Submit to Materials Review for Materials Propose a Special Issue

Journal Browser

► Journal Browser

Layered Double Hydroxides (LDH) and LDH-Based Hybrid Composites

Print Special Issue Flyer
Special Issue Editors
Special Issue Information
Keywords
Published Papers

A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Advanced Composites".

Deadline for manuscript submissions: closed (30 September 2020) | Viewed by 29652

Share This Special Issue

Special Issue Editor

Dr. Jakub Matusik

E-Mail Website
Guest Editor

Department of Mineralogy, Petrography and Geochemistry Faculty of Geology, Geophysics and Environmental Protection AGH University of Science and Technology, al. Mickiewicza 30, 30-059 Kraków, Poland
Interests: clays and clay minerals; layered double hydroxides (LDHs); zeolites; organominerals; advanced adsorbents; mineral-based composites; mineral-based structures for wastewater purification and remediation; polymer–mineral nanocomposites
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

LDHs are a class of two-dimensional layered anionic structures. They are composed of positively charged brucite-like layers and charge balancing hydrated anions located in the interlayer. The features of LDH phases include the following: ease of synthesis, controllable and flexible chemical composition, and relatively large surface area. These contribute to their potential applications in adsorption-based processes, catalysis, electrochemistry, polymer chemistry, biomedicine, and wastewater treatment.

In recent years, LDH materials have been extensively studied as components of hybrid materials. It is possible and desirable that the support can play a synergistic role in the tested system (e.g. it can induce dual adsorption properties, increase the composite stability at a low pH). Such approach can also reduce production costs of the materials where the active LDH component is in a sufficient amount for the desired application.

The Special Issue will cover, but not be limited to, the following topics:

+ the synthesis of pure LDH phases of different chemical compositions by various experimental approaches;

+ the synthesis of hybrid LDH-based materials involving the use of clays and clay minerals, zeolites, metals, and oxides/hydroxides;

+ the characterization of LDH and LDH-based materials at an atomic level with advanced analytical methods;

+ applications of LDH and LDH-based materials in the adsorption, catalysis, and synthesis of polymer composites and drug delivery.

It is my pleasure to invite you to submit a manuscript for this Special Issue. Full research papers, short communications, and reviews are welcome.

Prof. Dr. Jakub Matusik
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Materials is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

layered double hydroxides
LDH-based hybrids
adsorption
catalysis
drug delivery
composites

Published Papers (11 papers)

Download All Papers

Editorial

Jump to: Research

3 pages, 167 KiB

Open AccessEditorial

Special Issue: Layered Double Hydroxides (LDH) and LDH-Based Hybrid Composites

by Jakub Matusik

Materials 2021, 14(10), 2582; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14102582 - 16 May 2021

Cited by 1 | Viewed by 1721

Abstract

LDHs are a class of two-dimensional layered anionic structures with unique properties [...] Full article

(This article belongs to the Special Issue Layered Double Hydroxides (LDH) and LDH-Based Hybrid Composites)

Research

Jump to: Editorial

17 pages, 7463 KiB

Open AccessArticle

Memory Effect on a LDH/zeolite A Composite: An XRD In Situ Study

by Breno G. P. Bezerra, Lindiane Bieseki, Mariele I. S. de Mello, Djalma R. da Silva, Cristiane B. Rodella and Sibele Pergher

Materials 2021, 14(9), 2102; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14092102 - 21 Apr 2021

Cited by 9 | Viewed by 2602

Abstract

In this memory effect study, hydrotalcite-type compounds in the lamellar double hydroxide-like (LDH)/zeolite A composite material were analyzed using X-Ray Diffration XRD) in situ experiments. Three samples were analyzed: Al,Mg-LDH, Al,Mg-LDH/ZA composite, and a physical mixture (50/50 wt%) of zeolite A and Al,Mg-LDH. The Al,Mg-LDH sample was treated at 500 °C in an O₂ atmosphere and subsequently rehydrated. The Al,Mg-LDH/ZA composites had three treatments: one was performed at 300 °C in a He atmosphere, and two treatments were performed with an O₂ atmosphere at 300 and 500 °C. In the physical mixture, two treatments were carried out under O₂ flow at 500 °C and under He flow at 300 °C. Both went through the rehydration process. All samples were also analyzed by energy dispersive spectroscopy (EDS) and scanning electron microscopy (SEM). The results show that the LDH phase in the Al,Mg-LDH/ZA compounds has memory effects, and thus, the compound can be calcined and rehydrated. For the LDH in the composite, the best heat treatment system is a temperature of 300 °C in an inert atmosphere. Full article

(This article belongs to the Special Issue Layered Double Hydroxides (LDH) and LDH-Based Hybrid Composites)

► Show Figures

Graphical abstract

11 pages, 2178 KiB

Open AccessArticle

Efficient Exfoliation of Layered Double Hydroxides; Effect of Cationic Ratio, Hydration State, Anions and Their Orientations

by Jayakumar Karthikeyan, Helmer Fjellvåg, Silje Bundli and Anja Olafsen Sjåstad

Materials 2021, 14(2), 346; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14020346 - 12 Jan 2021

Cited by 11 | Viewed by 2408

Abstract

The exfoliation ability of nitrate based Mg_1−xAl_x(OH)₂(NO₃)_x·mH₂O layered double hydroxides (Mg-Al LDH) in formamide into single or multilayer nanosheets depends strongly on nitrate anion orientation and layer charge. Our systematic studies used materials that were likely to disclose differences with respect to anion type and their concentrations in the interlayer gallery. We assured to avoid any carbonate incorporation into the galleries for nitrate, chloride, iodide, and sulfate based Mg-Al LDHs. Furthermore, the comparative exfoliation experiments were conducted for fully hydrated samples with as similar particle morphology as possible. The exfoliation of nitrate Mg-Al LDH is far superior to similar clays with carbonate, sulfate, chloride, or iodide as charge balancing anions. Quantitative analysis of exfoliation yield for pre-treated, fully hydrated samples, shows an optimum composition for exfoliation into single nanosheets of around x ≈ 0.25, while double or triple layered sheets are encountered for other x-values. We observe a clear correlation between the expansion of the interlayer gallery due to progressing tilts of nitrate anions and water molecules out of the horizontal interlayer plane, suspension turbidity, and degree of exfoliation. The established correlations extends to nitrate Ni-Al LDH materials. We finally claim that morphology is a dominating parameter, with house-of-card morphology particles exfoliation far less than platelet-like particles. Hence, hydrothermal treatment may be favorable to enhance exfoliation yields. Full article

(This article belongs to the Special Issue Layered Double Hydroxides (LDH) and LDH-Based Hybrid Composites)

► Show Figures

Figure 1

17 pages, 6440 KiB

Open AccessArticle

Fumonisin B₁ Interaction with Mg-Al and Mg-Fe Layered Double Hydroxides: Removal Efficiency and Mechanisms

by Jakub Matusik and Youjun Deng

Materials 2020, 13(19), 4344; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13194344 - 29 Sep 2020

Cited by 10 | Viewed by 2024

Abstract

Mycotoxins in feed and food are highly toxic and pose a serious danger even at very low concentrations. The use of bentonites in animal diet can reduce toxin bioavailability. However, some mycotoxins like fumonisin B1 (FB1) form anionic species which excludes the use of negatively charged clays. Layered double hydroxides (LDH) with anion-exchange properties, in theory, can be perfect candidates to adsorb FB1. However, fundamental research on the use of LDH for mycotoxins removal is scarce and incomplete. Thus, the presented study was designed to explore such a possibility. The LDH materials with differing chemistry and layer charge were synthesized by co-precipitation both from metal nitrates and chlorides and were then tested for FB1 removal. XRD, FTIR, XPS, and chemical analysis were used for the LDH characterization and to obtain insight into the removal mechanisms. A higher adsorption capacity was observed for the Mg/Al LDH samples (~0.08–0.15 mol/kg) in comparison to the Mg/Fe LDH samples (~0.05–0.09 mol/kg) with no difference in removal efficiency between Cl and NO₃ intercalated LDH. The adsorption capacity increased along with lower layer charge of Mg/Al and was attributed to the lower content of bonded carbonates and the increase of non-polar sites which led to matching between the adsorption domains of LDH with FB1. The FTIR analysis confirmed the negative effect of carbonates which hampered the adsorption at pH 7 and led to the highest adsorption at pH 5 (FB1 content ~15.8 ± 0.75 wt.%). The fast surface adsorption (1–2 min) was dominant and XRD analysis of the basal spacing indicated that no FB1 intercalation occurred in the LDH. The XPS confirmed a strong interaction of FB1 with Mg sites of LDH at pH 5 where the interaction with FB1 carboxylate moieties COO⁻ was confirmed. The research confirmed a high affinity and selectivity of LDH structures towards anionic forms of FB1 mycotoxin. Full article

(This article belongs to the Special Issue Layered Double Hydroxides (LDH) and LDH-Based Hybrid Composites)

► Show Figures

Graphical abstract

16 pages, 2029 KiB

Open AccessArticle

Birnessite: A New Oxidant for Green Rust Formation

by Amira Doggaz, Romain Coustel, Pierrick Durand, François Humbert and Christian Ruby

Materials 2020, 13(17), 3777; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13173777 - 26 Aug 2020

Cited by 2 | Viewed by 2411

Abstract

Iron and manganese are ubiquitous in the natural environment. Fe^II-Fe^III layered double hydroxide, commonly called green rust (GR), and Mn^III-Mn^IV birnessite (Bir) are also well known to be reactive solid compounds. Therefore, studying the chemical interactions between Fe and Mn species could contribute to understanding the interactions between their respective biogeochemical cycles. Moreover, ferromanganese solid compounds are potentially interesting materials for water treatment. Here, a {Fe(OH)₂, Fe^II_aq} mixture was oxidized by Bir in sulphated aqueous media in the presence or absence of dissolved O₂. In oxic conditions for an initial Fe^II/OH⁻ ratio of 0.6, a single GR phase was obtained in a first step; the oxidation kinetics being faster than without Bir. In a second step, GR was oxidised into various final products, mainly in a spinel structure. A partial substitution of Fe by Mn species was suspected in both GR and the spinel. In anoxic condition, GR was also observed but other by-products were concomitantly formed. All the oxidation products were characterized by XRD, XPS, and Mössbauer spectroscopy. Hence, oxidation of Fe^II species by Bir can be considered as a new chemical pathway for producing ferromanganese spinels. Furthermore, these results suggest that Bir may participate in the formation of GR minerals. Full article

(This article belongs to the Special Issue Layered Double Hydroxides (LDH) and LDH-Based Hybrid Composites)

► Show Figures

Graphical abstract

20 pages, 4315 KiB

Open AccessFeature PaperArticle

Synthesis and Properties of New Multilayer Chitosan@layered Double Hydroxide/Drug Loaded Phospholipid Bilayer Nanocomposite Bio-Hybrids

by Dan A. Lerner, Sylvie Bégu, Anne Aubert-Pouëssel, Ramona Polexe, Jean-Marie Devoisselle, Thierry Azaïs and Didier Tichit

Materials 2020, 13(16), 3565; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13163565 - 12 Aug 2020

Cited by 9 | Viewed by 3207

Abstract

A novel bio-hybrid drug delivery system was obtained involving a Mg/Al-NO₃ layered double hydroxide (LDH) intercalated either with ibuprofenate anions (IBU) or a phospholipid bilayer (BL) containing a neutral drug, i.e., 17β-estradiol, and then embedded in chitosan beads. The combination of these components in a hierarchical structure led to synergistic effects investigated through characterization of the intermediates and the final bio-composites by XRD, TG, SEM, and TEM. That allowed determining the presence and yield of IBU and of BL in the interlayer space of LDH, and of the encapsulated LDH in the beads, as well as the morphology of the latter. Peculiar attention has been paid to the intercalation process of the BL for which all available data substantiate the hypothesis of a first interaction at the defect of the LDH, as well as on the interaction mode of these components. ¹H, ³¹P and ²⁷Al MAS-NMR studies allowed establishing that the intercalated BL is not homogeneous and likely formed patches. Release kinetics were performed for sodium ibuprofenate as well as for the association of 17β-estradiol within the negatively charged BL, each encapsulated in the LDH/chitosan hybrid materials. Such new bio-hybrids offer an interesting outlook into the pharmaceutical domain with the ability to be used as sustained release systems for a wide variety of anionic and, importantly, neutral drugs. Full article

(This article belongs to the Special Issue Layered Double Hydroxides (LDH) and LDH-Based Hybrid Composites)

► Show Figures

Graphical abstract

15 pages, 4942 KiB

Open AccessArticle

Designing Dual-Effect Nanohybrids for Removing Heavy Metals and Different Kinds of Anions from the Natural Water

by Osama Saber, Sarah Mousa Asiri, Mohamed Farouk Ezzeldin, Waleed I. M. El-Azab and Mohammed Abu-Abdeen

Materials 2020, 13(11), 2524; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13112524 - 01 Jun 2020

Cited by 4 | Viewed by 1803

Abstract

In the present study, well-designed nanohybrids are used to act as effective dual-function adsorbents for removing both anions and heavy metals from natural water, at the same time. In this trend, Zn-Al LDHs and graphene oxide are applied to build up building blocks to produce a series of nanohybrids. These nanohybrids were characterized by X-ray diffraction, thermal analyses, Fourier transform infrared spectroscopy, Raman spectroscopy, and scanning and transmission electron microscopy. These techniques confirmed that the prepared nanohybrids contained nanolayered structures with three–dimensional porous systems. These porous systems were identified by the nitrogen adsorption-desorption isotherms and water purification experiments. The obtained results indicated that these nanohybrids included suitable structures to act as dual function materials. The first function was achieved by removing more than 80% of both cadmium and lead from the natural water. The second function was accomplished by eliminating of 100% of hydrogen phosphate and bromide anions alongside with 80%–91% of sulfate, chloride, and fluoride anions. To conclude, these well-designed nanohybrids convert two-dimensional nanolayered structures to three-dimensional porous networks to work as dual-function materials for removing of heavy metals and different kinds of anions naturally found in the fresh tap water sample with no parameters optimization. Full article

(This article belongs to the Special Issue Layered Double Hydroxides (LDH) and LDH-Based Hybrid Composites)

► Show Figures

Figure 1

19 pages, 19949 KiB

Open AccessArticle

Zein-layered hydroxide biohybrids: strategies of synthesis and characterization

by Ana C. S. Alcântara, Margarita Darder, Pilar Aranda and Eduardo Ruiz-Hitzky

Materials 2020, 13(4), 825; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13040825 - 11 Feb 2020

Cited by 7 | Viewed by 3181

Abstract

This work constitutes a basic study about the first exploration on the preparation of biohybrids based on the corn protein zein and layered metal hydroxides, such as layered double hydroxides (LDH) and layered single hydroxides (LSHs). For this purpose, MgAl layered double hydroxide and the Co₂(OH)₃ layered single hydroxide were selected as hosts, and various synthetic approaches were explored to achieve the formation of the zein-layered hydroxide biohybrids, profiting from the presence of negatively charged groups in zein in basic medium. Zein-based layered hydroxide biohybrids were characterized by diverse physicochemical techniques such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis/differential thermal analysis (TG/DTA), solid state ¹³C cross-polarization magical angle spinning nuclear magnetic resonance (CP-MAS NMR), field emission-scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), etc., which suggest that the different synthesis procedures employed and the anion located in the interlayer region of the inorganic host material seem to have a strong influence on the final features of the biohybrids, resulting in mixed, single intercalated, or highly exfoliated intercalated phases. Thus, the resulting biohybrids based on zein and layered hydroxides could have interest in applications in biomedicine, biosensing, materials for electronic devices, catalysis, and photocatalysis. Full article

(This article belongs to the Special Issue Layered Double Hydroxides (LDH) and LDH-Based Hybrid Composites)

► Show Figures

Graphical abstract

11 pages, 2732 KiB

Open AccessArticle

Synthesis of Nanocrystalline Mg-Al Hydrotalcites in the Presence of Starch—the Effect on Structure and Composition

by Alicja Michalik, Bogna D. Napruszewska, Anna Walczyk, Joanna Kryściak-Czerwenka, Dorota Duraczyńska and Ewa M. Serwicka

Materials 2020, 13(3), 602; https://0-doi-org.brum.beds.ac.uk/10.3390/ma13030602 - 29 Jan 2020

Cited by 8 | Viewed by 2082

Abstract

The study describes the synthesis of Mg-Al hydrotalcite (Ht) with the use of starch as a structure controlling biotemplate. Syntheses were carried out at room temperature, by co-precipitation at pH = 10. The investigated synthesis parameters included the nature of the precipitating agent (NaOH/Na₂CO₃ or NH₃aq/(NH₄)₂CO₃), the nature of starch (potato, corn and cassava), the method of starch addition to reagents, the method of drying and the effect of washing. The materials were examined with X-ray diffraction, scanning electron microscopy/energy dispersive X-ray spectroscopy and infrared spectroscopy. The data show that synthesis of Ht materials in the presence of starch, with use of the ammonia-based precipitant, enabled preparation of nanocrystalline Ht with very fine (<50 nm) particle size. All investigated starches had a similar effect on the crystallinity and the grain size of Ht precipitates. Ht with the smallest nanocrystals was obtained when starch was present in all solutions used for synthesis, and the final product subjected to freeze drying. Washing with water was found to enhance recrystallization and exchange of nitrates for carbonates. Infrared spectra showed that an interaction exists between the biopolymer template and the Ht particles, resulting in a higher degree of order within the Ht-adhering starch component. Full article

(This article belongs to the Special Issue Layered Double Hydroxides (LDH) and LDH-Based Hybrid Composites)

► Show Figures

Figure 1

16 pages, 8183 KiB

Open AccessArticle

Performance of Halloysite-Mg/Al LDH Materials for Aqueous As(V) and Cr(VI) Removal

by Jakub Matusik, Jakub Hyla, Paulina Maziarz, Karolina Rybka and Tiina Leiviskä

Materials 2019, 12(21), 3569; https://0-doi-org.brum.beds.ac.uk/10.3390/ma12213569 - 31 Oct 2019

Cited by 21 | Viewed by 3483

Abstract

This research focused on the investigation of layered double hydroxide (LDH)/halloysite materials’ adsorption efficiency and mechanisms in reactions with aqueous As(V) and Cr(VI) in a broad pH range. The materials consisting of Mg/Al LDH and halloysite were synthesized using both direct precipitation and physical mixing methods. The XRD, FTIR, DTA, SEM and XPS methods were used to evaluate the quality of the obtained materials and get insight into removal mechanisms. The XRD, FTIR and DTA confirmed LDH formation and showed the dominating presence of intercalated carbonates in the LDH structure. The SEM of the materials revealed characteristic agglomerates of layered LDH particles deposited on halloysite tubular forms. The raw LDH phases showed high removal efficiency of both As(V) and Cr (VI) for initial pH in the range of 3–7. In the studied concentration range the materials containing 25 wt % of LDH exhibited a removal efficiency very similar to the raw LDH. In particular, the halloysite presence in the materials’ mass had a positive effect in the reactions with As(V), which was removed by chemisorption. At a low pH the LDH component underwent partial dissolution, which lowered the adsorption efficiency. Apart from the anion exchange mechanism at a low pH the Cr(VI) was removed via formation of MgCrO₄ with Mg (II) being released from the LDH structure. The XPS spectra for As(V) did not show changes in oxidation state in the reactions. In turn, a partial reduction of Cr(VI) to Cr(III) was observed, especially at a high pH. The use of materials composed of two different minerals is promising due to reduction of costs as well as prevention of adsorbent swelling. This opens the possibility of its use in dynamic adsorption flow through systems. Full article

(This article belongs to the Special Issue Layered Double Hydroxides (LDH) and LDH-Based Hybrid Composites)

► Show Figures

Graphical abstract

13 pages, 2883 KiB

Open AccessArticle

Mg/Al LDH Enhances Sulfate removal and Clarification of AMD Wastewater in Precipitation Processes

by Paulina Maziarz, Jakub Matusik and Tiina Leiviskä

Materials 2019, 12(14), 2334; https://0-doi-org.brum.beds.ac.uk/10.3390/ma12142334 - 23 Jul 2019

Cited by 14 | Viewed by 2884

Abstract

The sulfate removal from acid mine drainage (AMD) water (initial concentration: 5301 mg/L) was investigated by precipitation and/or adsorption using calcium hydroxide (Ca(OH)₂) and synthetic layered double hydroxide (LDH) of the Mg/Al type. The exclusive use of LDH efficiently removed sulfates (64.2% reduction); however, alteration of its structure was observed due to low pH. The use of Ca(OH)₂ in different doses calculated in relation to gypsum stoichiometry allowed to achieve an 86% removal of sulfates. Depending on the equilibrium pH, gypsum or ettringite were the main identified phases. The two-step removal, involving the use of Ca(OH)₂ followed by LDH, was less efficient than the use of the Ca(OH)₂/LDH mixture when the stoichiometric amount of Ca(OH)₂ in relation to gypsum was applied. The application of mixture resulted in a fast pH increase, which prevented destruction of the LDH structure. Most importantly, the use of mixture significantly reduced the sludge volume and enhanced its settling velocity. Full article

(This article belongs to the Special Issue Layered Double Hydroxides (LDH) and LDH-Based Hybrid Composites)

► Show Figures