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Article
Reductant-Free Synthesis of Silver Nanoparticles-Doped
Cellulose Microgels for Catalyzing and Product Separation
Yangyang Han, Xiaodong Wu, Xinxing Zhang, Zehang Zhou, and Canhui Lu
ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/
acssuschemeng.6b00889 • Publication Date (Web): 28 Sep 2016
Downloaded from http://pubs.acs.org on October 4, 2016

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Reductant-Free Synthesis of Silver Nanoparticles-
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9 Doped Cellulose Microgels for Catalyzing and
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13 Product Separation
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18 Yangyang Han, Xiaodong Wu, Xinxing Zhang* , Zehang Zhou and Canhui Lu*
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20 State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute of Sichuan
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22 University, No. 24 South Section 1 of First Ring Road, Chengdu 610065, China
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26 Abstract
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29 A novel and straightforward synthetic strategy was developed to prepare silver nanoparticles-doped cellulose
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31 microgels (Ag NPs@CMG) nanohybrids at room temperature. Residual alkali (sodium hydroxide/urea) from
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33 cellulose dissolving system was reused and acted as a functional accelerant, which made it possible for Ag+ to
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35 be reduced to Ag0 by CMG at room temperature, yielding Ag NPs decorated on CMG. The as-prepared Ag
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37 NPs@CMG nanohybrids exhibited excellent catalytic performance in reduction of 4-nitrophenol and organic
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39 dyes. Moreover, the Ag NPs@CMG nanohybrids were capable to form a desirable porous membrane for
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41 catalyzing and simultaneous product separation. Reactants passing through the membrane could be
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43 catalytically transformed to product, which is of great significance for water treatment. As a demonstration,
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45 three kinds of organic dye solutions were successfully decolorized by using Ag NPs@CMG nanohybrids based
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47 membrane. The simplicity, sustainability, and straightforwardness of this approach to prepare high-efficient
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49 catalyst and functional membrane open up new possibilities for large-scale production and application of bio-
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resources/noble metal nanohybrids in various fields.
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55 Corresponding author: Xinxing Zhang and Canhui Lu
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57 *E-mail address: xxzwwh@scu.edu.cn & canhuilu@scu.edu.cn
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Key words: cellulose microgels, silver nanoparticles, residual alkali, catalyzing, product
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6 separation
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9 Introduction
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12 Noble metal-based nanohybrid materials play an important role in physical, chemical and biological
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14 industries due to their unique photonic1, magnetic2, electrochemical3, especially catalytic properties4-5.
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16 Tremendous efforts have been made to efficiently fabricate functional noble metal nanohybrids.6-8 However,
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18 poisonous reducing agents (such as sodium borohydride and hydrazine) are usually employed in the synthesis
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of these noble metal nanohybrids.9-10 On the other hand, extra capping or dispersing agents are generally
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necessary to obtain uniform and stable dispersion of metal nanomaterials. This is against the present trend
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towards sustainable as well as economical development. Therefore, synthesis of noble metal nanohybrids with
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27 lower environmental and economic cost is highly demanded in various fields.
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29 Cellulose is an inexhaustible natural resource which represents the most abundant polysaccharide material
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31 on earth.11 In recent years, several methods have been established for cost-efficient and sustainable synthesis of
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33 noble metal nanohybrids by using cellulose as green reducing agents or supporting matrices.12-17 For example,
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35 Thielemans et al. developed a one-step synthesis of palladium nanoparticles (Pd NPs) supported on cellulose
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37 nanocrystals, which acted as both reducing agent and support material.15 Liu et al. prepared gold (Au)
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39 NPs@bacterial cellulose nanohybrids at 110 °C using amidoxime-grafted bacterial cellulose as a reducing
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41 agent and carrier for the synthesis of Au NPs.16 Besides, Moores et al. reported that cellulose nanocrystals
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43 could perform as support and reductant for the synthesis of silver (Ag) NPs from bulk Ag metal.17 Despite of
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these pioneering works, there are still big challenges for their practical application because of drawbacks such
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48 as low volume output of cellulose nanocrystals, sophisticated surface functionalization procedure, and
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50 particularly high temperatures employed in the reactions. Hence, the development of simple, economical and
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52 large-scale compliant approach to noble metal nanohybrids by utilizing cellulose becomes a fascinating issue.
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54 Cellulose gels prepared by sol-gel method have high porosity, a large surface area, abundant available
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56 functional groups and high mechanical strength,18-19 which make it an attractive candidate as supporting
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3 materials. The recently developed low-cost, low-toxicity and effective alkali aqueous solution system as a
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5 cellulose solvent provides a straightforward way to design and fabricate functional cellulose gels.20
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Unfortunately, the massive residual alkali from the dissolving system has to be removed by time-consuming
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(usually several days) and water-consuming dialysis, which is economically and ecologically infeasible for
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12 practical application. Therefore, rational dispose of the waste alkali is of great significance as far as the call of
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14 the world for energy and sustainability.
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16 In this work, we propose a novel and mild approach to synthesize Ag NPs-doped cellulose microgels (Ag
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18 NPs@CMG) at room temperature by reusing residual alkali as a functional accelerant. The CMG with a unique
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20 microstructure acted as a reducing agent and supporting matrix for non-agglomerated synthesis of Ag NPs.
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22 Notably, residual alkali from the dissolving system dramatically accelerated the reduction of Ag+ by CMG at
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24 room temperature, yielding well dispersed Ag NPs supported on CMG. The resultant flexible and porous Ag
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26 NPs@CMG nanohybrids exhibited high activity in catalytic reduction of 4-nitrophenol (4-NP) and organic
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28 dyes. This excellent catalytic performance of Ag NPs@CMG nanohybrids allowed us to fabricate a porous
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30 membrane for efficient catalyzing and simultaneous product filtration. Because of the cost-efficient and
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32 sustainable characteristics, the present approach is suitable for industrial scale production and application of
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34 bio-resources/noble metal nanohybrids.
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37 Materials and Methods
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39 Materials
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41 Filter paper was purchased from commercial sources and subjected to cutting and shredding processes.
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43 Silver nitrate (AgNO3), 4-nitrophenol (4-NP), sodium borohydride (NaBH4), sodium hydroxide (NaOH), urea,
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45 carboxymethylcellulose sodium, methylene blue (MB), and methyl orange (MO) were purchased from
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47 Chengdu Kelong Chemical Plant (China). Rhodamine 6G (R6G) was purchased from Aladdin Company. All
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reagents were used without further purification.
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52 Fabrication of Ag NPs@CMG nanohybrids
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54 Filter paper cellulose was dried at 80 °C for 12 h to remove the moisture. The aqueous dissolving system
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56 that contained 7 wt% NaOH and 12 wt% urea was pre-cooled to -12 oC in a refrigerator. Then a desired
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3 amount of cellulose (2 wt%, according to the weight of aqueous solution) was added to the pre-cooled
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5 dissolving system and stirred vigorously for 5 min to obtain a transparent solution. Subsequently, 10 g of the
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viscous cellulose solution was dropwise added into 100 mL deionized water with magnetic stirring, forming
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CMG suspension. Without removing the residual NaOH and urea, a desired amount of AgNO3 solution was
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12 added to the CMG suspensions (the final concentrations of Ag+ in CMG suspension were 0.2, 0.5 and 1.0 mM,
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14 respectively), and stirred for 24 h at room temperature (about 25 oC). The resultant product (Ag NPs@CMG)
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16 was filtered and washed with deionized water to remove the residual chemical reagents. The Ag NPs@CMG
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18 nanohybrids were dispersed in deionized water (100 g) and sonicated for 10 min to obtain Ag NPs@CMG
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20 nanohybrids suspension.
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22 Catalytic performance test
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24 In order to evaluate the catalytic activity of the synthesized Ag NPs@CMG nanohybrids, the reduction of 4-
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26 NP by NaBH4 catalyzed with Ag NPs@CMG nanohybrids was employed as the model reaction. In a typical
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experiment, NaBH4 aqueous solution (45 mL, 40 mM) was mixed with 4-NP solution (5 mL, 1.2 mM). As a
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result, the concentration of 4-NP and NaBH4 in the reaction solution was 0.12 and 36 mM, respectively. Then
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33 the Ag NPs@CMG nanohybrids were added into the mixture solution at room temperature (containing 0.014
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35 mg Ag). Subsequently, a certain amount of the mixtures was taken in a sealed quartz cuvette with an optical
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37 path of 1 cm and analyzed via UV-vis spectroscopy at intervals of 2 min.
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39 For catalyzing and simultaneous product filtration, Ag NPs@CMG (25 mL, 0.5 mM, containing 1.35 mg
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41 Ag) was deposited on a filter paper in a glass sand funnel equipped with filter conical flask. 50 mL mixture
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43 solution (0.12 mM 4-NP and 36 mM NaBH4) was added to the vacuum filtration funnel coated with a layer of
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45 Ag NPs@CMG membrane. The collected solution in conical flask was analyzed by UV-vis spectroscopy. In
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47 order to testify the reusability of the Ag NPs@CMG catalyst, the membrane washed with deionized water, and
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49 reused in the next cycle.
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51 Catalytic reduction of dyes
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54 In a typical experiment for catalytic reduction of organic dyes, MB aqueous solution (40 mL, 10 mg/L) was
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56 mixed with fresh NaBH4 aqueous solution (40 mL, 50 mM). The Ag NPs@CMG nanohybrids (1 mL, 0.5 mM,
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58 containing 0.054 mg Ag) as the catalyst were added into the mixture solution at room temperature. In addition,
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3 the catalytic reduction of MO and R6G by NaBH4 in the presence of Ag NPs@CMG nanohybrids was also
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5 explored respectively. NaBH4 aqueous solution (10 mL, 50 mM) was added into MO aqueous solution (40 mL,
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10 mg/L) and subsequently Ag NPs@CMG nanohybrids (0.2 mL, 0.5 mM, containing 0.011 mg Ag) were
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added into the mixed solution. R6G aqueous solution (40 mL, 10 mg/L) was mixed with NaBH4 aqueous
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12 solution (10 mL, 50 mM) and then Ag NPs@CMG nanohybrids (0.5 mL, 0.5 mM, containing 0.027 mg Ag)
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14 were used to catalyze the reduction of the R6G. The catalytic reduction of organic dyes was recorded by
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16 monitoring the maximum absorbance (λmax) of the dyes with UV-vis spectrophotometer.
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18 Characterization
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20 The morphology of the Ag NPs@CMG sample was observed by scanning electron microscope (SEM, JEOL
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22 JSM-5600, Japan) and transmission electron microscope (JEOL JEM-100CX, Japan) equipped with high
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24 resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED). The
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26 particle sizes of Ag NPs@CMG on SEM image and Ag NPs on TEM image were measured using Image-J
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software. At least 100 particles were analyzed. The UV-vis spectra were recorded on a Shimadzu UVmini-
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1240 spectrophotometer (Japan) by using a quartz cuvette with an optical path of 1 cm at room temperature.
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33 Carboxymethylcellulose sodium was used as a stabilizer for samples in the process of UV-vis measurement,
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35 which has no characteristic UV-vis absorption peak as shown in Figure S1. Fourier transform infrared
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37 spectroscopy (FTIR) studies were conducted on a Nicolet 6700 spectrophotometer (USA) and the spectra were
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39 recorded from 4000 to 500 cm-1 at a resolution of 2 cm-1. X-ray diffraction (XRD) patterns were recorded on a
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41 Philips Analytical X'Pert X-diffractometer (Philips Co., Netherlands) with Cu Ka radiation (λ=0.1540 nm) at
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43 an accelerating voltage of 40 kV and a current of 35 mA in the range of 5-80o with a step interval of 0.03o at
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45 room temperature. Samples for XRD and FTIR characterizations were prepared by freeze-drying the CMG and
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47 Ag NPs@CMG nanohybrids followed by oven-drying. The morphology of the Ag NPs@CMG membrane
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49 after filtration was observed by scanning electron microscopy (SEM, JEOL JSM-5900LV, Japan). The sample
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53 Results and discussion
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56 Synthesis of Ag NPs@CMG nanohybrids
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3 In order to better understand the facile approach to Ag NPs@CMG nanohybrids, the entire synthesis process
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5 is schematically illustrated in Figure 1a. Firstly, cellulose was dissolved in a NaOH/urea system and formed a
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homogeneous and transparent solution. CMG was formed via sol-gel transition by dropwise adding cellulose
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solution into water under vigorous magnetic stirring. Then, AgNO3 solution was directly added to the alkali
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12 CMG suspension without removing the residual alkali. In this strong alkali condition, CMG was capable of
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14 reducing Ag+ to Ag0 at room temperature, simultaneously yielding Ag NPs anchored on the CMG supporting
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16 matrix. The reducing process of Ag+ by CMG in strong alkali condition at room temperature can be revealed
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18 by the concomitant change in the color of the reaction mixture. As given in Figure 1b, the color of the reaction
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20 mixture was light yellow at the beginning and gradually changed to dark brown as a function of time. Notably,
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22 the entire process just proceeded at room temperature without any heating and employing any other reducing,
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24 capping or dispersing agents. The economic and ecological benefits of this process, including reuse of residual
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26 alkali and avoiding energy consumption, make it promising for industrial application.
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53 Figure 1. Schematic illustration for the facile synthesis of Ag NPs@CMG nanohybrids (a) and
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55 digital camera photos showing the color changes of CMG-Ag+ (0.5 mM) mixture as a function of
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Characterization of Ag NPs@CMG nanohybrids
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5 UV-vis spectra show that a surface plasmon resonance (SPR) band around 400 nm can be observed for Ag
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NPs@CMG nanohybrids as shown in Figure 2a, confirming the presence of Ag NPs.21 With increasing
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concentration of Ag+, the SPR band of Ag NPs@CMG nanohybrids becomes higher and broader. Besides, the
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12 characteristic band of Ag NPs@CMG nanohybrids shifts from 390 nm to 426 nm. These results indicate that
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14 higher concentration of Ag+ leads to larger Ag NPs with higher dispersity. In addition, the colors of Ag
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16 NPs@CMG suspensions differ from each other with increasing the concentration of Ag+, from yellow (0.2
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18 mM Ag+) to dark brown (1.0 mM Ag+) as shown in Figure 2a (inset photos), indicating more Ag NPs formed
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20 with higher Ag+ concentration.22
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22 In order to investigate the roles of CMG and alkali in synthesis of Ag NPs, contrast experiments were
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24 conducted. When Ag+ was added into the alkali solution (same concentration) in the absence of CMG, no Ag
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26 NPs could be obtained as revealed from the UV-vis spectra (Figure 2b). Similarly, characteristic absorption
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28 band of Ag NPs was not observed in Figure 2b when the residual alkali was removed from CMG suspension.
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30 These results suggest that both CMG and residual alkali play indispensable roles in the synthesis of Ag
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32 NPs@CMG nanohybrids at room temperature.
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52 Figure 2. UV-vis spectra and digital camera photos (inset) of Ag NPs@CMG nanohybrids with
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54 different concentrations: 0.2, 0.5, and 1.0 mM (a). UV-vis spectra of Ag NPs prepared under
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3 XRD patterns (Figure S2a) reveal the crystal structure of CMG and Ag NPs@CMG nanohybrids. For CMG,
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5 the diffraction peaks at 2θ = 12o, 20o and 22o, corresponding to the (11-0), (110), and (200) crystal planes, are
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characteristic peaks of cellulose II crystal.23 In the spectrum of Ag NPs@CMG nanohybrids (0.5 mM), peaks
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at 2θ= 38 o, 64 o and 77 o, assigned to the (111), (220) and (311) lattice planes, can be indexed to the face centre
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12 cubic crystal structure of Ag in accordance with the values in standard card (JCPDS Card No. 4-783),22
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14 indicating that metal Ag was successfully synthesized in Ag NPs@CMG nanohybrids. In order to further
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16 investigate the role of CMG played in the reduction of Ag+, the change in the chemical structure of CMG was
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18 investigated by FTIR. As shown in Figure S2b, original CMG exhibits typical characteristics of cellulose
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20 around 3200-3500 cm−1 (νOH), 2850-3000 cm−1 (νCH), and 1059-1162 cm−1 (νC-O and νC-O-C).24 After the
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22 reducing reaction, a new peak at 1655 cm−1 can be observed, which can be assigned to the C=O stretching.25
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24 This revealed that the abundant hydroxyl groups of CMG were oxidized during the reduction of Ag+, which is
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26 in accordance with our previous works.24-25
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28 Morphology observation of Ag NPs@CMG nanohybrids
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30 The morphology of Ag NPs@CMG nanohybrids was characterized by SEM and shown in Figure 3. The Ag
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32 NPs@CMG nanohybrids display random shapes (Figure 3a) and are highly dispersed with an average size of
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34 2.8 µm according to the distribution histogram (Figure 3b). It is worth noting that the individual Ag
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36 NPs@CMG nanohybrid exhibits a three dimensional porous structure at high magnification as shown in Figure
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3c-d. The 3D porous structure of CMG played as a good scaffold/template for the growth of Ag NPs and could
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obstruct the agglomeration of Ag NPs during synthesis. Compared with cellulose bulk gel, the micro-size and
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43 the porous microstructure of CMG are expected to endow the resultant Ag NPs@CMG nanohybrids with
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45 higher catalytic activity.
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39 Figure 3. SEM image (a, scale bar=100 µm) and particle size distribution (b) of Ag NPs@CMG
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41 nanohybrids. SEM images with high magnifications (c, scale bar=5 µm) (d, scale bar=1 µm) of
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44 Ag NPs@CMG nanohybrids.
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47 To further investigate the microstructure of Ag NPs@CMG nanohybrids, TEM observations combined with
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49 HRTEM and SAED were carried out. As shown in Figure 4a, virtually spherical Ag NPs with desirable
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51 dispersion are anchored on the surface of interconnected network of CMG, and no aggregation of Ag NPs is
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53 observed. The corresponding statistical histogram (Figure 4b) shows that the sizes of the formed Ag NPs are
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55 almost in the range 2.0-16.0 nm, with a mean diameter of 8 nm. These results confirm that aggregation of Ag
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3 to that the oxygen-containing groups (C-O-H, C=O) on CMG can act as anchor points to immobilize Ag NPs
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5 through the complexing or electrostatic interaction26, which played an important role in uniform growth and
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distribution of Ag NPs. In addition, few large Ag NPs can also be observed. Figure 4c and e show a HRTEM
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image of two individual Ag NPs, respectively. Lattice fringes are random arranged in Figure 4c and co-
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12 directionally arranged in Figure 4e, suggesting that both polycrystalline and single crystalline Ag NPs are
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14 existed in Ag NPs@CMG nanohybrids. The lattice fringe spacing in Figure 4e is measured to be 0.235 nm,
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16 corresponding to the (111) plane of the face-centered cubic (fcc) structure of AgNPs.27 Moreover, SAED
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18 pattern recorded from the Ag NPs exhibits spotty diffraction rings in Figure 4d and diffraction spots in Figure
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20 4f, respectively, confirming the coexistence of polycrystalline and single crystalline nature. These results
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22 clearly demonstrate that well dispersed Ag NPs can be synthesized and deposited on CMG using this green
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47 Figure 4. TEM image of the Ag NPs@CMG nanohybrids (0.5 mM) (scale bar, 100 nm) (a) and
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49 particle size distribution of the Ag NPs (b). The HRTEM images (c and e) (scale bar, 5 nm) and
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the SAED patterns (d and f) of individual Ag NPs.
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55 Proposed formation mechanism of Ag NPs@CMG using residual alkali as an accelerant
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3 Based on the aforementioned results, a possible formation mechanism of Ag NPs@CMG nanohybrids using
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5 residual alkali as an accelerant is proposed in Figure 5. Cellulose is a natural polysaccharide which consists of
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β-(1, 4)-linked D-glucose units and contains three hydroxyl groups per anhydroglucose unit. These abundant
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hydroxyl groups could form intra- and intermolecular hydrogen bonding, which traps the hydroxyl groups in a
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12 low-reactivity state and weaken their reactivity. Zhang et al. demonstrated that aqueous NaOH/urea system
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14 could dramatically weaken the hydrogen bonding of cellulose and thus dissolve cellulose.28 In this study, the
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16 residual alkali during regeneration of dissolving cellulose to form CMG was intentionally reserved, aiming at
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18 weakening the hydrogen bonding of cellulose and activating the hydroxyl groups on CMG as illustrated in
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20 Figure 5. Thus, more activated hydroxyl groups could be liberated from the hydrogen bonding in cellulose,
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22 which provide great advantage for the reduction of Ag+.
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25 On the other hand, Ag+ ions are unstable in alkaline conditions and tend to form insoluble Ag2O particles.
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27 When AgNO3 was added into the CMG suspension containing massive residual alkali, Ag2O particles were
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29 formed rapidly and anchored on the interconnected network of CMG, forming Ag2O@CMG nanohybrids.
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31 Importantly, the reduction of Ag2O, which is of a different type from Ag+ species, to Ag metal is much easier
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33 than the reduction of Ag+ to Ag metal, as widely reported in literature.29-31 Consequently, another role of
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35 residual alkali in the reaction was the production of Ag2O@CMG, which created another reaction pathway for
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37 formation of the Ag NPs@CMG in an easier manner. Hence, according to the discussion above, the residual
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39 alkali accelerant not only liberated and activated more hydroxyl groups on CMG, but also promoted the
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formation of Ag2O, which is easier to be reduced by the activated hydroxyl groups on CMG. As a synergistic
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effect of the two aspects mentioned above, mild and straightforward synthesis of Ag NPs@CMG nanohybrid
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46 at room temperature without employing any other reducing, capping or dispersing agents was realized.
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Figure 5. Reaction scheme for the Ag NP@CMG formation.
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33 Catalytic performance of Ag NPs@CMG nanohybrids
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36 As a model catalytic reaction, the reducing reaction of 4-NP by NaBH4 was employed to evaluate the
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38 catalytic activity of the as-prepared Ag NPs@CMG nanohybrids. The process of the catalytic reaction was
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40 monitored by recording the change in characteristic absorption band of 4-NP at 400 nm with the evolution of
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42 reaction time. As shown in Figure 6a, the absorption band of 4-NP at 400 nm gradually decreases,
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44 accompanied with the appearance of a new band around 300 nm, corresponding to 4-aminophenol (4-AP).
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46 These indicate the conversion of 4-NP to 4-AP.32 The conversion rate of 4-NP was depicted by At/A0 at λ=400
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48 nm versus reaction time, where At is the absorbance at reaction time t and A0 is the initial absorbance. In
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Figure 6a (inset), it is noticed that this catalytic reaction proceeded quickly at first, and slowed down as the
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time went on. Figure 6b shows the plot of ln(At/A0) versus reaction time. The results indicate that ln(At/A0)
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55 decreases linearly with reaction time, which is consistent with the pseudo-first-order kinetics behavior. The
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57 pseudo-first-order rate constant k at room temperature calculated from the slope is 3.4 × 10-3 s-1. The catalytic
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3 reactions of 0.2 and 1.0 mM Ag NPs@CMG nanohybrids were shown in Figure S3. Turnover frequency (TOF,
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5 in mol 4-NP mol-1 Ag min-1) was calculated to evaluate the catalytic activity. The TOF value of 0.5 mM Ag
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NPs@CMG nanohybrids is 230.4 h-1 which suggesting that Ag NPs@CMG nanohybrids has an eminent
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catalytic activity comparing with other materials as shown in Table S1. For catalytic reduction of 4-NP,
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12 electron transferred from BH4− to 4-NP through adsorption of the reactant molecules onto the Ag catalyst
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14 surface (Figure 6c). Ag NPs with small sizes and better dispersity result more contact opportunity with
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16 reactants, thus exhibiting high catalytic activity.
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19 To intuitively show the excellent catalytic performance, Ag NPs@CMG nanohybrids were deposited on
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21 glass sand funnel to form an Ag NPs@CMG based catalytic membrane. When the reactants (4-NP and BH4-)
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23 passed through the catalytic membrane under vacuum condition, the highly active Ag NPs@CMG catalyst
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25 could catalyze this reaction (Figure 6f). The change in color from yellow to colorless directly demonstrates the
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27 fast catalytic reaction (Figure 6d). According to the UV-vis spectra in Figure 6g, the conversion rate of 4-NP
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29 was 98% after passing through the membrane. Moreover, the high conversion rate is nearly invariable through
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31 ten cycles (Figure 6h), which exhibits the eminent reusability of this Ag NPs@CMG nanohybrids as a catalyst.
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33 SEM was used to elucidate the microscopic structure of this Ag NPs@CMG catalytic membrane. As given in
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35 Figure 6e, this catalytic membrane consisting of the Ag NP@CMG nanohybrid possesses a porous
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nanostructure. This unique porous nanostructure could extend the pathways of the reactants passing through
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the membrane, which increased the contact opportunity of reactants and catalyst and contributed to a high
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42 conversion rate. Additionally, CMG acts as a good template which can anchor the Ag NPs firmly, avoiding
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44 their exfoliation during the cyclic catalytic process. This sustainable catalytic membrane with outstanding
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46 catalytic performance might have a great potential for industrial applications.
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37 Figure 6. Time dependent UV-vis spectra for reduction of 4-NP catalyzed with 0.5 mM Ag
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39 NPs@CMG nanohybrids (containing 0.125 µmol Ag): plot of At/Ao against time (inset) (a), plot
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41 of ln(At/Ao) against time (b). Schematic diagram for the catalytic reaction (c). Digital photograph
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44 (d) and schematic illustration (f) showing the fast reduction of 4-NP catalyzed by Ag
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46 NPs@CMG catalytic membrane. SEM micrograph of Ag NPs@CMG catalytic membrane after
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filtration (e). UV-vis spectra for 4-NP solution before and after passing through the catalytic
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51 membrane (g). The conversion rate of 4-NP during cyclic test (h).
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54 Catalytic performance of Ag NPs@CMG in dye reductive decolorization
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3 Organic dyes have wide applications in industries such as printing, textile, paper, paints, and plastics.33 The
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5 hazardous effects of organic dyes in waste water have become a serious environmental issue and received
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significant attention.34-36 In this study, we demonstrated the capabilities of Ag NPs@CMG nanohybrids in
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catalytic reduction of organic pollutant dyes (including MB, MO, and R6G). After the addition of Ag
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12 NPs@CMG nanohybrids into the system, the color of the mixture gradually vanished and finally bleached,
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14 revealing the catalytic reduction of the dyes. Figure 7a shows the time-dependent UV-vis absorption of MB
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16 during the reduction process. The characteristic absorption band of MB declines gradually and nearly
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18 disappears eventually after 8 min, indicating that the reduction of MB proceed completely. MO and R6G also
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20 experienced similar bleaching processes (Figure 7b-c). While, the decolorization completed at 7 and 11 min for
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22 MO and R6G respectively. These suggest that Ag NPs@CMG nanohybrids have prominent catalytic ability for
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24 dye reductive decolorization. The fast reductive decolorization of dyes could be attributed to the high catalytic
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26 activity of Ag NPs anchored on micro-sized and porous cellulose gels, which own good dispersity and large
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28 specific surface area.
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31 Aforementioned Ag NPs@CMG based catalytic membrane is also suitable for catalyzing the reduction of
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33 organic dyes. As shown in Video 1, the decolorization of R6G was achieved during reactants passing through
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35 the membrane. The solution in conical flask was analyzed by UV-vis spectroscopy (Figure 7d). The
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37 characteristic absorption band of R6G nearly vanished after passing through the membrane, indicating the
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39 complete decolorization of R6G.
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42 For comparison, bulk cellulose gel supported Ag NPs (Ag NPs@bulk gel) was prepared (see Supporting
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44 Information for method) and the catalytic performance was also evaluated. Ag NPs@bulk gel was used as a
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46 platform for the catalytic reduction of R6G and the process was recorded in Video 2. The red color of original
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48 solution faded after passing through the gel, while light red color could still be seen. As shown in Figure 7d,
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50 the characteristic band of R6G catalyzed by Ag NPs@bulk gel still remained partly, which suggests that the
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52 reduction of R6G was incomplete. The section of Ag NPs@bulk gel was observed by optical microscope
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54 (Figure S4). Ag NPs mostly concentrated in the surface layer of the gel. Although both CMG and bulk gel
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5 application as a membrane for fast catalyzing and product separation.
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8 As another contrast experiment, we prepared cellulose nanocrystals-supported Ag NPs nanohybrid to form a
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10 similar catalytic membrane. Unfortunately, the glass sand funnel was blocked off by the nano-sized cellulose
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12 nanocrystals-supported Ag NPs nanohybrid. This indicates that Ag NPs@CMG nanohybrid is a specialized
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14 material capable of forming porous membrane on traditional glass sand funnel and exhibiting high catalytic
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16 activity. The well dispersed Ag NPs doped CMG could have potential application in membrane catalyzing and
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18 product separation.
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34 Figure 7. Time dependent UV-vis spectra and digital camera photos (inset) for reduction of MB
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36 (a), MO (b) and R6G (c) catalyzed by Ag NPs@CMG nanohybrids and plot of At/Ao against
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time (inset). UV-vis spectra for reduction R6G (d) and digital photographs (inset) showing the
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41 reduction of R6G catalyzed by Ag NPs@bulk gel (left) and Ag NPs@CMG (right).
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44 Apart from the desirable features in catalysis field, Ag NPs@CMG nanohybrids possess the versatility to
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46 form aerogel and film. As shown in Figure S5a, a porous and low-density (0.062 g/cm3) Ag NPs@CMG
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48 aerogel can be obtained by freeze drying, which is attributed to the distinctive porous structure of CMG. Under
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50 air-drying, Ag NPs@CMG nanohybrids formed flexile solid film (Figure S5b). Due to unique properties of Ag
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52 NPs (such as antibacterial activity, surface plasmon resonance and electrical conductivity) as well as the
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54 sustainability and environmental friendliness of CMG, the facile and mild approach to Ag NPs@CMG might
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56 provide an optional method to manufacture functional aerogels and films.
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Conclusions
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6 In this work, novel Ag NPs@CMG nanohybrids with high catalytic activity and product separation
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8 functionality were successfully prepared at room temperature by reusing residual alkali as a functional
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10 accelerant. Specifically, Ag NPs with mean size of 8 nm were synthesized by using regenerated CMG as a
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12 reducer as well as a supporting matrix. Meanwhile, residual alkali from the dissolving system acted as a
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14 functional accelerant, and signally promoted the reduction of Ag+ by CMG. This synthesized Ag NPs@CMG
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16 nanohybrids exhibited eminent activity in catalyzing the reduction of 4-NP and organic dyes. Moreover, a
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18 catalytic membrane based on Ag NPs@CMG was fabricated, which could continuously catalyze these
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20 reductive reactions and separate the product. This mild and straightforward synthetic approach to Ag
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22 NPs@CMG by reusing residual alkali as functional accelerant provided a new economical and sustainable
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24 strategy to design and synthesize various noble metal based nanohybrid materials.
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Author information
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30 Corresponding author: Xinxing Zhang and Canhui Lu
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33
*E-mail address: xxzwwh@scu.edu.cn & canhuilu@scu.edu.cn
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Tel: +86-28-85460607 Fax: +86-28-85402465
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Acknowledgements
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42 The authors thank the National Natural Science Foundation of China (51673121 and 51433006) and
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44 Outstanding Young Scholars Fund of Sichuan University (2016SCU04A16) for financial support.
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47 Supporting Information
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49 UV-vis spectrum of carboxymethylcellulose sodium. XRD patterns and FTIR spectra of CMG and Ag
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51 NPs@CMG nanohybrids. UV-visible spectra of the reduction of 4-NP catalyzed with 0.2 and 1.0 mM Ag
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53 NPs@CMG nanohybrids. Table of comparison of various catalysts for reduction of 4-NP. Optical microscope
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55 photographs of the section of Ag NPs@bulk gel. Digital photographs of Ag NPs@CMG aerogel and film.
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3 Video 1: the reduction of R6G catalyzed by Ag NPs@CMG. Video 2: the reduction of R6G catalyzed by Ag
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5 NPs@bulk gel. These materials are available free of charge via the Internet at http://pubs.acs.org.
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Reductant-Free Synthesis of Silver Nanoparticles-
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12 Doped Cellulose Microgels for Catalyzing and
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Product Separation
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Yangyang Han, Xiaodong Wu, Xinxing Zhang*, Zehang Zhou and Canhui Lu*
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41 Ag nanoparticles supported by cellulose microgels under vacuum filtration for the rapid catalyzing in reduction
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28 Schematic illustration for the facile synthesis of Ag NPs@CMG nanohybrids (a) and digital camera photos
29 showing the color changes of CMG-Ag+ (0.5 mM) mixture as a function of time (b).
30 Figure 1
31 152x96mm (300 x 300 DPI)
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22 UV-vis spectra and digital camera photos (inset) of Ag NPs@CMG nanohybrids with different concentrations:
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38 SEM image (a, scale bar=100 µm) and particle size distribution (b) of Ag NPs@CMG nanohybrids. SEM
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29 Reaction scheme for the Ag NP@CMG formation.
30 Figure 5
31 98x63mm (300 x 300 DPI)
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35 Time dependent UV-vis spectra for reduction of 4-NP catalyzed with 0.5 mM Ag NPs@CMG nanohybrids
36 (containing 0.125 µmol Ag): plot of At/Ao against time (inset) (a), plot of ln(At/Ao) against time (b).
37 Schematic diagram for the catalytic reaction (c). Digital photograph (d) and schematic illustration (f)
showing the fast reduction of 4-NP catalyzed by Ag NPs@CMG catalytic membrane. SEM micrograph of Ag
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NPs@CMG catalytic membrane after filtration (e). UV-vis spectra for 4-NP solution before and after passing
39 through the catalytic membrane (g). The conversion rate of 4-NP during cyclic test (h).
40 Figure 6
41 131x110mm (300 x 300 DPI)
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33 Time dependent UV-vis spectra and digital camera photos (inset) for reduction of MB (a), MO (b) and R6G
34 (c) catalyzed by Ag NPs@CMG nanohybrids and plot of At/Ao against time (inset). UV-vis spectra for
35 reduction R6G (d) and digital photographs (inset) showing the reduction of R6G catalyzed by Ag NPs@bulk
36 gel (left) and Ag NPs@CMG (right).
Figure 7
37 118x91mm (300 x 300 DPI)
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32 Ag nanoparticles supported by cellulose microgels under vacuum filtration for the rapid catalyzing in
33 reduction of 4-nitrophenol to 4-aminophenol by sodium borohydride
34 For Table of Contents Only
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