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A special issue of Nanomaterials (ISSN 2079-4991). This special issue belongs to the section "Synthesis, Interfaces and Nanostructures".

Deadline for manuscript submissions: closed (31 October 2021) | Viewed by 30158

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Dr. Benedicte Prelot

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Institut Charles Gerhardt, University Montpellier, CNRS, Montpellier, France
Interests: adsorption; interfacial phenomena; depollution; decontamination; calorimetry

Dr. Fabrice Salles

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Institute Charles Gerhardt des Matériaux (ICGM), Université de Montpellier, CNRS, ENSCM, 34090 Montpellier, France
Interests: molecular simulation; adsorption/diffusion; porous solides (clays, MOFS, and LDHs); environmental, energy, and health applications

Special Issue Information

Dear Colleagues,

Nanostructured materials have progressively drawn the attention of a large part of the scientific community, in particular for their interfacial and sorption properties. The main characteristics of nanostructured materials are their ability to demonstrate enhanced adsorption efficiency because of their surface reactivity or their structured porosity.

We invite investigators to submit papers that discuss the recent developments and results about materials exhibiting nanostructuration (nanoparticles, micro and/or mesoporous materials, lamellar materials, hierarchical adsorbents, hybrids materials, etc.) with regard to the modification of their adsorption properties (capacity, transport and diffusion, affinity and energy of interaction, confinement, etc.). Experimental as well as theoretical inquiries will be addressed, with new techniques, including local and dynamic developments, and the various types of progress in simulation (GCMC, DFT, and multiscale approaches). This includes adsorption in the gas phase or in the liquid phase, for applications in the fields of depollution, separation, purification, drug delivery, energy storage, CO₂ capture, etc.

Dr. Benedicte Prelot
Dr. Fabrice Salles
Guest Editors

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Keywords

porous materials
layered materials
nanoparticles
hybrid adsorbent
depollution
gas separation
drug delivery
energy storage and conversion

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Published Papers (10 papers)

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Research

22 pages, 7815 KiB

Open AccessArticle

Heat and Mass Transfer in an Adsorbed Natural Gas Storage System Filled with Monolithic Carbon Adsorbent during Circulating Gas Charging

by Evgeny M. Strizhenov, Sergey S. Chugaev, Ilya E. Men’shchikov, Andrey V. Shkolin and Anatoly A. Zherdev

Nanomaterials 2021, 11(12), 3274; https://doi.org/10.3390/nano11123274 - 2 Dec 2021

Cited by 15 | Viewed by 2572

Abstract

Adsorbed natural gas (ANG) technology is a promising alternative to traditional compressed (CNG) and liquefied (LNG) natural gas systems. Nevertheless, the energy efficiency and storage capacity of an ANG system strongly depends on the thermal management of its inner volume because of significant heat effects occurring during adsorption/desorption processes. In the present work, a prototype of a circulating charging system for an ANG storage tank filled with a monolithic nanoporous carbon adsorbent was studied experimentally under isobaric conditions (0.5–3.5 MPa) at a constant volumetric flow rate (8–18 m³/h) or flow mode (Reynolds number at the adsorber inlet from 100,000 to 220,000). The study of the thermal state of the monolithic adsorbent layer and internal heat exchange processes during the circulating charging of an adsorbed natural gas storage system was carried out. The correlation between the gas flow mode, the dynamic gas flow temperature, and the heat transfer coefficient between the gas and adsorbent was determined. A one-dimensional mathematical model of the circulating low-temperature charging process was developed, the results of which correspond to the experimental measurements. Full article

(This article belongs to the Special Issue Nanostructured Materials for Adsorption)

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12 pages, 6047 KiB

Open AccessArticle

Impact of Structural Functionalization, Pore Size, and Presence of Extra-Framework Ions on the Capture of Gaseous I₂ by MOF Materials

by Fabrice Salles and Jerzy Zajac

Nanomaterials 2021, 11(9), 2245; https://doi.org/10.3390/nano11092245 - 30 Aug 2021

Cited by 9 | Viewed by 2681

Abstract

A computational approach is used on MOF materials to predict the structures showing the best performances for I₂ adsorption as a function of the functionalization, the pore size, the presence of the compensating ions, and the flexibility on which to base future improvements in selected materials in view of their targeted application. Such an approach can be generalized for the adsorption of other gases or vapors. Following the results from the simulations, it was evidenced that the maximum capacity of I₂ adsorption by MOF solids with longer organic moieties and larger pores could exceed that of previously tested materials. In particular, the best retention performance was evidenced for MIL-100-BTB. However, if the capacity to retain traces of gaseous I₂ on the surface is considered, MIL-101-2CH₃, MIL-101-2CF₃, and UiO-66-2CH₃ appear more promising. Furthermore, the impact of temperature is also investigated. Full article

(This article belongs to the Special Issue Nanostructured Materials for Adsorption)

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11 pages, 1714 KiB

Open AccessArticle

Adsorption of Sb(III) from Aqueous Solution by nZVI/AC: A Magnetic Fixed-Bed Column Study

by Huijie Zhu, Qiang Huang, Mingyan Shi, Shuai Fu, Xiuji Zhang, Zhe Yang, Jianhong Lu and Bo Liu

Nanomaterials 2021, 11(8), 1912; https://doi.org/10.3390/nano11081912 - 25 Jul 2021

Cited by 5 | Viewed by 2033

Abstract

The effectiveness of nanoscale zero-valent iron(nZVI) immobilized on activated carbon (nZVI/AC) in removing antimonite (Sb(III)) from simulated contaminated water was investigated with and without a magnetic fix-bed column reactor. The experiments were all conducted in fixed-bed columns. A weak magnetic field (WMF) was proposed to increase the exclusion of paramagnetic Sb(III) ions by nZVI/AC. The Sb(III) adsorption to the nZVI and AC surfaces, as well as the transformation of Sb(III) to Sb(V) by them, were both increased by using a WMF in nZVI/AC. The increased sequestration of Sb(III) by nZVI/AC in the presence of WMF was followed by faster nZVI corrosion and dissolution. Experiments were conducted as a function of the pH of the feed solution (pH 5.0–9.0), liquid flow rate (5–15 mL·min⁻¹), starting Sb(III) concentration (0.5–1.5 mg·L⁻¹), bed height nZVI/AC (10–40 cm), and starting Sb(III) concentration (0.5–1.5 mg·L⁻¹). By analyzing the breakthrough curves generated by different flow rates, different pH values, different inlet Sb(III) concentrations, and different bed heights, the adsorbed amounts, equilibrium nZVI uptakes, and total Sb(III) removal percentage were calculated in relation to effluent volumes. At pH 5.0, the longest nZVI breakthrough time and maximal Sb(III) adsorption were achieved. The findings revealed that the column performed effectively at the lowest flow rate. With increasing bed height, column bed capacity and exhaustion time increased as well. Increasing the Sb(III) initial concentration from 0.5 to 1.5 mg·L⁻¹ resulted in the rise of adsorption bed capacity from 3.45 to 6.33 mg·g⁻¹. Full article

(This article belongs to the Special Issue Nanostructured Materials for Adsorption)

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20 pages, 5466 KiB

Open AccessArticle

Characterization of an Isostructural MOF Series of Imidazolate Frameworks Potsdam by Means of Sorption Experiments with Water Vapor

by Dirk Otter, Suvendu Sekhar Mondal, Anas Alrefai, Lorenz Krätz, Hans-Jürgen Holdt and Hans-Jörg Bart

Nanomaterials 2021, 11(6), 1400; https://doi.org/10.3390/nano11061400 - 25 May 2021

Cited by 8 | Viewed by 2563

Abstract

Sorption measurements of water vapor on an isoreticular series of Imidazolate Frameworks Potsdam (IFP), based on penta-coordinated metal centers with secondary building units (SBUs) connected by multidentate amido-imidate-imidazolate linkers, have been carried out at 303.15 K. The isotherm shapes were analyzed in order to gain insight into material properties and compared to sorption experiments with nitrogen at 77.4 K and carbon dioxide at 273.15 K. Results show that water vapor sorption measurements are strongly influenced by the pore size distribution while having a distinct hysteresis loop between the adsorption and desorption branch in common. Thus, IFP-4 and -8, which solely contain micropores, exhibit H4 (type I) isotherm shapes, while those of IFP-1, -2 and -5, which also contain mesopores, are of H3 (type IV) shape with three inflection points. The choice of the used linker substituents and transition metals employed in the framework has a tremendous effect on the material properties and functionality. The water uptake capacities of the examined IFPs are ranging 0.48 mmol g⁻¹ (IFP-4) to 6.99 mmol g⁻¹ (IFP-5) and comparable to those documented for ZIFs. The water vapor stability of IFPs is high, with the exception of IFP-8. Full article

(This article belongs to the Special Issue Nanostructured Materials for Adsorption)

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11 pages, 3559 KiB

Open AccessArticle

Gas Porosimetry by Gas Adsorption as an Efficient Tool for the Assessment of the Shaping Effect in Commercial Zeolites

by Alejandro Orsikowsky-Sanchez, Christine Franke, Alexander Sachse, Eric Ferrage, Sabine Petit, Julien Brunet, Frédéric Plantier and Christelle Miqueu

Nanomaterials 2021, 11(5), 1205; https://doi.org/10.3390/nano11051205 - 1 May 2021

Cited by 4 | Viewed by 2396

Abstract

A set of three commercial zeolites (13X, 5A, and 4A) of two distinct shapes have been characterized: (i) pure zeolite powders and (ii) extruded spherical beads composed of pure zeolite powders and an unknown amount of binder used during their preparation process. The coupling of gas porosimetry experiments using argon at 87 K and CO₂ at 273 K allowed determining both the amount of the binder and its effect on adsorption properties. It was evidenced that the beads contain approximately 25 wt% of binder. Moreover, from CO₂ adsorption experiments at 273 K, it could be inferred that the binder present in both 13X and 5A zeolites does not interact with the probe molecule. However, for the 4A zeolite, pore filling pressures were shifted and strong interaction with CO₂ was observed leading to irreversible adsorption of the probe. These results have been compared to XRD, IR spectroscopy, and ICP-AES analysis. The effect of the binder in shaped zeolite bodies can thus have a crucial impact on applications in adsorption and catalysis. Full article

(This article belongs to the Special Issue Nanostructured Materials for Adsorption)

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22 pages, 4054 KiB

Open AccessArticle

Design of Hybrid PAH Nanoadsorbents by Surface Functionalization of ZrO₂ Nanoparticles with Phosphonic Acids

by Nadine Bou Orm, Thomas Gréa, Marwa Hamandi, Alexandre Lambert, Florent Lafay, Emmanuelle Vulliet and Stéphane Daniele

Nanomaterials 2021, 11(4), 952; https://doi.org/10.3390/nano11040952 - 8 Apr 2021

Cited by 4 | Viewed by 2218

Abstract

This study focuses on the preparation of innovative nanocomposite materials based on surface modification of commercial nano-ZrO₂ optimized from Brønsted acid–base surface reactions. This surface modification was carried out by direct grafting of suitable phosphonic acids bearing a vinylic or phenylic substituent in aqueous solution. Different loading quantities of the anchoring organophosphorus compounds were applied for each materials synthesis. The resulting nanohybrids were thoroughly characterized by infrared spectroscopy (DRIFT), solid-state nuclear magnetic resonance (NMR), nitrogen adsorption-desorption (BET), thermogravimetric analysis (TG), and X-ray photoelectron spectroscopy (XPS), demonstrating the reliability and efficient tunability of the surface functionalization based on the starting Zr/P ratio. Our nanocomposite materials exhibited a high specific surface area as well as complex porosity networks with well-defined meso-pore. The as-prepared materials were investigated for the adsorption of a mixture of 16 polycyclic aromatic hydrocarbons (PAHs) at 200 ng·mL⁻¹ in an aqueous solution. Adsorption kinetics experiments of each individual material were carried out on the prepared PAHs standard solution for a contact time of up to 6 h. Pretreatments of the adsorption test samples were performed by solid-phase extraction (SPE), and the resulting samples were analyzed using an ultrasensitive GC-orbitrap-MS system. The pseudo-first-order and the pseudo-second-order models were used to determine the kinetic data. The adsorption kinetics were best described and fitted by the pseudo-second-order kinetic model. The correlation between the nature of the substituent (vinylic or phenylic) and the parameters characterizing the adsorption process were found. In addition, an increase of PAHs adsorption rates with phosphonic acid loading was observed. Full article

(This article belongs to the Special Issue Nanostructured Materials for Adsorption)

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12 pages, 4498 KiB

Open AccessArticle

Preparation of Carbon-Covered Phosphorus-Modified Alumina with Large Pore Size and Adsorption of Rhodamine B

by Shuaiqi Chen, Xuhui Wang, Weiyi Tong, Jianchuan Sun, Xiangyu Xu, Jiaqing Song, Jianyi Gong and Wei Chen

Nanomaterials 2021, 11(3), 799; https://doi.org/10.3390/nano11030799 - 20 Mar 2021

Cited by 4 | Viewed by 2539

Abstract

In this study, phosphorus-modified alumina with large pore size was synthesized through a coprecipitation method. The carbon-covered, phosphorus-modified alumina with large pores was prepared by impregnating with glucose and carbonizing to further improve the adsorption of organic dyes. The morphology and structure of these composites were characterized by various analysis methods, and Rhodamine B (RhB) adsorption was also examined in aqueous media. The results showed that the specific surface area and pore size of the phosphorus-modified alumina sample AP7 (prepared with a P/Al molar ratio of 0.07) reached 496.2 m²·g⁻¹ and 21.9 nm, while the specific surface area and pore size of the carbon-covered phosphorus-modified alumina sample CAP7–27 (prepared by using AP7 as a carrier for glucose at a glucose/Al molar ratio of 0.27) reached 435.3 m²·g⁻¹ and 21.2 nm. The adsorption experiment of RhB revealed that CAP7–27 had not only an equilibrium adsorption capacity of 198 mg·g⁻¹, but also an adsorption rate of 162.5 mg·g⁻¹ in 5 min. These superior adsorption effects can be attributed to the similar pore structures of CAP7–27 with those of alumina and the specific properties with those of carbon materials. Finally, the kinetic properties of these composites were also studied, which were found to be consistent with a pseudo-second-order kinetic model and Langmuir model for isothermal adsorption analysis. This study indicates that the prepared nanomaterials are expected to be promising candidates for efficient adsorption of toxic dyes. Full article

(This article belongs to the Special Issue Nanostructured Materials for Adsorption)

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20 pages, 5147 KiB

Open AccessArticle

Combined Cutaneous Therapy Using Biocompatible Metal-Organic Frameworks

by Seyed Dariush Taherzade, Sara Rojas, Janet Soleimannejad and Patricia Horcajada

Nanomaterials 2020, 10(12), 2296; https://doi.org/10.3390/nano10122296 - 25 Nov 2020

Cited by 22 | Viewed by 3760

Abstract

Combined therapies emerge as an interesting tool to overcome limitations of traditional pharmacological treatments (efficiency, side effects). Among other materials, metal-organic frameworks (MOFs) offer versatilities for the accommodation of multiple and complementary active pharmaceutical ingredients (APIs): accessible large porosity, availability of functionalization sites, and biocompatibility. Here, we propose topical patches based on water-stable and biosafe Fe carboxylate MOFs (MIL-100 and MIL-127), the biopolymer polyvinyl alcohol (PVA) and two co-encapsulated drugs used in skin disorders (azelaic acid (AzA) as antibiotic, and nicotinamide (Nic) as anti-inflammatory), in order to develop an advanced cutaneous combined therapy. Exceptional MOF drug contents were reached (total amount 77.4 and 48.1 wt.% for MIL-100 and MIL-127, respectively), while an almost complete release of both drugs was achieved after 24 h, adapted to cutaneous delivery. The prepared cutaneous PVA-MOF formulations are safe and maintain the high drug-loading capacity (total drug content of 38.8 and 24.2 wt.% for MIL-100 and MIL-127, respectively), while allowing a controlled delivery of their cargoes, permeating through the skin to the active target sites. The total amount of drug retained or diffused through the skin is within the range (Nic), or even better (AzA) than commercial formulations. The presented results make these drug combined formulations promising candidates for new cutaneous devices for skin treatment. Full article

(This article belongs to the Special Issue Nanostructured Materials for Adsorption)

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13 pages, 2719 KiB

Open AccessArticle

Rapid Room-Temperature Preparation of Hierarchically Porous Metal–Organic Frameworks for Efficient Uranium Removal from Aqueous Solutions

by Chongxiong Duan, Yi Zhang, Jiexin Li, Le Kang, Yawei Xie, Wenxiong Qiao, Chunxia Zhu and Haochuan Luo

Nanomaterials 2020, 10(8), 1539; https://doi.org/10.3390/nano10081539 - 6 Aug 2020

Cited by 20 | Viewed by 3569

Abstract

The effective removal of uranium from an aqueous solution is a highly valuable process for the environment and health. In this study, we developed a facile and rapid method to synthesize hierarchically porous Cu-BTC (RT-Cu-BTC) using a cooperative template strategy. The as-synthesized RT-Cu-BTC exhibited hierarchically porous structure and excellent thermostability, as revealed by X-ray powder diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis. Compared with conventional metal–organic frameworks (MOFs) and zeolites, the obtained RT-Cu-BTC exhibited enhanced adsorption capacity (839.7 mg·g⁻¹) and high removal efficiency (99.8%) in the capture of uranium (VI) from aqueous solutions. Furthermore, the conditions such as adsorbent dose, contact time, and temperature in adsorption of uranium (VI) by RT-Cu-BTC were investigated in detail. The thermodynamics data demonstrated the spontaneous and endothermic nature of the uranium (VI) adsorption process. The Langmuir isotherm and pseudo-second-order models could better reflect the adsorption process of uranium (VI) onto RT-Cu-BTC. In addition, the as-synthesized RT-Cu-BTC showed excellent stability in removing uranium (VI) from an aqueous solution. This work provides a facile and rapid approach for fabricating hierarchically porous MOFs to realize a highly efficient removal of uranium (VI) from aqueous systems. Full article

(This article belongs to the Special Issue Nanostructured Materials for Adsorption)

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18 pages, 5752 KiB

Open AccessArticle

Partial Oxidation Strategy to Synthesize WS₂/WO₃ Heterostructure with Enhanced Adsorption Performance for Organic Dyes: Synthesis, Modelling, and Mechanism

by Guiping Li, Yongli Wang, Jingtao Bi, Xin Huang, Yafei Mao, Liang Luo and Hongxun Hao

Nanomaterials 2020, 10(2), 278; https://doi.org/10.3390/nano10020278 - 6 Feb 2020

Cited by 40 | Viewed by 4593

Abstract

In this work, a facile oxidation strategy was developed to prepare novel tungsten disulfide/tungsten trioxide (WS₂/WO₃) heterostructures for adsorbing organic dyes efficiently by combining the hydrophilic property of WO₃ and the superior dye affinity of WS₂. The structural and elemental properties of the synthesized hybrid materials were systematically investigated, and the results demonstrated the retained flower-like morphology of the primitive WS₂ and the successful introduction of WO₃. Furthermore, surface properties such as a superior hydrophilicity and negative-charged potential were also demonstrated by a water contact angle characterization combined with a Zeta potential analysis. The performance of the obtained WS₂/WO₃ hybrid materials for removing Rhodamine B (RhB) from wastewater was evaluated. The results showed that the maximum adsorption capacity of the newly synthesized material could reach 237.1 mg/g. Besides, the adsorption isotherms were also simulated by a statistical physics monolayer model, which revealed the non-horizontal orientation of adsorbates and endothermic physical interaction. Finally, the adsorption mechanism and the recyclability revealed that the partial oxidation strategy could contribute to a higher adsorption capacity by modulating the surface properties and could be applied as a highly efficient strategy to design other transition metal dichalcogenides (TMDs) heterostructures for removing organic dyes from wastewater. Full article

(This article belongs to the Special Issue Nanostructured Materials for Adsorption)

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