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Creators/Authors contains: "Duan, Hanyi"

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  1. We summarize recent advances in the design of hybrid nanostructures through the combination of synthetic polymers and plasmonic nanoparticles (NPs). We categorize the synthetic methods of those polymer-coated metal NPs into two main strategies: direct encapsulation and chemical grafting, based on how NPs interact with polymers. In direct encapsulation, NPs with hydrophobic ligands are physically encapsulated into polymer micelles, primarily through hydrophobic interactions. We discuss strategies for controlling the loading numbers and locations of NPs within polymer micelles. On the other hand, polymer-grafted NPs (PGNPs) have synthetic polymers as ligands chemically grafted on NPs. We highlight that polymer ligands can asymmetrically coat metal NPs through hydrophobicity-driven phase segregation using homopolymers, BCPs and blocky random copolymers. This review provides insights into the methodologies and mechanisms to design new nanostructures of polymers and NPs, aiming to enhance the understanding of this rapidly evolving field. 
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    Free, publicly-accessible full text available May 1, 2025
  2. We report a new design of polymer phenylacetylene (PA) ligands and the ligand exchange methodology for colloidal noble metal nanoparticles (NPs). PA-terminated poly(ethylene glycol) (PEG) can bind to metal NPs through acetylide (M-CC-R) that affords a high grafting density. The ligand−metal interaction can be switched between σ bonding and extended π backbonding by changing grafting conditions. The σ bonding of PEG−PA with NPs is strong and it can compete with other capping ligands including thiols, while the π backbonding is much weaker. The σ bonding is also demonstrated to improve the catalytic performance of Pd for ethanol oxidation and prevent surface absorption of the reaction intermediates. Those unique binding characteristics will enrich the toolbox in the control of colloidal surface chemistry and their applications using polymer ligands. 
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    Free, publicly-accessible full text available May 15, 2025
  3. Free, publicly-accessible full text available September 1, 2024
  4. This paper reports a robust strategy to catalyze in situ C–H oxidation by combining cobalt (Co) single-atom catalysts (SACs) and horseradish peroxidase (HRP). Co SACs were synthesized using the complex of Co phthalocyanine with 3-propanol pyridine at the two axial positions as the Co source to tune the coordination environment of Co by the stepwise removal of axial pyridine moieties under thermal annealing. These structural features of Co sites, as confirmed by infrared and X-ray absorption spectroscopy, were strongly correlated to their reactivity. All Co catalysts synthesized below 300 °C were inactive due to the full coordination of Co sites in octahedral geometry. Increasing the calcination temperature led to an improvement in catalytic activity for reducing O2, although molecular Co species with square planar coordination obtained below 600 °C were less selective to reduce O2 to H2O2 through the two-electron pathway. Co SACs obtained at 800 °C showed superior activity in producing H2O2 with a selectivity of 82–85% in a broad potential range. In situ production of H2O2 was further coupled with HRP to drive the selective C–H bond oxidation in 2-naphthol. Our strategy provides new insights into the design of highly effective, stable SACs for selective C–H bond activation when coupled with natural enzymes. 
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    Free, publicly-accessible full text available August 30, 2024
  5. Free, publicly-accessible full text available July 11, 2024
  6. We report the use of polymer N -heterocyclic carbenes (NHCs) to control the microenvironment surrounding metal nanocatalysts, thereby enhancing their catalytic performance in CO 2 electroreduction. Three polymer NHC ligands were designed with different hydrophobicity: hydrophilic poly(ethylene oxide) (PEO–NHC), hydrophobic polystyrene (PS–NHC), and amphiphilic block copolymer (BCP) (PEO- b -PS–NHC). All three polymer NHCs exhibited enhanced reactivity of gold nanoparticles (AuNPs) during CO 2 electroreduction by suppressing proton reduction. Notably, the incorporation of hydrophobic PS segments in both PS–NHC and PEO- b -PS–NHC led to a twofold increase in the partial current density for CO formation, as compared to the hydrophilic PEO–NHC. While polymer ligands did not hinder ion diffusion, their hydrophobicity altered the localized hydrogen bonding structures of water. This was confirmed experimentally and theoretically through attenuated total reflectance surface-enhanced infrared absorption spectroscopy and molecular dynamics simulation, demonstrating improved CO 2 diffusion and subsequent reduction in the presence of hydrophobic polymers. Furthermore, NHCs exhibited reasonable stability under reductive conditions, preserving the structural integrity of AuNPs, unlike thiol-ended polymers. The combination of NHC binding motifs with hydrophobic polymers provides valuable insights into controlling the microenvironment of metal nanocatalysts, offering a bioinspired strategy for the design of artificial metalloenzymes. 
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    Free, publicly-accessible full text available August 1, 2024
  7. We report a new design of polymer-patched gold nanoparticles (AuNPs) with controllable interparticle interactions in terms of their direction and strength. Patchy AuNPs (pAuNPs) are prepared through hydrophobicity-driven surface dewetting under deficient ligand exchange conditions. Using the exposed surface on pAuNPs as seeds, a highly controllable growth of AuNPs is carried out via seed-mediated growth while retaining the size of polymer domains. As guided by ligands, these pAuNPs can self-assemble directionally in two ways along the exposed surface (head-to-head) or the polymer-patched surface of pAuNPs (tail-to-tail). Control of the surface asymmetry/coverage on pAuNPs provides an important tool in balancing interparticle interactions (attraction vs. repulsion) that further tunes assembled nanostructures as clusters and nanochains. The self-assembly pathway plays a key role in determining the interparticle distance and therefore plasmon coupling of pAuNPs. Our results demonstrate a new paradigm in the directional self-assembly of anisotropic building blocks for hierarchical nanomaterials with interesting optical properties. 
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  8. Abstract We report the synthesis of ordered mesoporous ceria ( m CeO 2 ) with highly crystallinity and thermal stability using hybrid polymer templates consisting of organosilanes. Those organosilane-containing polymers can convert into silica-like nanostructures that further serve as thermally stable and mechanically strong templates to prevent the collapse of mesoporous frameworks during thermal-induced crystallization. Using a simple evaporation-induced self-assembly process, control of the interaction between templates and metal precursors allows the co-self-assembly of polymer micelles and Ce 3+ ions to form uniform porous structures. The porosity is well-retained after calcination up to 900 °C. After the thermal engineering at 700 °C for 12 h ( m CeO 2 -700-12 h), m CeO 2 still has a specific surface area of 96 m 2 g −1 with a pore size of 14 nm. m CeO 2 is demonstrated to be active for electrochemical oxidation of sulfite. m CeO 2 -700-12 h with a perfect balance of crystallinity and porosity shows the fastest intrinsic activity that is about 84 times more active than bulk CeO 2 and 5 times more active than m CeO 2 that has a lower crystallinity. 
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  9. null (Ed.)