Highly Efficient and Chemoselective Tandem Hydroformylation-Hydrogenation of Alkenes to Alcohols over g-CN Supported Bimetallic Rh and Co Nanoparticles Catalysts.

The objective of the tandem hydroformylation-hydrogenation of alkenes to corresponding alcohols was to design an efficient and stable heterogeneous catalyst. To this end, a series of novel heterogeneous graphitic carbon nitride (g-CN) supported bimetallic Rh-Co nanoparticle catalysts (Rh-Co/g-CN) were prepared and subsequently studied for this one-pot two-step reaction. The lamellar structure makes Rh and Co nanoparticles with diameters of <1 nm and 20 nm, respectively, homogeneously deposited on the surface of g-CN layers, exhibit remarkable conversion of styrene (99.9 %) and chemoselectivity for alcohol (87.8 %). More importantly, Co nanoparticles are found to play an important role in the improvement of the chemoselectivity for alcohol due to the formation of catalytic active species [HCo(CO)y ]. Besides the detailed investigation of the catalytic properties of Rh-Co/g-CN under different reaction conditions, the reuse of Rh-Co/g-CN was conducted for five times and no evident decrease in the activity and chemoselectivity was observed. Therefore, we expect that this work could offer an initial insight into g-CN-based heterogeneous catalyst on the tandem hydroformylation-hydrogenation reaction.

Novel visible-light-active P-g-CN-based α-Bi2O3/WO3 ternary photocatalysts with a dual Z-scheme heterostructure for the efficient decomposition of refractory ultraviolet filters and environmental hormones: Benzophenones.

The ubiquitous and refractory benzophenone (BP)-type ultraviolet filters, which are also endocrine disruptors, were commonly detected in the aquatic matrix and could not be efficiently removed by conventional wastewater treatment processes, thus causing extensive concern. Herein, a novel ternary nanocomposite, P-g-CN/α-Bi2O3/WO3 (P-gBW), was successfully fabricated by mixing cocalcinated components and applied to the decomposition of BP-type ultraviolet filters. The dual-Z-scheme heterostructure of P-gBW enhances visible-light absorption, efficiently facilitates separation and mobility, and prolongs the lifetime of photoinduced charge carriers via double charge transfer mechanisms. The optimum 95 wt% P-gBW exhibited excellent photocatalytic activity, degrading 96% 4-hydroxy benzophenone (4HBP) within 150 min and 93% 2,2',4,4'-tetrahydroxybenzophenone (BP-2) within 100 min under visible-light illumination, respectively. The pseudo-first-order rate constant of 4HBP (1.15 h-1) was 6.8-, 3.1-, 3.3- and 2.2-fold higher than those of WO3, P-g-CN, α-Bi2O3, and P-g-CN/α-Bi2O3, respectively, while that of BP-2 (1.71 h-1) was 5.2-, 2.2-, 3.2- and 1.5-fold higher, respectively. The improved photocatalytic degradation was attributed to efficient photoinduced charge carrier separation and migration and prevented the recombination of electron holes, as verified by photoluminescence, transient photocurrent response, and electrochemical impedance spectroscopy. Trapping experiments, electron paramagnetic resonance, and band energy position indicated an efficient dual-Z-scheme heterostructure.

Electrochemical determination of vanillin using 2D/2D heterostructure based on ZnCr-layered double hydroxide and g-CN.

A ZnCr-LDH@g-CN composite was synthesized through a one-pot hydrothermal method to fabricate an effective sensor for detecting vanillin. The prepared material was investigated by using structural and physical studies. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) with applied potential (Epa = + 0.68 V vs Ag/AgCl) were used to examine the electrochemical behavior of vanillin. The fabricated electrode exhibited a linear detection range of 0.001-143.2 µM, a low detection limit of 0.9 nM, sensitivity of 4.72 µA µM-1 cm-2, selectivity, stability, reproducibility (RSD = 4.40%), and repeatability (RSD = 4.46%). The optimized sensor was successfully applied to detect vanillin in real samples, including ice cream, chocolate, and water, and their recovery was 98.46-99.80%. Overall, the ZnCr-LDH@g-CN composite sensor offers a promising solution for precise vanillin detection.

High-Throughput Screening of Synergistic Transition Metal Dual-Atom Catalysts for Efficient Nitrogen Fixation.

Great enthusiasm in single-atom catalysts (SACs) for the nitrogen reduction reaction (NRR) has been aroused by the discovery of metal-Nx as a promising catalytic center. However, the poor activity and low selectivity of available SACs are far away from the industrial requirement. Through the first-principles high-throughput screening, we find that Fe-Fe distributed on graphite carbon nitride (Fe2/g-CN) can manipulate the binding strength of the target reaction species (compromises the ability to adsorb N2H and NH2), therefore achieving the best NRR performance among 23 transition metal (TM) centers. Our results show that Fe2/g-CN achieves a high theoretical Faradaic efficiency of 100% and, impressively, the lowest limiting potential of -0.13 V. Particularly, multiple-level descriptors shed light on the origin of NRR activity, achieving a fast prescreening among various candidates. Our predictions not only accelerate discovery of catalysts for ammonia synthesis but also contribute to further elucidate the structure-performance correlations.

The role of supported dual-atom on graphitic carbon nitride for selective and efficient CO2electrochemical reduction.

The electrochemical reduction of CO2into value-added fuels and chemicals using single atom (SACs) or dual-atom catalysts (DACs) has been extensively studied, but the reaction mechanism and design rules are still unclear. Here, we studied the role of dual-metal atoms on graphite carbon nitride (M1M2@g-CN, M1M2 = CuCu, FeFe, RuRu, RuCu, RuFe, CuFe) for selective and efficient CO2electrochemical reduction based on density functional theory. Our results show that CO2RR on RuRu@g-CN catalyst prefers the *COOH pathway, while for CuCu@g-CN, FeFe@g-CN, RuCu@g-CN, RuFe@g-CN, CuFe@g-CN catalysts, the *OCHO pathway is more suitable. Among all the DACs combinations, we found that RuCu@g-CN and RuFe@g-CN are the most promising electrocatalysts for CO2RR with a lower limiting potential, which is attributed to the synergistic effect of different O- and C-affinity of the heterocenters in DACs. The selectivity of RuCu@g-CN and RuFe@g-CN to the production of CH4is better than that of H2evolution. In addition, we also found that the adsorption free energy of intermediate on heteroatomic DACs can be predicted by those on homoatomic DACs, which can be used to further predict the limiting potential.

Metal-Free B@g-CN: Visible/Infrared Light-Driven Single Atom Photocatalyst Enables Spontaneous Dinitrogen Reduction to Ammonia.

Conversion of naturally abundant dinitrogen (N2) to ammonia (NH3) is one of the most attractive and challenging topics in chemistry. Current studies mainly focus on electrocatalytic nitrogen reduction reaction (NRR) using metal-based electrocatalysts, while metal-free and solar-driven photocatalysts have been rarely explored. Here, on the basis of the "σ donation-π* back-donation" concept, single B atom supported on holey g-CN (B@g-CN) can serve as metal-free photocatalyst for highly efficient N2 fixation and reduction under visible and even infrared spectra. Our results reveal that N2 can be efficiently activated and reduced to NH3 with extremely low overpotential of 0.15 V and activation barrier of 0.61 eV, lower than most of metal-based NRR catalysts, thereby guaranteeing low energy cost and fast kinetics of NRR. The inherent properties of B@g-CN, such as centralized spin-polarization on the B atom, efficient prohibition of competitive hydrogen evolution reaction (HER), and reduced exciton binding energy, are responsible for the high selectivity and Faradaic efficiency for NRR under ambient conditions. Moreover, for the first time, we theoretically disclose that the external potential provided by photogenerated electrons for NRR/HER endowing B@g-CN spontaneous NRR and inaccessible HER. This work may provide a promising lead for designing efficient and robust metal-free single atom catalysts toward photocatalytic NRR under visible/infrared spectrum.

Facile synthesis of graphitic carbon-nitride supported antimony-doped tin oxide nanocomposite and its application for the adsorption of volatile organic compounds.

Antimony-doped tin oxide (ATO) nanoparticles with an average size of ~ 6 nm were prepared by co-precipitation and subsequent heat treatment. Graphitic carbon nitride (g-CN)/ATO hybrid nanocomposite was designed by the combination of thermally synthesized g-CN and ATO nanoparticles by ultrasonication. The materials were characterized using N2 adsorption/desorption (BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR). A mixture of five volatile organic compounds (VOCs, chloroform, benzene, toluene, xylene and styrene) was used to compare the adsorption capacity of the samples. The adsorption capacity of ATO nanoparticles was improved by the addition of g-CN. Experimental data showed that, among the five VOCs, chloroform was the least adsorbed, regardless of the samples. The g-CN/ATO showed nearly three times greater adsorption capacity for the VOC mixture than pure ATO. The unchanged efficiency of VOC adsorption during cyclic use demonstrated the completely reversible adsorption and desorption behavior of the nanocomposite at room conditions. This economically and environmentally friendly material can be a practical solution for outdoor and indoor VOC removal.

Reversible Hydrogen Storage Media by g-CN Monolayer Decorated with NLi4: A First-Principles Study.

A two-dimensional graphene-like carbon nitride (g-CN) monolayer decorated with the superatomic cluster NLi4 was studied for reversible hydrogen storage by first-principles calculations. Molecular dynamics simulations show that the g-CN monolayer has good thermal stability at room temperature. The NLi4 is firmly anchored on the g-CN monolayer with a binding energy of -6.35 eV. Electronic charges are transferred from the Li atoms of NLi4 to the g-CN monolayer, mainly due to the hybridization of Li(2s), C(2p), and N(2p) orbitals. Consequently, a spatial local electrostatic field is formed around NLi4, leading to polarization of the adsorbed hydrogen molecules and further enhancing the electrostatic interactions between the Li atoms and hydrogen. Each NLi4 can adsorb nine hydrogen molecules with average adsorption energies between -0.152 eV/H2 and -0.237 eV/H2. This range is within the reversible hydrogen storage energy window. Moreover, the highest achieved gravimetric capacity is up to 9.2 wt%, which is superior to the 5.5 wt% target set by the U.S. Department of Energy. This study shows that g-CN monolayers decorated with NLi4 are a good candidate for reversible hydrogen storage.

DFT study of therapeutic potential of graphitic carbon nitride as a carrier for controlled release of melphalan: an anticancer drug.

In the present research, the drug-delivery efficiency of graphitic carbon nitride (g-CN) for melphalan (an anti-cancer drug) was evaluated. To investigate the efficacy of g-CN as a drug-delivery system, the electronic properties of melphalan drug, g-CN, and g-CN-melphalan were calculated at the ground and excited states. The adsorption energy calculated for g-CN-melphalan complex in the water phase is - 1.51 eV. The interactions between g-CN and melphalan were investigated by a non-covalent interactions (NCl) analysis, which showed that there were weak interactions between g-CN and melphalan drug. These low intermolecular forces will allow for easy off-loading of the melphalan at the targeted site. Frontier molecular-orbitals (FMOs) analysis showed that the charge was transferred from melphalan to g-CN during the excitation process. Charge transfer was studied by charge decomposition analysis. Calculations at the excited state revealed that the g-CN-melphalan complex's λmax showed a redshift of 15 nm and 39 nm in the gas and water phase, respectively. The photoinduced electron transfer (PET) process was studied for 1-2 excited state by using electron hole theory. PET process suggests that fluorescence quenching may take place. The findings demonstrated that g-CN can be used as a drug-delivery system for melphalan drug to treat cancer. This investigation may also encourage more consideration of different 2D substances for drug delivery.

Visible light activation of photocatalysts formed from the heterojunction of sludge-generated TiO2 and g-CN towards NO removal.

The feasibility of preparing TiO2/g-CN heterojunction from Ti-incorporated dried dye wastewater sludge is explored in this study. Two reaction routes of composite formation were evaluated. In the initial approach, one-step calcination of dried sludge and melamine mixture @600 °C was carried out. Detailed morphological and chemical characterizations showed that the one-step calcination route did not create TiO2/g-CN composites; instead, only N-doped anatase TiO2 composites were formed. Moreover, due to the non-uniform composition of organic content in the dried sludge, it was not easy to control the N doping level by varying melamine content (0-100%) in the precursor mix. However, successful formation of anatase TiO2 and g-CN was observed when a two-step calcination route was followed, i.e., via synthesis of anatase TiO2 from dried sludge, and later development of heterojunction by calcining (@550 °C) the TiO2 and melamine mixture. X-ray diffraction along with infrared and X-ray photoelectron spectroscopy verified the effective heterojunction. In addition, maximum atmospheric NO removal under UV and visible light were observed for the prepared composite when the melamine content in the precursor mixture was 70%. After 1 h of UV and visible light irradiation, the best TiO2/g-CN composite removed 25.71% and 13.50% of NO, respectively. Optical characterization suggested that the enhanced NO oxidation under UV/visible light was due to the bandgap narrowing and diminished photogenerated electron-hole recombination.

Three-dimensional porous MoS2 nanobox embedded g-C3N4@TiO2 architecture for highly efficient photocatalytic degradation of organic pollutant.

Herein, a simple, highly efficient and stable MoS2 nanobox embedded graphitic-C3N4@TiO2 (g-CN@TiO2) nanoarchitecture was synthesized by a facile solvothermal approach. The nano-hybrid photocatalyst was constructed by TiO2 nanoparticles anchored on the surface of g-CN nanosheets. Then highly crystalline three-dimensional porous MoS2 nanobox was homogeneously distributed on the g-CN@TiO2 surface. The g-CN@TiO2/MoS2 hybrid achieved a high photocatalytic degradation efficiency of 97.5% for methylene blue (MB) dye pollutant under visible-light irradiant in an hour which was much better than TiO2@MoS2, g-CN@TiO2, MoS2, TiO2 and g-CN. Furthermore, the reaction rate (k) value of g-CN@TiO2/MoS2 for MB dye is as high as 3.18 X 10-2 min-1, which is ~ 2.65 times better than those of g-CN@TiO2 and MoS2. This work presents a rational structure design, interfacial construction and suitable band gap strategy to synthesize advanced nano-hybrid photocatalyst for degradation of organic pollutant with excellent performance and long-term stability.

Molecular engineering of carbon nitride towards photocatalytic H2 evolution and dye degradation.

The development of superior heterogeneous catalyst for hydrogen (H2) evolution is a significant feature and challenging for determining the energy and environmental crises. However, the dumping of numerous lethal colorants (dye) as of textile manufacturing has fascinated widespread devotion-aimed water pollution anticipation and treatment. In this regard, a photocatalytic H2 evolution by visible light using low-dimensional semiconducting materials having pollutant degradable capacity for Rhodamine B dyes (RhB) has been anticipated as a route towards environmental aspect. Here we fabricated the incorporation of organic electron-rich heterocyclic monomer 2,6-dimethylmorpholine (MP), inside electron-poor graphitic carbon nitride (g-CN) semiconductor by solid-state co-polymerization. The supremacy of copolymerization process was successfully examined via absorbent, calculated band gap, and migration of electrons on the photocatalytic performance of as-constructed CN-MP copolymer. The density functional theory (DFT) calculation provides extra support as evident for the successful integration of MP into the g-CN framework by this means-reduced band gap upon co-polymerization. The hydrogen evolution rate (HER) for g-CN was found as 115.2 µmol/h, whereas for CN-PM0.1was estimated at 641.2 µmol/h (six times higher). In particular, the pseudo-order kinetic constant of CN-MP0.1 for photodegradation of RhB was two times higher than that ofg-CN. Results show an important step toward tailor-designed and explain the vital role of the D-A system for the rational motifs of productive photocatalysts with effective pollutant degradable capability for future demand.

Synthesis and NOx removal performance of anatase S-TiO2/g-CN heterojunction formed from dye wastewater sludge.

In this study, sludges generated from Ti-based flocculation of dye wastewater were used to retrieve photoactive titania (S-TiO2). It was heterojunctioned with graphitic carbon nitride (g-CN) to augment photoactivity under UV/visible light irradiance. Later the as-prepared samples were utilized to remove nitrogen oxides (NOx) in the atmospheric condition through photocatalysis. Heterojunction between S-TiO2 and g-CN was prepared through facile calcination (@550 °C) of S-TiO2 and melamine mix. Advanced sample characterization was carried out and documented extensively. Successful heterojunction was confirmed from the assessment of morphological and optical attributes of the samples. Finally, the prepared samples' level of photoactivity was assessed through photooxidation of NOx under both UV and visible light irradiance. Enhanced photoactivity was observed in the prepared samples irrespective of the light types. After 1 h of UV/visible light-based photooxidation, the best sample STC4 was found to remove 15.18% and 9.16% of atmospheric NO, respectively. In STC4, the mixing ratio of S-TiO2, to melamine was maintained as 1:3. Moreover, the optical bandgap of STC4 was found as 2.65 eV, where for S-TiO2, it was 2.83 eV. Hence, the restrained rate of photogenerated charge recombination and tailored energy bandgap of the as-prepared samples were the primary factors for enhancing photoactivity.

Facile synthesis and characterization of anatase TiO2/g-CN composites for enhanced photoactivity under UV-visible spectrum.

For the purpose of atmospheric NO removal, anatase TiO2/g-CN photocatalytic composites were prepared by using a facile template-free calcination route in atmospheric conditions. Considerably fiscal NP400 and laboratory-grade melamine were used as the precursor of the composites. Additionally, samples were prepared with different wt. ratios of TiO2 and melamine by using two distinct calcination temperatures (550 °C/600 °C). The morphological attributes of the composites were assessed with X-ray diffraction, scanning and transmission electron microscopy, infrared spectroscopy, and X-ray photoelectron spectroscopy. Additionally, the optical traits were evaluated and compared using UV-visible diffuse reflectance spectroscopy and photoluminescence analysis. Finally, the photodegradation potentials for atmospheric NO by using the as-prepared composites were assessed under both UV and visible light irradiation. All the composites showed superior NO oxidation compared to NP400 and bulk g-CN. For the composites prepared by using the calcination temperature of 550 °C, the maximum NO removal was observed when the NP400 to melamine ratio was 1:2, irrespective of the utilized light irradiation type. Whereas for increased calcination temperature (600 °C), the maximum NO removal was observed at the precursor mix ratio of 1:3 (NP400:melamine). Successfully narrowed energy bandgaps were perceived in the as-prepared composites. Moreover, a subsequent drop in NO2 generation during NO oxidation was observed under both UV and visible light irradiation. Interestingly, higher calcination temperature during the synthesis of the catalysts has shown a significant drop in NO2 generation during the photodegradation of NO.

Versatile Functional Porous Cobalt-Nickel Phosphide-Carbon Cocatalyst Derived from a Metal-Organic Framework for Boosting the Photocatalytic Activity of Graphitic Carbon Nitride.

Metal-organic framework-templated g-C3N4-NiCoP2-porous carbon (PC) ternary hybrid nanomaterials were designed by taking full advantage of the metal-organic framework (MOF) derivative in the photocatalytic reaction for the first time. The MOF-templated porous structure could prevent the stacking of the carbon nitride nanosheet, and the carefully designed NiCoP2, possessing low electrocatalytic hydrogen evolution reaction (HER) overpotential and flat-band potential, could improve the separation as well as the utilization efficiency of photogenerated electron-hole pairs. Moreover, the ligand-templated porous carbon, acting as an interface mediator between g-C3N4 and the NiCoP2 cocatalyst, could boost the charge carrier transport. Consequently, the optimal ternary g-C3N4-NiCoP2-PC heterostructure exhibited enhanced photocatalytic HER performance and considerable H2 evolution performance of 5.8 µmol/h/g under UV-visible light with stoichiometric H2O2 production even in pure water. This work took full advantage of the MOF derivative for improving the photocatalytic reaction activity and provided a method that can hopefully help in designing a novel high-performance catalyst for solar conversion.

Toward Efficient Preconcentrating Photocatalysis: 3D g-C3N4 Monolith with Isotype Heterojunctions Assembled from Hybrid 1D and 2D Nanoblocks.

The macroscopic integration of the microscopic catalyst is one of the most promising strategies for photocatalytic technology in facing practical applications. However, in addition to the unsatisfactory photoactivated exciton separation, a new problem restricting the catalytic efficiency is the unmatched kinetics between the reactant diffusion and the photochemical reaction. Here, we report an isotype heterojunctional three-dimensional g-C3N4 monolith which is assembled from the hybrid building blocks of the nanowires and nanosheets. Benefiting from its hierarchically porous network and abundant heterojunctions, this catalytic system exhibits inherently promoted efficiency in light absorption and exciton separation, thus leading to a desirably improved photocatalytic performance. Furthermore, thanks to the structural and functional advantages of the constructed g-C3N4 monolith, a novel strategy of preconcentrating photocatalysis featuring the successive filtration, adsorption, and photocatalysis has been further developed, which could technically coordinate the kinetic differences and result in over-ten-time enhancement on the efficiency compared with the traditional photocatalytic system. Beyond providing new insights into the structural design and innovative application of the monolithic photocatalyst, this work may further open up novel technological revolutions in sewage treatment, air purification, microbial control, etc.

Colorimetric Immunosensor Based on Au@g-C3N4-Doped Spongelike 3D Network Cellulose Hydrogels for Detecting α-Fetoprotein.

A colorimetric immunoassay is a powerful tool for detecting tumor markers, with outstanding advantages of visualization and convenience. This study designed a colorimetric immunoassay using the antibody/antigen to control the catalytic activity to be "switched on/off". This system, where Au NPs (18.5 ± 3.9 nm) were loaded on the g-C3N4 nanosheets that were fixed in a three-dimensional porous cellulose hydrogel, was used as a binding site for the antibody/antigen. After being incubated with an antibody of a cancer marker, the turned-off catalytic sites on Au NPs in Au@g-C3N4/microcrystalline cellulose hydrogels would not be "turned on" until the corresponding antigen was added. The number of the recovered Au active sites was related to the amount of the antigen added. The Fourier transform infrared and X-ray photoelectron spectroscopy measurements did not detect the existence of Au-S bonds. Catalyzed by the turned-on Au NPs, 4-nitrophenol was reduced to 4-aminophenol accompanied by a color fading. The color and the absorption spectrum changes in the process were used as the colorimetric quantitative basis for immunoassays. The colorimetric immunoassay showed a linear relationship with the liver cancer marker (α-fetoprotein, AFP) in the range of 0.1-10 000 ng/mL with the detection limit of 0.46 ng/mL. In addition, 4-nitrophenol had a significant color fading when the AFP concentration exceeded the healthy human threshold. The clinical patient's serum test results obtained from the developed colorimetric immunosensor were consistent with those obtained from the commercial enzyme-linked immunosorbent assay. Furthermore, the immunosensor exhibited a good selectivity, repeatability, and stability, which demonstrated its potential for practical diagnostic application.

In-Situ Growing Mesoporous CuO/O-Doped g-C3N4 Nanospheres for Highly Enhanced Lithium Storage.

The development of lithium-ion batteries using transition metal oxides has recently become more attractive, due to their higher specific capacities, better rate capability, and high energy densities. Herein, the in situ growth of advanced mesoporous CuO/O-doped g-C3N4 nanospheres is carried out in a two step hydrothermal process at 180 °C and annealing in air at 300 °C. When used as an anode material, the CuO/O-doped g-C3N4 nanospheres achieve a high reversible discharge specific capacity of 738 mAhg-1 and a capacity retention of ∼75.3% after 100 cycles at a current density 100 mAg-1 compared with the pure CuO (412 mAhg-1, 47%) and O-doped g-C3N4 (66 mAhg-1, 53%). Even at high current density 1 Ag-1, they exhibit a reversible discharge specific capacity of 503 mAhg-1 and capacity retention ∼80% over 500 cycles. The excellent electrochemical performance of the CuO/O-doped g-C3N4 nanocomposite is attributed to the following factors: (I) the in situ growing CuO/O-doped g-C3N4 avoids CuO nanoparticle aggregation, leading to the improved lithium ion transfer and electrolyte penetration inside the CuO/O-doped g-C3N4 anode, thus promoting the utilization of CuO; (II) the porous structure provides efficient space for Li+ transfer during the insertion/extraction process to avoid large volume changes; (III) the O-doping g-C3N4 decreases its band gap, ensuring the increased electrical conductivity of CuO/O-doped g-C3N4; and (IV) the strong interaction between CuO and O-doped g-C3N4 ensures the stability of the structure during cycling.

Ag-Bridged Z-Scheme 2D/2D Bi5FeTi3O15/g-C3N4 Heterojunction for Enhanced Photocatalysis: Mediator-Induced Interfacial Charge Transfer and Mechanism Insights.

Heterojunction photocatalysts have attracted widespread interest in photocatalysis because of their high-efficiency interfacial charge-transfer characteristics of nanoarchitectures. In this study, Ag-bridged 2D/2D Bi5FeTi3O15/ultrathin g-C3N4 Z-scheme heterojunction photocatalysts with powerful interfacial charge transfer has been synthesized via a facile ultrasound method coupled with a photoreduction strategy for efficient photocatalytic degradation of antibiotics. The morphology analysis displays that the bridged Ag nanoparticles were anchored on the interface of layered Bi5FeTi3O15 and ultrathin g-C3N4 nanosheets. Owing to its unique 2D/2D ternary heterostructure, the Bi5FeTi3O15/2%Ag/10% ultrathin g-C3N4 composite exhibited the best tetracycline degradation performance under visible-light and simulated solar irradiation. Meanwhile, the intermediates and degradation pathways were proposed by a liquid-phase mass spectrometry system. Characterizations and density functional theory studies together verify that the matched band structure of Bi5FeTi3O15 and g-C3N4 could induce a superfast Z-scheme interfacial charge-transfer path. More importantly, bridged Ag nanoparticles in the 2D/2D heterojunction extended the light absorption range and prolonged the lifetime of photogenerated electron-holes induced by Bi5FeTi3O15. This work affords a promising approach for designing multicomponent Z-scheme heterojunction photocatalysts for highly efficient photocatalytic application.

Salt-Assisted Synthesis of 3D Porous g-C3N4 as a Bifunctional Photo- and Electrocatalyst.

Graphitic carbon nitride (g-C3N4), characterized with a suitable bandgap, has aroused great interest as a robust and efficient catalyst for solar energy utilization. Herein, we introduce a new strategy to fabricate a three-dimensional (3D) porous g-C3N4 by a facile NaCl-assisted ball-milling strategy. The porous structure-induced advantages, such as a higher specific surface area, more efficient charge separation, and faster electron-transfer efficiency, enable the 3D porous g-C3N4 to achieve impressive properties as a bifunctional catalyst for both photocatalytic hydrogen evolution and electrocatalytic oxygen evolution reaction (OER). As a result, the 3D porous g-C3N4 exhibits a hydrogen evolution rate of 598 µmol h-1 g-1 with an apparent quantum yield of 3.31% at 420 nm for photocatalytic H2 generation, which is much higher than that of the bulk g-C3N4. Simultaneously, the porous g-C3N4 also presents an attractive OER performance with a low onset potential of 1.47 V (vs reversible hydrogen electrode) in an alkaline electrolyte after rational cobalt-doping. Accordingly, the NaCl-assisted ball-milling strategy paves the way to the rational design of a controllable porous structure.