Charge transformation of hollow mesoporous hydroxyapatite (HM-HAP) and its application in the efficient removal of anionic dyes

IF 4.7 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials Pub Date : 2025-09-09 DOI:10.1016/j.micromeso.2025.113852

Farishta Shafiq , Chenyu Liu , Simiao Yu , Yongxin Pan , Min Ji , Qingzhao Shi , Weihong Qiao

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Abstract

Surface functionalization plays a critical role in modifying the properties of adsorbents for selective removal of dyes from aqueous solutions. However, achieving controlled functionalization of hollow mesoporous hydroxyapatite (HM-HAP) particles while maintaining its structural integrity continuous to be a significant problem in adsorption research. This work involved hydrothermal synthesis of HM-HAP particles by utilizing a CaCO₃ core template followed by surface functionalization with different concentrations of (3-Aminopropyl)triethoxysilane (APTES). The functionalization altered the negatively charged HM-HAP surface to a positively charged one, as shown by a change in point of zero charge (PZC), zeta potential and surface morphology. The adsorption performance of APTES/HM-HAP adsorbent was examined using RYD-145 and SY as model anionic dyes. The equilibrium data was best described by the Langmuir isotherm model with R² value 0.99, indicating monolayer adsorption, with maximum uptake capacity (q_m) values of 525.6 mg g⁻¹ for RYD-145 and 297.13 mg g⁻¹ for SY. Kinetic investigations indicated that the adsorption process followed the pseudo-second-order model with R² values 0.97 and 0.96 for RYD-145 and SY, suggesting a chemisorption mechanism. Thermodynamic studies revealed that the adsorption of RYD-145 was endothermic, whereas SY was exothermic, with both processes being spontaneous (ΔG° < 0). Desorption studies demonstrated that NaOH was the most effective eluent, with desorption efficiencies of 88.5 % for RYD-145 and 87.3 % for SY. The adsorbent retained approximately 80 % of its adsorption efficiency during four consecutive cycles, demonstrating excellent reusability. Moreover, the adsorbent was applied to real industrial dye wastewater, exhibiting remarkable efficiency in reducing dye concentration. A guppy fish bioassay validated a substantial decrease in toxicity, with the APTES/HM-HAP treated water exhibiting no fish mortality or dermal damage, unlike the untreated sample. Furthermore, the chemical oxygen demand (COD) was decreased from 2316 mg L⁻¹ to 755 mg L⁻¹ post treatment, signifying effective removal of the organic pollutants. This study offers a comprehensive strategy for designing functionalized adsorbents, emphasizing the significance of surface chemistry in improving dye adsorption. APTES-modified HM-HAP provides an efficient, selective, and reusable method for the removal of anionic dyes from wastewater, addressing a significant environmental issue.

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中空介孔羟基磷灰石（HM-HAP）的电荷转化及其在高效脱除阴离子染料中的应用

表面功能化在改变吸附剂的性能以选择性去除水溶液中的染料方面起着至关重要的作用。然而，如何在保持中空介孔羟基磷灰石（HM-HAP）颗粒结构完整性的同时实现其可控功能化一直是吸附研究中的重要问题。本研究利用CaCO3核心模板水热合成了ham - hap颗粒，然后用不同浓度的（3-氨基丙基）三乙氧基硅烷（APTES）进行表面功能化。功能化将带负电荷的HM-HAP表面转变为带正电荷的HM-HAP表面，表现为零电荷点（PZC）、zeta电位和表面形貌的变化。以RYD-145和SY为模型阴离子染料，考察了APTES/HM-HAP吸附剂的吸附性能。Langmuir等温线模型最适合描述平衡数据，R2值为0.99，表明单层吸附，RYD-145的最大吸收容量（qm）值为525.6 mg g -1， SY的最大吸收容量（qm）值为297.13 mg g -1。动力学研究表明，RYD-145和SY的吸附过程符合拟二阶模型，R2分别为0.97和0.96，表明其吸附机理为化学吸附。热力学研究表明，RYD-145的吸附是吸热的，而SY是放热的，两个过程都是自发的（ΔG°< 0）。解吸研究表明，NaOH是最有效的洗脱液，RYD-145的解吸效率为88.5%，SY的解吸效率为87.3%。在连续四个循环中，吸附剂保持了约80%的吸附效率，表现出良好的可重复使用性。并将该吸附剂应用于实际工业染料废水中，表现出显著的降低染料浓度的效果。一项孔雀鱼生物测定证实了毒性的显著降低，与未经处理的样品不同，APTES/HM-HAP处理过的水没有显示鱼类死亡或皮肤损伤。处理后的化学需氧量（COD）从2316 mg L−1降至755 mg L−1，有效去除了有机污染物。本研究为功能化吸附剂的设计提供了一个全面的策略，强调了表面化学在改善染料吸附方面的意义。aptes改性的HM-HAP为废水中阴离子染料的去除提供了一种高效、选择性和可重复使用的方法，解决了一个重要的环境问题。

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来源期刊

Microporous and Mesoporous Materials 化学-材料科学：综合

CiteScore

10.70

自引率

5.80%

发文量

649

审稿时长

26 days

期刊介绍： Microporous and Mesoporous Materials covers novel and significant aspects of porous solids classified as either microporous (pore size up to 2 nm) or mesoporous (pore size 2 to 50 nm). The porosity should have a specific impact on the material properties or application. Typical examples are zeolites and zeolite-like materials, pillared materials, clathrasils and clathrates, carbon molecular sieves, ordered mesoporous materials, organic/inorganic porous hybrid materials, or porous metal oxides. Both natural and synthetic porous materials are within the scope of the journal. Topics which are particularly of interest include: All aspects of natural microporous and mesoporous solids The synthesis of crystalline or amorphous porous materials The physico-chemical characterization of microporous and mesoporous solids, especially spectroscopic and microscopic The modification of microporous and mesoporous solids, for example by ion exchange or solid-state reactions All topics related to diffusion of mobile species in the pores of microporous and mesoporous materials Adsorption (and other separation techniques) using microporous or mesoporous adsorbents Catalysis by microporous and mesoporous materials Host/guest interactions Theoretical chemistry and modelling of host/guest interactions All topics related to the application of microporous and mesoporous materials in industrial catalysis, separation technology, environmental protection, electrochemistry, membranes, sensors, optical devices, etc.