A Prussian blue analog-based copper-aluminum layered double hydroxide for cesium removal from water: fabrication, density functional theory-based molecular modeling, and the adsorption mechanism.

A new type of adsorbent, a Prussian blue analog-based copper-aluminum layered double hydroxide (PBA@CuAl-LDH), was successfully synthesized using a one-step method for the removal of radioactive Cs+ from wastewater. The adsorption performance, characteristics and the underlying adsorption mechanism of PBA@CuAl-LDH were systematically examined. The results showed that PBA@CuAl-LDH exhibited excellent adsorption performance, with a maximum adsorption capacity of 109.2 mg g-1. Over 85% of PBA@CuAl-LDH can be recycled, and the material exhibited only a 6.6% loss in adsorption performance. The adsorption process was well-fitted using the pseudo-second-order kinetic model and the Freundlich isotherm model, revealing the surface heterogeneity of the composite adsorbent. A molecular model of PBA@CuAl-LDH was constructed by combining density functional theory and multiple instrumental characterization techniques. Our results indicate that PBA crystals can be generated between layers and on the surface. Ion exchange was revealed as the main adsorption mechanism of Cs+ by PBA@CuAl-LDH. Specifically, the interstitial spaces of the PBA crystals generated between the layers and on the surface played an important role in ion exchange. These findings provide concrete theoretical support for radioactive pollution control and have significant value in directing the fabrication of cesium removal materials and their future engineering application.

Regulatory roles of extracellular polymeric substances in uranium reduction via extracellular electron transfer by Desulfovibrio vulgaris UR1.

The pathway of reducing U(VI) to insoluble U(IV) using electroactive bacteria has become an effective and promising approach to address uranium-contaminated water caused by human activities. However, knowledge regarding the roles of extracellular polymeric substances (EPS) in the uranium reduction process involving in extracellular electron transfer (EET) mechanisms is limited. Here, this study isolated a novel U(VI)-reducing strain, Desulfovibrio vulgaris UR1, with a high uranium removal capacity of 2.75 mM/(g dry cell). Based on a reliable EPS extraction method (45 °C heating), manipulation of EPS in D. vulgaris UR1 suspensions (removal or addition of EPS) highlighted its critical role in facilitating uranium reduction efficiency. On the second day, U(VI) removal rates varied significantly across systems with different EPS contents: 60.8% in the EPS-added system, 48.5% in the pristine system, and 22.2% in the EPS-removed system. Characterization of biogenic solids confirmed the reduction of U(VI) by D. vulgaris UR1, and the main products were uraninite and UO2 (2.88-4.32 nm in diameter). As EPS formed a permeable barrier, these nanoparticles were primarily immobilized within the EPS in EPS-retained/EPS-added cells, and within the periplasm in EPS-removed cells. Multiple electroactive substances, such as tyrosine/tryptophan aromatic compounds, flavins, and quinone-like substances, were identified in EPS, which might be the reason for enhancement of uranium reduction via providing more electron shuttles. Furthermore, proteomics revealed that a large number of proteins in EPS were enriched in the subcategories of catalytic activity and electron transfer activity. Among these, iron-sulfur proteins, such as hydroxylamine reductase (P31101), pyruvate: ferredoxin oxidoreductase (A0A0H3A501), and sulfite reductase (P45574), played the most critical role in regulating EET in D. vulgaris UR1. This work highlighted the importance of EPS in the uranium reduction by D. vulgaris UR1, indicating that EPS functioned as both a reducing agent and a permeation barrier for access to heavy metal uranium.

Theoretical and experimental investigations of enhanced uranium(VI) adsorption using a nitrogen doping strategy.

With the ongoing development and utilization of nuclear energy, uranium pollution has become an increasingly serious issue. Although many adsorbents are able to remove hexavalent uranium (U(VI)) from aqueous solution, the development of a high capacity adsorbent exhibiting superior stability would be beneficial. Grafting poly(amidoxime) (PAO) onto reduced graphene oxide (rGO) provides suitable U(VI) adsorption performance but the PAO is prone to agglomeration. The present work used density functional theory calculations to predict that PAO would bond with pyrrolic N atoms in nitrogen-doped rGO (N-rGO). To confirm this, PAO-grafted rGO (PAO-rGO) and PAO-grafted N-rGO (PAO-N-rGO) were prepared and characterized and the successful grafting of PAO on N-rGO was demonstrated. Adsorption experiments demonstrated that PAO-N-rGO exhibit superb U(VI) adsorption performance compared with the original PAO-rGO under acidic conditions. As for competing metal ions, Cu2+, Al3+, and Ca2+ have a greater impact on U(VI) adsorption than Na+, Mg2+, and K+ both for PAO-rGO and PAO-N-rGO. The maximum adsorption capacities of PAO-rGO and PAO-N-rGO for U(VI) were calculated to be 1500.26 and 1545.95 mg g-1, respectively. The mechanism of nitrogen doping promoting uranium(VI) adsorption can be attributed to enhanced PAO grafting and improvement of adsorption performance of the rGO. This work demonstrates that nitrogen doping is a viable strategy for enhancing the U(VI) adsorption performance of PAO-rGO.

Bibliometric insights into the evolution of uranium contamination reduction research topics: Focus on microbial reduction of uranium.

Confronting the threat of environment uranium pollution, decades of research have yielded advanced and significant findings in uranium bioremediation, resulting in the accumulation of tremendous amount of high-quality literature. In this study, we analyzed over 10,000 uranium reduction-related papers published from 1990 to the present in the Web of Science based on bibliometrics, and revealed some critical information on knowledge structure, thematic evolution and additional attention. Methods including contribution comparison, co-occurrence and temporal evolution analysis are applied. The results of the distribution and impact analysis of authors, sources, and journals indicated that the United States is a leader in this field of research and China is on the rise. The top keywords remained stable, primarily focused on chemicals (uranium, iron, plutonium, nitrat, carbon), characters (divers, surfac, speciat), and microbiology (microbial commun, cytochrome, extracellular polymeric subst). Keywords related to new strains, reduction mechanisms and product characteristics demonstrated the strongest uptrend, while some keywords related to mechanism and performance were clearly emerging in the past 5 years. Furthermore, the evolution of the thematic progression can be categorized into three stages, commencing with the discovery of the enzymatic reduction of hexavalent uranium to tetravalent uranium, developing in the groundwater remediation process at uranium-contaminated sites, and delving into the research on microbial reduction mechanisms of uranium. For future research, enhancing the understanding of mechanisms, improving uranium removal performance, and exploring practical applications can be considered. This study provides unique insights into microbial uranium reduction research, providing valuable references for related studies in this field.