Citation: GUO Hai-yan, REN Jun, FENG Gang, LI Chang-sheng, PENG Xing, CAO Duan-lin. Distribution of Al and adsorption of NH₃ in mordenite:A computational study[J]. Journal of Fuel Chemistry and Technology, ;2014, 42(5): 582-590. shu

Distribution of Al and adsorption of NH₃ in mordenite:A computational study

GUO Hai-yan ¹ ,
REN Jun ^1,, ,
FENG Gang ^2,, ,
LI Chang-sheng ¹ ,
PENG Xing ¹ ,
CAO Duan-lin ¹

1.
1. College of Chemical Engineering and Environment, North University of China, Taiyuan 030051, China;

Corresponding author: REN Jun, FENG Gang,
Received Date: 31 October 2013
Available Online: 7 January 2014
Fund Project: Supported by the National Science Foundation of China (21371159) (21371159) the Natural Science Foundation of Shanxi Province (2009011014) (2009011014)Shenzhen Strategic Emerging Industries Special Fund Program of China (GGJS20120619101655715). (GGJS20120619101655715)

Dispersion corrected density functional theory (DFT-D2) were employed to investigate the distribution of Al in the framework of H-[Al]MOR and the strengths of Brönsted acid sites by NH₃ adsorption. Thermodynamically, the most favorable site for distribution of Al is T2O5, followed by T4O2, T1O7 and T3O1, which are a little higher in energy when Al is incorporated. It was found that the energy differences for Al in different T sites are 0.03~ 0.07 eV, indicating that the Al atoms might distribute in all kinds of four non-equivalent crystallographic tetrahedral sites of MOR. Moreover, it is also suggested that the location of protons plays an important role in the stability of the Al substitution site. In addition, we also computed the adsorption energies for NH₃ adsorbed at each crystallographic position of H-[Al]MOR by DFT and DFT-D2, respectively. By comparison, the DFT method always underestimates the substitution energy by 0.41 eV for the adsorption of NH₃, indicating that the dispersion correction is necessary to calculate the adsorption of NH₃ in H-[Al]MOR. The results show that the Brönsted acid site at T2O5 is stronger than the other acid sites, and the adsorption of NH₃ on the Lewis acid sites is clearly weaker than on the Brönsted acid sites.
- mordenite,
- Al distribution,
- NH₃ adsorption,
- DFT-D2
1. [1]
  [1] BURBIDGE B W, KEEN I M, EYLES M K. Physical and catalytic properties of the zeolite mordenite[M]. In: Molecular Sieve Zeolites-II. Adv Chem Ser, 1971, 102: 400-409.
2. [2]
  [2] LEACH H. Application of molecular sieve zeolites to catalysis[J]. Annu Rep Pro Chem Sect A: Inorg Chem, 1971, 68: 195-219.
3. [3]
  [3] BUSCA G. Acid catalysts in industrial hydrocarbon chemistry[J]. Chem Rev, 2007, 107(11): 5366-5410.
4. [4]
  [4] NIWA M, SUZUKI K, KATADA N, KANOUGI T, ATOGUCHI T . Ammonia IRMS-TPD study on the distribution of acid sites in mordenite[J]. J Phys Chem B, 2005, 109(40): 18749-18757.
5. [5]
  [5] MARIE O, MASSIANI P, THIBAULT-STARZYK F. Infrared evidence of a third brønsted site in mordenites[J]. J Phys Chem B, 2004, 108(16): 5073-5081.
6. [6]
  [6] BAJPAI P K, RAO M S, GOKHALE K. Synthesis of mordenite type zeolites[J]. Ind Eng Chem Prod Res Dev, 1978, 17(3): 223-227.
7. [7]
  [7] BAJPAI P K. Synthesis of mordenite type zeolite[J]. Zeolites, 1986, 6(1): 2-8.
8. [8]
  [8] ALBERTI A. Location of Brønsted sites in mordenite[J]. Zeolites, 1997, 19(5/6): 411-415.
9. [9]
  [9] ALBERTI A, DAVOLI P, VEZZALINI G. The crystal structure refinement of a natural mordenite[J]. Z Kristallogr -Cryst Mater, 1986, 175(3/4): 249-256.
10. [10]
  [10] LIU B, GARCÍA-PÍREZ E, DUBBELDAM D, SMIT B, CALERO S. Understanding aluminum location and non-framework ions effects on alkane adsorption in aluminosilicates: A molecular simulation study[J]. J Phys Chem C, 2007, 111(28): 10419-10426.
11. [11]
  [11] BAN S, VLUGT T J H. Adsorption and diffusion of alkanes in Na-MOR: Modeling the effect of the aluminum distribution[J]. J Chem Theory Comput, 2009, 5(10): 2858-2865.
12. [12]
  [12] RAMACHANDRAN C E, WILLIAMS B A, VAN BOKHOVEN J A, MILLER J T. Observation of a compensation relation for n-hexane adsorption in zeolites with different structures: Implications for catalytic activity[J]. J Catal, 2005, 233(1): 100-108.
13. [13]
  [13] BRÄNDLE M, SAUER J. Acidity differences between inorganic solids induced by their framework structure. A combined quantum mechanics/molecular mechanics ab initio study on zeolites[J]. J Am Chem Soc, 1998, 120(7): 1556-1570.
14. [14]
  [14] DEMUTH T, HAFNER J, BENCO L, TOULHOAT H. Structural and acidic properties of mordenite. An ab initio density-functional study[J]. J Phys Chem B, 2000, 104(19): 4593-4607.
15. [15]
  [15] OUMI Y, KANAI T, LU B, SANO T. Structural and physico-chemical properties of high-silica mordenite[J]. Micropor Mesopor Mater, 2007, 101(1/2):127-133.
16. [16]
  [16] YUAN S, WANG J, LI Y, PENG S. Siting of B, Al, Ga or Zn and bridging hydroxyl groups in mordenite: an ab initio study[J]. J Mol Catal A: Chem, 2001, 175(1/2):131-138.
17. [17]
  [17] MAACHE M, JANIN A, LAVALLEY J C, BENAZZI E. FT infrared study of Brnsted acidity of H-mordenites: Heterogeneity and effect of dealumination[J]. Zeolites, 1995, 15(6): 507-516.
18. [18]
  [18] LAMBEROV A A, KUZNETSOV A M, SHAPNIK M S, MASLIY A N, BORISEVICH S V, ROMANOVA R G, EGOROVA S R. Quantum-chemical investigation of the formation of Lewis acid centers of high-siliceous zeolites[J]. J Mol Catal A: Chem, 2000, 158(1): 481-486.
19. [19]
  [19] FENG G, LIAN Y Y, YANG D Q, LIU J W, KONG D J. Distribution of Al and adsorption of NH₃ and pyridine in ZSM-12: A computational study[J]. Can J Chem, 2013, 91(10): 925-934.
20. [20]
  [20] ELANANY M, VERCAUTEREN D P, KOYAMA M, KUBO M, SELVAM P, BROCLAWIK E, MIYAMOTO A. H-MOR: Density functional investigation for the relative strength of Brnsted acid sites and dynamics simulation of NH₃ protonation-deprotonation[J]. J Mol Catal A: Chem, 2006, 243(1): 1-7.
21. [21]
  [21] DÍAZ L, SIERRAALTA A, NASCIMENTO MAC, A[WTBZ]Й[WTB1]EZ R. Evaluation of Brnsted sites inside the H-MOR employing NH₃: A theoretical study[J]. J Phys Chem C, 2013, 117(10): 5112-5117.
22. [22]
  [22] HUO H, PENG L, GAN Z, GREY C P. Solid-state MAS NMR studies of Brnsted acid sites in zeolite H-mordenite[J]. J Am Chem Soc, 2012, 134(23): 9708-9720.
23. [23]
  [23] BLUMENFELD A L, COSTER D, FRIPIAT J J. Broensted acid sites and surface structure in zeolites: A high-resolution 29Si NMR REDOR study[J]. J Phys Chem, 1995, 99(41): 15181-15191.
24. [24]
  [24] JACOBS W, DE HAAN J, VAN DE VEN L, VAN SANTEN R. Interaction of ammonia with Brnsted acid sites in different cages of zeolite Y as studied by proton MAS NMR[J]. J Phys Chem, 1993, 97(40): 10394-10402.
25. [25]
  [25] JACOBS W P J H, VAN WOLPUT J H M C, VAN SANTEN R A. An in situ Fourier transform infrared studyof zeolitic vibrations: Dehydration, deammoniation, and reammoniation of ion-exchanged Y zeolites[J]. Zeolites, 1993, 13(3): 170-182.
26. [26]
  [26] KRESSE G, FURTHM LLER J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set[J]. Comput Mater Sci, 1996, 6(1): 15-50.
27. [27]
  [27] KRESSE G, FURTHM LLER J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set[J]. Phys Rev B, 1996, 54(16): 11169-11186.
28. [28]
  [28] KERBER T, SIERKA M, SAUER J. Application of semiempirical long-range dispersion corrections to periodic systems in density functional theory[J]. J Comput Chem, 2008, 29(13): 2088-2097.
29. [29]
  [29] GRIMME S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction[J]. J Comput Chem, 2006, 27(15): 1787-1799.
30. [30]
  [30] PERDEW JP, BURKE K, ERNZERHOF M. Generalized gradient approximation made simple[J]. Phys Rev Lett, 1996, 77(18): 3865-3868.
31. [31]
  [31] BLÖCHL P E, FÖRST C, SCHIMPL J. Projector augmented wave method: ab initio molecular dynamics with full wave functions[J]. Bull Mater Sci, 2003, 26(1): 33-41.
32. [32]
  [32] BLÖCHL P E. Projector augmented-wave method[J]. Phys Rev B, 1994, 50(24):17953-17979.
33. [33]
  [33] REN L M, GUO Q, ZHANG H Y, ZHU L F, YANG C G, WANG L, MENG X J, FENG Z C, LI C, XIAO F S. Organotemplate-free and one-pot fabrication of nano-rod assembled plate-like micro-sized mordenite crystals[J]. J Mater Chem, 2012, 22(14): 6564-6567.
34. [34]
  [34] ORTMANN F, BECHSTEDT F, SCHMIDT W G. Semiempirical van der Waals correction to the density functional description of solids and molecular structures[J]. Phys Rev B, 2006, 73(20): 205101.
1. [1]
  Yang Li , Yanan Dong , Zhihong Wei , Changzeng Yan , Zhen Li , Lin He , Yuehui Li . Fluoride-promoted Ni-catalyzed cyanation of C–O bond using CO₂ and NH₃. Chinese Chemical Letters, 2025, 36(5): 110206-. doi: 10.1016/j.cclet.2024.110206
2. [2]
  Jijoe Samuel Prabagar , Kumbam Lingeshwar Reddy , Dong-Kwon Lim . Visible-light responsive gold nanoparticle and nano-sized Bi2O3-x sheet heterozygote structure for efficient photocatalytic conversion of N2 to NH3. Chinese Journal of Structural Chemistry, 2025, 44(4): 100564-100564. doi: 10.1016/j.cjsc.2025.100564
3. [3]
  Kexin Yan , Zhaoqi Ye , Lingtao Kong , He Li , Xue Yang , Yahong Zhang , Hongbin Zhang , Yi Tang . Seed-Induced Synthesis of Disc-Cluster Zeolite L Mesocrystals with Ultrashort c-Axis: Morphology Control, Decoupled Mechanism, and Enhanced Adsorption. Acta Physico-Chimica Sinica, 2024, 40(9): 2308019-0. doi: 10.3866/PKU.WHXB202308019
4. [4]
  Jun Huang , Pengfei Nie , Yongchao Lu , Jiayang Li , Yiwen Wang , Jianyun Liu . 丝光沸石负载自支撑氮掺杂多孔碳纳米纤维电容器及高效选择性去除硬度离子. Acta Physico-Chimica Sinica, 2025, 41(7): 100066-0. doi: 10.1016/j.actphy.2025.100066
5. [5]
  Jiali CHEN , Guoxiang ZHAO , Yayu YAN , Wanting XIA , Qiaohong LI , Jian ZHANG . Machine learning exploring the adsorption of electronic gases on zeolite molecular sieves. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 155-164. doi: 10.11862/CJIC.20240408
6. [6]
  Cuiwu MO , Gangmin ZHANG , Chao WU , Zhipeng HUANG , Chi ZHANG . A(NH₂SO₃) (A=Li, Na): Two ultraviolet transparent sulfamates exhibiting second harmonic generation response. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1387-1396. doi: 10.11862/CJIC.20240045
7. [7]
  Xueqi Yang , Juntao Zhao , Jiawei Ye , Desen Zhou , Tingmin Di , Jun Zhang . 调节NNU-55(Fe)的d带中心以增强CO₂吸附和光催化活性. Acta Physico-Chimica Sinica, 2025, 41(7): 100074-0. doi: 10.1016/j.actphy.2025.100074
8. [8]
  Fei Xie , Chengcheng Yuan , Haiyan Tan , Alireza Z. Moshfegh , Bicheng Zhu , Jiaguo Yu . d-Band Center Regulated O₂ Adsorption on Transition Metal Single Atoms Loaded COF: A DFT Study. Acta Physico-Chimica Sinica, 2024, 40(11): 2407013-0. doi: 10.3866/PKU.WHXB202407013
9. [9]
  Haojie Duan , Hejingying Niu , Lina Gan , Xiaodi Duan , Shuo Shi , Li Li . Reinterpret the heterogeneous reaction of α-Fe₂O₃ and NO₂ with 2D-COS: The role of SDS, UV and SO₂. Chinese Chemical Letters, 2024, 35(6): 109038-. doi: 10.1016/j.cclet.2023.109038
10. [10]
  Yuan Teng , Zichun Zhou , Jinghua Chen , Siying Huang , Hongyan Chen , Daibin Kuang . Dual atom-bridge effect promoting interfacial charge transfer in 2D/2D Cs₃Bi₂Br₉/BiOBr epitaxial heterojunction for efficient photocatalysis. Chinese Chemical Letters, 2025, 36(2): 110430-. doi: 10.1016/j.cclet.2024.110430
11. [11]
  Jiawei Hu , Kai Xia , Ao Yang , Zhihao Zhang , Wen Xiao , Chao Liu , Qinfang Zhang . Interfacial Engineering of Ultrathin 2D/2D NiPS₃/C₃N₅ Heterojunctions for Boosting Photocatalytic H₂ Evolution. Acta Physico-Chimica Sinica, 2024, 40(5): 2305043-0. doi: 10.3866/PKU.WHXB202305043
12. [12]
  Hualin Jiang , Wenxi Ye , Huitao Zhen , Xubiao Luo , Vyacheslav Fominski , Long Ye , Pinghua Chen . Novel 3D-on-2D g-C₃N₄/AgI._x._y heterojunction photocatalyst for simultaneous and stoichiometric production of H₂ and H₂O₂ from water splitting under visible light. Chinese Chemical Letters, 2025, 36(2): 109984-. doi: 10.1016/j.cclet.2024.109984
13. [13]
  Liuyun Chen , Wenju Wang , Tairong Lu , Xuan Luo , Xinling Xie , Kelin Huang , Shanli Qin , Tongming Su , Zuzeng Qin , Hongbing Ji . Soft template-induced deep pore structure of Cu/Al₂O₃ for promoting plasma-catalyzed CO₂ hydrogenation to DME. Acta Physico-Chimica Sinica, 2025, 41(6): 100054-0. doi: 10.1016/j.actphy.2025.100054
14. [14]
  Cailiang Yue , Nan Sun , Yixing Qiu , Linlin Zhu , Zhiling Du , Fuqiang Liu . A direct Z-scheme 0D α-Fe₂O₃/TiO₂ heterojunction for enhanced photo-Fenton activity with low H₂O₂ consumption. Chinese Chemical Letters, 2024, 35(12): 109698-. doi: 10.1016/j.cclet.2024.109698
15. [15]
  Xinyu Yin , Haiyang Shi , Yu Wang , Xuefei Wang , Ping Wang , Huogen Yu . Spontaneously Improved Adsorption of H₂O and Its Intermediates on Electron-Deficient Mn^(3+δ)+ for Efficient Photocatalytic H₂O₂ Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312007-0. doi: 10.3866/PKU.WHXB202312007
16. [16]
  Zehao Zhang , Zheng Wang , Haibo Li . Preparation of 2D V₂O₃@Pourous Carbon Nanosheets Derived from V₂CF_x MXene for Capacitive Desalination. Acta Physico-Chimica Sinica, 2024, 40(8): 2308020-0. doi: 10.3866/PKU.WHXB202308020
17. [17]
  Yue Li , Minghao Fan , Conghui Wang , Yanxun Li , Xiang Yu , Jun Ding , Lei Yan , Lele Qiu , Yongcai Zhang , Longlu Wang . 3D layer-by-layer amorphous MoS_x assembled from [Mo₃S₁₃]^2- clusters for efficient removal of tetracycline: Synergy of adsorption and photo-assisted PMS activation. Chinese Chemical Letters, 2024, 35(9): 109764-. doi: 10.1016/j.cclet.2024.109764
18. [18]
  Ao Sun , Zipeng Li , Shuchun Li , Xiangbao Meng , Zhongtang Li , Zhongjun Li . Stereoselective synthesis of α-3-deoxy-D-manno-oct-2-ulosonic acid (α-Kdo) derivatives using a C3-p-tolylthio-substituted Kdo fluoride donor. Chinese Chemical Letters, 2025, 36(3): 109972-. doi: 10.1016/j.cclet.2024.109972
19. [19]
  Hongyi LI , Aimin WU , Liuyang ZHAO , Xinpeng LIU , Fengqin CHEN , Aikui LI , Hao HUANG . Effect of Y(PO₃)₃ double-coating modification on the electrochemical properties of Li[Ni_0.8Co_0.15Al_0.05]O₂. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1320-1328. doi: 10.11862/CJIC.20230480
20. [20]
  Haitao Wang , Lianglang Yu , Jizhou Jiang , Arramel , Jing Zou . S-Doping of the N-Sites of g-C₃N₄ to Enhance Photocatalytic H₂ Evolution Activity. Acta Physico-Chimica Sinica, 2024, 40(5): 2305047-0. doi: 10.3866/PKU.WHXB202305047

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(333)
HTML views(15)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Distribution of Al and adsorption of NH3 in mordenite:A computational study

Metrics

通讯作者: 陈斌, bchen63@163.com

Distribution of Al and adsorption of NH₃ in mordenite:A computational study