Ultra-highly efficient enrichment of uranium from seawater via studtite nanodots growth-elution cycle.

Consecutive uranium extraction from seawater is a promising approach to secure the long-term supply of uranium and the sustainability of nuclear energy. Here, we report an ultra-highly efficient strategy via studtite nanodots growth with impressive uranyl uptake capacity of ~ 154.50 mg/g from natural seawater in 12 consecutive days (i.e., average for ~ 12.875 mg/g/day). Uranyl can be extracted as studtite under visible light via the reaction between the adsorbed uranyl and the photogenerated H2O2 with imine-based Covalent-Organic Framework photocatalysts. In detail, over Tp-Bpy, Tp-Bpy-2 and Tp-Py with multiple uranyl chelating sites, uranyl is found extracted as studtite nanodots which can be eluted readily, while over Tp-Bd and Tb-Bpy, uranyl is transformed into studtite nanorods that is more inert for elution. Abundant chelating sites of uranyl via structural regulation of COF photocatalysts are proved to facilitate the formation and efficient elution of studtite nanodots.

Low-temperature synthesis of porous organic polymers with donor-acceptor structure and ß-ketoenamine for photocatalytic oxidative coupling of amines.

In light of the widespread use of fossil fuels and the resulting environmental pollution, it is crucial to develop efficient photocatalysts for renewable energy applications that utilize visible light. Organic photocatalysts based on ß-ketoenamine offer several advantages, including facile preparation, high stability, structural controllability, and excellent photovoltaic properties. However, in previous studies, the synthesis of porous organic polymers (POPs) often involved long, high-temperature processes. In this study, POPs with donor (D)-acceptor (A) structure were constructed by utilizing various branched bridging groups and 2,4,6-triformylphloroglucinol, across multiple temperature gradients. Through adjustments in hydrothermal temperature, we successfully synthesized a series of POPs with varying enol-keto structure ratios. Among these POPs, the dimethoxybenzidine-POPs (DMDPOPs) with methoxy electron-rich branched chains exhibited superior photovoltaic performance, electron transfer rate, and photocatalytic activity compared to the dihydroxybenzidine-POPs (DHDPOPs) with electron-deficient hydroxyl branched chains. Notably, DMDPOP-30 demonstrated outstanding performance, achieving a conversion rate of 98% within 3 h. Additionally, other POPs exhibited favorable conversions (90%), further confirming the feasibility of this synthetic approach. Moreover, the synthesis of DMDPOP-30 was achieved under mild conditions at room temperature, highlighting its significant potential for practical applications.

Selective and Efficient Photoextraction of Aqueous Cr(VI) as a Solid-State Polyhydroxy Cr(V) Complex for Environmental Remediation and Resource Recovery.

Aqueous hexavalent chromium (Cr(VI)) treatment and chromium resource recovery toward Cr-containing wastes are of significant importance and necessity to both wastewater remediation and resource recovery. Herein, via mild photoreaction conditions with isopropanol (IPA) as an electron donor, a catalyst-free strategy for aqueous Cr(VI) extraction to form an insoluble polyhydroxy Cr(V) complex is developed for the first time. Aqueous Cr(VI) with concentration from 5 to 150 ppm can be efficiently extracted with high selectivity even in the presence of coexisting ions, and the total Cr concentration in residue solution can be as low as 0.5 ppm. The Cr resource could be efficiently recovered as pure Cr2O3 by calcinating the resulting Cr(V) precipitate. Outstanding extraction efficiency could be realized with various IPA concentrations (1.3-12.0 mol/L) by coordinately tuning the pH value to promote the formation of Cr(VI)-IPA ester. The formed ester undergoes intramolecular electron transition under visible light irradiation, resulting in a polyhydroxy solid-state Cr(V) intermediate complex. The controlled pH value blocks further reduction of Cr(V) to soluble Cr(III); thus the insoluble Cr(V) intermediate complex is stabilized thermodynamically under ambient conditions. Because of its electric neutrality property and the strong intermolecule interaction via hydrogen bonds, a dioxo-bridged di-nuclear Cr(V) complex {Cr2(µ-O)2(OH)4[OCH(CH3)2]2} is finally precipitated as the main product. Satisfactory extraction and recovery of Cr from chromium-plating wastewater and discarded stainless steel verify that this approach is ideal for both one-step purification of Cr(VI)-containing wastewater and selective resource recovery from Cr-containing solid wastes in practical application.

State-of-the-art progress for the selective crystallization of actinides, synthesis of actinide compounds and their functionalization.

Crystallization and immobilization of actinides to form actinide compounds are of significant importance for the extraction and reutilization of nuclear waste in the nuclear industry. In this paper, the state-of-art progress in the crystallization of actinides are summarized, as well as the main functionalization of the actinide compounds, i.e., as adsorbents for heavy metal ions and organic pollutant in waste management, as (photo)catalysts for organic degradation and conversion, including degradation of organic dyes and antibiotics, dehydrogenation of N-heterocycles, CO2 cycloaddition, selective alcohol oxidation and selective oxidation of sulfides. This review will give a comprehensive summary about the synthesis and application exploration of solid actinide crystalline salts and actinide-based metal organic frameworks in the past decades. Finally, the future perspectives and challenges are proposed in the end to give a promising direction for future investigation.

Application of aluminosilicate clay mineral-based composites in photocatalysis.

Aluminosilicate clay mineral (ACM) is a kind of typical raw materials that used widely in manufacturing industry owing to the abundant reserve and low-cost exploring. In past two decades, in-depth understanding on unique layered structure and abundant surface properties endows ACM in the emerging research and application fields. In field of solar-chemical energy conversion, ACM has been widely used to support various semiconductor photocatalysts, forming the composites and achieving efficient conversion of reactants under sunlight irradiation. To date, classic ACM such as kaolinite and montmorillonite, loaded with semiconductor photocatalysts has been widely applied in photocatalysis. This review summaries the recent works on ACM-based composites in photocatalysis. Focusing on the properties of surface and layered structure, we elucidate the different features in the composition with various functional photocatalysts on two typical kinds of ACM, i.e., type 1:1 and type 2:1. Not only large surface area and active surface hydroxyl group assist the substrate adsorption, but also the layered structure provides more space to enlarge the application of ACM-based photocatalysts. Besides, we overview the modifications on ACM from both external surface and the inter-layer space that make the formation of composites more efficiently and boost the photo-chemical process. This review could inspire more upcoming design and synthesis for ACM-based photocatalysts, leading this kind of economic and eco-friendly materials for more practical application in the future.

Carbonation of gypsum from wet flue gas desulfurization process: experiments and modeling.

In this paper, waste gypsum from wet flue gas desulfurization (WFGD) mixed with NH3·H2O was applied for CO2 absorption in the solid-liquid-gas phase system. The effects of operation temperature, CO2 flow rates, and ammonia-to-gypsum ratio on carbonation process were discussed. Meanwhile, a model for CO2 absorption in the suspension of WFGD gypsum and ammonia was established. The results indicate that higher temperature favors the reaction, and WFGD gypsum conversion can be achieved above 90% even at lower ammonia-to-gypsum ratio, while CO2 conversion reaches 90% and ammonia utilization is up to 83.69%. The model fits well with the experimental results at various CO2 flow rates and predicts the concentration distribution of the main species, including CO2 absorbed, NH2COO-, and HCO3-.