Abstract
The two-dimensional (2D) layered photocatalysts are promising to improve the separation efficiency of photogenerated electron-hole pairs. Herein, 2D graphitic carbon nitride (g-C3N4)/BiOBr heterojunctions were successfully prepared via a facile solvothermal method. The micromorphology, structure, and chemical composition/states were characterized. The visible light–induced photocatalytic properties were estimated by the degradation of rhodamine B (RhB), photocurrent responses, Nyquist spectra, and Mott-Schottky measurement. Comparing with pure g-C3N4 and BiOBr, 2D g-C3N4/BiOBr heterojunctions exhibit the enhanced visible light photodegradation. After coupling between (001) crystal planes of BiOBr with (002) planes of g-C3N4, 2D g-C3N4/BiOBr heterojunctions have the large and intimate contact surface allowing fast interfacial charge transfer rate. It is explored that photoinduced superoxide radicals (·O2−) and holes (h+) actively participate in the photodegradation, while the contribution of hydroxyl (·OH) radicals is negligible.
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References
Asahi R, Morikawa T, Ohwaki T, Aoki K, Taga Y (2001) Visible-light photocatalysis in nitrogen-doped titanium oxides. Science 293:269–271. https://doi.org/10.1126/science.1061051
Cao S, Low J, Yu J, Jaroniec M (2015) Polymeric photocatalysts based on graphitic carbon nitride. Adv Mater 27:2150–2176. https://doi.org/10.1002/adma.201500033
Chang C, Zhu L, Wang S, Chu X, Yue L (2014a) Novel mesoporous graphite carbon nitride/BiOI heterojunction for enhancing photocatalytic performance under visible-light irradiation. ACS Appl Mater Interfaces 6:5083–5093. https://doi.org/10.1021/am5002597
Chang F et al. (2014b) Enhanced photocatalytic performance of g-C3N4 nanosheets-BiOBr hybrids. Superlattices Microstruct 76:90-104https://doi.org/10.1016/j.spmi.2014.10.002
Chen X, Shen S, Guo L, Mao SS (2010) Semiconductor-based photocatalytic hydrogen generation. Chem Rev 110:6503–6570. https://doi.org/10.1021/cr1001645
Chou S-Y, Chen C-C, Dai Y-M, Lin J-H, Lee WW (2016) Novel synthesis of bismuth oxyiodide/graphitic carbon nitride nanocomposites with enhanced visible-light photocatalytic activity. RSC Adv 6:33478–33491. https://doi.org/10.1039/c5ra28024a
Di J et al (2013) A g-C3N4/BiOBr visible-light-driven composite: synthesis via a reactable ionic liquid and improved photocatalytic activity. RSC Adv 3:19624. https://doi.org/10.1039/c3ra42269k
Di J et al (2014) One-pot solvothermal synthesis of Cu-modified BiOCl via a Cu-containing ionic liquid and its visible-light photocatalytic properties. RSC Adv 4:14281–14290. https://doi.org/10.1039/c3ra45670f
Feng Y, Li L, Li J, Wang J, Liu L (2011) Synthesis of mesoporous BiOBr 3D microspheres and their photodecomposition for toluene. J Hazard Mater 192:538–544. https://doi.org/10.1016/j.jhazmat.2011.05.048
Fu J, Tian Y, Chang B, Xi F, Dong X (2012) BiOBr-carbon nitride heterojunctions: synthesis, enhanced activity and photocatalytic mechanism. J Mater Chem 22:21159–21166. https://doi.org/10.1039/c2jm34778d
Ge L, Han C, Liu J (2011) Novel visible light-induced g-C3N4/Bi2WO6 composite photocatalysts for efficient degradation of methyl orange. Appl Catal B Environ 108:100–107
Guo W, Qin Q, Geng L, Wang D, Guo Y, Yang Y (2016) Morphology-controlled preparation and plasmon-enhanced photocatalytic activity of Pt-BiOBr heterostructures. J Hazard Mater 308:374–385. https://doi.org/10.1016/j.jhazmat.2016.01.077
Hisatomi T, Kubota J, Domen K (2014) Recent advances in semiconductors for photocatalytic and photoelectrochemical water splitting. Chem Soc Rev 43:7520–7535
Hou Y, Wen Z, Cui S, Guo X, Chen J (2013) Constructing 2D porous graphitic C3N4 nanosheets/nitrogen-doped graphene/layered MoS2 ternary nanojunction with enhanced photoelectrochemical. Activity Adv Mater 25:6291–6297. https://doi.org/10.1002/adma.201303116
Houas A, Lachheb H, Ksibi M, Elaloui E, Guillard C, Herrmann JM (2001) Photocatalytic degradation pathway of methylene blue in water. Appl Catal B-Environ 31:145–157. https://doi.org/10.1016/s0926-3373(00)00276-9
Huang C, Hu J, Cong S, Zhao Z, Qiu X (2015) Hierarchical BiOCl microflowers with improved visible-light-driven photocatalytic activity by Fe (III) modification. Appl Catal B-Environ 174:105–112. https://doi.org/10.1016/j.apcatb.2015.03.001
Huang H, Xiao K, Yu S, Dong F, Zhang T, Zhang Y (2016) Iodide surface decoration: a facile and efficacious approach to modulating the band energy level of semiconductors for high-performance visible-light photocatalysis. Chem Commun 52:354–357. https://doi.org/10.1039/c5cc08239k
Jie F, Tian Y, Chang B, Xi F, Dong X (2012) BiOBr-carbon nitride heterojunctions: synthesis, enhanced activity and photocatalytic mechanism. J Mater Chem 22:21159–21166
Kong L, Jiang Z, Xiao T, Lu L, Jones MO, Edwards PP (2011) Exceptional visible-light-driven photocatalytic activity over BiOBr-ZnFe2O4 heterojunctions. Chem Commun 47:5512–5514. https://doi.org/10.1039/c1cc10446b
Kong L, Jiang Z, Lai HH, Nicholls RJ, Xiao T, Jones MO, Edwards PP (2012) Unusual reactivity of visible-light-responsive AgBr-BiOBr heterojunction photocatalysts. J Catal 293:116–125. https://doi.org/10.1016/j.jcat.2012.06.011
Kuo WS, Ho PH (2006) Solar photocatalytic decolorization of dyes in solution with TiO2 film. Dyes Pigments 71:212–217. https://doi.org/10.1016/j.dyepig.2005.07.003
Lee YY, Jung HS, Kang YT (2017) A review: effect of nanostructures on photocatalytic CO2 conversion over metal oxides and compound semiconductors. J CO2 Util 20:163–177
Li H, Liu J, Liang X, Hou W, Tao X (2014a) Enhanced visible light photocatalytic activity of bismuth oxybromide lamellas with decreasing lamella thicknesses. J Mater Chem A 2:8926–8932. https://doi.org/10.1039/c4ta00236a
Li L, Ai L, Zhang C, Jiang J (2014b) Hierarchical {001}-faceted BiOBr microspheres as a novel biomimetic catalyst: dark catalysis towards colorimetric biosensing and pollutant degradation. Nanoscale 6:4627–4634. https://doi.org/10.1039/c3nr06533b
Li XR, Dai Y, Ma YD, Han SH, Huang BB (2014c) Graphene/g-C3N4 bilayer: considerable band gap opening and effective band structure engineering. Phys Chem Chem Phys 16:4230–4235. https://doi.org/10.1039/c3cp54592j
Li B, Huang L, Zhong M, Li Y, Wang Y, Li J, Wei Z (2016a) Direct vapor phase growth and optoelectronic application of large band offset SnS2/MoS2 vertical bilayer heterostructures with high lattice mismatch. Adv Electronic Mater 2:1600298
Li H, Hu T, Du N, Zhang R, Liu J, Hou W (2016b) Wavelength-dependent differences in photocatalytic performance between BiOBr nanosheets with dominant exposed (001) and (010) facets. Appl Catal B-Environ 187:342–349. https://doi.org/10.1016/j.apcatb.2016.01.053
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
Liu M, Qiu X, Miyauchi M, Hashimoto K (2013) Energy-level matching of Fe (III) ions grafted at surface and doped in bulk for efficient visible-light photocatalysts. J Am Chem Soc 135:10064–10072. https://doi.org/10.1021/ja401541k
Liu C et al (2017) Constructing Z-scheme charge separation in 2D layered porous BiOBr/graphitic C3N4 nanosheets nanojunction with enhanced photocatalytic activity. J Alloys Compd 723:1121–1131. https://doi.org/10.1016/j.jallcom.2017.07.003
Low J, Cao S, Yu J, Wageh S (2014) Two-dimensional layered composite photocatalysts. Chem Commun 50:10768–10777. https://doi.org/10.1039/c4cc02553a
Lv J, Dai K, Zhang J, Liu Q, Liang C, Zhu G (2017) Facile constructing novel 2D porous g-C3N4/BiOBr hybrid with enhanced visible-light-driven photocatalytic activity. Sep Purif Technol 178:6–17
Niu P, Zhang L, Liu G, Cheng H-M (2012) Graphene-like carbon nitride nanosheets for improved photocatalytic activities. Adv Funct Mater 22:4763–4770. https://doi.org/10.1002/adfm.201200922
Ouyang SX et al (2012) Surface-alkalinization-induced enhancement of photocatalytic H-2 evolution over SrTiO3-based photocatalysts. J Am Chem Soc 134:1974–1977. https://doi.org/10.1021/ja210610h
Qiu X, Miyauchi M, Yu H, Irie H, Hashimoto K (2010) Visible-light-driven Cu (II)-(Sr1-yNay)(Ti1-xMox)O-3 photocatalysts based on conduction band control and surface ion modification. J Am Chem Soc 132:15259–15267. https://doi.org/10.1021/ja105846n
Su T, Shao Q, Qin Z, Guo Z, Wu Z (2018) Role of interfaces in two-dimensional photocatalyst for water splitting. ACS Catal 8:2253–2276
Tang L et al. (2016) Simulated solar driven catalytic degradation of psychiatric drug carbamazepine with binary BiVO4 heterostructures sensitized by graphene quantum dots. Appl Catal B: Environ 205:587-596 https://doi.org/10.1016/j.apcatb.2016.10.067
Wang P, Huang B, Zhang X, Qin X, Jin H, Dai Y, Wang Z, Wei J, Zhan J, Wang S, Wang J, Whangbo MH (2009a) Highly efficient visible-light plasmonic photocatalyst Ag@AgBr. Chem-Eur J 15:1821–1824. https://doi.org/10.1002/chem.200802327
Wang X et al (2009b) A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nat Mater 8:76
Wang X-j, Wang Q, Li F-T, Yang W-Y, Zhao Y, Hao Y-J, Liu S-J (2013) Novel BiOCl–C3N4 heterojunction photocatalysts: in situ preparation via an ionic-liquid-assisted solvent-thermal route and their visible-light photocatalytic activities. Chem Eng J 234:361–371. https://doi.org/10.1016/j.cej.2013.08.112
Wang J-C, Yao H-C, Fan Z-Y, Zhang L, Wang J-S, Zang S-Q, Li Z-J (2016) Indirect Z-scheme BiOl/g-C3N4 photocatalysts with enhanced photoreduction CO2 activity under visible light irradiation. ACS Appl Mater Interfaces 8:3765–3775. https://doi.org/10.1021/acsami.5b09901
Wang C-Y, Zhang X, Qiu H-B, Huang G-X, Yu H-Q (2017) Bi24O31Br10 nanosheets with controllable thickness for visible-light-driven catalytic degradation of tetracycline hydrochloride. Appl Catal B-Environ 205:615–623. https://doi.org/10.1016/j.apcatb.2017.01.015
Wang Q, Wang W, Zhong LL, Liu DM, Cao XZ, Cui FY (2018) Oxygen vacancy-rich 2D/2D BiOCl-g-C3N4 ultrathin heterostructure nanosheets for enhanced visible-light-driven photocatalytic activity in environmental remediation. Appl Catal B-Environ 220:290–302. https://doi.org/10.1016/j.apcatb.2017.08.049
Wu X, Ng YH, Wang L, Du Y, Dou SX, Amal R, Scott J (2017) Improving the photo-oxidative capability of BiOBr via crystal facet engineering. J Mater Chem A 5:8117–8124. https://doi.org/10.1039/c6ta10964k
Wu J, Xie Y, Ling Y, Dong Y, Li J, Li S, Zhao J (2019) Synthesis of flower-like g-C3N4/BiOBr and enhancement of the activity for the degradation of bisphenol A under visible light irradiation. Front Chem 7:649
Yan H, Yang H (2011) TiO2–g-C3N4 composite materials for photocatalytic H2 evolution under visible light irradiation. J Alloys Compd 509:L26–L29
Yan S, Lv S, Li Z, Zou Z (2010) Organic–inorganic composite photocatalyst of gC 3 N 4 and TaON with improved visible light photocatalytic activities. Dalton Trans 39:1488–1491
Yang Z, Li J, Cheng F, Chen Z, Dong X (2015) BiOBr/protonated graphitic C3N4 heterojunctions: intimate interfaces by electrostatic interaction and enhanced photocatalytic activity. J Alloys Compd 634:215–222. https://doi.org/10.1016/j.jallcom.2015.02.103
Yang L, Liang L, Wang L, Zhu J, Gao S, Xia X (2019) Accelerated photocatalytic oxidation of carbamazepine by a novel 3D hierarchical protonated g-C3N4/BiOBr heterojunction: performance and mechanism. Appl Surf Sci 473:527–539
Ye L, Zan L, Tian L, Peng T, Zhang J (2011) The {001} facets-dependent high photoactivity of BiOCl nanosheets. Chem Commun 47:6951–6953
Ye L, Liu J, Jiang Z, Peng T, Zan L (2013) Facets coupling of BiOBr-g-C3N4 composite photocatalyst for enhanced visible-light-driven photocatalytic activity. Appl Catal B Environ 142-143:1–7. https://doi.org/10.1016/j.apcatb.2013.04.058
Yu Y, Cao C, Liu H, Li P, Wei F, Jiang Y, Song W (2014) A Bi/BiOCl heterojunction photocatalyst with enhanced electron-hole separation and excellent visible light photodegrading activity. J Mater Chem A 2:1677–1681. https://doi.org/10.1039/c3ta14494a
Yuan L, Yang M-Q, Xu Y-J (2014) Tuning the surface charge of graphene for self-assembly synthesis of a SnNb 2 O 6 nanosheet–graphene (2D–2D) nanocomposite with enhanced visible light photoactivity. Nanoscale 6:6335–6345
Zhang G, Zhang J, Zhang M, Wang X (2012) Polycondensation of thiourea into carbon nitride semiconductors as visible light photocatalysts. J Mater Chem 22:8083–8091
Zhang D, Li J, Wang Q, Wu Q (2013) High {001} facets dominated BiOBr lamellas: facile hydrolysis preparation and selective visible-light photocatalytic activity. J Mater Chem A 1:8622–8629. https://doi.org/10.1039/c3ta11390f
Zhang H, Yang Y, Zhou Z, Zhao Y, Liu L (2014) Enhanced photocatalytic properties in BiOBr nanosheets with dominantly exposed (102) facets. J Phys Chem C 118:14662–14669. https://doi.org/10.1021/jp5035079
Zong X, Yan H, Wu G, Ma G, Wen F, Wang L, Li C (2008) Enhancement of photocatalytic H-2 evolution on CdS by loading MOS2 as cocatalyst under visible light irradiation. J Am Chem Soc 130:7176−+. https://doi.org/10.1021/ja8007825
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This research was funded by the National Natural Science Foundation of China (51303022) and the Shanghai Municipal Natural Science Foundation (12ZR1400400), the Fundamental Research Funds for the Central Universities (2232015D3-17, 15D110558), and Industry-University-Institute Project (Booster Plan) of Shanghai Municipal Education Commission (15cxy55).
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Zhou, M., Huang, W., Zhao, Y. et al. 2D g-C3N4/BiOBr heterojunctions with enhanced visible light photocatalytic activity. J Nanopart Res 22, 13 (2020). https://doi.org/10.1007/s11051-019-4739-3
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DOI: https://doi.org/10.1007/s11051-019-4739-3