Microwave hydrothermal synthesis of gallotannin/carbon nanotube composites for the recovery of gallium ion

doi:10.1016/j.apsusc.2020.145414

Applied Surface Science

Volume 510, 30 April 2020, 145414

https://doi.org/10.1016/j.apsusc.2020.145414 Get rights and content

Highlights

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Easy dissolution of gallotannin is solved by combining its with carbon nanotubes.
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Microwave hydrothermal synthesis method makes the synthesis period shorter.
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It has a good adsorption selectivity for Ga(III) from Ge(IV) and As(II) solution.

Abstract

Ultrafast and facile microwave hydrothermal approach was applied to synthesize gallotannin modified carbon nanotube composites (CNT-GT) for effective recovery of Ga(III) from aqueous solutions. The successful preparation of CNT-GT composites was ascertained by a series of characterization techniques including TEM, FTIR, TGA, BET, Raman, XPS and Boehm titration. The CNT-GT obviously enhanced Ga(III) adsorption capability (170.8 mg g⁻¹) as compared with the unmodified carboxylic carbon nanotubes (CNT-COOH). The CNT-GT composites had superior selectivity and excellent reusability. The adsorption mechanism of CNT-GT is based on the ion exchange of the surface hydroxyl hydrogen of CNT-GT with Ga(OH)²⁺, Ga(OH)₂⁺, or Ga³⁺. In a word, the method described in this paper should be a quick and simple way to prepare highly efficient adsorbents, which has definite significance for the application of the environment.

Graphical abstract

In this work, it provides an efficient and concise steps to synthetize the gallotannin/carbon nanotube composites for gallium(III) adsorption.

Introduction

Gallium is an important strategic resource widely used in various high-tech fields, such as semiconductors (integrated circuits [1], optoelectronics [2], photovoltaic solar cells [3], etc), phase change material [4], fibers [5], medicine [6] and catalysis [7]. It is expected that the demand for gallium will continue to grow in the future because gallium is mainly used for green technology. Gallium distribution in nature is relatively dispersed, although bauxite and zinc ore contains relatively more gallium resources. However, the amount of gallium resources that can be developed and recovered from the current is very small. At present, gallium is mainly recovered from aluminum smelting gallium arsenide sludge, red mud, alunite, diode waste and other acidic alkaline leaching liquid [8], [9], [10], [11]. Therefore, the separation and enrichment of gallium have attracted extensive attention, and the development of green and efficient adsorbent for gallium has become a hot topic.

The method of adsorption attracts considerable attention for its simplicity, low cost, efficiency and wide application range [12], [13], [14], [15], [16], [17], [18], [19]. Currently, adsorbents such as carbon nanotubes (CNT), magnetic and silica materials have been popular due to their small size and great specific surface area [20], [21], [22], [23]. CNT has a high surface area, hydrophobicity, favorable electroconductivity, excellent thermal stability and mechanical properties, which attracted a great deal of interest in adsorption field [24]. However, the absence of sufficient surface for active sites and the agglomeration properties in aqueous solution limit their adsorption efficiency. Therefore, it is necessary to introduce an active adsorption center to CNT for improving its adsorption performance. Although there are many ways to modify the surface of carbon nanotubes, such as amidoamine functionalized multi-walled carbon nanotubes [25], multi-walled carbon nanotubes/chitosan nanocomposite [26], diglycolamide functionalized multi-walled carbon nanotubes [27], etc. However, most of them are complicated, inefficient. Therefore, novel, simple and effective surface modification strategies are still an ideal way for promoting the performance of CNT in adsorption applications. Gallotannin has non-toxic, biocompatible, biodegradable, low cost, rich in nature, good adsorption capacity and other characteristics. It possesses abundant hydroxyl functional groups, which can serve as functional sites and can be exchanged with metal ions. However, the application of gallotannin is hindered by its less density, incomparable surface area and instability in solutions [28], [29], [30], [31], [32], [33]. So, the combination of gallotannin and CNT to form CNT/gallotannin nanocomposites could overcome the disadvantages both of CNT and gallotannin. However, the traditional water bath synthesis method is time-consuming and labor-intensive. A new method named microwave hydrothermal synthesis has been developed for synthesis of nanocomposites in recent years. Compared with traditional heating, microwave heating has the strengths of rapid crystallization, small crystal sizes and broad synthesis composition by shortening the synthesis time [34], [35], [36], [37], [38], [39].

In this work, the gallotannin/carbon nanotube composites adsorbent in an aqueous solution having phenolic hydrogen groups were synthetized using the dicyclohexylcarbodiimide (DCC) as a coupling agent by microwave hydrothermal synthesis, and characterized by a series of methods. By exploring the recovery performance of CNT-GT on Ga(III), the optimal recovery conditions, influence of coexisting ions, recovery mechanism and recycling of CNT-GT were discussed.

Section snippets

Synthesis of CNT-GT

The high efficiency synthesis of adsorbent consists of two steps. All the synthesis steps are performed in a microwave hydrothermal synthesizer. Firstly, carboxylated carbon nanotube was synthetized by reaction of 1 g CNT and 200 mL strong acid (the volume ratio of HNO₃ and H₂SO₄ is 1:3) for 30 min at 40 °C and power 400 W. And then, it was filtered and washed with distilled water until the pH of the filtrate became neutral. The filtered product (CNT-COOH) was dried at 50 °C under vacuum over

FT-IR analysis

The FTIR spectrum (Fig. 1) showed the abundant functional groups and chemical bonds of CNT, CNT-COOH, GT and CNT-GT. From Fig. 1(A), there are no other oxygen-containing functional groups on the original carbon nanotubes except the peak of the carbon skeleton. However, the stretching vibration peak of single bond OH (3460 cm⁻¹), the C double bond O peak (1650 cm⁻¹), the OH in-plane bending vibration peak (1430 cm⁻¹) and the out-of-plane bending vibration peak (950 cm⁻¹) appeared respectively on the CNT-COOH, which

Conclusions

This work shows that a gallotannin/ carbon nanotube composites (CNT-GT) contains hydroxyl as reactive sites for recovery Ga(III) by ion exchange. The composite material retained the tubular shape of carbon nanotubes with a diameter of 57.10 nm. The CNT-GT maximum adsorption capacity achieved to 170.80 mg g⁻¹ for Ga(III) at pH 3 and 156.80 mg g⁻¹ at pH 10, and fitted Langmuir model and pseudo-second-order kinetics. Adsorption equilibrium can be reached within 4 h. Studies have shown that the low

CRediT authorship contribution statement

Ying Xiong: Conceptualization, Methodology. Xiaoxiao Cui: Data curation, Writing - original draft. Mengmeng Zhang: Visualization, Investigation. Yuejiao Wang: Writing - review & editing. Zhenning Lou: Supervision. Weijun Shan: .

Acknowledgments

This project is supported by National Natural Science Foundation of China (51674131, 21373005, 51902149), Natural Science Foundation of Liaoning Province of China (2019-MS-156, RC190346, XLYC1907197), Project supported National Science Technology Ministry (2015BAB02B03) and Natural Science Foundation of Liaoning University (LDGY2019009, LDGY2019014).

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Full Length ArticleMicrowave hydrothermal synthesis of gallotannin/carbon nanotube composites for the recovery of gallium ion

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Synthesis of CNT-GT

FT-IR analysis

Conclusions

CRediT authorship contribution statement

Acknowledgments

Opt. Commun.

Opt.

Energy Proced.

Ceram. Int.

J. Inorg. Biochem.

Coordin. Chem. Rev.

Hydrometallurgy

Hydrometallurgy

J. Environ. Chem. Eng.

Waste Manage.

Carbohyd. Polym.

J. Mol. Liq.

Bioresour. Technol.

Mat. Sci. Eng. C

J. Taiwan. Inst. Chem. E

Microp. Mesopor. Mat.

Powder Technol.

Chemosphere

J. Taiwan Inst. Chem. E

Chem. Eng. J.

Int. J. Bio. Macromol.

Colloid Surf. A

Microp. Mesopor. Mat.

Full Length Article
Microwave hydrothermal synthesis of gallotannin/carbon nanotube composites for the recovery of gallium ion