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采用基于密度泛函理论的第一性原理平面波超软赝势方法，在广义梯度近似下，研究了立方WO3，WO3（001）表面结构及其氢吸附机理. 计算结果表明立方晶体WO3理论带隙宽度为0.587 eV. WO3（001）表面有WO终止（001）表面和O终止（001）表面两种结构，表面结构优化后W-O键长和W-O-W键角改变，从而实现表面弛豫；WO终止（001）表面和O终止（001） 表面分别呈现n型半导体特征和p型半导体特征. 分别计算了H原子吸附在WO终止（001）表面和O终止（001）表面的H-O2c-H，H-O2cH-O2c，H-O1c-H 和H-O1cH-O1c四种吸附构型，其中H-O1c-H 吸附构型的吸附能最小，H-O 键最短，H失去电子数最多，分别为-3.684 eV，0.0968 nm和0.55e，此吸附构型最稳定. 分析其吸附前后的态密度，带隙从吸附前的0.624 eV 增加到1.004 eV，价带宽度基本不变. H的1s轨道电子与O 的2p，2s轨道电子相互作用，在-8和-20 eV附近各形成了一个较强的孤立电子峰，两个H原子分别与一个O1c原子形成化学键，最终吸附反应生成了一个H2O分子，同时产生了一个表面氧空位.With the development of modern industrial technology, tungsten products prepared from normal tungsten powder cannot meet the demands of industry. The tungsten product produced from ultra-fine tungsten powder exhibits high strength, high toughness, and low metal plasticity-brittleness transition temperature, which greatly improves the performance of materials. Hence, it is necessary to carry out theoretical research on the micro adsorption dynamics during hydrogen reduction of tungsten trioxide to prepare ultra fine tungsten powder. In order to understand crystal characteristics of WO3 and WO3(001) surface characteristics, and to provide beneficial theoretical support for reaction law of hydrogen reduction on the WO3(001) surface, the mechanisms of H atom adsorption on cubic WO3 and WO3(001) surface are studied by the first-principles calculation based on the density functional theory (DFT) plane wave pseudo-potential method. The results show that theoretically calculated band gap of the cubic crystalline WO3 is 0.587 eV. There are two kinds of WO3(001) surfaces, WO-terminated (001) surface and O-terminated (001) surface. The W-O bond length and the bond angle of W-O-W structure change after the geometric optimization of the surface, and thus the surface relaxation is realized. The WO-terminated (001) surface shows n-type semiconductor characteristics while the O-terminated (001) surface shows p-type semiconductor characteristics. Four adsorption configurations of H atoms on the WO-terminated (001) surface and the O-terminated (001) surface, including H-O2c-H, H-O2 cH-O2c, H-O1c-H, and H-O1cH-O1c, are calculated. Among them, the adsorption energy of the H-O1c-H configuration is the smallest (-3.684 eV) with the shortest bond length of H-O bond (0.0968 nm), and hydrogen atoms lose the most of electrons (0.55e), which indicates that the H-O1c-H adsorption configuration is the most stable one. The band gap of the H-O1c-H configuration increases from 0.624 eV to 1.004 eV after adsorption, while the bandwidth of valence band is almost unchanged. The results about the density of states (DOS) reveal that 1s state of the H atom interacts with 2p and 2s states of the O atom. Strong isolated electron peaks are formed to be at about -8 and -20 eV. The outermost O1c atoms of O-terminated (001) surface contain an unsaturated bond, facilitating the bonding between two H atoms and one O1c atom. Thus, two H atoms and one O1c atom form chemical bonds respectively, and an H2O molecule is generated, leaving an oxygen vacancy on the surface after adsorption reaction. By combining experimental observations with simulation results, the mechanism of hydrogen reducing tungsten trioxide can be elaborated profoundly from a micro view.
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Keywords:
- first principles /
- tungsten trioxide /
- hydrogen /
- adsorption energy
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[22] Yu Y X 2016 J. Phys. Chem. C 120 5288
[23] Yang G M, Xu Q, Li B, Zhang H Z, He X G 2015 Acta Phys. Sin. 64 127301 (in Chinese) [杨光敏, 徐强, 李冰, 张汉壮, 贺小光 2015 64 127301]
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[25] Yu Y X 2014 ACS Appl. Mater. Interfaces 6 16267
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[27] Gholizadeh R, Yu Y X 2015 Appl. Surf. Sci. 357 1187
[28] Chatten R, Chadwick A V, Rougier A, Lindan P J D 2005 J. Phys. Chem. B 109 3146
[29] Yakovkin I N, Gutowski M 2007 Surf. Sci. 601 1481
[30] Tanner R E, Meethunkij P, Altman E I 2000 J. Phys. Chem. B 104 12315
[31] Ma S, Frederick B G 2003 J. Phys. Chem. B 107 11960
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[34] Wang Y, Perdew J P, Chevary J A, Macdonald L D, Vosko S H 1990 Phys. Rev. A 41 40
[35] Perdew J P, Chevary J A, Vosko S H, Jackson K A, Pederson M R, Singh D J, Fiolhais C 1992 Phys. Rev. B 46 6671
[36] Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188
[37] Fletcher R 1970 Comput. J. 13 317
[38] Tian X G, Zhang Y, Yang T S 2012 Acta Phys. Chim. Sin. 28 1063
[39] Yamaguchi O, Tomihisa D, Kawabata H, Shimizu K 1987 J. Am. Ceram. Soc. 70 94
[40] Setyawan W, Curtarolo S 2010 Comput. Mater. Sci. 49 299
[41] Sun X, Kurahashi M, Pratt A, Yamauchi Y 2011 Sur. Sci. 605 1067
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[1] Yang Y H, Xie R R, Li H, Liu C J, Liu W H, Zhan F Q 2016 Trans. Nonferrous Met. Soc. China 26 2390
[2] Chen Z, Wang W, Zhu K G 2015 Acta Metall. Sin. 28 1
[3] Dai F P, L S Y, Feng B X, Jiang S R, Chen C 2003 Acta Phys. Sin. 52 1003 (in Chinese) [代富平, 吕淑媛, 冯博学, 蒋生蕊, 陈冲 2003 52 1003]
[4] Kukkola J, Mklin J, Halonen N, Kyllnen T, Tth G, Szab M, Shchukarev A, Mikkola J P, Jantunen H, Kords K 2011 Sensor. Actuat. B 153 293
[5] Fang C, Wang H, Shi S Q 2016 Acta Phys. Sin. 65 168201 (in Chinese) [方成, 汪洪, 施思齐 2016 65 168201]
[6] Zhang T, Zhu Z L, Chen H N, Bai Y, Xiao S, Zheng X L, Xue Q Z, Yang S H 2015 Nanoscale 7 2933
[7] Liu X H, Zhou Y, Liang F Y, Qu H N, Wen H R 2015 Nonferrous Met. Sci. Eng. 6 53 (in Chinese) [刘喜慧, 周阳, 梁福永, 曲慧男, 温和瑞 2015 有色金属科学与工程 6 53]
[8] Qin Y X, Liu C Y, Liu Y 2015 Chin. Phys. B 24 027304
[9] Zhang F, Wang H Q, Wang S, Wang J Y, Zhong Z C, Jin Y 2014 Chin. Phys. B 23 098105
[10] Vesel A, Mozetič M, Balat-Pichelin M 2015 Thin Solid Films 591 174
[11] Guo F 2007 Mat. Sci. Eng. Powder Metall. 12 205 (in Chinese) [郭峰 2007 粉末冶金材料科学与工程 12 205]
[12] Li H G, Yang J G, Li K 2010 Tungsten Metallurgy (Changsha: Central South University Press) pp36-39 (in Chinese) [李洪桂, 羊建高, 李昆 2010 钨冶金学 (长沙: 中南大学出版社) 第36-39页]
[13] Yu G, Han Q G, Li M Z, Jia X P, Ma H A, Li Y F 2012 Acta Phys. Sin. 61 040702 (in Chinese) [于歌, 韩奇钢, 李明哲, 贾晓鹏, 马红安, 李月芬 2012 61 040702]
[14] Qiu K Q, Wang A M, Zhang H F, Qiao D C, Ding B Z, Hu Z Q 2002 Acta Metall. Sin. 38 1091 (in Chinese) [邱克强, 王爱民, 张海峰, 乔东春, 丁炳哲, 胡壮麒 2002 金属学报 38 1091]
[15] Hua J S, Jing F Q, Dong Y B, Tan H, Shen Z Y, Zhou X M, Hu S L 2003 Acta Phys. Sin. 52 2005 (in Chinese) [华劲松, 经福谦, 董玉斌, 谭华, 沈中毅, 周显明, 胡绍楼 2003 52 2005]
[16] Tan J, Zhou Z J, Zhu X P, Guo S Q, Qu D D, Lei M K, Ge C C 2012 Trans. Nonferrous Met. Soc. China 22 1081
[17] Liu H M, Fan J L, Tian J M, You F 2009 China Tungsten Ind. 24 29 (in Chinese) [刘辉明, 范景莲, 田家敏, 游峰 2009 中国钨业 24 29]
[18] Hessel S, Shpigler B, Botstein O 1993 Rev. Chem. Eng. 9 345
[19] Wu X W, Luo J S, Lu B Z, Xie C H, Pi Z M, Hu M Z, Xu T, Wu G G, Yu Z M, Yi D Q 2009 Trans. Nonferrous Met. Soc. China 19 785
[20] Xu L, Yan Q Z, Xia M, Zhu L X 2013 Int. J. Refract. Met. Hard Mater. 36 238
[21] Yu Y X 2013 Phys. Chem. Chem. Phys. 15 16819
[22] Yu Y X 2016 J. Phys. Chem. C 120 5288
[23] Yang G M, Xu Q, Li B, Zhang H Z, He X G 2015 Acta Phys. Sin. 64 127301 (in Chinese) [杨光敏, 徐强, 李冰, 张汉壮, 贺小光 2015 64 127301]
[24] Xue L, Ren Y M 2016 Acta Phys. Sin. 65 156301 (in Chinese) [薛丽, 任一鸣 2016 65 156301]
[25] Yu Y X 2014 ACS Appl. Mater. Interfaces 6 16267
[26] Li B, Wu T Q, Wang C C, Jiang Y 2016 Acta Phys. Sin. 65 216301 (in Chinese) [李白, 吴太权, 汪辰超, 江影 2016 65 216301]
[27] Gholizadeh R, Yu Y X 2015 Appl. Surf. Sci. 357 1187
[28] Chatten R, Chadwick A V, Rougier A, Lindan P J D 2005 J. Phys. Chem. B 109 3146
[29] Yakovkin I N, Gutowski M 2007 Surf. Sci. 601 1481
[30] Tanner R E, Meethunkij P, Altman E I 2000 J. Phys. Chem. B 104 12315
[31] Ma S, Frederick B G 2003 J. Phys. Chem. B 107 11960
[32] Tian X G, Zhang Y, Yang T S 2012 J. Syn. Cryst. 41 323 (in Chinese) [田相桂, 张跃, 杨泰生 2012 人工晶体学报 41 323]
[33] Segall M D, Lindan P J D, Probert M J, Pickard C J, Hasnip P J, Clark S J, Payne M C 2002 J. Phys. Condens. Matter 14 2717
[34] Wang Y, Perdew J P, Chevary J A, Macdonald L D, Vosko S H 1990 Phys. Rev. A 41 40
[35] Perdew J P, Chevary J A, Vosko S H, Jackson K A, Pederson M R, Singh D J, Fiolhais C 1992 Phys. Rev. B 46 6671
[36] Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188
[37] Fletcher R 1970 Comput. J. 13 317
[38] Tian X G, Zhang Y, Yang T S 2012 Acta Phys. Chim. Sin. 28 1063
[39] Yamaguchi O, Tomihisa D, Kawabata H, Shimizu K 1987 J. Am. Ceram. Soc. 70 94
[40] Setyawan W, Curtarolo S 2010 Comput. Mater. Sci. 49 299
[41] Sun X, Kurahashi M, Pratt A, Yamauchi Y 2011 Sur. Sci. 605 1067
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