Experimental and computational insights into nitrogen retention and controlled release in glauconite-based nanocomposites

IF 5.2 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids Pub Date : 2026-04-15 Epub Date: 2026-02-08 DOI:10.1016/j.molliq.2026.129359

Evgeny Tararushkin , Alexey Ruban , Hongling Bu , Wei Yanfu , Maxim Rudmin

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Abstract

This study investigates the molecular mechanisms governing ammonium interactions with glauconite, a potassium- and iron-rich phyllosilicate, focusing on the structure and dynamics of aqueous NH₄NO₃ solutions confined at mineral interfaces. Glauconite-ammonium nanocomposites (GANs) were prepared with varying ammonium concentrations and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, Brunauer-Emmett-Teller method, and differential thermogravimetric analysis. Molecular dynamics simulations were performed to resolve ion coordination modes, hydrogen-bonding environments, and interfacial organization within the confined aqueous phase. Controlled-release behavior was evaluated through leaching experiments, and molecular simulations elucidated the adsorption mechanisms. Oat growth experiments assessed the agricultural efficacy of GANs.

Ammonium incorporation into glauconite basal planes was confirmed, with basal reflection shifts to 17.0 Å indicating effective adsorption. The combined structural and spectroscopic evidence confirms that NH₄⁺ retention is controlled by inner- and outer-sphere complexation and by the stability of the interfacial hydrogen-bond network. Simulations further reveal concentration-dependent reorganization of the interfacial layers and variations in ion mobility that govern ammonium release. Leaching experiments demonstrated controlled release of ammonium, nitrate, and potassium, highlighting the potential of GANs to reduce nutrient losses. Oat growth tests showed a yield increase of up to 15.9%, demonstrating the efficacy of GANs in enhancing agricultural productivity.

The multiscale integration of experimental data and molecular simulations provides a molecular-level framework describing ion coordination, interfacial hydration, and transport processes in confined NH₄NO₃ solutions. These findings are relevant for understanding ion behavior in layered mineral systems and for designing mineral-based matrices with tunable release properties.

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海绿石基纳米复合材料中氮保留和控制释放的实验和计算见解

本研究研究了铵与海绿石（一种富含钾和铁的层状硅酸盐）相互作用的分子机制，重点研究了局限于矿物界面的NH4NO3水溶液的结构和动力学。采用x射线衍射、傅里叶变换红外光谱、透射电子显微镜、扫描电子显微镜、布鲁诺尔-埃米特-泰勒法和差示热重分析对制备的海绿石-铵纳米复合材料进行了表征。通过分子动力学模拟来解析离子配位模式、氢键环境和受限水相中的界面组织。通过浸出实验评价了其控释行为，并通过分子模拟阐明了吸附机理。燕麦生长试验评价了gan的农业功效。证实了海绿石基面有铵的掺入，基底反射移至17.0 Å，表明有效吸附。结合结构和光谱证据证实，NH4+的保留受内外球络合作用和界面氢键网络的稳定性控制。模拟进一步揭示了界面层的浓度依赖性重组和控制铵释放的离子迁移率的变化。浸出实验证明了铵、硝和钾的可控释放，突出了gan减少养分损失的潜力。燕麦生长试验结果表明，施用GANs可使燕麦增产15.9%，证明了GANs在提高农业生产力方面的有效性。实验数据和分子模拟的多尺度整合提供了一个分子水平的框架来描述在受限NH4NO3溶液中的离子配位、界面水化和运输过程。这些发现对于理解层状矿物系统中的离子行为以及设计具有可调释放特性的矿物基基质具有重要意义。

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来源期刊

Journal of Molecular Liquids 化学-物理：原子、分子和化学物理

CiteScore

10.30

自引率

16.70%

发文量

2597

审稿时长

78 days

期刊介绍： The journal includes papers in the following areas: – Simple organic liquids and mixtures – Ionic liquids – Surfactant solutions (including micelles and vesicles) and liquid interfaces – Colloidal solutions and nanoparticles – Thermotropic and lyotropic liquid crystals – Ferrofluids – Water, aqueous solutions and other hydrogen-bonded liquids – Lubricants, polymer solutions and melts – Molten metals and salts – Phase transitions and critical phenomena in liquids and confined fluids – Self assembly in complex liquids.– Biomolecules in solution The emphasis is on the molecular (or microscopic) understanding of particular liquids or liquid systems, especially concerning structure, dynamics and intermolecular forces. The experimental techniques used may include: – Conventional spectroscopy (mid-IR and far-IR, Raman, NMR, etc.) – Non-linear optics and time resolved spectroscopy (psec, fsec, asec, ISRS, etc.) – Light scattering (Rayleigh, Brillouin, PCS, etc.) – Dielectric relaxation – X-ray and neutron scattering and diffraction. Experimental studies, computer simulations (MD or MC) and analytical theory will be considered for publication; papers just reporting experimental results that do not contribute to the understanding of the fundamentals of molecular and ionic liquids will not be accepted. Only papers of a non-routine nature and advancing the field will be considered for publication.