Rational construction of visible-light-driven perylene diimides/Fe2O3@C derived from MIL-88A (Fe) heterojunction with S-scheme electron transfer pathway to activate peroxymonosulfate for degradation of antibiotics.

The novel composite photocatalytic material perylene diimides/Fe2O3@C (PDIs/Fe2O3@C) was constructed by a simple hydrothermal-calcination method and an oil bath method. 20 % PDIs/Fe2O3@C displayed a 16.4-fold increase in the rate of tetracycline (TC) removal over Fe2O3@C at 8 min. The main factor that enhanced photocatalytic performance was due to the combination of PDIs with Fe2O3@C, which effectively improved the phenomenon during the self-assembly of highly agglomerative PDIs, increased the specific surface area of Fe2O3@C, exposed more reaction sites, and promoted the activation of peroxymonosulfate (PMS) by Fe2+/Fe3+; and secondly, the composite of two different materials, both organic and inorganic, which effectively promoted the photogenerated electron transfer and the separation of electron-hole pairs, the a new S-scheme electron transport pathway is formed, which effectively promoted the photogenerated electron transfer as well as the e--h+ separation, which was more favorable for the activation of PMS. The whole reaction pathway and product toxicity were thoroughly evaluated by Fukui function calculations, Liquid Chromatograph Mass Spectrometer (LC-MS), and Toxicity Estimation Software Tool (T.E.S.T.) simulation results, which demonstrated the rationality of the degradation pathway and the greatly reduced product toxicity. Moreover, the composites were effective and versatile for all other antibiotics (chlortetracycline (CTC), ciprofloxacin (CIP) and sulfadiazine (SDZ)). As an advanced oxidation process, the activation of PDIs/Fe2O3@C under visible light shows its potential application in pollutant degradation, which provides new perspectives and ideas for further effective treatment of real wastewater.

Cyano-Rich g-C3 N4 in Photochemistry: Design, Applications, and Prospects.

Cyano-rich g-C3 N4 materials are widely used in various fields of photochemistry due to the very powerful electron-absorbing ability and electron storage function of cyano, as well as its advantages in improving light absorption, adjusting the energy band structure, increasing the polarization rate and electron density in the structure, active site concentration, and promoting oxygen activation ability. Notwithstanding, there is yet a huge knowledge break in the design, preparation, detection, application, and prospect of cyano-rich g-C3 N4 . Accordingly, an overall review is arranged to substantially comprehend the research progress and position of cyano-rich g-C3 N4 materials. An overall overview of the current research position in the synthesis, characterization (determination of their location and quantity), application, and reaction mechanism analysis of cyano-rich g-C3 N4 materials to provide a quantity of novel suggestions for cyano-modified carbon nitride materials' construction is provided. In view of the prevailing challenges and outlooks of cyano-rich g-C3 N4 materials, this paper will purify the growth direction of cyano-rich g-C3 N4 , to achieve a more in-depth exploration and broaden the applications of cyano-rich g-C3 N4 .

Dual-channel fluorescent probe for discriminative detection of H2S and N2H4: Exploring sensing mechanism and real-time applications.

A highly efficient system incorporates the real-time visualization of the two toxic molecules (H2S and N2H4) and the recognition of corresponding transforms using a fluorescent sensor. In this paper, a dual-responsive probe (QS-DNP) based on methylquinolinium-salicyaldehyde-2,4-dinitrophenyl was developed that can simultaneously detect H2S and N2H4 at two independent fluorescent channels without signal crosstalk. QS-DNP showed excellent anti-interference, high selectivity, outstanding water solubility, low LOD values (H2S: 51 nM; N2H4: 40 nM), low cytotoxicity, and mitochondrial localization properties. The 2,4-dinitrophenyl site was sensitive to H2S, and the CC bridge was reactive to N2H4, with strong fluorescence at 680 and 488 nm, respectively. The wavelength gap between these two channels is 192 nm; verify that there is no signal crosstalk throughout detection. By this means, the probe was used to simultaneously detect H2S and N2H4 in real soil samples, food samples, and living cells. The endogenous H2S and N2H4 were monitored in HeLa cells and investigated the mitochondria organelle of living cells with a positive charge on QS-DNP. Overall, all results emphasize that the QS-DNP probe is a powerful tool for the simultaneous detection of H2S and N2H4 and presents a potential new sensing approach.

Synergistically Coupled Ni/CeOx@C Electrocatalysts for the Hydrogen Evolution Reaction: Remarkable Performance to Pt/C at High Current Density.

Incredibly active electrocatalysts comprising earth-abundant materials that operate as effectively as noble metal catalysts are essential for the sustainable generation of hydrogen through water splitting. However, the vast majority of active catalysts are produced via complicated synthetic processes, making scale-up considerably tricky. In this work, a facile strategy is developed to synthesize superhydrophilic Ni/CeOx nanoparticles (NPs) integrated into porous carbon (Ni/CeOx@C) by a simple two-step synthesis strategy as efficient hydrogen evolution reaction (HER) electrocatalysts in 1.0 M KOH. Benefiting from the electron transport induced by the heterogeneous interface between Ni and CeOx NPs and the superhydrophilic structure of the catalyst, the resultant Ni2Ce1@C/500 catalysts exhibit a low overpotential of 26 and 184 mV at a current density of 10 and 300 mA cm-2, respectively, for HER with a small Tafel slope of 62.03 mV dec-1 and robust durability over 300 h, and its overpotential at a high current density is much better than the benchmark commercial Pt/C. Results revealed that the electronic rearrangement between Ni and CeOx integrated into porous carbon could effectively regulate the local conductivity and charge density. In addition, the oxygen vacancies and Ni/CeOx heterointerface promote water adsorption and hydrogen intermediate dissociation into H2 molecules, which ultimately accelerate the HER reaction kinetics. Notably, the electrochemical results demonstrate that structural optimization by regulating synthesis temperature and metal concentration could improve the surface features contributing to high electrical conductivity and increase the number of electrochemically active sites on the Ni/CeOx@C heterointerface, high crystal purity, and better electrical conductivity, resulting in its exceptional electrocatalytic performance toward the HER. These results indicated that the Ni/CeOx@C electrocatalyst has the potential for practical water-splitting applications because of its controlled production strategy and outstanding Pt-like HER performance.

Recent advances in understanding and design of efficient hydrogen evolution electrocatalysts for water splitting: A comprehensive review.

An unsustainable reliance on fossil fuels is the primary cause of the vast majority of greenhouse gas emissions, which in turn lead to climate change. Green hydrogen (H2), which may be generated by electrolyzing water with renewable power sources, is a possible substitute for fossil fuels. On the other hand, the increasing intricacy of hydrogen evolution electrocatalysts that are presently being explored makes it more challenging to integrate catalytic theories, catalytic fabrication procedures, and characterization techniques. This review will initially present the thermodynamics, kinetics, and associated electrical and structural characteristics for HER electrocatalysts before highlighting design approaches for the electrocatalysts. Secondly, an in-depth discussion regarding the rational design, synthesis, mechanistic insight, and performance improvement of electrocatalysts is centered on both the intrinsic and extrinsic influences. Thirdly, the most recent technological advances in electrocatalytic water-splitting approaches are described. Finally, the difficulties and possibilities associated with generating extremely effective HER electrocatalysts for water-splitting applications are discussed.

Construction lamellar BaFe12O19/Bi3.64Mo0.36O6.55 photocatalyst for enhanced photocatalytic activity via a photo-Fenton-like Mo6+/Mo4+redox cycle.

The novel BaFe12O19/Bi3.64Mo0.36O6.55 composite materials were constructed as magnetically recyclable photo-Fenton-like degradation systems. The composite catalyst not only promoted the effective transfer of photo-generated electrons and improved the Mo6+/Mo4+ cycle consequent, but also activated hydrogen peroxide to generate oxidizing free radicals. BaFe12O19/Bi3.64Mo0.36O6.55-0.25 exhibited an outstanding degradation performance for tetracycline hydrochloride it is 1.3 times to Bi3.64Mo0.36O6.55. The thermal catalytic performance of the Bi3.64Mo0.36O6.55 monomer is similar to that of the BaFe12O19/Bi3.64Mo0.36O6.55 material without light. However, the removal rate of BaFe12O19/Bi3.64Mo0.36O6.55 material reaches 84.5% after 60 min with light, far exceeding that of Bi3.64Mo0.36O6.55 material. By way of the contrast experiment with light and without light, it is further demonstrated that interfacial interaction between BaFe12O19 and Bi3.64Mo0.36O6.55 acted a key role in the photocatalytic reaction system. It is also a good advantage that pollutants can be efficiently degraded without adjusting the pH. The characterization of photocurrent and X-ray photoelectron spectroscopy (XPS) also further proved the synergy between the two materials, which is useful to the separation of electrons and holes. The synergy ultimately improves the degradation performance. Besides, BaFe12O19/Bi3.64Mo0.36O6.55 can be easily separated by an external magnetic field after the photocatalytic activity reaction owing to BaFe12O19's magnetic properties. It provides a new research idea for the construction and iron-based heterogeneous Fenton-like system for magnetic degradation of antibiotics.

C-O band structure modified broad spectral response carbon nitride with enhanced electron density in photocatalytic peroxymonosulfate activation for bisphenol pollutants removal.

Here, a simple one-step calcination method uses glycolic acid (GA) and urea to synthesize C-O band structure modified carbon nitride with broad spectral response, which is used to construct a peroxymonosulfate/visible light (PMS/vis) system. The solid-state 13C NMR proved that C-O band structure was successfully introduced into the carbon nitride. Density functional theory (DFT) calculation show that the introduction of C-O band structure shortens the band gap of 0.05 g GA modified CN (0.05 GA-CN). Besides, Ultraviolet photoelectron spectroscopy (UPS) further illustrate that the 0.05 GA-CN has a higher charge density and promotes the degradation of pollutants. In PMS/vis system, 0.05 GA-CN can completely degrade bisphenol A (BPA) within 36 min. In addition, 0.05 GA-CN can also degrade bisphenol E (BPE) and bisphenol F (BPF). The cyclic voltammetry (CV) curve show that the introduction of C-O band structure enhances the activation ability of PMS. At the same time, 0.05 GA-CN/PMS has enhanced the activity of degrading BPA under blue light (450-462 nm), green light (510-520 nm) and red light (610-625 nm). This research provides a new method to synthesize carbon nitride with enhanced electron density for degradation of bisphenol pollutants in PMS/vis system.

A new recognition moiety diphenylborinate in the detection of pyruvate via Lewis acid/base sensing pathway and its bioimaging applications.

Developing new reaction based recognizing units can enhance the specificity of target analyte molecules in practical applications of real samples and biosystems. Therefore, introducing a recognizing moiety diphenylborinate was encountered for the detection of pyruvate biomolecule through Lewis acid-base reaction based sensing strategy. The construction of the Schiff-base back bone between quinoline and N-(diethylamino)salicylaldehyde-diphenylborinate (QSB) were expressed the red shift from blue emission of quinoline in to green as that of dative bond developed between Schiff base nitrogen and boron atoms. The new sensing approach was involved such a way that fluorophore QSB is a Lewis acid while pyruvate acts as Lewis base, where the elimination of Lewis pair produced a weak green fluorescence including the formation of quinoline, N-(diethylamino)salicylaldehyde (QS). The switching products were witnessed through 1H NMR titration, HR-MS and FT-IR studies. The good selectivity and interference ability were achieved in presence of 1000-fold excess of possible interferences with LOD of 16 nM. Moreover, the tracking ability of the probe was employed towards pyruvate in live HeLa cell imaging for evaluating an exogenous and endogenous signals producing ability and its mitochondria targeting property was investigated successfully. Further, the practical utility of the probe was tested with milk samples and obtained good recovery results.

Prostate cancer biomarker citrate detection using triaminoguanidinium carbon dots, its applications in live cells and human urine samples.

Citrate is a tricarboxylate, plays vital role in prostate cancer (PC) and the level of citrate is an indicator for PC identification. Herein, triaminoguanidine carbon dots (TAG-CDs) prepared by one step hydrothermal method and used as a citrate receptor. Notably the TAG-CDs without alkaline treatment were highly fluorescent at pH 7 with high quantum yield (11.3%). TAG-CDs were characterized through TEM, XRD, FT-IR, UV-vis and spectrofluorimetry. It is noted that the average size was of 2.8 nm, the presence of highly disordered carbon, retain the functionality of TAG. The absorbance maxima obtained at 294 nm and good emitting response observed at 396 nm. The Y-aromaticity of receptor guanidinium moiety acts as Lewis acid and have peculiar interaction with Lewis base citrate via electrostatic interaction and also protons in the TAG participate hydrogen bonds with citrate, which causes quenching of TAG-CDs. From the obtained linear quenching equation the LOD was found to be 4 nM. The probe expressed high selectivity, high interference tolerance (500 - fold), fast response in 15 mins and good biocompatible. Finally, TAG-CDs utilized for the intracellular imaging of citrate in live MCF-7 cells, it showed good cytotoxicity and delivered contrast images in presence, absence of citrate. TAG-CDs detected the citrate level in human urine samples, the obtained results are validated with HPLC method.

Silk fibroin-derived carbon aerogels embedded with copper nanoparticles for efficient electrocatalytic CO2-to-CO conversion.

Metal-carbon matrix catalyst has attracted a great deal of interest in electrochemical carbon dioxide reduction reaction (CO2RR) due to its excellent electrocatalytic performance. However, the design of highly active metal-carbon matrix catalyst towards CO2RR using natural biomass and cheap chemical precursors is still under challenge. Herein, a self-assembly strategy, along with CO2 gas as acidifying agent, to fabricate silk fibroin (SF) derived carbon aerogels (CA) combining trace copper nanoparticles (SF-Cu/CA) is developed. Zinc nitrate was introduced as a pore-forming agent to further optimize the pore structure of the as-prepared catalysts to form SF-Cu/CA-1. The rich mesoporous structure and unique constitute of SF-Cu/CA-1 is conducive to exposed numerous active sites, fast electron transfer rate, and the desorption of *CO intermediate, thus leading to the electrocatalytic CO2RR of SF-Cu/CA-1 catalyst with an excellent current density of 29.4 mA cm-2, Faraday efficiency of 83.06% towards carbon monoxide (CO), high the ratio value of CO/H2 (19.58), and a long-term stability over a 10-hour period. This performance is superior to that of SF-Cu/CA catalyst (13.0 mA cm-2, FECO=58.43%, CO/H2 = 2.16). This work not only offers a novel strategy using natural biomass and cheap chemicals to build metal-carbon matrix catalyst for electrocatalytic CO2-to-CO conversion, but also is expected to promote the industrial-scale implementations of CO2 electroreduction.

Tetraphenylethene-based fluorescent probe with aggregation-induced emission behavior for Hg2+ detection and its application.

A tetraphenylethene (TPE) derivative was designed and synthesized upon conjugation with bis(thiophen-2-ylmethyl) amine (BTA) containing a mercury-binding moiety and further characterized by using Nuclear magnetic resonance (NMR), LC-MS, UV-Vis, and fluorescence spectroscopic methods. The resulting TPE-BTA exhibited comprehensive aggregation-induced emission while expressing a high quantum yield and emission intensity at 70% water fraction. The probe exhibited a good photochromic effect with a Stokes shift of 178 nm, and the emission intensity at 550 nm increased considerably with the color turning from dark green to bright green under a UV lamp upon the addition of 5 µM Hg2+. The lowest-energy conformation of the probe showed that two thiophene rings were perpendicular to the phenyl ring, while two BTA molecules were situated in a staggered form to each other. The sulfur and nitrogen atoms present in TPE-BTA were coordinated to the Hg2+ ion, and these binding sites were confirmed by the NMR parameters, X-ray photoelectron spectroscopy signals, and structural calculations. The binding of Hg2+ to TPE-BTA was believed to restrict the intramolecular motion of TPE-BTA, thus inducing it to shine brighter according to the unique aggregation-induced emission effect. The concentration of Hg2+ was determined based on the enhancement of the emission intensity, and the present probe showed an extremely high sensitivity with a limit of detection of 10.5 nM. Furthermore, TPE-BTA enabled selective detection of Hg2+ even in the presence of a 1000-fold excess of other interfering metal ions. The proposed method was successfully employed to determine Hg2+ in living HeLa cells and real water samples.

Realizing the synergistic effect of electronic modulation over graphitic carbon nitride for highly efficient photodegradation of bisphenol A and 2-mercaptobenzothiazole: Mechanism, degradation pathway and density functional theory calculation.

Here, we successfully synthesized a brown carbon nitride (CY-C3N4) co-modified with oxygen bridge and porous defects via a universal acylation method. Excitingly, density functional theory (DFT) calculation shows that the introduction of oxygen bridges in the calcination polymerization process can adjust the electronic structure and energy band position of the new material. Further, the results of elemental analysis and X-ray photoemission spectroscopy test indicate that the oxygen bridge structure was successfully introduced into the skeleton of carbon nitride. The results show that 0.1CY-C3N4 can remove bisphenol A (BPA) and 2-mercaptobenzothiazole (MBT) with a removal rate of approximately 99% in 90 min and 20 min, respectively. Its degradation rate is 17.94 times and 3.85 times faster than that the original carbon nitride, respectively. Further, through HPLC-MS analysis, the intermediate products of the reaction process were analyzed in depth to propose a possible photocatalytic degradation route. Free radical capturing test and ESR spectroscopy indicate that the formative hydroxyl radical (OH), superoxide radical (O2-), singlet oxygen (1O2) and hole (h+) all play a key role in the photodegradation. This study provides a new way to synthesize brown carbon nitrides with oxygen bridges and porous defects for environmental applications.

An efficient broad spectrum-driven carbon and oxygen co-doped g-C3N4 for the photodegradation of endocrine disrupting: Mechanism, degradation pathway, DFT calculation and toluene selective oxidation.

In this study, a new type of carbon and oxygen co-doped g-C3N4 (PACN) was successfully synthesized by a one-step thermal polymerization method for the photodegradation of Bisphenol A (BPA) and selective oxidation of toluene to benzaldehyde. The degradation rate of BPA was 23.58 times higher than that of pristine g-C3N4 and the efficiency benzaldehyde formation rate without the need of any solvent increased to 5.43 times that of g-C3N4. At the same time, the band structure calculation of its simulated structure is performed by DFT, which shows that the introduction of oxygen linking band can adjust its band structure and obtain a smaller band gap. In addition, the PACN displays an enhanced photocatalytic degradation of BPA under the long wavelength (λ ≥ 550 nm) and NIR light irradiation (λ ≥ 760 nm), which indicates that the synthesized materials have a broad spectrum of photocatalytic activity. According to the results of secondary ion mass spectrometry (SIMS) and nuclear magnetic resonance spectroscopy (NMR), C atoms and O atoms were introduced into the original g-C3N4 skeleton. In addition, the intermediate products were detected by mass spectrometry (HPLC-MS), and the BPA degradation pathway was proposed. A feasible photocatalytic reaction mechanism was also proposed.

Novel broad-spectrum-driven g-C3N4 with oxygen-linked band and porous defect for photodegradation of bisphenol A, 2-mercaptophenthiazole and ciprofloxacin.

Abundant active oxygen free radicals could efficiently remove refractory organic pollutants. In previous research, the original carbon nitride can form more hydrogen peroxide, however, owing to the limitation of its band structure, the original carbon nitride cannot decompose the hydrogen peroxide to generate more active oxygen free radicals. Herein, this work reports a simple bottom-up synthesis method, which synthesize a broad-spectrum-response carbon nitride (CN-CA) with oxygen-linked band and porous defect structure, while adjusting the band structure, and the introduction of the oxygen-linked band structure can also decompose the hydrogen peroxide produced by the original carbon nitride to form more active oxygen free radicals. Instrumental characterization and analysis of experimental results revealed the important role of oxygen-linked band and porous defects in adjusting the CN-CA energy band structure and improving its visible light absorption. The optimal CN-CA displays an outstanding photocatalytic degradation ability, that degradation rate of bisphenol A (BPA) reaches 99.8% within 150 min, the reaction rate constant of which is 6.77 times higher than that of pure g-C3N4, as also demonstrated with 2-mercaptophenthiazole (MBT) and ciprofloxacin (CIP). Meanwhile, the excellent degradation performance under blue LED (450-462 nm) and green LED (510-520 nm) exhibits the broad-spectrum characteristics of CN-CA. The degradation pathways of BPA and MBT were analyzed via HPLC-MS. Moreover, the primary active species were detected as O2-, OH and h+ based on the trapping experiments and ESR. This research provides a new strategy for g-C3N4 modified by porous defects and oxygen-linked band structure for environmental remediation.

Size-controllable synthesis of zinc ferrite/reduced graphene oxide aerogels: efficient electrochemical sensing of p-nitrophenol.

In this study, a nonaqueous method for the synthesis of size-controlled highly crystalline zinc ferrite/reduced graphene oxide (ZFO/rGO) aerogel was provided by using benzyl alcohol as the medium. In our findings, benzyl alcohol was introduced not only as the solvent, but the structure-directing agent and strong reducing agent during the nucleation and growth of ZnFe2O4 nanoparticles (NPs). The characterization analysis indicated that ZnFe2O4 NPs were immobilized on the multilayer rGO with a controllable size of 12 nm. Moreover, the 3D ZFO/rGO aerogel shows excellent electrochemical property as a facile electrochemical sensor for the detection of p-nitrophenol (p-NP). The ZFO/rGO electrochemical sensing offers the advantages of wide linear range (1-500 µmol l-1), excellent sensitivity (23.985 mA mM-1 cm-2), good stability and selectivity (<8.8%). In addition, the possible reaction mechanism of 3D ZFO/rGO aerogel was explained during the detection process under acidic condition. Significantly, our results not only provided insight into the possible reaction mechanism of 3D ZFO/rGO nanocomposite, but proposed the way for the synthesis of highly crystalline materials through a benzyl alcohol-mediated method.

Novel broad-spectrum-driven oxygen-linked band and porous defect co-modified orange carbon nitride for photodegradation of Bisphenol A and 2-Mercaptobenzothiazole.

Here, we successfully synthesized the oxygen-linked band and porous defect co-modified orange carbon nitride (AF-C3N4) using a simple method. Further, the band structure calculation of its simulated structure is performed by DFT, which shows that the introduction of oxygen-linked band can adjust its band structure. The photocatalytic degradation rates of 0.3AF-C3N4 for bisphenol A and 2-mercaptobenzothiazole were 8 times and 2.73 times that of the original g-C3N4, respectively. Moreover, 0.3AF-C3N4 also shows photocatalytic activity under different wavelength light (blue, green and red light), which indicates that the synthesized materials have a broad spectrum of photocatalytic activity. Further, we proposed a possible photocatalytic degradation pathway by HPLC-MS analysis. Free radical quenching test and ESR spectra show that the generated superoxide radicals (•O2-), hydroxyl radicals (•OH) and holes (h+) cause photodegradation, while enhancing singlet oxygen (1O2) and weaken the content of hydrogen peroxide has further proved that active oxygen groups play an important role in the photocatalytic degradation process. Additionally, the 0.3AF-C3N4 can also be a photoelectrochemical sensor to detect the concentration of bisphenol A (λ ≥ 550 nm). This study provides a new strategy for the synthesis of orange carbon nitride by oxygen-linked band and porous defect co-modification for photocatalytic applications.

Reactions of CO2 and ethane enable CO bond insertion for production of C3 oxygenates.

Reacting CO2 and ethane to synthesize value-added oxygenate molecules represents opportunities to simultaneously reduce CO2 emissions and upgrade underutilized ethane in shale gas. Herein, we propose a strategy to produce C3 oxygenates using a tandem reactor. This strategy is achieved with a Fe3Ni1/CeO2 catalyst (first reactor at 600-800 °C) for CO2-assisted dehydrogenation and reforming of ethane to produce ethylene, CO, and H2, and a RhCox/MCM-41 catalyst (second reactor at 200 °C) enabling CO insertion for the production of C3 oxygenates (propanal and 1-propanol) via the heterogeneous hydroformylation reaction at ambient pressure. In-situ characterization using synchrotron spectroscopies and density functional theory (DFT) calculations reveal the effect of Rh-Co bimetallic formation in facilitating the production of C3 oxygenates. The proposed strategy provides an opportunity for upgrading light alkanes in shale gas by reacting with CO2 to produce aldehydes and alcohols.

Porous defective carbon nitride obtained by a universal method for photocatalytic hydrogen production from water splitting.

For the first time, herein this work, we have developed an effective and adaptable method to introduce defects onto the polymeric carbon nitride by simply grinding urea with urea nitrate which resulting new carbon nitride composite (UNU-C3N4) and melamine with urea nitrate which resulting new carbon nitride composite (UNM-C3N4). The UNU-C3N4 reveals high performance towards photocatalytic hydrogen production and as well as photocatalytic removal of contaminants. The results confirm that the defects enhanced the specific surface area, and improved performance of adsorbed oxygen which beneficial to generate more active radicals and more conducive sties to improve d the overall photocatalytic performance. The high N, H, and O content-enhanced electron polarization effects, by introducing the additional N, H, and O atoms into the g-C3N4 matrix, which will increase the charge transfer rate and charge separation efficiency. At the same time, the results of ESR also expression that the new type of as-prepared carbon nitride samples exhibit abundant of hydrogen radical (H) formation, which is also assist to improve the photocatalytic hydrogen production performance. As expected, the H2 evolution rate of UNU-C3N4(or UNM-C3N4) underneath simulated solar light irradiation is 9.93 times (13.76 times) than that of U-C3N4 (urea as raw material) (or M-C3N4 (melamine as raw material)). The high hydrogen evolution rates of UNU-C3N4 and UNM-C3N4 are 830.94 and 556.79 µmol g-1  h-1 under the visible-light irradiation, respectively. Meanwhile, the synthesized UNU-C3N4 and UNM-C3N4 material are demonstrated an efficient ability to degrade pollutants. In general, this work provides a viable way to introduce defects and hydrogen bands into the structure of carbon nitride.

In situ construction efficient visible-light-driven three-dimensional Polypyrrole/Zn3In2S6 nanoflower to systematically explore the photoreduction of Cr(VI): Performance, factors and mechanism.

Photoreduction of highly toxic Cr(VI) has been regarded as an efficient and green method to achieve water purification. In this process, better charge carrier separation is vital to achieving excellent performance. Besides, it is vital to systematically explore the influencing factors and reaction mechanism. Herein, a novel 3D PPy/Zn3In2S6 nanoflower composite was successfully fabricated via in-situ polymerization. The remarkable conductivity of PPy provides a good electron transport path to facilitate the separation and migration of charge carriers, which benefits to the activity improvement. The results show that 5% PPy/Zn3In2S6 exhibits superior photocatalytic activity with almost 100% Cr(VI) reduction just within 24 min and 99.4% of Methyl orange (MO) is degraded in 25 min. On this basis, factors of different catalyst dosage, concentration, ions and pH under the reduction system were systematically investigated. Especially, different organic acids were in-depth analyzed and the activity could be significantly enhanced just adding 0.1 mmol organic acids. 5% 3D PPy/Zn3In2S6 nanoflower composites (with tartaric acid) exhibits superior photocatalytic activity, which can achieve 100% photoreduction of Cr(VI) just within 6 min. Finally, a possible reaction mechanism was proposed. Moreover, 3D PPy/Zn3In2S6 nanoflower also presented an efficient photodegradation activity for organic pollution.

Tailoring of crystalline structure of carbon nitride for superior photocatalytic hydrogen evolution.

Light absorption and carrier transfer, are two sequential and complementary steps related to photocatalysis performance, whereas the collective integration of these two aspects into graphitic carbon nitride (g-C3N4) photocatalyst through polycondensation optimization have seldom been achieved. Herein, we report on tailoring the crystalline structure of g-C3N4 by avoiding the formation of incompletely reacted N-rich intermediates and selective breaking the hydrogen bonds between the layers of g-C3N4 simultaneously. The obtained layer plane ordered porous carbon nitride (LOP-CN) material shows efficient photocatalytic H2 generation performance. The highest H2 evolution rate achieved is 53.8 µmol under λ ≥ 400 nm light irradiation, which is 7.4 times higher than that of g-C3N4 prepared by convention thermal polycondensation. The substantially boosted photocatalytic activity is mainly ascribed to the efficient charge separation on long-range atomic order layer plane and the extended visible light harvesting ability. This work highlights the importance of crystalline structure tailoring in improving charge separation and light absorption of g-C3N4 photocatalyst for boosting its photocatalytic H2 evolution activity.