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Fe and Cu co-doped graphitic carbon nitride as an eco-friendly photo-assisted catalyst for aniline degradation

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Abstract

A novel bimetallic coordinated g-C3N4 with Fe2O3 composite catalyst (FeCu-g-C3N4) was synthesized by simple calcination of Fe3+/Cu2+/melamine precursor. Its catalytic performance was analyzed via photodegrading aniline. The X-ray diffraction (XRD), field emission scanning electronic microscopy (FESEM), Fourier transform infrared (FT-IR), and X-ray photoelectron spectroscopy (XPS) were employed to characterize the composition and structure of the catalysts. Results indicated that Fe mainly distributed in the Fe(III)-N coordination form and partly in Fe2O3 lattice, and Cu inserted at the interstitial positions of g-C3N4 in the Cu(I)-N form. The great optical property was also proved by ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis DRS), photoluminescence (PL) spectroscopy, and photocurrent responses. The heterogeneous photo-assisted catalyst exhibited excellent performance in activation of H2O2, resulting in 80% decomposition of aniline with low metal leaching in 6 h. The incorporation of Cu elevated the performance of degradation compared to that only iron doped. A synergistic catalytic effect between solid Cu(I) and Fe(III) accelerated the reduction of Fe(III). The ·OH and 1O2 were confirmed as major reactive oxygen species (ROS) identified by scavenging experiments and ESR, and e was the most essential since it not only led to the generation of ROS but also participated in the circulation of Fe3+/Fe2+, Cu2+/Cu+, and Fe3+/Cu+. Furthermore, the possible catalytic mechanism was proposed based on the analysis.

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References

  • Bicalho HA, Lopez JL, Binatti I, Batista PFR, Ardisson JD, Resende RR, Lorençon E (2017) Facile synthesis of highly dispersed Fe(II)-doped g-C3N4 and its application in Fenton-like catalysis. J Mol Catal 435:156–165

    CAS  Google Scholar 

  • Briviba K, Devasagayam T, Sies H, Steenken S (1993) Selective para-hydroxylation of phenol and aniline by singlet molecular-oxygen. Chem Res Toxicol 6:548–553

    CAS  Google Scholar 

  • Cao P, Zhao K, Quan X, Chen S, Yu H (2019) Separation and purification technology. Volume 238, 1 May 2020, 116424 https://doi.org/10.1016/j.seppur.2019.116424https://doi.org/10.1016/j.seppur.2019.116424

  • Chen W, Chen X, Lu W, Xu T, Li N, Zhu Z, Wang G (2017) Visible-light-assisted generation of high-valent iron-oxo species anchored axially on g-C3N4 for efficient degradation of organic pollutants. Chem Eng J 328:853–861

    CAS  Google Scholar 

  • Chen W, Bao Y, Li X, Huang J, Tang Y, Li L (2019) Mineralization of salicylic acid via catalytic ozonation with Fe-Cu@SiO2 core-shell catalyst: a two-stage first order reaction. Chemosphere 235:470–480

    CAS  Google Scholar 

  • Christoforidis KC, Montini T, Bontempi E, Zafeiratos S, Jaén JJD, Fornasiero P (2016) Synthesis and photocatalytic application of visible-light active β-Fe2O3/g-C3N4 hybrid nanocomposites. Appl Catal B Environ 187:171–180

    CAS  Google Scholar 

  • Chu L, Wang J, Dong J, Liu H, Sun X (2012) Treatment of coking wastewater by an advanced Fenton oxidation process using iron powder and hydrogen peroxide. Chemosphere 86:409–414

    CAS  Google Scholar 

  • De Luca A, Dantas RF, Esplugas S (2014) Assessment of iron chelates efficiency for photo-Fenton at neutral pH. Water Res 61:232–242

    Google Scholar 

  • Dong Q, Chen Y, Wang L, Ai S, Ding H (2017) Cu-modified alkalinized g-C3N4 as photocatalytically assisted heterogeneous Fenton-like catalyst. Appl Surf Sci 426:1133–1140

    CAS  Google Scholar 

  • Dou H, Zheng S, Zhang Y (2018) The effect of metallic Fe(II) and nonmetallic S codoping on the photocatalytic performance of graphitic carbon nitride. RSC Adv 8:7558–7568

    CAS  Google Scholar 

  • Feng Y, Wu D, Deng Y, Zhang T, Shih K (2016) Sulfate radical-mediated degradation of sulfadiazine by CuFeO2rhombohedralcrystal-catalyzed peroxymonosulfate: synergistic effects and mechanisms. Environ Sci Technol 50:3119–3127

    CAS  Google Scholar 

  • Feng Y, Liao C, Kong L, Wu D, Liu Y, Lee P, Shih K (2018) Facile synthesis of highly reactive and stable Fe-doped g-C3N4 composites for peroxymonosulfate activation: a novel nonradical oxidation process. J Hazard Mater 354:63–71

    CAS  Google Scholar 

  • Gao J, Wang Y, Zhou S, Lin W, Kong Y (2017) A facile one-step synthesis of Fe-doped g-C3N4nanosheets and their improved visible-light photocatalytic performance. ChemCatChem 9:1708–1715

    CAS  Google Scholar 

  • Guan Y, Ma J, Ren Y, Liu Y, Xiao J, Lin L, Zhang C (2013) Efficient degradation of atrazine by magnetic porous copper ferrite catalyzed peroxymonosulfate oxidation via the formation of hydroxyl and sulfate radicals. Water Res 47:5431–5438

    CAS  Google Scholar 

  • He J, Yang X, Men B, Wang D (2016) Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials: a review. J Environ Sci-China 39:97–109

    CAS  Google Scholar 

  • Hu S, Jin R, Lu G, Liu D, Gui J (2014) The properties and photocatalytic performance comparison of Fe3+-doped g-C3N4 and Fe2O3/g-C3N4 composite catalysts. RSC Adv 4:24863–24869

    CAS  Google Scholar 

  • Hu S, Qu X, Li P, Wang F, Li Q, Song L, Zhao Y, Kang X (2018) Photocatalytic oxygen reduction to hydrogen peroxide over copper doped graphitic carbon nitride hollow microsphere: the effect of Cu(I)-N active sites. Chem Eng J 334:410–418

    CAS  Google Scholar 

  • Huang Y, Su C, Yang Y, Lu M (2013) Degradation of aniline catalyzed by heterogeneous Fenton-like reaction using iron oxide/SiO2. Environ Prog Sustain 32:187–192

    CAS  Google Scholar 

  • Huang Q, Hu D, Chen M, Bao C, Jin X (2019) Sequential removal of aniline and heavy metal ions by jute fiber biosorbents: a practical design of modifying adsorbent with reactive adsorbate. J Mol Liq 285:288–298

    CAS  Google Scholar 

  • Hussain I, Zhang Y, Li M, Huang S, Hayat W, He L, Du X, Liu G, Du M (2018) Heterogeneously degradation of aniline in aqueous solution using persulfate catalyzed by magnetic BiFeO3 nanoparticles. Catal Today 310:130–140

    CAS  Google Scholar 

  • Jiang L, Liu L, Xiao S, Chen J (2016) Preparation of a novel manganese oxide-modified diatomite and its aniline removal mechanism from solution. Chem Eng J 284:609–619

    CAS  Google Scholar 

  • Jiang L, Yuan X, Pan Y, Liang J, Zeng G, Wu Z, Wang H (2017) Doping of graphitic carbon nitride for photocatalysis: a review. Appl Catal B Environ 217:388–406

    CAS  Google Scholar 

  • Jiang S, Xu H, Sun Y, Song Y (2019a) Performance analysis of Fe-N compounds based on valence electron structure. J Alloys Compd 779:427–432

    CAS  Google Scholar 

  • Jiang Y, Wei L, Yang K, Wang H (2019b) Investigation of rapid granulation in SBRs treating aniline-rich wastewater with different aniline loading rates. Sci Total Environ 646:841–849

    CAS  Google Scholar 

  • Koyuncu H, Kul AR (2019) Removal of aniline from aqueous solution by activated kaolinite: kinetic, equilibrium and thermodynamic studies. Colloids Surf A Physicochem Eng Asp 569:59–66

    CAS  Google Scholar 

  • Li X, Jin X, Zhao N, Angelidaki I, Zhang Y (2017) Efficient treatment of aniline containing wastewater in bipolar membrane microbial electrolysis cell-Fenton system. Water Res 119:67–72

    CAS  Google Scholar 

  • Li H, Shan C, Pan B (2018) Fe(III)-doped g-C3N4 mediated peroxymonosulfate activation for selective degradation of phenolic compounds via high-valent iron-oxo species. Environ Sci Technol 52:2197–2205

    CAS  Google Scholar 

  • Li Y, Zhang Q, Li M, Sang W, Wang Y, Wu L, Yang Y (2020) Bioaugmentation of sequencing batch reactor for aniline treatment during start-up period: investigation of microbial community structure of activated sludge. Chemosphere 243:125426

    CAS  Google Scholar 

  • Lin Z, Chen H, Zhou Y, Ogawa N, Lin JM (2012) Self-catalytic degradation of ortho-chlorophenol with Fenton’s reagent studied by chemiluminescence. J Environ Sci (China) 24:550–557

    CAS  Google Scholar 

  • Liu Q, Guo Y, Chen Z, Zhang Z, Fang X (2016) Constructing a novel ternary Fe(III)/graphene/g-C3N4 composite photocatalyst with enhanced visible-light driven photocatalytic activity via interfacial charge transfer effect. Appl Catal B Environ 183:231–241

    CAS  Google Scholar 

  • Liu Y, Zhang H, Sun J, Liu J, Shen X, Zhan J, Zhang A, Ognier S, Cavadias S, Li P (2018) Degradation of aniline in aqueous solution using non-thermal plasma generated in microbubbles. Chem Eng J 345:679–687

    CAS  Google Scholar 

  • Liu C, Liu L, Tian X, Wang Y, Li R, Zhang Y, Song Z, Xu B, Chu W, Qi F, Ikhlaq A (2019) Coupling metal–organic frameworks and g-CN to derive Fe@N-dopedgraphene-like carbon for peroxymonosulfate activation: upgrading framework stability and performance. Appl Catal B Environ 255:117763

    CAS  Google Scholar 

  • Lotsch BV, Schnick W (2006) From triazines to heptazines: novel nonmetal tricyanomelaminates as precursors for graphitic carbon nitride materials. Chem Mater 18:1891–1900

    CAS  Google Scholar 

  • Lyu L, Yan D, Yu G, Cao W, Hu C (2018) Efficient destruction of pollutants in water by a dual-reaction-center Fenton-like process over carbon nitride compounds-complexed Cu(II)-CuAlO2. Environ Sci Technol 52:4294–4304

    CAS  Google Scholar 

  • Ma J, Yang Q, Wen Y, Liu W (2017) Fe-g-C3N4/graphitized mesoporous carbon composite as an effective Fenton-like catalyst in a wide pH range. Appl Catal B Environ 201:232–240

    CAS  Google Scholar 

  • Miao W, Liu Y, Chen X, Zhao Y, Mao S (2020) Tuning layered Fe-doped g-C3N4 structure through pyrolysis for enhanced Fenton and photo-Fenton activities. Carbon 159:461–470

    CAS  Google Scholar 

  • Mohammed M, Mekala LP, Chintalapati S, Chintalapati VR (2020) New insights into aniline toxicity: aniline exposure triggers envelope stress and extracellular polymeric substance formation in Rubrivivax benzoatilyticus JA2. J Hazard Mater 385:121571

    Google Scholar 

  • Muniandy L, Adam F, Mohamed AR, Iqbal A, Rahman NRA (2017) Cu2+ coordinated graphitic carbon nitride (Cu-g-C3N4) nanosheets from melamine for the liquid phase hydroxylation of benzene and VOCs. Appl Surf Sci 398:43–55

    CAS  Google Scholar 

  • Nie C, Ao Z, Duan X, Wang C, Wang S, An T (2018) Degradation of aniline by electrochemical activation of peroxydisulfate at MWCNT cathode: the proofed concept of nonradical oxidation process. Chemosphere 206:432–438

    CAS  Google Scholar 

  • Ong W, Tan L, Ng YH, Yong S, Chai S (2016) Graphitic carbon nitride (g-C3N4)-based photocatalysts for artificial photosynthesis and environmental remediation: are we a step closer to achieving sustainability? Chem Rev 116:7159–7329

    CAS  Google Scholar 

  • Ou B, Wang J, Wu Y, Zhao S, Wang Z (2019) Degradation of aniline by photoelectro-Fenton process using g-C3N4 based cathode. J Electroanal Chem 848:113273

    CAS  Google Scholar 

  • Poulin S, França R, Moreau-Bélanger L, Sacher E (2010) Confirmation of X-ray photoelectron spectroscopy peak attributions of nanoparticulate iron oxides, using symmetric peak component line shapes. J Phys Chem C 114:10711–10718

    CAS  Google Scholar 

  • Sudrajat H (2017) Reducing agent-free formation of Cu(I) nanoclusters on gC3N4 for enhanced photocatalysis. J Alloys Compd 716:119–127

    CAS  Google Scholar 

  • Sun Y, Yang Z, Tian P, Sheng Y, Xu J, Han Y (2019) Oxidative degradation of nitrobenzene by a Fenton-like reaction with Fe-Cu bimetallic catalysts. Appl Catal B Environ 244:1–10

    CAS  Google Scholar 

  • Tahir B, Tahir M, Amin NAS (2017) Photo-induced CO2 reduction by CH4/H2O to fuels over Cu-modified g-C3N4 nanorods under simulated solar energy. Appl Surf Sci 419:875–885

    CAS  Google Scholar 

  • Tan P (2016) Active phase, catalytic activity, and induction period of Fe/zeolite material in nonoxidative aromatization of methane. J Catal 338:21–29

    CAS  Google Scholar 

  • Tian X, Jin H, Nie Y, Zhou Z, Yang C, Li Y, Wang Y (2017) Heterogeneous Fenton-like degradation of ofloxacin over a wide pH range of 3.6–10.0 over modified mesoporous iron oxide. Chem Eng J 328:397–405

    CAS  Google Scholar 

  • Tonda S, Kumar S, Kandula S, Shanker V (2014) Fe-doped and -mediated graphitic carbon nitride nanosheets for enhanced photocatalytic performance under natural sunlight. J Mater Chem A 2:6772–6780

    CAS  Google Scholar 

  • Wang X, Chen X, Thomas A, Fu X, Antonietti M (2009) Metal-containing carbon nitride compounds: a new functional organic-metal hybrid material. Adv Mater 21:1609–1612

    CAS  Google Scholar 

  • Wang Y, Wang X, Antonietti M (2012) Polymeric graphitic carbon nitride as a heterogeneous organocatalyst: from photochemistry to multipurpose catalysis to sustainable chemistry. Angewandte Int Edition 51:68–89

    CAS  Google Scholar 

  • Wang Y, Zhao H, Zhao G (2015a) Iron-copper bimetallic nanoparticles embedded within ordered mesoporous carbon as effective and stable heterogeneous Fenton catalyst for the degradation of organic contaminants. Appl Catal B Environ 164:396–406

    CAS  Google Scholar 

  • Wang Z, Guan W, Sun Y, Dong F, Zhou Y, Ho W (2015b) Water-assisted production of honeycomb-like g-C3N4 with ultralong carrier lifetime and outstanding photocatalytic activity. Nanoscale 7:2471–2479

    CAS  Google Scholar 

  • Wang Q, Jiang C, Wang Y, Yang Z, Xu T (2016) Reclamation of aniline wastewater and CO2capture using bipolar membrane electrodialysis. ACS Sustain Chem Eng 4:5743–5751

    CAS  Google Scholar 

  • Wang X, Li D, Nan Z (2019) Effect of N content in g-C3N4 as metal-free catalyst on H2O2 decomposition for MB degradation. Sep Purif Technol 224:152–162

    CAS  Google Scholar 

  • Wu H, Li H, Zhao X, Liu Q, Wang J, Xiao J, Xie S, Si R, Yang F, Miao S, Guo X, Wang G, Bao X (2016) Highly doped and exposed Cu(I)-N active sites within graphene towards efficient oxygen reduction for zinc-air batteries. Energy Environ Sci 9:3736–3745

    CAS  Google Scholar 

  • Wu Y, Guo J, Han Y, Zhu J, Zhou L, Lan Y (2018) Insights into the mechanism of persulfate activated by rice straw biochar for the degradation of aniline. Chemosphere 200:373–379

    CAS  Google Scholar 

  • Xue G, Wang Q, Qian Y, Gao P, Su Y, Liu Z, Chen H, Li X, Chen J (2019) Simultaneous removal of aniline, antimony and chromium by ZVI coupled with H2O2: implication for textile wastewater treatment. J Hazard Mater 368:840–848

    Google Scholar 

  • Yang D, Jiang T, Wu T, Zhang P, Han H, Han B (2016) Highly selective oxidation of cyclohexene to 2-cyclohexene-1-one in water using molecular oxygen over Fe–Co–g-C3N4. Catal Sci Technol 6:193–200

    Google Scholar 

  • Yuan X, Pham AN, Xing G, Rose AL, Waite TD (2012) Effects of pH, chloride, and bicarbonate on Cu(I) oxidation kinetics at circumneutral pH. Environ Sci Technol 46:1527–1535

    CAS  Google Scholar 

  • Zhang X, Gu X, Lu S, Miao Z, Xu M, Fu X, Qiu Z, Sui Q (2016) Application of calcium peroxide activated with Fe(II)-EDDS complex in trichloroethylene degradation. Chemosphere 160:1–6

    CAS  Google Scholar 

  • Zhu J, Zhu X, Cheng F, Li P, Wang F, Xiao Y, Xiong W (2019) Preparing copper doped carbon nitride from melamine templated crystalline copper chloride for Fenton-like catalysis. Appl Catal B Environ 256:117830

    CAS  Google Scholar 

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Li, L., Liang, M., Huang, J. et al. Fe and Cu co-doped graphitic carbon nitride as an eco-friendly photo-assisted catalyst for aniline degradation. Environ Sci Pollut Res 27, 29391–29407 (2020). https://doi.org/10.1007/s11356-020-08148-x

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