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The passive NOx adsorbent, Pd-SSZ-13 with a Pd loading of 1.64wt.%, was prepared by the ion-exchange method. Then, the Pd-SSZ-13 was subjected to thermal and hydrothermal aging treatments separately for 10h under mild conditions: at a temperature of 700℃ and in an atmosphere consisting of 10%O2, 2%H2O (for hydrothermal treatment only), and N2 as the balance. The effects of these treatments on the NOx adsorption/desorption performance of Pd-SSZ-13 were investigated. The physicochemical properties of adsorbents and the NO adsorption process were characterized using N2 adsorption-desorption, XRF, ICP-OES, XRD, SSNMR, XPS, TEM, NH3-TPD and in situ Drifts techniques. The results showed that when the feed gas contained 2%H2O, the SSZ-13 support was unable to adsorb NOx, whereas Pd-SSZ-13 exhibited NOx adsorption during both the adsorption stage and the temperature-programmed stage (100~230℃), demonstrating an adsorption capacity of 81.3μmol/g. The NOx desorption temperature range (230~493℃) fell within the active temperature window of SCR catalysts, and complete NOx desorption was achieved. After undergoing thermal and hydrothermal aging treatments, the NOx adsorption capacity of Pd-SSZ-13 in the presence of H2O further increased to 113.4 and 126.2μmol/g, respectively, and the thermally aged sample showed better cyclic stability. Although thermal and hydrothermal aging treatments induced partial dealumination of the SSZ-13 framework, they neither altered the micropore characteristics of SSZ-13 nor caused structural collapse or framework destruction. Instead, the aging processes promoted the migration of Pd species from external surfaces to interior pores, enhanced the dispersion of Pd, and increased the amount of Pd2+(Z-[Pd2+(OH)]+ and Z2-Pd2+) sites, thereby improving the NOx adsorption-storage capability of Pd-SSZ-13. Compared with the hydrothermally-aged Pd-SSZ-13, the thermally-aged sample showed less framework dealumination, a higher specific surface area and a larger micropore volume, and better dispersion of Pd species, all of which likely contributed to its superior cyclic stability. With H2O in the feed gas, NO was mainly adsorbed and stored at the Pd2+ sites in the forms of Pd+-NO, Pd2+-NO and hydrated Pd2+-NO species, with the competitive adsorption of H2O attenuated at elevated temperatures. During the thermal and hydrothermal aging of Pd-SSZ-13, the abundant Brønsted acid sites likely played an important role in facilitating the migration of Pd species and the formation of Pd2+ sites.

, authors=Ruo-wen LIU, Xing FAN*, Jing-wen MIAO, authorsList=Ruo-wen LIU, Xing FAN, Jing-wen MIAO, authorCompany=null, correspAuthors=Xing FAN, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1314917857675272617, articleId=1314917856429564326, tenantId=1146029695717560320, journalId=1234093305789726721, language=CN, title=热和水热老化处理提升Pd-SSZ-13吸附储存NOx性能, columnId=1234106388364981004, journalTitle=中国环境科学, columnName=大气污染与控制, runingTitle=null, highlight=null, articleAbstract=

采用离子交换法制备了Pd负载量为1.64wt.%的Pd-SSZ-13被动式NOx吸附剂,并在温度为700℃,气氛为10%O2、2%H2O(水热处理时)、N2平衡的温和条件下对Pd-SSZ-13分别进行了10h的热和水热老化处理,考察了热和水热老化处理对Pd-SSZ-13吸脱附NOx性能的影响.采用N2吸脱附、XRF、ICP-OES、XRD、SSNMR、XPS、TEM、NH3-TPD和in situ Drifts等手段对吸附剂理化特性和NO吸附过程进行了表征.结果表明,进气中含2%H2O时SSZ-13载体不具备吸附储存NOx的能力,而Pd-SSZ-13能够在吸附阶段以及程序升温至100~230℃时吸附储存NOx,NOx吸附容量为81.3μmol/g;NOx脱附温度(230~493℃)处于SCR催化剂高效工作的温度区间内,脱附较为完全.热和水热老化处理Pd-SSZ-13后,其含水条件下的NOx吸附容量进一步提高至113.4和126.2μmol/g,热老化处理后的样品具有更好的循环使用稳定性.热和水热老化处理虽然造成了一定程度的分子筛骨架脱Al,但没有改变SSZ-13的微孔特性,也未造成分子筛骨架结构坍塌或破坏,且促使分子筛表面Pd物种向孔道内部迁移,提高了Pd的分散度,增加了Pd2+离子(Z-[Pd2+(OH)]+和Z2-Pd2+)位点的数量,进而提高了Pd-SSZ-13吸附储存NOx的能力.与水热老化处理的样品相比,热老化处理的样品分子筛骨架脱Al较轻微,比表面积和微孔孔容更高,Pd分散更好,可能是其具有更好的循环使用稳定性的原因.含水条件下NO主要吸附储存在Pd2+离子位点上,形成Pd+-NO、Pd2+-NO和水合Pd2+-NO物种,温度升高后H2O对Pd2+离子位点的竞争吸附减弱.Pd-SSZ-13含有的大量Brønsted酸位点可能在热和水热老化处理促使Pd迁移和Pd2+离子的形成中发挥了重要作用.

, authors=刘若雯, 樊星*, 苗静文, authorsList=刘若雯, 樊星, 苗静文, authorCompany=null, correspAuthors=樊星, authorNote=

刘若雯(2000-),女,河北邯郸人,北京工业大学硕士研究生,主要从事大气污染控制工程研究.发表论文2篇..

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* 责任作者,副教授,
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刘若雯(2000-),女,河北邯郸人,北京工业大学硕士研究生,主要从事大气污染控制工程研究.发表论文2篇..

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刘若雯(2000-),女,河北邯郸人,北京工业大学硕士研究生,主要从事大气污染控制工程研究.发表论文2篇..

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热和水热老化处理提升Pd-SSZ-13吸附储存NOx性能
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刘若雯 , 樊星 * , 苗静文
中国环境科学 | 大气污染与控制 2025,45(8): 4195-4206
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中国环境科学 |大气污染与控制 2025 , 45 (8) : 4195 -4206
热和水热老化处理提升Pd-SSZ-13吸附储存NOx性能
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刘若雯(2000-),女,河北邯郸人,北京工业大学硕士研究生,主要从事大气污染控制工程研究.发表论文2篇..

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刘若雯 , 樊星* , 苗静文
作者信息
  • 北京工业大学,区域大气复合污染防治北京市重点实验室,北京 100124
通讯作者:
* 责任作者,副教授,
作者简介:

刘若雯(2000-),女,河北邯郸人,北京工业大学硕士研究生,主要从事大气污染控制工程研究.发表论文2篇..

Improved NOx storage performance of Pd-SSZ-13 by thermal and hydrothermal aging treatment
Ruo-wen LIU , Xing FAN* , Jing-wen MIAO
Affiliations
  • Key Laboratory of Beijing on Regional Air Pollution Control, Beijing University of Technology, Beijing 100124, China
出版时间: 2025-08-20
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采用离子交换法制备了Pd负载量为1.64wt.%的Pd-SSZ-13被动式NOx吸附剂,并在温度为700℃,气氛为10%O2、2%H2O(水热处理时)、N2平衡的温和条件下对Pd-SSZ-13分别进行了10h的热和水热老化处理,考察了热和水热老化处理对Pd-SSZ-13吸脱附NOx性能的影响.采用N2吸脱附、XRF、ICP-OES、XRD、SSNMR、XPS、TEM、NH3-TPD和in situ Drifts等手段对吸附剂理化特性和NO吸附过程进行了表征.结果表明,进气中含2%H2O时SSZ-13载体不具备吸附储存NOx的能力,而Pd-SSZ-13能够在吸附阶段以及程序升温至100~230℃时吸附储存NOx,NOx吸附容量为81.3μmol/g;NOx脱附温度(230~493℃)处于SCR催化剂高效工作的温度区间内,脱附较为完全.热和水热老化处理Pd-SSZ-13后,其含水条件下的NOx吸附容量进一步提高至113.4和126.2μmol/g,热老化处理后的样品具有更好的循环使用稳定性.热和水热老化处理虽然造成了一定程度的分子筛骨架脱Al,但没有改变SSZ-13的微孔特性,也未造成分子筛骨架结构坍塌或破坏,且促使分子筛表面Pd物种向孔道内部迁移,提高了Pd的分散度,增加了Pd2+离子(Z-[Pd2+(OH)]+和Z2-Pd2+)位点的数量,进而提高了Pd-SSZ-13吸附储存NOx的能力.与水热老化处理的样品相比,热老化处理的样品分子筛骨架脱Al较轻微,比表面积和微孔孔容更高,Pd分散更好,可能是其具有更好的循环使用稳定性的原因.含水条件下NO主要吸附储存在Pd2+离子位点上,形成Pd+-NO、Pd2+-NO和水合Pd2+-NO物种,温度升高后H2O对Pd2+离子位点的竞争吸附减弱.Pd-SSZ-13含有的大量Brønsted酸位点可能在热和水热老化处理促使Pd迁移和Pd2+离子的形成中发挥了重要作用.

NOx  /  PNA  /  Pd-SSZ-13  /  热老化  /  水热老化

The passive NOx adsorbent, Pd-SSZ-13 with a Pd loading of 1.64wt.%, was prepared by the ion-exchange method. Then, the Pd-SSZ-13 was subjected to thermal and hydrothermal aging treatments separately for 10h under mild conditions: at a temperature of 700℃ and in an atmosphere consisting of 10%O2, 2%H2O (for hydrothermal treatment only), and N2 as the balance. The effects of these treatments on the NOx adsorption/desorption performance of Pd-SSZ-13 were investigated. The physicochemical properties of adsorbents and the NO adsorption process were characterized using N2 adsorption-desorption, XRF, ICP-OES, XRD, SSNMR, XPS, TEM, NH3-TPD and in situ Drifts techniques. The results showed that when the feed gas contained 2%H2O, the SSZ-13 support was unable to adsorb NOx, whereas Pd-SSZ-13 exhibited NOx adsorption during both the adsorption stage and the temperature-programmed stage (100~230℃), demonstrating an adsorption capacity of 81.3μmol/g. The NOx desorption temperature range (230~493℃) fell within the active temperature window of SCR catalysts, and complete NOx desorption was achieved. After undergoing thermal and hydrothermal aging treatments, the NOx adsorption capacity of Pd-SSZ-13 in the presence of H2O further increased to 113.4 and 126.2μmol/g, respectively, and the thermally aged sample showed better cyclic stability. Although thermal and hydrothermal aging treatments induced partial dealumination of the SSZ-13 framework, they neither altered the micropore characteristics of SSZ-13 nor caused structural collapse or framework destruction. Instead, the aging processes promoted the migration of Pd species from external surfaces to interior pores, enhanced the dispersion of Pd, and increased the amount of Pd2+(Z-[Pd2+(OH)]+ and Z2-Pd2+) sites, thereby improving the NOx adsorption-storage capability of Pd-SSZ-13. Compared with the hydrothermally-aged Pd-SSZ-13, the thermally-aged sample showed less framework dealumination, a higher specific surface area and a larger micropore volume, and better dispersion of Pd species, all of which likely contributed to its superior cyclic stability. With H2O in the feed gas, NO was mainly adsorbed and stored at the Pd2+ sites in the forms of Pd+-NO, Pd2+-NO and hydrated Pd2+-NO species, with the competitive adsorption of H2O attenuated at elevated temperatures. During the thermal and hydrothermal aging of Pd-SSZ-13, the abundant Brønsted acid sites likely played an important role in facilitating the migration of Pd species and the formation of Pd2+ sites.

NOx  /  PNA  /  Pd-SSZ-13  /  thermal aging  /  hydrothermal aging
刘若雯, 樊星, 苗静文. 热和水热老化处理提升Pd-SSZ-13吸附储存NOx性能. 中国环境科学, 2025 , 45 (8) : 4195 -4206 .
Ruo-wen LIU, Xing FAN, Jing-wen MIAO. Improved NOx storage performance of Pd-SSZ-13 by thermal and hydrothermal aging treatment[J]. China Environmental Science, 2025 , 45 (8) : 4195 -4206 .
  • 国家自然科学基金资助项目(21707004)
  • 北京市自然科学基金资助项目(8152011)
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  • 首发时间:2026-10-08
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  • 收稿日期:2025-01-03
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国家自然科学基金资助项目(21707004)
北京市自然科学基金资助项目(8152011)
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    北京工业大学,区域大气复合污染防治北京市重点实验室,北京 100124

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