O2、SO2对As2O3在W-Cu/γ-Al2O3催化剂表面吸附特性的影响：实验及理论模拟

邢佳颖; 王春波; 李顺; 黄玉林; 岳爽

doi:10.19906/j.cnki.JFCT.2022033

O₂、SO₂对As₂O₃在W-Cu/γ-Al₂O₃催化剂表面吸附特性的影响：实验及理论模拟

doi: 10.19906/j.cnki.JFCT.2022033

华北电力大学动力工程系河北省低碳高效发电技术重点实验室, 河北保定 071003

基金项目: 国家重点研发计划（2020YFB0606301）和国家自然科学基金(51976059)资助

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E-mail: 120192102130@ncepu.edu.cn

中图分类号: X511
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出版历程
- 收稿日期: 2022-03-05
- 修回日期: 2022-04-01
- 网络出版日期: 2022-04-22
- 刊出日期: 2022-10-31

Effects of O₂ and SO₂ on As₂O₃ adsorption over W-Cu/γ-Al₂O₃ surface: An experimental combined theoretical analysis

Department of Energy Power & Mechanical Engineering, North China Electric Power University, Hebei Key Laboratory of Low Carbon and High Efficiency Power Generation Technology, Baoding 071003, China

Funds: The project was supported by National Key R&D Program of China (2020YFB0606301) and National Natural Science Foundation of China (51976059)

More Information

Corresponding author: E-mail: 120192102130@ncepu.edu.cn

摘要

摘要: 采用实验及量子化学方法探究了O₂和SO₂对As₂O₃在W-Cu/γ-Al₂O₃催化剂表面吸附特性的影响。实验结果表明，O₂促进了As₂O₃在催化剂表面的吸附，随着SO₂体积分数的增加，As₂O₃的吸附量表现出先升高后降低的趋势。为进一步探究烟气组分对气相砷吸附的影响机理，采用密度泛函理论（DFT）方法，模拟了预吸附不同气体后催化剂表面As₂O₃的吸附。结果表明，O₂对气相砷的促进影响主要归因于吸附氧的形成。预吸附的O原子明显增强了临近原子的吸附活性，而预吸附的O₂分子则主要通过提供吸附活性位点促进As₂O₃的吸附。SO₂在W-Cu/γ-Al₂O₃表面形成了${{\rm{SO}}^{2-} _4}$和${\rm{HSO}}^-_4 $，改变了基底表面的势场，从而促进了As₂O₃的吸附。随体积分数的进一步增加，SO₂与气相As₂O₃的竞争吸附作用增强，As₂O₃吸附量减少。
- O₂ /
- SO₂ /
- As₂O₃ /
- W-Cu/γ-Al₂O₃ /
- 吸附 /
- 表面 /
- DFT
Abstract: In this work, the effects of O₂ and SO₂ on gaseous As₂O₃ adsorption over W-Cu/γ-Al₂O₃ catalyst were investigated through adsorption experiment and density functional theory (DFT) method. Experimental results show that the As₂O₃ adsorption is facilitated by O₂, and intensified with the increasing concentrations of SO₂. However, it is slightly weakened with the SO₂ concentration of 2.0×10⁻³. The As₂O₃ adsorption on W-Cu/γ-Al₂O₃ surface with adsorbed gas constituents was calculated by DFT simulation to reveal the effect mechanism. The promoting effect of O₂ on arsenic adsorption is attributed to the formation of adsorbed oxygen. The pre-adsorbed O atom significantly enhances the adsorption activities of adjacent atoms, and the pre-adsorbed O₂ molecule provides the active sites for As₂O₃ adsorption. When SO₂ is introduced, the ${{\rm{SO}}^{{2}-} _{4}}$ and ${\rm{HSO}}^-_{4} $ are formed, which change the potential field of substrate surface, and further enhance the As₂O₃ adsorption. However, the competitive adsorption between SO₂ with As₂O₃ is strengthened with increasing SO₂ concentration, and it is the reason for the decreasing trend of As₂O₃ adsorption with high concentrations of SO₂.
- O₂ /
- SO₂ /
- As₂O₃ /
- W-Cu/γ-Al₂O₃ /
- adsorption /
- surface /
- DFT

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FIG. 1930. FIG. 1930.

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图 1 气相砷吸附系统示意图

Figure 1 Schematic diagram of the experimental system for gaseous arsenic adsorption

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图 2 W-Cu/γ-Al₂O₃表面稳定构型

Figure 2 Stable structure of W-Cu/γ-Al₂O₃ surface (Al, light blue; O, red; Cu, blue; W, brown)

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图 3 O₂、SO₂对砷吸附的影响

Figure 3 Effects of O₂ and SO₂ on As₂O₃ adsorption

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图 4 SO₂在W-Cu/γ-Al₂O₃表面吸附的FT-IR谱图

Figure 4 FT-IR analysis of SO₂ adsorption on W-Cu/γ-Al₂O₃ catalyst

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图 5 O₂、SO₂在W-Cu/γ-Al₂O₃表面吸附的稳定吸附构型

Figure 5 Stable configurations of O₂ and SO₂ on W-Cu/γ-Al₂O₃ surface

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图 6 O₂对As₂O₃在W-Cu/γ-Al₂O₃表面的吸附影响

Figure 6 Effect of O₂ on As₂O₃ adsorption

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图 7 ${{\rm{SO}}^{{2}-} _{4}} $和${{\rm{HSO}}^{-} _{4}} $对As₂O₃吸附的影响

Figure 7 Effect of ${{\rm{SO}}^{{2}-} _{4}} $ and ${{\rm{HSO}}^{-} _{4}} $ on As₂O₃ adsorption

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表 1 As₂O₃在吸附氧上的吸附能

Table 1 Adsorption energies of As₂O₃ on adsorbed oxygen

Configuration	E_ads/eV	Configuration	E_ads /eV
As−O_ads	−0.04	O−O_ads	−0.95
As−O_ads1	−1.91	O−O_ads1	−0.13
As−O_ads2	−3.23	O−O_ads2	−3.21

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表 2 As₂O₃在${{\bf{SO}}^{{{\boldsymbol{2}}}-} _{{\boldsymbol{4}}}}$和${{\bf{HSO}}^- _{{\boldsymbol{4}}}}$上的吸附能

Table 2 Adsorption energies of As₂O₃ on ${{\rm{SO}}^{{2}-} _{4}} $ and ${{\rm{HSO}}^{-} _{4}} $

Configuration (${{\rm{SO}}^{{2}-} _{4}} $)	E_ads/eV	Configuration (${{\rm{HSO}}^- _{4}} $)	E_ads/eV
As−O3_ads	−0.16	As−O3_ads	−0.67
As−O4_ads	−0.23	As−O4_ads	−0.66
O−O3_ads	−0.22	O−H	−0.75
O−O4_ads	−0.18	O−H	−0.57

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