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1. Catalytic Activity of Water-Soluble Palladium Nanoparticles with Anionic and Cationic Capping Ligands for Reduction, Oxidation, and C-C Coupling Reactions in Water

   https://doi.org/10.3390/nano15050405  

   Farag, Jan W; Khalil, Ragaa; Avila, Edwin; Shon, Young-Seok (March 2025, Nanomaterials)

   The availability of water-soluble nanoparticles allows catalytic reactions to occur in highly desirable green environments. The catalytic activity and selectivity of water-soluble palladium nanoparticles capped with 6-(carboxylate)hexanethiolate (C6-PdNP) and 5-(trimethylammonio)pentanethiolate (C5-PdNP) were investigated for the reduction of 4-nitrophenol, the oxidation of α,β-conjugated aldehydes, and the C-C coupling of phenylboronic acid. The study showed that between the two PdNPs, C6-PdNP exhibits better catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol in the presence of sodium borohydride and the selective oxidation of conjugated aldehydes to conjugated carboxylic acids. For the latter reaction, molecular hydrogen (H2) and H2O act as oxidants for the surface palladium atoms on PdNPs and conjugated aldehyde substrates, respectively. The results indicated that the competing addition activities of Pd-H and H2O toward the π-bond of different unsaturated substrates promote either reduction or oxidation reactions under mild conditions in organic solvent-free environments. In comparison, C5-PdNP exhibited higher catalytic activity for the C-C coupling of phenylboronic acid. Gas chromatography–mass spectrometry (GC-MS) was mainly used as an analytical technique to examine the products of catalytic reactions. 

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2. Boron tribromide as a reagent for anti-Markovnikov addition of HBr to cyclopropanes

   https://doi.org/10.1039/D0SC02567D  

   Gieuw, Matthew H.; Chen, Shuming; Ke, Zhihai; Houk, K. N.; Yeung, Ying-Yeung (September 2020, Chemical Science)

   null (Ed.)

   Although radical formation from a trialkylborane is well documented, the analogous reaction mode is unknown for trihaloboranes. We have discovered the generation of bromine radicals from boron tribromide and simple proton sources, such as water or tert -butanol, under open-flask conditions. Cyclopropanes bearing a variety of substituents were hydro- and deuterio-brominated to furnish anti-Markovnikov products in a highly regioselective fashion. NMR mechanistic studies and DFT calculations point to a radical pathway instead of the conventional ionic mechanism expected for BBr 3 . 

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3. A new quinoline-based cobalt(II) catalyst capable of bifunctional water splitting

   https://doi.org/10.1039/d5qi01196e  

   Lucecki, Carlos A; Rani, Neha; Kpogo, Kenneth K; Niklas, Jens; Poluektov, Oleg G; Schlegel, H Bernhard; Verani, Cláudio N (July 2025, Inorganic Chemistry Frontiers)

   We report on a new water-soluble cobalt(II) complex capable of water splitting bifunctionality, i.e., water reduction and water oxidation. The species [CoII(LQpy)H2O]ClO4 (1), where LQpy is the deprotonated form of the new tripodal ligand N1,N1-bis(pyridin-2-ylmethyl)-N2-(quinolin-8-yl)benzene-1,2-diamine, HLQpy, was developed aiming to replace an oxidation prone methylene group by a sturdy and redox stable quinoline. The molecular and electronic structures of 1 were evaluated by multiple spectroscopic, spectrometric, electrochemical and computational methods, and detailed pre- and post-catalytic studies were conducted to ascertain the molecular nature of the conversions. Complex 1 performs water reduction at a low onset overpotential (eta) of 0.65 V at pH 7, reaching TON3h 2900 (TOF 970 h-1) and TON18h 12 100 (TOF 672 h-1) with up to 98% faradaic efficiency (FE). Species 1 also promotes water oxidation at eta = 0.34 V under pH 8, achieving TON3h 193 (TOF 64 h-1) at 84% FE. Experimental and DFT results enabled us to propose reaction intermediates and mechanisms. 

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4. Reactivity of Pd–MO ₂ encapsulated catalytic systems for CO oxidation

   https://doi.org/10.1039/D1CY01916C  

   Paz Herrera, Laura; Freitas de Lima e Freitas, Lucas; Hong, Jiyun; Hoffman, Adam S.; Bare, Simon R.; Nikolla, Eranda; Medlin, J. Will (March 2022, Catalysis Science & Technology)

   In this study, we present an investigation aimed at characterizing and understanding the synergistic interactions in encapsulated catalytic structures between the metal core ( i.e. , Pd) and oxide shell ( i.e. , TiO 2 , ZrO 2 , and CeO 2 ). Encapsulated catalysts were synthesized using a two-step procedure involving the initial colloidal synthesis of Pd nanoparticles (NPs) capped by various ligands and subsequent sol–gel encapsulation of the NPs with porous MO 2 (M = Ti, Zr, Ce) shells. The encapsulated catalytic systems displayed higher activity than the Pd/MO 2 supported structures due to unique physicochemical properties at the Pd–MO 2 interface. Pd@ZrO 2 exhibited the highest catalytic activity for CO oxidation. Results also suggested that the active sites in Pd encapsulated by an amorphous ZrO 2 shell structure were significantly more active than the crystalline oxide encapsulated structures at low temperatures. Furthermore, CO DRIFTS studies showed that Pd redispersion occurred under CO oxidation reaction conditions and as a function of the oxide shell composition, being observed in Pd@TiO 2 systems only, with potential formation of smaller NPs and oxide-supported Pd clusters after reaction. This investigation demonstrated that metal oxide composition and (in some cases) crystallinity play major roles in catalyst activity for encapsulated catalytic systems. 

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5. Impact of Flame Conditions on the Pd‐O Structure and Methane Oxidation Activity over Ceria Support

   https://doi.org/10.1002/cctc.202401449  

   Wang, Can; Najimu, Musa; Ko, Ben; Sasmaz, Erdem (October 2024, ChemCatChem)

   Abstract In this work, we employed flame spray pyrolysis (FSP), a high‐temperature synthesis method, to control the formation of Pd structures on the CeO₂support. Multiple types of Pd structures deposited on CeO₂are observed on FSP‐made samples. Our results show that the oxidizing environment during FSP synthesis facilitates the formation of incorporated Pd²⁺structures, along with highly dispersed Pd²⁺, Pd⁰nanoparticles, and Pd° clusters formed under the reducing synthesis condition. Notably, these Pd²⁺species remained stable at temperatures up to 400 °C. The catalysts containing both highly dispersed Pd²⁺nanoparticles and incorporated Pd²⁺species demonstrated superior methane oxidation activity, with higher turnover frequencies than those containing only one type of Pd²⁺structure. However, hydrothermal pretreatment in the presence of water vapor led to partial deactivation, likely due to structural alterations in the Pd species or the interaction with the CeO₂support, which reduced the stability and effectiveness of the active sites. This study underscores the importance of both highly dispersed and incorporated Pd²⁺species in enhancing catalytic performance and highlights the challenges posed by water‐induced deactivation in practical applications. 

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