@article{Multifunctional:3368,
      recid = {3368},
      author = {Song, Yang},
      title = {Development of Multifunctional Metal-Organic Frameworks  for Catalytic Applications},
      publisher = {University of Chicago},
      school = {Ph.D.},
      address = {2021-08},
      pages = {231},
      abstract = {Metal-organic frameworks (MOFs) have emerged as a highly  versatile and tunable platform for the design of  structurally uniform solid catalysts. Highly active  multifunctional MOF catalysts have been developed via a  number of novel post-synthetic strategies, including  functionalization at MOF linkers/ligands, functionalization  at MOF SBUs, and entrapment of catalytically active species  (e.g. metal nanoparticles, metal complexes, and organic  molecules) in MOF pores, channels, and cavities. The  resultant multifunctional MOF catalysts have been used to  catalyze a broad scope of reactions. This dissertation  focuses on the design and synthesis of multifunctional MOFs  for several catalytic reactions, including reductive  reactions, Lewis acid promoted reactions, and  photocatalysis.The first part of this dissertation (Chapter  2 and Chapter 3) discusses MOF-promoted C-O bond cleavage.  In Chapter 2, we showed that Ti8-BDC works as an excellent  platform to support a single-site Ni-H catalyst for aryl  ether hydrogenolysis. The C-O bond linkages of the model  compounds for typical bonds in lignin were selectively  cleaved by the Ni-H catalyst to produce aromatic molecules  as well as cyclohexanol under mild conditions. In Chapter  3, we further developed a multifunctional aluminum  MOF-based catalytic system (1-OTf-PdNP) for one-pot tandem  C-O bond cleavage. This tandem catalysis overcomes the  strong C-O binding energy and transforms biomass into  valuable hydrocarbon fuels. The synergistic Lewis acids and  Pd NPs in the MOF showed outstanding catalytic activities  in the C-O bond cleavage of a broad scope of ethers,  alcohols, and esters to exclusively generate deoxygenated  saturated alkanes under relatively mild conditions.
The  second part of this dissertation (Chapter 4) focuses on  photocatalytic organic synthesis. While the multifunctional  catalytic system in Chapter 3 showed outstanding  performance in tandem catalysis for C-O bond cleavage, we  further utilized the same MOF platform to incorporate  Ir-based photosensitizers (Ir-PSs) to construct a  bioinspired MOF-based photocatalytic system. Strongly Lewis  acidic sites and Ir-PSs sites were installed in 1-OTf-Ir  for reductive cross-coupling reactions between  N-hydroxyphthalimide (NHP) esters or aryl bromomethyl  ketones with vinyl- or alkynyl-azaarenes to afford  functionalized azaarene derivatives.
The third part of this  dissertation (Chapter 5 and Chapter 6) further discusses  photocatalysis with MOFs, specifically photocatalytic  hydrogen evolution reaction (HER), an important half  reaction of water splitting. In Chapter 5, we  hierarchically assembled photosensitizers and catalytic  sites in Ti3-BPDC. The proximity of multiple  photosensitizers to the catalytic Ti3(OH)2 SBU facilitates  multielectron transfer upon photoexcitation, leading to  80-fold enhancement in HER activity over the corresponding  homogeneous controls. In Chapter 6, we developed a  two-dimensional Ce-based MOF in order to overcome the  shortcomings of MOF materials in photocatalysis. The  reduction of one dimension reduces light scattering and  allows free diffusion of reactive species throughout the  framework. The proximity of PSs to the catalytic Ce6 SBUs  facilitated electron transfer upon photoexcitation, leading  to 8.7- to 9.3-fold enhancement in HER activity over their  homogeneous controls.

},
      url = {http://knowledge.uchicago.edu/record/3368},
      doi = {https://doi.org/10.6082/uchicago.3368},
}