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Three Ru-based catalysts were synthesized using in-situ synthesis, impregnation, and deposition-precipitation methods in combination with MFI zeolites to investigate their catalytic oxidation activity toward propane (C3H8). The catalyst synthesized via the in-situ method, denoted as Ru@MFI, exhibited the highest low-temperature oxidation activity, achieving a 90% conversion rate at 270℃, along with remarkable thermal stability at high temperatures and hydrophobicity. Characterization techniques, including X-ray diffraction (XRD), N2 adsorption-desorption, high-angle annular dark-field scanning transmission electron microscopy(HAADF-STEM), and temperature-programmed desorption of CO (CO-TPD), revealed that Ru confined within the MFI zeolite channels possessed the smallest particle size and highest dispersion, thereby increasing the number of active Ru sites. Further characterization using Raman spectroscopy and hydrogen temperature-programmed reduction (H2-TPR) indicated that interactions between Ru and the MFI framework led to a redistribution of charge around Ru or oxygen, enhancing the reduction capabilities.Consequently, the Ru@MFI catalyst demonstrated superior propane oxidation activity. Additionally, the geometric confinement within the MFI channels maintained the stability and dispersion of Ru species during high-temperature calcination, effectively preventing Ru aggregation and further ensuring the catalyst's high-temperature thermal stability.

, correspAuthors=Yan-fei JIAN, Chi HE, 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, authorCompany=null, fund=null, authors=null, authorsList=Jing-jing WANG, Liang-hui XIA, Ya-ni WU, Yu-jie LIU, He XU, Qi-yuan LIU, Ji-chen LIU, Yan-fei JIAN, Chi HE), CN=ArticleExt(id=1241049974587314593, articleId=1241049966513279278, tenantId=1146029695717560320, journalId=1234093305789726721, language=CN, title=MFI分子筛限域Ru催化剂的制备及其丙烷催化燃烧性能, columnId=1241049969449292093, journalTitle=中国环境科学, columnName=臭氧污染与控制, runingTitle=null, highlight=null, articleAbstract=

采用原位合成法、浸渍法和沉积沉淀法制备Ru与MFI分子筛结合的3种催化剂,用于丙烷(C3H8)的催化氧化活性研究.结果显示,通过原位合成法将Ru限域在MFI分子筛孔道内时,Ru@MFI催化剂展现出最佳的低温C3H8氧化活性,在270℃时达到90%转化率,并表现出卓越的高温热稳定性和抗水性.通过XRD、N2吸脱附、HAADF-STEM以及CO-TPD等表征技术发现,限域在MFI分子筛孔道内部的Ru具有最小的粒径和最高的分散度,增加了活性Ru位点的数量.拉曼和H2-TPR表征结果表明,孔道内的Ru与MFI之间相互作用导致电荷重新分布,增强了还原性能.因此,Ru@MFI催化剂呈现出最优异的C3H8氧化活性.此外,MFI孔道的几何限制作用在高温焙烧过程中维持Ru的稳定性和分散度,有效避免了Ru的聚集,进一步确保了催化剂的高温热稳定性.

, correspAuthors=建艳飞, 何炽, authorNote=null, correspAuthorsNote=
*责任作者,教授,
**助理教授,
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王晶晶(1993-),女,甘肃定西人,西安交通大学博士研究生,主要从事挥发性有机污染物降解和分子筛封装贵金属研究..

, authorsList=王晶晶, 夏良辉, 武雅妮, 刘昱洁, 徐赫, 刘起源, 刘基丞, 建艳飞, 何炽)}, authors=[Author(id=1241049975505867212, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049966513279278, orderNo=0, firstName=null, middleName=null, lastName=null, nameCn=null, orcid=null, stid=null, country=null, authorPic=null, dead=0, email=ijjwang@stu.xjtu.edu.cn, emailSecond=null, emailThird=null, correspondingAuthor=0, authorType=1, ext={EN=AuthorExt(id=1241049975749136855, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049966513279278, authorId=1241049975505867212, language=EN, stringName=Jing-jing WANG, firstName=Jing-jing, middleName=null, lastName=WANG, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=1, address=1.State Key Laboratory of Multiphase Flow in Power Engineering, School of Energy and Power Engineering, Xi'an Jiaotong University, Xi'an 710049, China, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null), CN=AuthorExt(id=1241049976055321058, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049966513279278, authorId=1241049975505867212, language=CN, stringName=王晶晶, firstName=null, middleName=null, lastName=null, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=1, address=1.西安交通大学能源与动力工程学院,动力工程多相流国家重点实验室,陕西 西安 710049, bio={"content":"

王晶晶(1993-),女,甘肃定西人,西安交通大学博士研究生,主要从事挥发性有机污染物降解和分子筛封装贵金属研究..

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王晶晶(1993-),女,甘肃定西人,西安交通大学博士研究生,主要从事挥发性有机污染物降解和分子筛封装贵金属研究..

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T50, T90, and T100 for C3H8 oxidation over fresh and high-temperature calcined catalysts

, figureFileSmall=null, figureFileBig=null, tableContent=
催化剂新鲜700℃高温
T50T90T100T50T90T100
Ru@MFI245270300262293320
Ru/MFI-IM258300340316445590
Ru/MFI-DP316390500>500--
), ArticleFig(id=1241049994036302058, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049966513279278, language=CN, label=表1, caption=

新鲜催化剂与高温焙烧后催化剂的C3H8氧化的T50,T90T100

, figureFileSmall=null, figureFileBig=null, tableContent=
催化剂新鲜700℃高温
T50T90T100T50T90T100
Ru@MFI245270300262293320
Ru/MFI-IM258300340316445590
Ru/MFI-DP316390500>500--
), ArticleFig(id=1241049994220851455, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049966513279278, language=EN, label=Table 2, caption=

Structural properties of catalysts

, figureFileSmall=null, figureFileBig=null, tableContent=
催化剂比表面积(m2/g)a微孔面积(m2/g)b总孔容(cm3/g)b微孔孔容(cm3/g)bRu含量(wt%)c
Ru@MFI399.32157.080.6620.1820.60
Ru/MFI-IM340.05183.330.4950.1570.59
Ru/MFI-DP329.74177.360.4840.1520.60
), ArticleFig(id=1241049994401206540, tenantId=1146029695717560320, journalId=1234093305789726721, articleId=1241049966513279278, language=CN, label=表2, caption=

催化剂的结构性质

, figureFileSmall=null, figureFileBig=null, tableContent=
催化剂比表面积(m2/g)a微孔面积(m2/g)b总孔容(cm3/g)b微孔孔容(cm3/g)bRu含量(wt%)c
Ru@MFI399.32157.080.6620.1820.60
Ru/MFI-IM340.05183.330.4950.1570.59
Ru/MFI-DP329.74177.360.4840.1520.60
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MFI分子筛限域Ru催化剂的制备及其丙烷催化燃烧性能
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王晶晶 1 , 夏良辉 1 , 武雅妮 1 , 刘昱洁 1 , 徐赫 1 , 刘起源 1 , 刘基丞 1 , 建艳飞 1, ** , 何炽 1, 2, *
中国环境科学 | 臭氧污染与控制 2025,45(1): 58-65
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中国环境科学 | 臭氧污染与控制 2025, 45(1): 58-65
MFI分子筛限域Ru催化剂的制备及其丙烷催化燃烧性能
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王晶晶1 , 夏良辉1, 武雅妮1, 刘昱洁1, 徐赫1, 刘起源1, 刘基丞1, 建艳飞1, ** , 何炽1, 2, *
作者信息
  • 1.西安交通大学能源与动力工程学院,动力工程多相流国家重点实验室,陕西 西安 710049
  • 2.挥发性有机物污染控制材料与技术国家工程实验室,北京 101408
  • 王晶晶(1993-),女,甘肃定西人,西安交通大学博士研究生,主要从事挥发性有机污染物降解和分子筛封装贵金属研究..

通讯作者:

*责任作者,教授,
**助理教授,
Synthesis of Ru confined in MFI zeolites catalyst and its study on the catalytic combustion performance of propane
Jing-jing WANG1 , Liang-hui XIA1, Ya-ni WU1, Yu-jie LIU1, He XU1, Qi-yuan LIU1, Ji-chen LIU1, Yan-fei JIAN1, ** , Chi HE1, 2, *
Affiliations
  • 1.State Key Laboratory of Multiphase Flow in Power Engineering, School of Energy and Power Engineering, Xi'an Jiaotong University, Xi'an 710049, China
  • 2.National Engineering Laboratory for VOCs Pollution Control Material & Technology, Beijing 101408, China
出版时间: 2025-01-20
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采用原位合成法、浸渍法和沉积沉淀法制备Ru与MFI分子筛结合的3种催化剂,用于丙烷(C3H8)的催化氧化活性研究.结果显示,通过原位合成法将Ru限域在MFI分子筛孔道内时,Ru@MFI催化剂展现出最佳的低温C3H8氧化活性,在270℃时达到90%转化率,并表现出卓越的高温热稳定性和抗水性.通过XRD、N2吸脱附、HAADF-STEM以及CO-TPD等表征技术发现,限域在MFI分子筛孔道内部的Ru具有最小的粒径和最高的分散度,增加了活性Ru位点的数量.拉曼和H2-TPR表征结果表明,孔道内的Ru与MFI之间相互作用导致电荷重新分布,增强了还原性能.因此,Ru@MFI催化剂呈现出最优异的C3H8氧化活性.此外,MFI孔道的几何限制作用在高温焙烧过程中维持Ru的稳定性和分散度,有效避免了Ru的聚集,进一步确保了催化剂的高温热稳定性.

分子筛限域贵金属  /  Ru@MFI  /  丙烷催化氧化  /  活性位点分散度  /  高温热稳定性

Three Ru-based catalysts were synthesized using in-situ synthesis, impregnation, and deposition-precipitation methods in combination with MFI zeolites to investigate their catalytic oxidation activity toward propane (C3H8). The catalyst synthesized via the in-situ method, denoted as Ru@MFI, exhibited the highest low-temperature oxidation activity, achieving a 90% conversion rate at 270℃, along with remarkable thermal stability at high temperatures and hydrophobicity. Characterization techniques, including X-ray diffraction (XRD), N2 adsorption-desorption, high-angle annular dark-field scanning transmission electron microscopy(HAADF-STEM), and temperature-programmed desorption of CO (CO-TPD), revealed that Ru confined within the MFI zeolite channels possessed the smallest particle size and highest dispersion, thereby increasing the number of active Ru sites. Further characterization using Raman spectroscopy and hydrogen temperature-programmed reduction (H2-TPR) indicated that interactions between Ru and the MFI framework led to a redistribution of charge around Ru or oxygen, enhancing the reduction capabilities.Consequently, the Ru@MFI catalyst demonstrated superior propane oxidation activity. Additionally, the geometric confinement within the MFI channels maintained the stability and dispersion of Ru species during high-temperature calcination, effectively preventing Ru aggregation and further ensuring the catalyst's high-temperature thermal stability.

MFI confined noble metals  /  Ru@MFI  /  propane catalytic oxidation  /  dispersion of active sites  /  high-temperature thermal stability
王晶晶, 夏良辉, 武雅妮, 刘昱洁, 徐赫, 刘起源, 刘基丞, 建艳飞, 何炽. MFI分子筛限域Ru催化剂的制备及其丙烷催化燃烧性能. 中国环境科学, 2025 , 45 (1) : 58 -65 .
Jing-jing WANG, Liang-hui XIA, Ya-ni WU, Yu-jie LIU, He XU, Qi-yuan LIU, Ji-chen LIU, Yan-fei JIAN, Chi HE. Synthesis of Ru confined in MFI zeolites catalyst and its study on the catalytic combustion performance of propane[J]. China Environmental Science, 2025 , 45 (1) : 58 -65 .
丙烷(C3H8)作为一种典型的低碳挥发性有机物(VOCs),在大气中具有较长的存留时间和较高的环境浓度,是地表臭氧和对流层光化学污染的重要前体[1-4].这些特性使C3H8在全球气候变化、空气质量甚至公共健康方面产生了显著的影响[5].C3H8的环境浓度不仅受到自然源如陆地和海洋的渗漏、地热和火山活动等的影响,同时也受到人为活动如交通运输、工业生产和能源消耗的影响[2,6].根据历史数据,尽管20世纪末全球对化石燃料的依赖减少导致C3H8浓度有所下降,但自2010年以来,全球石油和天然气产业的扩张已使这一趋势逆转,C3H8排放再次上升[6].然而,C3H8分子中的强C-H键赋予其较高的热稳定性和化学稳定性,使得其比长链的碳氢化合物更难以降解,因此是VOCs研究的重点和难点.催化燃烧法由于其低能耗且无二次污染物的特点,已成为当前末端处理C3H8的主流技术[3,7].鉴于此,开发高效且低能耗的C3H8催化氧化技术是大气污染控制领域面临的关键挑战和研究焦点.
贵金属基催化剂由于其在VOCs氧化反应中表现出的卓越催化性能而受到广泛关注[8].然而,传统的非均相催化剂通常采用将贵金属负载在载体表面的方法,这些贵金属在高温反应条件下容易通过奥斯特瓦尔德成熟过程聚集,从而影响催化剂的活性和长期稳定性[9].为克服这一限制,采用分子筛封装贵金属(metal@zeolite)可以有效防止贵金属烧结和浸出,显著提高氧化反应的活性和稳定性[10]. Silicalite-1是一种纯硅质MFI型微孔分子筛,因其在吸收轻烷烃方面的卓越能力而被广泛应用[11].值得注意的是,尽管利用配体-金属前驱体的稳定策略成功地在MFI分子筛中封装了小粒径的Pt、Pd和Rh物种,但这些贵金属基催化剂在商业应用中常面临因贵金属丰度低和成本高的挑战[10,12-14].因此,探索具有高活性和稳定性的低成本替代品,仍是实现C3H8高效氧化的关键挑战.
Ru,作为Pt/Pd/Rh的低成本替代品,因其在低碳烷烃氧化中展现出显著活性而引起广泛关注,其成本仅为Pt的1/3[15].然而,尽管Ru在低温下具有优越的C3H8燃烧性能,但它在高温下极易发生氧化失活[16-17].因此,本文采用金属-配体保护的原位封装法将Ru限域在MFI分子筛中的催化剂,并通过与不同浸渍法制备的负载型催化剂进行比较,结合X射线衍射(XRD),氮气(N2)吸脱附分析,透射电子显微镜(TEM),一氧化碳程序升温解吸(CO-TPD),拉曼和氢气程序升温还原(H2-TPR)等多种物理化学表征,系统地探讨了MFI封装与负载Ru催化剂在C3H8氧化反应中的性能差异.通过这些研究,旨在揭示分子筛封装技术在提高催化剂性能方面的潜在优势,也对解决丙烷等低碳烷烃污染问题提供了新的思路和方法,并为未来的催化剂设计提供了有价值的指导.
采用配体保护的原位水热合成法制备Ru@MFI催化剂.具体步骤如下:将24.36g TPAOH(40wt.%)与60.13mL去离子水混合,然后将24.72g TEOS加入上述溶液中,所得溶液于室温下搅拌6h至原料呈透明状.然后加入4.313×10-4mol RuCl3⋅3H2O水溶液和0.9mL乙二胺,搅拌3h后将该溶液转移到聚四氟乙烯(PTFE)材质的高压反应釜(方氟隆,200mL),密封后置于170℃烘箱中晶化96h.反应结束后迅速冷却降温,用蒸馏水和丙酮过滤洗涤至pH=7,所得固体置于80℃的烘箱中干燥过夜.然后于560℃(2℃/min的升温速率)马弗炉中煅烧8h,得到Ru@MFI催化剂.
采用浸渍法制备Ru/MFI-IM催化剂.首先,将2.5g Ru/MFI加入25mL的H2O中,然后加入1.48×10-4mol RuCl3⋅3H2O水溶液.上述溶液搅拌3h后进行与Ru@MFI相同的干燥和煅烧过程,得到Ru/MFI-IM催化剂.
采用沉积沉淀法制备Ru/MFI-DP催化剂.首先,将2.5g Ru/MFI加入25mL的H2O中,然后缓慢加1mol/L NaOH使溶液的pH值调整为9,再加入1.48×10-4mol RuCl3⋅3H2O水溶液.上述溶液搅拌3h后进行与Ru@MFI相同的干燥和煅烧过程,得到Ru/MFI-DP催化剂.
X射线衍射谱图(XRD)采用德国Bruker D8Advance衍射仪进行测试.测试条件:Cu Kα辐射(λ=0.15406nm),扫描速度为5°/min,扫描范围为2θ=6°~80°.Ru含量组成采用电感耦合等离子体发射光谱(ICP-OES,Agilent,USA)测定.采用气体吸附分析仪(Builder SSA-6000)测定氮气吸附和解吸等温线.利用配备超高亮度场发射电子枪和洛伦兹透镜的高角环形暗场扫描透射电子显微镜(Talos-F200X),在200kV加速电压下,观察Ru物种在的色散和相应的元素映射.采用英国Renishaw拉曼光谱仪对催化剂的分子结构进行分析,激光波长为532nm.
采用配备热导率检测器(TCD)的化学吸附仪(PCA-1200,北京比奥德)进行CO-TPD,H2-TPR测试,以表征Ru的分散度和氧化还原性.CO-TPD的具体测试步骤如下:首先,将50mg样品置于U型石英管中,通入5% H2/Ar混合气,升温至400℃还原2h后用高纯N2气吹扫30min.然后降至室温并切换成5% CO/N2混合气吸附1h随后在N2气氛中以10℃/min的升温速率从室温升温至500℃进行程序升温脱附,同时利用TCD记录信号变化,得到CO-TPD谱图.H2-TPR的具体测试步骤如下:首先,将50mg样品置于U型石英管中,在Ar气氛中以10℃/min的升温速率升温至300℃,保持1h以除去水分和杂质气体后降至室温,随后在10%H2/Ar气氛中从室温升温至800℃,同时利用TCD记录信号变化,得到H2-TPR谱图.
C3H8氧化活性和CO2收率通过连续流的石英床反应器(内径10mm)评价,具体步骤如下:将0.30g样品(40~60目)装入管式反应器,通入流速为100mL/min的混合气(0.1% C3H8/N2和21% O2/N2),气体重量空速(WHSV)为20000mL/(g·h).待稳定后,以2℃/min的升温速率,在100~600℃的温度范围内,每个温度点下稳定30min.使用配备有氢火焰电离检测器(FID)和TCD的双通道在线气相色谱(GC-9890E,中国灵华)来监测出口处的C3H8和CO2的浓度.为保证数据的可靠性,所报告的结果为五次分析的平均值,其中C3H8浓度的精确度可达0.2%;CO2产率的精确度可达1%.C3H8转化率和CO2产率的计算公式为:
式中:[C3H8]inlet和[C3H8]outlet分别为反应器进口和出口处的C3H8浓度;[CO2]inlet和[CO2]outlet分别为反应器进口处和出口处的CO2浓度.
图1(a)表1展示了新鲜催化剂在C3H8氧化反应中的性能.T50T90T100分别表示C3H8转化率达到50%,90%和100%时的反应温度.研究结果表明,将Ru限域在MFI分子筛中的催化剂比直接负载在MFI表面的催化剂,表现出更优异的C3H8氧化活性.具体而言,Ru@MFI催化剂的T50比Ru/MFI-IM和Ru/MFI-DP分别降低了13和71℃.随着温度的增加,3类催化剂C3H8转化率的差异更加显著:Ru@MFI催化剂在270℃时达到T90,远优于Ru/MFI-IM(300℃)和Ru/MFI-DP(390℃)催化剂;Ru@MFI催化剂在300℃时达到T100,较Ru/MFI-IM和Ru/MFI-DP催化剂分别高出40℃和200℃.此外,如图1(b)所示,CO2产率的变化趋势与C3H8转化率一致,即Ru@MFI>Ru/MFI-IM> Ru/MFI-DP.
稳定性和耐久性是评估催化剂在实际应用中性能的关键标准[18-20].因此,本文探讨了催化剂的高温热稳定性和抗水性,结果如图1(c)和1(d)所示.考虑到工业应用的实际需求和分子筛的再生能力,本文将3种催化剂在700℃于空气气氛中处理了6h,以评估其高温热稳定性,处理后的催化剂分别命名为Ru@MFI-700,Ru/MFI-IM-700和Ru/MFI-DP-700.图1c的研究结果表明,与新鲜催化剂相比,3种催化剂在700℃高温处理后,C3H8转化率的T50T90T100温度均有所增加.具体来说,Ru@MFI-700的T50T90T10温度分别略微增加了17℃,23℃和20℃;相比之下,Ru/MFI-IM-700的对应温度则分别显著增加了58℃,145℃和250℃;而Ru/MFI-DP-700催化剂在同等条件下几乎完全失活.此外,在T89下稳定3h后,向Ru@MFI和Ru/MFI-IM催化剂中引入5%的水蒸气(H2O)时,Ru/MFI-IM催化剂的C3H8转化率从89%下降到80%,且在切断H2O后,转化率未能恢复到初始值.相反,无论H2O通入或者切断,Ru@MFI催化剂的C3H8转换率几乎未变.此外,我们在T100下对Ru@MFI催化剂进行了48h的长时间稳定性测试,C3H8转换率也未发生改变.以上结果表明Ru@MFI催化剂展现出卓越的高温热稳定性和水热稳定性.
所有催化剂的X射线衍射(XRD)谱图(图2)在2θ=7.93°,8.82°和23.07°处显示出MFI(JCPDS no.1)的典型衍射峰[11,21].结果表明无论是原位封装还是负载Ru物种,载体MFI分子筛的晶体结构均保持完整并未受到破坏.此外,由于Ru的负载量较低,在所有催化剂的XRD衍射谱图中均未检测到金属Ru(JCPDS#89-4903)或RuO2(JCPD#70-2662)的衍射峰.
图3所示,3种催化剂在低相对压力下均表现出氮气吸附量的迅速增加,并随后逐渐趋于饱和.在接近P/P0=1时,吸附量略有增加,这表明存在少量较大的孔隙或微量介孔.然而,总体而言,3种催化剂的吸附特性仍主要由微孔结构主导,符合典型I型等温线的特征[22].表1展示了3种催化剂的具体结构性质.Ru@MFI催化剂具有最高的比表面积399.32m2/g,而Ru/MFI-IM和Ru/MFI-DP的比表面积相对较低,分别为340.05m2/g和329.74m2/g.这一对比表明,Ru的封装并不会降低催化剂的总体可用表面积,而Ru的负载会导致可访问表面积的减少.以往的研究表明广泛的可访问表面通常有利于催化反应中的物质吸附和反应过程[23-24].总孔容在3种样品中相对接近,但主要差异体现在微孔体积上:Ru@MFI显示出较高的微孔体积(0.662cm3/g),Ru/MFI-IM和Ru/MFI-DP的微孔体积较低,分别为0.495cm3/g和0.484cm3/g.这种差异可能源于Ru的不同分布方式:原位封装Ru可以实现更均匀的分布,而直接负载Ru则可能导致部分孔隙被占据.这种非均匀分布在小分子催化反应中可能限制了催化剂的效率.
通过透射电子显微镜(TEM)技术,对3种催化剂进行了详细的微观形貌和Ru分布以及其粒径对催化性能影响的分析.
图4(a)~(c)所示,3种催化剂都展示出六边形结构的形貌,这表明无论是负载还是封装,MFI分子筛都保持了相对良好的晶体完整性和结构均一性.此外,Ru@MFI催化剂的表面相对干净,表明大部分Ru已成功封装于MFI分子筛的内部.相比之下,Ru/MFI-IM和Ru/MFI-DP催化剂表面则明显显示出不同程度的Ru聚集.值得注意的是,如图4(d)~(f),Ru@MFI催化剂中的Ru粒径较小,约1.75nm,并且粒径分布较窄,表明Ru在MFI分子筛内部呈高度分散的状态.而Ru/MFI-IM催化剂中的Ru物种平均粒径增至7.55nm,显示出更大的寸和更宽的分布,Ru/MFI-DP催化剂则展现出最大的Ru物种平均粒径约10.64nm,进一步揭示了在这类催化剂中Ru物种的生长和聚集现象更为明显.先前的研究已经证明,较小的粒径有助于提高会提高催化剂与反应物之间的相互作用,使得催化过程中的氢转移和氧化还原反应更为迅速和高效[25-26].
小粒径的金属有助于增加活性位点数量和提高表面活性,从而显著提升催化剂的效率[27-28].因此,Ru@MFI催化剂中,小粒径的Ru物种是具有高C3H8氧化活性的原因之一.此外,由于分子筛孔道的几何限制,位于分子筛内部的Ru物种在高温焙烧过程中能够维持稳定的粒径,避免了Ru聚集现象.因此,Ru@MFI催化剂在C3H8氧化中表现出了优异的高温热稳定性.
CO-TPD(一氧化碳程序升温解吸)分析进一步评估了3种催化剂中Ru的分散度.如图5所示,Ru@MFI催化剂的CO-TPD曲线显示出一个集中且尖锐的峰,位于约200℃,表明该催化剂的Ru位点均一且粒子尺寸小.相比之下,Ru/MFI-IM和Ru/MFI-DP的CO-TPD曲线呈现更平坦且宽散的峰,位于略低的温度(约175℃),表明Ru粒子较大,分布不均或者聚集,从而导致活性位点的不同程度暴露.3种催化剂中Ru粒径的结果进一步印证了TEM电镜的结果.进一步的定量分析结果表明,Ru@MFI催化剂中Ru的分散度为34.16%,显著高于Ru/MFI-IM的20.78%和Ru/MFI-DP的14.44%,这表明原位封装的Ru具有更高分散度.高分散度意味着更多的Ru原子暴露,使得更多的C3H8和O2分子能够在催化剂表面得到有效吸附和激活,从而提高Ru@MFI催化剂在C3H8氧化反应中的活性.此外,高分散度催化剂在高温氧化条件下表现出更好的表面金属原子稳定性,不易发生团聚或烧结现象,因此,Ru@MFI催化剂表现出卓越的高温热稳定性.
进一步通过拉曼光谱图研究催化剂的结构如图6所示,在288~472cm-1和787~833cm-1的波数范围内,3种催化剂均显示出MFI分子筛中5元、6元和10元环的典型Si-O-Si弯曲振动或伸缩振动[29-30].相比其他2种负载型催化剂,Ru@MFI催化剂的Si-O-Si振动峰强度最弱.这表明较多的Ru物种被封装在MFI分子筛的孔道内部,增强了Ru与MFI之间的相互作用,从而影响了分子筛骨架上Si和O原子的电荷分布[31-32].这种电子重新分配可能改变了拉曼活性区域的振动模式,进而影响了MFI分子筛的整体振动强度.此外,在513~520cm-1和631~640cm-1波数范围内,观察到Ru-O键的Eg模式弯曲振动和A1g模式对称伸缩振动[33-34].值得注意的是,相比其他两种负载型催化剂,Ru@MFI催化剂的Ru-O键呈现显著的红移.这表明Ru与MFI之间相互作用可能改变Ru或O周围电荷的重新分布.
为研究催化剂的氧化还原性,对3种不同催化剂进行了H2-TPR(氢气程序升温还原)分析.一般认为,MFI分子筛不易被H2还原且无明显还原峰,因此,图中的H2还原峰可以归属于Ru物种的还原.如图7所示,Ru@MFI显示出最低的还原峰位于139℃,Ru/MFI-IM和Ru/MFI-DP的还原峰分别出现在更高温度163℃和194℃,这表明Ru@MFI催化剂中的Ru氧化物具有最好的还原性.较低的还原温度通常指示出催化剂具备更优越的氧化还原特性,这一特征与电子在催化反应中的传递能力紧密相关.在VOCs氧化过程中,催化剂需要从VOCs分子接受氢原子,并在反应过程中将这些氢原子转移至其他分子或气体[35].这一系列反应涉及到氧化还原过程,催化剂的活性位点必须能在氧化态与还原态之间有效转换[36].因此,出色的氧化还原性能可以使Ru@MFI催化剂更有效地参与C3H8活化反应.
3.1 Ru物种在分子筛中的位置可显著影响催化剂的C3H8氧化活性.限域型催化剂Ru@MFI表现出最优异的低温C3H8氧化活性,其T90由负载型Ru/MFI-IM和Ru/MFI-DP催化剂的300℃和390℃降至270℃.Ru@MFI催化剂同时表现出最卓越的高温热稳定性,与新鲜催化剂相比,700℃焙烧后的Ru@MFI-700催化剂的T90仅上升了23℃,而Ru/MFI-700催化剂显著上升了145℃.
3.2 Ru物种的粒径大小和分散度可显著影响催化剂的C3H8氧化活性.限域型催化剂Ru@MFI中的Ru仅有1.75nm,分散度为34.16%,远优于负载型催化剂中的Ru粒径和分散度. Ru@MFI催化剂中小粒径和高分散的Ru物种是其具有优良低温高活性和高温热稳定性的重要原因.
3.3 限域型催化剂Ru@MFI中Ru与MFI分子筛的相互作用可调节Ru周围电荷的重新分布,使得其Ru氧化物具有最好的还原性,从而使Ru@MFI催化剂更有效地参与C3H8氧化反应.
  • 国家重点研发计划(2022YFB4101500)
  • 国家自然科学基金资助项目(22276145)
  • 国家自然科学基金资助项目(21922606)
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  • 接收时间:2024-06-07
  • 首发时间:2026-03-18
  • 出版时间:2025-01-20
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  • 收稿日期:2024-06-07
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国家重点研发计划(2022YFB4101500)
国家自然科学基金资助项目(22276145)
国家自然科学基金资助项目(21922606)
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    1.西安交通大学能源与动力工程学院,动力工程多相流国家重点实验室,陕西 西安 710049
    2.挥发性有机物污染控制材料与技术国家工程实验室,北京 101408

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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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