Accepted Manuscript

Synthesis and characterization of Mn intercalated Mg-Al hydrotalcite

Chengxue Yang, Libing Liao, Guocheng Lv, Limei Wu, Lefu Mei, Zhaohui Li

PII: S0021-9797(16)30422-2
DOI: http://dx.doi.org/10.1016/j.jcis.2016.06.057
Reference: YJCIS 21367

To appear in: Journal of Colloid and Interface Science

Received Date: 1 April 2016

Revised Date: 23 June 2016
Accepted Date: 26 June 2016

Please cite this article as: C. Yang, L. Liao, G. Lv, L. Wu, L. Mei, Z. Li, Synthesis and characterization of Mn
intercalated Mg-Al hydrotalcite, Journal of Colloid and Interface Science (2016), doi: http://dx.doi.org/10.1016/
j.jcis.2016.06.057

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Synthesis and characterization of Mn intercalated Mg-Al
hydrotalcite

Chengxue Yanga, Libing Liaoa,*, Guocheng Lva,*, Limei Wua, Lefu Meia,

Zhaohui Lia,b
a
Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals

and Solid Wastes, National Laboratory of Mineral Materials, School of

Materials Science and Technology, China University of Geosciences,

Beijing, 100083, China

b
Geosciences Department, University of Wisconsin – Parkside, Kenosha,

WI 53141-2000, USA

Corresponding author:

Libing Liao,

Address: School of Material Science and Technology, China University

of Geosciences, Beijing, 100083, P R China.

Phone: +86-137-0131-3964

E-mail: clayl@cugb.edu.cn

1
 Synthesis and characterization of Mn intercalated

Mg-Al hydrotalcite

Chengxue Yanga, Libing Liaoa,*, Guocheng Lva,*, Limei Wua , Lefu Meia, Zhaohui Lia,b

a
Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes,

National Laboratory of Mineral Materials, School of Materials Science and Technology, China

University of Geosciences, Beijing, 100083, China

b
Geosciences Department, University of Wisconsin – Parkside, Kenosha, WI 53141-2000, USA

Abstract: Mn intercalated hydrotalcite was prepared using a reconstruction method. And Mn

intercalation was confirmed by XRD, FTIR, and thermal analyses. The different valences of Mn

were present as determined by XPS. Calcination slightly promoted the isomorphic replacement of

Mn2+ and Mn3+ for Mg2+ and Al3+, especially the replacement of Mn2+ for Mg2+ and Al3+, and to

some extent, reduced Mn intercalation. Ultrasonic treatment significantly increased Mn

intercalation in permanganate form (Mn7+), and promoted the replacement of Mn2+ for Mg2+ and

Al3+. XRF analysis showed that ultrasonic treatment decreased the unbalanced layer charge of Mn

intercalated hydrotalcite, while prolonged calcination increased it. These results may provide

guidance on the preparation and application of Mn intercalated hydrotalcite. Extended calcination

time and ultrasonic vibration increased the interlayer spacing of hydrotalcite, as a result of

reduction in layer charge. As the layer charge was not completely balanced after Mn intercalation,

a certain amount of CO 32- was re-adsorbed into the interlayer space. Mn-hydrotalcites with

different layer charges, different contents of Mn with varying valences are expected to have

different performances in the process of adsorption, degradation, and catalysis.

Keywords: hydrotalcite, Mn intercalation, chemical state, layer charge

*
Corresponding author, Email: clayl@cugb.edu.cn (Liao), guochenglv@cugb.edu.cn (Lv)

2
1. Introduction
Hydrotalcite is a type of layered double hydroxide, which can be described by the chemical

formula [M1-x2+Mx3+(OH)2]x+Ax/mm-·nH2O where M2+ and M3+ are divalent and trivalent metal

cations, Am- is m-valent anion [1]. The interlayer space of hydrotalcite is composed of anions, water

molecules, and other neutral moieties. The weak chemical bond between structure sheet and

interlayer anions or molecules contributes to the ion-exchange ability of hydrotalcite, which is an

important and exceptional feature comparing to other materials [2]. A variety of anion exchange or

intercalation reactions were carried on hydrotalcite [3], making it a versatile host material for

ion-exchange materials [4], adsorbents [5], catalysts [6], and a wide range of applications [7,8].

As most clay minerals are composed of negatively charged sheets and positive charged interlayer

cations, interlayer space of hydrotalcite is different [9]. Current researches are mainly focused on

intercalating hydrotalcite with functional ions of negative charge [10]. To date, three approaches to

synthesize intercalated hydrotalcites are widely used by researchers: co-precipitation,

ion-exchange, and reconstitution methods [11].

KMnO4 is an efficient oxidant in degradation of organic contaminants, including volatile

organic compounds (VOCs), antibiotics, and organic dyes [12]. Mn ions with different chemical

valences play important roles in pollution treatment [13]. For Mn under lower chemical valence, e.g.

in manganese oxides, due to its higher non-electric dipole moment in the crystal structure [14], it

has a stronger removal efficiency of organics under microwave irradiation.

It has been reported that researchers used reconstruction method to intercalate MnO4- into

Mg-Al hydrotalcites, to oxidize ethylbenzene and diphenylmethane in gas condition as a

solvent-free catalyst [15], which is selective and reusable. However, the form of MnO4- anions in

the interlayer space and the structure of the intercalated hydrotalcite have not been discussed.

Intercalating MnO4- into hydrotalcite by an ion-exchange method was also reported, the

intercalated material was used to study the influence of basicity and electronegativity of

hydrotalcite on CO2 sorption, and to compare gas adsorption features of hydrotalcites with

different cations in structure layer [16]. Previous studies were mainly concentrated on incorporating

MnO4- anion into hydrotalcite interlayer and its adsorption and oxidation performance in gas

condition, while this work is more focused on the structure of Mn intercalated hydrotalcite,

including the amount of intercalation and the chemical states of Mn.

3
2. Experiment and methods

2.1 Experiments

Mg-Al hydrotalcites were synthesized by a co-precipitated method as follows. Stoichiometric

ratio of magnesium nitrate (30.7688 g, 0.12 mol) and aluminum nitrate (11.2540 g, 0.03 mol) were

dissolved in 150 mL deionized water, marked as solution A. Then 12.0 g (0.3 mol) sodium

hydroxide and 1.5900 g (0.015 mol) sodium carbonate were dissolved in 150 mL deionized water

to form solution B. Solution A and solution B were added dropwise using a burette at a rate about

2 drops per second into a flask simultaneously, the mixture was stirred to be homogeneous and

kept the pH value stable at about 10. The slurry was aged for 12 h at the temperature of 70 oC, then

centrifuged, dried, and ground to get hydrotalcite sample with different Mg/Al ratios and CO 32- as

interlayer anion.

Mn intercalated Mg-Al hydrotalcites were prepared by a reconstructed method: hydrotalcites

with different Mg/Al ratios were calcined at 500oC for 2, 7, 11, and 15 h, respectively, then soaked

in KMnO4 aqueous solution with N2 flow to prevent influence of carbonate ions, after 30 min of

ultrasonic vibration at a power of 600W, the mixture was stirred at 70oC for 12 h, then centrifuged

and dried to get Mn intercalated Mg-Al hydrotalcites for further measurement. The Mn

intercalated hydrotalcite prepared from the hydrotalcite calcined for 2 h but without ultrasonic

treatment during the intercalation process is referred to Mn-HT-2h, and the similar sample with

ultrasonic treatment is referred to Mn-HT-2h-u, samples for other calcination time are abbreviated

in similar way.

2.2 Methods

Powder XRD analyses were performed on a Rigaku D/max-IIIa diffractometer (Tokyo, Japan)

with a Ni-filtered CuK radiation at 30 kV and 20 mA. Orientated samples were scanned from 3

to 70 at 8/min with a scanning step of 0.01. Powder samples were packed in horizontally held

trays. The Bragg equation was applied to calculate the basal spacing of hydrotalcite. The gallery

heights of the intercalated hybrids were deduced from XRD peak positions of the (003) reflection

of the samples.

Thermal gravimetric analyses were carried out on TGA Q-500 (TA Instruments, New Castle,

USA) from room temperature to 800 °C, at a heating rate of 10 °C/min under a nitrogen flow with

60 mL/min. TG curves were used to determine the percentage of weight loss. Differential
4
scanning calorimetry (DSC) was performed using a differential scanning calorimeter (TA

Instruments Q100) fitted with a cooling system using liquid nitrogen. It was calibrated with an

indium standard. Samples of 6 mg of hydrotalcite were accurately weighed into aluminum pans,

sealed and then heated from 50 to 800 °C at 10 °C/min under a nitrogen flow of 60 mL/min.

FTIR spectra of samples were collected on a Nicolet-560 spectrometer (Thermal Nicolet Co.,

USA) from 400 to 4000 cm−1 with a nominal resolution of 4 cm−1. For each spectrum 16 runs were

collected and averaged. The hydrotalcite samples for FTIR measurement were prepared by adding

approximately 1% of the sample powder to dry KBr powder and pressed into tablet.

The valence of Mn after intercalating into hydrotalcite interlayer was determined by X-ray

photoelectron spectroscopy (XPS, Thermo Scientific Co., Ltd.) under a CuK radiation of 150 W,

and a background pressure of 6.5×10-10 mbar.

Mg, Al and Mn content of hydrotalcite was determined by X-Ray Fluorescence spectrometry

(XRF) before and after intercalation. It was carried out using a portable XRF spectrometer

(Oxford Instruments) with a molybdenum anode at 25 kV and 0.1 mA. A Si-PIN detector from

AMPTEK was employed and characterized by an energy resolution of about 200 eV at 5.9 keV.

3. Results and discussion

3.1 XRD characterization

The prepared hydrotalcites with Mg/Al ratios of 2, 3, and 4 are of high purity as all

diffraction peaks were indexed by hydrotalcite (JCPDS 89-460) and agreed with previous studies

(Fig. 1)[17,18]. For samples with Mg/Al ratios of 2 and 3, the d003 values after MnO4- intercalation

increased by 0.3 and 0.2Å only, indicating small amount of MnO4- intercalated. While for the

sample with a Mg/Al ratio of 4, the d003 value after Mn intercalation increased by 1.5 Å,

illustrating successful intercalation of Mn into hydrotalcite interlayer. Therefore, hydrotalcite with

Mg/Al ratio of 4 was adopted for the experiments investigating the influence of calcination time

and ultrasonic vibration treatment on intercalation. The XRD patterns showed that extended

calcination and ultrasonic vibration both promote the intercalation revealed by the increase of d003

spacing (Fig. 2).

3.2 TG-DSC Analysis

The DSC curves (Fig. 3a) of these three samples showed that Mn-intercalated hydrotalcites

5
(Mn-HT-2h and Mn-HT-15h-u) have different thermal behaviors from the original hydrotalcite.

The original hydrotalcite shows three stages of weight loss. An endothermic peak at about 153°C

is ascribed to the loss of physically adsorbed surface water and interlayer water, corresponding to

a weight loss of 14.4% (Fig. 3b). At 392°C, an intense endothermic peak is due to
[19,20]
dehydroxylation of brucite-like layer , accompanied by a weight loss of 23.2%. At about
[21]
503°C, another endothermic peak begins for the release of interlayer carbonate anions , with a

weight loss of 7.7%. The total weight loss for original hydrotalcite is 45.3%.

For Mn intercalated hydrotalcites (Mn-HT-2h and Mn-HT-15h-u), endothermic peaks due to

removal of surface and interlayer water are at 147°C and 137°C respectively. The weight loss at

this stage is 13.4% for Mn-HT-2h and 11.1% for Mn-HT-15h-u. Intense endothermic peaks

occurring at 393°C and 372°C may be ascribed to dehydroxylation of brucite-like layer and

interlayer permanganate and manganite (transformed to MnO 2), with weight losses of 24.2% and

21.0% for Mn-HT-2h and Mn-HT-15h-u, respectively. The total weight losses of Mn-HT-2h and

Mn-HT-15h-u are 43.2% and 37.6%, lower than that of original hydrotalcite.

Decomposition temperature for interlayer carbonate anions and dehydroxylation temperature

for Mn intercalated hydrotalcites are obviously lower than that of original hydrotalcite, which

means that Mn intercalation lowers the thermal stability of hydrotalcite. Comparing the two

intercalated samples, Mn-HT-2h is a little more thermal stable and has larger weight loss. XRD

and XRF show that Mn-HT-15h-u has larger basal spacing, larger amount of re-adsorbed CO 32-

and Mn intercalation (Table 1) relative to Mn-HT-2h, which again confirms that Mn intercalation

lowers the thermal stability of hydrotalcite.

3.3 FTIR Spectroscopy

The FTIR spectra of original hydrotalcite, calcined hydrotalcite and Mn-hydrotalcites of

different compositions were shown in Fig. 4. The absorption bands appearing in the region

3400~3600cm-1 correspond to the stretch vibration of hydroxyl, and bands at 1640 cm-1 correspond

to the bending vibration of hydroxyl, and antisymmetric vibration bands of carbonate ions appear

at 1390 cm-1.[22] The vibration bands at 590 cm-1 due to structural water are observed in original

hydrotalcite and Mn intercalated hydrotalcites[23]. Bands at the position of 910 cm-1 result from the

adsorption of MnO4- ions [15]

, which does not appear on FTIR curve of original hydrotalcite and

calcined hydrotalcite. The antisymmetric vibration bands of carbonate ions at 1390 cm-1 in the
6
FTIR spectra of Mn-hydrotalcites and calcined hydrotalcite indicated the presence of interlayer

carbonate ions, probably re-adsorbed from the air during testing. However, this band obviously

weakens for Mn-hydrotalcite, indicating the amount of interlayer CO32- anions is much reduced

after MnO4- intercalation, which is consistent with TG-DSC analysis.

3.4 XPS Analysis

XPS spectra were collected to determine the state and content of Mn ions in Mn-hydrotalcites
[24]
(Fig. 5). After peak fitting, the content of Mn in different chemical states are calculated and

listed in Table 1.

Table 1. The proportion of Mn with different chemical valence in intercalated hydrotalcite samples

Mn2+ Mn3+ Mn4+ Mn6+ Mn7+ Mn2+~Mn3+ Mn6+,

Mn7+

Mn-HT-2h 8.6% 45.3% 28.8% 11.2% 6.1% 53.9% 17.3%

Mn-HT-2h-u 18.3% 41.0% 15.8% 13.6% 11.3% 59.3% 24.8%

Mn-HT-7h 10.9% 45.1% 28.3% 12.1% 3.6% 56.0% 15.7%

Mn-HT-7h-u 20.3% 39.1% 18.7% 10.1% 11.7% 59.4% 21.9%

Mn-HT-11h 14.8% 45.8% 25.5% 9.6% 4.3% 60.6% 13.9%

Mn-HT-11h-u 22.4% 36.3% 17.2% 12.2% 11.9% 58.7% 24.0%

Mn-HT-15h 16.4% 46.5% 24.0% 10.8% 2.3% 62.9% 13.1%

Mn-HT-15h-u 22.4% 37.4% 19.7% 10.4% 10.1% 59.8% 20.5%

Table 1 demonstrates that, for samples without ultrasonic treatment, as calcination time

increasing, the content of Mn2+ increased while the content of Mn4+ and Mn7+ decreased, and the

contents of Mn3+ and Mn6+ did not change significantly. For samples with ultrasonic vibration, as

increasing the calcinations time, the content of Mn2+ and Mn4+ increased while the content of

Mn3+ decreased, no obvious changes were observed for the contents of Mn6+ and Mn7+. By

comparing samples with same calcination time, it can be found that ultrasonic treatment raises the

content of Mn2+ and Mn7+, while reduces that of Mn3+ and Mn4+, and has no obvious influence on

Mn6+. Mn6+ and Mn7+ are considered to enter the interlayer space as permanganate and manganate

anions. Mn2+ and Mn3+ are considered to isomorphically replace Mg2+ and Al3+ in the structure

7
layer of hydrotalcite, while Mn4+ is considered to exist as MnO2 on the out surface of the sample.

Therefore, calcination slightly promotes the isomorphic replacement of Mg2+ and Al3+ by Mn2+

and Mn3+, especially the replacement of Mn2+ for Mg2+ and/or Al3+, and to some extent, reduces

the Mn(Mn6++Mn7+) intercalation. However, for samples with the same calcination time,

ultrasonic treatment significantly increase the Mn intercalation in permanganate form (Mn7+), and

promote the replacement of Mn2+ for Mg2+ and /or Al3+. In contrast, the replacement of Mn3+ for

Mg2+ and/or Al3+ is limited. XRD analysis shows that prolonged calcination time and ultrasonic

vibration both increase the interlayer spacing of hydrotalcite, thus the basal spacing increase

should be also ascribed to the replacement of Mn2+ for Mg2+ and/or Al3+ in the structure layer,

which result in the reduction of layer charge.

Table 2. Molar proportion of Mg, Mn, and Al of different intercalated hydrotalcite samples

Mg Mn Al Mg+Mn2+/Al+Mn3+

Mn-HT-2h 66.1% 19.6% 14.3% 2.92

Mn-HT-2h-u 65.8% 18.8% 15.4% 3.00

Mn-HT-7h 65.3% 20.3% 14.5% 2.86

Mn-HT-7h-u 66.1% 19.1% 14.8% 3.15

Mn-HT-11h 65.2% 19.9% 14.9% 2.84

Mn-HT-11h-u 65.0% 20.4% 14.7% 3.15

Mn-HT-15h 65.7% 19.7% 14.7% 2.89

Mn-HT-15h-u 65.7% 19.3% 15.0% 3.15

3.5 XRF analysis

The XRF results showed that for most intercalated samples, ultrasonic treatment raises

M2+/M3+ (ratio of divalent cation to trivalent cation) for samples with same calcination time (Table

1). Longer calcination also slightly increases M2+/M3+ for samples with ultrasonic treatment while

calcination time has no obvious influence on this ratio for samples without ultrasonic treatment.

Larger M2+/M3+ ratio means less positive charge of the structure layer, which should accommodate

less amount of anions in the interlayer space. However, Table 2 showed that ultrasonic treatment

increased the content of interlayer Mn (Mn6++Mn7+) when calcination time is the same, which

means ultrasonic treatment mainly decrease the amount of re-adsorbed CO32- in the interlayer

8
space and the total amount of the interlayer anion, which was confirmed by the thermal analysis

(Fig. 3). XRD shows that the basal spacing of Mn intercalated hydrotalcite increases with

increasing the calcinations time and with ultrasonic treatment. So we believe that the slight

increase of the basal spacing of Mn intercalated hydrotalcites is ascribed to the slight reduce of

their interlayer charge. Less interlayer charge makes it more flexible to expand (larger basal

spacing).

The residual layer charge of Mn intercalated hydrotalcites were calculated based on XPS and

XRF analyses (Table 3) and illustrated in Fig 6, where positive charge of Mn2+, Mn3+, Mg2+ and

Al4 are partially balanced by hydroxyl in brucite-like structure, as well as permanganate and

manganate in the gallery. It shows that the layer charge is still not balanced by the intercalated

permanganate and manganate anions for all Mn intercalated samples. To balance the residual

positive layer charge, a certain amount of CO 32- was re-adsorbed into the interlayer space

(confirmed by TG-DSC and FTIR analyses). It can be seen that the residual layer charge of Mn

intercalated hydrotalcites increases slightly with calcination time and samples without ultrasonic

treatment have higher residual layer charge. For Mn-HT-2h and Mn-HT-15h-u, the former has a

little higher residual layer charge, so should re-adsorbed more CO32- into the interlayer, which is in

agreement with TG-DSC analysis.

4. Conclusion
In this study, the Mn intercalated hydrotalcite was prepared by a reconstruction method.

Prolonged calcination and ultrasonic treatment greatly promote the intercalation of Mn into the

hydrotalcite gallery. Mn existed in different chemical states after intercalation. Mn6+ and Mn7+ are

considered as permanganate and manganate anions, which entered the interlayer space, and Mn2+

and Mn3+ are considered entering structure lattice of hydrotalcite replacing Mg2+ and Al3+, while

Mn4+ is considered as MnO2 on the out surface of the sample. Calcination slightly promotes the

isomorphic replacement of Mn2+ and Mn3+ for Mg2+ and Al3+ , especially the replacement of Mn2+

for Mg2+ and /or Al3+, and to some extent, reduces the Mn(Mn6+ +Mn7+) intercalation. For samples

with the same calcination time, ultrasonic treatment significantly increase the Mn intercalation in

permanganate form (Mn7+), and promote the replacement of Mn2+ for Mg2+ and /or Al3+.

Prolonged calcination time and ultrasonic vibration, which result in the reduction of layer charge,

both increase the interlayer spacing of hydrotalcite. The layer charge is not balanced by the
9
intercalated permanganate and manganate anions for all Mn intercalated samples. To balance the

residual positive layer charge, a certain amount of CO32- was re-adsorbed into the interlayer space.

Mn-hydrotalcites with different layer charges, different contents of Mn with varying valences are

expected to have different performances in the process of adsorption, degradation, and catalysis.

Acknowledgment
This research was supported by International S & T Cooperation (No. S2014ZR0062) and the

Fundamental Research Funds for the Central Universities (2-9-2015-279 and 2-9-2015-278).

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Figure Captions

Figure 1︱X-ray diffraction patterns of hydrotalcites and MnO4- intercalated hydrotalcites with

different Mg/Al ratio (a) Mg2Al-hydrotalcite, (a’) MnO4- intercalated Mg2Al-hydrotalcite, (b)

Mg3Al-hydrotalcite, (b’) MnO4- intercalated Mg2Al-hydrotalcite, (c) Mg4Al-hydrotalcite, (c’) MnO4-

intercalated Mg4Al-hydrotalcite.

Figure 2∣X-ray patterns of Mg4Al-hydrotalcite and MnO4- intercalated Mg4Al-hydrotalcites

with different conditions: (a) Mg4Al-hydrotalcite, (b) Mn-HT-2h, (c) Mn-HT-2h-u, (d) Mn-HT-7h,

(e) Mn-HT-7h-u, (f) Mn-HT-11h, (g) Mn-HT-11h-u. The values are in Å

Figure 3∣DSC and TG curves of original hydrotalcite, Mn intercalated hydrotalcite

(Mn-HT-2h and Mn-HT-15h-u).

Figure 4∣FTIR analysis of original hydrotalcitie, calcined hydrotalcite and Mn intercalated

hydrotalcites at different conditions.

Figure 5∣Mn 2p3/2 spectra of Mn intercalated hydrotalcites prepared at different conditions

Figure 6∣Calculated residual layer charge of Mn intercalated hydrotalcites.

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Graphical abstract

21