Dye adsorption selectivity in pristine and aluminum-doped MCM-41 mesoporous silica: A density functional theory investigation

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron Pub Date : 2025-06-21 DOI:10.1016/j.poly.2025.117651

Natthakit Singhanatkaisi , Thitirat Sirihengcharoen , Thanaphon Janyodha , Piyachol Polnarai , Kotchaphon Linthong , Jonggol Tantirungrotechai , Yuthana Tantirungrotechai

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Abstract

The adsorption behaviors of cationic (methylene blue), neutral (neutral red), and anionic (methyl orange) dyes on pristine MCM-41 and aluminum-doped MCM-41 (Al-MCM-41) mesoporous silica represented as surface slab cluster model were investigated using ONIOM2(revPBE-D4/def2-SVP:GFN-FF) geometry optimizations and CPCM-revPBE-D4/def2-TZVP energy calculations. This study aims to elucidate molecular-level interactions and the impact of aluminum doping on dye adsorption selectivity. Methyl orange exhibited the strongest average adsorption energy on both MCM-41 (−42.17 ± 8.28 kcal/mol) and Al-MCM-41 (−38.49 ± 4.76 kcal/mol), likely due to multiple hydrogen bonds and reduced steric hindrance arising from its molecular shape and orientation. An independent t-test analysis was carried out to assess the statistically significant changes in the average adsorption energy upon doping. Aluminum substitution enhanced the averaged adsorption energy of cationic methylene blue (from −20.08 ± 6.24 to −23.31 ± 5.45 kcal/mol), while reducing that of anionic methyl orange. The adsorption of the neutral red dye remained statistically unchanged. These findings suggest that aluminum doping of MCM-41 can selectively enhance cationic dye adsorption from aqueous solutions, primarily through modified electrostatic interactions at the surface.

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原始和掺铝MCM-41介孔二氧化硅染料吸附选择性：密度泛函理论研究

通过ONIOM2（revPBE-D4/def2-SVP:GFN-FF）几何优化和CPCM-revPBE-D4/def2-TZVP能量计算，研究了阳离子（亚甲基蓝）、中性（中性红）和阴离子（甲基橙）染料对原始MCM-41和掺铝MCM-41 （Al-MCM-41）介孔二氧化硅的吸附行为。本研究旨在阐明分子水平的相互作用以及铝掺杂对染料吸附选择性的影响。甲基橙在MCM-41（- 42.17±8.28 kcal/mol）和Al-MCM-41（- 38.49±4.76 kcal/mol）上表现出最强的平均吸附能，这可能是由于甲基橙的分子形状和取向导致的多个氢键和较低的位阻。采用独立的t检验分析来评估掺杂后平均吸附能的变化是否具有统计学意义。铝取代提高了阳离子亚甲基蓝的平均吸附能（从- 20.08±6.24增加到- 23.31±5.45 kcal/mol），降低了阴离子甲基橙的平均吸附能。中性红色染料的吸附在统计学上保持不变。这些发现表明，MCM-41的铝掺杂可以选择性地增强水溶液对阳离子染料的吸附，主要是通过修饰表面的静电相互作用。

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来源期刊

Polyhedron 化学-晶体学

CiteScore

4.90

自引率

7.70%

发文量

515

审稿时长

2 months

期刊介绍： Polyhedron publishes original, fundamental, experimental and theoretical work of the highest quality in all the major areas of inorganic chemistry. This includes synthetic chemistry, coordination chemistry, organometallic chemistry, bioinorganic chemistry, and solid-state and materials chemistry. Papers should be significant pieces of work, and all new compounds must be appropriately characterized. The inclusion of single-crystal X-ray structural data is strongly encouraged, but papers reporting only the X-ray structure determination of a single compound will usually not be considered. Papers on solid-state or materials chemistry will be expected to have a significant molecular chemistry component (such as the synthesis and characterization of the molecular precursors and/or a systematic study of the use of different precursors or reaction conditions) or demonstrate a cutting-edge application (for example inorganic materials for energy applications). Papers dealing only with stability constants are not considered.