Mechanistic investigation on the green recovery of ionic, nanocrystalline, and metallic gold by two anionic nanocelluloses

doi:10.1016/j.cej.2014.05.069

Chemical Engineering Journal

Volume 253, 1 October 2014, Pages 316-324

https://doi.org/10.1016/j.cej.2014.05.069 Get rights and content

Highlights

•
Potential recovery of gold from anionic nanocellulose.
•
Recovery of ionic, nanoparticulate, and metallic Au from dilute solutions.
•
Least interference of pH and competing ions on Au recovery.
•
A plausible mechanism suggested for adsorptive–reduction pathways.

Abstract

The modified cellulose (ADAC samples) used as backbone to obtain biodegradable hydrogels, which demonstrated high affinity to concentrate precious gold species. The primary foci of the study were to develop green techniques to recover Au from dilute solutions by providing the mechanistic evidences for the adsorption coupled reduction pathways. The derivatives of anionic nanocellulose were used for recovery of the ionic, nanoparticulate, and metallic forms of Au. The ADAC samples were promising sorbing phase (57 and 60 mg/g capacity) even at low pH for the treatment of the gold-polluted waters. Thermodynamically, ADAC hydrogels were remained active at moderate to higher temperature (295–333 K) in an endothermic way. Reduction of Au occurred at different stages of kinetic curves, facilitating the formation of zerovalent gold (48 and 41 nm particle size). The Au recovery minimally altered by the competing heavy metals (Cd, Co, Cr, Ni, and As), either at equivalent or lower concentrations. A significant amount of Au(III) (83–99%) regenerated by a strong complexing eluent (0.5 M thiourea in 1 M HCl), moreover thermal crystallization yielded metallic gold in an excellent amount (94%). The mechanism of adsorptive–reduction of gold-nanocellulose were investigated and characterized by the spectroscopic studies including X-ray photoelectron spectroscopy. Overall, recovery of gold in desired forms from nanocellulose can be viewed as an effective biomaterial management strategy.

Introduction

Novel technological innovations in water treatment are among the most exciting and promising field [1]. Due to ever increasing demand of precious metal, recovery of gold has always been a matter of interest due to the huge economic potential and several applications [2]. Gold is usually recovered from dilute solutions by precipitation, adsorption by activated carbons (ACs), solvent exchange methods and ionic exchange resins [3] and [4]. However drawbacks such as low selectivity for gold, low efficiency in dilute solutions, and high-cost operations make them inappropriate techniques. Other techniques, such as thermal evaporation and precipitation are often expensive or less-efficient. Among them, adsorption reports a definite edge over other techniques to concentrate gold species in practised water treatment systems [5]. However materials with high capacity, selectivity, and regenerability are still under improvement to meet increasingly strict regulations and reducing the dosage and huge waste controlling issues. Consequently application of sustainable, biodegradable, and environmental friendliness materials from natural resources have increased attention towards the novel, high-value natural products [6].

The crude untreated biomass of cellulose, one of the most abundant and renewable organic polymer, is also an appropriate biofibers for the synthesis of various advanced functional materials [7]. For example periodate oxidized the vicinal hydroxyl groups (of glucopyranose ring of cellulose) at positions 2 and 3 to aldehyde groups, resulting 2,3-dialdehyde cellulose [8]. This way, the reactive aldehydic groups underwent selective modifications to form carboxylic, sulfonate, and imine-derivatives [9], [10] and [11]. Thus growing interest in derivatives of cellulose broadens the potential for high-end applications [12]. More recently, application of cationic and anionic cellulose has been investigated in water treatments [13] and [14].

Moreover recovery of soft metals such as, gold in zerovalent forms from biomaterials is being explored at atomic levels for desired shape and size [15]. Potentially, metal nanoparticles within the nanostructured network of the hydrogels are good candidates for applications in catalysis, sensing, electronics, and biomedical instruments [16] and [17]. Additionally the thermal crystallization is a conventional technique used to recover precious metals from low-grade ores and wastewaters [18]. Also, application of thermal crystallization has recently been used in trace measurement of the labile Au from natural waters [19].

The green recovery of precious metals by the adsorptive–reduction process is less-discussed without comprehensive characterizing methods. The aim of the research is to investigate adsorption coupled reduction pathways on the recovery of ionic, nanocrystalline, and metallic gold from dilute solutions by the anionic nanocellulose. A combination technique of adsorption, nanocrystallization, and thermal crystallization has been explored on recovery of the gold species.

Section snippets

Materials

A 1000 mg/L Au(III) stock solution prepared using HAuCl₄·3H₂O. All working standards were prepared from the stock solution according to the required concentrations. All reagents, unless otherwise specified, were analytical grade obtained from the Sigma–Aldrich.

Preparation of anionic sulfonated nanocelluloses

The material synthesis involved two step reaction; first periodate oxidation that produced dialdehyde cellulose (DAC), the reactive DAC further underwent sulfonation reaction yielding the ADAC products (Scheme 1). Detailed information for

Effect of dosing and pH

Ten mL of Au solution (50 and 100 mg/L) was exposed to 1, 5, 10, 20, and 40 mg of ADAC I and ADAC II samples. Gold concentration was measured after 24 h of contact time. Fig. S1a (in supplementary data) showed the dose variation and percentage Au recovery from aqueous solutions at different time and nanocellulose dose. Nearly 100% recovery obtained for ⩾10 mg (dry weight) dosing after 24 h for both the samples at 50 mg/L concentration, however it was slightly lower (∼95 to 96%) for 100 mg/L

Conclusions

The modified nanocellulose exhibit the required performance profile combined with environmental friendliness toward the precious gold recovery. The concentrated aqueous dispersions of nanocellulose show excellent recovery, even at low pH and in the presence of various competing ions from the dilute solutions. This study can provide new openings for the utilization of biodegradable nanocellulose derivatives for the recovery or decontamination of Au from mine waters with typically low pH

Acknowledgements

Finnish Funding Agency for Technology and Innovation (Tekes) is thanked for the financial support. First author (A.D.D.) would also like to acknowledge Lappeenranta University of Technology, for providing post-doctoral funding at the Laboratory of Green Chemistry, Mikkeli, Finland. The authors are grateful to the fibre and particle engineering laboratory, University of Oulu for providing the cellulose materials.

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Mechanistic investigation on the green recovery of ionic, nanocrystalline, and metallic gold by two anionic nanocelluloses

Highlights

Abstract

Introduction

Section snippets

Materials

Preparation of anionic sulfonated nanocelluloses

Effect of dosing and pH

Conclusions

Acknowledgements

Hydrometallurgy

Bioresour. Technol.

J. Chromatogr. A

Carbohydr. Res.

Carbohydr. Polym.

Chem. Eng. J.

Chem. Eng. J.

Spectrochim. Acta A

Colloids Surf. B

Bioresour. Technol.

Mar. Chem.

Process Biochem.

Hydrometallurgy

Chem. Eng. J.

J. Colloid Interface Sci.

Carbohydr. Res.

Advances in water treatment by adsorption technology

Nat. Protoc.