymmetric charge distribution, originated from the oxygen dopants and nitrogen vacancies over melon-based organic semiconductors, reduces exciton binding energy and boosts exciton dissociation. The as-formed charge polarization sites not only donate electrons to CO2 molecules but also accelerate the coupling of asymmetric *CO*CO intermediates for CO2 photoreduction into ethanol by lowering the energy barrier of this process. Consequently, an exceptionally high selectivity of up to 97% for C2H5OH and C2H5OH yield of 0.80 mmol g-1 h-1 have been achieved on this dual active sites organic semiconductor. This work, with its potential applicability to a variety of non-metal multi-site catalysts, represents a versatile strategy for the development of advanced catalysts tailored for CO2 photoreduction reactions.

Modulating dual carrier-transfer channels and band structure in carbon nitride to amplify ROS storm for enhanced cancer photodynamic therapy

Graphite carbon nitride (CN) eliminates cancer cells by converting H2O2 to highly toxic •OH under visible light. However, its in vivo applications are constrained by insufficient endogenous H2O2, accumulation of OH− and finite photocarriers. We designed Fe/NV-CN, co-modified CN with nitrogen vacancies (NV) and ferric ions (Fe3+). NV and Fe3+, not only adjust the band structure of CN through quantum confinement effect and the altered coupled oscillations of atomic orbitals to facilitates •OH production by oxidizing OH−, but also construct dual carrier-transfer channels for electrons and holes to respective active sites by introducing stepped electrostatic potential and shortening three-electron bonds, thereby involving more carriers in •OH production. Fe/NV-CN, the novel reactor, effectually produces vast •OH under illumination by expanding OH− as the raw material of •OH and augmenting carriers at active sites, which induces cancer cell apoptosis by disrupting mitochondrial function for significant shrinkage of Cal27 cell-induced tumor under illumination. This work provides not only an effective photosensitizer avoiding the accumulation of OH− for cancer therapy but also a novel strategy by constructing dual carrier-transfer channels on semiconductor photosensitizers for improving the therapeutic effect of photodynamic therapy.

Atomic defects (vacancy, substitutional, and Stone-Wales) in monolayer aluminum nitride: a density-functional-theory simulation

Abstract Aluminum nitride (AlN) is a mechanically strong material with a high melting point and excellent thermal conductivity. In this study, the AlN is modeled with defects in vacancies, substitutions, and Stone-Wales using a density functional theory (DFT). We model six configurations, two configurations of monovacancies: aluminum vacancy (VAl) and vacancy nitrogen (VN), two configurations of substitutions: aluminum substitution (SN→Al) and nitrogen substitution (SAl→N), the interchange (IAl↔N), and Stone-Wales (S–W). We find structural changes in each defect with outward relaxation and VN with inward relaxation. the band structure calculations show that the geometric structure introduces new states near the Fermi level except for the VAl system.

Metal nitrides as electrocatalysts in green ammonia synthesis

Green ammonia is assumed to be an important part of the European hydrogen economy and one of the most important substrates of chemical industry. The future development of its manufacturing processes can be related to the electrocatalytic studies yielding in the development of the catalytic materials that would effectively break the nitrogen-nitrogen bond to successfully drive the N2RR—a process of molecular nitrogen electroreduction to ammonia. Molecular nitrogen is characterized with strong triple bond energies (942 kJ/mol) which leading into large dissociation energy of N2 (9,76 eV) and also large energy barrier of the first step of triple bond dissociation 410 kJ/mol (4,25 eV). Those large energies makes reduction to ammonia an extremely difficult task. Metal nitrides of d and f block became in interest due to their activity in ammonia production from molecular nitrogen and hydrogen. Practically all the transition elements occurs in one of the four types of crystalline structures: regular, regular face cantered, hexagonal and hexagonal close packed. The reactions of these metals with nitrogen (or ammonia) typically yields in nitride compounds of an identical type of crystalline structure as the initial metal. Dealing with single metal systems, their ternary counterparts and metal–metal nitride heterostructures, the presented review shows that nitrides are promising groups of electrocatalytic materials. Being property-prone to their internal structural features such as non-stoichiometry and correlated concentration of nitrogen vacancies, metal nitrides are a good candidate for joined investigations spanned between electrochemistry, inorganic chemistry and material engineering.

Rapid Detection of Explicit Volatile Organic Compounds for Early Diagnosis of Lung Cancer Using MoSi2N4 Monolayer.

In this study, we investigate the adsorption of MoSi2N4) and MoSi2N4-VNtowards five potential lung cancer volatile organic compounds (VOCs).Density functional theory calculations reveal that MoSi2N4 weakly adsorb the mentioned VOCs, whereas introduction of nitrogen vacancies significantly enhances the adsorption energies ([[EQUATION]]), both in gas phase and aqueous medium. The MoSi2N4-VN monolayers exhibit a reduced bandgap and facilitate charge transfer upon VOCs adsorption, resulting in enhanced [[EQUATION]] values of -0.83, -0.76, -0.49, -0.61, and -0.50 eV for 2,3,4-trimethyl hexane, 4-methyl octane, o-toluidine, Aniline, and Ethylbenzene, respectively. Bader charge analysis and spin-polarized density of states (SPDOS) elucidate the charge redistribution and hybridization between MoSi2N4-VN and the adsorbed VOCs. The work function of MoSi2N4-VN is significantly reduced upon VOCs adsorption due to induced dipole moments, enabling smooth charge transfer and selective VOCs sensing. Notably, MoSi2N4-VN monolayers exhibit sensor responses ranging from 16.2% to 26.6% towards the VOCs, with discernible selectivity. Importantly, the recovery times of the VOCs desorption is minimal, reinforcing the suitability of MoSi2N4-VN as a rapid, and reusable biosensor platform for efficient detection of lung cancer biomarkers. Thermodynamic analysis based on Langmuir adsorption model shows improved adsorption and detection capabilities MoSi2N4-VN under diverse operating conditions of temperatures and pressures.

Efficient photocatalytic CO2 and Cr(VI) reduction on carbon spheres/g-C3N4 composites with enriched nitrogen vacancies

In this study, carbon spheres (CS)/g-C3N4 composite materials were fabricated by a hydrothermal method, and the characterizations have confirmed the successful anchoring of CS onto the surface of g-C3N4, constructing enriched nitrogen vacancies during the synthesis process. The photocatalytic CO2 reduction activity of g-C3N4 is enhanced by all of these advantageous factors. The significant enhancement can be attributed to the tight interfacial interaction between CS and g-C3N4, which endows with the photocatalyst a larger specific surface area, higher light utilization efficiency and stronger capability for photoinduced charges separation. Furthermore, the presence of nitrogen vacancies further accelerates the separation and migration efficiency of photogenerated charges, provides additional active sites to promote the adsorption and activation of CO2 molecules, thereby effectively boosting the photocatalytic activity for CO2 reduction. The CO2 conversion rate on CS/g-C3N4 composite materials is higher than that on the reference g-C3N4. The apparent quantum yield (AQY) is also superior to that of the reference g-C3N4 under three different monochromatic light irradiations. The stability of the catalyst was verified through cycling experiments, indicating promising potential practical industrial application. The CO2 reduction mechanism and transformation pathways were elucidated using in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The photocatalytic reduction rate constant of Cr(VI) by 50CS/CN is 2.9 times higher than that by CN. This study introduces a facile approach for synthesizing g-C3N4-based photocatalytic materials, providing an interesting strategy to boost photocatalytic activity of g-C3N4 for photocatalytic CO2 and Cr(VI) reduction.

Engineering nitrogen vacancies and cyano groups into C3N4 nanosheets for highly efficient photocatalytic H2O2 production

Thermal oxidation of bulky carbon nitride (C3N4, CN) to expose more active sites is an important method to improve the activity of the as-prepared CN nanosheets. Unfortunately, the yield of thermal oxidation is low. Herein, we report dual-deficient CN (DDCN) ultrathin nanosheets engineered with nitrogen vacancies and cyano groups by two-step bottom-up thermal polymerization of belt-like melamine with a high yield of 65%. Featured with abundant exposed active sites, short charge migration distance, wide visible-light absorption, quick charge separation/transfer, enhanced oxygen adsorption ability and 2e oxygen reduction reaction selectivity, the DDCN exhibits a high H2O2 production rate of ∼1031 μmol g1 h1, which is 19.5 times that of CN (53 μmol g1 h1) under visible light irradiation (λ ≥ 420nm). Specifically, the apparent quantum yield (AQY) of DDCN reached 10.7% at 420nm. This study provides a facile dual-defect engineering method to develop highly efficient ultrathin CN-based photocatalysts.

Iron single atoms and nitrogen vacancies on graphitic carbon nitride synergically shallowing deep electron traps towards efficient photocatalytic ozonation

The coupling of photocatalysis and ozonation has been approved a very efficient strategy for hydroxyl radicals (•OH) production and wastewater decontamination, yet it remains challenging to enrich surface-reaching charges around reaction centers to accelerate this process. This paper explored the strategy of single-atoms (SAs) modification and defects control, aiming to enhance the activity of graphite carbon nitride (CN) in the visible light photocatalytic ozonation. It was found that the presence of iron SAs on CN greatly altered the impact of nitrogen vacancies (NVs), which behaved as recombination centers of photogenerated charge carriers and deteriorated activity of CN, while positively promoting the separation and migration of photogenerated carriers in the case for Fe-CNV (consist of iron SAs and NVs) catalysts. Based on photoluminescence (PL) emission, time-resolved PL spectra, ultrafast transient absorption spectroscopy and first-principles calculations, we found that adjacent iron SAs revived electrons trapped at NVs by elevating their energy level and mediating their interfacial transfer, leading to the decreased loss during electron transfer. This finding demonstrates the feasible tailor of energy level alignment for defect states to shallow deep electron traps.

Engineering Carrier Density and Effective Mass of Plasmonic TiN Films by Tailoring Nitrogen Vacancies.

The introduction of nitrogen vacancies has been shown to be an effective way to tune the plasmonic properties of refractory titanium nitrides. However, its underlying mechanism remains debated due to the lack of high-quality single-crystalline samples and a deep understanding of electronic properties. Here, a series of epitaxial titanium nitride films with varying nitrogen vacancy concentrations (TiNx) were synthesized. Spectroscopic ellipsometry measurements revealed that the plasmon energy could be tuned from 2.64 eV in stoichiometric TiN to 3.38 eV in substoichiometric TiNx. Our comprehensive analysis of electrical and plasmonic properties showed that both the increased electronic states around the Fermi level and the decreased carrier effective mass due to the modified electronic band structures are responsible for tuning the plasmonic properties of TiNx. Our findings offer a deeper understanding of the tunable plasmonic properties in epitaxial TiNx films and are beneficial for the development of nitride plasmonic devices.

Hydrogen bond-induced supramolecular self-assembly strategy to fabricate ultra-dispersed Cu-loaded porous tubular graphitic carbon nitride with rich nitrogen vacancies and CuNx sites for efficient photo-Fenton catalysis

The low utilization of visible light and easy recombination of charge carriers of graphitic carbon nitride (CN) restrain its application as photo-electron donor and metal site support in photo-Fenton system. Herein, a hydrogen bond-induced supramolecular self-assembly strategy was created to fabricate an ultra-dispersed Cu-loaded porous tubular CN composite (CA-Cu/TCN) by the hydrothermal–pyrolysis method with citric acid (CA) as initiator and chelating agent. CA-Cu/TCN with rich nitrogen vacancies (NVs) and abundant ultra-dispersed CuNx sites exhibited narrow bandgap, favorable visible light absorption capability, and high separation and transfer efficiency of charge carriers. CA-Cu/TCN effectively catalyzed the activation of H2O2 for generating abundant reactive oxygen species under visible light irradiation, contributing to efficient degradation of ciprofloxacin (CIP) with removal rate of 95.9 % and kinetic rate constant of 0.0948 min−1. The superior catalytic activity of CA-Cu/TCN can be ascribed to the effective transport of photogenerated electrons, high specific surface area, atomically dispersed Cu species, and enriched surface NVs. The mechanism of photo-Fenton catalytic degradation of CIP and possible degradation pathways were proposed as the dominant role of 1O2. Toxicity evaluation of CIP and intermediates indicated that the degradation of CIP was a gradual detoxification process. This work offers a novel self-assembly strategy to design and synthesize highly active and sustainable visible light-driven photo-Fenton catalysts for effectively degrading organic pollutants.