CONSTRUCTION AND PHOTOCATALYTIC PERFORMANCE OF CARBON-DOPED FLOWER SPHERICAL Bi4O5Br1.87Cl0.13
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摘要: 卤氧化铋(BiOX)基光催化材料因具有优异的光催化性能近年来发展突飞猛进。为开发可见光响应的高效BiOX基光催化剂,以盐酸四环素为氯源和碳源,结合水热法和退火处理成功合成了碳掺杂的微纳米花球状固溶体(Bi4O5Br1.87Cl0.13)。利用TEM,SEM,XPS,XRD等分析技术对其进行了微观形貌、化学结构、光电化学性质、光催化降解性能的表征。结果表明:Bi4O5Br1.87Cl0.13为纳米片组装的花球状形貌,其中Cl和C元素的引入诱导其价带和导带轨道发生高程度的杂化,产生一定的杂质能级。该杂质能级增强了催化剂对可见光的吸收,同时提供电荷传输的通道,促进电荷分离。另外,Bi4O5Br1.87Cl0.13相比于未改性的Bi4O5Br2具有更窄的禁带宽度,在可见光下可获得更高的电子-空穴激发效率。通过300 ℃的退火处理,获得碳掺杂量为3.58%(质量分数)的Bi4O5Br1.87Cl0.13-300,其具有最优异的光催化性能。在35 W卤素灯光照下,1 h内Bi4O5Br1.87Cl0.13-300对甲基橙(10 mg/L)的降解率可达到88.29%,而Bi4O5Br2在相同条件下对甲基橙的降解率仅有28.53%。分步降解研究表明,Bi4O5Br1.87Cl0.13-300优异的光催化性能主要是球形表面的纳米片状多级结构提供了大量的表面位点参与反应。研究成果为增强BiOX材料的光催化性能提供了新的参考。Abstract: Bismuth halide oxide based photocatalytic materials have made rapid progress in recent years due to their excellent photocatalytic performace. In this project, in order to develop effective visible light responsive BiOX based photocatalyst, carbon-doped micro and nano-flower spherical solid solution (Bi4O5Br1.87Cl0.13) were successfully synthesized by combining the hydrothermal method and annealing treatment, with tetracycline hydrochloride as the chlorine and carbon sources. TEM, SEM, XPS, XRD and other analytical techniques were used to characterize its micro morphology, chemical structure, photoelectrochemical properties, and photocatalytic degradation performance. The results showed that Bi4O5Br1.87Cl0.13 was a spherical morphology of nanosheet assembly, in which the introduction of chlorine and carbon elements induced a high degree of hybridization in the valence and conduction band orbitals, resulting in a certain impurity energy level. This impurity energy level enhanced the absorption of visible light by the catalyst, while providing a channel for charge transport and promoting charge separation. Moreover, Bi4O5Br1.87Cl0.13 had a narrower forbidden bandwidth compared to the unmodified Bi4O5Br2, which meant that a higher electron-hole excitation efficiency obtained in visible light. The Bi4O5Br1.87Cl0.13-300 with a carbon doping of 3.58% (mass fraction) was obtained by annealing at 300 ℃ with the most excellent photocatalytic performance. The degradation of methyl orange (10 mg/L) by Bi4O5Br1.87Cl0.13-300 could reach 88.29% in one hour under the light of 35 W halogen lamp, while the degradation of methyl orange by Bi4O5Br2 under the same conditions was only 28.53%. The stepwise degradation study showed that the excellent photocatalytic degradation performance of Bi4O5Br1.87Cl0.13-300 mainly came from the nanosheet-like multistage structure on the spherical surface, which provided a large number of surface sites involved in the reaction. The present work provided a new reference for the enhancement of the photocatalytic performance of bismuth halide oxide materials.
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[1] 张静雯, 李英华. 卤氧化铋光催化剂的改性研究与应用[J]. 硅酸盐通报, 2021, 40(7): 2374-2379. [2] YANG C Y, WANG Z, LIN T Q, et al. Core-shell nanostructured "Black" rutile titania as excellent catalyst for hydrogen production enhanced by sulfur doping[J]. Journal of the American Chemical Society, 2013, 135(47): 17831. [3] HE C N, XU L, HUANG W Q, et al. Origin of photocatalytic activity of nitrogen-doped germanium dioxide under visible light from first principles[J]. Materials Science in Semiconductor Processing, 2015, 31: 517-524. [4] JIANG G H, WANG X H, WEI Z, et al. Photocatalytic properties of hierarchical structures based on Fe-doped BiOBr hollow microspheres[J]. Journal of Materials Chemistry A, 2013, 1(7):2406-2410. [5] ZHANG X, ZHANG L Z. Electronic and band structure tuning of ternary semiconductor photocatalysts by self doping: the case of BiOI[J]. The Journal of Physical Chemistry C, 2010, 114(42): 18198-18206. [6] LIU H, CAO W R, SU Y, et al. Synthesis, characterization and photocatalytic performance of novel visible-light-induced Ag/BiOI[J]. Applied Catalysis B: Environmental, 2012, 111/112: 271-279. [7] JIANG Z Y, LIU Y Y, JING T, et al. One-pot solvothermal synthesis of S doped BiOCl for solar water oxidation[J]. RSC Advances, 2015, 5(58): 47261-47264. [8] LI J, CAI L, SHANG J, et al. Giant enhancement of internal electric field boosting bulk charge separation for photocatalysis[J]. Adv Mater, 2016, 28(21): 4059-4064. [9] 金晓丽. 富铋基卤氧铋光催化剂的构筑及性能研究[D]. 哈尔滨:哈尔滨工业大学, 2020. [10] ZHANG H J, LIU L, ZHOU Z. Towards better photocatalysts: first-principles studies of the alloying effects on the photocatalytic activities of bismuth oxyhalides under visible light[J]. Phys Chem Chem Phys, 2012, 14(3): 1286-1292. [11] LIU Y Y, SON W J, LU J B, et al. Composition dependence of the photocatalytic activities of BiOCl1-xBrx solid solutions under visible light[J]. Chemistry-A European Journal, 2011. [12] DONG F, SUN Y J, FU M, et al. Room temperature synthesis and highly enhanced visible light photocatalytic activity of porous BiOI/BiOCl composites nanoplates microflowers[J]. J Hazard Mater, 2012, 219/220: 26-34. [13] REN K, LIU J, LIANG J, et al. Synthesis of the bismuth oxyhalide solid solutions with tunable band gap and photocatalytic activities[J]. Dalton Trans, 2013, 42(26): 9706-9712. [14] SHANG J, CHEN T Z, WANG X W, et al. Facile fabrication and enhanced photocatalytic performance: from BiOCl to element-doped BiOCl[J]. Chemical Physics Letters, 2018, 706:483-487. [15] ZHANG X, WANG C Y, WANG L W, et al. Fabrication of BiOBrxI1-x photocatalysts with tunable visible light catalytic activity by modulating band structures[J]. Sci Rep, 2016, 6: 22800. [16] YE L Q, LIU J Y, JIANG Z, et al. Facets coupling of BiOBr-g-C3N4 composite photocatalyst for enhanced visible-light-driven photocatalytic activity[J]. Applied Catalysis B: Environmental, 2013, 142/143: 1-7. [17] ZHUANG L Z, GE L, YANG Y S, et al. Ultrathin iron-cobalt oxide nanosheets with abundant oxygen vacancies for the oxygen evolution reaction[J]. Adv Mater, 2017, 29(17):1606793. [18] JIN X L, LV C D, ZHOU X, et al. A bismuth rich hollow Bi4O5Br2 photocatalyst enables dramatic CO2 reduction activity[J]. Nano Energy, 2019, 64:103955. [19] TAUC J, GRIGOROVICI R, VANCU A. Optical properties and electronic structure of amorphous germanium[J]. Physica Status Solidi (b), 1966, 15(2):627-637. [20] DAVIS E A, MOTT N F. Conduction in non-crystalline systems V. Conductivity, optical absorption and photoconductivity in amorphous semiconductors[J]. Philosophical Magazine, 1970, 22(179):903-922. [21] GELDERMAN K, LEE L, DONNE S W. Flat-band potential of a semiconductor: using the Mott-Schottky equation[J]. Journal of Chemical Education, 2007, 84(4): 685-688. [22] BERANEK R. (Photo)electrochemical methods for the determination of the band edge positions of TiO2-based nanomaterials[J]. Advances in Physical Chemistry, 2011: 1-20. [23] YANG Y, CHEN Y Y, LI Z H, et al. Homojunction type of carbon nitride as a robust photo-catalyst for reduction conversion of CO2 in water vapor under visible light[J]. Chemical Engineering Journal, 2022, 430(P1):132668. [24] WANG L X. Proposal for a new class of materials: spin gapless semiconductors[J]. Physical review letters, 2008, 100(15):205-208. [25] LV C D, CHEN G, ZHOU X, et al. Oxygen-induced Bi5+-self-doped Bi4V2O11 with a p-n homojunction toward promoting the photocatalytic performance[J]. ACS Appl Mater Interfaces, 2017, 9(28): 23748-23755. [26] IVAN G, G. S K, H. J D, et al. Wavelength-dependent ultrafast charge carrier separation in the WO3/BiVO4 coupled system[J]. ACS Energy Letters, 2017, 2(6):1362-1367. [27] HUANG W L, ZHU Q S. Electronic structures of relaxed BiOX (X=F, Cl, Br, I) photocatalysts[J]. Computational Materials Science, 2008, 43(4): 1101-1108. [28] LIN X P, HUANG T, HUANG F Q, et al. Photocatalytic activity of a Bi-based oxychloride Bi3O4Cl[J]. Journal of physical chemistry B, 2006, 110(48): 24629-24634. [29] FRIEDMANN D, MENDIVE C, BAHNEMANN D. TiO2 for water treatment: parameters affecting the kinetics and mechanisms of photocatalysis[J]. Applied Catalysis B: Environmental, 2010, 99(3/4): 398-406. [30] CHLADKOVA B, EVGENIDOU E, KVITEK L, et al. Adsorption and photocatalysis of nanocrystalline TiO2 particles for Reactive Red 195 removal: effect of humic acids, anions and scavengers[J]. Environ Sci Pollut Res Int, 2015, 22(21): 16514-16524. [31] LINSEBIGLER A L, LU G Q, YATES J T. Photocatalysis on TiO2 surfaces-principles, mechanisms, and selected results[J]. Chemical Reviews, 1995, 95(3): 735-758. [32] WANG N N, ZHOU Y, CHEN C H, et al. A g-C3N4 supported graphene oxide/Ag3PO4 composite with remarkably enhanced photocatalytic activity under visible light[J]. Catalysis Communications, 2016, 73: 74-79. [33] SHAN W J, HU Y, BAI Z G, et al. In situ preparation of g-C3N4/bismuth-based oxide nanocomposites with enhanced photocatalytic activity[J]. Applied Catalysis B: Environmental, 2016, 188: 1-12. [34] SUN J W, BIAN J, LI J D, et al. Efficiently photocatalytic conversion of CO2 on ultrathin metal phthalocyanine/g-C3N4 heterojunctions by promoting charge transfer and CO2 activation[J]. Applied Catalysis B: Environmental, 2020, 277:119199. [35] MA X M, HAO H M, SHENG W L, et al. Bridging green light photocatalysis over hierarchical Nb2O5 for the selective aerobic oxidation of sulfides[J]. Jouranal of Materials Chemistry A, 2021, 9(4): 2214-2222.
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