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Green Synthesis and Characterizations of Copper Nanoparticles

M.I.M. Ismail

PII: S0254-0584(19)31098-3
DOI: https://doi.org/10.1016/j.matchemphys.2019.122283
Reference: MAC 122283

To appear in: Materials Chemistry and Physics

Received Date: 06 July 2019

Accepted Date: 07 October 2019

Please cite this article as: M.I.M. Ismail, Green Synthesis and Characterizations of Copper
Nanoparticles, Materials Chemistry and Physics (2019), https://doi.org/10.1016/j.matchemphys.
2019.122283

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Green Synthesis and Characterizations of Copper Nanoparticles

M. I. M. Ismail1,2,*
1Physics Department, Faculty of Science/ Port Said University, Port Said, Egypt.
2 Physics Department, Faculty of Arts and Science in Almikhwah, AlBaha University, Almikhwah, Saudi Arabia.

Abstract

Present work describes the synthesis of copper nanoparticles (CuNPs) using aqueous
sumaq (Rhuscoriaria L.) fruits extract as a stabilizing agent. The preparation of
CuNPs using aqueous Rhus coriaria L. fruits extract has desired quality with low cost
and eco-friendly method. The Rhuscoriaria L. fruits extract was mixed with copper
sulphate solution and hydrazine hydrate as reducing agent and sodium hydroxide as
catalyst. The solution heated to a temperature of 60˚C and the reduction reaction was
followed by observing the color change. The synthesized CuNPs were characterized
by UV-Visible spectra, FTIR, XRD and TEM. CuNPs display an absorption peak at
560 nm. TEM photograph showed that synthesized CuNPs had semi-spherical shapes
with diameter of 22–27 nm. The XRD data exposed that the average crystallite size
was 18 nm. Parameters such as direct energy band gap (DEBG), indirect energy band
gap (IDEBG), Urbach energy (EU) and Fermi energy (EF) were calculated by using
UV-Visible absorption. CuNPs had shown an inhibitory effect versus Gram-positive
bacteria during the antimicrobial studies.

Keywords: Green synthesis; Copper nanoparticles; Energy band gap; Rhus coriaria
L.; Antibacterial activity.

1. Introduction
As of late, nanomaterials have gotten specific consideration for its positive
influence in improving numerous segments of economy and potential applications in
different fields including cosmetic products, pharmaceuticals, antimicrobial agents
and agriculture. A great interest of copper-based nanoparticles may be due to
relatively low costs, availability and its excellent electrical conductivity [1 – 4]. It
finds applications in catalysis and as antimicrobial, bactericidal agents used to coat

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hospital equipments [5 – 11]. Different physical and chemical strategies have been
created for the synthesis of CuNPs such as pulsed laser ablation [12], decomposition,
plasma, pulsed wire discharge [13], sol-gel methods, vacuum vapor deposition [14],
electrochemical [15] and sonochemical reduction [16]. Most of these methods have
shortcomings like the use of hazardous organic solvents, toxic by-product, expensive
reagents, harsh reaction condition, difficult to isolate NPs and longer time.
Bionanotechnologists have great an interest by biosynthesis of unadulterated
metallic CuNPs in an aqueous phase, because of Cu inclination to fast oxidize at room
temperature, make it very difficult to synthesize stable copper CuNPs with desired
and controlled size and shape [17]. Generally, ascorbic acid [18], ethylene glycol [19],
hydrazine [20],sodium borohydride [20], and sodium hypophosphite [21] were
utilized for the synthesis of CuNPs in non-attendance and existence of stabilizers, for
example, surfactants and polymers.

Obraztsova, et al. [22] and Carroll, et al. [23] synthesized copper nanoparticles
with average size of 10-100 nm at high temperature (135–185 0C) in organic mediums
without stabilizer. On the other hand, using ethylene glycol as the reducing agent and
polyvinyl pyrrolidone (PVP) as the stabilizer at 140-200 0C, CuNPs with mediocre
size of 46 nm were obtained by Blosi et al [24]

Later, a lot of researchers take advantage of inactivated plant tissue, plant extracts,
exudates, gums and different parts of plants for the synthesis of CuNPs [25, 26]. For
examples, soybeans extract, extract of plant leaf Magnolias, leaf extracts of Brassica
juncea, Medicago sativa, Helianthus Annuus and Tridaxprocumbens, leaf extract of
Lantana camara, Zingiber officinale, Syzygium aromaticum, extract of Magnolia leaf
and of Euphorbia nivulia stem latex, and Calotropis Procera L. latex were used to
synthesis of CuNPs [27 – 33]

India have been used a traditional medicinal plant called Ocimum sanctum as bio-
reduction sources and stabilizers for CuNPs synthesis [34].In the present work, green
synthesis of CuNPs using copper salts as basic precursors, Rhus coriaria L. fruits
extract as stabilizer, hydrazine hydrate as reducing agent and sodium hydroxide as a
catalyst and also to adjust the pH was described.

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2. Materials and Methods

2.1. Materials:
CuSO4.5H2O 99.9% was purchased from Aldrich, Portulaca oleracea L. seeds and
Rhus coriaria L. fruits were purchased from standard vendors. Hydrochloric acid and
sodium hydroxide used for pH monitoring were also purchased from Sigma Aldrich.
A 1x10-2M stock solution of copper sulphate pent hydrate [CuSO4.5H2O] was
prepared by dissolving 0.25g of the copper sulphate salt in 100 ml deionized water. A
2%, hydrazine solution was prepared by taking 2ml of hydrazine solution in 100ml of
deionized water.

2.2. Samples preparation:

2.2.1. Preparation of Rhus coriaria L. (sumaq) extract

The plant extract (2% w/v) was prepared by boiling 2.0g of dried, well grinded
Rhus coriaria L. (sumaq) fruits for 20 min, filtering, and completing to 100 ml
deionized water. The extract was stored at 4ºC for further experiments.
2.2.2. CuNPs synthesis using sumaq extract:
To synthesize nanoparticles using (Sumaq) as stabilizer, 3ml of plant extract
were added to 1ml of CuSO4.5H2O (0.01M), 2ml of NaOH (0.01M) and 1ml of
hydrazine (2%v:v) at room temperature then complete the volume to 10 ml with
deionized water. The reduction reaction could be expressed as:

2 Cu2++ 2 N2H4+ 4OH- −→2Cu0 + N2+ 4NH4OH

The mixture was heated for 10 minutes in water bath. The solution color changed
from faint blue to pale yellow and by heating become deep red. The wavelength of the
surface Plasmon resonance peak of the CuNPs was determined using absorption
measurement.
2.3. Characterization of CuNPs
XRD measurement of the CuNPs, where only 3ml of the extract was added,
was done on a Shimadzu XRD- 6000 diffractometer operating at a voltage of 40 KV
and current of 20 mA with Cu Kα radiation. (λ= 1.54 Å). The size and morphology of
the nanoparticles were examined for both 1ml and 3ml of the extract were added and
the TEM images were obtained on a JEOL-1200JEM.

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CuNPs was tested by Perkin Elmer Spectrometer of model number 783 to

record its infrared (IR) absorption spectra between 500–4000 cm−1. Helios SP Pye-
Unicam UV-Vis spectrophotometer was used to observe the bioreduction of Cu2+ ions
in solution by measuring the UV–Vis spectra.
2.4. Antimicrobial activity assay
Antimicrobial activities of the sumaq extract, Sumaq and CuNPs were
studied on Gram Positive bacteria (Bacillus subtilis, Staphylococcus aureus), Gram
negative bacteria (E. coli). This was done through using the agar well diffusion
technique. The bacteria and fungi were maintained on nutrient agar medium and
Czapek Dox agar medium, respectively. The agar media were inoculated with
different microorganisms. The diameter of inhibition zone (mm) was measured, after
24 h of incubation at 30 ºC for bacteria and 48 h of incubation at 28 ºC for fungi.

3. Results and Discussion

3.1. X-ray Diffraction
The synthesized CuNPs crystal phases have been identified by the XRD
analysis test (Fig. 1).Fig. 1 shows that peaks at 2θ = 43.35°, 50.48° and 74.04° match
the crystal facets of (111), (200) and (220), respectively (JCPDS, file No. 89-2838)
and (JCPDS, file No. 85-1326). So, the diffraction peaks at Fig. 1 prove the
fashioning of a face-centered cubic (FCC) pure copper phase. By using Debye–
Scherrer formula, the average crystallite size Dhkl can be evaluated [35 - 38]
0.9𝜆
𝐷ℎ𝑘𝑙 = (1)
𝛽cos 𝜃
Where β is the full-width at half-maximum (FWHM) value of XRD lines, the
wavelength λ = 0.154056 nm and θ is the half diffraction angle of 2θ. The synthesized
CuNPs size is determined by taking the normal of the sizes at the crystal facets D111,
D200 and D220. It was observed to be 14.9 nm.
The lattice parameter "ao" of the synthesized CuNPs is evaluated by Eq. (3)

Bragg's law (Eq. (2)) [37 and 38]. It was observed to be 8.386 Å.

𝜆
𝑑h𝑘𝑙 = (2)
2 𝑠𝑖𝑛𝜃

𝑎°
𝑑h𝑘𝑙 = (3)
h2 + 𝑘2 + 𝑙2

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Fig 2. shows the plotting h2 + 𝑘2 + 𝑙2 as a function of 1 𝑑h𝑘𝑙, the lattice

parameters "ao" are calculated by tacking the slope of the curve of fig 2.

The lattice parameter for the prepared sample is 3.626 Å which is much closer
to the values reported for (JCPDS, file No. 89-2838 (ao = 3.615 Å)) and (JCPDS, file

No. 85-1326(ao = 3615 Å)).

Using Williamson-Hall method, both particle size and lattice strain can
calculate by Eq. (4) [35 and 38]

𝑘𝜆
𝛽𝑐𝑜𝑠𝜃 = + 4𝜀 𝑠𝑖𝑛𝜃 (4)
𝐷

Where β, θ, λ, D and ε are a measurement of FWHM in radians, Bragg's angle of the

diffraction peaks, the wavelength of the X-rays used, the effective particle size, and is
the amount of strain [37 and 38].

Fig.3. shows the relation between (β cosθ) and (4sinθ) for the CuNPs.
Accordingly, D and ε can be determined by y-intersect and the slope of the fitted line,
respectively. Fig. 3 shows +ε for the synthesized CuNPs. +ε may be explained as
lattice expansion. The calculated particle size from Williamson-Hall method is much
closer to the calculated particle size from Debye–Scherrer formula, see table 1.

3.2. TEM measurements

To examine the size and shape of synthesized CuNPs, TEM measurements
were performed at two extract concentrations to confirm the utility of the extract as
stabilizing agent for synthesized CuNPs. TEM images analysis of synthesized CuNPs,
as shown in Fig. 4. The image in Fig. 4.a, where only 1ml of the extract was added in
presence of 0.2% hydrazine, confirmed that synthesized CuNPs were not completely
spherical in shape and the sizes were in the range of 14 to 24 nm. Fig. 4.b shows the
image of synthesized CuNPs when the concentration of the extract was increased to 3
mL, the particles are spherical with diameters about 7 -10 nm. This confirms the
hypothesis that the extract work as capping agent to acquire the dominant fashioning
of spherical CuNPs.

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3.3. FTIR measurements

FTIR measurements were done to distinguish the bearable phytochemical
biomolecules dependable for the reduction and capping of the CuNPs synthesized by
sumaq aqueous extract. Aqueous fruit of sumaq extract was investigated for the
presence of hydrolysable tannins mainly pentagalloyl glucose [39], anthocyanin such
as cyanidin, peonidin, pelargonidin, petunidin, delphinidin glycosides and coumarates
[40], gallic acid [41], flavonoids such as myricetin, quercetin and kaempferol [42].
Fig. 5a shows The FTIR spectrum of dried sumaq fruit powder exhibited different
functional groups. The IR bands (Fig. 5a) observed at 3410 and 1743 cm-1in are
characteristic of the O-H and C=O stretching modes of the OH and C=O groups
possibly of cyanidin, peonidin, pelargonidin, myricetin, quercetin kaempferol, and/or
delphinidin glucosides present in the sumaq leaf. The band at 1651 cm-1 assigned to
the amide carbonyl stretching frequency. The bands at 2925 and 2860 cm-1 assigned
to C-H stretching frequency. The shift of the band of OH group from 3410 to 3400
cm-1 and the carbonyl stretching frequency of C=O from 1743 to 1721cm-1 with
decreasing in its intensity suggest that these groups are involved in the capping of
CuNPs.

3.4. UV-Vis Spectrophotometry

When the copper ion is exposure to the plant leaf extract, the copper ion is
reduced to copper nanoparticles, after reducing Cu ions, the color of the solution may
be change and thus UV–Vis spectroscopy. Addition of Rhus coriaria L. (sumaq)
extract (3mL) to the CuSO4 solution in presence of 0.2% hydrazine and heating the
solution for 10 min resulted in changing the solution color from faint blue to yellow
and finally deep red. Rhus coriaria L. extract was used as reducing and stabilizing
agent in preparation of AuNPs [43]. Preparation of CuNPs suspensions using Rhus
coriaria L. extract without any hydrazine resulted in the formation of yellowish green
solution and difficulty in determination of the surface Plasmon resonance of CuNPs.
Addition of lower or higher extract concentration than 3mL in presence of 0.2%
hydrazine leads to precipitation of the CuNPs as shown in Fig. 6. At lower extract
concentration the extract is not enough to stabilize CuNPs and at higher extract
concentration the agglomeration of the capped particles occurs. This indicates that the
Rhus coriaria L. highly stabilized the Cu nanoparticles due to its high capping power

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but has low ability to reduce Cu2+ to Cu0. Fig. 7 shows that the maximum absorbance
of CuNPs takes place at 568 nm, and the absorbance intensity of CuNPs increases as
reaction time increases until the end of the reaction at which all Cu ions are reduced.
UV-Vis absorption spectrum peak at 568 nm is features of the surface Plasmon
resonance of nano-sized particles [44]. Many capping agents such as Polyvinyl
Pyrrolidone (PVP), Polyethylene glycol [45], cetyltrimethylammonium bromide
(CTAB) [44] and SDS are used to prevent agglomeration.

3.4.1. Determination of DEBG and IDEBG of the synthesized CuNPs

DEBG and IDEBG of the synthesized CuNPs can be determined by Eq. 5
𝛼𝜊(ℎ𝜈 ― 𝐸𝑜𝑝𝑡
𝑔 )
𝛼(𝜈) = (5)
ℎ𝜈
E gopt
where (), o, , and n are the absorption coefficient of the sample, constant
E gopt
related to the extent of the band tailing, is the optical band gap energy, and the
exponent n = 2 for allowed indirect transition, while n = 1/2 for allowed direct
transition.
E gopt1 E gopt2
The optical DEBG and IDEBG transition can be determined by plotting
(hα)2 and (hα)1/2 versus photon energy (h), respectively.
E gopt
The respective values of are obtained by extrapolating to (hα)2 = 0 for
direct transition and (hα)1/2 = 0 for indirect transition as shown in Figs. 8 and 9,
respectively. Table 2 shows DEBG and IDEBG values. It may be noted that the
IDEBG value is smaller than the corresponding DEBG value. Both DEBG and
IDEBG values of the synthesized CuNPs would classify it as semiconductor materials
[46].

Urbach energy Fermi energy level of the synthesized CuNPs can be calculated
as Fouad El-Diasty, et al. [35] and H. El-Ghandoor, et al. [37] were reported. It was
found that Urbach energy and Fermi energy level of the synthesized CuNPs are 0.15
and 2.15 eV, respectively.

3.5. Antimicrobial Activities

The antibacterial activity of the synthesized CuNPs was tested against bacteria
by zone inhibition disc diffusion method. The copper nanoparticles showed good

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bacterial activity against E. coli, Staphylococcus aureus, Bacillus cereus and

Pseudomonas aeruginosa. The results showed that inhibition zone for the studied
strains were: 10, 8, 7 and 8 mm, for E. coli, Staphylococcus aureus, Bacillus cereus
and Pseudomonas aeruginosa, respectively. In any case, the definite mechanism
behind bactericidal impact of the synthesized CuNPs isn't known and should be
additionally examined on the more extensive scope of bacteria strains.

4. Conclusions
In this work, synthesis of copper nanoparticles using aqueous sumaq
(Rhuscoriaria L.) fruits extract as a stabilizing agent was investigated. The
synthesized copper nanoparticles were characterized by XRD and TEM, FT-IR and by
UV-Visible spectra. The values of both DEBG and IDEBG would classify the
synthesized CuNPs as a semiconductor. The synthesized CuNPs showed good
bacterial activity against E. coli, Bacillus cereus, Staphylococcus aureus, and
Pseudomonas aeruginosa.

References:
1- Ahmadi S.J, Outokesh M., Hosseinpour M., Mousavand T., Particuology. 9
(2011) 480 – 485.
2- Ramgir N., Datta N., Kaur M., Kailasaganapathi S., Debnath A.K., Aswal
D.K., Gupta S.K., Colloids Surf. A Physicochem Eng. Asp. 439 (2013) 101–
116.
3- Guogang Ren, Dawei Hu, Eileen W.C. Cheng, Miguel A. Vargas-Reus, Paul
Reip, Robert P. Allaker, The International Journal of Antimicrobial Agents.
33(6) (2009) 587- 590.
4- T. Theivasanthi, M. Alagar, Annals of Biological Research. 2(3) (2011) 368-
373.
5- Stoimenov P.K., Klinger R.L., Marchin R.L., Klabunde K.J., Langmuir. 18(7)
(2002) 6679 – 6686.
6- Gabbay J., Mishal J., Magen E., Zatcoff R.C., Shemer-Avni Y., Borkow G., J
Ind Textil. 35 (2006) 323 – 335.
7- Borkow G., Zatcoff R.C., Gabbay J., Med. Hypotheses. 73(6) (2009) 883 –
886.

8
 Journal Pre-proof

8- Borkow G., Gabbay J., Dardik R., Eidelman A.I., Lavie Y., Grunfeld Y., Ikher
S., Huszar M., Zatcoff C., Marikovsky M., Repair Regen. 18 (2) (2010) 266 –
275.
9- Asim Umer, Shahid Naveed, Naveed ramzan, Muhammad Shahid Rafique,
NANO: Brief Reports and Reviews. 7(5) (2012) 1- 18.
10- A. Nasirian, International Journal of Nano Dimension. 2(3) (2012) 159- 164.
11- Magayer R., Zhao J., Bowman L., Ding M., Experimental and Therapeutic
Medicine. 4 (2012) 551- 561.
12- Yeh M. S., Yang Y.-S., Lee Y.P., Journal of Physical Chemistry-B. 103 (33)
(1999) 6851-6857.
13- Yatsui K., Grigoriu C., Kubo H., Applied Physics Letters. 67 (9) (1995) 1214-
1216.
14- Liu Z., Bando Y., Advanced Materials. 15 (4) (2003) 303- 305.
15- Molares M., Buscmann V., Dobrev D., Advanced Materials. 13 (1) (2001) 62-
65.
16- Kumar R., Mastai Y., Diamant Y., Journal of Materials Chemistry. 11 (4)
(2001) 1209- 1213.
17- Mott D., Galkowski J., Wang L., Luo J., Zhong C.J., Langmuir. 23 (2007)
5740- 5745.
18- Wu C., Mosher B., Zeng T., J Nanoparticle Res. 8 (2006) 965-969.
19- Yu Zhao, Jun‐Jie Zhu, Jian‐Min Hong, NingshengBian, Hong‐Yuan Chen,
Eur. J. Inorg. Chem. (2004) 4072-4080.
20- Lisiecki I., Billoudet F., Pileni M., J. Phys. Chem. 100 (1996) 4160-4166.
21- Dongzhi Lai, Tao Liu. Guohua Jiang, Wenxing Chen, J Appl. Polym. Sci. 128
(3) (2012) 1443-1449.
22- I. I. Obraztsova, G. Y. Simenyuk, N. K. Eremenko, Russ. J. Appl. Chem.82
(2009) 981- 985.
23- K. J. Carroll, J. U. Reveles, M. D. Shultz, S. N. Khanna, E. E. Carpenter, J.
Phys. Chem. C115 (2011) 2656- 2664.
24- M. Blosi, S. Albonetti, M. Dondi, C. Martelli, G. Baldi, J. Nanopart. Res.13
(2011) 127- 138.
25- Kavitha K.S., Syed Baker, Rakshith D., Kavitha H.U.,Yashwantha Rao H.C.,
Harini B.P., Satish S., Int. Res. J. Biological Sci. 2 (6) (2013) 66 – 76.
26- Iravani S., Green Chemistry. 13(10) (2011) 2638-2650.

9
 Journal Pre-proof

27- Guajardo-Pacheco J., Morales-Sanchez J.E., Gonzalez-Hernandez J., Ruiz F.,

Materials letters. 64 (12) (2010) 1361- 1364.
28- Hyo-Jeoung Lee, Geummi Lee, Na Ri Jang, Jung Hyun Yun, Jae Yong Song,
Beom Soo Kim, TechConnect Briefs. 1 (2011) 371- 374.
29- AbdulHameed.M. Al-Samarrai, International Journal of Scientific and
Research Publications. 2 (4) (2012) 1 – 4.
30- D. R. Majumder, International Journal of Engineering Science and
Technology. 4 (10) (2012) 4380 – 4389.
31- Ipsa Subhankari, P.L. Nayak, World Journal of Nano Science & Technology.
2 (1) (2013) 14 – 17.
32- Hyo-Jeoung Lee, Jae Yong Song, Beom Soo Kim, Journal of Chemical
Technology and Biotechnology. 8 (11) (2013) 1971- 1977.
33- Harne S., Sharma A., Dhaygude M., Joglekar S., Kodam K., Hudlikar M.,
Colloids Surf. B Biointerfaces. 15 (95) (2012) 284 – 288.
34- Vasudev D. Kulkarni, Pramod S. Kulkarni, International Journal of Chemical
Studies. 1(3) (2013) 1- 4.
35- Fouad El-Diasty, H.M. El-Sayed, F.I. El-Hosiny, M.I.M. Ismail, Current
Opinion in Solid State and Materials Science. 13 (2009) 28 – 34.
36- H. El-Ghandoor, H.M. Zidan, Mostafa M.H. Khalil, M.I.M. Ismail, Phys. Scr.
86 (2012) 015403- 015410.
37- H. El-Ghandoor, H.M. Zidan, Mostafa M.H. Khalil, M.I.M. Ismail, Int. J.
Electrochem. Sci. 7 (2012) 5734 – 5745.
38- M. I. M. Ismail, Eman Elesh, IOSR Journal of Applied Physics. 9 (4 IV)
(2017) 57 – 66.
39- Kosar M., Bozan B., Temelli F., Baser K.H.C., Food Chemistry. 103 (3)
(2007) 952- 959.
40- A. Guvenc, Mehmet. Koyuncu, In Turkish J. Med. Sci. 20 (1) (1994) 11- 14.
41- EL Sissi H.I., Ishak S., Abd El Wahid M.S., In Planta Med. 21 (1) (1972) 67-
71.
42- Mehrdad M., Zebardas M., Abedi G., Koupaei M.N., Rasouli H., Talebi M.,
Int J. AOAC Int. 92 (4) (2009) 1035- 1043.
43- Hamed M. O., Synthesis of gold nanoparticles capped with constituents of
some medicinal plants. M.Sc. Thesis, Ain Shams University. (2015)

10
 Journal Pre-proof

44- Park B. K., Jeong S., Kim D., Moon J., Lim S., Kim J. S., Journal of Colloid
and Interface Science. 311 (2007) 417- 424.
45- Sinha T., Ahmaruzzaman M., Materials Letters. 159 (2015) 168 – 171.
46- W. H. Strehlow, E. L. Cook, J. Phys. Chem. Ref Data. 2 (1) (1973) 163 – 199.
47- M. Abdel-Baki, F. El-Diasty, F. A. Abdel-Wahab, Opt. Comm. 261 (2006) 65
– 70.
48- M.A. Hassan, C.A. Hogarth, J. Mater. Sci. 23 (7) (1988) 2500 – 2504.

Figures Captures

Fig. 1: XRD pattern of the CuNPs synthesized using sumaq extract.

Fig. 2: ℎ2 + 𝑘2 + 𝑙2Vs. (1/d) of the dried CuNPs.

Fig. 3: The W-H analysis of dried CuNPs.

Fig. 4: TEM images of the synthesized CuNPs using a) 1ml extract b) 3 ml extract
Fig. 5: FTIR of (a) sumaq powder and (b) as-produced CuNPs.
Fig. 6: The synthesized CuNPs as a function of extract concentrations (a) 1mL; (b)
2mL; (c) 3mL and (d) 5mL
Fig. 7: UV-Vis absorption spectra of the synthesized CuNPs
Fig. 8: Determination of the optical DEBG E gopt2 of the synthesized CuNPs.

Fig. 9: Determination of the optical IDEBG E gopt1 of the synthesized CuNPs.

Fig. 10: Determination of EU of the synthesized CuNPs.

Fig. 11: Absorption index versus wavelength of the synthesized CuNPs.

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Table 1 : Geometric parameters of the synthesized CuNPs.

averaging the particle size

estimated from
Lattice
parameter Scherrer Williamson-Hall methods TEM
"ao"(Å) method

D (nm) D (nm) Ɛ no Unit D ±5

×10-3 (nm)
8.386 14.87 17.20 7.97 19
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Table 2. Optical parameters of the synthesized CuNPs.

Indirect energy Direct energy Urbach Fermi energy

band gap band gap (eV) (eV)
𝑬𝒐𝒑𝒕
𝒈𝟐 (eV) 𝑬𝒐𝒑𝒕
𝒈𝟏 (eV)

1.77 2.02 0.15 2.15