Density functional theory study of adsorption of As2O3 on CeO2 surface by Fe, La doping and oxygen defects

LU Kunpeng; ZHANG Kaihua; ZHANG Kai

doi:10.19906/j.cnki.JFCT.2024005

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LU Kunpeng, ZHANG Kaihua, ZHANG Kai. Density functional theory study of adsorption of As2O3 on CeO2 surface by Fe, La doping and oxygen defects[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2024005

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LU Kunpeng, ZHANG Kaihua, ZHANG Kai. Density functional theory study of adsorption of As₂O₃ on CeO₂ surface by Fe, La doping and oxygen defects[J]. Journal of Fuel Chemistry and Technology. doi: 10.19906/j.cnki.JFCT.2024005

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Density functional theory study of adsorption of As₂O₃ on CeO₂ surface by Fe, La doping and oxygen defects

doi: 10.19906/j.cnki.JFCT.2024005

Beijing Key Laboratory of Emission Surveillance and Control for Thermal Power Generation, North China Electric Power University, Beijing 102206, China

Funds: The project was supported by the National Natural Science Foundation of China (U1910215) and the National Key R&D Program of China (2020YFB0606201).

Received Date: 2024-01-08
Accepted Date: 2024-02-05
Rev Recd Date: 2024-02-05

Available Online: 2024-03-13

Abstract

Abstract

Density functional theory (DFT) was used to study the adsorption behavior of As₂O₃ (g) on iron and lanthanum doped CeO₂ (110) and oxygen-deficient LaCeO (110) surfaces, and the reasons for the arsenic adsorption capacity of LaCeO surface was significantly higher than that of FeCeO surface was explored. The results show that the adsorption effect of As₂O₃ (g) is closely related to the number of adsorption sites, adsorption energy, bond length and charge transfer amount. Ce and O atoms on the surface of pure CeO₂ are both active sites, and the adsorption is mainly chemisorption, the absolute adsorption energy is greater than −4.22 eV, and the charge transfer amount is −0.19− −0.31 e. As₂O₃ has a negative charge and acts as a surface accepter, while CeO₂ loses electrons and has a positive charge on the surface, which acts as a surface donor. The number of free electrons in the CeO₂ conduction band gradually decreases, the conductivity decreases, and it is difficult to provide more electrons continuously, so the adsorption amount is small. Two adsorption sites are added on the surface of FeCeO (110): Fe top site and Bridge-2 Bridge site, where Fe top site is chemical adsorption and Bridge-2 Bridge site is physical adsorption. The gap doping of Fe changes the electron distribution and lattice structure on the surface of FeCeO, resulting in obvious deformation of the lattice and reducing the difficulty of bonding, thus increasing the configurational adsorption energy of some configurations. However, it does not change the charge transfer direction between As₂O₃ and FeCeO, thus not changing the surface adsorption form of As₂O₃. As₂O₃ is still adsorbed in the form of negative ions, which plays the role of surface acceptor, and the adsorption amount is small. LaCeO (110) has three new adsorption sites: La top site, Bridge-3 Bridge site and Hollow-2 vacancy, among which the La top site and Bridge-3 Bridge site are chemical adsorption. La doping changes the charge transfer direction between As₂O₃ and LaCeO, resulting in positive ion adsorption of As₂O₃ with electron loss and surface donor function. The electrons on the surface of LaCeO play the role of surface acceptor. With the progress of adsorption, the number of free electrons in the conduction band increases, and the conductivity increases. Therefore, the adsorption capacity of As₂O₃ on the surface of LaCeO increases. In the absence of O₂, the number of chemical bonds and bond energy formed on the surface of LaCeO (110) with single O defect are smaller than those on the surface of LaCeO, and the charge transfer on the surface of the defect is less, so the adsorption energy decreases. In this case, As₂O₃ obtains electrons and acts as the surface donor, and the adsorption capacity is lower than that on the complete LaCeO surface. In the presence of O₂, the adsorption energy and charge transfer number increase in the ortho-configuration after O₂ supplementation with O defect. As₂O₃ is positively adsorbed in ionic form, and the adsorption energy is also higher than that on the intact LaCeO surface. The adsorption capacity of As₂O₃ is better than that on the LaCeO surface, indicating that O defect is conducive to the adsorption of As₂O₃ in the presence of O₂.
- density functional theory,
- CeO₂,
- Fe、La doping,
- As₂O₃ adsorption,
- oxygen deficiency

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References(39)

References

[1]	刘明亮, 卫浩, 盖玉龙, 等. 中国、美国、欧盟及世界一次能源消费现状与展望[J]. 煤化工, 2022, 50(02): 1-5. LIU Mingliang, WEI Hao , GAI Yulong, et al. Current situation and outlook of primary energy consumption in China, US, EU and the world [J]. Coal Chem. Ind, 2022, 50(02): 1-5.)
[2]	TIAN H Z, WANG Y, XUE Z G, et al. Trend and characteristics of atmospheric emissions of Hg, As, and Se from coal combustion in china, 1980–2007[J]. Atmos. Chem. Phy,2010,10(23):11905−11919. doi: 10.5194/acp-10-11905-2010
[3]	TANG Q, LIU G, YAN Z, et al. Distribution and fate of environmentally sensitive elements (arsenic, mercury, stibium and selenium) in coal-fired power plants at huainan, anhui, china[J]. Fuel,2012,95:334−339. doi: 10.1016/j.fuel.2011.12.052
[4]	QUISPE D, PÉREZ-LÓPEZ R, SILVA L F O, et al. Changes in mobility of hazardous elements during coal combustion in santa catarina power plant (brazil)[J]. Fuel,2012,94:495−503. doi: 10.1016/j.fuel.2011.09.034
[5]	XUE Y, WANG Y. Effective industrial regeneration of arsenic poisoning waste selective catalytic reduction catalyst: contaminants removal and activity recovery[J]. Environ. Sci. Pollut. Res,2018,25(34):34114−34122. doi: 10.1007/s11356-018-3369-0
[6]	CIMINO S, LISI L. Catalyst deactivation, poisoning and regeneration[J]. Catalysts,2019,9(8):668. doi: 10.3390/catal9080668
[7]	王俊杰, 张亚平, 李娟, 等. 砷中毒商业V₂O₅-WO_3/TiO₂催化剂的再生方法[J]. 工程热物理学报,2018,39(2):450−456. WANG Junjie, ZHANG YaPing, LI Juan, et al. Regeneration Method of arsenic poisoned commerical SCR Catalyst[J]. J. Eng. Thermophys,2018,39(2):450−456.
[8]	HU P, WANG S, ZHUO Y. Research on As₂O₃ adsorption enhancement characteristics of Mn-modified γ-Al₂O₃[J]. Chem. Eng. J,2021,426:131660. doi: 10.1016/j.cej.2021.131660
[9]	曹蕃, 苏胜, 向军, 等. Mn-Ce-Zr/γ-Al₂O₃催化剂低温选择性催化还原脱硝性能分析[J]. 中国电机工程学报,2015,35(9):2238. CAO Fan, SU Sheng, XIANG Jun, et al. Performances of Mn-Ce-Zr/γ-Al₂O₃ Catalyst for Low Temperature Selective Catalytic Reduction of NO[J]. CSEE JPES,2015,35(9):2238.
[10]	ZHANG Y, LIU J. Density functional theory study of arsenic adsorption on the Fe₂O₃(001) surface[J]. Energy Fuels,2019,33(2):1414−1421. doi: 10.1021/acs.energyfuels.8b04155
[11]	HU H Y, CHEN D K, LIU H, et al. Adsorption and reaction mechanism of arsenic vapors over γ-Al₂O₃ in the simulated flue gas containing acid gases[J]. Chemosphere,2017,180(1):186−191.
[12]	HWANG S, KIM Y, LEE J, et al. Promoting effect of CO on low-temperature NOx adsorption over Pd/CeO₂ catalyst[J]. Catal. Today,2022,384-386:88−96. doi: 10.1016/j.cattod.2021.05.022
[13]	ZHAO G, LI M, LI H, et al. La-doped micro-angular cube ZnSnO3 with nano-La2O3 decoration for enhanced ethylene glycol sensing performance at low temperature[J]. Sens. Actuators, A,2023,362:114649. doi: 10.1016/j.sna.2023.114649
[14]	ZHANG K, HU L, WANG C, et al. Middle-low-temperature oxidation and adsorption of arsenic from flue gas by Fe–Ce-based composite catalyst[J]. Chemosphere,2022,288:132425. doi: 10.1016/j.chemosphere.2021.132425
[15]	侯书阳, 张凯华, 王传风, 等. Fe-Ce-La复合氧化物在中低温烟气脱砷过程中的协同作用[J]. 中国电机工程学报,2023,43(2):640−651. HOU Shuyang, ZHANG Kaihua, WANG Chuanfeng, et al. Synergistic Effect of Fe-Ce-La Composite Oxide in the Process of Arsenic Removal From Flue Gas at Middle-Low-Temperatures[J]. CSEE JPES,2023,43(2):640−651.
[16]	唐楠楠, 张姝, 李强林. 密度泛函理论的基本计算方法研究进展[J]. 成都纺织高等专科学校学报, 2015, 32(2): 39-43. TANG Nannan, ZHANG Shu , LI Qianghlin. Basic Algorithms Research Progress of Density Functional Theory [J]. J. Chengdu Text. Coll, 2015, 32(2): 39-43.)
[17]	马生贵, 田博文, 周雨薇, 等. 氮掺杂Stone-Wales缺陷石墨烯吸附H₂S的密度泛函理论研究[J]. 化工学报,2021,72(9):4496−4503. doi: 10.11949/0438-1157.20210215 MA Shenggui, TIAN Bowen, ZHOU Yuwei, et al. DFT study of adsorption of H₂S on N-doped Stone-Wales defected graphene[J]. J. Chem. Eng,2021,72(9):4496−4503. doi: 10.11949/0438-1157.20210215
[18]	周文波, 牛胜利, 刘思彤, 等. γ-Fe₂O₃抗As₂O₃中毒能力的分子模拟[J]. 中国环境科学,2022,42(8):3600−3609. doi: 10.3969/j.issn.1000-6923.2022.08.014 ZHOU Wenbo, NIU Shengli, LIU Sitong, et al. Molecular simulation study on the anti-As₂O₃ poisoning ability of γ-Fe₂O₃[J]. China Environ. Sci,2022,42(8):3600−3609. doi: 10.3969/j.issn.1000-6923.2022.08.014
[19]	YU Y, ZHAO R, LI X, et al. Mechanism of CaO and Fe₂O₃ capture gaseous arsenic species in the flue gas: dft combined thermodynamic study[J]. Fuel,2022,312:122838. doi: 10.1016/j.fuel.2021.122838
[20]	ZHANG Y, ZHAO B, WANG C, et al. Dual-functional effect encompassing adsorption and catalysis by mn-modified iron-based sorbents for arsenic removal: experimental and DFT study[J]. J. Hazard. Mater,2023,459:132079. doi: 10.1016/j.jhazmat.2023.132079
[21]	ZHAO S, WANG Y, XIE X, et al. Arsenic removal from Coal-fired flue gas by MnO₂ coated magnetic flower-like Fe₃O₄ composites: experimental and DFT study[J]. Chem. Eng. J,2023,478:147481. doi: 10.1016/j.cej.2023.147481
[22]	DELLEY B. Dmol3 DFT studies: from molecules and molecular environments to surfaces and solids[J]. Comp Mater Sci,2000,17(2):122−126.
[23]	PERDEW J P, BURKE K, WANG Y. Generalized gradient approximation for the exchange-correlation hole of a many-electron system[J]. Phys Rev B Condens Matter,1996,54(23):16533−16539. doi: 10.1103/PhysRevB.54.16533
[24]	PERDEW J P, BURKE K, ERNZERHOF M. Generalized gradient approximation made simple[J]. Phys. Rev. Lett,1996,77(18):3865−3868. doi: 10.1103/PhysRevLett.77.3865
[25]	NOLAN M, GRIGOLEIT S, SAYLE D C, et al. Density functional theory studies of the structure and electronic structure of pure and defective low index surfaces of ceria[J]. Surf. Sci,2005,576(1-3):217−229. doi: 10.1016/j.susc.2004.12.016
[26]	YANG Y, HU K, ZHANG J, et al. Adsorption properties of noble-metal (Ag, Rh, or Au)-doped CeO₂(110) to CO: a DFT + U study[J]. Comput. Mater. Sci,2024,231:112543. doi: 10.1016/j.commatsci.2023.112543
[27]	HE P, WU J, JIANG X, et al. Effect of SO₃ on elemental mercury adsorption on a carbonaceous surface[J]. Appl. Surf. Sci,2012,258(22):8853−8860. doi: 10.1016/j.apsusc.2012.05.104
[28]	YANG Y, LIU J, ZHANG B, et al. Density functional theory study on the heterogeneous reaction between Hg⁰ and Hcl over spinel-type MnFe₂O₄[J]. Chem. Eng. J,2017,308:897−903. doi: 10.1016/j.cej.2016.09.128
[29]	李宗宝, 贾礼超, 王霞等. N、C掺杂比例对锐钛矿TiO₂电子结构影响的第一性原理研究[J]. 黑龙江大学工程学报,2014,5(1):41−46. LI Zongbao, JIA Lichao, WANG Xia, et al. Density function theory on the electronic structure property of anatase TiO₂ doped by N or C with different percents[J]. J. Eng. HeiLongJiang. Univ,2014,5(1):41−46.
[30]	LYU Z, NIU S, LU C, et al. A density functional theory study on the selective catalytic reduction of NO by NH₃ reactivity of α-Fe₂O₃ (001) catalyst doped by Mn, Ti, Cr and Ni[J]. Fuel,2020,267:117147. doi: 10.1016/j.fuel.2020.117147
[31]	HUANG X, ZHANG K, PENG B, et al. Ceria-based materials for thermocatalytic and photocatalytic organic synthesis[J]. ACS Catal,2021,11(15):9618−9678. doi: 10.1021/acscatal.1c02443
[32]	YANG Z X, YU X H, LU Z S, et al. Oxygen vacancy pairs on CeO₂(110): A DFT + U study[J]. Phys. Lett. A,2009(373):312786−2792.
[33]	REN D, GUI K. Study of the adsorption of NH₃ and NO_x on the nanoγ-Fe₂O₃ (001) surface with density functional theory[J]. Appl. Surf. Sci,2019,487:171−179. doi: 10.1016/j.apsusc.2019.04.250
[34]	LI L, SONG L, ZHANG X, et al. Effect of substitutional and interstitial boron-doped NiCO₂S₄ on the electronic structure and surface adsorption: high rate and long-term stability[J]. ACS Appl. Energy Mater,2022,5(2):2505−2513. doi: 10.1021/acsaem.1c04033
[35]	HU P, WENG Q, LI D, et al. Effects of O₂, SO₂, H₂O and CO₂ on As₂O₃ adsorption by γ-Al₂O₃ based on DFT analysis[J]. J. Hazard. Mater,2021,403:123866. doi: 10.1016/j.jhazmat.2020.123866
[36]	XU H X, CHENG D J, CAO D P, et al. A universal principle for a rational design of single-atom electrocatalysts[J]. Nat. Catal,2018,1:339−348. doi: 10.1038/s41929-018-0063-z
[37]	WU Y, ZHOU X, MI T, et al. Theoretical insight into the interaction mechanism between V₂O₅/TiO₂ (001) surface and arsenic oxides in flue gas[J]. Appl. Surf. Sci,2021,535:147752. doi: 10.1016/j.apsusc.2020.147752
[38]	张佳松, 王辉, 王宁等. CO在不同氧缺陷Cu1/CeO2(110)表面的吸附: DFT+U[J]. 燃料化学学报,2022,50(3):326−336. doi: 10.1016/S1872-5813(21)60149-4 ZHANG Jiasong, WANG Hui, WANG ning, et al. Adsorption of CO on Cu1/CeO2(110) surface with different oxygen defects: DFT + U[J]. J. Fuel Chem. Technol,2022,50(3):326−336. doi: 10.1016/S1872-5813(21)60149-4
[39]	LIU Z, YU F, DONG D, et al. Transition-metal‐doped ceria carried on two-dimensional vermiculite for selective catalytic reduction of NO with CO: experiments and density functional theory[J]. Appl. Surf. Sci,2021,566:150704. doi: 10.1016/j.apsusc.2021.150704