Bis (2-ethylhexyl)phosphoric acid (HDEHP) is a renowned extractant, favored for its affinity to selectively remove uranium via its P=O groups. We previously synthesized HDEHP-functionalized mesoporous silica microspheres for solid-phase uranium adsorption. Herein, we investigated the kinetic and isothermal behavior of uranyl ion adsorption in mesoporous silica microspheres functionalized with phosphate groups. Adsorption experiments were conducted by equilibrating 20 mg of silica samples with 50 mL of uranium solutions, with concentrations ranging from 10 to 100 mgU L−1 for isotherms and 100 mgU L−1 for kinetics. Three distinct samples were prepared with varying HDEHP to TEOS molar ratios (x = 0.16 and 0.24) and underwent hydrothermal treatment at different temperatures, resulting in distinct textural properties. Contact times spanned from 1 to 120 hours. For x = 0.16 samples, it took around 50 and 11 hours to reach equilibrium for the hydrothermally treated samples at 343 K and 373 K, respectively. Adsorbed quantities were similar (99 and 101 mg g-1, respectively), indicating consistent functional group content. This suggests that the key factor influencing uranium adsorption kinetics is pore size of the silica. The sample treated at 373 K, with a larger pore size (22.7 nm) compared to 343 K (11.5 nm), experienced less steric hindrance, allowing uranium species to diffuse more easily through the mesopores. The data confirmed the excellent fit of pseudo-second-order kinetic model (R2 > 0.999) and closely matched the experimental value, suggesting that chemisorption governs the rate-controlling step. To gain further insights into uranium adsorption behavior, we conducted an adsorption isotherm analysis at various initial concentrations under a constant pH of 4. Both the Langmuir and Freundlich isotherm models were applied, with the Langmuir model providing a superior fit. The relatively high R2 value indicated its effectiveness in describing the adsorption process, suggesting homogenous sorbate adsorption on an energetically uniform adsorbent surface via a monolayer adsorption and constant adsorption site density, without any interaction between adsorbates on adjacent sites. Remarkably, differences in surface area did not significantly impact uranium removal efficiency. This observation strongly suggests that the adsorption capacity is primarily governed by the loading amount of HDEHP and the inner-sphere complexation with the phosphoryl group (O=P). Our silica composite exhibited an impressive adsorption capacity of 133 mg g-1, surpassing the results reported in the majority of other silica literature.

In this study, we evaluated the performance of phosphate-functionalized silica in adsorbing uranium and provided insights into optimizing the initial conditions of the uranium solution (concentration and pH), which are often overlooked in uranium adsorption studies. While most studies take into account the effect of pH on both the surface charge of the adsorbents and the dissolved speciation of uranium in solution, they often overlook the formation of solid phases such as β-UO2(OH)2 (cr) and UO3· 2H2O(cr), leading to an overestimation of the adsorption capacity. To address this issue, we considered the speciation of U(VI) calculated using thermodynamic data. Our findings suggest that it is reasonable to evaluate the adsorption performance at pH 4 and concentration below 1.35 mM. The formation of β-UO2(OH)2 (cr) starts at 23 μM (pH 5) and 1 μM (pH 6) and increases sharply with increasing concentration. To avoid interference from the formation of solid phases, experiments should be conducted at lower concentrations, which in turn require very small msorbent/Vsolution ratios. However, controlling small amounts of sorbent can be challenging, and increasing the volume of the solution can generate significant amounts of radioactive waste. We also used UV-vis spectra analysis to investigate the formation of solid phases. We found that a 100 mg L-1 uranium solution resulted in the formation of colloidal particles in the solid phase after 2.5 hours at pH 6, while at pH 4, no significant changes in absorbance were observed over 120 hours, indicating a stable ion phase. Based on these conditions, we obtained an excellent adsorption capacity of 110 mg g-1.

The rise of nuclear power plants to meet escalating global energy needs has made environmental pollution including the contamination of uranium due to improper disposal of radioactive wastewater during uranium milling and mining processes. Adsorption, a water purification method known for its fast kinetics, high selectivity, and ease of use, has emerged as a popular choice for the treatment of radioactive wastewater. In response to the critical need for the purification of radioactive wastewater contaminated with U(VI), this review provides a comprehensive summary of the various types of materials, synthetic methods, and adsorption mechanisms used for the purification process. The materials are categorized into four main groups: organic, inorganic, composite/nanomaterials, and framework materials. To enhance the adsorption capacity for U(VI), researchers have explored physical and chemical modifications as well as the development of organic-inorganic hybrids. The improved adsorption performance resulting from these modifications is mostly attributed to electrostatic interaction, surface complexation, and ion exchange mechanisms. However, despite the present understanding of the processes involved, further research is still needed to fully determine the optimal approach for purifying contaminated radioactive wastewater.

폐기물 용액의 pH 변화에 따른 고정층에서 우라늄 및 코발트 이온의 흡착거동을 다성분 흡착시스템으로 가정하여 이론적으로 예측하였다. 즉 pH 변화에 따라 존재 분율이 달라지는 각 이온 성분들이 상호 경쟁적으로 흡착한다는 가정 하에서, 평형실험에서 얻어진 결과와 우라늄 및 코발트 이온의 용액특성 (Solution chemistry)을 상호 결합하여 각 이온 성분들의 Langmuir 평형상수 값을 Ideal Adsorbed Solution Theory를 도입하여 구하였으며, 이상의 결과를 이용하여 고정층 파과곡선을 이론적으로 계산한 결과 pH 변화에 따른 흡착거동을 비교적 잘 예측할 수 있었다 따라서 본 연구에서 시도한 방법은 이온 농도와 pH가 높은 경우를 제외하고 pH 변화에 따라 용액 내에 이온의 형태가 다양하게 존재하는 흡착 시스템을 이론적으로 예측하는 데 비교적 유용하게 사용할 수 있을 것으로 판단된다.

아미드옥심기와 복합재료 섬유흡착제를 제조하였고 해수로부터 우라늄이온의 분리 특성을 조사하였다. 흡착량은 흡착시간이 증가함에 따라 증가하였고 An:TEGMA:DVB의 몰비가 1:0.1:0.003인 수지가 pH 8 부근에서 최대 흡착능을 나타내었다. 또한 흡착량은 CFA에 첨가한 흡착제의 양이 증가함에 따라 증가하였으며 1시간 까지 선형적으로 증가하였고, 25˚C에서 최대흡착량을 나타내었다. 한편 Ca, Mg 이온은 흡-탈착 cycle이 반복될수록 증가하였으며 그양은 각각 0.3, 0.9mmole/g-Ads로 우라늄 이온의 그것보다 매우 낮았다. 흡착된 우라늄 이온의 탈착은 흡착제의 종류에 관계없이 약 30분 이내에 거의 100% 탈착되었다.