Efficient recovery and recycling/upcycling of precious metals using hydrazide-functionalized star-shaped polymers.

There is a growing demand for adsorption technologies for recovering and recycling precious metals (PMs) in various industries. Unfortunately, amine-functionalized polymers widely used as metal adsorbents are ineffective at recovering PMs owing to their unsatisfactory PM adsorption performance. Herein, a star-shaped, hydrazide-functionalized polymer (S-PAcH) is proposed as a readily recoverable standalone adsorbent with high PM adsorption performance. The compact chain structure of S-PAcH containing numerous hydrazide groups with strong reducibility promotes PM adsorption by enhancing PM reduction while forming large, collectable precipitates. Compared with previously reported PM adsorbents, commercial amine polymers, and reducing agents, S-PAcH exhibited significantly higher adsorption capacity, selectivity, and kinetics toward three PMs (gold, palladium, and platinum) with model, simulated, and real-world feed solutions. The superior PM recovery performance of S-PAcH was attributed to its strong reduction capability combined with its chemisorption mechanism. Moreover, PM-adsorbed S-PAcH could be refined into high-purity PMs via calcination, directly utilized (upcycled) as catalysts for dye reduction, or regenerated for reuse, demonstrating its high practical feasibility. Our proposed PM adsorbents would have a tremendous impact on various industrial sectors from the perspectives of environmental protection and sustainable development.

Tannic acid-assisted in-situ interfacial formation of Prussian blue-assembled adsorptive membranes for radioactive cesium removal.

There is a growing interest in advanced materials that can effectively treat wastewater contaminated with radioactive cesium (137Cs), which is an extremely hazardous material. Here, we report a new class of Cs-adsorptive membranes compactly assembled with Cs-adsorptive Prussian blue (PB) particles. The PB particle assembly was formed via an in-situ interfacial reaction between two PB precursors in the presence of tannic acid (TA) as a binder on a porous support. While the interfacial reaction enabled the formation of a defect-less PB network, TA enhanced the PB-PB and PB-support compatibilities, consequently producing a uniform, densely packed PB assembly near the support surface. The fabricated TA-assisted PB membrane (PB/TA-M) synergistically rejected Cs via a combination of adsorption and membrane filtration, although adsorption predominantly determined Cs rejection initially. Hence, the PB/TA-M membrane showed considerably higher Cs removal performance than commercial nanofiltration (NF) and reverse osmosis (RO) polyamide (PA) membranes for a sufficiently long operation time. Furthermore, the PB/TA-M membrane displayed excellent radioactive 137Cs removal performance, significantly exceeding those of commercial NF and RO PA membranes due to its higher radiation stability, indicating its viability for application in treating actual radioactive wastewater.

Poly(acryloyl hydrazide)-grafted cellulose nanocrystal adsorbents with an excellent Cr(VI) adsorption capacity.

In this study, we prepared poly(acryloyl hydrazide) (PAH)-grafted cellulose nanocrystal (CNC-PAH) particles via the atom transfer radical polymerization method for application to Cr(VI) adsorption. The closely-packed PAH chains grafted on the cellulose nanocrystal (CNC) surface provide a high density of amine groups that can adsorb Cr(VI) through strong electrostatic, hydrogen bonding and chelating interactions. CNC-PAH exhibited the optimum Cr(VI) adsorption capacity at the solution pH = 3, where its electrostatic attraction with Cr(VI) was maximized. Cr(VI) was chemisorbed in CNC-PAH by following the Langmuir isotherm mechanism (homogeneous monolayer adsorption). The Cr(VI) adsorption kinetics of CNC-PAH was controlled predominantly by intra-particle diffusion resistance imparted by the PAH shell layer. Thermodynamic analysis revealed that Cr(VI) adsorption of CNC-PAH is a spontaneous and endothermic process. Importantly, CNC-PAH grafted with the higher Mw (∼50 kg mol-1) PAH exhibited a rapid Cr(VI) adsorption rate and remarkably high Cr(VI) adsorption capacity (∼457.6 mg g-1 at 298.15 K), exceeding those of previously reported adsorbents owing to its numerous Cr(VI)-adsorptive amine groups provided by the closely-packed grafted PAH polymers. Furthermore, CNC-PAH showed excellent reusability to maintain its high adsorption ability during repeated adsorption-desorption cycles owing to the covalently binding nature of the PAH polymers.

Primary, secondary, and tertiary amines for CO2 capture: designing for mesoporous CO2 adsorbents.

CO(2) emissions, from fossil-fuel-burning power plants, the breathing, etc., influence the global worming on large scale and the man's work efficiency on small scale. The reversible capture of CO(2) is a prominent feature of CO(2) organic-inorganic hybrid adsorbent to sequester CO(2). Herein, (3-aminopropyl) trimethoxysilane (APTMS), [3-(methylamino)propyl] trimethoxysilane (MAPTMS), and [3-(diethylamino) propyl] trimethoxysilane (DEAPTMS) are immobilized on highly ordered mesoporous silicas (SBA-15) to catch CO(2) as primary, secondary, and tertiary aminosilica adsorbents. X-ray photoelectron spectroscopy was used to analyze the immobilized APTMS, MAPTMS, and DEAPTMS on the SBA-15. We report an interesting discovery that the CO(2) adsorption and desorption on the adsorbent depend on the amine type of the aminosilica adsorbent. The adsorbed CO(2) was easily desorbed from the adsorbent with the low energy consumption in the order of tertiary, secondary, and primary amino-adsorbents while the adsorption amount and the bonding-affinity increased in the reverse order. The effectiveness of amino-functionalized (1(o), 2(o), and 3(o) amines) SBA-15s as a CO(2) capturing agent was investigated in terms of adsorption capacity, adsorption-desorption kinetics, and thermodynamics. This work demonstrates apt amine types to catch CO(2) and regenerate the adsorbent, which may open new avenues to designing "CO(2) basket".

Gelation of chitin and chitosan dispersed suspensions under electric field: effect of degree of deacetylation.

Herein, the effect of the degree of deacetylation (DD) on the gelation of the chitosan dispersed suspension as an electrorheological (ER) fluid under an electric field is presented. The fluids were prepared by dispersing the chitin and the chitosan particles having various DDs into silicone oil, and they were evaluated under various electric fields. The alignment of chitosan particles in the fluid was also observed using an optical microscope under the electric field. The formed fibrous structure between electrodes are though to continue to the viscosity increase, because an attempt to move one electrode relative to the order would be hindered by the drag of the dangling fibrils. A noteworthy result is that the region of the frequency for gel state of the ER fluids increased in the order of chitosan DD 99.3, 93.4, 73.2, 83.8, and 87.3% under electric fields while the modulus of the fluids increased in the reverse order. This order was well-matched with the result of dielectric constants and yield stresses of ER fluids. The study of influence of DD on the gelation of the chitosan dispersed suspension under an electric field shows the relevance of the chemical composition of the heteropolysaccharide (chitin-chitosan copolymer) to the rheological and electric properties of ER suspensions.