% IMPORTANT: The following is UTF-8 encoded.  This means that in the presence
% of non-ASCII characters, it will not work with BibTeX 0.99 or older.
% Instead, you should use an up-to-date BibTeX implementation like “bibtex8” or
% “biber”.

@ARTICLE{Singhvi:1043631,
      author       = {Singhvi, Charvi and Sharma, Gunjan and Verma, Rishi and
                      Paidi, Vinod K. and Glatzel, Pieter and Paciok, Paul and
                      Patel, Vashishtha B. and Mohan, Ojus and Polshettiwar,
                      Vivek},
      title        = {{T}uning the electronic structure and {SMSI} by integrating
                      trimetallic sites with defective ceria for the {CO}2
                      reduction reaction},
      journal      = {Proceedings of the National Academy of Sciences of the
                      United States of America},
      volume       = {122},
      number       = {3},
      issn         = {0027-8424},
      address      = {Washington, DC},
      publisher    = {National Acad. of Sciences},
      reportid     = {FZJ-2025-02939},
      pages        = {e2411406122},
      year         = {2025},
      abstract     = {Heterogeneous catalysts have emerged as a potential key for
                      closing the carbon cycle by converting carbon dioxide (CO2)
                      into value-added chemicals. In this work, we report a highly
                      active and stable ceria (CeO2)-based electronically tuned
                      trimetallic catalyst for CO2 to CO conversion. A unique
                      distribution of electron density between the defective ceria
                      support and the trimetallic nanoparticles (of Ni, Cu, Zn)
                      was established by creating the strong metal support
                      interaction (SMSI) between them. The catalyst showed CO
                      productivity of 49,279 mmol g−1 h−1 at 650 °C. CO
                      selectivity up to $99\%$ and excellent stability (rate
                      remained unchanged even after 100 h) stemmed from the
                      synergistic interactions among Ni-Cu-Zn sites and their SMSI
                      with the defective ceria support. High-energy-resolution
                      fluorescence-detection X-ray absorption spectroscopy
                      (HERFD-XAS) confirmed this SMSI, further corroborated by in
                      situ electron energy loss spectroscopy (EELS) and density
                      functional theory (DFT) simulations. The in situ studies
                      (HERFD-XAS $\&$ EELS) indicated the key role of oxygen
                      vacancies of defective CeO2 during catalysis. The in situ
                      transmission electron microscopy (TEM) imaging under
                      catalytic conditions visualized the movement and growth of
                      active trimetallic sites, which completely stopped once SMSI
                      was established. In situ FTIR (supported by DFT) provided a
                      molecular-level understanding of the formation of various
                      reaction intermediates and their conversion into products,
                      which followed a complex coupling of direct dissociation and
                      redox pathway assisted by hydrogen, simultaneously on
                      different active sites. Thus, sophisticated manipulation of
                      electronic properties of trimetallic sites and defect
                      dynamics significantly enhanced catalytic performance during
                      CO2 to CO conversion.},
      cin          = {ER-C-2},
      ddc          = {500},
      cid          = {I:(DE-Juel1)ER-C-2-20170209},
      pnm          = {5351 - Platform for Correlative, In Situ and Operando
                      Characterization (POF4-535) / ReMade-at-ARI - RECYCLABLE
                      MATERIALS DEVELOPMENT at ANALYTICAL RESEARCH INFRASTRUCTURES
                      (101058414)},
      pid          = {G:(DE-HGF)POF4-5351 / G:(EU-Grant)101058414},
      typ          = {PUB:(DE-HGF)16},
      pubmed       = {39813253},
      UT           = {WOS:001413631400007},
      doi          = {10.1073/pnas.2411406122},
      url          = {https://juser.fz-juelich.de/record/1043631},
}