000626128 001__ 626128 000626128 005__ 20250625124414.0 000626128 0247_ $$2doi$$a10.1021/acscatal.4c02077 000626128 0247_ $$2datacite_doi$$a10.3204/PUBDB-2025-01319 000626128 0247_ $$2altmetric$$aaltmetric:168413307 000626128 0247_ $$2WOS$$aWOS:001325925200001 000626128 037__ $$aPUBDB-2025-01319 000626128 041__ $$aEnglish 000626128 082__ $$a540 000626128 1001_ $$0P:(DE-H253)PIP1096383$$aGashnikova, Daria$$b0 000626128 245__ $$aLifecycle of Pd Clusters: Following the Formation and Evolution of Active Pd Clusters on Ceria During CO Oxidation by In Situ/Operando Characterization Techniques 000626128 260__ $$aWashington, DC$$bACS$$c2024 000626128 3367_ $$2DRIVER$$aarticle 000626128 3367_ $$2DataCite$$aOutput Types/Journal article 000626128 3367_ $$0PUB:(DE-HGF)16$$2PUB:(DE-HGF)$$aJournal Article$$bjournal$$mjournal$$s1744367946_218626 000626128 3367_ $$2BibTeX$$aARTICLE 000626128 3367_ $$2ORCID$$aJOURNAL_ARTICLE 000626128 3367_ $$00$$2EndNote$$aJournal Article 000626128 500__ $$a(DFG) through grant no. INST 40/575-1 FUGG (JUSTUS2, RVs bw17D011). 000626128 520__ $$aFor maximizing the atomic efficiency in noble metal-based catalysts, dedicated preparation routes and high lifetime are essential. Both aspects require an in-depth understanding of the fate of noble metal atoms under reaction conditions. For this purpose, we used a combination of complementary in situ/operando characterization techniques to follow the lifecycle of the Pd sites in a 0.5% Pd/5% CeO2–Al2O3 catalyst during oxygen-rich CO oxidation. Time-resolved X-ray absorption spectroscopy showed that Pd cluster formation under reaction conditions is important for a high CO oxidation activity. In combination with density functional theory calculations, we concluded that the ideal Pd cluster size amounts to about 10–30 Pd atoms. The cluster formation and stability were affected by the applied temperature and reaction conditions. Already short pulses of 1000 ppm CO in the lean reaction feed were found to trigger sintering of Pd at temperatures below 200 °C, while at higher temperatures oxidation processes prevailed. Environmental transmission electron microscopy unraveled redispersion at higher temperatures (400–500 °C) in oxygen atmosphere, leading to the formation of single sites and thus the loss of activity. However, due to the reductive nature of CO, clusters formed again upon cooling in reaction atmosphere, thus closing the catalytic cycle. Exploiting the gained knowledge on the lifecycle of Pd clusters, we systematically investigated the effect of catalyst composition on the cluster formation tendency. As uncovered by DRIFTS measurements, the Pd to CeO2 ratio seems to be a key descriptor for Pd agglomeration under reaction conditions. While for higher Pd loadings, the probability of cluster formation increased, a higher CeO2 content leads to the formation of oxidized dispersed Pd species. According to our results, a Pd:CeO2 weight ratio of 1:10 for CeO2–Al2O3-supported catalysts leads to the highest CO oxidation activity under lean conditions independent of the applied synthesis method. 000626128 536__ $$0G:(DE-HGF)POF4-6G3$$a6G3 - PETRA III (DESY) (POF4-6G3)$$cPOF4-6G3$$fPOF IV$$x0 000626128 536__ $$0G:(GEPRIS)446697387$$aSFB 1441 A03 - Reaktivität und hochentwickelte Elektronenmikroskopie von massenselektierten Clustern auf Oxidträgern (A03) (446697387)$$c446697387$$x1 000626128 536__ $$0G:(GEPRIS)446700158$$aSFB 1441 B01 - Synthese und Charakterisierung von Metalloxidträgern mit hoher Oberfläche (B01) (446700158)$$c446700158$$x2 000626128 536__ $$0G:(GEPRIS)446700275$$aSFB 1441 B02 - Systematische Synthese und katalytische Tests von definierten Edelmetallspezies auf Pulverträgern (B02) (446700275)$$c446700275$$x3 000626128 536__ $$0G:(GEPRIS)446701131$$aSFB 1441 B03 - In situ/operando-Charakterisierung von Edelmetallclustern und Partikeln auf Metalloxiden unter Reaktionsbedingungen (B03) (446701131)$$c446701131$$x4 000626128 536__ $$0G:(GEPRIS)446701677$$aSFB 1441 B04 - DFT-Gestützte Mikrokinetische Modellierung der Oxidativen Beseitigung von Schadstoffen (B04) (446701677)$$c446701677$$x5 000626128 536__ $$0G:(GEPRIS)460248799$$aDFG project G:(GEPRIS)460248799 - DAPHNE4NFDI - DAten aus PHoton- und Neutronen Experimenten für NFDI (460248799)$$c460248799$$x6 000626128 588__ $$aDataset connected to CrossRef, Journals: bib-pubdb1.desy.de 000626128 693__ $$0EXP:(DE-H253)P-P65-20150101$$1EXP:(DE-H253)PETRAIII-20150101$$6EXP:(DE-H253)P-P65-20150101$$aPETRA III$$fPETRA Beamline P65$$x0 000626128 7001_ $$0P:(DE-H253)PIP1031645$$aMaurer, Florian$$b1 000626128 7001_ $$aBauer, Miriam R.$$b2 000626128 7001_ $$0P:(DE-H253)PIP1103564$$aBernart, Sarah$$b3 000626128 7001_ $$aJelic, Jelena$$b4 000626128 7001_ $$aLützen, Mads$$b5 000626128 7001_ $$aMaliakkal, Carina B.$$b6 000626128 7001_ $$0P:(DE-H253)PIP1015086$$aDolcet, Paolo$$b7 000626128 7001_ $$0P:(DE-H253)PIP1085186$$aStudt, Felix$$b8 000626128 7001_ $$00000-0001-5701-4006$$aKübel, Christian$$b9 000626128 7001_ $$0P:(DE-H253)PIP1016086$$aDamsgaard, Christian D.$$b10 000626128 7001_ $$0P:(DE-H253)PIP1009506$$aCasapu, Maria$$b11 000626128 7001_ $$0P:(DE-H253)PIP1008522$$aGrunwaldt, Jan-Dierk$$b12$$eCorresponding author 000626128 773__ $$0PERI:(DE-600)2584887-2$$a10.1021/acscatal.4c02077$$gVol. 14, no. 19, p. 14871 - 14886$$n19$$p14871 - 14886$$tACS catalysis$$v14$$x2155-5435$$y2024 000626128 8564_ $$uhttps://bib-pubdb1.desy.de/record/626128/files/gashnikova-et-al-2024-lifecycle-of-pd-clusters-following-the-formation-and-evolution-of-active-pd-clusters-on-ceria.pdf$$yOpenAccess 000626128 8564_ $$uhttps://bib-pubdb1.desy.de/record/626128/files/gashnikova-et-al-2024-lifecycle-of-pd-clusters-following-the-formation-and-evolution-of-active-pd-clusters-on-ceria.pdf?subformat=pdfa$$xpdfa$$yOpenAccess 000626128 909CO $$ooai:bib-pubdb1.desy.de:626128$$pdnbdelivery$$pdriver$$pVDB$$popen_access$$popenaire 000626128 9101_ $$0I:(DE-HGF)0$$6P:(DE-H253)PIP1096383$$aExternal Institute$$b0$$kExtern 000626128 9101_ $$0I:(DE-HGF)0$$6P:(DE-H253)PIP1031645$$aExternal Institute$$b1$$kExtern 000626128 9101_ $$0I:(DE-HGF)0$$6P:(DE-H253)PIP1103564$$aExternal Institute$$b3$$kExtern 000626128 9101_ $$0I:(DE-HGF)0$$6P:(DE-H253)PIP1015086$$aExternal Institute$$b7$$kExtern 000626128 9101_ $$0I:(DE-HGF)0$$6P:(DE-H253)PIP1085186$$aExternal Institute$$b8$$kExtern 000626128 9101_ $$0I:(DE-588)1043621512$$6P:(DE-H253)PIP1085186$$aEuropean XFEL$$b8$$kXFEL.EU 000626128 9101_ $$0I:(DE-HGF)0$$6P:(DE-H253)PIP1016086$$aExternal Institute$$b10$$kExtern 000626128 9101_ $$0I:(DE-HGF)0$$6P:(DE-H253)PIP1009506$$aExternal Institute$$b11$$kExtern 000626128 9101_ $$0I:(DE-HGF)0$$6P:(DE-H253)PIP1008522$$aExternal Institute$$b12$$kExtern 000626128 9131_ $$0G:(DE-HGF)POF4-6G3$$1G:(DE-HGF)POF4-6G0$$2G:(DE-HGF)POF4-600$$3G:(DE-HGF)POF4$$4G:(DE-HGF)POF$$aDE-HGF$$bForschungsbereich Materie$$lGroßgeräte: Materie$$vPETRA III (DESY)$$x0 000626128 9141_ $$y2024 000626128 915__ $$0StatID:(DE-HGF)0200$$2StatID$$aDBCoverage$$bSCOPUS$$d2025-01-07 000626128 915__ $$0StatID:(DE-HGF)0300$$2StatID$$aDBCoverage$$bMedline$$d2025-01-07 000626128 915__ $$0LIC:(DE-HGF)CCBYNCND4$$2HGFVOC$$aCreative Commons Attribution-NonCommercial-NoDerivs CC BY-NC-ND 4.0 000626128 915__ $$0StatID:(DE-HGF)0100$$2StatID$$aJCR$$bACS CATAL : 2022$$d2025-01-07 000626128 915__ $$0StatID:(DE-HGF)0113$$2StatID$$aWoS$$bScience Citation Index Expanded$$d2025-01-07 000626128 915__ $$0StatID:(DE-HGF)9910$$2StatID$$aIF >= 10$$bACS CATAL : 2022$$d2025-01-07 000626128 915__ $$0StatID:(DE-HGF)0150$$2StatID$$aDBCoverage$$bWeb of Science Core Collection$$d2025-01-07 000626128 915__ $$0StatID:(DE-HGF)0510$$2StatID$$aOpenAccess 000626128 915__ $$0StatID:(DE-HGF)1150$$2StatID$$aDBCoverage$$bCurrent Contents - Physical, Chemical and Earth Sciences$$d2025-01-07 000626128 915__ $$0StatID:(DE-HGF)0160$$2StatID$$aDBCoverage$$bEssential Science Indicators$$d2025-01-07 000626128 915__ $$0StatID:(DE-HGF)0199$$2StatID$$aDBCoverage$$bClarivate Analytics Master Journal List$$d2025-01-07 000626128 9201_ $$0I:(DE-H253)FS_DOOR-User-20241023$$kFS DOOR-User$$lFS DOOR-User$$x0 000626128 980__ $$ajournal 000626128 980__ $$aVDB 000626128 980__ $$aUNRESTRICTED 000626128 980__ $$aI:(DE-H253)FS_DOOR-User-20241023 000626128 9801_ $$aFullTexts