Reusable photoresponsive Ag/AgCl nanocube-catalyzed one-pot synthesis of seleno[2,3-b]pyridine derivatives

Article abstract of DOI:10.1007/s11164-020-04143-6

In this study, a facile and rapid method was developed to synthesize intensely organoselenium compounds, namely ethylseleno[2,3-b]pyridine carboxylate, seleno[2,3-b]pyridine-2-carbonitrile and 2-benzoylseleno[2,3-b]pyridine derivatives from starting compound, 2-chloro-3-cyano-4,6-dimethylpyridine, in one-pot synthesis using Ag/AgCl nanoparticles (NPs) under visible light irradiation. Three different shapes of Ag/AgCl nanoparticles (nanospheres (NS), nanocubes (NC) and nanowires (NW)) were synthesized by controlling the concentration ratio between silver nitrate (AgNO₃) and hydrochloric acid. The Ag/AgCl NPs were characterized using different tools such as scanning electron microscopy, UV–Vis spectrophotometry and X-ray diffraction. The catalytic activity of the photoresponsive Ag/AgCl nanoparticles with different morphology was evaluated towards organoselenium compounds production. The following rate order of seleno[2,3-b]pyridine derivatives production and organic dye degradation under visible light irradiation was Ag/AgCl-NC > Ag/AgCl-NW > Ag/AgCl-NS. The mechanism of the production of seleno[2,3-b]pyridine derivatives has been proposed. It is clearly shown from the results that high yield of selective organoselenium compounds (> 90%) was obtained under mild conditions with short reaction time and the photocatalytic activity of the prepared Ag/AgCl nanoparticles depends on their morphology.

Full text of DOI:10.1007/s11164-020-04143-6

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-020-04143-6
Reusable photoresponsive Ag/AgCl nanocube‑catalyzed
one‑pot synthesis of seleno[2,3‑b]pyridine derivatives
Yasser Attia Attia1 · Shams H. Abdel‑Hafez2,3
Received: 14 January 2020 / Accepted: 27 March 2020
©
Springer Nature B.V. 2020
Abstract
In this study, a facile and rapid method was developed to synthesize intensely orga-
noselenium compounds, namely ethylseleno[2,3-b]pyridine carboxylate, seleno[2,3-
b]pyridine-2-carbonitrile and 2-benzoylseleno[2,3-b]pyridine derivatives from start-
ing compound, 2-chloro-3-cyano-4,6-dimethylpyridine, in one-pot synthesis using
Ag/AgCl nanoparticles (NPs) under visible light irradiation. Three diꢀerent shapes
of Ag/AgCl nanoparticles (nanospheres (NS), nanocubes (NC) and nanowires
(
(
NW)) were synthesized by controlling the concentration ratio between silver nitrate
AgNO ) and hydrochloric acid. The Ag/AgCl NPs were characterized using dif-
3
ferent tools such as scanning electron microscopy, UV–Vis spectrophotometry and
X-ray diꢀraction. The catalytic activity of the photoresponsive Ag/AgCl nanoparti-
cles with diꢀerent morphology was evaluated towards organoselenium compounds
production. The following rate order of seleno[2,3-b]pyridine derivatives production
and organic dye degradation under visible light irradiation was Ag/AgCl-NC>Ag/
AgCl-NW>Ag/AgCl-NS. The mechanism of the production of seleno[2,3-b]pyri-
dine derivatives has been proposed. It is clearly shown from the results that high
yield of selective organoselenium compounds (>90%) was obtained under mild
conditions with short reaction time and the photocatalytic activity of the prepared
Ag/AgCl nanoparticles depends on their morphology.
Keywords Ag/AgCl nanoparticles · Catalysis · Organoselenium compounds ·
Pyridines · Selective reaction
*
Yasser Attia Attia
yasserniles@niles.edu.eg
Shams H. Abdel-Hafez
shams_abdelhafez@yahoo.com
1
2
3
National Institute of Laser Enhanced Sciences, Cairo University, Giza 12613, Egypt
Department of Chemistry, Faculty of Science, Assiut University, Assiut 71516, Egypt
Department of Chemistry, Faculty of Science, Taif University, Taif 21974, Saudi Arabia
Vol.:(012
1
3456789)
3

Y. A. Attia, S. H. Abdel-Hafez
Introduction
The development of high-performance catalysts with aimed catalytic activity, selec-
tivity, and prolonged lifetime would beneꢁt the chemical industry enormously; such
research endeavors have been persistently pursued by both academia and industry
[
1]. A new understanding and mastery of catalysis could have broad societal impacts
since about 80% of the processes in the chemical industry depend on catalysts to
work eꢂciently [2–7]. The advent of nanoscience and nanotechnology is providing
the ability to create controlled structures and geometries to investigate and optimize
a broad range of catalytic processes [8, 9]. As a result, researchers are obtaining
fundamental insight into key features that inꢃuence the activity, selectivity and life-
time of nanocatalysts [10, 11]. In recent years, heterocyclic compounds based on
selenium atom have attracted the attention of scientists working in a variety of ꢁelds
due to their reactivity, chemical properties and pharmaceutical applications [12–17].
Abdel-Hafez et al. tried to prepare seleno[2,3-b]pyridine derivatives (2–4) in one-
step from compound (1) after 3 h of reꢃuxing (harsh reaction conditions) and unfor-
tunately poor chemoselectivity with low yield obtained (<15%) [18–20]. Hence, in
this report we wonder if there is a relation between the shape of Ag/AgCl NPs and
their catalytic performance towards organoselenum compounds production and the
possibilities to develop an approach for the synthesis of valuable seleno[2,3-b]pyri-
dine derivatives.
The Ag/AgX NPs (Cl, Br and I) are being widely used instead of the highly dis-
persed AgX species that can improve the separation eꢂciency of photogenerated
charge carriers and enhance the photocatalytic activity of the substrates. Further-
more, under visible light irradiation, the generated electron–hole pairs are separated
on the surface of Ag NPs due to the surface plasmon resonance (SPR) eꢀect. Hence,
recently these plasmonic photocatalysts have been developed for the high adsorp-
tion of visible light and excellent photodegradation of organic pollutants due to the
strong surface plasmon resonance (SPR) eꢀect of metallic Ag nanoparticles (Ag
NPs) [21–25]. Among Ag/AgX hybrid photocatalysts, considerable attention has
been paid to Ag/AgCl due to its relatively high stability and excellent photocatalytic
activity under UV and visible light irradiation. Although the band gap energy of
AgCl is higher than the edge of visible light (the direct and indirect band gaps of
AgCl are 5.15 eV and 3.25 eV, and the edge of visible light is located at 3.1 eV), it
is a photosensitive compound and can adsorb photons and then electron–hole pairs
+
can be generated and subsequently the Ag on the surface of AgCl particle can be
reduced to metallic Ag to form Ag/AgCl composite and extend the light response
into the visible light region [26]. However, some of the reported synthesis proce-
dures are multi-steps and time-consuming, and some need high temperature [27].
Together, the size and the shape introducing sharp corners and edges to the shape
of the nanocatalysts are considered as inꢃuencing parameters that can increase the
catalytic eꢂciency because of the presence of surface atoms that can be displayed as
active sites [28]. Herein, the catalytic synthesis of seleno[2,3-b]pyridine derivatives
was investigated to study the catalytic eꢂciency of Ag/AgCl nanocatalysts in diꢀer-
ent shapes (sphere, wires and cubes) under visible light.
1
3

Reusable photoresponsive Ag/AgCl nanocube‑catalyzed one‑pot…
Experimental
All chemicals were obtained from Sigma-Aldrich company and used as received.
UV–Vis spectra were measured with a PerkinElmer Lambda 40 UV–visible spec-
trophotometer using 1-cm-path length Hellma quartz cuvettes. X-ray diꢀraction
(
XRD) measurements were performed using a Philips PW1710 X-ray diꢀrac-
tometer using Cu Ka radiation (k = 1.54186 Å). The XRD patterns were recorded
from 20° to 70° 2H with a step size of 0.020° 2θ and collecting 10 s per step.
Scanning electron microscopy (SEM) images were obtained with a ZEISS FE-
SEM ULTRA Plus (equipped with EDX analyzer) microscope with a Philips
CM20 microscope, operating at an accelerating voltage of 200 kV. Several drops
from the sample dispersion were deposited onto an aluminium pin stubs and left
to evaporate at room temperature. Melting points (m.p.) were uncorrected using
IA9100M-Digital Melting Point Apparatus. Thin-layer chromatography (TLC)
1
was performed by silica gel plates 60 GF254, cellulose plates (20 × 20 cm). H
1
3
NMR and C NMR spectra were determined on Bruker Avance DPX spectrom-
1
13
eter at 300 MHZ for H NMR and 75 MHz for C NMR.
Preparation of Ag/AgCl nanoparticles (spheres, cubes and wires)
AgCl and Ag/AgCl nanoparticles were synthesized via the reaction of AgNO and
3
HCl in ethylene glycol in the presence of a capping agent (PVP); 425 mg of
AgNO (~ 50 mM) and 415 mg of PVP (~ 75 mM) were dissolved in 50 mL of
3
ethylene glycol (EG). After mixing the solution with a magnetic stirrer for 5 min,
the solution was kept without motion to age for 1 h. Then a small amount of HCl
was added to the solution. Final concentration of HCl was adjusted to 50 mM,
1
50 mM and 300 mM with 1:1, 1:3 and 1:6 ratio, respectively, to produce Ag/
AgCl nanoparticles with diꢀerent shapes. The solution was then heated to 150 °C.
The reaction lasted at this temperature for 20 min unless speciꢁed. After the solu-
tion was cooled down to room temperature, 100 mL of acetone and 150 mL of
deionized (DI) water were added and centrifuged at 2000 rpm for 20 min. The
resulting precipitates were white and dark white powders, and after that the pow-
der was dried in an oven for 3 h. The formed powders were characterized using
SEM, XRD and UV–Vis measurements for further work.
Photocatalytic degradation of amaranth dye (C.I. Food Red 9)
Ten milligrams of the prepared Ag/AgCl nanoparticles (nanospheres, nanowires
and nanocubes) was added to 50 mL of 0.1 mM of amaranth dye under stirring
and then irradiated with halogen lamp (HALOPAR 20 75 W 230 V 30-GU10,
Italy). The photodegradation of the dye was followed by measuring the UV–Vis
absorption at diꢀerent times.
1
3

Y. A. Attia, S. H. Abdel-Hafez
General Procedure for the production of 3‑amino‑2‑substituted
seleno[2,3‑b]pyridine (2; C H N O Se) (3; C H N Se) and (4; C H N OSe)
12
14
2
2
10
9
3
16 14 2
from 2‑chloro‑3‑cyano‑4,6‑dimethylpyridine (1)
4
,6‑Dimethyl‑2‑chloro‑3‑cyanopyridine 1 (1 mmol) was added stepwise in a mix-
ture of selenium metal (1 g, 12 mmol) and sodium borohydride (1.2 g, 32 mmol)
in ethanol. The reaction mixture was stirred for 15 min at room temperature after
the addition of Ag/AgCl NPs (0.05 mmol); then, 3 mmol of chloroethylacetate or
chloroacetonitrile or benzoyl chloride was added instead of halo ester or alkyl hal-
ide. The resulting mixture was irradiated with halogen lamp (HALOPAR 20 75 W
2
30 V 30-GU10, Italy) for diꢀerent times (0–2 h) and then poured onto an ice water.
The precipitated compounds were collected and the yield was measured. m.p.s., and
all spectral data were in agreement with those of the reported compounds [29].
3
1
‑Amino‑4,6‑dimethyl‑2‑ethylseleno[2,3‑b]pyridine carboxylate (5a) m.p. 155–
1
56 °C (crystallization of ethanol). H NMR: δ=1.38–1.68 (t, J=9.00 Hz, 3H, CH
3
ester), 2.50, 2.75 (2 s, 6H, 2CH pyridine), 4.30 (q, J=7.50 Hz, 2H, CH ), 6.88 (s,
3
2
1
H, CH pyridine), 7.28 (s, 2H, NH2) ppm; mass spectra of compounds 2 exhibited
+
molecular ion peak at m/z, (%) 298 (M +1
‏
3
‑Amino‑4,6‑dimethylseleno[2,3‑b]pyridine‑2‑carbonitrile (5b) m.p. 208–209 °C
1
(
crystallization of ethanol). H NMR: δ=2.55, 2.75 (2 s, 6H, 2CH pyridine), 6.88
3
(
s, 1H, CH pyridine), 7.28 (s, 2H, NH ) ppm; mass spectra of compounds 6a exhib-
2
+
ited molecular ion peak at m/z, (%) 251 (M +1
‏
2
‑Benzoyl‑3‑amino‑4,6‑dimethylseleno[2,3‑b]pyridine (5c) m.p. 250–252 °C (Crys-
1
tallization ethanol). H NMR: δ=2.50, 2.70 (2 s, 6H, 2CH pyridine), 6.85 (s, 1H,
3
CH pyridine), 7.30 (s, 2H, NH ), 7.55–8.00 (m, 5H, Ph-H) ppm; mass spectra of
2
+
compounds 6a exhibited molecular ion peak at m/z, (%) 330 (M +1
‏
Results and discussion
Diꢀerent shapes of Ag/AgCl nanoparticles were prepared by controlling the concen-
tration ration between AgNO and HCl. The morphology of the prepared shapes is
3
shown in Fig. 1. Ag/AgCl nanospheres (Fig. 1a) were prepared with equal concen-
trations of AgNO3 and HCl (1:1), while Ag/AgCl (Fig. 1b) nanowires and nano-
cubes (Fig. 1c) were formed with ratios 1:3 and 1:6, respectively. The synthesis of
mono dispersed silver nanocubes using polyol method via the EG reduction of silver
nitrate at 140 °C in the presence of PVP and HCl was reported by Im and Km et al.,
in which the selective etching and dissolution of twinned-crystal silver seeds was
proposed to play the key role [28, 30]. In this work, we report an interesting ꢁnding
that this synthesis route for silver chloride nanocubes can be modiꢁed to synthesize
silver clusters at the corners of silver chloride nanocubes at a very high yield only by
1
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Reusable photoresponsive Ag/AgCl nanocube‑catalyzed one‑pot…
1
3

Y. A. Attia, S. H. Abdel-Hafez
aging the fresh AgNO /PVP/EG for 1 h solution under ambient atmosphere without
3
the change in any other reaction parameters and also without any further reducing
process as described by Kim et al. [30]. Morphologies of the ꢁnal products were
greatly aꢀected by the molar ratio of AgNO and HCl. Uniform nanospheres with
3
size distribution ranging from 45 nm to 386 nm were formed when the Ag:Cl ratio
was 1:1. Non-uniform nanowires with an aspect ratio of 18± 2.1 nm and various
forms with a wide size distribution were obtained when the AgNO /HCl ratio was
3
1
:3. At the ratio of 1:6, uniform nanocubes with smaller size (l=241± 46 nm) were
observed together with small silver clusters (<5 nm) as shown in Fig. 1c.
As shown previously, the maximum absorption peak depends on the shape of the
nanostructures [8]. The absorbance spectra of the prepared samples are shown in
Fig. 2. Ag/AgClNSs showed a maximum absorbance at 427 nm (Fig. 2a) that shifted
to shorter wavelength at 362 nm with another peak appears at 549 nm when the con-
centration ratio AgNO /HCl changed to 1:2 as Ag/AgClNCs formed (Fig. 2c) while,
3
increasing the concentration ratio to 1:6, Ag/AgClNWs were formed with maximum
absorbance at 358 nm with prediction appearance of longitudinal band at more than
+
−
1
200 nm (Fig. 1e). When the ratio of Ag ions to Cl ions is above a certain level,
small Ag atom clusters may form locally in the solution and act as nucleation seeds,
of which nucleation kinetics could be diꢀerent from that of silver chloride seeds.
Therefore, the presence of diꢀerent nucleation seeds under high Ag/Cl ratio may
explain the wide size distribution of the AgCl particles at the initial stage of growth.
The band gap of the Ag/AgCln anocatalysts can be calculated from the estimated
absorption edge wavelength of the spherical, cubic and wire shapes by using Tauc
plot to be 2.96, 2.23, 5.25 eV, respectively (Fig. 2b, d and e). The photolumines-
cence of the formed Ag/AgCl NPs are shown in Fig. 1g. The sample Ag/AgCl NCs
has shown the highest intensity of luminescence in visible light range.
The Ag/AgCl has a porous and uniform morphology, cluster at the face of the
cube and concentrated at the corners of the cubes while concentrated at the tips of
the wires which can enlarge the speciꢁc surface area and accelerate the photocata-
lytic activity of the photocatalyst. To conꢁrm the morphology of the as-prepared
particles, XRD analysis was carried out as shown in Fig. 3. The XRD patterns of the
photocatalysts Ag/AgCl are mainly composed of AgCl nanoparticle with the peaks
at (2θ=29.23°, 35.95°, 44.74°, 54.7° and 57.3°) corresponding to planes {(111),
(
(
(
200), (220), (311) and (222)} in addition to the peaks of silver cluster sat the peaks
2θ=38.05°, 44.24°, 64.39° and 73.6°) corresponding to the planes {(111), (200),
220) and (420)} [28, 30].
The photocatalytic performance of the samples Ag/AgCl (nanospheres, nano-
cubes and nanowires) was monitored by degradation of amaranth dye in aqueous
solution under visible irradiation as recorded in Fig. 4. The amaranth dye under
visible light for 3 h without catalyst (Fig. 4a) and with Ag/AgCl nanocatalyst
in cubic shape under dark condition for 3 h (Fig. 4b) did not show any degrada-
tion performance. Amaranth dye is photodegraded within 240 min in the presence
of Ag/AgCl NPs in spherical shape (Fig. 4c) and within 120 min with Ag/AgCl
nanowires under visible light as shown in Fig. 4d. However, for complete degrada-
tion of amaranth dye, only 40 min was enough with Ag/AgCl nanocubes (Fig. 4e).
The photodegradation rate order under visible light irradiation of the samples is:
1
3

Reusable photoresponsive Ag/AgCl nanocube‑catalyzed one‑pot…
Fig. 2 Absorption spectra of the formed Ag/AgCl NSs (a), NCs (c) and NWs (e). Tauc plot for the pre-
pared samples: NSs (b), NCs (d) and NWs (f). The photoluminescence of the formed Ag/AgCl NPs (g)
at λ =271 nm
ex
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3

Y. A. Attia, S. H. Abdel-Hafez
800
600
400
200
Ag/AgCl Nanowires
Ag/AgCl Nanocubes
Ag/AgCl Nanospheres
30
40
50
60
70
80
2-Theta/degrees
Fig. 3 XRD patterns of the prepared Ag/AgCl nanoparticles with diꢀerent morphology
nanospheres<nanowires<nanocubes. These results indicate that the photocatalytic
activity can be enhanced by the presence of Ag clusters at the corners of the cubes
and at the tips of nanowires.
Investigation of optical properties of the Ag/AgClNCs showed that as-synthe-
sized Ag/AgClNCs absorb light not only in the UV but also in visible region.
In addition, the absorption peak in the visible region was red-shifted as the size
of NCs increased. This visible light absorption mainly due to thin Ag clusters
formed on the AgCl nanocube surfaces. On the other hand, it has been shown
that Ag nanoparticles deposited on AgCl show the plasmonic absorption of vis-
ible light. As the Ag/Cl ratio increases, the formation of catalytic Ag clusters on
the surface of AgCl is increased. The enhancement of catalytic photodegradation
of Ag/AgClNCs is also due to the cubic shape nanoparticles with the presence
of semiconducting silver clusters that have two band gaps direct and indirect as
reported [28]. The illumination of suspended AgCl in an aqueous solution of dye
with unꢁltered light (polychromatic light) leads to the possibility of two path-
ways. The ꢁrst pathway, a part of light with energy equal to or more than the
band gap of the illuminated semiconductor will cause a promotion of an electron
to conduction band of the AgCl and as a result, a positive hole will be created
in the valence band. The formed photoholes and photoelectrons can move to the
surface of the semiconductor in the presence of light energy. The positive hole
·
will react with adsorbed water molecules on the surface of AgCl producing OH
radicals, and the electron will react with adsorbed oxygen on the surface. Moreo-
ver, they can react with deliquescent oxygen and water in suspended liquid and
·
produce per hydroxyl radicals (HO ) with high chemical activity. The processes
2
in this pathway can be summarized by the following equations. Photocatalysis on
AgCl oxides relies on the absorption of photons with energy equal to or greater
than the band gap of the oxide, so that electrons are promoted from the valence
1
3

Reusable photoresponsive Ag/AgCl nanocube‑catalyzed one‑pot…
Fig. 4 Absorption spectra showing the amaranth dye photodegradation with Ag/AgCl nanocubes under
dark (a) and with using diꢀerent shapes of Ag/AgCl NSs (b), NWs (c) and NCs (d) under visible light
irradiation
band to the conduction band. In the second pathway, the other part of light with
energy which is less than the band gap of the catalyst AgCl will be absorbed by
the adsorbed dye molecules. Dye molecules will be decolorized by a photosen-
sitization process. The photocatalytic decolorization of dyes, which is described
as photosensitization processes, is also characterized by a free radical mecha-
nism. In this process, the adsorbed dye molecules on the surface of the catalyst
can absorb a radiation in the visible range in addition to the radiation with short
1
3

Y. A. Attia, S. H. Abdel-Hafez
wavelengths. The excited colored dye (dye*) will inject an electron to the conduc-
tion band of the semiconductor.
Chemoselective production reaction of seleno[2,3‑b]pyridine derivatives
The eꢀect of the three morphologies of Ag/AgCl nanoparticles was ꢁrstly examined
on the reaction of 4,6-dimethyl-2-chloro-3-cyanopyridine(1) by using three diꢀer-
ent forms of Ag/AgCl in presence of sodium borohydride, Se metal and ClCH X
2
(
(
X=–COOEt, –CN and –COPh) in ethanol under illumination with visible light
Table 1).
As shown in Table 1, ꢁrstly under catalyst-free condition and reꢃuxing the mix-
ture reaction for 3 h (entry 1), there was low yield of compounds 5a–c was obtained
in our previously work [18]. Then, under catalyst-free conditions in dark (entry
2
) and in visible light (entry 3) conditions, there was no reaction and no yield for
seleno[2,3-b]pyridine derivatives. We then started to use the Ag/AgCl-NS as cat-
alyst in dark, adducts 5a–c were not formed (entry 4). Whereas by operating the
reaction under visible light irradiation, compounds 5a–c were formed in 64%, 54%
and 57% isolated yield, respectively (entry 5). When Ag/AgCl-NW was used in the
catalyzed reduction reaction in dark condition, the reaction did not proceed (entry
6
). However, products 5a–c were resulted under visible light condition in 79%, 61%
and 65% isolated yield, respectively (entry 7). Finally, again when the reaction was
employed using Ag/AgCl-NC in dark (entry 8), the reaction was not performed,
while high yield of products 5a–c under visible light irradiation for 1 h (94%, 82%
and 85%) (entry 9) and under visible irradiation for 2 h (97%, 89% and 90%) (entry
1
0) was obtained.
The proposed mechanism depends on the reaction of 4,6-dimethyl-2-chloro-3-cy-
anopyridine (1) with ethyl chloroacetate or chloroacetonitrile or phenacyl chloride in
the presence of sodium borohydride under the same conditions and gave ꢁrstly, the
Table 1 The photocatalytic
Entry Catalyst
Rx condition Time/h Isolated
activity of Ag/AgCl
yield%c
nanoparticles with diꢀerent
shapes towards the production
of seleno[2,3-b]pyridine
derivatives 5a–c
5a 5b 5c
1
2
3
4
5
6
7
8
9
1
Nona
Reꢃux
Dark
Visible light
Dark
Visible light
3
24
24
24
2
15 10 11
a
Non
Non
–
–
–
–
–
–
–
–
–
b
Ag/AgCl-NS
Ag/AgCl-NS
Ag/AgCl-NW Dark
64 54 57
24
2
–
–
–
Ag/AgCl-NW Visible light
79 61 65
Ag/AgCl-NC
Ag/AgCl-NC
Ag/AgCl-NC
Dark
Visible light
24
1
–
–
–
94 82 85
0
Visible light
2
97 89 90
(
a) Without catalyst, (b) visible light in the range of 450–600 and (c)
the crude reduced product was puriꢁed and isolated
1
3

Reusable photoresponsive Ag/AgCl nanocube‑catalyzed one‑pot…
Scheme 1 The proposed mechanism of the production of ethyl carboxylate or carbonitrile or benzoyl
seleno[2,3-b]pyridine derivatives
corresponding intermediate ethyl selenoacetate or selenoacetonitrile or benzoylse-
leno pyridine derivatives. Secondly, the intermediate compounds underwent smooth
Thorpe–Ziegler cyclization (as shown in scheme 1), to form the corresponding com-
pound derivatives [31]. The presence of photoresponsive Ag/AgCl NPs accelerates
the reaction and enhances the yield of the products. The cube-shaped Ag/AgCl NPs
have shown the highest catalytic activity for the organoselenium compounds pro-
duction due to the presence of silver clusters. It was indicated that the incident light
has an energetic role in heterogeneous catalyzed multi-component reaction (MCR).
Ag nanoparticles helped in absorbance of the light; then, the electrons and holes in
AgCl were moved to conduction band which then participated in accelerating the
reaction between the produced intermediates. Under the inꢃuence of visible light,
absorption of light occurs through the catalytic action of the Ag/AgCln anocom-
posite which in turn activates the reaction to form the sodium salt of intermediate
(
2) by nucleophilic substitution reaction of NaSeH and eliminates the chlorine atom
in compound (1). Salt of compound 2 was generated in ethanol and reacted with
1
3

Y. A. Attia, S. H. Abdel-Hafez
Table 2 Study of the reusability
of Ag/AgCl-NC photocatalyst
in the production of compound
Cycle
Isolated yield%
1
2
3
4
5
st
94
93
93
91
91
5
a under visible light irradiation
nd
rd
th
th
for 1 h
2
halo acid (Cl–CH –X) via the SN mechanism to form the intermediate (3a–c). The
2
subsequent intramolecular Thrope–Ziegler cyclization proceeded via the formation
of intermediate (4a–c) to give the ꢁnal products (5a–c) [32]. To conꢁrm the high
stability and catalytic activity of the cube shape, catalyst recovery experiment has
been done.
Catalyst recovery
The Ag/AgCl-NC was ꢁltered and reused in 5 cycles in the production of compound
5
a; it was revealed that the catalyst was active in the 5 cycles and the yield of com-
pound 5a was obtained in ca~94–91% isolated yield under visible light irradiation
for 1 h (Table 2).
Conclusions
In this work, the controlled synthesis of Ag/AgCl-NSs, Ag/AgCl-NWs and Ag/
AgCl-NCs with adjustable sizes was realized by controlling the concentration ratio
AgNO /HCl. We disclosed that the rate of organic dye degradation was increased
3
in case of Ag/AgCl-NCs compared with other the Ag/AgCl-NSs and the Ag/AgCl-
NWs forms. As a result, we examined the Ag/AgCl-NCs photocatalyst in chemose-
lective production of organoselenium compounds. It was concluded that this catalyst
displayed high catalytic activity in production of seleno[2,3-b]pyridine derivatives
under mild conditions with low cost and reusable catalyst, besides the use of visible
light as available energy source for performing the reaction.
Acknowledgement We would like to express special words of thanks with deepest appreciation to
the team of this study. We would like to acknowledge RanaEssa, Eman Mohamed and AmanyKhalifa,
NILES, Cairo University for useful participation in experimental research.
Funding This research did not receive any speciꢁc grant from funding agencies in the public, commercial
or not-for-proꢁt sectors.
Compliance with ethical standards
Conꢀict of interest The authors declare that they have no conꢃict of interest.
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Reusable photoresponsive Ag/AgCl nanocube‑catalyzed one‑pot…
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