Considering the circular economy and environmental protection, sustainable recovery of high-value metals from wastewater has become a prominent concern. Unlike conventional methods featuring extensive chemicals or energy consumption, membrane separation technology plays a crucial role in facilitating the sustainable and efficient recovery of valuable metals from wastewater due to its attractive features. In this review, we first briefly summarize the sustainable supply chain and significance of sustainable recovery of aqueous high-value metals. Then, we review the most recent advances and application potential in promising state-of-the-art membrane-based technologies for recovery of high-value metals (silver, gold, rhenium, platinum, ruthenium, palladium, iridium, osmium, and rhodium) from wastewater effluents. In particular, pressure-based membranes, liquid membranes, membrane distillation, forward osmosis, electrodialysis and membrane-based hybrid technologies and their mechanism of high-value metal recovery is thoroughly discussed. Then, engineering application and economic sustainability are also discussed for membrane-based high-value metal recovery. The review finally concludes with a critical and insightful overview of the techno-economic viability and future research direction of membrane technologies for efficient high-value metal recovery from wastewater.

Advanced membrane-based high-value metal recovery from wastewater

Advancing membranes with enhanced solute-solute selectivity is essential for expanding membrane technology applications, yet it presents a notable challenge. Drawing inspiration from the unparalleled selectivity of biological systems, which benefit from the sophisticated spatial organization of functionalities, we posit that manipulating the arrangement of the membrane’s building blocks, an aspect previously given limited attention, can address this challenge. We demonstrate that optimizing the face-to-face orientation of building blocks during the assembly of covalent-organic-framework (COF) membranes improves ion-π interactions with multivalent ions. This optimization leads to extraordinary selectivity in differentiating between monovalent cations and anions from their multivalent counterparts, achieving selectivity factors of 214 for K + /Al 3+ and 451 for NO 3 − /PO 4 3− . Leveraging this attribute, the COF membrane facilitates the direct extraction of NaCl from seawater with a purity of 99.57%. These findings offer an alternative approach for designing highly selective membrane materials, offering promising prospects for advancing membrane-based technologies. 

Optimizing selectivity via membrane molecular packing manipulation for simultaneous cation and anion screening

Ferroptosis is a type of regulated cell death driven by the iron-dependent accumulation of lipid peroxides. The high involvement of ferroptosis in diverse human diseases highlights the need for the identification of new chemotypes with anti-ferroptotic activity. Here, we performed a natural product library screening in HT1080 fibrosarcoma cells and identified licochalcone A (LA), isoeugenyl acetate (ISA), and isoliensinine (ISL) as suppressors of either RSL3- or IKE-induced ferroptosis. Mechanistically, ferroptosis resistance conferred by these compounds is mainly through GPX4/NRF2-independent mechanisms. Among them, only ISL could effectively rescue ferroptosis induced by FINO 

Identification of Isoliensinine as a Ferroptosis Suppressor with Iron-Chelating Activity

Hydrated cation–π interactions at liquid–solid interfaces between hydrated cations and aromatic ring structures of carbon-based materials are pivotal in many material, biological, and chemical processes, and water serves as a crucial mediator in these interactions. However, a full understanding of the hydrated cation–π interactions between hydrated alkaline earth cations and aromatic ring structures, such as graphene remains elusive. Here, we present a molecular picture of hydrated cation–π interactions for Mg2+ and Ca2+ by using the density functional theory methods. Theoretical results show that the graphene sheet can distort the hydration shell of the hydrated Ca2+ to interact with Ca2+ directly, which is water–cation–π interactions. In contrast, the hydration shell of the hydrated Mg2+ is quite stable and the graphene sheet interacts with Mg2+ indirectly, mediated by water molecules, which is the cation–water–π interactions. These results lead to the anomalous order of adsorption energies for these alkaline earth cations, with hydrated Mg2+–π &amp;lt; hydrated Ca2+–π when the number of water molecules is large (n ≥ 6), contrary to the order observed for cation–π interactions in the absence of water molecules (n = 0). The behavior of hydrated alkaline earth cations adsorbed on a graphene surface is mainly attributed to the competition between the cation–π interactions and hydration effects. These findings provide valuable details of the structures and the adsorption energy of hydrated alkaline earth cations adsorbed onto the graphene surface. 

Hydrated cation–π interactions of π-electrons with hydrated Mg2+ and Ca2+ cations

Abstract Biological ion channels play an important role in living processes, such as maintaining osmotic pressure, signal transduction, and transmitting nerve impulses, and can selectively regulate the transmembrane transport of substances. Inspired by the structure and function of biological ion channels, researchers have prepared a variety of biomimetic nanochannels using advanced nanofabrication techniques to study the mechanism of ion transport in the nanoconfined space. In this study, we mainly introduce the current materials and preparation methods of nanochannels; compare the advantages and disadvantages of the current mainstream theoretical models and simulation software; clarify the influence of confinement effect and surface interface effect on the hydrogen bond structure characteristics and phase transition behavior of confined water in graphene nanochannels, revealing the driving effect of separation pressure in nanochannels on water transport, the micromechanical nature of the water flow boundary slip of nanochannels, and the dominant micromechanical mechanism behind the confined mass transfer phenomenon of nanochannels at different scales; and expound the regulation of nanomaterials based on ionic bond modification and the influence of ion transport properties in industrial desalination, energy enrichment, and detection. The future applications of nanochannel bionic design and regulation, ion-exchange filtration membranes, and ultra-high-speed water transport mechanisms are prospected. 

Preparation, types, and applications of one- and two-dimensional nanochannels and their transport properties for water and ions

Abnormal salt crystals with unconventional stoichiometries, such as Na2 Cl, Na3 Cl, K2 Cl, and CaCl crystals that have been explored in reduced graphene oxide membranes (rGOMs) or diamond anvil cell, hold great promise in applications due to their unique electronic, magnetic, and optical properties predicted in theory. However, the low content of these crystals, only less than 1% in rGOM, limits their research interest and utility in applications. Here, w e report a high-yield synthesis of 2D abnormal crystals with unconventional stoichiometries achieved by applying negative potential on rGOM. W e obtained a more than ten-fold increase in the abnormal Na2 Cl crystals using potential of -0.6 V, resulting in an atomic content of 13.4 ± 4.7% for Na on rGOM. Direct observations by transmission electron microscopy and piezoresponse force microscopy demonstrated a unique piezoelectric behavior arise from 2D Na2 Cl crystals with square structure. The output voltage increased from 0 to ∼180 mV in broad 0°-150° bending angle regime, which meets the voltage requirement of most nanodevices in realistic applications. Density functional theory calculations reveal that the applied negative potential of the graphene surface can strengthen the effect of the Na+ -π interaction and reduce the electrostatic repulsion between cations, making more Na2 Cl crystals formed. This article is protected by copyright. All rights reserved.

High-yield Synthesis of Sodium Chlorides of Unconventional Stoichiometries.


 Fe2+ is of considerable importance in plant growth and crop production. However, in nature most Fe elements favor existing in the trivalent state, which often causes the deficiency of Fe2+ in plants. Here, we report the Fe valence state change from Fe3+ to Fe2+ by using leaves. This valence state change was confirmed by x-ray photoelectron spectroscopy in Fe-Cl@leaves. Fourier transform infrared and ultraviolet-visible spectroscopy demonstrated that aromatic ring groups were included in leaves, and cation-π interactions between Fe cations and the components containing aromatic rings in leaves were measured. Further, density functional theory calculations revealed that, the most stable adsorption site for hydrated Fe3+ cation was the region where hydroxyl groups and aromatic rings coexist. Moreover, molecular orbital and charge decomposition analysis revealed that, the aromatic rings took the major part (59%) of the whole net charge transfer between leaves and Fe cations. This work provides a high-efficiency and eco-friendly way to transform the Fe valence state from Fe3+ to Fe2+, and affords a new insight into the valance change between plant organisms with cations.

New insight of Fe valence state change using leaves-A combined experimental and theoretical study

School of Physics and School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China School of Physical Science and Technology, Ningbo University, Ningbo 315211, China CAS Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China Shanghai Applied Radiation Institute, Shanghai University, Shanghai 200444, China Interdisciplinary Research Center, Shanghai Synchrotron Radiation Facility, Zhangjiang Laboratory (SSRF, ZJLab), Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201204, China Department of Engineering Mechanics, Zhejiang University, Hangzhou 310027, China Oujiang Laboratory and Wenzhou Institute, University of Chinese Academy of Sciences, Wenzhou, Zhejiang 325000, China

Remarkably strong magnetic response in molecules with polar groups

The recovery of gold from water is an important research area. Recent reports have highlighted the ultrahigh capacity and selective extraction of gold from electronic waste using reduced graphene oxide (rGO). Here, we made a further attempt with the thermal rGO membranes and found that the thermal rGO membranes also had a similarly high adsorption efficiency (1.79 g gold per gram of rGO membranes at 1000 ppm). Furthermore, we paid special attention to the detailed selectivity between Au3+ and other ions by rGO membranes. The maximum adsorption capacity for Au3+ ions was about 16 times that of Cu2+ ions and 10 times that of Fe3+ ions in a mixture solution with equal proportions of Au3+/Cu2+ and Au3+/Fe3+. In a mixed-ion solution containing Au3+:Cu2+:Na+:Fe3+:Mg2+ of printed circuit board (PCB), the mass of Au3+:Cu2+:Na+:Fe3+:Mg2+ in rGO membranes is four orders of magnitude higher than the initial mass ratio. A theoretical analysis indicates that this selectivity may be attributed to the difference in the adsorption energy between the metal ions and the rGO membrane. The results are conducive to the usage of rGO membranes as adsorbents for Au capture from secondary metal resources in the industrial sector. 

Thermally Reduced Graphene Oxide Membranes Revealed Selective Adsorption of Gold Ions from Mixed Ionic Solutions

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High-yield Synthesis of Sodium Chlorides of Unconventional Stoichiometries.

New insight of Fe valence state change using leaves-A combined experimental and theoretical study

Remarkably strong magnetic response in molecules with polar groups

Thermally Reduced Graphene Oxide Membranes Revealed Selective Adsorption of Gold Ions from Mixed Ionic Solutions