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1. Investigation of the Bimodal Leaching Response of RAM Chip Gold Fingers in Ammonia Thiosulfate Solution

   https://doi.org/10.3390/ma16144940  

   Lin, Peijia ; Ali, Zulqarnain Ahmad ; Werner, Joshua ( July 2023 , Materials)

   Oxidative thiosulfate leaching using Cu(II)-NH3 has been explored for both mining and recycling applications as a promising method for Au extraction. This study seeks to understand the dissolution behavior of Au from waste RAM chips using a Cu(II)-NH3-S2O3 solution. In the course of this work, bimodal leaching and Au loss were observed in a manner that we have not identified in the literature. Identification of the existence of a specific Au-Ni-Cu lamellar structure in the gold fingers from RAM chips by scanning electron microscopy and energy dispersive X-ray spectroscopy (SEM-EDS) revealed the possibility of interference between Au recovery and the existence of Cu and Ni. During leaching, the co-extraction of Ni was found to predict a negative impact on the Au recovery, as a result of chemical interactions from the Au-Ni-Cu interlayer. Decopperization as a pretreatment was found necessary to remove the pre-existing Cu and promote Au leaching. As part of the study parameters, such as Cu(II) concentration, aeration rates, thiosulfate and ammonia concentrations, particle sizes, and temperatures, were investigated. A satisfactory Au recovery of 98% was achieved using 50 mM Cu(II), 120 mL/min aeration rate, 0.5 M (NH3)2S2O3, and 0.75 M NH4OH (i.e., AT/AH ratio of 0.67) for 4 h residence time at room temperature (25 °C). However, there were several high recoveries prior to Au loss from the lixiviant. It was revealed that the main cause of lower Au recovery was due to a precipitation or cementation reaction that included a sulfur species formation. Because of the bimodal leaching, a composite response comprised of the time to Au loss and maximum recovery was developed, termed leaching proclivity, to facilitate statistical analysis. Furthermore, this study explores the interactions between Au-Ni-Cu and provides suggestions for improving Au thiosulfate leaching under the interference of co-existing metals from waste PCB materials. 

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2. Boosting the Recycling Efficiency of Spent Lithium‐Ion Battery Cathodes Using a Green Reductant

   https://doi.org/10.1002/aesr.202100040  

   Rose, Satchit ; Xu, Panpan ; Gao, Hongpeng ; Li, Mingqian ; Yu, Xiaolu ; Chen, Zheng ( May 2021 , Advanced Energy and Sustainability Research)

   One major bottleneck of today's industrial hydrometallurgical lithium‐ion battery recycling processes is the limited operation efficiency, particularly for leaching Co, Li, and Ni elements. Boosting the leaching rate and solid to liquid (S/L) ratio can increase the productivity and yield of recycled materials, which can save chemicals and energy cost. Herein, the use of ethylene glycol (EG), a green and sustainable reducing agent, for the separation of spent cathode materials resulting in high leaching efficiencies for very high loadings is demonstrated. The dramatically improved leaching efficiency is attributed to the EG reducing moieties that enable better cathode reduction and dissolution. The separation process avoids the use of toxic organic solvents, making the overall leaching process greener. The leaching efficiency is shown to remain high despite the use of high loadings as compared to the state‐of‐the‐art works. The cathode separation process is then modified to allow for a facile separation of a cathode and anode mixture. This mixture is demonstrated to attain high leaching efficiencies at comparable loadings for cathode‐only process. This redox leaching‐based recovery process holds a potential for industry adoption due to the elimination of energy‐intensive pretreatment step and the high efficiencies obtained.

    

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3. Microfluidic Synthesis of Elastomeric Microparticles: A Case Study in Catalysis of Palladium-Mediated Cross-Coupling

   Bennett, Jeffrey A ; Genzer, Jan ; Abolhasani, Milad ( October 2018 , 2018 AIChE Annual Meeting)

   Metal-mediated cross-coupling reactions offer organic chemists a wide array of stereo- and chemically-selective reactions with broad applications in fine chemical and pharmaceutical synthesis.1 Current batch-based synthesis methods are beginning to be replaced with flow chemistry strategies to take advantage of the improved consistency and process control methods offered by continuous flow systems.2,3 Most cross-coupling chemistries still encounter several issues in flow using homogeneous catalysis, including expensive catalyst recovery and air sensitivity due to the chemical nature of the catalyst ligands.1 To mitigate some of these issues, a ligand-free heterogeneous catalysis reaction was developed using palladium (Pd) loaded into a polymeric network of a silicone elastomer, poly(hydromethylsiloxane) (PHMS), that is not air sensitive and can be used with mild reaction solvents (ethanol and water).4 In this work we present a novel method of producing soft catalytic microparticles using a multiphase flow-focusing microreactor and demonstrate their application for continuous Suzuki-Miyaura cross-coupling reactions. The catalytic microparticles are produced in a coaxial glass capillary-based 3D flow-focusing microreactor. The microreactor consists of two precursors, a cross-linking catalyst in toluene and a mixture of the PHMS polymer and a divinyl cross-linker. The dispersed phase containing the polymer, cross-linker, and cross-linking catalyst is continuously mixed and then formed into microdroplets by the continuous phase of water and surfactant (sodium dodecyl sulfate) introduced in a counter-flow configuration. Elastomeric microdroplets with a diameter ranging between 50 to 300 micron are produced at 25 to 250 Hz with a size polydispersity less than 3% in single stream production. The physicochemical properties of the elastomeric microparticles such as particle swelling/softness can be tuned using the ratio of cross-linker to polymer as well as the ratio of polymer mixture to solvent during the particle formation. Swelling in toluene can be tuned up to 400% of the initial particle volume by reducing the concentration of cross-linker in the mixture and increasing the ratio of polymer to solvent during production.5 After the particles are produced and collected, they are transferred into toluene containing palladium acetate, allowing the particles to incorporate the palladium into the polymer network and then reduce the palladium to Pd0 with the Si-H functionality present on the PHMS backbones. After the reduction, the Pd-loaded particles can be washed and dried for storage or switched into an ethanol/water solution for loading into a micro-packed bed reactor (µ-PBR) for continuous organic synthesis. The in-situ reduction of Pd within the PHMS microparticles was confirmed using energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and focused ion beam-SEM, and TEM techniques. In the next step, we used the developed µ-PBR to conduct continuous organic synthesis of 4-phenyltoluene by Suzuki-Miyaura cross-coupling of 4-iodotoluene and phenylboronic acid using potassium carbonate as the base. Catalyst leaching was determined to only occur at sub ppm concentrations even at high solvent flow rates after 24 h of continuous run using inductively coupled plasma mass spectrometry (ICP-MS). The developed µ-PBR using the elastomeric microparticles is an important initial step towards the development of highly-efficient and green continuous manufacturing technologies in the pharma industry. In addition, the developed elastomeric microparticle synthesis technique can be utilized for the development of a library of other chemically cross-linkable polymer/cross-linker pairs for applications in organic synthesis, targeted drug delivery, cell encapsulation, or biomedical imaging. References 1. Ruiz-Castillo P, Buchwald SL. Applications of Palladium-Catalyzed C-N Cross-Coupling Reactions. Chem Rev. 2016;116(19):12564-12649. 2. Adamo A, Beingessner RL, Behnam M, et al. On-demand continuous-flow production of pharmaceuticals in a compact, reconfigurable system. Science. 2016;352(6281):61 LP-67. 3. Jensen KF. Flow Chemistry — Microreaction Technology Comes of Age. 2017;63(3). 4. Stibingerova I, Voltrova S, Kocova S, Lindale M, Srogl J. Modular Approach to Heterogenous Catalysis. Manipulation of Cross-Coupling Catalyst Activity. Org Lett. 2016;18(2):312-315. 5. Bennett JA, Kristof AJ, Vasudevan V, Genzer J, Srogl J, Abolhasani M. Microfluidic synthesis of elastomeric microparticles: A case study in catalysis of palladium-mediated cross-coupling. AIChE J. 2018;0(0):1-10. 

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4. Cobalt mineralogy at the Iron Creek deposit, Idaho cobalt belt, USA: Implications for domestic critical mineral production

   https://doi.org/10.1130/G51160.1  

   Holley, E.A. ; Zaronikola, N. ; Trouba, J. ; Pfaff, K. ; Thompson, J. ; Spiller, E. ; Anderson, C. ; Eggert, R. ( June 2023 , Geology)

   Abstract Current U.S. policies aim to establish domestic supply chains of critical minerals for the energy transition. The Iron Creek deposit in the Idaho cobalt belt (ICB) is one of the most promising cobalt (Co) targets. Our case study illustrates the importance of mineralogy in strategic evaluations of critical mineral potential. Most of the Co at Iron Creek occurs as Fe substitution in pyrite, with lattice-bound and inclusion-hosted Ag, As, Bi, Ni, Pb, Se, Te ± trace Au and Sb. Cobalt also occurs in minor cattierite-vaesite. The Co minerals are intergrown with Co-poor chalcopyrite hosting Cu ± minor In and Zn. Worldwide, most Co is recovered from deposits mineralogically distinct from the ICB, and the United States currently lacks infrastructure to recover this Co and its associated metals. ICB ore minerals could be processed by autoclave, roaster, smelter, bioleach, or heap leach. Recovery of the Ag, As, Au, Bi, In, Pb, Se, Te, and Zn would be costly by autoclave, and construction of a custom smelter for ICB ores is likely uneconomic, so these elements would become waste irrespective of criticality. The Co-Fe and Co-As sulfide minerals are most suitable for Co and Ni recovery by a hydrometallurgical autoclave process, with potential pretreatment of cobaltiferous pyrite/arsenopyrite in an inert-atmosphere roaster, in new domestic or anticipated international facilities. The ICB is the second largest known Co resource in the United States. Consideration of ore mineralogy in the ICB is essential in strategies for domestic production. 

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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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