李海霞, 杨昌泽, 张安超,等.基于Mn-MOF制备MeO<italic>_x</italic>/MnO<italic>_x</italic>催化剂的低温NH₃-SCR活性研究[J].河南理工大学学报（自然科学版）,2023,42(5):111-120.

LI Haixia, YANG Changze, ZHANG Anchao, SUN Zhijun, ZHANG Xinmin,et al.Investigation of low temperature NH₃-SCR activity of MeO<italic>_x</italic>/MnO<italic>_x</italic> catalyst prepared based on Mn-MOF[J].Journal of Henan Polytechnic University(Natural Science) ,2023,42(5):111-120.

基于Mn-MOF制备MeO_x/MnO_x催化剂的低温NH ₃-SCR活性研究

李海霞, 杨昌泽, 张安超, 孙志君, 张新民

河南理工大学 机械与动力工程学院，河南 焦作 454000

摘要:采用不同金属硝酸盐浸渍Mn-MOF前体制备一系列MeO_x/MnO_x（Me=Co，Cr）复合金属氧化物催化剂用于低温NH₃-SCR反应。分析金属掺杂和空速对锰基催化剂脱硝效率和N₂O生成量的影响。通过XRD、SEM、N₂吸附-脱附、XPS、H₂-TPR、NH₃-TPD等表征测试对制得的催化剂物理化学性质进行分析，结果表明，两种金属掺杂可不同程度上改善MnO_x脱硝性能和抗硫性能。与MnO_x催化剂相比，掺杂催化剂的外观呈现无规则的多孔结构。更大的比表面积为活性分子提供更多的活性位点，有利于脱硝反应进行。掺杂催化剂中Mn元素相以Mn₃O₄相为主，且峰强度较低，表明Mn元素相呈现高分散态。掺杂金属与锰氧化物产生相互作用，改变了锰元素的价态，提高了Mn⁴⁺ 和表面氧的含量。金属离子掺杂增强了催化剂的氧化还原性能，改善了MnO_x的表面活性。因此，金属硝酸盐浸渍Mn-MOF前体法在制备低温NH₃-SCR脱硝催化剂领域具有很好的应用前景。

关键词:Mn-MOF;Mn基催化剂;NH₃-SCR;抗硫性能;过渡金属

doi:10.16186/j.cnki.1673-9787.2022010039

基金项目:河南省高等学校重点科研项目（23A470002）；河南理工大学创新科研团队项目（T2020-3）

收稿日期:2022/01/13

修回日期:2022/03/28

出版日期:2023/09/25

Investigation of low temperature NH₃-SCR activity of MeO_x/MnO_x catalyst prepared based on Mn-MOF

LI Haixia, YANG Changze, ZHANG Anchao, SUN Zhijun, ZHANG Xinmin

School of Mechanical and Power Engineering，Henan Polytechnic University，Jiaozuo 454000，Henan，China

Abstract:A series of MeO_x/MnO_x（Me=Co，Cr）mixed metal oxide catalysts were prepared by impregnating the Mn-MOF precursors with different metal nitrates.The catalytic activities of catalysts were tested in a low-temperature NH₃-SCR denitrification device.The effects of different metal doping and gaseous hourly space velocity（GHSV）were analyzed about the denitrification efficiency and N₂O production of manganese-based catalyst.In addition，the physicochemical properties of the prepared catalysts were analyzed by XRD，SEM，N₂ adsorption-desorption，XPS，H₂-TPR，and NH₃-TPD.The results showed that the doping of the two metals improved the denitrification performance and sulfur resistance of the MnO_x catalyst to different degrees.Compared with the MnO_x  catalyst，the doping catalysts had an irregular porous structure.The large specific surface area of the doped catalysts provided more active sites for the active molecules，which were beneficial to the denitrification reaction.The Mn element phase in the doped catalysts was dominated by the Mn₃O₄ phase.Due to its low peak intensity in XRD results，it indicated that the Mn element phase showed a highly dispersed state.The doped metal interacted with manganese oxide and changed the valence state of manganese.As a result，the Mn⁴⁺ and the surface oxygen content were increased of the catalysts.In addition，the doping of metal ions enhanced redox properties and improved surface activity of the MnO_x catalyst.Therefore，the preparation of low-temperature NH₃-SCR denitrification catalysts by metal nitrate impregnation of Mn-MOF precursors had great application prospect.

Key words:Mn-MOF;Mn-based catalyst;NH₃-SCR;sulfur tolerance;transition element

基于Mn-MOF制备MeO...温NH_3-SCR活性研究_李海霞.pdf