Polyethyleneimine-Modified Polymer as an Efficient Palladium Scavenger and Effective Catalyst Support for a Functional Heterogeneous Palladium Catalyst

Yamada, Tsuyoshi; Kobayashi, Yutaka; Ito, Naoya; Ichikawa, Tomohiro; Park, Kwihwan; Kunishima, Kouki; Ueda, Shigenori; Mizuno, Masahiro; Adachi, Tadashi; Sawama, Yoshinari; Monguchi, Yasunari; Sajiki, Hironao

doi:10.1021/acsomega.9b00707

Cited by 19 publications

(11 citation statements)

References 59 publications

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“…Hybrid materials have also been used to recover precious metals (e.g., Pd, Au, Pt). − Previous studies have reported a high-recovery material based on a polymer consisting of thiocarbonyl groups for metal coordination and amino groups for hydrophilicity . Gelation occurred through self-assembly between the thiocarbonyl groups and metal ions, precipitating the self-assembled polymer–metal complexes, which were then separated by filtration (Figure ).…”

Section: Introductionmentioning

confidence: 99%

Pd- and Au-Induced Circular and Fibrous Polymer Gelation via Thiocarbonyl Groups and High Pd Catalyst Activity

Nagai

Kubo

Morita

et al. 2020

ACS Appl. Polym. Mater.

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Self-assembled gelation behavior of a hydrophilic polymer bearing a metal-coordination unit with metal ions (PdII or AuIII) was investigated upon addition of a dispersed aqueous solution of the polymer to an aqueous solution of metal ions. Self-assembled gels with different morphologies were formed depending on the metal ions used. Spherical and fibrous gels were formed by gelation with PdII and AuIII ions, respectively. The mechanism for formation of the different gel morphology was examined by measuring cross-linking rates, examining coordination sites, and determining mechanical properties. The PdII self-assembled gels efficiently catalyzed the Mizoroki-Heck cross-coupling reaction of a variety of aryl halides and olefins with a turnover number (TON) and turnover frequency (TOF) of greater than 2,762,000 and 138,100 h–1, respectively. These are the greatest TON and TOF values for heterogeneous polymeric catalysts of the Mizoroki-Heck reaction. The AuIII self-assembled fibrous gels, which had nano-order diameter, contained uniformly dispersed gold nanoparticles and could be synthesized by a facile method, i.e., the dropwise addition of a dispersed aqueous solution of the polymer to an aqueous solution of AuIII ion.

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Section: Introductionmentioning

confidence: 99%

Pd- and Au-Induced Circular and Fibrous Polymer Gelation via Thiocarbonyl Groups and High Pd Catalyst Activity

Nagai

Kubo

Morita

et al. 2020

ACS Appl. Polym. Mater.

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“…A promising field, particularly in pressure-driven processes, is organic solvent nanofiltration (OSN) [ 3 ]. Lab-scale and commercial-scale applications of OSN membranes have been reported [ 4 , 5 ]. In the advance and application of the membrane process, characterization of modelling and optimization are essential steps [ 6 , 7 ].…”

Section: Introductionmentioning

confidence: 99%

Characterization of Selected Polymeric Membranes Used in the Separation and Recovery of Palladium-Based Catalyst Systems

et al. 2020

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Membrane separation processes tender a capable option for energy-demanding separation processes. Nanofiltration (NF) and reverse osmosis (RO) membranes are among the most explored, with a latent use in the chemical industry. In this study, four commercial membranes (NF90, NF270, BW30, and XLE) were investigated for their applicability based on the key structural performance characteristics in the recycling of Pd-based catalysts from Heck coupling post-reaction mixture. Pure water and organic solvent permeabilities, uncharged solute permeability, swelling, and catalyst rejection studies of the membranes were conducted as well as the morphological characterization using Fourier transform infrared, field emission gun scanning electron microscopy, and atomic force microscopy. Characterization results showed trends consistent with the manufactures’ specifications. Pure water and organic solvent fluxes generally followed the trend NF270 > NF90 > BW30 > XLE, with the solvent choice playing a major role in the separation process. Pd(PPh3)2Cl2 was well rejected by almost all membranes in 2-propanol; however, XLE rejects Pd(OAc)2 better at high pressure in acetonitrile. Our study, therefore, revealed that the separation and reuse of the two catalysts by NF90 at 10 bar resulted in 97% and 49% product yields with 52% and 10% catalyst retention for Pd(OAc)2 while Pd(PPh3)2Cl2. gave 87% and 6% yields with 58% and 36% catalyst retention in the first and second cycles, respectively. Considering, the influence of membrane–solute interactions in Pd-catalyst rejection, a careful selection of the polymeric membrane and solvent, a satisfactory separation, and recovery can be achieved.

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“…This is accomplished through screenings of dozens of potential workup protocols and scavengers, among other purification techniques. − This process generates several dozens of samples in which to quantify palladium. Meanwhile, new scavengers continue to emerge, ,− adding options to explore.…”

Section: Introductionmentioning

confidence: 99%

Third-Generation Method for High-Throughput Quantification of Trace Palladium by Color or Fluorescence

Lukomski

Pohorilets

Koide

2019

Org. Process Res. Dev.

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Chemists frequently encounter problems associated with trace palladium in synthetic samples because palladium is widely used in synthetic organic chemistry. We previously reported a colorimetric method for trace palladium quantification, the only high-throughput method implemented in the pharmaceutical industry. However, slight changes from the published reaction conditions have caused reproducibility problems, with little understanding of underlying molecular mechanisms. In the current study, we took a combinatorial approach to investigate the method and found that excess NaOH was a culprit for the lack of reproducibility. We changed the reaction conditions and procedure accordingly, which substantially improved reproducibility. The reaction under current conditions followed Michaelis–Menten kinetics, allowing for predicting reaction rates on the basis of the substrate concentrations. The current method showed 57 and 72% average error, respectively, when drugs spiked with known amounts of palladium and synthetic samples with unknown amounts of palladium were analyzed. The trend of palladium concentrations determined by the current method boded well with actual palladium concentrations.

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Polyethyleneimine-Modified Polymer as an Efficient Palladium Scavenger and Effective Catalyst Support for a Functional Heterogeneous Palladium Catalyst

Cited by 19 publications

References 59 publications

Pd- and Au-Induced Circular and Fibrous Polymer Gelation via Thiocarbonyl Groups and High Pd Catalyst Activity

Pd- and Au-Induced Circular and Fibrous Polymer Gelation via Thiocarbonyl Groups and High Pd Catalyst Activity

Characterization of Selected Polymeric Membranes Used in the Separation and Recovery of Palladium-Based Catalyst Systems

Third-Generation Method for High-Throughput Quantification of Trace Palladium by Color or Fluorescence

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