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pH responsive intelligent nano-engineer of nanostructures applicable for discoloration of reactive dyes
Journal of Colloid and Interface Science 561 (2020) 147–161
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pH responsive intelligent nano-engineer of nanostructures applicable for discoloration of reactive dyes Hanan B. Ahmed a,⇑, Mary M. Mikhail a, Samya El-Sherbiny a, Khaled S. Nagy b, Hossam E. Emam c,⇑ a
Chemistry Department, Faculty of Science, Helwan University, Ain-Helwan, Cairo 11795, Egypt Food Engineering and Packaging Department, Agricultural Research Center, 9 Cairo University St., Giza, Egypt c Department of Pretreatment and Finishing of Cellulosic based Textiles, Textile Industries Research Division, National Research Centre, Scopus affiliationID 60014618, 33 EL Buhouth St., Dokki, Giza 12622, Egypt b
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
Investigation of pH response for
Lignin as intelligent nano-engineer under different temperatures. 1 g/L lignin is sufficient for synthesis of size and shape regulated AgNPs, AuNPs & PdNPs. Acidic reaction condition is advisable for synthesis of small sized AgNPs (13.8 nm) & AuNPs (5.7 nm). Basic reaction condition is recommended for generation of size regulated PdNPs (4.5 nm). The half time of reactive dye degradation is 21.87, 18.34 and 1.45 min at using AgNPs, AuNPs and PdNPs, respectively.
a r t i c l e
i n f o
Article history: Received 23 September 2019 Revised 10 November 2019 Accepted 15 November 2019 Available online 29 November 2019 Keywords: pH response Intelligent nano-engineer Nano-catalysts Reductive discoloration Reactive yellow dye
a b s t r a c t Multifunctional polymers were commonly ascribed as intelligent materials due to the presence of different functional groups on the polymeric skeleton which causes the high sensitivity to the interchanging of physicochemical conditions. Herein, under different temperatures, monitoring the pH response of lignin as intelligent nano-engineer (reducer and stabilizer) for synthesis of size and shape regulated silver nanoparticles (AgNPs), gold nanoparticles (AuNPs) & palladium nanoparticles (PdNPs) is systematically studied. The regulation of the particle size and stability of NPs were remarkably affected by acidity and basicity of the reaction medium at which they were prepared. TEM and zetasizer data showed that, highly size and shape regulated AgNPs & AuNPs is successively produced under acidic conditions with particle size of 13.8 and 5.7 nm, respectively. While basic conditions is more advisable in case of PdNPs to be produced with particle size of 4.5 nm. Catalytic performance of biphasic NPs in reductive discoloration of azo dye (reactive yellow dye 145) was followed the order of PdNPs > AuNPs > AgNPs. The half time for discoloration of dye with basic prepared NPs was dramatically decreased from 21.87 min for AgNPs and 18.34 for AuNPs to 1.45 min for PdNPs. Ó 2019 Elsevier Inc. All rights reserved.
⇑ Corresponding authors. E-mail addresses: [email protected] (H.B. Ahmed), [email protected] (H.E. Emam). https://doi.org/10.1016/j.jcis.2019.11.060 0021-9797/Ó 2019 Elsevier Inc. All rights reserved.
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1. Introduction Engineering of highly regulated sized and shaped nanoparticles with good stability is interestingly studied due to their special chemical, physical and biological properties [1,2]. Numerous noteworthy reports concerned in preparation of multifunctional nanostructures to be independently employed in sensing, photo-thermal conversion [3], simultaneous detection and imaging [4], and targeted chemo-photo-thermal treatments [5]. Due to biological or environmental-related requirements, there is an increasing demand on preparation NPs with nontoxic chemicals, and solvents [6–9]. Exploitation the superiority of natural polymers for as green nano-synthesizers was widely studied for engineering of NPs with diverse applications [10–17]. Lignin, a one of the natural polymer, is well-known as the second-most abundant natural polymer and the main by-product of the paper industry [18]. In recent reports, researchers interestingly have observed that the reducing groups and 3D spatial structure of lignin realize the possibility for exploiting lignin in green preparation of different nanostructures [19–21]. In spite of lignin is ascribed to exhibit chemically heterogeneous and complex structure, but it is advantageous with various powerful functional groups, i.e., reductive aliphatic hydroxyls and phenolic hydroxyls. On the other hand, the presence of different functional groups along the polymeric chain, often causes high sensitivity to various conditions of surrounding environment, such as temperature [22,23], pH [24–26], ionic strength [27] and magnetic field [28], which makes polymeric materials with diverse functional groups to be ascribed as intelligent materials. Nano-catalysts based on MNPs have reported to be characterized with superior advantage of combining both of the capability of homogeneous and heterogeneous catalytic systems. It could be clarified as follows; (i) nano-catalytic system promotes the fast, selective chemical transformations with formidable product yield in addition to the possibility of catalyst separation and recovery, (ii) the nano sized particles with high surface area significantly increased the contact with reacting materials, where, this phenomenon is similar to homogeneous catalysts, and, (iii) due to the insolubility of zero-valence nanoparticles in the reaction sol-
vent, this makes the nano-catalyst to be similar to heterogeneous catalysts and hence could be easily separated out from the reaction mixture [29–33]. In the current work, the co-authors have demonstrated a new study for monitoring the pH response of lignin as intelligent nano-engineer (reducer and stabilizer) under different temperatures for synthesis of size and shape controlled silver (AgNPs), gold (AuNPs) and palladium (PdNPs) nanoparticles. Lignin is ascribed to serve as multi-functional binding, complexion and reducing agents for metal cations as well as stabilizing agent for the so-engineered AgNPs, AuNPs and PdNPs. Different instrumental analyses like UVVisible spectrophotometer, transmission electron microscope (TEM), Zetasizer, BET and X-ray diffraction (XRD) were carried out in order to approve the successive engineering of required nanoparticles. Spectral data of infrared (FTIR) were also presented to confirm the predicted mechanism of redox reaction between lignin macromolecules and metals precursors. Monitoring the catalytic performance of the synthesized NPs in discoloration of reactive yellow dye 145 was lastly organized and interpreted. 2. Expermental 2.1. Materials and Chemicals: All the chemicals of silver nitrate (AgNO3, 99.5%, from Panreac, Barcelona – Spain), Gold chloride (AuCl3, 99%,from Sigma-Aldrich – USA), Palladium chloride (PdCl2, 99%, from Sigma-Aldrich – USA), Sodium hydroxide (99%, from Merck, Darmstadt–Germany), lignin (C31H34O11)n, El-Nasser Company for Pharmaceuticals and Chemicals, Egypt), reactive yellow dye 145 (C28H20ClN9Na4O16S5, from Merck, Darmstadt–Germany) and Sodium borohydride (NaBH4, 96%, from Sigma-Aldrich – USA), were used without any further purification. 2.2. Synthesis of NPs: The experimental work for synthesis of AgNPs, AuNPs & PdNPs using lignin as nano-engineer (reducer and stabilizer) is detailed in Table 1. It could be briefly illustrated as follows; to 1 g/L of lignin
Table 1 Description of the prepared nanosilver samples. Sample
Medium
Temp (C)
Time (min.)
Ag1 Ag2 Ag3 Ag4 Ag5 Ag6 Ag7 Ag8 Ag9 Ag10 Ag11 Ag12 Ag13 Ag14 Ag15 Ag16 Ag17 Ag18 Ag19 Ag20 Ag21 Ag22 Ag23 Ag24
Acidic Acidic Acidic Acidic Basic Basic Basic Basic Acidic Acidic Acidic Acidic Basic Basic Basic Basic Acidic Acidic Acidic Acidic Basic Basic Basic Basic
30 30 30 30 30 30 30 30 60 60 60 60 60 60 60 60 90 90 90 90 90 90 90 90
5 15 30 60 5 15 30 60 5 15 30 60 5 15 30 60 5 15 30 60 5 15 30 60
Lignin: 1 g/L.
Surface area (m2/g)
Particle size (nm)
PdI
21.6 ± 4.2
0.40 ± 0.11
25.2 ± 3.5
0.25 ± 0.09
13.8 ± 3.1
0.47 ± 0.10
31.9 ± 5.6
0.20 ± 0.08
15.5 ± 2.4 15.1 ± 3.0
0.29 ± 0.07 0.25 ± 0.10
23.16 ± 2.71
26.6 ± 5.2 33.7 ± 4.8
0.27 ± 0.02 0.21 ± 0.03
12.19 ± 1.62
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Fig. 1. Time dependent absorption spectra for the prepared nanosilver by 1 g/L lignin; [a] in acidic medium at 60 °C (Ag9-Ag12), [b] in acidic medium after 30 min (Ag3, Ag11, Ag19) [c] in basic medium at 60 °C (Ag13-Ag16) and [d] in basic medium after 30 min (Ag7, Ag15, Ag23).
Fig. 2. Time dependent absorption spectra for the prepared nanogold by 1 g/L lignin; [a] in acidic medium at 60 °C (Au9-Au12), [b] in acidic medium after 30 min (Au3, Au11, Au19) [c] in basic medium at 60 °C (Au13-Au16) and [d] in basic medium after 30 min (Au7, Au15, Au23).
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solution, metal salt solution (silver, gold, palladium) was added drop-wisely under continuous stirring at acidic (pH 2–4) and/or basic (pH 11) conditions and certain temperatures (30, 60 & 90 °C), considering that the weight ratio between metal salts and lignin was 1:10. Certain volume of the reaction liquor was withdrawn from time to time to follow up the progress the reaction of NPs generation under UV–Visible absorption spectroscopy. The solid form of nanocomposites were obtained by transferring the prepared NPs colloidal solutions to petri-dish, for drying at 100 °C overnight. The obtained solids were used for X-ray diffraction and fourier transformation infrared spectroscopy.
2.3. Instrumental analyses and measurements: The colloidal solutions of the prepared NPs were manifested by an intense absorption peak of the Surface Plasmon Resonance (SPR), which is detected under UV-Visible absorption spectroscopy for first affirmation of engineering the required NPs. The UVVisible absorption spectra of nanocolloids were detected in the wavelength range of 250–750 nm using a multichannel spectrophotometer (Jasco V-360 UV/VIS, d = 10 mm, Japan). Geometrical features and particle size of the engineered NPs were presented by anticipating of a JEOL-JEM-1230 (HighResolution Transmission Electron Microscope, HRTEM from Japan) with an electron beam from Oxford instruments. Nanocolloids were drop wisely added to 400 copper grid coated by carbon film, and then evaporated in air at room temperature before detected by the microscope. The diameter and particle size of NPs were measured by 4 pi analysis software using TEM photos. The average diameter of NPs was evaluated for at least 50 particles. The size distribution and poly-dispersity index of the engineered NPs were measured by Zetasizer analyzer (Malvern Zeta-
sizer Nano ZS, from Malvern Instruments Ltd – UK). The instrument was attached with a He-Ne laser lamp (0.4 mW) at wavelength of 633 nm. Measurements were carried out at 25 °C in insulated chamber using dynamic light scattering technique. Both of native lignin and nanocomposites were measured under X-ray diffraction using X’Pert PRO PANalytical diffractometer, at room temperature. Diffraction patterns were detected in the diffraction angle (2h) range of 5–80° using monochromatized (CuKa X-radiation at 40 kV, 50 mA and k = 1.5406 Å) with a step size of 0.03° and scanning rate of 1 s. Infrared spectral data were also represented for native lignin and nanocomposites using infrared Spectrometer (Jasco FT/IR 6100, from Japan) conducted to detector of deuteratedtriglycine sulfate (TGS). The spectra were recorded in range of 4000– 500 cm 1 using transmission mode (T%), resolution of 4 cm 1 with 2 cm 1 interval scanning and scanning speed of 2 mm/sec. The surface area (BET) of the engineered NPs (AgNPs, AuNPs & PdNPs) was detected by NOVA touch 4 LX Quanta chrome version 1.21. Firstly, samples were degassed under vacuum at 100 ◦C and then the adsorption of nitrogen gas was performed at 77 K.
2.3.1. Reductive discoloration of reactive yellow dye 145 The catalytic performance of the engineered AgNPs, AuNPs and PdNPs was monitored for the discoloration of reactive yellow dye 145. The discoloration of reactive yellow dye 145 by NaBH4 in presence of NPs (NPs) as a catalyst was performed as follows: to a vial containing 8 mL of dye (50 mg/L dye), 1 mL of NPs and1 mL of NaBH4 (150 mM) were added, respectively. Blank sample without NPs was used as a blank sample. After the immediate addition of borohydride, the catalytic discoloration was followed up by detection of the absorbance at wavelength range of 200–800 nm
Fig. 3. Time dependent absorption spectra for the prepared nanopalladium by 1 g/L lignin; [a] in acidic medium at 60 °C (Pd9-Pd12), [b] in acidic medium after 30 min (Pd3, Pd11, Pd19) [c] in basic medium at 60 °C (Pd13-Pd16) and [d] in basic medium after 30 min (Pd7, Pd15, Pd23).
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using a spectrophotometer (Cary 5000 UV-Vis-NIR Systems,version 1.12 from Agilent), at a given time intervals up to 60 min.
the reductive discoloration of reactive yellow dye 145 for waste water treatment.
3. Results and disscusion
3.1. UV–Visible spectroscopic data
The physicochemical conditions of the reaction medium such like, pH, ionic strength and metal concentrations are principally affected on the MNPs stability, size and geometrical shape [22– 27]. Lignin ascribed as intelligent material, is a multifunctional polymer which is very sensitive to the interchanging in physicochemical conditions. Hence, the current study purposed on investigating the pH sensitivity of lignin as intelligent nano-engineer (reducer and stabilizer) for production of size and shape regulated AgNPs, AuNPs & PdNPs under different temperatures. Moreover, the catalytic performance of the prepared NPs was monitored in
Following up UV–Visible spectroscopic data for the prepared samples gives an initial confirmation of the stable ingraining of the required NPs, where, color tuning of the reaction liquor is mainly correlated to the excitation of Surface Plasmon Resonance (SPR) exhibited by the existed AgNPs, AuNPs & PdNPs [15–17]. This section represents the UV–Visible spectral mapping data (Figs. 1– 3) monitored for all of the prepared samples to show premier information for pH response of lignin as intelligent nanoengineer under different temperatures for regulation of size and shape controlled NPs.
Fig. 4. HRTEM micrographs for the prepared nanoparticles at two different magnifications; [a] AgNPs (Ag11), [b] AuNPs (Au11) and [c] PdNPs (Pd11). Histogram figure is presented for the corresponding microimages.
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Fig. 4 (continued)
Compared to the spectral data of native lignin and metal salts (see supplementary data, Fig. S1), Figs. 1–3 showed the spectral data for AgNPs, AuNPs & PdNPs colloids prepared using lignin (1 g/L) under acidic and basic conditions at different temperatures. Under acidic conditions the characteristic SPR band of AgNPs at 425 nm is significantly appeared at 60 °C (Fig. 1). The low temperature (30 °C) is resulted in decrement in the intensity of SPR band while raising reaction temperature to 90 °C is accompanied by disappearing of SPR band. Prolonging the reaction duration more than 30 min is not significantly affected on the SPR band. Under alkaline medium, the SPR band of AgNPs is not affected by the experimental conditions of time and temperature. There is non-sensible detection of AuNPs even under basic and acidic conditions at different temperatures with time (Fig. 2). The SPR band of PdNPs at 285 nm is significantly observed under both of basic and acidic conditions (Fig. 3). Elevation of reaction temperature resulted in increment of band intensity of PdNPs in acidic conditions, while not affected in basic conditions. Prolonging of the reaction duration is insignificantly affected on the PdNPs band. These data are explained by the sufficient activation of lignin macromolecules in basic conditions at lower temperature and shorter time. While in acidic medium, the activation of lignin needs high temperature and/or quite longer time. 3.2. TEM micrographs and zetasizer data For representing the topographical features and geometrical shapes of the prepared MNPs and according to UV–Visible data, some of samples were selected (Ag11, Au11, Pd11) to be detected under HRTEM and the micrographs were plotted in Fig. 4. Under acidic conditions, lignin is successfully acted as a compatible nano-synthesizer for production of spherical/size controlled NPs. Well distributed AgNPs, AuNPs and PdNPs are seen in the micro-images with size of 12.5 nm, 10.9 nm and 14.4 nm, respectively. The pH response for both of lignin and metal precursors and its reflected effect on the particle size of NPs is also detected via zetasizer analyzer for more approval (Fig. 5 and Table 1). Under acidic conditions, AgNPs & AuNPs are exhibited by smaller size (Ag11,
13.1 nm & Au11, 8.1 nm) rather than under basic conditions (Ag15, 31.9 nm & Au15, 17.1 nm). In contrast to PdNPs which are detected with smaller size under basic conditions (Pd15, 8.8 nm) compared to that prepared under acidic conditions (Pd11, 52.4 nm). Under acidic conditions, elevation of reaction temperature (Ag3, Ag11, Ag19) is not observably affected on the particle size in case of AgNPs (13.8 – 21.6 nm). While in case of AuNPs & PdNPs, the particle size is significantly diminished by raising reaction temperature (Au, decreased from 79.4 nm to 5.7 nm & Pd, decreased from 52.4 nm to 13.2 nm). Comparing between the particle size detected via HRTEM and zetasizer for Ag11, Au11&Pd11 to could be observed that, in case of silver and gold NPs there no sensible difference in the particle size detected via the two different techniques, while in case of palladium NPs there was a significant difference as the particle size which was higher enlarged in zetasizer data rather than that of HRTEM, which could be interpreted due to the non-spherical shape of PdNPs [13]. Under basic conditions, raising temperature more than 60 ⁰C is not significantly tuned the particle size in case of AgNPs (25.2 – 31.9 nm), while in case of AuNPs the particle size is increased (from 9.9 nm to 22.1 nm). For PdNPs, elevation of temperature resulted in shrinkage and more regulation of particle size (27.9 nm at 30 °C & 8.9 nm at 90 °C). Additionally, the prolongation of reaction duration is not significantly affected on the regulation of particle size for all of the prepared NPs. Regulated nucleation and well dispersion of the produced NPs can be approved through the detected value of polydispersity index (PdI) from zetasizer analyzer [10,34]. The synthesized nanocolloids are shown to exhibit well-regulated shape and size as all the samples were detected with values of PdI ranged in 0.23–0.61 (Table 1). From the afore-mentioned data could be depicted that, by using only small concentration of lignin (1 g/L), highly controllable size growth of AgNPs & AuNPs is proceeded under acidic conditions, in contrary to PdNPs which is performed under basic conditions. Especially in case of PdNPs, elevation of reaction temperature resulted in enhanced dissolution of lignin macromolecules to smaller and more reducible fragments to play the main role of reducing and stabilizing of NPs.
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Fig. 5. Size distribution of the prepared nanoparticles from zetasizer analyzer; [a] AgNPs in acidic medium after 30 min (Ag3, Ag11, Ag19), [b] AgNPs in basic medium after 30 min (Ag7, Ag15, Ag23), [c] AuNPs in acidic medium after 30 min (Au3, Au11, Au19), [d] AuNPs in basic medium after 30 min (Au7, Au15, Au23), [e] PdNPs in acidic medium after 30 min (Pd3, Pd11, Pd19) and [f] PdNPs in basic medium after 30 min (Pd7, Pd15, Pd23).
The effect of pH sensitivity for nano-synthesizers on the surface area of the as prepared NPs is evaluated via detection of BET for the adsorption of N2 gas. According to literature, the surface area is basically affected by the particle size, where, the smaller is the particle size; the larger is the surface area of NPs, which is in accordance with the presented data (Table 1). In case of AgNPs, under acidic conditions the particles exhibited by smaller particle size (15.5 nm) with higher surface area (23.16 m2/g) compared to that prepared under basic conditions (12.19 m2/g). In case of AuNPs, the nanoparticles were detected with smaller particle size accompanied with higher surface area of 11.06 m2/g in acidic conditions compared to that synthesized under basic conditions (surface area 6.05 m2/g). For PdNPs, in acidic medium the particles had larger
size of 13.2 nm with diminished surface area (10.27 m2/g) compared to PdNPs produced under basic conditions (surface area 34.89 m2/g). 3.3. XRD patterns Lignin, NPs-lignin composites which were prepared under acidic (Ag19, Au19 & Pd19) and basic conditions (Ag23, Au23 & Pd23) were characterized by XRD patterns and the data are figured out in Fig. 6. The pristine lignin was detected with certain intense diffraction bands at 2h = 24.6°, observable for the crystalline structure of lignin. However, in case of all NPs-lignin composites and regardless to the pH sensitivity of lignin and metal precursors,
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Fig. 6. X-ray diffraction for the prepared nanoparticles; [a] prepared in acidic medium (Ag19, Au19, Pd19) and [b] prepared in basic medium (Ag23, Au23, Pd23).
the crystalline structure of lignin was dramatically affected and the characteristic lignin diffraction bands were completely disappeared, attributing to the exploitation of lignin macromolecules in production and stabilization of NPs. New intense diffraction peaks were detected at 2h = 38.5° and 38.7° for AgNPs@lignin and AuNPs@lignin, respectively. In accordance with diffraction data of international center, these diffractions are cited to be typical for (1 1 1) and (1 1 1) of face centered crystalline (FCC) structures for silver and gold (JCPDS data number 04–0783 card and 4–0784 card) [15,17,35–38]. In case of PdNPs@lignin, five diffraction bands are detected at 2h = 31.7°, 40.2°, 45.5°, 47.7° and 68.1°. The diffraction peak at 45.5° is belonging to (2 0 0) of face centered crystalline (FCC) structures for Pd (JCPDS data number 89–4897 card) [16,37–39]. There were no difference in diffraction of NPs prepared in acidic and basic conditions. Under basic conditions, the diffraction patterns of NPs were observable with
more intense reflecting their high crystalline structure. The represented data were further approved the above-mentioned data of absorbance spectra, zetasizer and TEM micrographs for successful interaction between metal ions and reducible end groups of lignin macromolecules.
3.4. ATR-FTIR data More confirmation of pH response and compatibility of lignin as nano-synthesizer (reducer and stabilizer) for production of highly size and shape controlled of AgNPs, AuNPs & PdNPs, and for giving more confirmation about the redox reaction between metal ions and lignin molecular back bone, the data of the attenuated total reflection – Fourier transformation infrared spectroscopy (ATRFTIR) were represented.
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Fig. 7. FTIR spectra for the prepared nanoparticles; [a] prepared in acidic medium (Ag19, Au19, Pd19) and [b] prepared in basic medium (Ag23, Au23, Pd23).
From Fig. 7a&b for selected samples prepared under acidic (7a) and basic (7b) conditions, it could be plausible that; native lignin macromolecule is exhibited by a broad peak of OAH bond stretching is detected at 3331 cm 1, while the shortened peak at 2922 cm 1 is referred to ACH group stretching. The CH2 group bending is detected at 1578 cm 1 and the bending of OH at 1034 cm 1. From the represented spectra for NPs prepared under acidic conditions (7a), it could be significantly observed that, a significant tuning in the characteristic bands of lignin was noted after its exploitation in the synthesis of MNPs. In case of nano-colloids,
band seen at 3331 cm 1 characterized for OH stretching is significantly broadened, and another significant new bands are detected for NPs at 1687–1363 cm 1, which is corresponding to carbonyl group (C@O of aldehyde and/or ketone units) [15,17,39,40]. While in basic conditions (7b), all the bands occurred in acidic conditions were typically detected for sample prepared under basic conditions in addition to two new bands at 1406 cm 1 which is characteristic for CAH bending of aldehyde and at 874 cm 1 for O-M (where M is referred to metal) owing to more accessibility and reducibility of lignin polymer under the alkaline conditions [15–17,39,41,42].
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Fig. 8. Spectral analysis for time dependent degradation of reactive yellow 145 dye; [a] without nanoparticles, [b] AgNPs-acidic (Ag19), [c] AgNPs-basic (Ag23), [d] AuNPsacidic (Au19), [e] AuNPs-basic (Au23), [f] PdNPs-acidic (Pd19), and [g] PdNPs-basic (Pd23). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
3.5. The catalytic activity of the as-synthesized NPs in discoloration of dyes Numerous types of synthetic colorants are widely applicable as dyes for coloration and fashionable decoration of textiles
and garments, as it was reported that, 10% of dyes are excluded to the aqueous bodies from textile factories. Additionally, some of dyes are well known as toxic contaminates in water and also act as a carcinogenic and mutagenic compounds in marine organisms and humans [43], and it might
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H.B. Ahmed et al. / Journal of Colloid and Interface Science 561 (2020) 147–161 Table 2 Description of the prepared nanogold samples. Sample Medium Temp (C) Time Particle (min.) size (nm) Au1 Au2 Au3 Au4 Au5 Au6 Au7 Au8 Au9 Au10 Au11 Au12 Au13 Au14 Au15 Au16 Au17 Au18 Au19 Au20 Au21 Au22 Au23 Au24
Acidic Acidic Acidic Acidic Basic Basic Basic Basic Acidic Acidic Acidic Acidic Basic Basic Basic Basic Acidic Acidic Acidic Acidic Basic Basic Basic Basic
30 RT 30 30 30 30 30 30 60 60 60 60 60 60 60 60 90 90 90 90 90 90 90 90
5 15 30 60 5 15 30 60 5 15 30 60 5 15 30 60 5 15 30 60 5 15 30 60
PdI
Surface area (m2/g)
79.4 ± 12.3 0.29 ± 0.04
9.9 ± 3.1
0.49 ± 0.12
8.1 ± 2.5
0.36 ± 0.10
17.1 ± 2.9
0.51 ± 0.12
5.7 ± 1.6 6.0 ± 1.2
0.61 ± 0.17 11.06 ± 1.20 0.50 ± 0.11
22.1 ± 4.2 21.3 ± 3.8
0.38 ± 0.07 6.05 ± 0.90 0.34 ± 0.09
Lignin: 1 g/L.
Fig. 9. Reduction percentage of reactive yellow 145 dye as function of time; [a] nanoparticle –acidic (Ag19, Au19, Pd19) and [b] nanoparticles in basic (Ag23, Au23, Pd23). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
cause some of medical disorders, intestinal cancer and harmful effects on the plant seed germination [44]. One of the classes for the as-referred toxic dyes is reactive azo dyes, when some types of it was discharged into the ecosystem, it produces some of aromatic fragments with hazard effects on the aquatic life and humans [45]. Treatment of colored wastewater is ascribed as a difficult process because of the aromatic structures for the dyes which causes high resistance to light, heat, and oxidizing agents. But, in the last two decades numerous processes were used for removing of dyes from wastewater, which could be classified to three main categories: (i) chemical, (ii) biological, and (iii) physical processes. Despite of these methods are effective, but they have different problems that limit their usage. The advantageous of employing nanostructures in catalytic applications is owing to its topographical heterogeneity and their special differences in size and geometrical shapes. Therefore, the catalytic discoloration of reactive yellow 145 dye by sodium borohydride was monitored in presence of the as-synthesized AgNPs, AuNPs &PdNPs under both acidic and basic conditions. The absorbance spectra for discoloration of reactive yellow dye 145 as function of time were viewed in Fig. 8, respectively, while, the reduction percentage was presented in Fig. 9. For reactive yellow 145 dye, two characteristic absorption bands were detected at 227 and 420 nm. In the absence of the
NPs, 20% of the tested dye was only decolorized after 60 min. Addition of the synthesized nanoparticles resulted in accelerating the reduction and discoloration rate. The reduction rate was significantly depending on the pH condition under which the NPs was prepared due the different in particle size. From the plotted data, it could be clarified that, in the absence of nano-colloids, even after 60 min no change in the spectral data of the tested dye was detected. While after addition of nano-colloid to the reaction liquor as nano-catalyst, reduction of the dye is obviously observed. By reduction process, the characteristic absorption peak at 420 nm was gradually diminished by time, while the absorption peak at 227 nm was disappeared. The enhancement in catalytic action of NPs is mainly correlated to the particle size, i.e. the smaller is the particle size the greater is the catalytic activity. The catalytic activity of the prepared nanocatalyst were followed the order of PdNPs AuNPs > AgNPs. Due to their smaller size, the prepared AgNPs in acidic medium (15.5 nm) showed slightly better catalytic action rather than that prepared in basic medium (26.6 nm). Full reduction of dye was observed after 20 min and 25 min for acidic and basic prepared AgNPs, respectively. Smaller sized nanogold (5.7 nm) prepared in acidic condition, showed greater accelerated dye reduction in 10 min compared to that prepared under basic condition (22.1 nm). In case of Pd nano-catalyst, full reduction of dye was detected after only 4 min regardless to pH conditions under which PdNPs were prepared, due to the small difference in particle size (8.9 nm & 13.2 nm). Kinetic studies for the reductive discoloration of reactive yellow dye 145 were calculated for zero-order, first-order and secondorder, and the kinetic parameters (rate constant, half time and coefficient determination) and presented in Table 2 [46,47]. As a statistical test for fitting the data, the Chi-square (x2) was calculated for the kinetics and the values were inserted in Table 2, [48]. For first-order model, the highest coefficient determination (R2) values (>0.97) and the lowest x2 values (<1.0) were obtained. These values confirmed that the reductive discoloration of the tested dye was well compatible for first-order model [49]. The rate of the dye discoloration was mainly dependent on the employment
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strong alkali, lignin macromolecular chains were supposed to be aggressively dissolved to low molecular weighted, higher reducible fragments with alcoholic groups which acts in reducing metal ions to give stable PdNPs and in turn were oxidized to have aldehyde and/or ketone groups [15,16,39,41,42,51], (ii) under acidic conditions, lignin macromolecules are supposed to be gently hydrolyzed, meanwhile it needs higher temperature and/or prolonged time to give sufficient amounts of reducible moieties to generate and stabilize the required AgNPs & AuNPs, and (iii) regardless to pH conditions, the first layer of generated NPs is suggested to act as a stable template for the rest of the NPs to controllable growth of NPs. (See Tables 3 and 4). For illustration of catalytic action of the as-prepared NPs in discoloration of reactive yellow dye 145 using NaBH4 as reducing agent, a schematic diagram in Fig. 10b is represented, from the diagrammed figure it could be summarized that; (i) reductive discoloration of reactive yellow dye 145 could be attributed to the liberation of hydride intermediate which mainly acts in reductive degradation of the dye conjugated system responsible for dye color to lower molecular weighted fragments, (ii) due to the potential difference between hydride and the dye fragments, the rate of reaction is find to be so slow, (iii) according to literature, NPs could act as adsorbent for hydride ions, (iv) the as-prepared NPs is supposed to act as accelerator for the as-mentioned reaction via playing the role of electron transporter between hydride ions as electron rich intermediate and dye molecules and decreased the electron bond dissociation for breaking bonds and building up new bonds, v) azo group which is the chromophore group responsible for the color of reactive yellow dye 145 is supposed to be reductively broken down by the electrons transported via NPs, while g/g* transitions in aromatic nucleus of dye is supposed to be increased due to dye fragmentation to lower molecular weighted/colorless fractions [16,39].
of nano-catalysts and the pH at which such nano-catalysts were specifically prepared. For the acidic prepared NPs, the rate constant (k1, min 1) for discoloration of the tested dye was significantly accelerated from 3.5x10-3 min 1 without nano-catalyst to 51.5x10-3 min 1, 33.6x10-3 min 1 and 314.0x10-3 min 1 by using AgNPs, AuNPs & PdNPs, respectively. While, the half time (t1/2, min) was dramatically decreased from 198.04 min without nanocatalyst to 13.64 min for AgNPs, 20.63 min for AuNPs and 2.21 min for PdNPs. The increments in the rate constant and the reduction in half time were both smaller in case of using the basic prepared NPs due to their rational bigger particle size. It could be summarized that, compared to AgNPs & AuNPs, PdNPs are characterized by the superior catalytic activity which is in accordance with literature [16,39,40,50]. Additionally, comparing with basic prepared PdNPs, the acidic prepared AgNPs and AuNPs showed a greater catalytic action due to their smaller particle size. 4. Assumption of reaction mechanisms Under both of acidic and basic conditions, the reaction mechanism could be hypothesized for the redox reaction between lignin and silver, gold and palladium ions Fig. 10a to generate the required NPs as follows; (i) under basic conditions with NaOH as
Table 3 Description of the prepared nanopalladium samples. Sample Medium Temp (C)
Time (min.)
Pd1 Pd2 Pd3 Pd4 Pd5 Pd6 Pd7 Pd8 Pd9 Pd10 Pd11 Pd12 Pd13 Pd14 Pd15 Pd16 Pd17 Pd18 Pd19 Pd20 Pd21 Pd22 Pd23 Pd24
5 15 30 60 5 15 30 60 5 15 30 60 5 15 30 60 5 15 30 60 5 15 30 60
Acidic Acidic Acidic Acidic Basic Basic Basic Basic Acidic Acidic Acidic Acidic Basic Basic Basic Basic Acidic Acidic Acidic Acidic Basic Basic Basic Basic
30 30 30 30 30 30 30 30 60 60 60 60 60 60 60 60 90 90 90 90 90 90 90 90
Particle size PdI (nm)
25.4 ± 4.4
Surface area (m2/g)
0.56 ± 0.13
5. Conclusion 27.9 ± 3.6
0.34 ± 0.02
52.4 ± 8.3
0.26 ± 0.04
8.8 ± 2.2
0.53 ± 0.15
13.2 ± 4.1 13.1 ± 2.8
0.39 ± 0.09 10.27 ± 1.32 0.23 ± 0.04
8.9 ± 2.1 4.5 ± 2.0
0.28 ± 0.08 34.89 ± 2.8 0.57 ± 0.15
Herein, the current work is designed for monitoring the pH response of lignin as intelligent nano-engineer (reducer and stabilizer) under different conditions for synthesis of size and shape regulated AgNPs, AuNPs &PdNPs. The as-prepared NPs were evaluated for their superior catalytic performance in reductive discoloration of reactive yellow dye 145. AgNPs & AuNPs were generated with controllable size of 13.8 & 5.7 nm under acidic conditions, while PdNPs were produced under basic conditions with particle size of 4.5 nm. The UV-Visible, FT-IR & XRD data affirmed that, NPs were generated under the reducible power of the alcoholic groups in lignin polymer, while, such groups were in turn oxidized to aldehyde and/or ketone groups. The systematic study for the catalytic potency of the so-synthesized NPs showed their compatibility in the reductive discoloration of reactive yellow dye 145. It was found that there was a relationship between the catalytic activity and the pH conditions under which NPs were pre-
Lignin: 1 g/L.
Table 4 Parameters of kinetics for the catalytic degradation of reactive yellow 145 dye in the presence of the prepared nanoparticles. Catalyst
Blank AgNPs-Acidic AgNPs-Basic AuNPs-Acidic AuNPs-Basic PdNPs-Acidic PdNPs–Basic
Zero-order
First-order
10-3 k0 (mg/L.min)
t1/2 (min)
X2
R2
10-3 k1 (min
1.1 ± 0.2 28.5 ± 2.3 19.5 ± 2.0 18.9 ± 1.7 18.3 ± 1.8 94.5 ± 6.5 158.8 ± 8.7
157.3 ± 7.6 15.2 ± 1.8 20.5 ± 1.6 21.3 ± 1.9 21.2 ± 2.0 2.7 ± 0.8 2.3 ± 0.7
1.82 7.56 32.13 14.64 15.25 25.11 47.78
0.98 0.99 0.98 0.98 0.94 0.96 0.94
3.5 ± 0.8 51.5 ± 3.1 37.8 ± 2.7 33.6 ± 2.4 31.7 ± 2.5 314.0 ± 18.4 478.2 ± 21.3
Second-order 1
)
t1/2 (min)
X2
R2
10-3 k2 (L/mg.min)
t1/2 (min)
X2
R2
198.0 ± 8.6 13.5 ± 1.1 18.3 ± 1.3 20.6 ± 1.8 21.9 ± 2.4 2.2 ± 0.8 1.5 ± 0.6
0.05 0.08 0.09 0.11 0.13 0.34 0.51
0.99 0.97 0.99 0.99 0.97 0.98 0.98
11.3 ± 1.9 99.9 ± 7.2 77.9 ± 5.5 62.5 ± 4.8 56.4 ± 5.0 1132.8 ± 132.7 1784.3 ± 228.1
255.8 ± 26.6 11.5 ± 1.7 16.1 ± 1.2 19.8 ± 1.9 22.8 ± 2.1 1.74 ± 0.7 0.78 ± 0.09
1.33 21.10 17.61 14.86 12.78 82.90 113.55
0.99 0.91 0.96 0.98 0.99 0.96 0.90
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Fig. 10. Schematic diagram represents [a] preparation of nanoparticles by lignin and [b] catalytic reduction of reactive yellow 145 dye with the prepared nanoparticles. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
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pared, due to the different in particle size, i.e. the smaller is the particle size the greater is the catalytic activity. Compared to AgNPs & AuNPs, PdNPs showed significantly higher catalytic performance and the t1/2 for dye reductive discoloration was only 1.45–2.21 min. These promising findings will open new challenges for employing such multi-functional polymers as intelligent engineers (reducer and stabilizer) in size/shape regulated nanostructures exhibiting superior various activity with applicability in different purposes. Compliance with ethical standards Authors declare that they have no conflict of interest. Declaration of Competing Interest The authors declare that there is no conflict of interest. Appendix A. Supplementary material Supplementary data to this article can be found online at https://doi.org/10.1016/j.jcis.2019.11.060. References [1] K. Saha, S.S. Agasti, C. Kim, X. Li, V.M. Rotello, Gold nanoparticles in chemical and biological sensing, Chem. Rev. 112 (5) (2012) 2739–2779. [2] E.C. Dreaden, A.M. Alkilany, X. Huang, C.J. Murphy, M.A. El-Sayed, The golden age: gold nanoparticles for biomedicine, Chem. Soc. Rev. 41 (7) (2012) 2740– 2779. [3] H.-B. Yao, L.-B. Mao, Y.-X. Yan, H.-P. Cong, X. Lei, S.-H. Yu, Gold nanoparticle functionalized artificial nacre: facile in situ growth of nanoparticles on montmorillonite nanosheets, self-assembly, and their multiple properties, ACS Nano 6 (9) (2012) 8250–8260. [4] N. Khlebtsov, V. Bogatyrev, L. Dykman, B. Khlebtsov, S. Staroverov, A. Shirokov, L. Matora, V. Khanadeev, T. Pylaev, N. Tsyganova, Analytical and theranostic applications of gold nanoparticles and multifunctional nanocomposites, Theranostics 3 (3) (2013) 167. [5] S.-M. Lee, H.J. Kim, Y.-J. Ha, Y.N. Park, S.-K. Lee, Y.-B. Park, K.-H. Yoo, Targeted chemo-photothermal treatments of rheumatoid arthritis using gold half-shell multifunctional nanoparticles, ACS Nano 7 (1) (2012) 50–57. [6] P. Raveendran, J. Fu, S.L. Wallen, Completely ‘‘green” synthesis and stabilization of metal nanoparticles, J. Am. Chem. Soc. 125 (46) (2003) 13940–13941. [7] M. Blosi, S. Albonetti, S. Ortelli, A. Costa, L. Ortolani, M. Dondi, Green and easily scalable microwave synthesis of noble metal nanosols (Au, Ag, Cu, Pd) usable as catalysts, New J. Chem. 38 (4) (2014) 1401–1409. [8] S. Iravani, Green synthesis of metal nanoparticles using plants, Green Chem. 13 (10) (2011) 2638–2650. [9] S. Fazal, A. Jayasree, S. Sasidharan, M. Koyakutty, S.V. Nair, D. Menon, Green synthesis of anisotropic gold nanoparticles for photothermal therapy of cancer, ACS Appl. Mater. Interf. 6 (11) (2014) 8080–8089. [10] H.B. Ahmed, A. Abdel-Mohsen, H.E. Emam, Green-assisted tool for nanogold synthesis based on alginate as a biological macromolecule, RSC Adv. 6 (78) (2016) 73974–73985. [11] H.B. Ahmed, M. Zahran, H.E. Emam, Heatless synthesis of well dispersible Au nanoparticles using pectin biopolymer, Int. J. Biol. Macromol. 91 (2016) 208– 219. [12] H.E. Emam, M. Zahran, H.B. Ahmed, Generation of biocompatible nanogold using H2O2–starch and their catalytic/antimicrobial activities, Eur. Polym. J. 90 (2017) 354–367. [13] H.E. Emam, H.B. Ahmed, Carboxymethyl cellulose macromolecules as generator of anisotropic nanogold for catalytic performance, Int. J. Biol. Macromol. 111 (2018) 999–1009. [14] H.B. Ahmed, N.S. El-Hawary, H.E. Emam, Self-assembled AuNPs for ingrain pigmentation of silk fabrics with antibacterial potency, Int. J. Biol. Macromol. 105 (2017) 720–729. [15] H.E. Emam, Arabic gum as bio-synthesizer for Ag–Au bimetallic nanocomposite using seed-mediated growth technique and its biological efficacy, J. Polym. Environ. 27 (1) (2019) 210–223. [16] H.E. Emam, H.B. Ahmed, Comparative study between homo-metallic & heterometallic nanostructures based agar in catalytic degradation of dyes, Int. J. Biol. Macromol. 138 (2019) 450–461. [17] H.B. Ahmed, M.A. Attia, F.M. El-Dars, H.E. Emam, Hydroxyethyl cellulose for spontaneous synthesis of antipathogenic nanostructures:(Ag & Au) nanoparticles versus Ag-Au nano-alloy, Int. J. Biol. Macromol. 128 (2019) 214–229. [18] H. Zhu, Y. Li, B. Pettersson, L. Zhang, M. Lindström, G. Henriksson, Technical soda lignin dissolved in urea as an environmental friendly binder in wood fiberboard, J. Adhes. Sci. Technol. 28 (5) (2014) 490–498.
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Contents lists available at ScienceDirect
Journal of Colloid and Interface Science journal homepage: www.elsevier.com/locate/jcis
pH responsive intelligent nano-engineer of nanostructures applicable for discoloration of reactive dyes Hanan B. Ahmed a,⇑, Mary M. Mikhail a, Samya El-Sherbiny a, Khaled S. Nagy b, Hossam E. Emam c,⇑ a
Chemistry Department, Faculty of Science, Helwan University, Ain-Helwan, Cairo 11795, Egypt Food Engineering and Packaging Department, Agricultural Research Center, 9 Cairo University St., Giza, Egypt c Department of Pretreatment and Finishing of Cellulosic based Textiles, Textile Industries Research Division, National Research Centre, Scopus affiliationID 60014618, 33 EL Buhouth St., Dokki, Giza 12622, Egypt b
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
Investigation of pH response for
Lignin as intelligent nano-engineer under different temperatures. 1 g/L lignin is sufficient for synthesis of size and shape regulated AgNPs, AuNPs & PdNPs. Acidic reaction condition is advisable for synthesis of small sized AgNPs (13.8 nm) & AuNPs (5.7 nm). Basic reaction condition is recommended for generation of size regulated PdNPs (4.5 nm). The half time of reactive dye degradation is 21.87, 18.34 and 1.45 min at using AgNPs, AuNPs and PdNPs, respectively.
a r t i c l e
i n f o
Article history: Received 23 September 2019 Revised 10 November 2019 Accepted 15 November 2019 Available online 29 November 2019 Keywords: pH response Intelligent nano-engineer Nano-catalysts Reductive discoloration Reactive yellow dye
a b s t r a c t Multifunctional polymers were commonly ascribed as intelligent materials due to the presence of different functional groups on the polymeric skeleton which causes the high sensitivity to the interchanging of physicochemical conditions. Herein, under different temperatures, monitoring the pH response of lignin as intelligent nano-engineer (reducer and stabilizer) for synthesis of size and shape regulated silver nanoparticles (AgNPs), gold nanoparticles (AuNPs) & palladium nanoparticles (PdNPs) is systematically studied. The regulation of the particle size and stability of NPs were remarkably affected by acidity and basicity of the reaction medium at which they were prepared. TEM and zetasizer data showed that, highly size and shape regulated AgNPs & AuNPs is successively produced under acidic conditions with particle size of 13.8 and 5.7 nm, respectively. While basic conditions is more advisable in case of PdNPs to be produced with particle size of 4.5 nm. Catalytic performance of biphasic NPs in reductive discoloration of azo dye (reactive yellow dye 145) was followed the order of PdNPs > AuNPs > AgNPs. The half time for discoloration of dye with basic prepared NPs was dramatically decreased from 21.87 min for AgNPs and 18.34 for AuNPs to 1.45 min for PdNPs. Ó 2019 Elsevier Inc. All rights reserved.
⇑ Corresponding authors. E-mail addresses: [email protected] (H.B. Ahmed), [email protected] (H.E. Emam). https://doi.org/10.1016/j.jcis.2019.11.060 0021-9797/Ó 2019 Elsevier Inc. All rights reserved.
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1. Introduction Engineering of highly regulated sized and shaped nanoparticles with good stability is interestingly studied due to their special chemical, physical and biological properties [1,2]. Numerous noteworthy reports concerned in preparation of multifunctional nanostructures to be independently employed in sensing, photo-thermal conversion [3], simultaneous detection and imaging [4], and targeted chemo-photo-thermal treatments [5]. Due to biological or environmental-related requirements, there is an increasing demand on preparation NPs with nontoxic chemicals, and solvents [6–9]. Exploitation the superiority of natural polymers for as green nano-synthesizers was widely studied for engineering of NPs with diverse applications [10–17]. Lignin, a one of the natural polymer, is well-known as the second-most abundant natural polymer and the main by-product of the paper industry [18]. In recent reports, researchers interestingly have observed that the reducing groups and 3D spatial structure of lignin realize the possibility for exploiting lignin in green preparation of different nanostructures [19–21]. In spite of lignin is ascribed to exhibit chemically heterogeneous and complex structure, but it is advantageous with various powerful functional groups, i.e., reductive aliphatic hydroxyls and phenolic hydroxyls. On the other hand, the presence of different functional groups along the polymeric chain, often causes high sensitivity to various conditions of surrounding environment, such as temperature [22,23], pH [24–26], ionic strength [27] and magnetic field [28], which makes polymeric materials with diverse functional groups to be ascribed as intelligent materials. Nano-catalysts based on MNPs have reported to be characterized with superior advantage of combining both of the capability of homogeneous and heterogeneous catalytic systems. It could be clarified as follows; (i) nano-catalytic system promotes the fast, selective chemical transformations with formidable product yield in addition to the possibility of catalyst separation and recovery, (ii) the nano sized particles with high surface area significantly increased the contact with reacting materials, where, this phenomenon is similar to homogeneous catalysts, and, (iii) due to the insolubility of zero-valence nanoparticles in the reaction sol-
vent, this makes the nano-catalyst to be similar to heterogeneous catalysts and hence could be easily separated out from the reaction mixture [29–33]. In the current work, the co-authors have demonstrated a new study for monitoring the pH response of lignin as intelligent nano-engineer (reducer and stabilizer) under different temperatures for synthesis of size and shape controlled silver (AgNPs), gold (AuNPs) and palladium (PdNPs) nanoparticles. Lignin is ascribed to serve as multi-functional binding, complexion and reducing agents for metal cations as well as stabilizing agent for the so-engineered AgNPs, AuNPs and PdNPs. Different instrumental analyses like UVVisible spectrophotometer, transmission electron microscope (TEM), Zetasizer, BET and X-ray diffraction (XRD) were carried out in order to approve the successive engineering of required nanoparticles. Spectral data of infrared (FTIR) were also presented to confirm the predicted mechanism of redox reaction between lignin macromolecules and metals precursors. Monitoring the catalytic performance of the synthesized NPs in discoloration of reactive yellow dye 145 was lastly organized and interpreted. 2. Expermental 2.1. Materials and Chemicals: All the chemicals of silver nitrate (AgNO3, 99.5%, from Panreac, Barcelona – Spain), Gold chloride (AuCl3, 99%,from Sigma-Aldrich – USA), Palladium chloride (PdCl2, 99%, from Sigma-Aldrich – USA), Sodium hydroxide (99%, from Merck, Darmstadt–Germany), lignin (C31H34O11)n, El-Nasser Company for Pharmaceuticals and Chemicals, Egypt), reactive yellow dye 145 (C28H20ClN9Na4O16S5, from Merck, Darmstadt–Germany) and Sodium borohydride (NaBH4, 96%, from Sigma-Aldrich – USA), were used without any further purification. 2.2. Synthesis of NPs: The experimental work for synthesis of AgNPs, AuNPs & PdNPs using lignin as nano-engineer (reducer and stabilizer) is detailed in Table 1. It could be briefly illustrated as follows; to 1 g/L of lignin
Table 1 Description of the prepared nanosilver samples. Sample
Medium
Temp (C)
Time (min.)
Ag1 Ag2 Ag3 Ag4 Ag5 Ag6 Ag7 Ag8 Ag9 Ag10 Ag11 Ag12 Ag13 Ag14 Ag15 Ag16 Ag17 Ag18 Ag19 Ag20 Ag21 Ag22 Ag23 Ag24
Acidic Acidic Acidic Acidic Basic Basic Basic Basic Acidic Acidic Acidic Acidic Basic Basic Basic Basic Acidic Acidic Acidic Acidic Basic Basic Basic Basic
30 30 30 30 30 30 30 30 60 60 60 60 60 60 60 60 90 90 90 90 90 90 90 90
5 15 30 60 5 15 30 60 5 15 30 60 5 15 30 60 5 15 30 60 5 15 30 60
Lignin: 1 g/L.
Surface area (m2/g)
Particle size (nm)
PdI
21.6 ± 4.2
0.40 ± 0.11
25.2 ± 3.5
0.25 ± 0.09
13.8 ± 3.1
0.47 ± 0.10
31.9 ± 5.6
0.20 ± 0.08
15.5 ± 2.4 15.1 ± 3.0
0.29 ± 0.07 0.25 ± 0.10
23.16 ± 2.71
26.6 ± 5.2 33.7 ± 4.8
0.27 ± 0.02 0.21 ± 0.03
12.19 ± 1.62
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Fig. 1. Time dependent absorption spectra for the prepared nanosilver by 1 g/L lignin; [a] in acidic medium at 60 °C (Ag9-Ag12), [b] in acidic medium after 30 min (Ag3, Ag11, Ag19) [c] in basic medium at 60 °C (Ag13-Ag16) and [d] in basic medium after 30 min (Ag7, Ag15, Ag23).
Fig. 2. Time dependent absorption spectra for the prepared nanogold by 1 g/L lignin; [a] in acidic medium at 60 °C (Au9-Au12), [b] in acidic medium after 30 min (Au3, Au11, Au19) [c] in basic medium at 60 °C (Au13-Au16) and [d] in basic medium after 30 min (Au7, Au15, Au23).
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solution, metal salt solution (silver, gold, palladium) was added drop-wisely under continuous stirring at acidic (pH 2–4) and/or basic (pH 11) conditions and certain temperatures (30, 60 & 90 °C), considering that the weight ratio between metal salts and lignin was 1:10. Certain volume of the reaction liquor was withdrawn from time to time to follow up the progress the reaction of NPs generation under UV–Visible absorption spectroscopy. The solid form of nanocomposites were obtained by transferring the prepared NPs colloidal solutions to petri-dish, for drying at 100 °C overnight. The obtained solids were used for X-ray diffraction and fourier transformation infrared spectroscopy.
2.3. Instrumental analyses and measurements: The colloidal solutions of the prepared NPs were manifested by an intense absorption peak of the Surface Plasmon Resonance (SPR), which is detected under UV-Visible absorption spectroscopy for first affirmation of engineering the required NPs. The UVVisible absorption spectra of nanocolloids were detected in the wavelength range of 250–750 nm using a multichannel spectrophotometer (Jasco V-360 UV/VIS, d = 10 mm, Japan). Geometrical features and particle size of the engineered NPs were presented by anticipating of a JEOL-JEM-1230 (HighResolution Transmission Electron Microscope, HRTEM from Japan) with an electron beam from Oxford instruments. Nanocolloids were drop wisely added to 400 copper grid coated by carbon film, and then evaporated in air at room temperature before detected by the microscope. The diameter and particle size of NPs were measured by 4 pi analysis software using TEM photos. The average diameter of NPs was evaluated for at least 50 particles. The size distribution and poly-dispersity index of the engineered NPs were measured by Zetasizer analyzer (Malvern Zeta-
sizer Nano ZS, from Malvern Instruments Ltd – UK). The instrument was attached with a He-Ne laser lamp (0.4 mW) at wavelength of 633 nm. Measurements were carried out at 25 °C in insulated chamber using dynamic light scattering technique. Both of native lignin and nanocomposites were measured under X-ray diffraction using X’Pert PRO PANalytical diffractometer, at room temperature. Diffraction patterns were detected in the diffraction angle (2h) range of 5–80° using monochromatized (CuKa X-radiation at 40 kV, 50 mA and k = 1.5406 Å) with a step size of 0.03° and scanning rate of 1 s. Infrared spectral data were also represented for native lignin and nanocomposites using infrared Spectrometer (Jasco FT/IR 6100, from Japan) conducted to detector of deuteratedtriglycine sulfate (TGS). The spectra were recorded in range of 4000– 500 cm 1 using transmission mode (T%), resolution of 4 cm 1 with 2 cm 1 interval scanning and scanning speed of 2 mm/sec. The surface area (BET) of the engineered NPs (AgNPs, AuNPs & PdNPs) was detected by NOVA touch 4 LX Quanta chrome version 1.21. Firstly, samples were degassed under vacuum at 100 ◦C and then the adsorption of nitrogen gas was performed at 77 K.
2.3.1. Reductive discoloration of reactive yellow dye 145 The catalytic performance of the engineered AgNPs, AuNPs and PdNPs was monitored for the discoloration of reactive yellow dye 145. The discoloration of reactive yellow dye 145 by NaBH4 in presence of NPs (NPs) as a catalyst was performed as follows: to a vial containing 8 mL of dye (50 mg/L dye), 1 mL of NPs and1 mL of NaBH4 (150 mM) were added, respectively. Blank sample without NPs was used as a blank sample. After the immediate addition of borohydride, the catalytic discoloration was followed up by detection of the absorbance at wavelength range of 200–800 nm
Fig. 3. Time dependent absorption spectra for the prepared nanopalladium by 1 g/L lignin; [a] in acidic medium at 60 °C (Pd9-Pd12), [b] in acidic medium after 30 min (Pd3, Pd11, Pd19) [c] in basic medium at 60 °C (Pd13-Pd16) and [d] in basic medium after 30 min (Pd7, Pd15, Pd23).
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using a spectrophotometer (Cary 5000 UV-Vis-NIR Systems,version 1.12 from Agilent), at a given time intervals up to 60 min.
the reductive discoloration of reactive yellow dye 145 for waste water treatment.
3. Results and disscusion
3.1. UV–Visible spectroscopic data
The physicochemical conditions of the reaction medium such like, pH, ionic strength and metal concentrations are principally affected on the MNPs stability, size and geometrical shape [22– 27]. Lignin ascribed as intelligent material, is a multifunctional polymer which is very sensitive to the interchanging in physicochemical conditions. Hence, the current study purposed on investigating the pH sensitivity of lignin as intelligent nano-engineer (reducer and stabilizer) for production of size and shape regulated AgNPs, AuNPs & PdNPs under different temperatures. Moreover, the catalytic performance of the prepared NPs was monitored in
Following up UV–Visible spectroscopic data for the prepared samples gives an initial confirmation of the stable ingraining of the required NPs, where, color tuning of the reaction liquor is mainly correlated to the excitation of Surface Plasmon Resonance (SPR) exhibited by the existed AgNPs, AuNPs & PdNPs [15–17]. This section represents the UV–Visible spectral mapping data (Figs. 1– 3) monitored for all of the prepared samples to show premier information for pH response of lignin as intelligent nanoengineer under different temperatures for regulation of size and shape controlled NPs.
Fig. 4. HRTEM micrographs for the prepared nanoparticles at two different magnifications; [a] AgNPs (Ag11), [b] AuNPs (Au11) and [c] PdNPs (Pd11). Histogram figure is presented for the corresponding microimages.
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Fig. 4 (continued)
Compared to the spectral data of native lignin and metal salts (see supplementary data, Fig. S1), Figs. 1–3 showed the spectral data for AgNPs, AuNPs & PdNPs colloids prepared using lignin (1 g/L) under acidic and basic conditions at different temperatures. Under acidic conditions the characteristic SPR band of AgNPs at 425 nm is significantly appeared at 60 °C (Fig. 1). The low temperature (30 °C) is resulted in decrement in the intensity of SPR band while raising reaction temperature to 90 °C is accompanied by disappearing of SPR band. Prolonging the reaction duration more than 30 min is not significantly affected on the SPR band. Under alkaline medium, the SPR band of AgNPs is not affected by the experimental conditions of time and temperature. There is non-sensible detection of AuNPs even under basic and acidic conditions at different temperatures with time (Fig. 2). The SPR band of PdNPs at 285 nm is significantly observed under both of basic and acidic conditions (Fig. 3). Elevation of reaction temperature resulted in increment of band intensity of PdNPs in acidic conditions, while not affected in basic conditions. Prolonging of the reaction duration is insignificantly affected on the PdNPs band. These data are explained by the sufficient activation of lignin macromolecules in basic conditions at lower temperature and shorter time. While in acidic medium, the activation of lignin needs high temperature and/or quite longer time. 3.2. TEM micrographs and zetasizer data For representing the topographical features and geometrical shapes of the prepared MNPs and according to UV–Visible data, some of samples were selected (Ag11, Au11, Pd11) to be detected under HRTEM and the micrographs were plotted in Fig. 4. Under acidic conditions, lignin is successfully acted as a compatible nano-synthesizer for production of spherical/size controlled NPs. Well distributed AgNPs, AuNPs and PdNPs are seen in the micro-images with size of 12.5 nm, 10.9 nm and 14.4 nm, respectively. The pH response for both of lignin and metal precursors and its reflected effect on the particle size of NPs is also detected via zetasizer analyzer for more approval (Fig. 5 and Table 1). Under acidic conditions, AgNPs & AuNPs are exhibited by smaller size (Ag11,
13.1 nm & Au11, 8.1 nm) rather than under basic conditions (Ag15, 31.9 nm & Au15, 17.1 nm). In contrast to PdNPs which are detected with smaller size under basic conditions (Pd15, 8.8 nm) compared to that prepared under acidic conditions (Pd11, 52.4 nm). Under acidic conditions, elevation of reaction temperature (Ag3, Ag11, Ag19) is not observably affected on the particle size in case of AgNPs (13.8 – 21.6 nm). While in case of AuNPs & PdNPs, the particle size is significantly diminished by raising reaction temperature (Au, decreased from 79.4 nm to 5.7 nm & Pd, decreased from 52.4 nm to 13.2 nm). Comparing between the particle size detected via HRTEM and zetasizer for Ag11, Au11&Pd11 to could be observed that, in case of silver and gold NPs there no sensible difference in the particle size detected via the two different techniques, while in case of palladium NPs there was a significant difference as the particle size which was higher enlarged in zetasizer data rather than that of HRTEM, which could be interpreted due to the non-spherical shape of PdNPs [13]. Under basic conditions, raising temperature more than 60 ⁰C is not significantly tuned the particle size in case of AgNPs (25.2 – 31.9 nm), while in case of AuNPs the particle size is increased (from 9.9 nm to 22.1 nm). For PdNPs, elevation of temperature resulted in shrinkage and more regulation of particle size (27.9 nm at 30 °C & 8.9 nm at 90 °C). Additionally, the prolongation of reaction duration is not significantly affected on the regulation of particle size for all of the prepared NPs. Regulated nucleation and well dispersion of the produced NPs can be approved through the detected value of polydispersity index (PdI) from zetasizer analyzer [10,34]. The synthesized nanocolloids are shown to exhibit well-regulated shape and size as all the samples were detected with values of PdI ranged in 0.23–0.61 (Table 1). From the afore-mentioned data could be depicted that, by using only small concentration of lignin (1 g/L), highly controllable size growth of AgNPs & AuNPs is proceeded under acidic conditions, in contrary to PdNPs which is performed under basic conditions. Especially in case of PdNPs, elevation of reaction temperature resulted in enhanced dissolution of lignin macromolecules to smaller and more reducible fragments to play the main role of reducing and stabilizing of NPs.
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Fig. 5. Size distribution of the prepared nanoparticles from zetasizer analyzer; [a] AgNPs in acidic medium after 30 min (Ag3, Ag11, Ag19), [b] AgNPs in basic medium after 30 min (Ag7, Ag15, Ag23), [c] AuNPs in acidic medium after 30 min (Au3, Au11, Au19), [d] AuNPs in basic medium after 30 min (Au7, Au15, Au23), [e] PdNPs in acidic medium after 30 min (Pd3, Pd11, Pd19) and [f] PdNPs in basic medium after 30 min (Pd7, Pd15, Pd23).
The effect of pH sensitivity for nano-synthesizers on the surface area of the as prepared NPs is evaluated via detection of BET for the adsorption of N2 gas. According to literature, the surface area is basically affected by the particle size, where, the smaller is the particle size; the larger is the surface area of NPs, which is in accordance with the presented data (Table 1). In case of AgNPs, under acidic conditions the particles exhibited by smaller particle size (15.5 nm) with higher surface area (23.16 m2/g) compared to that prepared under basic conditions (12.19 m2/g). In case of AuNPs, the nanoparticles were detected with smaller particle size accompanied with higher surface area of 11.06 m2/g in acidic conditions compared to that synthesized under basic conditions (surface area 6.05 m2/g). For PdNPs, in acidic medium the particles had larger
size of 13.2 nm with diminished surface area (10.27 m2/g) compared to PdNPs produced under basic conditions (surface area 34.89 m2/g). 3.3. XRD patterns Lignin, NPs-lignin composites which were prepared under acidic (Ag19, Au19 & Pd19) and basic conditions (Ag23, Au23 & Pd23) were characterized by XRD patterns and the data are figured out in Fig. 6. The pristine lignin was detected with certain intense diffraction bands at 2h = 24.6°, observable for the crystalline structure of lignin. However, in case of all NPs-lignin composites and regardless to the pH sensitivity of lignin and metal precursors,
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Fig. 6. X-ray diffraction for the prepared nanoparticles; [a] prepared in acidic medium (Ag19, Au19, Pd19) and [b] prepared in basic medium (Ag23, Au23, Pd23).
the crystalline structure of lignin was dramatically affected and the characteristic lignin diffraction bands were completely disappeared, attributing to the exploitation of lignin macromolecules in production and stabilization of NPs. New intense diffraction peaks were detected at 2h = 38.5° and 38.7° for AgNPs@lignin and AuNPs@lignin, respectively. In accordance with diffraction data of international center, these diffractions are cited to be typical for (1 1 1) and (1 1 1) of face centered crystalline (FCC) structures for silver and gold (JCPDS data number 04–0783 card and 4–0784 card) [15,17,35–38]. In case of PdNPs@lignin, five diffraction bands are detected at 2h = 31.7°, 40.2°, 45.5°, 47.7° and 68.1°. The diffraction peak at 45.5° is belonging to (2 0 0) of face centered crystalline (FCC) structures for Pd (JCPDS data number 89–4897 card) [16,37–39]. There were no difference in diffraction of NPs prepared in acidic and basic conditions. Under basic conditions, the diffraction patterns of NPs were observable with
more intense reflecting their high crystalline structure. The represented data were further approved the above-mentioned data of absorbance spectra, zetasizer and TEM micrographs for successful interaction between metal ions and reducible end groups of lignin macromolecules.
3.4. ATR-FTIR data More confirmation of pH response and compatibility of lignin as nano-synthesizer (reducer and stabilizer) for production of highly size and shape controlled of AgNPs, AuNPs & PdNPs, and for giving more confirmation about the redox reaction between metal ions and lignin molecular back bone, the data of the attenuated total reflection – Fourier transformation infrared spectroscopy (ATRFTIR) were represented.
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Fig. 7. FTIR spectra for the prepared nanoparticles; [a] prepared in acidic medium (Ag19, Au19, Pd19) and [b] prepared in basic medium (Ag23, Au23, Pd23).
From Fig. 7a&b for selected samples prepared under acidic (7a) and basic (7b) conditions, it could be plausible that; native lignin macromolecule is exhibited by a broad peak of OAH bond stretching is detected at 3331 cm 1, while the shortened peak at 2922 cm 1 is referred to ACH group stretching. The CH2 group bending is detected at 1578 cm 1 and the bending of OH at 1034 cm 1. From the represented spectra for NPs prepared under acidic conditions (7a), it could be significantly observed that, a significant tuning in the characteristic bands of lignin was noted after its exploitation in the synthesis of MNPs. In case of nano-colloids,
band seen at 3331 cm 1 characterized for OH stretching is significantly broadened, and another significant new bands are detected for NPs at 1687–1363 cm 1, which is corresponding to carbonyl group (C@O of aldehyde and/or ketone units) [15,17,39,40]. While in basic conditions (7b), all the bands occurred in acidic conditions were typically detected for sample prepared under basic conditions in addition to two new bands at 1406 cm 1 which is characteristic for CAH bending of aldehyde and at 874 cm 1 for O-M (where M is referred to metal) owing to more accessibility and reducibility of lignin polymer under the alkaline conditions [15–17,39,41,42].
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Fig. 8. Spectral analysis for time dependent degradation of reactive yellow 145 dye; [a] without nanoparticles, [b] AgNPs-acidic (Ag19), [c] AgNPs-basic (Ag23), [d] AuNPsacidic (Au19), [e] AuNPs-basic (Au23), [f] PdNPs-acidic (Pd19), and [g] PdNPs-basic (Pd23). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
3.5. The catalytic activity of the as-synthesized NPs in discoloration of dyes Numerous types of synthetic colorants are widely applicable as dyes for coloration and fashionable decoration of textiles
and garments, as it was reported that, 10% of dyes are excluded to the aqueous bodies from textile factories. Additionally, some of dyes are well known as toxic contaminates in water and also act as a carcinogenic and mutagenic compounds in marine organisms and humans [43], and it might
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H.B. Ahmed et al. / Journal of Colloid and Interface Science 561 (2020) 147–161 Table 2 Description of the prepared nanogold samples. Sample Medium Temp (C) Time Particle (min.) size (nm) Au1 Au2 Au3 Au4 Au5 Au6 Au7 Au8 Au9 Au10 Au11 Au12 Au13 Au14 Au15 Au16 Au17 Au18 Au19 Au20 Au21 Au22 Au23 Au24
Acidic Acidic Acidic Acidic Basic Basic Basic Basic Acidic Acidic Acidic Acidic Basic Basic Basic Basic Acidic Acidic Acidic Acidic Basic Basic Basic Basic
30 RT 30 30 30 30 30 30 60 60 60 60 60 60 60 60 90 90 90 90 90 90 90 90
5 15 30 60 5 15 30 60 5 15 30 60 5 15 30 60 5 15 30 60 5 15 30 60
PdI
Surface area (m2/g)
79.4 ± 12.3 0.29 ± 0.04
9.9 ± 3.1
0.49 ± 0.12
8.1 ± 2.5
0.36 ± 0.10
17.1 ± 2.9
0.51 ± 0.12
5.7 ± 1.6 6.0 ± 1.2
0.61 ± 0.17 11.06 ± 1.20 0.50 ± 0.11
22.1 ± 4.2 21.3 ± 3.8
0.38 ± 0.07 6.05 ± 0.90 0.34 ± 0.09
Lignin: 1 g/L.
Fig. 9. Reduction percentage of reactive yellow 145 dye as function of time; [a] nanoparticle –acidic (Ag19, Au19, Pd19) and [b] nanoparticles in basic (Ag23, Au23, Pd23). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
cause some of medical disorders, intestinal cancer and harmful effects on the plant seed germination [44]. One of the classes for the as-referred toxic dyes is reactive azo dyes, when some types of it was discharged into the ecosystem, it produces some of aromatic fragments with hazard effects on the aquatic life and humans [45]. Treatment of colored wastewater is ascribed as a difficult process because of the aromatic structures for the dyes which causes high resistance to light, heat, and oxidizing agents. But, in the last two decades numerous processes were used for removing of dyes from wastewater, which could be classified to three main categories: (i) chemical, (ii) biological, and (iii) physical processes. Despite of these methods are effective, but they have different problems that limit their usage. The advantageous of employing nanostructures in catalytic applications is owing to its topographical heterogeneity and their special differences in size and geometrical shapes. Therefore, the catalytic discoloration of reactive yellow 145 dye by sodium borohydride was monitored in presence of the as-synthesized AgNPs, AuNPs &PdNPs under both acidic and basic conditions. The absorbance spectra for discoloration of reactive yellow dye 145 as function of time were viewed in Fig. 8, respectively, while, the reduction percentage was presented in Fig. 9. For reactive yellow 145 dye, two characteristic absorption bands were detected at 227 and 420 nm. In the absence of the
NPs, 20% of the tested dye was only decolorized after 60 min. Addition of the synthesized nanoparticles resulted in accelerating the reduction and discoloration rate. The reduction rate was significantly depending on the pH condition under which the NPs was prepared due the different in particle size. From the plotted data, it could be clarified that, in the absence of nano-colloids, even after 60 min no change in the spectral data of the tested dye was detected. While after addition of nano-colloid to the reaction liquor as nano-catalyst, reduction of the dye is obviously observed. By reduction process, the characteristic absorption peak at 420 nm was gradually diminished by time, while the absorption peak at 227 nm was disappeared. The enhancement in catalytic action of NPs is mainly correlated to the particle size, i.e. the smaller is the particle size the greater is the catalytic activity. The catalytic activity of the prepared nanocatalyst were followed the order of PdNPs AuNPs > AgNPs. Due to their smaller size, the prepared AgNPs in acidic medium (15.5 nm) showed slightly better catalytic action rather than that prepared in basic medium (26.6 nm). Full reduction of dye was observed after 20 min and 25 min for acidic and basic prepared AgNPs, respectively. Smaller sized nanogold (5.7 nm) prepared in acidic condition, showed greater accelerated dye reduction in 10 min compared to that prepared under basic condition (22.1 nm). In case of Pd nano-catalyst, full reduction of dye was detected after only 4 min regardless to pH conditions under which PdNPs were prepared, due to the small difference in particle size (8.9 nm & 13.2 nm). Kinetic studies for the reductive discoloration of reactive yellow dye 145 were calculated for zero-order, first-order and secondorder, and the kinetic parameters (rate constant, half time and coefficient determination) and presented in Table 2 [46,47]. As a statistical test for fitting the data, the Chi-square (x2) was calculated for the kinetics and the values were inserted in Table 2, [48]. For first-order model, the highest coefficient determination (R2) values (>0.97) and the lowest x2 values (<1.0) were obtained. These values confirmed that the reductive discoloration of the tested dye was well compatible for first-order model [49]. The rate of the dye discoloration was mainly dependent on the employment
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strong alkali, lignin macromolecular chains were supposed to be aggressively dissolved to low molecular weighted, higher reducible fragments with alcoholic groups which acts in reducing metal ions to give stable PdNPs and in turn were oxidized to have aldehyde and/or ketone groups [15,16,39,41,42,51], (ii) under acidic conditions, lignin macromolecules are supposed to be gently hydrolyzed, meanwhile it needs higher temperature and/or prolonged time to give sufficient amounts of reducible moieties to generate and stabilize the required AgNPs & AuNPs, and (iii) regardless to pH conditions, the first layer of generated NPs is suggested to act as a stable template for the rest of the NPs to controllable growth of NPs. (See Tables 3 and 4). For illustration of catalytic action of the as-prepared NPs in discoloration of reactive yellow dye 145 using NaBH4 as reducing agent, a schematic diagram in Fig. 10b is represented, from the diagrammed figure it could be summarized that; (i) reductive discoloration of reactive yellow dye 145 could be attributed to the liberation of hydride intermediate which mainly acts in reductive degradation of the dye conjugated system responsible for dye color to lower molecular weighted fragments, (ii) due to the potential difference between hydride and the dye fragments, the rate of reaction is find to be so slow, (iii) according to literature, NPs could act as adsorbent for hydride ions, (iv) the as-prepared NPs is supposed to act as accelerator for the as-mentioned reaction via playing the role of electron transporter between hydride ions as electron rich intermediate and dye molecules and decreased the electron bond dissociation for breaking bonds and building up new bonds, v) azo group which is the chromophore group responsible for the color of reactive yellow dye 145 is supposed to be reductively broken down by the electrons transported via NPs, while g/g* transitions in aromatic nucleus of dye is supposed to be increased due to dye fragmentation to lower molecular weighted/colorless fractions [16,39].
of nano-catalysts and the pH at which such nano-catalysts were specifically prepared. For the acidic prepared NPs, the rate constant (k1, min 1) for discoloration of the tested dye was significantly accelerated from 3.5x10-3 min 1 without nano-catalyst to 51.5x10-3 min 1, 33.6x10-3 min 1 and 314.0x10-3 min 1 by using AgNPs, AuNPs & PdNPs, respectively. While, the half time (t1/2, min) was dramatically decreased from 198.04 min without nanocatalyst to 13.64 min for AgNPs, 20.63 min for AuNPs and 2.21 min for PdNPs. The increments in the rate constant and the reduction in half time were both smaller in case of using the basic prepared NPs due to their rational bigger particle size. It could be summarized that, compared to AgNPs & AuNPs, PdNPs are characterized by the superior catalytic activity which is in accordance with literature [16,39,40,50]. Additionally, comparing with basic prepared PdNPs, the acidic prepared AgNPs and AuNPs showed a greater catalytic action due to their smaller particle size. 4. Assumption of reaction mechanisms Under both of acidic and basic conditions, the reaction mechanism could be hypothesized for the redox reaction between lignin and silver, gold and palladium ions Fig. 10a to generate the required NPs as follows; (i) under basic conditions with NaOH as
Table 3 Description of the prepared nanopalladium samples. Sample Medium Temp (C)
Time (min.)
Pd1 Pd2 Pd3 Pd4 Pd5 Pd6 Pd7 Pd8 Pd9 Pd10 Pd11 Pd12 Pd13 Pd14 Pd15 Pd16 Pd17 Pd18 Pd19 Pd20 Pd21 Pd22 Pd23 Pd24
5 15 30 60 5 15 30 60 5 15 30 60 5 15 30 60 5 15 30 60 5 15 30 60
Acidic Acidic Acidic Acidic Basic Basic Basic Basic Acidic Acidic Acidic Acidic Basic Basic Basic Basic Acidic Acidic Acidic Acidic Basic Basic Basic Basic
30 30 30 30 30 30 30 30 60 60 60 60 60 60 60 60 90 90 90 90 90 90 90 90
Particle size PdI (nm)
25.4 ± 4.4
Surface area (m2/g)
0.56 ± 0.13
5. Conclusion 27.9 ± 3.6
0.34 ± 0.02
52.4 ± 8.3
0.26 ± 0.04
8.8 ± 2.2
0.53 ± 0.15
13.2 ± 4.1 13.1 ± 2.8
0.39 ± 0.09 10.27 ± 1.32 0.23 ± 0.04
8.9 ± 2.1 4.5 ± 2.0
0.28 ± 0.08 34.89 ± 2.8 0.57 ± 0.15
Herein, the current work is designed for monitoring the pH response of lignin as intelligent nano-engineer (reducer and stabilizer) under different conditions for synthesis of size and shape regulated AgNPs, AuNPs &PdNPs. The as-prepared NPs were evaluated for their superior catalytic performance in reductive discoloration of reactive yellow dye 145. AgNPs & AuNPs were generated with controllable size of 13.8 & 5.7 nm under acidic conditions, while PdNPs were produced under basic conditions with particle size of 4.5 nm. The UV-Visible, FT-IR & XRD data affirmed that, NPs were generated under the reducible power of the alcoholic groups in lignin polymer, while, such groups were in turn oxidized to aldehyde and/or ketone groups. The systematic study for the catalytic potency of the so-synthesized NPs showed their compatibility in the reductive discoloration of reactive yellow dye 145. It was found that there was a relationship between the catalytic activity and the pH conditions under which NPs were pre-
Lignin: 1 g/L.
Table 4 Parameters of kinetics for the catalytic degradation of reactive yellow 145 dye in the presence of the prepared nanoparticles. Catalyst
Blank AgNPs-Acidic AgNPs-Basic AuNPs-Acidic AuNPs-Basic PdNPs-Acidic PdNPs–Basic
Zero-order
First-order
10-3 k0 (mg/L.min)
t1/2 (min)
X2
R2
10-3 k1 (min
1.1 ± 0.2 28.5 ± 2.3 19.5 ± 2.0 18.9 ± 1.7 18.3 ± 1.8 94.5 ± 6.5 158.8 ± 8.7
157.3 ± 7.6 15.2 ± 1.8 20.5 ± 1.6 21.3 ± 1.9 21.2 ± 2.0 2.7 ± 0.8 2.3 ± 0.7
1.82 7.56 32.13 14.64 15.25 25.11 47.78
0.98 0.99 0.98 0.98 0.94 0.96 0.94
3.5 ± 0.8 51.5 ± 3.1 37.8 ± 2.7 33.6 ± 2.4 31.7 ± 2.5 314.0 ± 18.4 478.2 ± 21.3
Second-order 1
)
t1/2 (min)
X2
R2
10-3 k2 (L/mg.min)
t1/2 (min)
X2
R2
198.0 ± 8.6 13.5 ± 1.1 18.3 ± 1.3 20.6 ± 1.8 21.9 ± 2.4 2.2 ± 0.8 1.5 ± 0.6
0.05 0.08 0.09 0.11 0.13 0.34 0.51
0.99 0.97 0.99 0.99 0.97 0.98 0.98
11.3 ± 1.9 99.9 ± 7.2 77.9 ± 5.5 62.5 ± 4.8 56.4 ± 5.0 1132.8 ± 132.7 1784.3 ± 228.1
255.8 ± 26.6 11.5 ± 1.7 16.1 ± 1.2 19.8 ± 1.9 22.8 ± 2.1 1.74 ± 0.7 0.78 ± 0.09
1.33 21.10 17.61 14.86 12.78 82.90 113.55
0.99 0.91 0.96 0.98 0.99 0.96 0.90
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Fig. 10. Schematic diagram represents [a] preparation of nanoparticles by lignin and [b] catalytic reduction of reactive yellow 145 dye with the prepared nanoparticles. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
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