Synergy of crystallinity modulation and intercalation engineering in carbon nitride for boosted H2O2 photosynthesis.

Photosynthesis of hydrogen peroxide (H2O2) by selective oxygen reduction is a green and cost-effective alternative to the energy-intensive anthraquinone process. Although inexpensive polymeric graphitic carbon nitride (g-C3N4) exhibits the ability to produce H2O2, its disordered and amorphous structure leads to a high recombination rate of photogenerated carriers and hinders charge transfer between layers. Herein, we predict that stacked polymeric g-C3N4 with ion intercalation (K+ and I-) can improve carrier separation and transfer by multiscale computational simulations. The electronic structures of g-C3N4 were tailored and modified by intercalating K+ and I- into the layer-by-layer structures. Guided by the computational predictions, we achieved efficient solar-driven H2O2 production by employing this facile and ion-intercalated crystalline g-C3N4. An H2O2 production rate of 13.1 mM g-1 h-1 and an apparent quantum yield of 23.6% at 400 nm were obtained. The synergistic effects of crystallinity regulation and dual interstitial doping engineering triggered the formation of new light absorption centers, the establishment of rapid charge diffusion channels, and the enhancement of two-electron oxygen reduction characteristics. This work sheds light on the dual tuning of crystallinity and electronic structure and broadens the design principles of organic-conjugated polymer photocatalysts for environmental remediation and energy conservation.

Effective Interfacing of Surface Homojunctions on Chemically Identical g-C3N4 for Efficient Visible-Light Photocatalysis without Sacrificial Agents.

Developing efficient homojunctions on g-C3N4 promises metal-free photocatalysis to realize truly sustainable artificial photosynthesis. However, current designs are limited by hindered charge separation due to inevitable grain boundaries and random formation of ineffective homojunctions embedded within the photocatalyst. Here, efficient photocatalysis is driven by introducing effective surface homojunctions on chemically and structurally identical g-C3N4 through leveraging its size-dependent electronic properties. Using a top-down approach, the surface layer of bulk g-C3N4 is partially exfoliated to create sheet-like g-C3N4 nanostructures on the bulk material. This hierarchical design establishes a subtle band energy offset between the macroscopic and nanoscopic g-C3N4, generating homojunctions while maintaining the chemical and structural integrities of the original g-C3N4. The optimized g-C3N4 homojunction demonstrates superior photocatalytic degradation of antibiotic pollutants at >96% efficiency in 2 h, even in different real water samples. It achieves reaction kinetics (≈0.041 min-1) up to fourfold better than standalone materials and their physical mixture. Mechanistic studies highlight the importance of the unique design in boosting photocatalysis by effectively promoting interfacial photocarrier manipulation and utilization directly at the point-of-catalysis, without needing co-catalysts or sacrificial agents. This work presents enormous opportunities for developing advanced and green photocatalytic platforms for sustainable light-driven environmental, energy, and chemical applications.

Design of a Single-Atom In-N3-S site to Modulate Exciton Behavior in Carbon Nitride for Enhanced Photocatalytic Performance.

Rational tailoring of the local coordination environment of single atoms has demonstrated a significant impact on the electronic state and catalytic performance, but the development of catalysts beyond noble/transition metals is profoundly significant and highly desired. Herein, the main-group metal indium (In) single atom is immobilized on sulfur-doped porous carbon nitride nanosheets (In@CNS) in the form of three nitrogen atoms coordinated with one sulfur atom (In-N3-S). Both theoretical calculations and advanced characterization investigations clearly elucidated that the single-atomic In-N3-S structures on In@CNS are powerful in promoting the dissociation of excitons into more free carriers as well as the charge separation, synergistically elevating electron concentration by 2.19 times with respect to pristine CNS. Meanwhile, the loading of In single atoms on CNS is responsible for altering electronic structure and lowering the Gibbs free energy for hydrogen adsorption. Consequently, the optimized In@CNS-5.0 exhibited remarkable photocatalytic performance, remarkable water-splitting and tetracycline hydrochloride degradation. The H2 production achieved to 10.11 mmol h-1g-1 with a notable apparent quantum yield of 19.70% at 400 nm and remained at 10.40% at 420 nm. These findings open a new perspective for in-depth comprehending the effect of the main-group metal single-atom coordination environment on promoting photocatalytic performance.

Electrochemiluminescence Enhancement and Passivation Mitigation in Carbon Nitride Semiconductors via an Integrated Ternary Heterostructure Strategy.

In recent years, carbon nitride (CN) has attracted substantial attention in the field of electrochemiluminescence (ECL) applications, owing to its outstanding optical and electronic properties. However, the passivation of CN during the ECL process has contributed to reduced stability and poor repeatability. While some studies have tried to boost ECL performance by altering CN through doping and vacancies, effectively suppressing CN passivation at high potentials continues to be challenge. In this study, the built-in electric field and the Schottky barrier effect is used to expedite the transfer of electrons from CN to the molybdenum disulfide (MoS2) conduction band. This transfer deterred excessive electron injection into the CN band, thus mitigating its electrochemical degradation. Moreover, by introducing nickel nanoparticles (Ni NPs) as catalytic active sites, it is facilitated that the decomposition of potassium persulfate (K2S2O8), thereby enhancing both the stability and intensity of ECL emission. In the end, the application of ternary heterostructure as sensing platform for the cancer biomarker carcinoembryonic antigen (CEA) demonstrated high sensitivity. This research introduces a novel approach to overcome CN passivation, paving the way for more promising applications of CN in energy, environmental, and biosensing fields.

Unravelling the Photoelectrochemical Water Splitting of Nanometer-Thick Carbon Nitride Layer.

Matching the thickness of the graphitic carbon nitride (CN) nanolayer with the charge diffusion length is expected to compensate for the poor intrinsic conductivity and charge recombination in CN for photoelectrochemical cells (PEC). Herein, the compact CN nanolayer with tunable thickness is in situ coated on carbon fibers. The compact packing along with good contact with the substrate improves the electron transport and alleviates the charge recombination. The PEC investigation shows CN nanolayer of 93 nm-thick yields an optimum photocurrent of 116 µA cm-2 at 1.23 V versus RHE, comparable to most micrometer-thick CN layers, with a low onset potential of 0.2 V in 1 m KOH under 1 sun illumination. This optimum performance suggests the electron diffusion length matches with the thickness of the CN nanolayer. Further deposition of NiFe-layered double hydroxide enhanced the surface water oxidation kinetics, delivering an improved photocurrent of 210 µA cm-2 with IPCE of 12.8% at 400 nm. The CN nanolayer also shows extended potential in PEC organic synthesis. This work experimentally reveals the PEC behavior of the nanometer-thick CN layer, providing new insights into CN in the application of energy and environment-related fields.

Photoreduction of Aqueous Protons Coupling with Alcohol Oxidation on a S-Scheme Heterojunction Photocatalyst MnO/Carbon Nitride.

Crystalline carbon nitride (CCN), derived from amorphous polymeric CN, is considered as a new generation of metal-free photocatalyst because of its high crystallinity. In order to further promote the photocatalytic performance of CCN, p-type MnO nanoparticles are in situ synthesized and merged with n-type CCN through a one-pot process to form p-n heterojunction. The formed interfacial electric field between the semiconductors with different work functions efficiently breaks the coulomb interaction between MnO and CCN. The prepared catalysts exhibit drastically increased photocatalytic hydrogen evolution (PHE) activity integrated with oxidation of alkyl and aryl alcohols under irradiation of visible light. In the aqueous solution of benzyl alcohol (BzOH), the hydrogen generation rate over MnO/CCN (39.58 µmol h-1) is nearly 7 times and 37 times that of pure CCN (5.76 µmol h-1) and CN (1.06 µmol h-1), respectively, combining with oxidation of BzOH to benzaldehyde. This work proposes an avenue for in situ construction of a novel 2D material-based S-scheme heterojunction and extends its application in solar energy conservation and utilization.

Tailoring C─N Containing Compounds into Carbon Nanomaterials with Tunable Morphologies for Electrocatalytic Applications.

Carbon materials with unique sp2 -hybridization are extensively researched for catalytic applications due to their excellent conductivity and tunable physicochemical properties. However, the development of economic approaches to tailoring carbon materials into desired morphologies remains a challenge. Herein, a convenient "bottom-up" strategy by pyrolysis of graphitic carbon nitride (g-C3 N4 ) (or other carbon/nitrogen (C, N)-enriched compounds) together with selected metal salts and molecules is reported for the construction of different carbon-based catalysts with tunable morphologies, including carbon nano-balls, carbon nanotubes, nitrogen/sulfur (S, N) doped-carbon nanosheets, and single-atom catalysts, supported by carbon layers. The catalysts are systematically investigated through various microscopic, spectroscopic, and diffraction methods and they demonstrate promising and broad applications in electrocatalysis such as in the oxygen reduction reaction and water splitting. Mechanistic monitoring of the synthesis process through online thermogravimetric-gas chromatography-mass spectrometry measurements indicates that the release of C─N-related moieties, such as dicyan, plays a key role in the growth of carbon products. This enables to successfully predict other widely available precursor compounds beyond g-C3 N4 such as caffeine, melamine, and urea. This work develops a novel and economic strategy to generate morphologically diverse carbon-based catalysts and provides new, essential insights into the growth mechanism of carbon nanomaterials syntheses.

Construction of Embedded Sulfur-Doped g-C3N4/BiOBr S-Scheme Heterojunction for Highly Efficient Visible Light Photocatalytic Degradation of Organic Compound Rhodamine B.

Constructing S-scheme heterojunction catalysts is a key challenge in visible-light catalysed degradation of organic pollutants. Most heterojunction materials are reported to face significant obstacles in the separation of photogenerated electron-hole pairs owing to differences in the material size and energy barriers. In this study, sulfur-doped g-C3N4 oxidative-type semiconductor materials are synthesized and then coupled with BiOBr reductive-type semiconductor to form S-g-C3N4/BiOBr S-scheme heterojunction. A strong and efficient internal electric field is established between the two materials, facilitating the separation of photogenerated electron-hole pairs. Notably, in situ XPS proved that after visible light irradiation, Bi3+ is converted into Bi(3+ɑ)+, and a large number of photogenerated holes are produced on the surface of BiOBr, which oxidized and activated H2O into •OH.  â€¢OH cooperated with •O2 - and 1O2 to attack Rhodamine B (RhB) molecules to achieve deep oxidation mineralization. The composite material is designed with a LUMO energy level higher than that of RhB, promoting the sensitization of RhB by injecting photogenerated electrons into the heterojunction, thereby enhancing the photocatalytic performance to 22.44 times that of pure g-C3N4. This study provides a new perspective on the efficient degradation of organic molecules using visible light catalysis.

Strong Interfacial Chemical Bonding in Regulating Electron Transfer and Stabilizing Catalytic Sites in a Metal-Semiconductor Schottky Junction for Enhanced Photocatalysis.

The weak electronic interaction at metal-photocatalyst heterointerfaces often compromises solar-to-fuel performance. Here, a trifunctional Schottky junction, involving chemically stabilized ultrafine platinum nanoparticles (Pt NPs, ≈3 nm in diameter) on graphitic carbon nitride nanosheets (CNs) is proposed. The Pt-CN electronic interaction induces a 1.5% lattice compressive strain in Pt NPs and maintains their ultrafine size, effectively preventing their aggregation during photocatalytic reactions. Density functional theory calculations further demonstrate a significant reduction in the Schottky barrier at the chemically bonded CN-Pt heterointerface, facilitating efficient interfacial electron transfer, as supported by femtosecond transient absorption spectra (fs-TAS) measurements. The combined effects of lattice strain, stabilized Pt NPs, and efficient interfacial charge transport collaboratively enhance the photocatalytic performance, leading to over an 11-fold enhancement in visible light H2 production (8.52 mmol g-1 h-1) compared to the CN nanosheets with the in situ photo-deposited Pt NPs (0.76 mmol g-1 h-1). This study highlights the effectiveness of strong metal-semiconductor electronic interactions and underscores the potential for developing high-efficiency photocatalysts.

In-Plane Palladium and Interplanar Copper Dual Single-Atom Catalyst in Bulk-Like Carbon Nitride for Cascade CO2 Photoreduction.

Dual single-atom catalysts (DSACs) are promising for breaking the scaling relationships and ensuring synergistic effects compared with conventional single-atom catalysts (SACs). Nevertheless, precise synthesis and optimization of DSACs with specific locations and functions remain challenging. Herein, dual single-atoms are specifically incorporated into the layer-stacked bulk-like carbon nitride, featuring in-plane three-coordinated Pd and interplanar four-coordinated Cu (Pd1-Cu1/b-CN) atomic sites, from both experimental results and DFT simulations. Using femtosecond time-resolved transient absorption (fs-TA) spectroscopy, it is found that the in-plane Pd features a charge decay lifetime of 95.6 ps which is much longer than that of the interplanar Cu (3.07 ps). This finding indicates that the in-plane Pd can provide electrons for the reaction as the catalytically active site in both structurally and dynamically favorable manners. Such a well-defined bi-functional cascade system ensures a 3.47-fold increase in CO yield compared to that of bulk-like CN (b-CN), while also exceeding the effects of single Pd1/b-CN and Cu1/b-CN sites. Furthermore, DFT calculations reveal that the inherent transformation from s-p coupling to d-p hybridization between the Pd site and CO2 molecule occurs during the initial CO2 adsorption and hydrogenation processes and stimulates the preferred CO2-to-CO reaction pathway.

Partial Thermal Condensation Mediated Synthesis of High-Density Nickel Single Atom Sites on Carbon Nitride for Selective Photooxidation of Methane into Methanol.

Direct selective transformation of greenhouse methane (CH4) to liquid oxygenates (methanol) can substitute energy-intensive two-step (reforming/Fischer-Tropsch) synthesis while creating environmental benefits. The development of inexpensive, selective, and robust catalysts that enable room temperature conversion will decide the future of this technology. Single-atom catalysts (SACs) with isolated active centers embedded in support have displayed significant promises in catalysis to drive challenging reactions. Herein, high-density Ni single atoms are developed and stabilized on carbon nitride (NiCN) via thermal condensation of preorganized Ni-coordinated melem units. The physicochemical characterization of NiCN with various analytical techniques including HAADF-STEM and X-ray absorption fine structure (XAFS) validate the successful formation of Ni single atoms coordinated to the heptazine-constituted CN network. The presence of uniform catalytic sites improved visible absorption and carrier separation in densely populated NiCN SAC resulting in 100% selective photoconversion of (CH4) to methanol using H2O2 as an oxidant. The superior catalytic activity can be attributed to the generation of high oxidation (NiIII═O) sites and selective C─H bond cleavage to generate •CH3 radicals on Ni centers, which can combine with •OH radicals to generate CH3OH.

Engineering of Graphitic Carbon Nitride (g-C3N4) Based Photocatalysts for Atmospheric Protection: Modification Strategies, Recent Progress, and Application Challenges.

Graphitic carbon nitride (g-C3N4) is a prominent photocatalyst that has attracted substantial interest in the field of photocatalytic environmental remediation due to the low cost of fabrication, robust chemical structure, adaptable and tunable energy bandgaps, superior photoelectrochemical properties, cost-effective feedstocks, and distinctive framework. Nonetheless, the practical application of bulk g-C3N4 in the photocatalysis field is limited by the fast recombination of photogenerated e--h+ pairs, insufficient surface-active sites, and restricted redox capacity. Consequently, a great deal of research has been devoted to solving these scientific challenges for large-scale applications. This review concisely presents the latest advancements in g-C3N4-based photocatalyst modification strategies, and offers a comprehensive analysis of the benefits and preparation techniques for each strategy. It aims to articulate the complex relationship between theory, microstructure, and activities of g-C3N4-based photocatalysts for atmospheric protection. Finally, both the challenges and opportunities for the development of g-C3N4-based photocatalysts are highlighted. It is highly believed that this special review will provide new insight into the synthesis, modification, and broadening of g-C3N4-based photocatalysts for atmospheric protection.

Synergistic Modulation of π-π* and n-π* Transitions by In Situ Phenol-Like Structure Integration for Efficiently Wide-Spectrum Hydrogen Production of Ultrathin Carbon Nitride.

2D carbon nitride nanosheets, exemplified by g-C3N4, offers significant structural benefits and enhanced photocatalytic activity. Nonetheless, the quantum confinement effect prevalent in nanoscale photocatalysts would result in an enlarged bandgap, potentially restricting the spectral absorption range and impeding improvements in photocatalytic efficiency. Here, a high-performance 2D photocatalyst with an extended spectral response is achieved by incorporating a novel phenol-like structure into the conjugated framework of ultrathin g-C3N4 nanosheet. This novel strategy features targeted pyrimidine doping to create a conjugated carbon zone in heptazine structure, offering a thermodynamically favorable pathway for hydroxyl functionalization during the annealing exfoliation process. Consequently, the π-π* transition energy in the material is significantly decreased, and the active lone pair electrons in phenol-like structure induces a new n-π* transition with notably enhanced absorption from 500 to 650 nm. The optimized material shows a dramatic enhancement in photocatalytic activity, achieving ≈72 times than the activity of bulk g-C3N4, and demonstrating a measurable H2 production rate of 6.57 µmol g-1 h-1 under 650 nm light. This study represents a significant step forward in the strategic design of 2D photocatalysts, with tailored electronic structures that significantly boost light absorption and photocatalytic efficiency.

Intramolecular Quaternary Carbon Nitride Homojunction for Enhanced Visible Light Hydrogen Production.

In this work, an intramolecular carbon nitride (CN)-based quaternary homojunction functionalized with pyridine rings is prepared via an in situ alkali-assisted copolymerization strategy of bulk CN and 2-aminopyridine for efficient visible light hydrogen generation. In the obtained structure, triazine-based CN (TCN), heptazine-based CN (HCN), pyridine unit incorporated TCN, and pyridine ring inserted HCN constitute a special multicomponent system and form a built-in electric field between the crystalline semiconductors by the arrangement of energy band levels. The electron-withdrawing function of the conjugated heterocycle can trigger the skeleton delocalization and edge induction effect. Highly accelerated photoelectron-hole transfer rates via multi-stepwise charge migration pathways are achieved by the synergistic effect of the functional group modification and molecular quaternary homojunction. Under the addition of 5 mg 2-aminopyridine, the resulting homojunction framework exhibits a significantly improved hydrogen evolution rate of 6.64 mmol g-1 h-1 with an apparent quantum efficiency of 12.27% at 420 nm. Further, the catalyst verifies its potential commercial value since it can produce hydrogen from various real water environments. This study provides a reliable way for the rational design and fabrication of intramolecular multi-homojunction to obtain high-efficient photocatalytic reactions.

Constructing B─N─P Bonds in Ultrathin Holey g-C3N4 for Regulating the Local Chemical Environment in Photocatalytic CO2 Reduction to CO.

The lack of intrinsic active sites for photocatalytic CO2 reduction reaction (CO2RR) and fast recombination rate of charge carriers are the main obstacles to achieving high photocatalytic activity. In this work, a novel phosphorus and boron binary-doped graphitic carbon nitride, highly porous material that exhibits powerful photocatalytic CO2 reduction activity, specifically toward selective CO generation, is disclosed. The coexistence of Lewis-acidic and Lewis-basic sites plays a key role in tuning the electronic structure, promoting charge distribution, extending light-harvesting ability, and promoting dissociation of excitons into active carriers. Porosity and dual dopants create local chemical environments that activate the pyridinic nitrogen atom between the phosphorus and boron atoms on the exposed surface, enabling it to function as an active site for CO2RR. The P-N-B triad is found to lower the activation barrier for reduction of CO2 by stabilizing the COOH reaction intermediate and altering the rate-determining step. As a result, CO yield increased to 22.45 µmol g-1 h-1 under visible light irradiation, which is ≈12 times larger than that of pristine graphitic carbon nitride. This study provides insights into the mechanism of charge carrier dynamics and active site determination, contributing to the understanding of the photocatalytic CO2RR mechanism.

Mediated Peroxymonosulfate Activation at the Single Atom Fe-N3O1 Sites: Synergistic Degradation of Antibiotics by Two Non-Radical Pathways.

The activation of persulfates to degrade refractory organic pollutants is a hot issue in advanced oxidation right now. Here, it is reported that single-atom Fe-incorporated carbon nitride (Fe-CN-650) can effectively activate peroxymonosulfate (PMS) for sulfamethoxazole (SMX) removal. Through some characterization techniques and DFT calculation, it is proved that Fe single atoms in Fe-CN-650 exist mainly in the form of Fe-N3O1 coordination, and Fe-N3O1 exhibited better affinity for PMS than the traditional Fe-N4 structure. The degradation rate constant of SMX in the Fe-CN-650/PMS system reached 0.472 min-1, and 90.80% of SMX can still be effectively degraded within 10 min after five consecutive recovery cycles. The radical quenching experiment and electrochemical analysis confirm that the pollutants are mainly degraded by two non-radical pathways through 1O2 and Fe(IV)═O induced at the Fe-N3O1 sites. In addition, the intermediate products of SMX degradation in the Fe-CN-650/PMS system show toxicity attenuation or non-toxicity. This study offers valuable insights into the design of carbon-based single-atom catalysts and provides a potential remediation technology for the optimum activation of PMS to disintegrate organic pollutants.

Dual Heterojunction of Etched MIL-68(In)-NH2 Supported Heptazine-/Triazine-Based Carbon Nitride for Improved Visible-Light Nitrogen Reduction.

This work reports a dual heterojunction of etched MIL-68(In)-NH2 (MN) supported heptazine-/triazine-based carbon nitride (HTCN) via a facile hydrothermal process for photocatalytic ammonia (NH3 ) synthesis. By applying the hydrothermal treatment, MN microrods are chemically etched into hollow microtubes, and HTCN with nanorod array structures are simultaneously tightly anchored on the outside surface of the microtubes. With the addition of 9 wt% HTCN, the resulting dual heterojunction presents an enhanced photocatalytic ammonia yield rate of 5.57 mm gcat -1 h-1 with an apparent quantum efficiency of 10.89% at 420 nm. Moreover, stable ammonia generation using seawater, tap water, lake water, and turbid water in the absence of sacrificial reagents verifies the potential of the dual-heterojunction composites as a commercially viable photosystem. The obtained one-dimensional (1D) microtubes and coating of HTCN confers this unique composite with extended visible-light harvesting and accelerated charge carrier migration via a multi-stepwise charge transfer pathway. This work provides a new strategy for optimizing nitrogen (N2 )-into-ammonia conversion efficiency by designing novel dual-heterojunction catalysts.

P-N Bonds-Mediated Atomic-Level Charge-Transfer Channel Fabricated between Violet Phosphorus and Carbon Nitride Favors Charge Separation and Water Splitting.

Heterostructures are widely employed in photocatalysis to promote charge separation and photocatalytic activity. However, their benefits are limited by the linkages and contact environment at the interface. Herein, violet phosphorus quantum dots (VPQDs) and graphitic carbon nitride (g-C3N4) are employed as model materials to form VPQDs/g-C3N4 heterostructures by a simple ultrasonic pulse excitation method. The heterostructure contains strong interfacial P-N bonds that mitigate interfacial charge-separation issues. P-P bond breakage occurs in the distinctive cage-like [P9] VPQD units during longitudinal disruption, thereby exposing numerous active P sites that bond with N atoms in g-C3N4 under ultrasonic pulse excitation. The atomic-level interfacial P-N bonds of the Z-scheme VPQDs/g-C3N4 heterostructure serve as photogenerated charge-transfer channels for improved electron-hole separation efficiency. This results in excellent photocatalytic performance with a hydrogen evolution rate of 7.70 mmol g-1 h-1 (over 9.2 and 8.5 times greater than those of pure g-C3N4 and VPQDs, respectively) and apparent quantum yield of 11.68% at 400 nm. Using atomic-level chemical bonds to promote interfacial charge separation in phosphorene heterostructures is a feasible and effective design strategy for photocatalytic water-splitting materials.

Matched Redox Kinetics on Triazine-Based Carbon Nitride/Ni(OH)2 for Stoichiometric Overall Photocatalytic CO2 Conversion.

Mismatched reaction kinetics of CO2 reduction and H2O oxidation is the main obstacle limiting the overall photocatalytic CO2 conversion. Here, a molten salt strategy is used to construct tubular triazine-based carbon nitride (TCN) with more adsorption sites and stronger activation capability. Ni(OH)2 nanosheets are then grown over the TCN to trigger a proton-coupled electron transfer for a stoichiometric overall photocatalytic CO2 conversion via "3CO2 + 2H2O = CH4 + 2CO + 3O2." TCN reduces the energy barrier of H2O dissociation to promote H2O oxidation to O2 and supply sufficient protons to Ni(OH)2, whereby the CO2 conversion is accelerated due to the enhanced proton-coupled electron transfer process enabled by the sufficient proton supply from TCN. This work highlights the importance of matching the reaction kinetics of CO2 reduction and H2O oxidation by proton-coupled electron transfer on stoichiometric overall photocatalytic CO2 conversion.

Unraveling the Synergistic Mechanism of Boosted Photocatalytic H2O2 Production over Cyano-g-C3N4/In2S3/Ppy Heterostructure and Enhanced Photocatalysis-Self-Fenton Degradation Performance.

In this work, cyano contained g-C3N4 comodified by In2S3 and polypyrrole (C≡N─CN/IS/Ppy) materials are synthesized for the photocatalytic production of H2O2 and photocatalysis-self-Fenton reaction for highly efficient degradation of metronidazole. The results from UV-vis spectrophotometry, surface photovoltage, and Kelvin probe measurements reveal the promoted transport and separation efficiency of photoinduced charges after the introduction of In2S3 and Ppy in the heterojunction. The existence of a built-in electric field accelerates the photoinduced charge separation and preserves the stronger oxidation ability of holes at the valence band of C≡N─CN. Linear sweep voltammetry measurements, zeta potential analyzations, nitroblue tetrazolium determination, and other measurements show that Ppy improves the conversion ratio of •O2 - to H2O2 and the utilization ratio of •O2 -, as well as suppresses decomposition of H2O2. Accordingly, the H2O2 evolution rate produced via a two-step single-electron reduction reaction reaches almost 895 µmol L-1 h-1, a value 80% and 7.2-fold higher than those obtained with C≡N─CN/IS and C≡N─CN, respectively. The metronidazole removal rate obtained via photocatalysis-self-Fenton reaction attains 83.7% within 120 minutes, a value much higher than that recorded by the traditional Fenton method. Overall, the proposed synthesis materials and route look promising for the H2O2 production and organic pollutants degradation.