Abstract
Graphitic carbon nitride (g-C3N4) with improved photocatalysis was prepared via thermal polymerization of dicyandiamide with the assistance of calcium chloride. The photocatalytic activity of the modified product was optimized by changing the weight ratio of calcium chloride to dicyanodiamine, and the final products were characterized by XRD, FTIR, SEM, TEM, XPS, BET, DRS and PL spectra. The results indicate that calcium chloride could lower the crystalline sizes of g-C3N4 due to its coordination effect with the edge ammonia of g-C3N4. The Valence band level decreased after the modification with higher oxidation capability. The photo-generated hole and the superoxide radical are the main active species in the degradation process. As a typical performance, the degradation rate of the modified sample is more than 50 times higher than that of the un-modified carbon nitride. Due to the weakened visible light absorption of the modified catalyst, the degradation of RhB can be mainly attributed to its excitation and enhanced transfer of electrons to the catalyst.
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Cui Y, Ding Z, Liu P, Antonietti M, Fu X, Wang X (2012) Metal-free activation of H2O2 by g-C3N4 under visible light irradiation for the degradation of organic pollutants. Phys Chem Chem Phys 14:1455–1462
Cheng N, Tian J, Liu Q, Ge C, Qusti AH, Asiri AM, Youbi A O A., Sun X (2013) Au-nanoparticle-loaded graphitic carbon nitride nanosheets: green photocatalytic synthesis and application toward the degradation of organic pollutants. ACS Appl Mater Interfaces 5:6815–6819
Liu J, Zhang Y, Lu L, Wu G, Chen W (2012) Self-regenerated solar-driven photocatalytic water-splitting by urea derived graphitic carbon nitride with platinum nanoparticles. Chem Commun 48:8826–8828
Lin J, Pan Z, Wang X (2014) Photochemical reduction of CO2 by graphitic carbon nitride polymers. ACS Sustainable. Chem Eng 2:353–358
Wang Y, Zhang J, Wang X, Antonietti M, Li H (2010) Boron- and fluorine-containing mesoporous carbon nitride polymers: metal-free catalysts for cyclohexane oxidation. Angew Chem Int Ed 49:3356–3359
Kroke E, Schwarz M, Horath Bordon E, Kroll P, Noll B, Norman AD (2002) Tri-s-triazine derivatives. Part I. From trichloro-tri-s-triazine to graphitic C3N4 structures Part II: alkalicyamelurates M3[C6N7O3], M = Li, Na, K, Rb, Cs, manuscript in preparation. New J Chem 26:508–512
Wang X, Maeda K, Thomas A, Takanabe K, Xin G, Carlsson JM, Domen K, Antonietti M (2009) A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nat Mater 8:76–80
Yan SC, Lv SB, Li ZS, Zou ZG (2010) Organic-inorganic composite photocatalyst of g-C3N4 and TaON with improved visible light photocatalytic activities. Dalton Trans 39:1488–1491
Gillan EG (2000) Synthesis of nitrogen-rich carbon nitride networks from an energetic molecular azide precursor. Chem Mater 12:3906–3912
Cao S, Low J, Yu J, Jaroniec M (2015) Polymeric photocatalysts based on graphitic carbon nitride. Adv Mater 27:2150–2176
Liu G, Niu P, Sun C, Smith SC, Chen Z, Lu G, Cheng H (2010) Unique electronic structure induced high photoreactivity of sulfur-doped graphitic C3N4. J Am Chem Soc 132:11642–11648
Zhang L, Chen X, Guan J, Jiang Y, Hou T, Mu X (2013) Facile synthesis of phosphorus doped graphitic carbon nitride polymers with enhanced visible-light photocatalytic activity. Mater Res Bull 48:3485–3491
Yan SC, Li ZS, Zou ZG (2010) Photodegradation of rhodamine B and methyl orange over boron-doped g-C3N4 under visible light irradiation. Langmuir 26:3894–3901
Lan Z, Zhang G, Wang X (2016) A facile synthesis of Br-modified g-C3N4 semiconductors for photoredox water splitting. Appl Catal B 192:116–125
Kondo K, Murakami N, Ye C, Tsubota T, Ohno T (2013) Development of highly efficient sulfur-doped TiO2 photocatalysts hybridized with graphitic carbon nitride. Appl Catal B 142–143:362–367
Liu W, Wang M, Xu C, Chen S, Fu X (2013) Significantly enhanced visible-light photocatalytic activity of g-C3N4 via ZnO modification and the mechanism study. J Mol Catal A 368–369:9–15
Ge L, Han C, Xiao X, Guo L (2013) Synthesis and characterization of composite visible light active photocatalysts MoS2–g-C3N4 with enhanced hydrogen evolution activity. Int J Hydrogen Energy 38:6960–6969
Xu H, Yan J, Xu Y, Song Y, Li H, Xia J, Huang C, Wan H (2013) Novel visible-light-driven AgX/graphite-like C3N4 (X = Br, I) hybrid materials with synergistic photocatalytic activity. Appl Catal B 129:182–193
Xu J, Wang Y, Zhu Y (2013) Nanoporous graphitic carbon nitride with enhanced photocatalytic performance. Langmuir 29:10566–10572
Wirnhier E, Doblinger M, Gunzelmann D, Senker J, Lotsch BV, Schnick W (2011) Poly(triazine imide) with intercalation of lithium and chloride ions [(C3N3)2(NHxLi1–x)3LiCl]: a crystalline 2D carbon nitride network. Chem Eur J 17:3213–3221
Yuan B, Chu Z, Li G, Jiang Z, Hu T, Wang Q, Wang C (2014) Water-soluble ribbon-like graphitic carbon nitride (g-C3N4): green synthesis, self-assembly and unique optical properties. J Mater Chem C 2:8212–8215
Zhang M, Bai X, Liu D, Wang J, Zhu Y (2015) Enhanced catalytic activity of potassium-doped graphitic carbon nitride induced by lower valence position. Appl Catal B 164:77–81
Wang J, Zhang C, Shen Y, Zhou Z, Yu J, Li Y, Wei W, Liu S, Zhang Y (2015) Environment-friendly preparation of porous graphite-phase polymeric carbon nitride using calcium carbonate as templates, and enhanced photoelectrochemical activity. J Mater Chem A 3:5126–5131
Thomas A, Fischer A, Goettmann F, Antonietti M, Müller JO, Schlögl R, Carlsson JM (2008) Graphitic carbon nitride materials: variation of structure and morphology and their use as metal-free catalysts. J Mater Chem 18:4893–4908
Liu J, Zhang T, Wang Z, Dawson G, Chen W (2011) Simple pyrolysis of urea into graphitic carbon nitride with recyclable adsorption and photocatalytic activity. J Mater Chem 21:14398–14401
Liao G, Chen S, Quan X, Yu H, Zhao H (2012) Graphene oxide modified g-C3N4 hybrid with enhanced photocatalytic capability under visible light irradiation. J Mater Chem 22:2721–2726
Liu Q, Zhang J (2013) Graphene supported Co-g-C3N4 as a novel metal-macrocyclic electrocatalyst for the oxygen reduction reaction in fuel cells. Langmuir 29:3821–3828
Khabashesku VN, Zimmerman JL, Margrave JL (2000) Powder synthesis and characterization of amorphous carbon nitride. Chem Mater 12:3264–3270
Li Y, Zhang J, Wang Q, Jin Y, Huang D, Cui Q, Zou G (2010) Nitrogen-rich carbon nitride hollow vessels: synthesis, characterization, and their properties. J Phys Chem B 114:9429–9434
Guo Q, Yang Q, Zhu L, Yi C, Zhang S, Xie Y (2004) A facile one-pot solvothermal route to tubular forms of luminescent polymeric networks [(C3N3)2(NH)3]n. Solid State Commun 132:369–374
Dai H, Gao X, Liu E, Yang Y, Hou W, Kang L, Fan J, Hu X (2013) Synthesis and characterization of graphitic carbon nitride sub-microspheres using microwave method under mild condition. Diam Relat Mater 38:109–117
Ye C, Li J, Li Z, Li X, Fan X, Zhang L, Chen B, Tung C, Wu L (2015) Enhanced driving force and charge separation efficiency of protonated g-C3N4 for photocatalytic O2 evolution. ACS Catal 5:6973–6979
Chai B, Yan J, Wang C, Ren Z, Zhu Y (2017) Enhanced visible light photocatalytic degradation of Rhodamine B over phosphorus doped graphitic carbon nitride. Appl Surf Sci 391:376–383
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The whole work was carried out at National University of Defense Technology (NUDT) through a Master Joint Supervision System.
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Long, X., Yan, T., Hu, T. et al. Enhanced Photocatalysis of g-C3N4 Thermally Modified with Calcium Chloride. Catal Lett 147, 1922–1930 (2017). https://doi.org/10.1007/s10562-017-2099-0
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DOI: https://doi.org/10.1007/s10562-017-2099-0