[{"has_accepted_license":"1","department":[{"_id":"MaIb"}],"file":[{"date_updated":"2023-12-11T11:55:09Z","access_level":"open_access","file_name":"2023_ACSCatalysis_.pdf","file_size":14813812,"date_created":"2023-12-11T11:55:09Z","checksum":"a97c771077af71ddfb2249e34530895c","content_type":"application/pdf","relation":"main_file","file_id":"14676","creator":"dernst","success":1}],"date_created":"2023-12-10T23:00:59Z","month":"11","date_published":"2023-11-06T00:00:00Z","article_type":"original","publisher":"American Chemical Society","scopus_import":"1","language":[{"iso":"eng"}],"issue":"22","publication":"ACS Catalysis","page":"15054-15073","file_date_updated":"2023-12-11T11:55:09Z","day":"06","type":"journal_article","intvolume":"        13","status":"public","tmp":{"image":"/images/cc_by.png","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","short":"CC BY (4.0)"},"ddc":["540"],"doi":"10.1021/acscatal.3c03893","year":"2023","title":"Microkinetic modeling with size-dependent and adsorbate-adsorbate interactions for the direct synthesis of H₂O₂ over Pd nanoparticles","date_updated":"2023-12-11T11:55:35Z","oa":1,"volume":13,"article_processing_charge":"Yes (in subscription journal)","_id":"14663","publication_identifier":{"eissn":["2155-5435"]},"user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","acknowledgement":"The authors acknowledge the financial support from the National Natural Science Foundation of China (22008211, 92045303, U21A20298), the National Key Research and Development Project of China (2021YFA1500900, 2022YFE0113800), and Zhejiang Innovation Team (2017R5203).","quality_controlled":"1","oa_version":"Published Version","publication_status":"published","citation":{"chicago":"Zhao, Jinyan, Zihao Yao, Rhys Bunting, P. Hu, and Jianguo Wang. “Microkinetic Modeling with Size-Dependent and Adsorbate-Adsorbate Interactions for the Direct Synthesis of H₂O₂ over Pd Nanoparticles.” <i>ACS Catalysis</i>. American Chemical Society, 2023. <a href=\"https://doi.org/10.1021/acscatal.3c03893\">https://doi.org/10.1021/acscatal.3c03893</a>.","apa":"Zhao, J., Yao, Z., Bunting, R., Hu, P., &#38; Wang, J. (2023). Microkinetic modeling with size-dependent and adsorbate-adsorbate interactions for the direct synthesis of H₂O₂ over Pd nanoparticles. <i>ACS Catalysis</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/acscatal.3c03893\">https://doi.org/10.1021/acscatal.3c03893</a>","ieee":"J. Zhao, Z. Yao, R. Bunting, P. Hu, and J. Wang, “Microkinetic modeling with size-dependent and adsorbate-adsorbate interactions for the direct synthesis of H₂O₂ over Pd nanoparticles,” <i>ACS Catalysis</i>, vol. 13, no. 22. American Chemical Society, pp. 15054–15073, 2023.","short":"J. Zhao, Z. Yao, R. Bunting, P. Hu, J. Wang, ACS Catalysis 13 (2023) 15054–15073.","ista":"Zhao J, Yao Z, Bunting R, Hu P, Wang J. 2023. Microkinetic modeling with size-dependent and adsorbate-adsorbate interactions for the direct synthesis of H₂O₂ over Pd nanoparticles. ACS Catalysis. 13(22), 15054–15073.","mla":"Zhao, Jinyan, et al. “Microkinetic Modeling with Size-Dependent and Adsorbate-Adsorbate Interactions for the Direct Synthesis of H₂O₂ over Pd Nanoparticles.” <i>ACS Catalysis</i>, vol. 13, no. 22, American Chemical Society, 2023, pp. 15054–73, doi:<a href=\"https://doi.org/10.1021/acscatal.3c03893\">10.1021/acscatal.3c03893</a>.","ama":"Zhao J, Yao Z, Bunting R, Hu P, Wang J. Microkinetic modeling with size-dependent and adsorbate-adsorbate interactions for the direct synthesis of H₂O₂ over Pd nanoparticles. <i>ACS Catalysis</i>. 2023;13(22):15054-15073. doi:<a href=\"https://doi.org/10.1021/acscatal.3c03893\">10.1021/acscatal.3c03893</a>"},"abstract":[{"lang":"eng","text":"As a bottleneck in the direct synthesis of hydrogen peroxide, the development of an efficient palladium-based catalyst has garnered great attention. However, elusive active centers and reaction mechanism issues inhibit further optimization of its performance. In this work, advanced microkinetic modeling with the adsorbate–adsorbate interaction and nanoparticle size effect based on first-principles calculations is developed. A full mechanism uncovering the significance of adsorbate–adsorbate interaction is determined on Pd nanoparticles. We demonstrate unambiguously that Pd(100) with main coverage species of O2 and H is beneficial to H2O2 production, being consistent with experimental operando observation, while H2O forms on Pd(111) covered by O species and Pd(211) covered by O and OH species. Kinetic analyses further enable quantitative estimation of the influence of temperature, pressure, and particle size. Large-size Pd nanoparticles are found to achieve a high H2O2 reaction rate when the operating conditions are moderate temperature and higher oxygen partial pressure. We reveal that specific facets of the Pd nanoparticles are crucial factors for their selectivity and activity. Consistent with the experiment, the production of H2O2 is discovered to be more favorable on Pd nanoparticles containing Pd(100) facets. The ratio of H2/O2 induces substantial variations in the coverage of intermediates of O2 and H on Pd(100), resulting in a change in product selectivity."}],"author":[{"full_name":"Zhao, Jinyan","last_name":"Zhao","first_name":"Jinyan"},{"last_name":"Yao","full_name":"Yao, Zihao","first_name":"Zihao"},{"id":"91deeae8-1207-11ec-b130-c194ad5b50c6","last_name":"Bunting","full_name":"Bunting, Rhys","orcid":"0000-0001-6928-074X","first_name":"Rhys"},{"last_name":"Hu","full_name":"Hu, P.","first_name":"P."},{"first_name":"Jianguo","full_name":"Wang, Jianguo","last_name":"Wang"}]},{"publication":"Journal of the American Chemical Society","issue":"27","page":"14894-14902","file_date_updated":"2023-07-12T10:22:04Z","day":"30","type":"journal_article","intvolume":"       145","status":"public","has_accepted_license":"1","department":[{"_id":"MaIb"},{"_id":"BiCh"}],"file":[{"date_updated":"2023-07-12T10:22:04Z","access_level":"open_access","date_created":"2023-07-12T10:22:04Z","checksum":"e07d5323f9c0e5cbd1ad6453f29440ab","file_name":"2023_JACS_Bunting.pdf","file_size":3155843,"file_id":"13219","creator":"cchlebak","content_type":"application/pdf","relation":"main_file","success":1}],"date_created":"2023-07-12T09:16:40Z","month":"06","article_type":"original","date_published":"2023-06-30T00:00:00Z","publisher":"American Chemical Society","language":[{"iso":"eng"}],"article_processing_charge":"Yes (via OA deal)","oa":1,"volume":145,"date_updated":"2023-10-11T08:45:10Z","publication_identifier":{"eissn":["1520-5126"],"issn":["0002-7863"]},"_id":"13216","pmid":1,"quality_controlled":"1","oa_version":"Published Version","user_id":"8b945eb4-e2f2-11eb-945a-df72226e66a9","acknowledgement":"B.C. acknowledges resources provided by the Cambridge Tier2 system operated by the University of Cambridge Research\r\nComputing Service funded by EPSRC Tier-2 capital grant EP/\r\nP020259/1.","citation":{"short":"R. Bunting, F. Wodaczek, T. Torabi, B. Cheng, Journal of the American Chemical Society 145 (2023) 14894–14902.","ista":"Bunting R, Wodaczek F, Torabi T, Cheng B. 2023. Reactivity of single-atom alloy nanoparticles: Modeling the dehydrogenation of propane. Journal of the American Chemical Society. 145(27), 14894–14902.","ama":"Bunting R, Wodaczek F, Torabi T, Cheng B. Reactivity of single-atom alloy nanoparticles: Modeling the dehydrogenation of propane. <i>Journal of the American Chemical Society</i>. 2023;145(27):14894-14902. doi:<a href=\"https://doi.org/10.1021/jacs.3c04030\">10.1021/jacs.3c04030</a>","mla":"Bunting, Rhys, et al. “Reactivity of Single-Atom Alloy Nanoparticles: Modeling the Dehydrogenation of Propane.” <i>Journal of the American Chemical Society</i>, vol. 145, no. 27, American Chemical Society, 2023, pp. 14894–902, doi:<a href=\"https://doi.org/10.1021/jacs.3c04030\">10.1021/jacs.3c04030</a>.","chicago":"Bunting, Rhys, Felix Wodaczek, Tina Torabi, and Bingqing Cheng. “Reactivity of Single-Atom Alloy Nanoparticles: Modeling the Dehydrogenation of Propane.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2023. <a href=\"https://doi.org/10.1021/jacs.3c04030\">https://doi.org/10.1021/jacs.3c04030</a>.","ieee":"R. Bunting, F. Wodaczek, T. Torabi, and B. Cheng, “Reactivity of single-atom alloy nanoparticles: Modeling the dehydrogenation of propane,” <i>Journal of the American Chemical Society</i>, vol. 145, no. 27. American Chemical Society, pp. 14894–14902, 2023.","apa":"Bunting, R., Wodaczek, F., Torabi, T., &#38; Cheng, B. (2023). Reactivity of single-atom alloy nanoparticles: Modeling the dehydrogenation of propane. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/jacs.3c04030\">https://doi.org/10.1021/jacs.3c04030</a>"},"publication_status":"published","abstract":[{"lang":"eng","text":"Physical catalysts often have multiple sites where reactions can take place. One prominent example is single-atom alloys, where the reactive dopant atoms can preferentially locate in the bulk or at different sites on the surface of the nanoparticle. However, ab initio modeling of catalysts usually only considers one site of the catalyst, neglecting the effects of multiple sites. Here, nanoparticles of copper doped with single-atom rhodium or palladium are modeled for the dehydrogenation of propane. Single-atom alloy nanoparticles are simulated at 400–600 K, using machine learning potentials trained on density functional theory calculations, and then the occupation of different single-atom active sites is identified using a similarity kernel. Further, the turnover frequency for all possible sites is calculated for propane dehydrogenation to propene through microkinetic modeling using density functional theory calculations. The total turnover frequencies of the whole nanoparticle are then described from both the population and the individual turnover frequency of each site. Under operating conditions, rhodium as a dopant is found to almost exclusively occupy (111) surface sites while palladium as a dopant occupies a greater variety of facets. Undercoordinated dopant surface sites are found to tend to be more reactive for propane dehydrogenation compared to the (111) surface. It is found that considering the dynamics of the single-atom alloy nanoparticle has a profound effect on the calculated catalytic activity of single-atom alloys by several orders of magnitude."}],"author":[{"id":"91deeae8-1207-11ec-b130-c194ad5b50c6","orcid":"0000-0001-6928-074X","full_name":"Bunting, Rhys","last_name":"Bunting","first_name":"Rhys"},{"first_name":"Felix","orcid":"0009-0000-1457-795X","full_name":"Wodaczek, Felix","last_name":"Wodaczek","id":"8b4b6a9f-32b0-11ee-9fa8-bbe85e26258e"},{"full_name":"Torabi, Tina","last_name":"Torabi","first_name":"Tina"},{"id":"cbe3cda4-d82c-11eb-8dc7-8ff94289fcc9","orcid":"0000-0002-3584-9632","last_name":"Cheng","full_name":"Cheng, Bingqing","first_name":"Bingqing"}],"keyword":["Colloid and Surface Chemistry","Biochemistry","General Chemistry","Catalysis"],"tmp":{"image":"/images/cc_by.png","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","short":"CC BY (4.0)"},"isi":1,"ddc":["540"],"doi":"10.1021/jacs.3c04030","year":"2023","external_id":{"pmid":["37390457"],"isi":["001020623900001"]},"title":"Reactivity of single-atom alloy nanoparticles: Modeling the dehydrogenation of propane"}]