[{"file":[{"date_created":"2023-12-11T11:55:09Z","checksum":"a97c771077af71ddfb2249e34530895c","file_size":14813812,"date_updated":"2023-12-11T11:55:09Z","file_name":"2023_ACSCatalysis_.pdf","content_type":"application/pdf","relation":"main_file","success":1,"access_level":"open_access","file_id":"14676","creator":"dernst"}],"status":"public","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","publication_identifier":{"eissn":["2155-5435"]},"oa":1,"tmp":{"legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","short":"CC BY (4.0)","image":"/images/cc_by.png","name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)"},"type":"journal_article","date_published":"2023-11-06T00:00:00Z","language":[{"iso":"eng"}],"oa_version":"Published Version","month":"11","has_accepted_license":"1","publication":"ACS Catalysis","volume":13,"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).","ddc":["540"],"day":"06","doi":"10.1021/acscatal.3c03893","abstract":[{"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.","lang":"eng"}],"year":"2023","citation":{"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>.","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.","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>","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.","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>."},"date_updated":"2023-12-11T11:55:35Z","publisher":"American Chemical Society","article_type":"original","quality_controlled":"1","page":"15054-15073","file_date_updated":"2023-12-11T11:55:09Z","article_processing_charge":"Yes (in subscription journal)","department":[{"_id":"MaIb"}],"date_created":"2023-12-10T23:00:59Z","publication_status":"published","intvolume":"        13","title":"Microkinetic modeling with size-dependent and adsorbate-adsorbate interactions for the direct synthesis of H₂O₂ over Pd nanoparticles","scopus_import":"1","_id":"14663","issue":"22","author":[{"full_name":"Zhao, Jinyan","last_name":"Zhao","first_name":"Jinyan"},{"last_name":"Yao","first_name":"Zihao","full_name":"Yao, Zihao"},{"id":"91deeae8-1207-11ec-b130-c194ad5b50c6","orcid":"0000-0001-6928-074X","full_name":"Bunting, Rhys","first_name":"Rhys","last_name":"Bunting"},{"last_name":"Hu","first_name":"P.","full_name":"Hu, P."},{"last_name":"Wang","first_name":"Jianguo","full_name":"Wang, Jianguo"}]},{"main_file_link":[{"url":"https://doi.org/10.1021/acscatal.2c04025","open_access":"1"}],"user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","status":"public","publication_identifier":{"eissn":["2155-5435"]},"oa":1,"type":"journal_article","date_published":"2022-10-27T00:00:00Z","keyword":["Catalysis","General Chemistry"],"language":[{"iso":"eng"}],"oa_version":"Published Version","month":"10","publication":"ACS Catalysis","volume":12,"extern":"1","day":"27","doi":"10.1021/acscatal.2c04025","abstract":[{"lang":"eng","text":"Photoredox-mediated Ni-catalyzed cross-couplings are powerful transformations to form carbon–heteroatom bonds and are generally photocatalyzed by noble metal complexes. Low-cost and easy-to-prepare carbon dots (CDs) are attractive quasi-homogeneous photocatalyst alternatives, but their applicability is limited by their short photoluminescence (PL) lifetimes. By tuning the surface and PL properties of CDs, we designed colloidal CD nano-photocatalysts for a broad range of Ni-mediated cross-couplings between aryl halides and nucleophiles. In particular, a CD decorated with amino groups permitted coupling to a wide range of aryl halides and thiols under mild, base-free conditions. Mechanistic studies suggested dynamic quenching of the CD excited state by the Ni co-catalyst and identified that pyridinium iodide (pyHI), a previously used additive in metallaphotocatalyzed cross-couplings, can also act as a photocatalyst in such transformations."}],"year":"2022","citation":{"ista":"Zhao Z, Pieber B, Delbianco M. 2022. Modulating the surface and photophysical properties of carbon dots to access colloidal photocatalysts for cross-couplings. ACS Catalysis. 12(22), 13831–13837.","mla":"Zhao, Zhouxiang, et al. “Modulating the Surface and Photophysical Properties of Carbon Dots to Access Colloidal Photocatalysts for Cross-Couplings.” <i>ACS Catalysis</i>, vol. 12, no. 22, American Chemical Society, 2022, pp. 13831–37, doi:<a href=\"https://doi.org/10.1021/acscatal.2c04025\">10.1021/acscatal.2c04025</a>.","short":"Z. Zhao, B. Pieber, M. Delbianco, ACS Catalysis 12 (2022) 13831–13837.","chicago":"Zhao, Zhouxiang, Bartholomäus Pieber, and Martina Delbianco. “Modulating the Surface and Photophysical Properties of Carbon Dots to Access Colloidal Photocatalysts for Cross-Couplings.” <i>ACS Catalysis</i>. American Chemical Society, 2022. <a href=\"https://doi.org/10.1021/acscatal.2c04025\">https://doi.org/10.1021/acscatal.2c04025</a>.","ieee":"Z. Zhao, B. Pieber, and M. Delbianco, “Modulating the surface and photophysical properties of carbon dots to access colloidal photocatalysts for cross-couplings,” <i>ACS Catalysis</i>, vol. 12, no. 22. American Chemical Society, pp. 13831–13837, 2022.","apa":"Zhao, Z., Pieber, B., &#38; Delbianco, M. (2022). Modulating the surface and photophysical properties of carbon dots to access colloidal photocatalysts for cross-couplings. <i>ACS Catalysis</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/acscatal.2c04025\">https://doi.org/10.1021/acscatal.2c04025</a>","ama":"Zhao Z, Pieber B, Delbianco M. Modulating the surface and photophysical properties of carbon dots to access colloidal photocatalysts for cross-couplings. <i>ACS Catalysis</i>. 2022;12(22):13831-13837. doi:<a href=\"https://doi.org/10.1021/acscatal.2c04025\">10.1021/acscatal.2c04025</a>"},"date_updated":"2023-05-15T08:30:13Z","publisher":"American Chemical Society","article_type":"original","quality_controlled":"1","page":"13831-13837","date_created":"2023-05-08T08:28:54Z","article_processing_charge":"No","publication_status":"published","intvolume":"        12","title":"Modulating the surface and photophysical properties of carbon dots to access colloidal photocatalysts for cross-couplings","scopus_import":"1","_id":"12923","issue":"22","author":[{"last_name":"Zhao","first_name":"Zhouxiang","full_name":"Zhao, Zhouxiang"},{"id":"93e5e5b2-0da6-11ed-8a41-af589a024726","first_name":"Bartholomäus","last_name":"Pieber","orcid":"0000-0001-8689-388X","full_name":"Pieber, Bartholomäus"},{"full_name":"Delbianco, Martina","last_name":"Delbianco","first_name":"Martina"}]},{"user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","status":"public","main_file_link":[{"open_access":"1","url":"https://doi.org/10.26434/chemrxiv.12444908"}],"date_published":"2020-11-02T00:00:00Z","type":"journal_article","oa":1,"publication_identifier":{"eissn":["2155-5435"]},"language":[{"iso":"eng"}],"publication":"ACS Catalysis","month":"11","oa_version":"Preprint","extern":"1","volume":10,"date_updated":"2023-02-21T10:09:09Z","citation":{"short":"S. Reischauer, V. Strauss, B. Pieber, ACS Catalysis 10 (2020) 13269–13274.","mla":"Reischauer, Susanne, et al. “Modular, Self-Assembling Metallaphotocatalyst for Cross-Couplings Using the Full Visible-Light Spectrum.” <i>ACS Catalysis</i>, vol. 10, no. 22, American Chemical Society, 2020, pp. 13269–13274, doi:<a href=\"https://doi.org/10.1021/acscatal.0c03950\">10.1021/acscatal.0c03950</a>.","ista":"Reischauer S, Strauss V, Pieber B. 2020. Modular, self-assembling metallaphotocatalyst for cross-couplings using the full visible-light spectrum. ACS Catalysis. 10(22), 13269–13274.","apa":"Reischauer, S., Strauss, V., &#38; Pieber, B. (2020). Modular, self-assembling metallaphotocatalyst for cross-couplings using the full visible-light spectrum. <i>ACS Catalysis</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/acscatal.0c03950\">https://doi.org/10.1021/acscatal.0c03950</a>","ama":"Reischauer S, Strauss V, Pieber B. Modular, self-assembling metallaphotocatalyst for cross-couplings using the full visible-light spectrum. <i>ACS Catalysis</i>. 2020;10(22):13269–13274. doi:<a href=\"https://doi.org/10.1021/acscatal.0c03950\">10.1021/acscatal.0c03950</a>","chicago":"Reischauer, Susanne, Volker Strauss, and Bartholomäus Pieber. “Modular, Self-Assembling Metallaphotocatalyst for Cross-Couplings Using the Full Visible-Light Spectrum.” <i>ACS Catalysis</i>. American Chemical Society, 2020. <a href=\"https://doi.org/10.1021/acscatal.0c03950\">https://doi.org/10.1021/acscatal.0c03950</a>.","ieee":"S. Reischauer, V. Strauss, and B. Pieber, “Modular, self-assembling metallaphotocatalyst for cross-couplings using the full visible-light spectrum,” <i>ACS Catalysis</i>, vol. 10, no. 22. American Chemical Society, pp. 13269–13274, 2020."},"year":"2020","abstract":[{"text":"The combination of nickel and photocatalysis has unlocked a variety of cross-couplings. These protocols rely on a few photocatalysts that can only convert a small portion of visible light (<500 nm) into chemical energy. The high-energy photons that excite the photocatalyst can result in unwanted side reactions. Dyes that absorb a much broader spectrum of light are not applicable because of their short-lived singlet excited states. Here, we describe a self-assembling catalyst system that overcomes this limitation. Immobilization of a nickel catalyst on dye-sensitized titanium dioxide results in a material that catalyzes carbon–heteroatom and carbon–carbon bond formations. The modular approach of dye-sensitized metallaphotocatalysts accesses the entire visible light spectrum and allows tackling selectivity issues resulting from low wavelengths strategically. The concept overcomes current limitations of metallaphotocatalysis by unlocking the potential of dyes that were previously unsuitable.","lang":"eng"}],"doi":"10.1021/acscatal.0c03950","day":"02","page":"13269–13274","quality_controlled":"1","article_type":"original","publisher":"American Chemical Society","author":[{"first_name":"Susanne","last_name":"Reischauer","full_name":"Reischauer, Susanne"},{"full_name":"Strauss, Volker","last_name":"Strauss","first_name":"Volker"},{"id":"93e5e5b2-0da6-11ed-8a41-af589a024726","last_name":"Pieber","first_name":"Bartholomäus","full_name":"Pieber, Bartholomäus","orcid":"0000-0001-8689-388X"}],"issue":"22","_id":"11954","scopus_import":"1","title":"Modular, self-assembling metallaphotocatalyst for cross-couplings using the full visible-light spectrum","intvolume":"        10","publication_status":"published","date_created":"2022-08-24T10:40:46Z","article_processing_charge":"No"}]