Polymeric Carbon Nitride Research Articles

Charge transfer between layers of polymeric carbon nitride driven by surface grafting phosphotungstic polyanions toward efficient photocatalytic hydrogen evolution

It is a challenging issue to achieve efficient charge transfer between layers for the layered polymer photocatalysts, because the photogenerated carriers would prefer random migration within layers and thus have high reverse recombination rate due to their inherent anisotropy and high exciton binding energy. Herein, an innovative surface grafting strategy is developed to modify the layered polymeric carbon nitride (PCN) making use of phosphotungstic (PWO) polyanions. The surface coupling effect of PWO on PCN effectively improves reduction ability and utility rate of luminous energy through shifting the conduction band (CB) upward and broadening light absorption range to cover near infrared region up to 1000 nm, respectively. In especial, the strong electron-withdrawing effect of surface PWO moieties can reduce layer spacing to shorten electron transfer path and attract the photogenerated electrons transfer from PCN matrix to surface, thus conquering the charge transfer restriction between layers to improve the carrier separation efficiency. As a result, the photocatalytic hydrogen evolution (PHE) performance is dramatically enhanced. The optimal PWO-PCN-1% sample achieves an average PHE rate of 9.6 times that of PCN, stable operation for a total of 28 h on 7 cycles, and an AQY up to 22.3% at 400 nm. This contribution affords a viable modification avenue to overcome the limitation of charge transfer between layers for layered polymer photocatalysts.

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.

ON-OFF switching of Photocatalytic Hydrogen Evolution by Built-in Pt-Nitrogen-Carbon Reticular Heterojunctions.

COF engineering with a built-in, high concentration of defined N-doped sites overcomes the "black-box" of trial-and-error N-doping methods (used in polymeric carbon nitride and graphene), that hamper a directed evolution of functional carbon interfaces. Herein, an ON-OFF gated photocatalytic H2 evolution (PHE) is dictated by the Pt-NPyridine-carbon active sites and probed with a dual COF platform, based on stable β-ketoenamine connectivities made of triformylphloroglucinol (Tp) as the acceptor knots and 1,4-diaminonaphtalene (Naph) or 5,8-diaminoisoquinoline (IsoQ) as donors. Our results showcase two novel COF-Naph-Tp and COF-IsoQ-Tp featuring quasi-identical structural,spectroscopic properties and PEIS response at the surface/water interface (Rct = 16-10 ±4 KΩ), while a divergent behaviour is indeed observed for COF-IsoQ-Tp with record photoelectrochemical outputs (J = -16 μA cm-2, Rt = 3 KΩ at 0.40 V vs RHE) and two orders of magnitude higher rate of PHE (11.3 mmol g-1 h-1, λ > 400 nm, pH 5) compared to the inactive COF-Naph-Tp analogue. It turns out that PHE is regulated by the isoquinoline residues at the COF pores where emergent Pt-NPyridine-carbon functional heterojunctions are formed upon photo-deposition of Pt nanoparticles as co-catalysts, as probed by combined XPS and DFT calculations evidence.

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.

Naphthalene Monoanhydride and Perylene Composites for Efficient Photocatalytic Hydrogen Evolution and Metal-Free Heterogeneous Oxidative Amidation.

This study explores the synthesis of two visible light active organic chromophore-based composites using naphthalene monoanhydride (Np) and 1,7-dibromoperylene monoanhydride diester (PMDE). These chromophores feature favorable optical and electronic properties and polyaromatic skeletons with anhydride functionalities that facilitate π-π interactions between the chromophore and polymeric carbon nitride (CN) or covalent connections of chromophores with NH2 groups of CN. Accordingly, heterogeneous chromophore-CN composite photocatalysts namely, Np/CN(c) and PMDE/CN(c) were prepared by adopting in situ calcination (c) and composites Np/CN(a) and PMDE/CN(a) were prepared by ex situ physical adsorption (a) methods. In situ prepared Np/CN(c) and PMDE/CN(c) composites exhibited H2 evolution rates (HER) of 1069 and 705 μmol h-1 g-1, respectively, which are significantly higher than ex situ Np/CN(a) and PMDE/CN(a) composites with HER of 465 and 252 μmol h-1 g-1, respectively. These rates are 10, 7, 4.8, and 2.5 times higher than the bulk-CN, indicating the potential of these composites for efficient photocatalytic H2 evolution. Surface area normalized HER enhancements were 3.8, 5.3, 6.6, and 4.2 times higher for Np/CN(c), PMDE/CN(c), Np/CN(a), and PMDE/CN(a) respectively compared to bulk-CN. These composite photocatalysts exhibited excellent stabilities under prolonged photoirradiation, with H2 evolution consistently increasing with the light exposure time. Additionally, these metal-free heterogeneous composites demonstrated efficient photocatalytic activities towards oxidative amidation of aromatic aldehydes, with up to 80% product yields, establishing the prospects of combining homogeneous and heterogeneous entities in a metal-free active material in solar energy harvesting.

Significant effect of crystallization of polymeric carbon nitride on photoconductivity and photocatalytic activity for visible-light CO 2 reduction

Significant effect of crystallization of polymeric carbon nitride on photoconductivity and photocatalytic activity for visible-light CO ₂ reduction

Natural AIEgens as Ultraviolet Sunscreens and Photosynergists for Solar Fuel Production.

Bio-nano hybrids (BNH), combining semiconductors and microorganisms, have shown great promise for effective solar-to-fuel energy conversion. However, the high-energy ultraviolet (UV) photons in the solar spectrum can cause severe photocorrosion of semiconductors and irreversible photodamage to microorganisms within BNH. Here, we developed an encapsulation strategy using natural luminogens with aggregation-induced emission characteristics (AIEgens) to construct a protective layer for BNH, effectively shielding them against high-energy UV photons. We incorporated natural berberine (BBR) into the BNH composed of Methanosarcina barkeri and polymeric carbon nitrides (CNx). The self-assembled BNH-BBR system displayed a 2.75-fold higher CH4 yield than BNH under simulated solar irradiation. Mechanism analysis revealed that BBR acted as a UV sunscreen for BNH by converting high-energy short wavelengths into low-energy long wavelengths, thereby reducing the accumulation of reactive oxygen species and alleviating the photocorrosion of CNx. Furthermore, BBR functioned as a photosynergist for BNH by regulating photoelectron production and utilization, enhancing the intracellular energy formation in M. barkeri for growth and metabolism. This work provides important insights into the effective and scalable conversion of CO2 into valuable biofuels with BNH under light illumination containing high-energy photons.

Building Asymmetric Zn-N3 Bridge between 2D Photocatalyst and Co-catalyst for Directed Charge Transfer toward Efficient H2O2 Synthesis.

Two-dimensional (2D) polymeric semiconductors are a class of promising photocatalysts; however, it remains challenging to facilitate their interlayer charge transfer for suppressed in-plane charge recombination and thus improved quantum efficiency. Although some strategies, such as π-π stacking and van der Waals interaction, have been developed so far, directed interlayer charge transfer still cannot be achieved. Herein, we report a strategy of forming asymmetric Zn-N3 units that can bridge nitrogen (N)-doped carbon layers with polymeric carbon nitride nanosheets (C3N4-Zn-N(C)) to address this challenge. The symmetry-breaking Zn-N3 moiety, which has an asymmetric local charge distribution, enables directed interfacial charge transfer between the C3N4 photocatalyst and the N-doped carbon co-catalyst. As evidenced by femtosecond transient absorption spectroscopy, charge separation can be significantly enhanced by the interfacial asymmetric Zn-N3 bonding bridges. As a result, the designed C3N4-Zn-N(C) catalyst exhibits dramatically enhanced H2O2 photosynthesis activity, outperforming most of the reported C3N4-based catalysts. This work highlights the importance of tailoring interfacial chemical bonding channels in polymeric photocatalysts at the molecular level to achieve effective spatial charge separation.

Building Asymmetric Zn–N3 Bridge between 2D Photocatalyst and Co‐catalyst for Directed Charge Transfer toward Efficient H2O2 Synthesis

Two‐dimensional (2D) polymeric semiconductors are a class of promising photocatalysts; however, it remains challenging to facilitate their interlayer charge transfer for suppressed in‐plane charge recombination and thus improved quantum efficiency. Although some strategies, such as π‐π stacking and van der Waals interaction, have been developed so far, directed interlayer charge transfer still cannot be achieved. Herein, we report a strategy of forming asymmetric Zn–N3 units that can bridge nitrogen (N)‐doped carbon layers with polymeric carbon nitride nanosheets (C3N4‐Zn‐N(C)) to address this challenge. The symmetry‐breaking Zn–N3 moiety, which has an asymmetric local charge distribution, enables directed interfacial charge transfer between the C3N4 photocatalyst and the N‐doped carbon co‐catalyst. As evidenced by femtosecond transient absorption spectroscopy, charge separation can be significantly enhanced by the interfacial asymmetric Zn–N3 bonding bridges. As a result, the designed C3N4‐Zn‐N(C) catalyst exhibits dramatically enhanced H2O2 photosynthesis activity, outperforming most of the reported C3N4‐based catalysts. This work highlights the importance of tailoring interfacial chemical bonding channels in polymeric photocatalysts at the molecular level to achieve effective spatial charge separation.

In‐situ Monitoring of Photocatalysis on Polymeric Carbon Nitride Thin Films

Polymeric carbon nitride has attracted significant interest in heterogeneous photocatalysis due to its activity under visible‐light irradiation. Herein, we report on using carbon nitride‐coated NMR tubes for in‐situ studies of photocatalytic reaction mechanisms. In a first step, we exploited carbon nitride‐coated crimp vials as batch photoreactors for visible photocatalytic fluorinations of unactivated C(sp3)‐H bonds, with moderate to excellent yields and reusability over multiple cycles. Eventually, carbon nitride‐coated NMR tubes were used as a photoreactor by coupling them with optical fiber irradiation directly inside the spectrometer. This enabled us to follow the reaction with in‐situ NMR spectroscopy identifying reactive intermediates otherwise elusive in conventional analyses. The method provides advantages for the study of photocatalytic mechanisms of complex reactions and substantially reduces the need of comparative tests for depicting reaction intermediates and conversion pathways.

In-situ Monitoring of Photocatalysis on Polymeric Carbon Nitride Thin Films.

Polymeric carbon nitride has attracted significant interest in heterogeneous photocatalysis due to its activity under visible-light irradiation. Herein, we report on using carbon nitride-coated NMR tubes for in-situ studies of photocatalytic reaction mechanisms. In a first step, we exploited carbon nitride-coated crimp vials as batch photoreactors for visible photocatalytic fluorinations of unactivated C(sp3)-H bonds, with moderate to excellent yields and reusability over multiple cycles. Eventually, carbon nitride-coated NMR tubes were used as a photoreactor by coupling them with optical fiber irradiation directly inside the spectrometer. This enabled us to follow the reaction with in-situ NMR spectroscopy identifying reactive intermediates otherwise elusive in conventional analyses. The method provides advantages for the study of photocatalytic mechanisms of complex reactions and substantially reduces the need of comparative tests for depicting reaction intermediates and conversion pathways.

Alkali metal cation adsorption–induced surface polarization in polymeric carbon nitride for enhanced photocatalytic hydrogen peroxide production

Photocatalytic hydrogen peroxide (H2O2) generation on the catalyst surface from oxygen is an electron-demanding process, making the construction of an electron-rich surface highly advantageous. In this study, a localized electric field was observed on the surface of polymeric carbon nitride (g-C3N4) when alkali metal cations were adsorbed onto it. These fields effectively inhibited surface carrier recombination and extended their lifespan, thereby enhancing H2O2 production. As a result, g-C3N4 achieved a superior H2O2 yield of 2.25 mM after 1 h in a 0.25 M K+ solution, which was 2.06 times greater than that (1.09 mM) achieved in a pure solvent. Notably, the increase in photocatalytic efficiency showed a remarkable dependence on ion species. At low concentrations, H2O2 generation efficiency was in the order of Li+ < Na+ < K+ < Rb+ < Cs+. However, after optimizing the ion concentration, the highest H2O2 production was achieved in a solution containing K+ instead of Cs+. Molecular dynamics simulations and temperature-dependent photocatalysis experiments revealed that the synergistic interaction between adsorption energy and adsorption distance was crucial in governing the extent to which alkali metal cation adsorption enhanced g-C3N4 photocatalytic H2O2 production. This study provides theoretical insights for the design of materials for electron-demanding photocatalysis and aids in understanding variations in photocatalytic behavior in natural waters.

Slowing down the hot electron cooling to activate near-infrared photocatalytic activity in potassium/carbon co-doped polymeric carbon nitride

The research on hot electron cooling in photocatalysis has been neglected. Here, taking polymeric carbon nitride as an example, a potassium/carbon (K/C) co-doping strategy is proposed to slow down hot electron cooling. The K/C co-doping reduces the specific arrangement and overlap of electronic band structures, and decreases the degeneracy of conduction band energy levels, thus exciting phonon bottleneck effect to effectively suppress the relaxation of hot electrons by reducing the interaction between hot electrons and phonons. Our work benefits to improve the efficiency of photocatalytic energy conversion.

Efficient photocatalytic CO2 and Cr(VI) reduction on carbon quantum dots/carbon nitride heterojunctions

Carbon quantum dots (CQDs), known for their exceptional optical properties, hold the potential to enhance light absorption, charges separation and transfer in semiconductor materials. However, using cheap medicinal materials as precursors in the field of photocatalysis to obtain CQDs has seldom concerned. In this study, we utilized biomass-derived CQDs from carbon-rich licorice powder to improve photocatalytic CO2 and Cr(VI) reduction in polymer carbon nitride (PCN). The CQDs/g-C3N4 heterojunctions were synthesized via a hydrothermal method, and the successful fabrication and integration of CQDs on g-C3N4 surfaces were confirmed through detailed characterization. The optimal sample with a licorice powder to PCN mass ratio of 0.05:1 ((50CQDs/CN) demonstrates a tripling in CO2 conversion efficiency under simulated sunlight compared to the reference PCN. Under visible light irradiation, the 50CQDs/CN also performs superior photocatalytic Cr (VI) removal efficiency, which is 2.48 times of that of the reference PCN. This significant boost is attributable to the successful construction of the CQDs/CN heterojunction and the abundance of functional groups on the CQDs surface, which provide more active sites, improve light absorption and increase charges migration rates. The stability of these new photocatalysts was confirmed through repeated photocatalytic cycles, indicating their potential for practical applications. Mechanistic studies reveal insights into the enhanced photocatalytic pathways and intermediate conversion processes. Our findings present a novel, efficient and sustainable route to fabricate g-C3N4-based photocatalysts, offering a promising strategy for further mitigate the greenhouse gas crisis and environmental pollution.

Cyano-determined mercury (II) ion selective fluorescence assay over polymeric carbon nitride

Selective response is the key index to evaluate the performance of polymeric carbon nitride (PCN)-based heavy metal ion fluorescence sensors. Herein, to explore the role of cyano groups on selectivity, four kinds of PCN, including PCN-Cl, PCN-Ac, PCN-B and PCN-K were prepared by the molten salt method of sodium chloride and sodium acetate, the reduction method of sodium borohydride and the etching method of potassium hydroxide, respectively. These PCNs exhibited different surface cyano characteristics, but all of them had significant blue emission under ultraviolet excitation. It is proved that the assistant of sodium chloride or potassium hydroxide is an effective method to prepare PCNs with abundant surface cyano group. A series of fluorescence quenching experiments of metal ions showed that the cyano-rich degree of PCN is closely related to its selective response to mercury (II) ions. PCN-Cl and PCN-K emerged good selective quenching of mercury (II) ions, which may be related to the soft acid-soft base strong interaction between mercury (II) ions and cyano groups. Both PCN-Cl and PCN-K fluorescent probes for mercury (II) ions had a linear range of 5 ∼ 50 μmol L−1, and PCN-Cl exhibited a lower detection limit of 0.38 μmol L−1. This work confirmed the selective fluorescence response of cyano-rich PCN to mercury (II) ions, proposed the mechanism of selective fluorescence quenching response of mercury (II) ions, and provided a new idea for the design of efficient and accurate PCN-based fluorescence probes.

Unveiling O2 adsorption on non-metallic active site for selective photocatalytic H2O2 production

Photocatalytic oxygen reduction reaction (ORR) offers a promising pathway for sustainable hydrogen peroxide (H2O2) production but faces challenges in developing catalysts with good ORR selectivity. Herein, we report that tailoring O2 adsorption on non-metallic active sites can optimize ORR selectivity. This concept is demonstrated on three carbon nitrides with different atomic configurations: polymeric carbon nitride (PCN), lithium-poly triazine imide (Li-PTI), and sodium-poly heptazine imide (Na-PHI). Na-PHI emerges as a strong candidate for H2O2 production due to the end-on adsorption mode and suitable adsorption strength with O2. Synthesized Na-PHI, PCN, and Li-PTI are characterized, with Na-PHI showing superior light absorption, charge carrier separation, and remarkable selectivity (92 %) for two-electron ORR. Consequently, Na-PHI achieves a high H2O2 generation rate of 3.48 mmol g−1 h−1, surpassing Li-PTI and PCN by 9.2 and 33 times, respectively. This study underscores the importance of O2 adsorption on non-metallic active sites for selective photocatalytic H2O2 generation.

Reliable determination of polymeric carbon nitride wettability: A standardized sessile drop method for pressed-tablet samples

The wettability of polymeric carbon nitride (PCN) is an important surface chemical factor affecting its catalytic and separation performance. However, due to the amphipathic characteristics of hydrophilic/lipophilic and porous powder properties, the contact angle (CA) of PCN measured by the common sessile drop method will be interfered by the substrate, resulting in randomness of the results. Herein, the pristine PCNs obtained by thermal polycondensation of different precursors in air or nitrogen atmosphere were used as the wettability research object. The CA of the PCNs was measured by a modified sessile drop method after the traditional powders were replaced by pressed-tablet samples. The influence of sample mass and applied pressure on specific surface area, pore volume, surface morphology and CA of the pressed-tablet samples was investigated carefully, and the optimal experimental conditions were determined. When the sample mass was 0.15 g and the applied pressure was 10 MPa, the measured water CA of PCNs was between 27 ∼ 34°, and the diiodomethane CA is between 24 ∼ 29°. The measurement results showed considerable stability and reproducibility. This improved CA measurement method provides a simple and standardized way to accurately explore the surface chemistry of PCN, and has the potential to be applied to other hydrophilic and/or oleophilic porous powder materials.

Interfacial Engineering over Pt-Calcium Ferrite/2D Carbon Nitride Nanosheet p-n Heterojunctions for Superior Photocatalytic Properties.

The present study discloses the fabrication of efficient p-n heterojunctions using n-type polymeric bulk carbon nitride (b-CN, E g = 2.7 eV) or exfoliated nanosheets of carbon nitride (NSCN, E g = 2.9 eV) with p-type spinel ferrite CaFe2O4 (CFO, E g = 1.9 eV) for photocatalytic hydrogen generation. A series of p-n combinations were fabricated and characterized by various techniques. The oxide-carbon nitride interactions, light absorption, band alignment at the interface, and water/H3O+ adsorption capability were elucidated over heterojunctions and correlated with the photocatalytic hydrogen yield. The main developments in the present study are as follows: (1) All heterojunctions were more active than pure phases. (2) The photocatalytic activity trend validated an increase in the lifetime of charge carriers from TRPL. Pt(1 wt %)-CFO(1 wt %)/NSCN (481.5 μmol/h/g under ultraviolet (UV)-visible-simulated light, 147.5 μmol/h/g under CFL illumination for 20 h, τavg = 10.33 ns) > Pt-NSCN > Pt-CFO/b-CN > CFO/NSCN > CFO/b-CN > NSCN > Pt/b-CN > mechanical mixture (MM) of 1 wt %CFO + NSCN-MM > 1 wt %CFO + b-CN-MM > CFO > b-CN (τavg = 4.5 ns). (3) Pt-CFO/NSCN was most active and exhibited 250 times enhanced photocatalytic activity as compared to parent bulk carbon nitride, 6.5 times more active than CFO/NSCN, and twice more active than Pt-NSCN. Thus, enhanced activity is attributed to the smooth channelizing of electrons across p-n junctions. (4) NSCN evidently offered improved characteristics as a support and photocatalyst over b-CN. The exfoliated NSCN occupied a superior few-layer morphology with 0.35 nm width as compared to parent b-CN. NSCN allowed 57% dispersion of 6 nm-sized CFO, while b-CN supported 14% dispersion of 7.8 nm-sized CFO particles, as revealed by small-angle X-ray scattering spectroscopy (SAXS). Sizes of 2-4 nm were observed for Pt nanoparticles in the 1 wt %Pt/1 wt % CFO/NSCN sample. A binding energy shift and an increase in the FWHM of X-ray photoelectron spectroscopy (XPS) core level peaks established charge transfer and enhanced band bending on p-n contact in Pt-CFO/NSCN. FsTAS revealed the decay of photogenerated electrons via trapping in shallow traps (τ1, τ2) and deep traps (τ3). Lifetimes τ1 (3.19 ps, 42%) and τ2 (187 ps, 31%) were higher in NSCN than those in b-CN (τ1 = 2.2 ps, 42%, τ2 = 30 ps, 31%), which verified that the recombination reaction rate was suppressed by 6 times in NSCN (k 2 = 0.53 × 1010 s-1) as compared to b-CN (k 2 = 3.33 × 1010 s-1). Deep traps lie below the H+/H2 reduction potential; thus, electrons in deep traps are not available for photocatalytic H2 generation. (5) The role of CFO in enhancing water adsorption capability was modeled by molecular dynamics. NSCN or b-CN both showed very poor interaction with water molecules; however, the CFO cluster adsorbed H3O+ ions very strongly through the electrostatic interaction between calcium and oxygen (of H3O+). Pt also showed a strong affinity for H2O but not for H3O+. Thus, both CFO and Pt facilitated NSCN to access water molecules, and CFO further sustained the adsorption of H3O+ molecules, crucial for the photocatalytic reduction of water molecules. (6) Band potentials of CFO and NSCN aligned suitably at the interface of CFO/NSCN, resulting in a type-II band structure. Valence band offset (VBO, ΔE VB) and conduction band offset (CBO, ΔE CB) were calculated at the interface, resulting in an effective band gap of 1.41 eV (2.9 - ΔE VB = 1.9 - ΔE CB), much lower than parent compounds. The interfacial band structure was efficient in driving photogenerated electrons from the CB of CFO to the CB of NSCN and holes from the VB of NSCN to the VB of CFO, thus successfully separating charge carriers, as supported by the increased lifetime of charge carriers and favorable photocatalytic H2 yield.

In-situ Fe–O co-doped carbon nitride heterogenous catalyst for enhanced photo-Fenton oxidation performance towards recalcitrant organic pollutants

One-step and in-situ FeCl3-participated molten urea thermal polymerization strategy is designed to prepare Fe–O co-doped carbon nitride photo-Fenton catalyst (Fe/OCN). Fe/OCN exhibits remarkable photo-Fenton catalytic oxidation capacity towards recalcitrant organic pollutants, in which 0.31 wt% Fe/OCN with optimal Fe-doping level exhibits significantly 60 and 6.3 times higher pseudo-first-order kinetic constant than single photocatalysis and Fenton system in the degradation of methyl orange. The enhancement of photo-Fenton catalytic performance is mainly ascribed to the realization of ideal Fe–O and Fe–N coordination structure in the framework of polymeric carbon nitride, which can not only serve as prime sites for the adsorption of target pollutants molecules and transfer channels for directed migration of photogenerated charges, but also well-modulate electronic structure and band structure of Fe/OCN. Accordingly, the resulting boosted charge carriers separation and transfer dynamics and increased electron density around Fe active centers facilitate ≡Fe(II) regeneration and H2O2 activation, leading to the significant production of plentiful reactive species responsible for degradation and mineralization of organic pollutants. The present work provides new insight into the optimized design and precise regulation of carbon nitride-based photo-Fenton system for advanced wastewater treatment.

Cascade internal electric field dominated carbon nitride decorated with gold nanoparticles as SERS substrate for thiram assay

The development of valid chemical enhancement strategy with charge transfer (CT) for semiconductors has great scientific significance in surface-enhanced Raman scattering (SERS) technology. Herein, a phosphorus doped crystalline/amorphous polymeric carbon nitride (PCPCN) is fabricated by a facile molten salt method, and is employed as a SERS substrate for the first time. Upon the synergies of phosphatization and molten salt etching, PCPCN owns a cascaded internal electric field (IEF) due to the formation of p-n homojunction (interface-IEF) and crystalline/amorphous homojunction (bulk-IEF). The interface-IEF and bulk-IEF could effectively suppress the recombination of charge carriers and promote electron transfer between PCPCN and target methylene blue (MB), respectively. The strong CT interaction endows PCPCN substrate with superior SERS activity with an enhancement factor (EF) of 5.53 × 105. Au nanoparticles (Au NPs) are subsequently decorated on PCPCN to introduce electromagnetic enhancement for a better SERS response. The Au/PCPCN substrate allows to reliably detect trace crystal violet, as well as the thiram residue on cherry tomato. This work offers an integrated solution to enhance CT efficiency based on collaborative homojunction and internal electric field, and may inspire the design of novel semiconductor-based SERS substrates.