Secondary metal ion-induced electrochemical reduction of U(VI) to U(IV) solids.

Recent studies have shown that aqueous U(VI) ions can be transformed into U(VI) precipitates through electrocatalytic redox reactions for uranium recovery. However, there have been no reports of U(IV) solids, such as UO2, using electrochemical methods under ambient conditions since low-valence states of uranium are typically oxidized to U(VI) by O2 or H2O2. Here we developed a secondary metal ion-induced strategy for electrocatalytic production of U(IV) solids from U(VI) solutions using a catalyst consisting of atomically dispersed gallium on hollow nitrogen-doped carbon capsules (Ga-Nx-C). This method relies on the presence of secondary metal ions, e.g., alkaline earth metals, transition metals, lanthanide metals, and actinide metals, which promote the generation of UO2 or bimetallic U(IV)-containing oxides through a two-electron transfer process. No U(IV) solid products were generated in the presence of alkali metal ions. Mechanistic studies revealed that the strong binding affinity between U(IV) and alkaline earth metals (Ca2+/Mg2+/Sr2+/Ba2+), transition metals (Ni2+/Zn2+/Pb2+/Fe3+, etc.) and lanthanide/actinide metals (Ce4+/Eu3+/Th4+/La3+) suppressed re-oxidation of U(IV) to U(VI), leading to the generation of U(IV)O2 and Mx(M = Ce, Eu, Th, La)U(IV)yO2. This work provides fundamental insights into the electrochemical behavior of uranium in aqueous media, whilst guiding uranyl capture from nuclear waste and contaminated water.

Single-Molecule Traps in Covalent Organic Frameworks for Selective Capture of C2H2 from C2H4-Rich Gas Mixtures.

Removing trace amounts of acetylene (C2H2) from ethylene (C2H4)-rich gas mixtures is vital for the supply of high-purity C2H4 to the chemical industry and plastics sector. However, selective removal of C2H2 is challenging due to the similar physical and chemical properties of C2H2 and C2H4. Here, we report a "single-molecule trap" strategy that utilizes electrostatic interactions between the one-dimensional (1D) channel of a covalent organic framework (denoted as COF-1) and C2H2 molecules to massively enhance the adsorption selectivity toward C2H2 over C2H4. C2H2 molecules are immobilized via interactions with the O atom of C=O groups, the N atom of C≡N groups, and the H atom of phenyl groups in 1D channels of COF-1. Due to its exceptionally high affinity for C2H2, COF-1 delivered a remarkable C2H2 uptake of 7.97 cm3/g at 298 K and 0.01 bar, surpassing all reported COFs and many other state-of-the-art adsorbents under similar conditions. Further, COF-1 demonstrated outstanding performance for the separation of C2H2 and C2H4 in breakthrough experiments under dynamic conditions. COF-1 adsorbed C2H2 at a capacity of 0.17 cm3/g at 2,000 s/g when exposed to 0.5 ml/min C2H4-rich gas mixture (99% C2H4) at 298 K, directly producing high-purity C2H4 gas at a rate of 3.95 cm3/g. Computational simulations showed that the strong affinity between C2H2 and the single-molecule traps of COF-1 were responsible for the excellent separation performance. COF-1 is also robust, providing a promising new strategy for the efficient removal of trace amounts of C2H2 in practical C2H4 purification.

Is anxiety and depression transmissible? Depressed mother rats transmit anxiety- and depression-like phenotypes to cohabited rat pups through gut microbiota assimilation.

OBJECTIVE: This study is to investigate the role of gut microbiota transmission in the development of anxiety/depression in offspring exposed to maternal depression. METHOD: Offspring rats were cohabitated with their depressed mother or father rats (which exposed to chronic unpredictable mild stress (CUMS)) for 2, 4, and 6 months, the anxiety- and depression-like behaviors, and interaction/caring activities between mother/father and their pups were detected. The gut microbiota composition and its relationship with behaviors were analyzed. Fecal microbiota transplantation (FMT) was performed to establish the gut microbiota of depressed/normal mother rats in the offspring rats to further confirm the role of "depressive gut microbiota" transmission in mediating the anxiety/depression in the pups. RESULTS: Anxiety and depression phenotypes can be transmitted from depressed mother rats to their cohabited offspring. Frequent interactions and gut microbiota assimilation were observed between rat mothers and their pups. Remodeling of the gut microbiota in pups by FMT could induce or attenuate anxiety- and depression-like phenotypes depending on the origin of the fecal microbiota. By comparison, the pups cohabiting with depressed father rats exhibited milder anxiety and depression. CONCLUSIONS: These data together support that depressed mothers can transmit anxiety/depression to their pups through gut microbiota assimilation, which is related to frequent interactions. Our study reinforces the significance of mental health of mothers in preventing the occurrence of childhood anxiety and depression, and pointing out the possibility of remodeling intestinal microbiota as an effective therapeutic approach for treating anxiety/depression in children.

Engineering the pore environment of antiparallel stacked covalent organic frameworks for capture of iodine pollutants.

Radioiodine capture from nuclear fuel waste and contaminated water sources is of enormous environmental importance, but remains technically challenging. Herein, we demonstrate robust covalent organic frameworks (COFs) with antiparallel stacked structures, excellent radiation resistance, and high binding affinities toward I2, CH3I, and I3- under various conditions. A neutral framework (ACOF-1) achieves a high affinity through the cooperative functions of pyridine-N and hydrazine groups from antiparallel stacking layers, resulting in a high capacity of ~2.16 g/g for I2 and ~0.74 g/g for CH3I at 25 °C under dynamic adsorption conditions. Subsequently, post-synthetic methylation of ACOF-1 converted pyridine-N sites to cationic pyridinium moieties, yielding a cationic framework (namely ACOF-1R) with enhanced capacity for triiodide ion capture from contaminated water. ACOF-1R can rapidly decontaminate iodine polluted groundwater to drinking levels with a high uptake capacity of ~4.46 g/g established through column breakthrough tests. The cooperative functions of specific binding moieties make ACOF-1 and ACOF-1R promising adsorbents for radioiodine pollutants treatment under practical conditions.

COF-based membranes for liquid phase separation: Preparation, mechanism and perspective.

Covalent organic frameworks (COFs) are a new kind of crystalline porous materials composed of organic molecules connected by covalent bonds, processes the characteristics of low density, large specific surface area, adjustable pore size and structure, and easy to functionalize, which have been widely used in the field of membrane separation technology. Recently, there are more and more researches focusing on the preparation methods, separation application, and mechanism of COF membranes, which need to be further summarized and compared. In this review, we primarily summarized several conventional preparation methods, such as two-phase interfacial polymerization, in-situ growth on substrate, unidirectional diffusion method, layer-by-layer assembly method, mixed matrix membranes, and so on. The advantages and disadvantages of each method are briefly summarized. The application potential of COF membrane in liquid separation are introduced from four aspects: dyeing wastewater treatment, heavy metal removal, seawater desalination and oil-water separation. Then, the mechanisms including pore structure, hydrophilic/hydrophobic, electrostatic repulsion/attraction and Donnan effect are introduced. For the efficient removal of different kind of pollutions, researchers can select different ligands to construct membranes with specific pore size, hydrophily, salt or organic rejection ability and functional group. The ideas for the design and preparation of COF membranes are introduced. Finally, the future direction and challenges of the next generation of COF membranes in the field of separation are prospected.

Non-contrast T1ρ dispersion versus Gd-EOB-DTPA-enhanced T1mapping for the risk stratification of non-alcoholic fatty liver disease in rabbit models.

PURPOSE: To investigate the diagnostic efficacy of T1ρ dispersion and Gd-EOB-DTPAenhanced T1mapping in the identification of early liver fibrosis (LF) and non-alcoholic steatohepatitis (NASH) in a non-alcoholic fatty liver disease (NAFLD) rabbit model induced by a high-fat diet using histopathological findings as the standard reference. METHODS: A total of sixty rabbits were randomly allocated into the standard control group (n = 12) and the NAFLD model groups (8 rabbits per group) corresponding to different high-fat high cholesterol diet feeding weeks. All rabbits underwent noncontrast transverse T1ρ mapping with varying spin-locking frequencies (FSL = 0 Hz and 500 Hz), native T1 mapping, and Gd-EOB-DTPA-enhanced T1 mapping during the hepatobiliary phase. The histopathological findings were assessed based on the NASH CRN Scoring System. Statistical analyses were conducted using the intraclass correlation coefficient, analysis of variance, multiple linear regression, and receiver operating characteristics. RESULTS: Except for native T1, T1ρ, T1ρ dispersion, HBP T1, and △T1 values significantly differed among different liver fibrosis groups (F = 14.414, 18.736, 10.15, and 9.799, respectively; all P < 0.05). T1ρ, T1ρ dispersion, HBP T1, and △T1 values also exhibited significant differences among different NASH groups (F = 4.138, 4.594, 21.868, and 22.678, respectively; all P < 0.05). In the multiple regression analysis, liver fibrosis was the only factor that independently influenced T1ρ dispersion (R2 = 0.746, P = 0.000). Among all metrics, T1ρ dispersion demonstrated the best area under curve (AUC) for identifying early LF (≥ F1 stage) and significant LF (≥ F2 stage) (AUC, 0.849 and 0.916, respectively). The performance of △T1 and HBP T1 (AUC, 0.948 and 0.936, respectively) were better than that of T1ρ and T1ρ dispersion (AUC, 0.762 and 0.769, respectively) for diagnosing NASH. CONCLUSION: T1⍴ dispersion may be suitable for detecting liver fibrosis in the complex background of NAFLD, while Gd-EOB-DTPA enhanced T1 mapping is superior to nonenhanced T1⍴ mapping (T1⍴ and T1⍴ dispersion) for identifying NASH.

Pore Space Partition Synthetic Strategy in Imine-linked Multivariate Covalent Organic Frameworks.

Partitioning the pores of covalent organic frameworks (COFs) is an attractive strategy for introducing microporosity and achieving new functionality, but it is technically challenging to achieve. Herein, we report a simple strategy for partitioning the micropores/mesopores of multivariate COFs. Our approach relies on the predesign and synthesis of multicomponent COFs through imine condensation reactions with aldehyde groups anchored in the COF pores, followed by inserting additional symmetric building blocks (with C2 or C3 symmetries) as pore partition agents. This approach allowed tetragonal or hexagonal pores to be partitioned into two or three smaller micropores, respectively. The synthesized library of pore-partitioned COFs was then applied for the capture of iodine pollutants (i.e., I2 and CH3I). This rich inventory allowed deep exploration of the relationships between the COF adsorbent composition, pore architecture, and adsorption capacity for I2 and CH3I capture under wide-ranging conditions. Notably, one of our developed pore-partitioned COFs (COF 3-2P) exhibited greatly enhanced dynamic I2 and CH3I adsorption performances compared to its parent COF (COF 3) in breakthrough tests, setting a new benchmark for COF-based adsorbents. Results present an effective design strategy toward functional COFs with tunable pore environments, functions, and properties.

Highly Selective Extraction of U(VI) from Solutions by Metal Organic Framework-Based Nanomaterials through Sorption, Photochemistry, and Electrochemistry Strategies.

With the rapid development of nuclear technology and peaceful utilization of nuclear energy, plentiful U(VI) not only is required to be extracted from solutions for a sustainable nuclear fuel supply but also is inevitably released into the surrounding environment to result in pollution and threaten human health. Thereby, realizing selective extraction of U(VI) from aqueous solutions is crucial for U(VI) pollution control and a sustainable nuclear industry. Metal organic frameworks (MOFs) have gained multidisciplinary attention due to their excellent properties including large specific surface areas, tunable pore structures, easy functionalization, etc. This Review comprehensively summarizes the research progress of MOFs and MOF-based materials on U(VI) removal from aqueous solutions by sorption, photocatalysis, electrocatalysis, membrane separation, etc. The efficient high extraction ability is dependent on the intrinsic properties of MOFs and the techniques used. The removal properties of MOF-based materials as adsorbents, photocatalysts, and electrocatalysts for U(VI) are discussed. Information about the interaction mechanisms between U(VI) and MOF-based materials are analyzed in-depth, including experiments, theoretical calculations, and advanced spectroscopy analysis. The removal properties for U(VI) of various MOF-based materials are assessed through different techniques. Finally, a summary and perspective on the direction and challenges of MOF-based materials and various pollutant removal technologies are proposed to provide some significant information on designing and fabricating MOF-based materials for environmental pollution management.

Recent progress of covalent organic frameworks membranes: Design, synthesis, and application in water treatment.

To date, significant efforts have been devoted to eliminating hazardous components to purify wastewater through the development of various nanomaterials. Covalent organic frameworks (COFs), an important branch of the porous crystalline family, possess the peculiarity of ultrahigh surface area, adjustable pore size, and facile functionality. Exciting studies from design fabrication to potential applications in water treatment by COF-based membranes (COMs) have emerged. This review summarizes various preparation strategies and synthesis mechanisms for COMs, including layer-by-layer stacking, in situ growth, interfacial polymerization, and electrochemical synthesis, and briefly describes the advanced characterization techniques for COMs. Moreover, the application of COMs in heavy metal removal, dye separation, purification of radionuclides, pollutant detection, sea water desalination, and so on, is described and discussed. Finally, the perspectives on future opportunities for designing COMs in water purification have been proposed.

Functional Carbon Capsules Supporting Ruthenium Nanoclusters for Efficient Electrocatalytic 99 TcO4 - /ReO4 - Removal from Acidic and Alkaline Nuclear Wastes.

The selective removal of the ß-emitting pertechnetate ion (99 TcO4 - ) from nuclear waste streams is technically challenging. Herein, a practical approach is proposed for the selective removal of 99 TcO4 - (or its surrogate ReO4 - ) under extreme conditions of high acidity, alkalinity, ionic strength, and radiation field. Hollow porous N-doped carbon capsules loaded with ruthenium clusters (Ru@HNCC) are first prepared, then modified with a cationic polymeric network (R) containing imidazolium-N+ units (Ru@HNCC-R) for selective 99 TcO4 - and ReO4 - binding. The Ru@HNCC-R capsules offer high binding affinities for 99 TcO4 - /ReO4 - under wide-ranging conditions. An electrochemical redox process then transforms adsorbed ReO4 - to bulk ReO3 , delivering record-high removal capacities, fast kinetics, and excellent long-term durability for removing ReO4 - (as a proxy for 99 TcO4 - ) in a 3 m HNO3 , simulated nuclear waste-Hanford melter recycle stream and an alkaline high-level waste stream (HLW) at the U.S. Savannah River Site (SRS). In situ Raman and X-ray absorption spectroscopy (XAS) analyses showed that adsorbed Re(VII) is electrocatalytically reduced on Ru sites to a Re(IV)O2 intermediate, which can then be re-oxidized to insoluble Re(VI)O3 for facile collection. This approach overcomes many of the challenges associated with the selective separation and removal of 99 TcO4 - /ReO4 - under extreme conditions, offering new vistas for nuclear waste management and environmental remediation.

Modulating Anion Nanotraps via Halogenation for High-Efficiency 99TcO4-/ReO4- Removal under Wide-Ranging pH Conditions.

Efficient and sustainable methods for 99TcO4- removal from acidic nuclear waste streams, contaminated water, and highly alkaline tank wastes are highly sought after. Herein, we demonstrate that ionic covalent organic polymers (iCOPs) possessing imidazolium-N+ nanotraps allow the selective adsorption of 99TcO4- under wide-ranging pH conditions. In particular, we show that the binding affinity of the cationic nanotraps toward 99TcO4- can be modulated by tuning the local environment around the nanotraps through a halogenation strategy, thereby enabling universal pH 99TcO4- removal. A parent iCOP-1 possessing imidazolium-N+ nanotraps showed fast kinetics (reaching adsorption equilibrium in 1 min), a high adsorption capacity (up to 1434.1 ± 24.6 mg/g), and exceptional selectivity for 99TcO4- and ReO4- (nonradioactive analogue of 99TcO4-) removal in contaminated water. By introducing F groups near the imidazolium-N+ nanotrap sites (iCOP-2), a ReO4- removal efficiency over 58% was achieved in 60 min in 3 M HNO3 solution. Further, introduction of larger Br groups near the imidazolium-N+ binding sites (iCOP-3) imparted a pronounced steric effect, resulting in exceptional adsorption performance for 99TcO4- under super alkaline conditions and from low-activity waste streams at US legacy Hanford nuclear sites. The halogenation strategy reported herein guides the task-specific design of functional adsorbents for 99TcO4- removal and other applications.

Tuning Local Charge Distribution in Multicomponent Covalent Organic Frameworks for Dramatically Enhanced Photocatalytic Uranium Extraction.

Optimizing the electronic structure of covalent organic framework (COF) photocatalysts is essential for maximizing photocatalytic activity. Herein, we report an isoreticular family of multivariate COFs containing chromenoquinoline rings in the COF structure and electron-donating or withdrawing groups in the pores. Intramolecular donor-acceptor (D-A) interactions in the COFs allowed tuning of local charge distributions and charge carrier separation under visible light irradiation, resulting in enhanced photocatalytic performance. By optimizing the optoelectronic properties of the COFs, a photocatalytic uranium extraction efficiency of 8.02 mg/g/day was achieved using a nitro-functionalized multicomponent COF in natural seawater, exceeding the performance of all COFs reported to date. Results demonstrate an effective design strategy towards high-activity COF photocatalysts with intramolecular D-A structures not easily accessible using traditional synthetic approaches.

Tuning excited state electronic structure and charge transport in covalent organic frameworks for enhanced photocatalytic performance.

Covalent organic frameworks (COFs) represent an emerging class of organic photocatalysts. However, their complicated structures lead to indeterminacy about photocatalytic active sites and reaction mechanisms. Herein, we use reticular chemistry to construct a family of isoreticular crystalline hydrazide-based COF photocatalysts, with the optoelectronic properties and local pore characteristics of the COFs modulated using different linkers. The excited state electronic distribution and transport pathways in the COFs are probed using a host of experimental methods and theoretical calculations at a molecular level. One of our developed COFs (denoted as COF-4) exhibits a remarkable excited state electron utilization efficiency and charge transfer properties, achieving a record-high photocatalytic uranium extraction performance of ~6.84 mg/g/day in natural seawater among all techniques reported so far. This study brings a new understanding about the operation of COF-based photocatalysts, guiding the design of improved COF photocatalysts for many applications.

Quantitative infrapatellar fat pad signal intensity alteration as an imaging biomarker of knee osteoarthritis progression.

OBJECTIVE: To determine the association of quantitative infrapatellar fat pad (IPFP) signal intensity alteration with knee osteoarthritis (OA) progression. METHOD: This study was performed based on the Foundation for the National Institutes of Health OA Biomarkers Consortium study, a nested case-control study consisting of 600 participants. The IPFP signal intensity alterations were quantitatively measured at baseline, 12 months and 24 months. The associations of baseline and time-integrated values over 12 and 24 months of IPFP signal intensity measures with knee OA progression over 48 months were evaluated with adjustment for baseline confounders. RESULTS: The baseline level of clustering effect of high signal intensity (Clustering factor (H)) was predictive of clinically relevant progression (both radiographic and pain progression) (OR 1.22). The time-integrated values of all IPFP signal intensity measures, except for mean value of IPFP signal intensity (Mean (IPFP)) over 24 months (ORs ranging from 1.23 to 1.39) as well was all except for Mean (IPFP) and mean value of IPFP high signal intensity (Mean (H)) over 12 months (ORs ranging from 1.20 to 1.31), were positively associated with clinically relevant progression. When the associations of quantitative IPFP signal intensity measures with radiographic and pain progression were examined separately, more IPFP signal intensity measures with stronger effect sizes were associated with radiographic progression compared with pain progression. CONCLUSION: The associations of short-term alteration in quantitative IPFP signal intensity measures with long-term knee OA progression suggest that these measures might serve as efficacy of intervention biomarkers of knee OA.

Modulating Uranium Extraction Performance of Multivariate Covalent Organic Frameworks through Donor-Acceptor Linkers and Amidoxime Nanotraps.

Covalent organic frameworks (COFs) can be designed to allow uranium extraction from seawater by incorporating photocatalytic linkers. However, often sacrificial reagents are required for separating photogenerated charges which limits their practical applications. Herein, we present a COF-based adsorption-photocatalysis strategy for selective removal of uranyl from seawater in the absence of sacrificial reagents. A series of ternary and quaternary COFs were synthesized containing the electron-rich linker 2,4,6-triformylphloroglucinol as the electron donor, the electron-deficient linker 4,4'-(thiazolo[5,4-d]thiazole-2,5-diyl)dibenzaldehyde as the acceptor, and amidoxime nanotraps for selective uranyl capture (with the quaternary COFs incorporating [2,2'-bipyridine-5,5'-diamine-Ru(Bp)2]Cl2 as a secondary photosensitizer). The ordered porous structure of the quaternary COFs ensured efficient mass transfer during the adsorption-photocatalysis capture of uranium from seawater samples, with photocatalytically generated electrons resulting in the reduction of adsorbed U(VI) to U(IV) in the form of UO2. A quaternary COF, denoted as COF 2-Ru-AO, possessed a high uranium uptake capacity of 2.45 mg/g/day in natural seawater and good anti-biofouling abilities, surpassing most adsorbents thus far. This work shows that multivariate COF adsorption-photocatalysts can be rationally engineered to work efficiently and stably without sacrificial electron donors, thus opening the pathway for the economic and efficient extraction of uranium from the earth's oceans.

Advanced porous materials and emerging technologies for radionuclides removal from Fukushima radioactive water.

Japan recently announced the plan to discharge over 1.2 million tons of radioactive water into the Pacific Ocean, which contained hazardous radionuclides such as 60Co, 90Sr, 125Sb, 129I, 3H, 137Cs, and 99TcO4-, etc. The contaminated water will pose an enormous threat to global ecosystems and human health. Developing materials and technologies for efficient radionuclide removal is highly desirable and arduous because of the extreme conditions, including super acidity or alkalinity, high ionic strength, and strong ionizing radiation. Recently, advanced porous material, such as porous POPs, MOFs, COFs, PAFs, etc., has shown promise of improved separation of radionuclides due to their intrinsic structural advantages. Furthermore, emerging technologies applied to radionuclide removal have also been summarized. In order to better deal with radionuclide contamination, higher requirements for the design of nanomaterials and technologies applied to practical radionuclide removal are proposed. Finally, we call for comprehensive implementation of strategies and strengthened cooperation to mitigate the harm caused by radioactive contamination to oceans, atmosphere, soil, and human health.

Pyridinium salt-based covalent organic framework with well-defined nanochannels for efficient and selective capture of aqueous 99TcO4.

Ionic covalent organic framework (COF) materials with high specific surface areas and well-defined pore structures are desired for many applications yet seldom reported. Herein, we report a cationic pyridinium salt-based COF (PS-COF-1) with a Brunauer-Emmett-Teller (BET) surface area of 2703 m2 g-1, state-of-the-art for an ionic COF. Aided by its ordered pore structure, chemical stability, and radiation resistance, PS-COF-1 showed exceptional adsorption properties toward aqueous ReO4- (1262 mg g-1) and 99TcO4-. Its adsorption performance surpassed its corresponding amorphous analogue. Importantly, PS-COF-1 exhibited fast adsorption kinetics, high adsorption capacities, and selectivity for 99TcO4- and ReO4- at high ionic strengths, leading to the successful removal of 99TcO4- under conditions relevant to low-activity waste streams at US legacy Hanford nuclear sites. In addition, PS-COF-1 can rapidly decontaminate ReO4-/99TcO4- polluted potable water (∼10 ppb) to drinking water level (0 ppb, part per billion) within 10 min. Density functional theory (DFT) calculations revealed PS-COF-1 has a strong affinity for ReO4- and 99TcO4-, thereby favoring adsorption of these low charge density anions over other common anions (e.g., Cl-, NO3-, SO42-, CO32-). Our work demonstrates a novel cationic COF sorbent for selective radionuclide capture and legacy nuclear waste management.

Metal-organic framework nanocrystal-derived hollow porous materials: Synthetic strategies and emerging applications.

Metal-organic frameworks (MOFs) have garnered multidisciplinary attention due to their structural tailorability, controlled pore size, and physicochemical functions, and their inherent properties can be exploited by applying them as precursors and/or templates for fabricating derived hollow porous nanomaterials. The fascinating, functional properties and applications of MOF-derived hollow porous materials primarily lie in their chemical composition, hollow character, and unique porous structure. Herein, a comprehensive overview of the synthetic strategies and emerging applications of hollow porous materials derived from MOF-based templates and/or precursors is given. Based on the role of MOFs in the preparation of hollow porous materials, the synthetic strategies are described in detail, including (1) MOFs as removable templates, (2) MOF nanocrystals as both self-sacrificing templates and precursors, (3) MOF@secondary-component core-shell composites as precursors, and (4) hollow MOF nanocrystals and their composites as precursors. Subsequently, the applications of these hollow porous materials for chemical catalysis, electrocatalysis, energy storage and conversion, and environmental management are presented. Finally, a perspective on the research challenges and future opportunities and prospects for MOF-derived hollow materials is provided.

Highly Efficient Electrocatalytic Uranium Extraction from Seawater over an Amidoxime-Functionalized In-N-C Catalyst.

Seawater contains uranium at a concentration of ≈3.3 ppb, thus representing a rich and sustainable nuclear fuel source. Herein, an adsorption-electrocatalytic platform is developed for uranium extraction from seawater, comprising atomically dispersed indium anchored on hollow nitrogen-doped carbon capsules functionalized with flexible amidoxime moieties (In-Nx -C-R, where R denotes amidoxime groups). In-Nx -C-R exhibits excellent uranyl capture properties, enabling a uranium removal rate of 6.35 mg g-1 in 24 h, representing one of the best uranium extractants reported to date. Importantly, In-Nx -C-R demonstrates exceptional selectivity for uranium extraction relative to vanadium in seawater (8.75 times more selective for the former). X-ray absorption spectroscopy (XAS) reveals that the amidoxime groups serve as uranyl chelating sites, thus allowing selective adsorption over other ions. XAS and in situ Raman results directly indicate that the absorbed uranyl can be electrocatalytically reduced to an unstable U(V) intermediate, then re-oxidizes to U(VI) in the form of insoluble Na2 O(UO3 ·H2 O)x for collection, through reversible single electron transfer processes involving InNx sites. These results provide detailed mechanistic understanding of the uranium extraction process at a molecular level. This work provides a roadmap for the adsorption-electrocatalytic extraction of uranium from seawater, adding to the growing suite of technologies for harvesting valuable metals from the earth's oceans.

Low-temperature plasma induced phosphate groups onto coffee residue-derived porous carbon for efficient U(VI) extraction.

For the continuous utilization of nuclear energy and efficient control of radioactive pollution, low-cost materials with high efficient U(VI) removal are of great importance. In this study, low temperature plasma method was applied for the successful modification of O-phosphorylethanolamine (O-PEA) on the porous carbon materials. The produced materials (Cafe/O-PEA) could adsorb U(VI) efficiently with the maximum sorption capacity of 648.54 mg/g at 1 hr, T=298 K, and pH=6.0, much higher than those of most carbon-based composites. U(VI) sorption was mainly controlled by strong surface complexation. From FTIR, SEM-EDS and XPS analyses, the sorption of U(VI) was related to the complexation with -NH2, phosphate and -OH groups on Cafe/O-PEA. The low temperature plasma method was an efficient, environmentally friendly and low-cost method for surface modification of materials for the effective enrichment of U(VI) from aqueous solutions.