MIL-125-NH2/MIL-88-NH2 composite as a dual-function adsorbent with enhanced photocatalytic and photo-Fenton-like behavior for the removal of organic pollutant in water

IF 2.6 4区材料科学 Q3 CHEMISTRY, MULTIDISCIPLINARY

Journal of Nanoparticle Research Pub Date : 2025-08-09 DOI:10.1007/s11051-025-06408-w

Wei Yee Low, Fuei Pien Chee, Norini Tahir, Nur Amira Solehah Pungut, Mohd Hafiz Abd Majid, Rachel Fran Mansa, Siow Hwa Teo, Pak Yan Moh

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引用次数: 0

Abstract

Metal–organic frameworks are nanoporous materials extensively studied for post-synthesis modification due to their exceptional adsorption and photocatalytic properties. However, their practical application is often limited by rapid electron–hole recombination, suboptimal band gap energies, and poor chemical and physical stability, limiting their reusability as adsorbents or photocatalysts. In this study, a novel Z-scheme MIL-125-NH₂/MIL-88-NH₂ composite was synthesized via reflux heating method. The composite demonstrated improved thermal stability compared to MIL-125-NH₂ and a higher surface area than MIL-88-NH₂, improving the physical and chemical properties. It selectively adsorbed cationic pollutants, following Langmuir isotherm with monolayer adsorption and physisorption mechanisms achieving a maximum adsorption capacity of 249 mg/g towards methylene blue (MB). Photocatalytic degradation of MB under visible and UV-A light irradiation reached 61% (k₁ = 0.0067 min⁻¹) and 69% (k₁ = 0.0087 min⁻¹), respectively. The addition of 1 mM hydrogen peroxide (H₂O₂), tripling MB removal to 89% removal (k₁ = 0.0155 min⁻¹) under visible light and 94% removal (k₁ = 0.0217 min⁻¹) under UV-A light. The synergistic effect of MIL-125-NH₂/MIL-88-NH₂ composite surpassed MIL-125-NH₂/H₂O₂/UV-A (k₁ = 0.0024 min⁻¹) and MIL-88-NH₂/H₂O₂/UV-A (k₁ = 0.0150 min⁻¹). Scavenger experiments identified hole (h⁺) and electron (e⁻) were the primary active species while hydroxyl radical (·OH) and superoxide (·O₂⁻) also played key roles, with their generation further amplified by H₂O₂. These findings demonstrate the enhanced photocatalytic performance of the MIL-125-NH₂/MIL-88-NH₂ composite, attributed to its Z-scheme heterojunction structure and photo-Fenton-like behavior. The composite exhibits a promising stability and capability in advanced water treatment applications.

Graphical Abstract

Schematic illustration of the photocatalytic mechanism of MIL-125-NH₂/MIL-88-NH₂ composite under visible and UV-A light with H₂O₂ activation.

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MIL-125-NH2/MIL-88-NH2复合材料作为一种双功能吸附剂，具有增强的光催化和光fenton -like行为去除水中有机污染物

金属有机骨架是一种纳米多孔材料，由于其优异的吸附和光催化性能，被广泛研究用于合成后改性。然而，它们的实际应用往往受到快速电子-空穴复合、次优带隙能量以及较差的化学和物理稳定性的限制，限制了它们作为吸附剂或光催化剂的可重复使用性。本研究采用回流加热法合成了新型Z-scheme MIL-125-NH2/MIL-88-NH2复合材料。与MIL-125-NH2相比，该复合材料表现出更好的热稳定性，比MIL-88-NH2具有更高的表面积，改善了物理和化学性能。对阳离子污染物的选择性吸附，遵循Langmuir等温线、单层吸附和物理吸附机制，对亚甲基蓝（MB）的最大吸附量为249 mg/g。可见光和UV-A光对MB的光催化降解率分别达到61% （k1 = 0.0067 min−1）和69% （k1 = 0.0087 min−1）。加入1mm过氧化氢（H2O2），可见光下MB去除率达到89% (k1 = 0.0155 min−1)，UV-A光下MB去除率达到94% （k1 = 0.0217 min−1）。MIL-125-NH2/MIL-88-NH2复合材料的协同效应优于MIL-125-NH2/H2O2/UV-A （k1 = 0.0024 min−1）和MIL-88-NH2/H2O2/UV-A （k1 = 0.0150 min−1）。清道夫实验发现空穴（h+）和电子（e−）是主要的活性物质，羟基自由基（·OH）和超氧化物（·O2−）也起关键作用，H2O2进一步放大了它们的产生。这些发现表明MIL-125-NH2/MIL-88-NH2复合材料的光催化性能增强，这归功于其Z-scheme异质结结构和光fenton -like行为。该复合材料在高级水处理应用中表现出良好的稳定性和性能。MIL-125-NH2/MIL-88-NH2复合材料在H2O2活化下的可见光和UV-A光催化机理示意图。

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来源期刊

Journal of Nanoparticle Research 工程技术-材料科学：综合

CiteScore

4.40

自引率

4.00%

发文量

198

审稿时长

3.9 months

期刊介绍： The objective of the Journal of Nanoparticle Research is to disseminate knowledge of the physical, chemical and biological phenomena and processes in structures that have at least one lengthscale ranging from molecular to approximately 100 nm (or submicron in some situations), and exhibit improved and novel properties that are a direct result of their small size. Nanoparticle research is a key component of nanoscience, nanoengineering and nanotechnology. The focus of the Journal is on the specific concepts, properties, phenomena, and processes related to particles, tubes, layers, macromolecules, clusters and other finite structures of the nanoscale size range. Synthesis, assembly, transport, reactivity, and stability of such structures are considered. Development of in-situ and ex-situ instrumentation for characterization of nanoparticles and their interfaces should be based on new principles for probing properties and phenomena not well understood at the nanometer scale. Modeling and simulation may include atom-based quantum mechanics; molecular dynamics; single-particle, multi-body and continuum based models; fractals; other methods suitable for modeling particle synthesis, assembling and interaction processes. Realization and application of systems, structures and devices with novel functions obtained via precursor nanoparticles is emphasized. Approaches may include gas-, liquid-, solid-, and vacuum-based processes, size reduction, chemical- and bio-self assembly. Contributions include utilization of nanoparticle systems for enhancing a phenomenon or process and particle assembling into hierarchical structures, as well as formulation and the administration of drugs. Synergistic approaches originating from different disciplines and technologies, and interaction between the research providers and users in this field, are encouraged.