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1. Reaction acceleration at air‐solution interfaces: Anisotropic rate constants for Katritzky transamination

   https://doi.org/10.1002/jms.4585  

   Li, Yangjie; Mehari, Tsdale_F; Wei, Zhenwei; Liu, Yong; Cooks, R_Graham (July 2020, Journal of Mass Spectrometry)

   Abstract To disentangle the factors controlling the rates of accelerated reactions in droplets, we used mass spectrometry to study the Katritzky transamination in levitated Leidenfrost droplets of different yet constant volumes over a range of concentrations while holding concentration constant by adding back the evaporated solvent. The set of concentration and droplet volume data indicates that the reaction rate in the surface region is much higher than that in the interior. These same effects of concentration and volume were also seen in bulk solutions. Three pyrylium reagents with different surface activity showed differences in transamination reactivity. The conclusion is drawn that reactions with surface‐active reactants are subject to greater acceleration, as seen particularly at lower concentrations in systems of higher surface‐to‐volume ratios. These results highlight the key role that air‐solution interfaces play in Katritzky reaction acceleration. They are also consistent with the view that reaction‐increased rate constant is at least in part due to limited solvation of reagents at the interface. 

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2. The role of analyte concentration in accelerated reaction rates in evaporating droplets

   https://doi.org/10.1039/d3sc00259d  

   Chen, Casey J.; Williams, Evan R. (May 2023, Chemical Science)

   Accelerated reactions in microdroplets have been reported for a wide range of reactions with some microdroplet reactions occurring over a million times faster than the same reaction in bulk solution. Unique chemistry at the air–water interface has been implicated as a primary factor for accelerated reaction rates, but the role of analyte concentration in evaporating droplets has not been as well studied. Here, theta-glass electrospray emitters and mass spectrometry are used to rapidly mix two solutions on the low to sub-microsecond time scale and produce aqueous nanodrops with different sizes and lifetimes. We demonstrate that for a simple bimolecular reaction where surface chemistry does not appear to play a role, reaction rate acceleration factors are between 10 2 and 10 7 for different initial solution concentrations, and these values do not depend on nanodrop size. A rate acceleration factor of 10 7 is among the highest reported and can be attributed to concentration of analyte molecules, initially far apart in dilute solution, but brought into close proximity in the nanodrop through evaporation of solvent from the nanodrops prior to ion formation. These data indicate that analyte concentration phenomenon is a significant factor in reaction acceleration where droplet volume throughout the experiment is not carefully controlled. 

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3. Reaction Acceleration Promoted by Partial Solvation at the Gas/Solution Interface

   https://doi.org/10.1002/cplu.202100373  

   Qiu, Lingqi; Wei, Zhenwei; Nie, Honggang; Cooks, R_Graham (September 2021, ChemPlusChem)

   Abstract The kinetics of organic reactions of different types in microvolumes (droplets, thin films, and sealed tubes) show effects of gas/solution interfacial area, reaction molecularity and solvent polarity. Partial solvation at the gas/solution interface is a major contributor to the 10⁴‐fold reaction acceleration seen in bimolecular but not unimolecular reactions in microdroplets. Reaction acceleration can be used to manipulate selectivity by solvent choice. 

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4. Mechanochemical in Situ Encapsulation of Palladium in Covalent Organic Frameworks

   https://doi.org/10.1021/acssuschemeng.4c04003  

   Brown, Normanda; Zhang, Qingsong; Alsudairy, Ziad; Dun, Chaochao; Nailwal, Yogendra; Campbell, Allea; Harrod, Chelsea; Chen, Linfeng; Williams, Spirit; Urban, Jeffrey J; et al (September 2024, ACS Sustainable Chemistry & Engineering)

   Palladium-encapsulated covalent organic frameworks (Pd/COFs) have garnered enormous attention in heterogeneous catalysis. However, the dominant ex situ encapsulation synthesis is tedious (multistep), time-consuming (typically 4 days or more), and involves the use of noxious solvents. Here we develop a mechanochemical in situ encapsulation strategy that enables the one-step, timeefficient, and environmentally benign synthesis of Pd/COFs. By ball milling COF precursors along with palladium acetate (Pd(OAc)2) in one pot under air at room temperature, Pd/COF hybrids were readily synthesized within an hour, exhibiting high crystallinity, uniform Pd dispersion, and superb scalability up to gram scale. Moreover, this versatile strategy can be extended to the synthesis of three Pd/COFs. Remarkably, the resulting Pd/DMTP-TPB showcases extraordinary activity (96−99% yield in 1 h at room temperature) and broad substrate scope (>10 functionalized biaryls) for the Suzuki−Miyaura coupling reaction of aryl bromides and arylboronic acids. Furthermore, the heterogeneity of Pd/DMTP-TPB is verified by recycling and leaching tests. The mechanochemical in situ encapsulation strategy disclosed herein paves a facile, rapid, scalable, and environmentally benign avenue to access metal/COF catalysts for efficient heterogeneous catalysis. 

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5. Heterogeneous catalysis by ultra-small bimetallic nanoparticles surpassing homogeneous catalysis for carbon–carbon bond forming reactions

   https://doi.org/10.1039/d0nr04105j  

   Norouzi, Nazgol; Das, Mrinmoy K.; Richard, Alexander J.; Ibrahim, Amr A.; El-Kaderi, Hani M.; El-Shall, M. Samy (October 2020, Nanoscale)

   null (Ed.)

   Palladium catalyzed cross-coupling reactions represent a significant advancement in contemporary organic synthesis as these reactions are of strategic importance in the area of pharmaceutical drug discovery and development. Supported palladium-based catalysts are highly sought-after in carbon–carbon bond forming catalytic processes to ensure catalyst recovery and reuse while preventing product contamination. This paper reports the development of heterogeneous Pd-based bimetallic catalysts supported on fumed silica that have high activity and selectivity matching those of homogeneous catalysts, eliminating the catalyst's leaching and sintering and allowing efficient recycling of the catalysts. Palladium and base metal (Cu, Ni or Co) contents of less than 1.0 wt% loading are deposited on a mesoporous fumed silica support (surface area SA BET = 350 m 2 g −1 ) using strong electrostatic adsorption (SEA) yielding homogeneously alloyed nanoparticles with an average size of 1.3 nm. All bimetallic catalysts were found to be highly active toward Suzuki cross-coupling (SCC) reactions with superior activity and stability for the CuPd/SiO 2 catalyst. A low CuPd/SiO 2 loading (Pd: 0.3 mol%) completes the conversion of bromobenzene and phenylboronic acid to biphenyl in 30 minutes under ambient conditions in water/ethanol solvent. In contrast, monometallic Pd/SiO 2 (Pd: 0.3 mol%) completes the same reaction in three hours under the same conditions. The combination of Pd with the base metals helps in retaining the Pd 0 status by charge donation from the base metals to Pd, thus lowering the activation energy of the aryl halide oxidative addition step. Along with its exceptional activity, CuPd/SiO 2 exhibits excellent recycling performance with a turnover frequency (TOF) of 280 000 h −1 under microwave reaction conditions at 60 °C. Our study demonstrates that SEA is an excellent synthetic strategy for depositing ultra-small Pd-based bimetallic nanoparticles on porous silica for SCC. This avenue not only provides highly active and sintering-resistant catalysts but also significantly lowers Pd contents in the catalysts without compromising catalytic activity, making the catalysts very practical for large-scale applications. 

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