Coupling of BiOCl Ultrathin Nanosheets with Carbon Quantum Dots for Enhanced Photocatalytic Performance

Abstract

Over the past few decades, photocatalysis technology has received extensive attention because of its potential to mitigate or solve energy and environmental pollution problems.Designing novel materials with outstanding photocatalytic activities has become a research hotspot in this field. In this study, we prepared a series of photocatalysts in which BiOCl nanosheets were modified with carbon quantum dots (CQDs) to form CQDs/BiOCl composites by using a simple solvothermal method. The photocatalytic performance of the resulting CQDs/BiOCl composite photocatalysts was assessed by rhodamine B and tetracycline degradation under visible-light irradiation. Compared with bare BiOCl, the photocatalytic activity of the CQDs/BiOCl composites was significantly enhanced, and the 5 wt% CQDs/BiOCl composite exhibited the highest photocatalytic activity with a degradation efficiency of 94.5% after 30 min of irradiation. Moreover, photocatalytic N₂ reduction performance was significantly improved after introducing CQDs. The 5 wt% CQDs/BiOCl composite displayed the highest photocatalytic N₂ reduction performance to yield NH₃ (346.25 μmol/(g h)), which is significantly higher than those of 3 wt% CQDs/BiOCl (256.04 μmol/(g h)), 7 wt% CQDs/BiOCl (254.07 μmol/(g h)), and bare BiOCl (240.19 μmol/(g h)). Our systematic characterizations revealed that the key role of CQDs in improving photocatalytic performance is due to their increased light harvesting capacity, remarkable electron transfer ability, and higher photocatalytic activity sites.

This work reports a novel CQDs/BiOCl composite photocatalyst for efficiently removing contaminants from water.

Keywords

Carbon quantum dots / BiOCl / Rhodamine B / Tetracycline / Photocatalysis

References

[1.] Choi SH, Yun SJ, Won YS, et al.. Large-scale synthesis of graphene and other 2D materials towards industrialization. Nat Commun, 2022, 13(1): 1484,

[2.] Li L, Xia Y, Zeng M, et al.. Facet engineering of ultrathin two-dimensional materials. Chem Soc Rev, 2022, 51(17): 7327-7343,

[3.] Zhou Y, Xu L, Liu M, et al.. Viscous solvent-assisted planetary ball milling for the scalable production of large ultrathin two-dimensional materials. ACS Nano, 2022, 16(7): 10179-10187,

[4.] Peng J, Dong W, Wang Z, et al.. Recent advances in 2D transition metal compounds for electrocatalytic full water splitting in neutral media. Mater Today Adv, 2020, 8,

[5.] Di J, Chen C, Zhu C, et al.. Bismuth vacancy-tuned bismuth oxybromide ultrathin nanosheets toward photocatalytic CO₂ reduction. ACS Appl Mater Interfaces, 2019, 11(34): 30786-30792,

[6.] Song P, Wang M, Di J, et al.. Reusable graphitic carbon nitride nanosheet-based aerogels as sorbents for oils and organic solvents. ACS Appl Nano Mater, 2020, 3(8): 8176-8181,

[7.] Sun Y, Gao S, Xie Y. Atomically-thick two-dimensional crystals: electronic structure regulation and energy device construction. Chem Soc Rev, 2014, 43(2): 530-546,

[8.] Zhou Y, Song P, Pan M, et al.. Super hydrophilic-electrons acceptor regulated rutile TiO₂ nanorods for promoting photocatalytic H₂ evolution. Appl Surf Sci, 2023, 623,

[9.] Zhang J, Song X, Wang L, et al.. Ultrathin two-dimensional hybrid perovskites toward flexible electronics and optoelectronics. Natl Sci Rev, 2021, 9(5): nwab129,

[10.] Shao T, Wang X, Dong H, et al.. A stacked plasmonic metamaterial with strong localized electric field enables highly efficient broadband light-driven CO₂ hydrogenation. Adv Mater, 2022, 34(28),

[11.] Song P, Di J, Chen H, et al.. A three-dimensional porous MoS₂–PVP aerogel as a highly efficient and recyclable sorbent for oils and organic solvents. Mater Adv, 2020, 1(4): 760-766,

[12.] Sun Y, Sun Z, Gao S, et al.. Fabrication of flexible and freestanding zinc chalcogenide single layers. Nat Commun, 2012, 3: 1057,

[13.] Zhang JJ, Di J, Zhao YP, et al.. Synergistic defect and doping engineering building strong bonded S-scheme heterojunction for photocatalysis. Chemosphere, 2023, 344,

[14.] Liang H, Song P, Jiang W, et al.. Indium-based atomic layer for photoreduction reactions: design, synthesis and performance optimization. Sep Purif Technol, 2023, 324,

[15.] Xiong J, Song P, Di J, et al.. Atomic-level active sites steering in ultrathin photocatalysts to trigger high efficiency nitrogen fixation. Chem Eng J, 2020, 402,

[16.] Di J, Chen C, Zhu C, et al.. Cobalt nitride as a novel cocatalyst to boost photocatalytic CO₂ reduction. Nano Energy, 2021, 79,

[17.] Yao L, Yang H, Chen Z, et al.. Bismuth oxychloride-based materials for the removal of organic pollutants in wastewater. Chemosphere, 2020, 273,

[18.] Dong Y, Pang S, Zhang F, et al.. A novel lateral epitaxial Bi₂O₃@BiOCl heterostructure for photocatalytic antibiotic degradation in an internal circulation fluidized bed reactor. Chem Eng J, 2023, 478,

[19.] Li Q, Ren J, Hao YJ, et al.. Insight into reactive species-dependent photocatalytic toluene mineralization and deactivation pathways via modifying hydroxyl groups and oxygen vacancies on BiOCl. Appl Catal B Environ, 2022, 317,

[20.] Song P, Du J, Ma X, et al.. Design of Bi₄O₅Br₂/g-_C3_N4 heterojunction for efficient photocatalytic removal of persistent organic pollutants from water. EcoEnergy, 2023, 1(1): 197-206,

[21.] Zhao K, Zhang L, Wang J, et al.. Surface structure-dependent molecular oxygen activation of BiOCl single-crystalline nanosheets. J Am Chem Soc, 2013, 135(42): 15750-15753,

[22.] Li ZQ, Chen XH, Li T, et al.. Crystal facet engineering of polar single crystal BiOCl with improved piezo-photocatalytic activity. Appl Surf Sci, 2023, 615,

[23.] Cao D, Xu W, Chen S, et al.. Visualizing catalytic dynamics processes via synchrotron radiation multitechniques. Adv Mater, 2023, 35(30),

[24.] Liu C, Ren Y, Wang Z, et al.. Flowerlike BiOCl nanospheres fabricated by an in situ self-assembly strategy for efficiently enhancing photocatalysis. J Colloid Interface Sci, 2022, 607(Pt 1): 423-430,

[25.] Cong W, Song P, Zhang Y, et al.. Supramolecular confinement pyrolysis to carbon-supported Mo nanostructures spanning four scales for hydroquinone determination. J Hazard Mater, 2022, 437,

[26.] Ma ZP, Zhang L, Ma X, et al.. A dual strategy for synthesizing crystal plane/defect co-modified BiOCl microsphere and photodegradation mechanism insights. J Colloid Interface Sci, 2022, 617: 73-83,

[27.] Senasu T, Lorwanishpaisarn N, Hemavibool K, et al.. Construction of g-C₃N₄/BiOCl/CdS heterostructure photocatalyst for complete removal of oxytetracycline antibiotic in wastewater. Sep Purif Technol, 2023, 306,

[28.] Lin B, Chaturvedi A, Di J, et al.. Ferroelectric-field accelerated charge transfer in 2D CuInP₂S₆ heterostructure for enhanced photocatalytic H₂ evolution. Nano Energy, 2020, 76,

[29.] Sun Y, Cheng H, Gao S, et al.. Freestanding tin disulfide single-layers realizing efficient visible-light water splitting. Angew Chem Int Ed Engl, 2012, 51(35): 8727-8731,

[30.] Jiang J, Zhao K, Xiao X, et al.. Synthesis and facet-dependent photoreactivity of BiOCl single-crystalline nanosheets. J Am Chem Soc, 2012, 134(10): 4473-4476,

[31.] Lim SY, Shen W, Gao Z. Carbon quantum dots and their applications. Chem Soc Rev, 2015, 44(1): 362-381,

[32.] Guo Y, Zhang R, Zhang S, et al.. Ultrahigh oxygen-doped carbon quantum dots for highly efficient H₂O₂ production via two-electron electrochemical oxygen reduction. Energy Environ Sci, 2022, 15(10): 4167-4174,

[33.] Ding C, Guo J, Chen P, et al.. All-solid-state Z-scheme In₂S₃/CQDs/TiO₂ heterojunction for highly efficient degradation of ofloxacin. Appl Surf Sci, 2022, 596,

[34.] Li H, Liu R, Liu Y, et al.. Carbon quantum dots/Cu₂O composites with protruding nanostructures and their highly efficient (near) infrared photocatalytic behavior. J Mater Chem, 2012, 22(34): 17470-17475,

[35.] Shao N, Hou Z, Zhu H, et al.. Novel 3D core-shell structured CQDs/Ag₃PO₄@Benzoxazine tetrapods for enhancement of visible-light photocatalytic activity and anti-photocorrosion. Appl Catal B Environ, 2018, 232: 574-586,

[36.] Li W, Wang Z, Li Y, et al.. Visible-NIR light-responsive 0D/2D CQDs/Sb₂WO₆ nanosheets with enhanced photocatalytic degradation performance of RhB: unveiling the dual roles of CQDs and mechanism study. J Hazard Mater, 2022, 424(Pt C),

[37.] Hou Y, Laursen AB, Zhang J, et al.. Layered nanojunctions for hydrogen-evolution catalysis. Angew Chem Int Ed Engl, 2013, 52(13): 3621-3625,

[38.] Yu C, Li G, Kumar S, et al.. Phase transformation synthesis of novel Ag₂O/Ag₂CO₃ heterostructures with high visible light efficiency in photocatalytic degradation of pollutants. Adv Mater, 2014, 26(6): 892-898,

[39.] Yu C, Yang K, Xie Y, et al.. Novel hollow Pt-ZnO nanocomposite microspheres with hierarchical structure and enhanced photocatalytic activity and stability. Nanoscale, 2013, 5(5): 2142-2151,

[40.] Xu M, Yu R, Guo Y, et al.. New strategy towards the assembly of hierarchical heterostructures of SnO₂/ZnO for NO₂ detection at a ppb level. Inorg Chem Front, 2019, 6(10): 2801-2809,

[41.] Di J, Xia J, Ge Y, et al.. Novel visible-light-driven CQDs/Bi₂WO₆ hybrid materials with enhanced photocatalytic activity toward organic pollutants degradation and mechanism insight. Appl Catal B Environ, 2015, 168–169: 51-61,

[42.] Di J, Xia J, Yin S, et al.. Preparation of sphere-like g-C₃N₄/BiOI photocatalysts via a reactable ionic liquid for visible-light-driven photocatalytic degradation of pollutants. J Mater Chem A, 2014, 2(15): 5340-5351,

[43.] Zhu S, Meng Q, Wang L, et al.. Highly photoluminescent carbon dots for multicolor patterning, sensors, and bioimaging. Angew Chem Int Ed Engl, 2013, 52(14): 3953-3957,

[44.] Duo F, Wang Y, Fan C, et al.. Enhanced visible light photocatalytic activity and stability of CQDs/BiOBr composites: the upconversion effect of CQDs. J Alloys Compd, 2016, 685: 34-41,

[45.] Xia J, Di J, Li H, et al.. Ionic liquid-induced strategy for carbon quantum dots/BiOX (X = Br, Cl) hybrid nanosheets with superior visible light-driven photocatalysis. Appl Catal B Environ, 2016, 181: 260-269,

[46.] Di J, Xia J, Ji M, et al.. The synergistic role of carbon quantum dots for the improved photocatalytic performance of Bi₂MoO₆. Nanoscale, 2015, 7(26): 11433-11443,

[47.] Gao X, Wu HB, Zheng L, et al.. Formation of mesoporous heterostructured BiVO₄/Bi₂S₃ hollow discoids with enhanced photoactivity. Angew Chem Int Ed Engl, 2014, 53(23): 5917-5921,

[48.] Di J, Xia J, Yin S, et al.. One-pot solvothermal synthesis of Cu-modified BiOCl via a Cu-containing ionic liquid and its visible-light photocatalytic properties. RSC Adv, 2014, 4(27): 14281-14290,

[49.] Wang S, Li D, Sun C, et al.. Synthesis and characterization of g-C₃N₄/Ag₃VO₄ composites with significantly enhanced visible-light photocatalytic activity for triphenylmethane dye degradation. Appl Catal B Environ, 2014, 144: 885-892,

[50.] Gu X, Yan Q, Wei Y, et al.. Visible-light-responsive photocatalyst with a microsphere structure: preparation and photocatalytic performance of CQDs@BiOCl. J Mater Sci Mater Electron, 2019, 30(17): 16321-16336,

[51.] Leelavathi A, Madras G, Ravishankar N. New insights into electronic and geometric effects in the enhanced photoelectrooxidation of ethanol using ZnO nanorod/ultrathin Au nanowire hybrids. J Am Chem Soc, 2014, 136(41): 14445-14455,

[52.] Zhu Y, Ji X, Pan C, et al.. A carbon quantum dot decorated RuO₂ network: outstanding supercapacitances under ultrafast charge and discharge. Energy Environ Sci, 2013, 6(12): 3665-3675,

[53.] Di J, Xia J, Yin S, et al.. A g-C₃N₄/BiOBr visible-light-driven composite: synthesis via a reactable ionic liquid and improved photocatalytic activity. RSC Adv, 2013, 3(42): 19624-19631,

[54.] Lv Y, Zhu Y, Zhu Y. Enhanced photocatalytic performance for the BiPO_{4– x} nanorod induced by surface oxygen vacancy. J Phys Chem C, 2013, 117(36): 18520-18528,

[55.] Hu Q, Ji M, Di J, et al.. Ionic liquid-induced double regulation of carbon quantum dots modified bismuth oxychloride/bismuth oxybromide nanosheets with enhanced visible-light photocatalytic activity. J Colloid Interface Sci, 2018, 519: 263-272,

[56.] Ye L, Chen J, Tian L, et al.. BiOI thin film via chemical vapor transport: photocatalytic activity, durability, selectivity and mechanism. Appl Catal B Environ, 2013, 130–131: 1-7

[57.] Chen C, Ma W, Zhao J. Semiconductor-mediated photodegradation of pollutants under visible-light irradiation. Chem Soc Rev, 2010, 39(11): 4206-4219,

[58.] Yu C, Wei L, Zhou W, et al.. Enhancement of the visible light activity and stability of Ag₂CO₃ by formation of AgI/Ag₂CO₃ heterojunction. Appl Surf Sci, 2014, 319: 312-318,