表面物理化学性质对不同晶型MnO<sub>2</sub>的NH<sub>3</sub>-SCR活性影响

引用本文: 公丕军, 谢峻林, 方德, 韩达, 何峰, 李凤祥, 齐凯. 表面物理化学性质对不同晶型MnO₂的NH₃-SCR活性影响[J]. 催化学报, 2017, 38(11): 1925-1934. doi: 10.1016/S1872-2067(17)62922-X shu

Citation: PiJun Gong, JunLin Xie, De Fang, Da Han, Feng He, FengXiang Li, Kai Qi. Effects of surface physicochemical properties on NH₃-SCR activity of MnO₂ catalysts with different crystal structures[J]. Chinese Journal of Catalysis, 2017, 38(11): 1925-1934. doi: 10.1016/S1872-2067(17)62922-X shu

表面物理化学性质对不同晶型MnO₂的NH₃-SCR活性影响

a 武汉理工大学硅酸盐建筑材料国家重点实验室, 湖北武汉 430070;
b 武汉理工大学材料研究与测试中心, 湖北武汉 430070;
c 武汉理工大学材料科学与工程学院, 湖北武汉 430070
基金项目:
国家自然科学基金（51502221）.

摘要: 氮氧化物（NO_x）是主要的大气污染物之一，给环境和人类健康带来巨大危害.NH₃选择性催化还原（NH₃-SCR）技术是处理氮氧化物最有效的方法之一，现已被广泛用于氮氧化物的处理，其中SCR催化剂是该技术的核心.
锰基催化剂具有相对较好的低温催化活性，而其中MnO₂的催化活性最为突出.二氧化锰可以形成多种晶型，如α，β，δ和γ.晶相结构可显著影响催化活性，不同晶型的MnO₂具有不同的催化性能，其在电化学催化和CO催化方面已经得到广泛应用和研究.然而对于不同晶型MnO₂的NH₃低温选择催化还原NO_x的催化活性和催化机理的研究特别少.α-，β-，γ-和δ-MnO₂具有不同的晶型尺寸，并在气体吸附、气体扩散和催化反应过程中表现出较大差异.因此，有必要揭示不同MnO₂晶型表面物理化学性质与SCR催化活性之间的关系.
本文成功制备出四种不同晶型的纳米MnO₂（α，β，δ和γ型）催化剂，并测试了其NH₃低温选择催化活性.此外，对催化剂进行了XRD，SEM，Raman，TG，BET，NH₃-TPD，XPS和H₂-TPR等一系列测试表征，探究了导致不同晶型MnO₂的NH₃催化还原NO_x差异的主要原因.结果表明，四种不同晶型纳米MnO₂的NH₃-SCR催化活性顺序为γ-MnO₂ > α-MnO₂ > δ-MnO₂ > β-MnO₂.γ-MnO₂和α-MnO₂上的NO_x转化率在140-200℃范围内可达90%以上，但β-MnO₂在200℃只有40%的NO_x转化率.分析表明，γ-MnO₂和α-MnO₂的纳米线形貌具有较好的分散性，导致它们的比表面积较高，这为活性位点提供了更多的分散空间，有利于活性气体分子的吸附和催化过程的进行.H₂-TPR和NH₃-TPD结果显示，γ-MnO₂和α-MnO₂比其他两种晶型的MnO₂催化剂具有较好的可还原性和更多更强的酸性位点.XPS分析结果表明，在γ-MnO₂和α-MnO₂表面存在更多的化学吸附氧.基于上述这些有利的物理化学性质，γ-MnO₂和α-MnO₂催化剂显示出较好的低温NH₃-SCR活性.尽管δ-MnO₂的比表面积较小，但是NH₃-TPD结果显示其层状形貌的纳米晶体表面分散有较多的酸性位点，从而有效提升了其催化效果，同时其较好的氧化还原性能也有助于催化性能的改善.

关键词:

English

Effects of surface physicochemical properties on NH₃-SCR activity of MnO₂ catalysts with different crystal structures

a State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, Hubei, China;
b Center for Materials Research and Analysis, Wuhan University of Technology, Wuhan 430070, Hubei, China;
c School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, Hubei, China
Received Date: 24 August 2017
Revised Date: 25 September 2017
Fund Project:
This work was supported by the National Natural Science Foundation of China (51502221).

Abstract: α-, β-, δ-, and γ-MnO₂ nanocrystals are successfully prepared. We then evaluated the NH₃ selective catalytic reduction (SCR) performance of the MnO₂ catalysts with different phases. The NO_x conversion efficiency decreased in the order:γ-MnO₂ > α-MnO₂ > δ-MnO₂ > β-MnO₂. The NO_x conversion with the use of γ-MnO₂ and α-MnO₂ catalysts reached 90% in the temperature range of 140-200℃, while that based on β-MnO₂ reached only 40% at 200℃. The γ-MnO₂ and α-MnO₂ nanowire crystal morphologies enabled good dispersion of the catalysts and resulted in a relatively high specific surface area. We found that γ-MnO₂ and α-MnO₂ possessed stronger reducing abilities and more and stronger acidic sites than the other catalysts. In addition, more chemisorbed oxygen existed on the surface of the γ-MnO₂ and α-MnO₂ catalysts. The γ-MnO₂ and α-MnO₂ catalysts showed excellent performance in the low-temperature SCR of NO to N₂ with NH₃.

Key words:

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表面物理化学性质对不同晶型MnO₂的NH₃-SCR活性影响

English

Effects of surface physicochemical properties on NH₃-SCR activity of MnO₂ catalysts with different crystal structures

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表面物理化学性质对不同晶型MnO2的NH3-SCR活性影响

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Effects of surface physicochemical properties on NH3-SCR activity of MnO2 catalysts with different crystal structures

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