α-Fe2 O3 表面 SO2 吸附及 SO3 催化生成的密度泛函分析

Yongbing Wang; Gaofeng Dai; Zhiliang Shan; Xuebin Wang; Hongjun You; Houzhang Tan

doi:10.13226/j.issn.1006-6772.19122101

α-Fe₂ O₃ 表面 SO₂ 吸附及 SO₃ 催化生成的密度泛函分析

Translated title of the contribution: DFT study on the adsorption of SO₂ and catalytic formation of SO₃ on the α-Fe₂O₃ surface

Yongbing Wang
, Gaofeng Dai
, Zhiliang Shan
, Xuebin Wang
, Hongjun You
, Houzhang Tan

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

A large amount of SO₂ and a small amount of SO₃ are emitted from coal-fired power plants.The generation of SO₃ is not only harmful to the environment,but also dangerous to the safe operation of the power plant.Current studies show that Fe₂O₃ contained in the fly ash and the boiler wall have a significant catalytic effect on the SO₃ formation. However,the research on the path and mechanism of SO₃ catalytic formation by Fe₂ O₃ is not deep enough.In this paper,the α-Fe₂ O₃(001) surface was established firstly,and the adsorp⁃ tion configuration of SO₂ and O₂ on α-Fe₂O₃(001)surface was studied by density functional theory(DFT).The stable adsorption configura⁃ tion of SO₂ and the dissociation pathway of O₂ on Fe₂O₃(001)surface were obtained.The reaction path and energy barrier of catalytic for⁃ mation of SO₃ on α-Fe₂ O₃ surface were studied by using transition state search method.Then the energy barrier of catalytic formation of SO₃ in gas phase reaction were compared.The results show that the most stable adsorption configuration of SO₂ is that O and S atom in SO₂ are adsorbed above Fe atoms on α - Fe₂O₃,while S atom is not easy to be adsorbed above lattice oxygen of α-Fe₂O₃ crystal.The adsorption energy of O₂ on α-Fe₂O₃ surface is greater than the maximum adsorption energy of SO₂,which means that O₂ is more easily ad⁃ sorbed on α-Fe₂O₃ surface.In addition,O₂ is easy to dissociate and form O atom on the defect Fe₂O₃ surface with oxygen vacancy,which indicates that α- Fe₂O₃ with oxygen vacancy is easier to promote the dissociation of O₂ and the generation of adsorbed oxygen on the sur⁃ face.The L-H mechanism of SO₃ formation is that SO₂ and O atoms in the gas phase are adsorbed firstly on the α-Fe₂O₃ surface,and then combine to form SO₃,and the reaction energy barrier is 231.65 kJ/ mol.The E-R mechanism is that SO₂ in the gas phase reacts with adsorbed oxygen on α-Fe₂O₃ surface to form SO₃ while the reaction energy barrier is 24.82 kJ/ mol,which is less than that of L-H mecha⁃ nism and far less than that of SO₃ formation in gas phase reaction.The above results confirm that Fe₂O₃ has a significant catalytic effect on the formation of SO₃,and the E-R mechanism is the dominant reaction mechanism.The existence of oxygen vacancy promotes the dissocia⁃ tion of O₂ on the surface of α - Fe₂O₃,and the surface adsorbed oxygen plays an important role in the catalytic process.

Translated title of the contribution	DFT study on the adsorption of SO₂ and catalytic formation of SO₃ on the α-Fe₂O₃ surface
Original language	Chinese (Traditional)
Pages (from-to)	203-209
Number of pages	7
Journal	Clean Coal Technology
Volume	26
Issue number	6
DOIs	https://doi.org/10.13226/j.issn.1006-6772.19122101
State	Published - 2020

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10.13226/j.issn.1006-6772.19122101

Cite this

@article{a3cfd0abce4445b982dd73fba3a295d2,

title = "α-Fe2 O3 表面 SO2 吸附及 SO3 催化生成的密度泛函分析",

abstract = "A large amount of SO2 and a small amount of SO3 are emitted from coal-fired power plants.The generation of SO3 is not only harmful to the environment,but also dangerous to the safe operation of the power plant.Current studies show that Fe2O3 contained in the fly ash and the boiler wall have a significant catalytic effect on the SO3 formation. However,the research on the path and mechanism of SO3 catalytic formation by Fe2 O3 is not deep enough.In this paper,the α-Fe2 O3(001) surface was established firstly,and the adsorp⁃ tion configuration of SO2 and O2 on α-Fe2O3(001)surface was studied by density functional theory(DFT).The stable adsorption configura⁃ tion of SO2 and the dissociation pathway of O2 on Fe2O3(001)surface were obtained.The reaction path and energy barrier of catalytic for⁃ mation of SO3 on α-Fe2 O3 surface were studied by using transition state search method.Then the energy barrier of catalytic formation of SO3 in gas phase reaction were compared.The results show that the most stable adsorption configuration of SO2 is that O and S atom in SO2 are adsorbed above Fe atoms on α - Fe2O3,while S atom is not easy to be adsorbed above lattice oxygen of α-Fe2O3 crystal.The adsorption energy of O2 on α-Fe2O3 surface is greater than the maximum adsorption energy of SO2,which means that O2 is more easily ad⁃ sorbed on α-Fe2O3 surface.In addition,O2 is easy to dissociate and form O atom on the defect Fe2O3 surface with oxygen vacancy,which indicates that α- Fe2O3 with oxygen vacancy is easier to promote the dissociation of O2 and the generation of adsorbed oxygen on the sur⁃ face.The L-H mechanism of SO3 formation is that SO2 and O atoms in the gas phase are adsorbed firstly on the α-Fe2O3 surface,and then combine to form SO3,and the reaction energy barrier is 231.65 kJ/ mol.The E-R mechanism is that SO2 in the gas phase reacts with adsorbed oxygen on α-Fe2O3 surface to form SO3 while the reaction energy barrier is 24.82 kJ/ mol,which is less than that of L-H mecha⁃ nism and far less than that of SO3 formation in gas phase reaction.The above results confirm that Fe2O3 has a significant catalytic effect on the formation of SO3,and the E-R mechanism is the dominant reaction mechanism.The existence of oxygen vacancy promotes the dissocia⁃ tion of O2 on the surface of α - Fe2O3,and the surface adsorbed oxygen plays an important role in the catalytic process.",

keywords = "catalytic reaction, density functional theory, SO adsorption, SO, α-FeO",

author = "Yongbing Wang and Gaofeng Dai and Zhiliang Shan and Xuebin Wang and Hongjun You and Houzhang Tan",

year = "2020",

doi = "10.13226/j.issn.1006-6772.19122101",

language = "繁体中文",

volume = "26",

pages = "203--209",

journal = "Clean Coal Technology",

issn = "1006-6772",

publisher = "China International Book Trading Corp. (Guoji Shudian)",

number = "6",

}

TY - JOUR

T1 - α-Fe2 O3 表面 SO2 吸附及 SO3 催化生成的密度泛函分析

AU - Wang, Yongbing

AU - Dai, Gaofeng

AU - Shan, Zhiliang

AU - Wang, Xuebin

AU - You, Hongjun

AU - Tan, Houzhang

PY - 2020

Y1 - 2020

N2 - A large amount of SO2 and a small amount of SO3 are emitted from coal-fired power plants.The generation of SO3 is not only harmful to the environment,but also dangerous to the safe operation of the power plant.Current studies show that Fe2O3 contained in the fly ash and the boiler wall have a significant catalytic effect on the SO3 formation. However,the research on the path and mechanism of SO3 catalytic formation by Fe2 O3 is not deep enough.In this paper,the α-Fe2 O3(001) surface was established firstly,and the adsorp⁃ tion configuration of SO2 and O2 on α-Fe2O3(001)surface was studied by density functional theory(DFT).The stable adsorption configura⁃ tion of SO2 and the dissociation pathway of O2 on Fe2O3(001)surface were obtained.The reaction path and energy barrier of catalytic for⁃ mation of SO3 on α-Fe2 O3 surface were studied by using transition state search method.Then the energy barrier of catalytic formation of SO3 in gas phase reaction were compared.The results show that the most stable adsorption configuration of SO2 is that O and S atom in SO2 are adsorbed above Fe atoms on α - Fe2O3,while S atom is not easy to be adsorbed above lattice oxygen of α-Fe2O3 crystal.The adsorption energy of O2 on α-Fe2O3 surface is greater than the maximum adsorption energy of SO2,which means that O2 is more easily ad⁃ sorbed on α-Fe2O3 surface.In addition,O2 is easy to dissociate and form O atom on the defect Fe2O3 surface with oxygen vacancy,which indicates that α- Fe2O3 with oxygen vacancy is easier to promote the dissociation of O2 and the generation of adsorbed oxygen on the sur⁃ face.The L-H mechanism of SO3 formation is that SO2 and O atoms in the gas phase are adsorbed firstly on the α-Fe2O3 surface,and then combine to form SO3,and the reaction energy barrier is 231.65 kJ/ mol.The E-R mechanism is that SO2 in the gas phase reacts with adsorbed oxygen on α-Fe2O3 surface to form SO3 while the reaction energy barrier is 24.82 kJ/ mol,which is less than that of L-H mecha⁃ nism and far less than that of SO3 formation in gas phase reaction.The above results confirm that Fe2O3 has a significant catalytic effect on the formation of SO3,and the E-R mechanism is the dominant reaction mechanism.The existence of oxygen vacancy promotes the dissocia⁃ tion of O2 on the surface of α - Fe2O3,and the surface adsorbed oxygen plays an important role in the catalytic process.

AB - A large amount of SO2 and a small amount of SO3 are emitted from coal-fired power plants.The generation of SO3 is not only harmful to the environment,but also dangerous to the safe operation of the power plant.Current studies show that Fe2O3 contained in the fly ash and the boiler wall have a significant catalytic effect on the SO3 formation. However,the research on the path and mechanism of SO3 catalytic formation by Fe2 O3 is not deep enough.In this paper,the α-Fe2 O3(001) surface was established firstly,and the adsorp⁃ tion configuration of SO2 and O2 on α-Fe2O3(001)surface was studied by density functional theory(DFT).The stable adsorption configura⁃ tion of SO2 and the dissociation pathway of O2 on Fe2O3(001)surface were obtained.The reaction path and energy barrier of catalytic for⁃ mation of SO3 on α-Fe2 O3 surface were studied by using transition state search method.Then the energy barrier of catalytic formation of SO3 in gas phase reaction were compared.The results show that the most stable adsorption configuration of SO2 is that O and S atom in SO2 are adsorbed above Fe atoms on α - Fe2O3,while S atom is not easy to be adsorbed above lattice oxygen of α-Fe2O3 crystal.The adsorption energy of O2 on α-Fe2O3 surface is greater than the maximum adsorption energy of SO2,which means that O2 is more easily ad⁃ sorbed on α-Fe2O3 surface.In addition,O2 is easy to dissociate and form O atom on the defect Fe2O3 surface with oxygen vacancy,which indicates that α- Fe2O3 with oxygen vacancy is easier to promote the dissociation of O2 and the generation of adsorbed oxygen on the sur⁃ face.The L-H mechanism of SO3 formation is that SO2 and O atoms in the gas phase are adsorbed firstly on the α-Fe2O3 surface,and then combine to form SO3,and the reaction energy barrier is 231.65 kJ/ mol.The E-R mechanism is that SO2 in the gas phase reacts with adsorbed oxygen on α-Fe2O3 surface to form SO3 while the reaction energy barrier is 24.82 kJ/ mol,which is less than that of L-H mecha⁃ nism and far less than that of SO3 formation in gas phase reaction.The above results confirm that Fe2O3 has a significant catalytic effect on the formation of SO3,and the E-R mechanism is the dominant reaction mechanism.The existence of oxygen vacancy promotes the dissocia⁃ tion of O2 on the surface of α - Fe2O3,and the surface adsorbed oxygen plays an important role in the catalytic process.

KW - catalytic reaction

KW - density functional theory

KW - SO adsorption

KW - SO

KW - α-FeO

UR - https://www.scopus.com/pages/publications/85086737048

U2 - 10.13226/j.issn.1006-6772.19122101

DO - 10.13226/j.issn.1006-6772.19122101

M3 - 文章

AN - SCOPUS:85086737048

SN - 1006-6772

VL - 26

SP - 203

EP - 209

JO - Clean Coal Technology

JF - Clean Coal Technology

IS - 6

ER -

α-Fe₂ O₃ 表面 SO₂ 吸附及 SO₃ 催化生成的密度泛函分析

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