Notes for PPT (19 May 2018)

1. Good afternoon to all! At first, I would like to give thanks to for giving me this opportunity to
share my research findings in front of the groupmates. Today, my presentation topic is ‘xxx’.
2. Here is the outline of my presentation, in introduction part, I will start with the rational and
motivation of my research based on the literature review and then, I will share the identified
research gaps and my research objectives in order to fill the gaps. Then research methodology
and; after that, experimental part has been split up into three major parts: first, material
synthesis of nano γ-Fe2O3 loaded magnetic anionic hydrogel, which will be regarded by the term
xx in my next slides. Then the second, material characterization and the last one is batch
studies. After that, I will share my experimental results. Finally, I will wrap up my finding
concisely in the conclusion part. Thereafter I will propose my future research plan.
3. So, why heavy metals ions such as Cu and Ni should be removed from water? The researchers
have often reported that, the most of the heavy metals are toxic and carcinogenic; thus, they
are considered as one of the major environmental threats and as well as to the human health.
Therefore, we need to find a low cost effective and environment friendly way to remove them
from aqueous solution. Now the question is how they come to the environment? Mainly from
electroplating industries and mining activities. Although few advanced technologies are there,
but due to high cost of operation these are not yet attractive options to the industry. On the
other hand, in China, the discharge standards for Cu and Ni is <1mg/L, as a result, to reach such
a low concentration by deploying existing technologies is one of the major challenges.
4. After doing intensive literature review, I have come up with these conclusions; in this table, we
can see that removal of heavy metals like Cu and Ni is moderately high using the AMPS-H+ acid
based bulk magnetic anionic hydrogel. However, the contact time for the adsorption is very high
which is may be due to the bulk hydrogel, having limited surface area, thus 800 min was
required to reach the equilibrium. And, the most important thing is that the reusability of the
existing magnetic anionic hydrogel is only up to 5 cycles, in which after first 3 cycles, the
magnetic property is seriously affected; which is may be due to the corrosion effect caused by
the acidic regeneration solution. From the 2D structure of AMPS-H +, we can see the sulfonic
group with a H+ ion which need to be regenerated by protonation using strong acidic solution.
So, we can say that one of the major limitations of using AMPS-H + based magnetic anionic
hydrogel is reusability. Besides, very high initial concentration of the heavy metal ions has not
been justified in the above studies, though the Cu and Ni concertation in the real effluent of the
electroplating industries is in the range of 10-200 mg/L. And, heavy metals usually precipitate as
metal hydroxide under high pH however, the real effluent from electroplating industries is acidic
(pH 3-5); thus, they remain soluble in aqueous solution.
5. So, the following research gaps have been identified so far: slow kinetics which means very long
time needed to remove the heavy metal ions; and recovery of fine hydrogel particles from
treated water and limited reusability in multiple cycles due to poor removal efficiency and
instability of the magnetic property. Besides, previous studies were mainly based on the
synthetic wastewater; therefore, the performance in removing metal cations using real
electroplating effluent is still unknown.

6. In order to fill the aforementioned research gaps: I have set the following research objectives:
  To develop a novel magnetically stable anionic hydrogel and characterize its
physicochemical properties
 To conduct pH study, sorption isotherms study, and sorption kinetics using the as-
synthesized nFeMAH
 To investigate reusability (adsorption-desorption-resorption) of the as-synthesized nFeMAH
over multiple cycles
 To investigate the underlying sorption-desorption mechanisms
 To evaluate the practical applicability of nFeMAH by studying the effects of copresence of
typical electroplating effluent’s constituents, and finally applying the nFeMAH in the
treatment of real electroplating effluent
7. In order to accomplish my research objectives, here, I have drawn the detailed outline of my
study, where you can see that yellow marked tasks have been already accomplished: especially,
hydrogel preparation and material characterization have been fully completed but the part of
batch studies yet to be done.
8. My material synthesis involves two parts:
 Synthesis of γ-Fe2O3
 Synthesis of nFeMAH
9. Before synthesizing nFeMAH, I had to synthesize magnetic nanoparticles of γ-Fe2O3 using typical
coprecipitation method which has been very clearly explained by this schematic diagram. At
first, FeCl3.6H2O and FeSO4.7H2O were mixed in (2:1 mol ratio) in 100 mL UPW. Then mixture
was agitated using mechanical stirrer. Later, 25 mL 6.5 M NaOH solution was added drop wise.
After 1 h mixing, the black precipitate of magnetite formed and then it was washed thoroughly
in UPW and ethanol. After that, it was dried in air oven @150 oC for 2 h to obtain ~5 to 10 nm
brown color maghemite i.e., γ-Fe2O3.
10. Then free radical polymerization method was used to synthesize of nFeMAH. This new method
of synthesizing nFeMAH was based on AMPS-Na+ salt solution based, because AMPS-H+ which is
acidic version of AMPS cannot be used in this method. If AMPS-H+ acidic version of the
monomer is used instead of AMPS-Na+ then hydrogel gel doesn’t form due to scission reaction.
Another reason for choosing AMPS-Na+ sodium salt solution is the presence of Na+ ions in the
sulfonic group which may be exchangeable with NaCl salt solution then corrosion effect of acid
can be avoided in the regeneration process, which may guarantee the stability of the hydrogel in
the multiple cycle. Let’s come back to the synthesis process. At first, 4 g of AMPS-Na+ salt
solution was purged with N2 gas for 5 min in order remove O2. Then under room temperature,
0.05 g methylene-bis-acrylamide (MBA) as crosslinker was added and allow 5 min mixing. After
that, 20 uL Tetramethyl-ethylene-diamine (TEMED) was used added as accelerator. Then 0.3 g of
MNP was added into the solution to give magnetic property to the hydrogel. Finally, 40 uL
saturated solution of the ammonium persulfate (APS) was added as redox initiator. Once the
redox initiator is added to the solution, the nFeMAH gel is formed so quickly and release heat
~55 oC. In the free radical polymerization method usually, heat is consumed and thus external
heating is necessary to make the reaction happen; however, in my case, the required heat was
produced during the reaction. So, you can say this new method is environment friendly as it
does not consume energy rather it produces energy in the form of heat. Interestingly, this
phenomenon has not been reported before. Another important feature of my method is
magnetic nano particles can be embedded in-situ whereas the other methods reported in the
 literature involve up to 3 days to embed the iron nano particles by soaking bulk hydrogel in the
mixed solution of ferrous solution. So, we can say this new method is time saving as well
compare to other method.
11. Then, I fine-tune my as-synthesized nFeMAH with different MBA X-linkers’ content. Among
different mol%, I used 3.6 mol% MBA as this was the optimized MBA content studied by
previous research group while synthesizing magnetic cationic hydrogel. Interestingly, I found the
optimized result (~99%) in terms of magnetic separation under the same MBA content in
nFeMAH. And, in order to determine magnetic separation efficiency, I also studied the
relationship between nFeMAH dosage and turbidity where linear relationship has been
observed.
12. Then I studied pH
 The removal of Cu2+ and Ni2+ increases with the increase of solution pH
 Max. adsorption: Cu2+ (134 mg/g) & Ni2+ (158 mg/g) at pH 6.0 & 8.0
 But, high pH causes metal hydroxide precipitation that may lead to inaccurate
interpretation of adsorption (Mahmoud, 2013)
 Additionally, strong competition between H+ & Mn+ for binding sites causes poor
adsorption at low pH (Mahmoud, 2013)
13. In this speciation study as a function of pH, we can see- the suggested pH for Cu and Ni is 5 and
6, respectively, whereas the researchers have studied Cu and Ni at different pH. For instance, Cu
has been studied @pH 5.0, 5.5, and at 6.8, whereas Ni was studied at 8.5. Therefore, I was
curious to examine the effect of the metal hydroxide formation by doing some control tests.
14. Although, for heavy metal analysis, two types of filter suggested in order to avoid interreference
i.e., PES and Nylon but I also used cellulose nitrate type typical filter paper as I might need to use
them later to recover magnetic hydrogel during reusability study. As there was no evidence
observed for the interference because of filter media in both cases: control study and physical
tests under the acidic pH which are 5.5 for Cu and 6.0 for Ni; therefore, I will be using this
optimized solution pH for the rest of the studies accordingly.
15. Results and Discussions: Material Characterization
I have conducted the following tests in order to characterize my novel hydrogel i.e., nFeMAH
16. Zeta-potential shows that the nFeMAH surface charge is permanently negative. The negative
zeta potential of nFeMAH may be attributed to dissociation of sulfonic (–SO3) and amide (–
CONH2) groups (Mahmod, 2013). At the low pH, the decrease of negative surface charge may be
due to the presence of high concentration of positively charged H+ ions.
17. Here we can see the mean particle size of nFeMAH is about 8 um.
18. VSM test for determining magnetic property of pristine γ-Fe2O3 and nFeMAH
 Both are superparamagnetic because no remanence detected in the absent of magnetic
field
 The saturation magnetization was found ~32 emu/g for pristine γ-Fe2O3, supported by the
literature for the same materials. If you see this graph where the green line representing γ-
Fe2O3 where the magnetization was found ~34 (emu/g) whereas in my case it was 32
(emu/g) which is comparable. Besides, for the fresh nFeMAH it was ~4 (emu/g) which is
~13% of the pristine γ-Fe2O3.
19. FT-IR analysis to identify the material
 Peaks of the bare hydrogel is well fit with the standard peaks of pure AMPS-Na+ sodium salt
solution. But, little deviation at the beginning may be due to the presence of other chemicals
such as MBA, APS and TEMED FTIR analysis of nFeMAH
20. FT-IR analysis of fresh nFeMAH
 The respective peaks in FT-IR analysis of AMPS-Na+ sodium salt based magnetic anionic
hydrogel nFeMAH confirm the presence of different functional groups, such as sulfonic
group, methylene, Nitrogen and Hydrogen bond, Carbon and Hydrogen bond and FeO,
representative of γ-Fe2O3 in the hydrogel network.
21. FT-IR analysis: Comparison between bare hydrogel and fresh nFeMAH
 Two peaks have been stretched upward for the case of nFeMAH may be because of the
respective peaks of γ-Fe2O3
 Changes in peaks of nFeMAH indicates that the γ-Fe2O3 nanoparticles have been properly
embedded within the 3-dimensional networks of the hydrogel
22. FT-IR analysis: Comparison among fresh nFeMAH and metal loaded nFeMAH
 Changes in peaks of metal loaded nFeMAH may be due to the sorbed Cu2+ and N2+ions on
the surface of nFeMAH
23. X-Ray diffraction (XRD) analysis
 Sharp peaks of γ-Fe2O3 are observed at 2θ = 24.125o, 33.115o, 35.612o, 49.417o, 54.005o,
62.385o and 63.966o corresponded to the (0 1 2), (1 0 4), (1 1 0), (0 2 4), (1 1 6), (2 1 4) and
(3 0 0) planes, respectively (PDF#00-024-0072).
 Bare hydrogel doesn’t exhibit any sharp peaks in XRD, but show a broad peak at ~35 o due to
the polymer network (Mahmoud, et al., 2013)
24. X-ray photoelectron spectroscopy: Bare hydrogel
 Full-scan spectra of the bare anionic hydrogel shows the presence of five constituent atoms,
viz., C, O, N, S, and Na without impurities
25. X-ray photoelectron spectroscopy: nFeMAH
 Full-scan spectra of the bare anionic hydrogel shows the presence of six constituent atoms,
viz., C, O, N, S, Fe and Na without impurities. Especially, the presence of Fe confirms the
proper binding of γ-Fe2O3 in the hydrogel network. Based on the Fe wt fraction I also
calculated the γ-Fe2O3 content in nFeMAH and found same as it was used during synthesis
process 13 wt%.
26. XPS analysis: Comparison between bare hydrogel and fresh nFeMAH
 In order to compare the high-resolution spectra of different elements, I merged them in
common axis under same scale where we can observe very slight shifting of peaks for
carbon and sulfur may be due to the binding with the Fe. But no shift of peaks observed for
the other elements.
27. XPS analysis: Comparison between bare hydrogel and nFeMAH (Cont’d)
 However, the respective peaks for Fe was clearly detected in nFeMAH whereas no peaks for
Fe in the bare hydrogel. If we go back and see exactly under the same binding energy, two
peaks detected in the full-scan spectra in the nFeMAH
28. SEM images of bare hydrogel and nFeMAH
 Particle size of bare hydrogel nonuniform and much bigger than nFeMAH
 Particle size of nFeMAH is quite uniform
 Mean particle size is reconfirmed (~8 um)
29. SEM images of bare hydrogel and nFeMAH (Cont’d)
 nFeMAH is mesoporous as per IUPAC classification and BET test results
 Surface area is high; thus, reaction kinetics is faster than the bulk hydrogel
30. TEM images of γ-Fe2O3
 Presence of lattice fringes of γ-Fe2O3 (as one of the fingerprint properties)
 d-spacing 0.37 nm correspond to (0 1 2) lattice plane (PDF 00-024-0072)
 d-spacing 0.25 nm correspond to (1 1 0) lattice plane (PDF 00-024-0072)
31. TEM images of nFeMAH
 5-10 nm γ-Fe2O3 magnetic nanoparticles is quite well dispersed inside hydrogel networks
32. EDS mapping of nFeMAH
 We can see the respective sharp of all the peaks of the element presents in the nFeMAH.
You might be confused to see the peak of Cu as it was fresh nFeMAH. Actually, it is due to
copper grids which was used as sample holder
33. TG analysis of Fe2O3, bare hydrogel and nFeMAH
 Significant weight loss is observed between 100 and 150 oC for both, probably due to
moisture evaporation
 The second degradation temperature for bare hydrogel and nFeMAH was observed between
300 and 350oC
34. Results and Discussion
Bach studies:
 Sorption kinetics study
 Sorption isotherm study
 Reusability study
35. Adsorption kinetic study of Cu2+ using nFeMAH
 99% removal achieved at equilibrium after 60 min.
 The initial increase in metal ion adsorption because of many available surface sites
 Due to repulsive forces between the solute molecules on the solid surface
36. Fitting curve with pseudo-second-order model
 The sorption process of Cu2+ions onto nFeMAH can be well described by a pseudo-second-
order model, thus, the sorption rates of metal ions onto the adsorbents were probably
controlled by a chemical process
37. Adsorption kinetic study of Ni2+ using nFeMAH
 90% removal achieved at equilibrium after 120 min.
Why Co = 50 mg/L?

38. Fitting curve with pseudo-second-order model

 The sorption process of Ni2+ ions onto nFeMAH can be well described by a pseudo-second-
order model, thus, the sorption rates of metal ions onto the adsorbents were probably
controlled by a chemical process
39. Fitting experimental data with Langmuir model
 qm = 115 mg Cu2+/g nFeMAH
  KL = 3.63 (L/mg)
 Best fit with Langmuir model which implies a monolayer sorption of Cu 2+ ions onto the
homogeneous surface of nFeMAH
40. Fitting curve for Langmuir isotherm model
41. Fitting experimental data with Langmuir model
 qm = 103 mg Ni2+/g nFeMAH
 KL = 1.73 (L/mg)
 Best fit with Langmuir model which implies a monolayer sorption of Ni2+ ions onto the
homogeneous surface of nFeMAH
Why adsorption capacity of Cu2+ > Ni2+ on nFeMAH surface?
 The smallest ionic radius and greatest charge density of Cu, implying that Cu2+ions possess
stronger attraction to the lone pair of electrons in the nitrogen and oxygen atoms to form
more stable complexes (Mahmoud, 2013).
42. Fitting curve for Langmuir isotherm model
43. Optimization of regeneration solution: Cu2+
 Feed-to-regeneration ratio (v/v) is 20:1
 4 M NaCl
44. Optimization of regeneration solution: Ni2+
 Feed-to-regeneration ratio (v/v) is 20:1
 4 M NaCl
45. Desorption kinetics study: Cu2+ and Ni2+
Equilibrium time:
 30 min for Cu2+
 60 min for Ni2+
 Equilibrium time for desorption is faster than sorption process for both the cases may be
due to the very high partial pressure of Na+ ions presents in the regeneration solution.
46. Cyclic study of Cu2+ using nFeMAH
 Sorption capacity has been reduced very slowly in every sorption-desorption cycle, which
may be due to the continuous accumulation of metal ions on the nFeMAH surface
 Although the removal efficiency is quite high, but it exceeds the discharge limit
 Need to increase the nFeMAH dosage
47. Cyclic study of Ni2+ using nFeMAH
 Within 10 cycles, the sorption capacity reduced significantly
 Need to increase the nFeMAH dosage in order to meet the discharge limit in multiple cycles
48. FT-IR analysis: Comparison among fresh nFeMAH and reused nFeMAH
 Certain changes in peaks of reused nFeMAH may be due to the presence of accumulated
Cu2+ and Ni2+ ions on the surface of nFeMAH after cyclic study.
49. Control study with 1 wt% of fresh nFeMAH
 This study was intended to justify the use of 1 wt% of fresh nFeMAH in order to compensate
the loss of nFeMAH mass in each cycle for washing using UPW.
50. Metal concentration in regeneration solution
 ~800 mg/L for Cu2+ until 20 cycles
 >600 mg/L for Ni2+ until 10 cycles
 Very high feed-to-regeneration solution volume ratio (v/v) =20:1
  Recovery of metal could be attractive option due to very high concentration of metals in the
regeneration solution.
51. Magnetic separation efficiency of reused nFeMAH
 Magnetic separation efficiency is consistently high until the end of 20 cycles for Cu2+ and 10
cycles for Ni2+
 Slightly poor efficiency observed at the first cycle that is may be due to the very fine
nFeMAH particles which were remained suspended
 Loss of magnetic property <4% after 20 cycles of reuse
52. Conclusions
 Magnetic separation efficiency of nFeMAH is very high (99%).
 Surface of nFeMAH is permanently negative over pH ranging from 2-12, which is able to
remove heavy metal cations irrespective of the solution pH.
 Maximum adsorption capacity of nFeMAH is moderately high, and comparable with other
adsorbents (115 mg/g and 103 mg/g for Cu2+ and Ni2+, respectively).
 Equilibrium time for adsorption has been significantly reduced from 800 min to 60 and 120
min for Cu2+ and Ni2+, respectively.
 Desorption kinetics is very fast: 30 min for Cu2+ and 60 min for Ni2+, using 4 M NaCl with
20:1 feed-to-regeneration solution volume ratio(v/v), whereas 24 h contact time with 1:1
feed-to regeneration solution volume ratio(v/v) using 0.1 M HNO3 was considered in the
previous studies.
53. Conclusions (Cont’d)
 Although the initial reusability study shows that the effluent metal concentration exceeds
the discharge limit, but it gives us a clue to increase the nFeMAH dosage by 20-30 wt% to
satisfy the discharge limit in the multiple cycles.
 Metal concentration in regeneration solution is exceptionally high (~800 mg Cu2+/L & >600
Ni2+/L), and which could be a very much attractive option for the metal recovery.
 Magnetic separation efficiency is consistently high (99%) of nFeMAH even after 20 cycles,
whereas the previous study reported that magnetic property was significantly affected right
after only 3 cycles.
54. Future Work
 Coexisting study (to understand the effect of copresence of typical electroplating effluent’s
constituents)
 To study the underlying sorption-desorption mechanisms
 Study the pollutant removal efficiency of nFeMAH using real electroplating effluent
55. Thanks.

T o −T ¿ .
Magnetic Seperation Efficiency (%)= ( To ) ×100
 C o−C e
Metal removed due ¿ precipitation( %)= ( Co ) ×100