New insights on nanostructure of ordered mesoporous FeMn bimetal oxides (OMFMs) by a novel inverse micelle method and their superior arsenic sequestration performance: Effect of calcination temperature and role of Fe/Mn oxides
Graphical abstract
Introduction
To address adverse human health effect resulting from the exposure of inorganic arsenic contaminated wastewater and/or drinking water, numerous effective technologies have been developed over the past few decades (Meng et al., 2012; Kumar et al., 2019; Moraga et al., 2019; Wang et al., 2019; Xi et al., 2019; Xiong et al., 2019; Wen et al., 2020a; Zhou et al., 2020). Among these arsenic purification techniques, adsorption is recognized as a promising method and best option available owing to its easy operation, low cost and high removal efficiency (Kim et al., 2020; Ma et al., 2020). Adsorption process between inorganic arsenic and natural minerals, especially iron/iron-based substances, plays an important role in its mobility, speciation and bioavailability in biosphere such as water, sediment and soil environment (Guo et al., 2012; Huang et al., 2019). Thus, some iron/iron-based adsorbents have been extensively used as effective adsorbents to remove inorganic arsenic due to their high selectivity and strong affinity (Li et al., 2015; Sun et al., 2017; Zhang et al., 2017a; Zhang et al., 2017b; Zhang et al., 2018; Sun et al., 2019b). Nevertheless, the primary disadvantage of those pure iron/iron-based (hydr)oxides is low uptake of arsenic, which may be associated with the inherent structural characteristics of adsorbents such as lower specific area and pore volume. Another drawback is that As(III) at natural environmentally-relevant pH adsorbs to various iron-based adsorbents less strongly than As(V) because of the non-ionic form of As(III) (H3AsO3) in water (Chen et al., 2018). Therefore, a pre-oxidation step is often required before conventional adsorption process in order to gain higher As(III) removal efficiency (Wen et al., 2015; Shan et al., 2020). However, any additional chemical oxidizing agents can not only induce the operating complexity and cost, but also generate the harmful by-products and cause the second pollution.
Considering the above-mentioned, a proper oxidant has been directly incorporated into the pure iron (hydr)oxides to fabricate excellent iron-based bimetallic adsorbents. Manganese (Mn) oxides, specifically MnO2, are deemed to be effective oxidants in As(III) oxidation. Although MnO2 could readily oxidize As(III) in water (Manning et al., 2002), however, the total As removal efficiency would sharply decrease with increasing the MnO2 percentage in iron-based bimetal composites due to the fact that pure MnO2 is much lower As(V) capacity than that of pure iron (hydr)oxides (Tresintsi et al., 2013). Thus, the exploitation and utilization of contained-MnO2 adsorbents is limited in As(III)-contaminated water/wastewater treatment. Therefore, facilitating the oxidation of soluble As(III) by manganese oxides and reducing the adverse effect of MnO2 is becoming a necessity to achieve effective total As removal efficiency by FeMn bimetal oxides. Previous study had shown that Mn(III/IV) content in FeMn binary oxides played an important role in high uptake of arsenic in aqueous owing to the oxidation process of As(III) (Zhang et al., 2014). This result indicated that Mn(III) content in binary oxides seems could effectively avoid the drawbacks and would not damage the oxidation capacity of pure Mn oxides. Consequently, Mn(III) content in FeMn bimetal oxides are anticipated to the excellent oxidants for As(III) because Mn(III) intermediates that produced along with the redox reactions between As(III) and MnO2 could also oxidize As(III) into As(V) in water (Manning et al., 2002). In addition, according to the evidence of oxidation capacity, some authors deduced that Mn(III), rather than Mn(IV), played a major role in the oxidation of organic compounds because it possessed a higher redox potential (McBride, 1989; Ukrainczyk and McBride, 1992; Nico and Zasoski, 2001; Remucal and Ginder-Vogel, 2014), and the content of Mn(III) in Mn oxides is a rate controlling factor during the process of contaminants oxidation (Sun et al., 2019a).
Additionally, except for remarkable oxidation property for As(III), this Mn-contained bimetal oxides adsorbent also needs remarkable adsorption performance for the generated As(V) to gain effective total As removal efficiency. Ordered mesoporous metal oxides (MMOs), have been focused on recently owing to their intrinsic larger specific surface area and pore volume, uniform and tunable pore size, as well as extremely well-ordered inner-connected nanostructure (Ren et al., 2012). Such features correspond well with the requirements as remarkable adsorbents (Wu and Zhao, 2011; Teng et al., 2013). Currently, soft template and hard template are two kinds of traditional and popular methods to fabricate the MMOs (Gregory et al., 2017). However, some drawbacks, such as the rapid hydrolysis and polymerization of metal ions precursors, the poor wettability of templates, stem from these two conventional methods extensively confine the practical application of MMOs (Gu and Schüth, 2014). In addition, calcination process in high temperature should be added in order to gain highly crystalline MMOs, because the stability of the adsorbents in water/wastewater treatment must also be carefully considered. Nevertheless, the ordered meso-structures of target products easily collapse when the templates are removed during the heat treatment, especially in soft template methods. Furthermore, calcination in different temperature may also dramatically affect the characteristics and properties of nanomaterials, for instance, crystallinity, crystallite size, specific surface areas, and valence state of nanomaterials, which are dependent on the adsorption performance of MMOs. To pursue this aim, it is imperative to develop a novel method to synthesize the perfect MMOs and clarify the correlation between the calcination temperature and the interface chemistry of MMOs.
In this study, we employ a novel and ingenious inverse micelle method, which can overcome the shortcomings from the soft and hard templates, to fabricate a series of ordered mesoporous FeMn bimetal oxides (OMFMs) via the heat treatment. The effect of calcination temperature on nanostructure characteristics and interface chemistry properties of OMFMs are extensively detected. Then, some efforts are made to examine the adsorption behavior and performance of arsenic in water by using the OMFMs. Finally, both As(III) and As(V) removal by OMFMs in liquid-solid two phase are systematically investigated to identify the respective role of Fe/Mn oxides. Aiming to deep understand the correlation between the calcination temperature and adsorption performance of OMFMs, clarify the respective role of iron/manganese oxides and design the superior adsorbents for arsenic elimination and immobilization from water.
Section snippets
Chemicals and nanomaterials
All chemicals involved in this work were analytical-grade and without further purification. Arsenic stock solution (1000 mg/L) were prepared by using inorganic As(III/V) (NaAsO2/Na2HAsO4·7H2O, Sigma-Aldrich). Manganese nitrate (Mn(NO3)2·4H2O), ferric nitrate (Fe(NO3)3·9H2O) and 1-butanol were purchased from Aladdin (Shanghai, China), and P123 (EO20PO70EO20) was obtained from Sigma-Aldrich. The working solution of As(III) and As(V) with desired concentration was prepared by diluting the arsenic
Textural and structural properties of nanomaterials
Fig. 1a–b demonstrates the N2 adsorption/desorption isotherms and BJH pore size distribution of nanomaterials in different calcination temperature. As can be seen, all type IV adsorption/desorption isotherms, the characteristic H1 hysteresis loops as well as narrow monomodal pore size distribution suggested that nanomaterials in this study maintained the ordered mesoporous structure (Mogudi et al., 2017). Besides, increasing the calcination temperature of ordered mesoporous FeMn bimetal oxides
Conclusions
A series of OMFMs were fabricated via a novel inverse micelle method in this work, and the correlation between the calcination temperature and the interface chemistry of OMFMs were extensively explored. The results indicated that the textural properties and nanostructure of obtained OMFMs were closely related to the calcination temperature, which further affected the removal efficiency of arsenic. OMFMs (except for OMFM-4) displayed excellent arsenic removal behavior than pure mesoporous Fe/Mn
CRediT authorship contribution statement
Jun Lu: Methodology, data collection and writing-original draft preparation;
Zhipan Wen: Conceptualization, draft writing and editing, revised the manuscript, supervision;
Yalei Zhang and Gang Cheng: Designed some experiments and made deep discussion;
Rui Xu, Xiaohu Gong and Xin Wang: Conducted some characterizations of the samples;
Rong Chen: Designed some experiments and made deep discussion.
All authors discussed the results and commented on the manuscript.
Declaration of competing interest
The authors declared that they have no conflicts of interest to this work.
Acknowledgements
This work was financed by the National Natural Science Foundation of China (No. 51708427). We also sincerely thank the Associate Editor (Prof. Daniel CW Tsang) and two anonymous reviewers, whose constructive comments and valuable suggestions significantly improved the quality of the manuscript.
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