第一性原理研究Ag掺杂及缺陷共存对ZnO光催化性质的影响

摘要/Abstract

摘要： 运用第一性原理研究了Ag掺杂及缺陷共存对ZnO光电性质的影响。计算结果表明富O条件有利于Ag的掺杂,贫O条件不利于Ag的掺杂。Ag掺杂浓度较低时有利于模型的稳定,其在富O或贫O条件下都以Ag_Zn为主要掺杂方式。当Ag掺杂浓度较高时,富O条件下以Ag_Zn-Ag_Zn为主要掺杂方式,贫O条件下Ag_Zn-Ag_i是较为有利的掺杂方式。富O条件下Ag掺杂较难引入V_Zn和O_i共存缺陷。贫O条件下优先出现的模型为V_O,V_O在一定程度上会促进Ag的掺杂。Ag掺杂降低了ZnO的带隙宽度,掺杂浓度越大模型带隙宽度越窄。V_Zn、V_O和O_i缺陷共存不同程度地增加了Ag掺杂模型的带隙宽度。Ag掺杂及V_Zn和O_i缺陷共存均使ZnO吸收边红移至可见光区,扩展了ZnO对太阳光的吸收范围,而Ag_Zn-V_O在可见光范围内依然是透明。在低能区紫外-可见光范围内,Ag_Zn-Ag_Zn表现出更高的光吸收率,但是相应形成能也高于Ag_Zn。V_Zn的引入提高了Ag_Zn-V_Zn和Ag_Zn-Ag_Zn-V_Zn对低能区紫外-可见光的吸收,V_O的引入有利于ZnO表面吸附更多的O₂进而产生更多的H₂O₂和·HO强氧化性物质,即V_Zn和V_O缺陷共存都有利于ZnO光催化性能的提高。

关键词: ZnO, Ag掺杂, 缺陷共存, 第一性原理, 光催化性质, 光电性质

Abstract: The effects of Ag doping and defect coexistence on the photoelectric properties of ZnO were studied by first-principles method. The calculation results indicate that O-rich condition is beneficial to Ag doping, while O-poor condition has an inhibitory effect. When Ag doping concentration is lower, Ag_Zn is dominant doping model under O-rich or O-poor conditions, and the model is more stable. When Ag doping concentration is higher, Ag_Zn-Ag_Zn is dominant doping model under O-rich condition, and that is Ag_Zn-Ag_i under O-poor condition. Under O-rich condition, it is difficult to introduce the coexistence defect of V_Zn and O_i by Ag doping. V_O is a preferred model under O-poor condition, and it can promote Ag doping to a certain extent. Ag doping reduces the band gap of ZnO. The higher of doping concentration is, the narrower of band gap will be. The defect coexistence of V_Zn, V_O and O_i increase the band gap of Ag doped models. Ag doping and the defect coexistence of V_Zn, O_i all red shift the absorption edge of ZnO to the visible region, which expands the absorption range of ZnO to sunlight. Ag_Zn-V_O is transparent in the visible region. In the low energy region, Ag_Zn-Ag_Zn shows higher optical absorptivity, but the corresponding formation energy is also higher than that of Ag_Zn. V_Zn improves the optical absorptivity of Ag_Zn-V_Zn and Ag_Zn-Ag_Zn-V_Zn in the low energy region. V_O is beneficial to the adsorption of O₂ by ZnO and can produce more H₂O₂ and ·HO. The defect coexistence of V_Zn and V_O both improve the photocatalytic performance of ZnO.

Key words: ZnO, Ag doping, defect coexistence, first-principle, photocatalytic property, photoelectric property

中图分类号:

O649

张海峰, 王彬, 程彩萍, 伊思静. 第一性原理研究Ag掺杂及缺陷共存对ZnO光催化性质的影响[J]. 人工晶体学报, 2021, 50(11): 2027-2035.

ZHANG Haifeng, WANG Bin, CHENG Caiping, YI Sijing. First-Principles Study on the Effects of Ag Doping and Defect Coexistence on the Photocatalytic Properties of ZnO[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2021, 50(11): 2027-2035.

参考文献

[1] THEERTHAGIRI J, SALLA S, SENTHIL R A, et al. A review on ZnO nanostructured materials: energy, environmental and biological applications[J]. Nanotechnology, 2019, 30(39): 392001.
[2] RASHID M, IKRAM M, HAIDER A, et al. Photocatalytic, dye degradation, and bactericidal behavior of Cu-doped ZnO nanorods and their molecular docking analysis[J]. Dalton Transactions, 2020, 49(24): 8314-8330.
[3] SAMADI M, ZIRAK M, NASERI A, et al. Design and tailoring of one-dimensional ZnO nanomaterials for photocatalytic degradation of organic dyes: a review[J]. Research on Chemical Intermediates, 2019, 45(4): 2197-2254.
[4] LIU J L, WANG Y H, MA J Z, et al. A review on bidirectional analogies between the photocatalysis and antibacterial properties of ZnO[J]. Journal of Alloys and Compounds, 2019, 783: 898-918.
[5] RAMASAMY B, JEYADHARMARAJAN J, CHINNAIYAN P. Novel organic assisted Ag-ZnO photocatalyst for atenolol and acetaminophen photocatalytic degradation under visible radiation: performance and reaction mechanism[J]. Environmental Science and Pollution Research, 2021, 28(29): 39637-39647.
[6] NIE M, LIAO J M, CAI H L, et al. Photocatalytic property of silver enhanced Ag/ZnO composite catalyst[J]. Chemical Physics Letters, 2021, 768: 138394.
[7] ONKANI S P, DIAGBOYA P N, MTUNZI F M, et al. Comparative study of the photocatalytic degradation of 2-chlorophenol under UV irradiation using pristine and Ag-doped species of TiO₂, ZnO and ZnS photocatalysts[J]. Journal of Environmental Management, 2020, 260: 110145.
[8] LIANG X Z, WANG P, GAO Y G, et al. Design and synthesis of porous M-ZnO/CeO₂ microspheres as efficient plasmonic photocatalysts for nonpolar gaseous molecules oxidation: insight into the role of oxygen vacancy defects and M=Ag, Au nanoparticles[J]. Applied Catalysis B: Environmental, 2020, 260: 118151.
[9] ZIASHAHABI A, PRATO M, DANG Z Y, et al. The effect of silver oxidation on the photocatalytic activity of Ag/ZnO hybrid plasmonic/metal-oxide nanostructures under visible light and in the dark[J]. Scientific Reports, 2019, 9: 11839.
[10] LI X L, HE S S, LIU X S, et al. Polymer-assisted freeze-drying synthesis of Ag-doped ZnO nanoparticles with enhanced photocatalytic activity[J]. Ceramics International, 2019, 45(1): 494-502.
[11] ASHEBIR M E, TESFAMARIAM G M, NIGUSSIE G Y, et al. Structural, optical, and photocatalytic activities of Ag-doped and Mn-doped ZnO nanoparticles[J]. Journal of Nanomaterials, 2018, 2018: 1-9.
[12] 张海峰,李鹏,卢士香,等.Cu/Ag单掺及Cu-Ag共掺对ZnO光催化性能影响的第一性原理研究[J].人工晶体学报,2020,49(6):1112-1120.
ZHANG H F, LI P, LU S X, et al. First-principles study on the photocatalytic activity of Cu/Ag doped and Cu-Ag codoped ZnO[J]. Journal of Synthetic Crystals, 2020, 49(6): 1112-1120(in Chinese).
[13] 郝艳艳,张影,赵琳.ZnO-SiO₂的制备及其光催化降解罗丹明B[J].人工晶体学报,2017,46(7):1379-1384.
HAO Y Y, ZHANG Y, ZHAO L. Fabrication of ZnO-SiO₂ and its photocatalytic degradation of rhodamine B[J]. Journal of Synthetic Crystals, 2017, 46(7): 1379-1384(in Chinese).
[14] HOU Q Y, SHA S L. First-principles study of acceptor Li/Ag/Cu doping and Zn vacancy on the magnetic mechanism of ZnO and the universality of itinerant electrons[J]. Materials Today Communications, 2021, 26: 101944.
[15] LIU Y J, HOU Q Y, SHA S L, et al. Electronic structure, optical and ferromagnetic properties of ZnO co-doped with Ag and Co according to first-principles calculations[J]. Vacuum, 2020, 173: 109127.
[16] LIU Y J, HOU Q Y, XU Z C, et al. Effects of Ag doping and point defect on the magnetism of ZnO[J]. Journal of Superconductivity and Novel Magnetism, 2019, 32(7): 2097-2106.
[17] BERDIYOROV G R, BOLTAYEV F, ESHONQULOV G, et al. Effect of vacancy defects on the electronic transport properties of an Ag-ZnO-Pt sandwich structure[J]. Journal of Computational Electronics, 2021, 20(2): 798-804.
[18] THANG H V, PACCHIONI G. H₂ adsorption on wurtzite ZnO and on ZnO/M(111) (M=Cu, Ag and Au) bilayer films[J]. ChemNanoMat, 2019, 5(7): 932-939.
[19] POSTICA V, VAHL A, SANTOS-CARBALLAL D, et al. Tuning ZnO sensors reactivity toward volatile organic compounds via Ag doping and nanoparticle functionalization[J]. ACS Applied Materials & Interfaces, 2019, 11(34): 31452-31466.
[20] MASOUMI S, NADIMI E, HOSSEIN-BABAEI F. Electronic properties of Ag-doped ZnO∶DFT hybrid functional study[J]. Physical Chemistry Chemical Physics, 2018, 20(21): 14688-14693.
[21] ZHANG M L, CHEN Y H, ZHANG C R, et al. Effect of intrinsic defects and copper impurities co-existing on electromagnetic optical properties of ZnO: first principles study[J]. Acta Physica Sinica, 2019, 68(8): 087101.
[22] MA Z H, REN F Z, MING X L, et al. Cu-doped ZnO electronic structure and optical properties studied by first-principles calculations and experiments[J]. Materials, 2019, 12(1): 196.
[23] HOU Q Y, ZHAO C W, JIA X F, et al. Effect of heavy Ag doping on the physical properties of ZnO[J]. International Journal of Modern Physics B, 2018, 32(9): 1850099.
[24] LI Y L, ZHAO X, FAN W L. Structural, electronic, and optical properties of Ag-doped ZnO nanowires: first principles study[J]. The Journal of Physical Chemistry C, 2011, 115(9): 3552-3557.
[25] JOTHIBAS M, MUTHUVEL A, SENTHILKANNAN K, et al. Structural, optical and photocatatic activity of Ag doped ZnO nanoparticles obtained by Sol-gel method[C]//Proceedings Of The International Conference on Advanced Materials: ICAM 2019. Kerala, India. AIP Publishing, 2019: 020151.
[26] WANG L L. Growth of well-aligned Ag-doped ZnO nanorods arrays on FTO substrate using electrochemical approach: optical properties and photocatalytic activity[J]. International Journal of Electrochemical Science, 2019: 9150-9158.
[27] TRAN M L, NGUYEN C H, FU C C, et al. Hybridizing Ag-Doped ZnO nanoparticles with graphite as potential photocatalysts for enhanced removal of metronidazole antibiotic from water[J]. Journal of Environmental Management, 2019, 252: 109611.
[28] OKOYE C I. Theoretical study of the electronic structure, chemical bonding and optical properties of KNbO₃in the paraelectric cubic phase[J]. Journal of Physics: Condensed Matter, 2003, 15(35): 5945-5958.
[29] CAZZANIGA M, CARAMELLA L, MANINI N, et al. Ab initiointraband contributions to the optical properties of metals[J]. Physical Review B, 2010, 82(3): 035104.
[30] YAN Y F, AL JASSIM M M, WEI S H. Oxygen-vacancy mediated adsorption and reactions of molecular oxygen on theZnO(1010)surface[J]. Physical Review B, 2005, 72(16): 161307.
[31] ZHA R H, SHI T, LI C, et al. Oxygen vacancy-engineered surfaces of ZnO-decorated porous BiOI microspheres for strongly enhanced visible-light NO oxidation[J]. Catalysis Science & Technology, 2021, 11(12): 4235-4244.
[32] YU F C, LIU Z Y, LI Y M, et al. Effect of oxygen vacancy defect regeneration on photocatalytic properties of ZnO nanorods[J]. Applied Physics A, 2020, 126(12): 1-12.