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Catalytic
Processes for
Water and
Wastewater
Treatment
Edited by
John Vakros
Printed Edition of the Special Issue Published in Catalysts
www.mdpi.com/journal/catalysts
Wastewater Treatment
Wastewater Treatment
Editor
John Vakros
MDPI • Basel • Beijing • Wuhan • Barcelona • Belgrade • Manchester • Tokyo • Cluj • Tianjin
Editor
John Vakros
Chemical Engineering
University of Patras
Patras
Greece
Editorial Office
MDPI
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4052 Basel, Switzerland
This is a reprint of articles from the Special Issue published online in the open access journal
Catalysts (ISSN 2073-4344) (available at: www.mdpi.com/journal/catalysts/special issues/catalytic
wastewater treatment).
For citation purposes, cite each article independently as indicated on the article page online and as
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Contents
About the Editor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
Preface to ”Catalytic Processes for Water and Wastewater Treatment” . . . . . . . . . . . . . . . ix
John Vakros
Catalytic Processes for Water and Wastewater Treatment
Reprinted from: Catalysts 2023, 13, 677, doi:10.3390/catal13040677 . . . . . . . . . . . . . . . . . . 1
Gururaj M. Neelgund, Sanjuana Fabiola Aguilar, Erica A. Jimenez and Ram L. Ray
Adsorption Efficiency and Photocatalytic Activity of Silver Sulfide Nanoparticles Deposited on
Carbon Nanotubes
Shakeel Khan, Awal Noor, Idrees Khan, Mian Muhammad, Muhammad Sadiq and Niaz
Muhammad
Photocatalytic Degradation of Organic Dyes Contaminated Aqueous Solution Using Binary
CdTiO2 and Ternary NiCdTiO2 Nanocomposites
Cristina Pei Ying Kong, Nurul Amanina A. Suhaimi, Nurulizzatul Ningsheh M. Shahri,
Jun-Wei Lim, Muhammad Nur and Jonathan Hobley et al.
Auramine O UV Photocatalytic Degradation on TiO2 Nanoparticles in a Heterogeneous
Aqueous Solution
Nurul Amanina A. Suhaimi, Cristina Pei Ying Kong, Nurulizzatul Ningsheh M. Shahri,
Muhammad Nur, Jonathan Hobley and Anwar Usman
Dynamics of Diffusion- and Immobilization-Limited Photocatalytic Degradation of Dyes by
Metal Oxide Nanoparticles in Binary or Ternary Solutions
Reprinted from: Catalysts 2022, 12, 1254, doi:10.3390/catal12101254 . . . . . . . . . . . . . . . . . 63
Jishu Rawal, Urooj Kamran, Mira Park, Bishweshwar Pant and Soo-Jin Park
Nitrogen and Sulfur Co-Doped Graphene Quantum Dots Anchored TiO2 Nanocomposites for
Enhanced Photocatalytic Activity
Souraya Goumri-Said and Mohammed Benali Kanoun

Insight into the Effect of Anionic–Anionic Co-Doping on BaTiO3 for Visible Light Photocatalytic
Water Splitting: A First-Principles Hybrid Computational Study
Luminita Isac, Cristina Cazan, Luminita Andronic and Alexandru Enesca

CuS-Based Nanostructures as Catalysts for Organic Pollutants Photodegradation
Marie Le Pivert, Aurélie Piebourg, Stéphane Bastide, Myriam Duc and Yamin Leprince-Wang
Direct One-Step Seedless Hydrothermal Growth of ZnO Nanostructures on Zinc: Primary
Study for Photocatalytic Roof Development for Rainwater Purification
v
Akbar Mehdizadeh, Zahra Derakhshan, Fariba Abbasi, Mohammad Reza Samaei,
Mohammad Ali Baghapour and Mohammad Hoseini et al.
The Effect of Arsenic on the Photocatalytic Removal of Methyl Tet Butyl Ether (MTBE) Using
Fe2 O3 /MgO Catalyst, Modeling, and Process Optimization
Maria Antonopoulou, Maria Papadaki, Ilaeira Rapti and Ioannis Konstantinou

Photocatalytic Degradation of Pharmaceutical Amisulpride Using g-C3 N4 Catalyst and UV-A
Irradiation
Ilaeira Rapti, Vasiliki Boti, Triantafyllos Albanis and Ioannis Konstantinou

Photocatalytic Degradation of Psychiatric Pharmaceuticals in Hospital WWTP Secondary
Effluents Using g-C3 N4 and g-C3 N4 /MoS2 Catalysts in Laboratory-Scale Pilot
Lalit Goswami, Anamika Kushwaha, Saroj Raj Kafle and Beom-Soo Kim
Surface Modification of Biochar for Dye Removal from Wastewater
Spyridon Giannakopoulos, John Vakros, Zacharias Frontistis, Ioannis D. Manariotis, Danae

Venieri and Stavros G. Poulopoulos et al.
Biochar from Lemon Stalks: A Highly Active and Selective Carbocatalyst for the Oxidation of
Sulfamethoxazole with Persulfate
Konstantinos Kouvelis, Adamantia A. Kampioti, Athanasia Petala and Zacharias Frontistis

Degradation of Sulfamethoxazole Using a Hybrid CuOx –BiVO4 /SPS/Solar System
vi
About the Editor
John Vakros
John Vakros serves as researcher in the Department of Chemical Engineering at University of
Patras. His teaching activities cover general chemistry, physical chemistry, catalysis and instrumental
chemical analysis. His research activities are in the field of heterogeneous catalysis, preparation
of catalysts, preparation and characterization of biochars and application of novel materials for
environmental protection.
vii
Preface to ”Catalytic Processes for Water and
Wastewater Treatment”
Water and wastewater treatment are still facing significant challenges today. Due to climate
change, water shortages are already noticeable in many regions of the world. To overcome these
problems, alternative water sources must be generated and used; for example, treated wastewater,
rainwater, surface water, etc. These water sources have to be treated before use since the
development of highly sensitive methods reveals the presence of hazardous compounds in low
concentrations. These pollutants should be removed, and many processes have been proposed for
their degradation/removal, among them catalytic methods.
Those where catalysts are in solid form in particular exhibit significant advantages.
Catalytic oxidation or reduction processes are among the most efficient processes. These include
photocatalysis, sulfate and hydroxyl-radical-based advanced oxidation processes.
This Special Issue contains the contributions of different research groups and discusses the recent
progress and advances in catalytic processes in water and wastewater treatment.
John Vakros
Editor
ix
catalysts
Editorial
Catalytic Processes for Water and Wastewater Treatment
John Vakros 1,2
1 Department of Chemical Engineering, University of Patras, Caratheodory 1, University Campus,

GR-26504 Patras, Greece; vakros@chemistry.upatras.gr
2 School of Sciences and Engineering, University of Nicosia, 2417 Nicosia, Cyprus
Water and wastewater treatment still face significant challenges today. Due to climate
change, water shortages are already noticeable in many regions of the world. To over-
come these problems, alternative water sources must be generated and used, for example,
treated wastewater, rainwater, surface water, etc. Since the development of highly sensitive
methods reveals the presence of hazardous compounds in low concentrations, these water
sources must be treated before use. The detected compounds include pharmaceuticals,
which have a serious influence on human health. Generally, the concentrations of these
compounds is low. However, recent statistics have revealed that the per capita consumption
of medicines within the European Union for the period of 2000–2014 has almost tripled,
reflecting the excessive and perhaps reckless use of similar products. In particular, there
are numerous different ways that remedies may permeate into surface recipients, such as
landfill leachates, excessive consumption by people themselves, high volumes of organic
hospital effluents, and the undeniably incorrect rejection of medicines that have expired or
were not used. Due to the incomplete biodegradation of complex organic molecules in con-
ventional wastewater treatment plants, the accumulation of organic pollutants on surface
waters endangers biodiversity through its potential toxicity. Thus, these pollutants should
be removed. Many processes have been proposed for their degradation/removal, including
catalytic methods. These methods, in which catalysts are in a solid form in particular,
exhibit significant advantages such as easy separation, better stability, higher activity, and a
lower cost of the process. Catalytic oxidation or reduction processes are among the most
efficient processes. These include photocatalysis and sulfate- and hydroxyl-radical-based
advanced oxidation processes.
The application of a solid catalyst in a removal experiment combines not only the
Citation: Vakros, J. Catalytic oxidation reaction but also the adsorption of the contaminant on the catalyst surface. The
Processes for Water and Wastewater adsorption is a necessary step for the catalytic process, and hydrophilicity of the surface
Treatment. Catalysts 2023, 13, 677. is required in such cases. By itself, adsorption very useful for removing heavy metal ions.
https://doi.org/10.3390/catal13040677 Heavy metals are highly soluble in water and are toxic, carcinogenic, and non-degradable.
In the study by Neelgund et al. [1], a nanocomposite CNTs-Ag2 S was prepared through the
Received: 27 March 2023
facile deposition of Ag2 S nanoparticles onto oxidized carbon nanotubes (CNTs), using the
Revised: 28 March 2023
Accepted: 29 March 2023
hydrothermal method. At first, the hydrophobic CNTs were treated with concentrated nitric
Published: 30 March 2023
and sulfuric acids under reflux. The modification increased the hydrophilic nature of the
CNTs by introducing oxygen species onto the surface. The Ag2 S nanoparticles were then
deposited onto the modified CNTs. The CNTs-Ag2 S is more efficient than CNTs and Ag2 S
and can completely adsorb Cd (II) within 80 min. The adsorption follows pseudo-second-
Copyright: © 2023 by the author. order kinetics, while intraparticle diffusion and the boundary layer effect contribute to the
Licensee MDPI, Basel, Switzerland. removal of Cd (II) [1]. The CNTs-Ag2 S can also act as a photocatalyst for the degradation
This article is an open access article of alizarin yellow R (AYR), a dye used in the textile industry. With the irradiation of the
distributed under the terms and material with natural sunlight, complete degradation of AYR is achieved. The degradation
conditions of the Creative Commons
follows pseudo-first-order kinetics. Different reactive species such as electrons, holes,
Attribution (CC BY) license (https://
hydrogen peroxide, and ROS are the active species for the degradation, and the CNTs-Ag2 S
creativecommons.org/licenses/by/
was found to be stable for three cycles [1].
4.0/).
1
Catalysts 2023, 13, 677
Photocatalysis is probably the most common method used for the degradation of
organic compounds in water matrices, and titania-based materials are widely used as
photocatalysts. In the study by Khan et al., [2] binary CdTiO2 and ternary NiCdTiO2
were compared with bare TiO2 for the photocatalytic degradation of organic dyes such
as methylene blue (MB) and methyl green (MG). It was found that the photocatalytic
degradation of TiO2 , CdTiO2 , and NiCdTiO2 for MB was 77, 82, and 86%, while for MG
the binary and ternary materials were even better, achieving a degradation of 63.5, 88, and
97.5%, respectively. In all three materials, the TiO2 was in the form of anatase, while the
deposition of Cd and Ni caused a red shift in the absorbance spectra by coupling with Ni
and Cd. This shift can be considered responsible for the enhanced photocatalytic activity.
Kong et. al. [3] used anatase TiO2 to degrade Auramine O (AO) under 365 nm light
irradiation. The titania nanoparticles had a mean diameter of 100nm. The degradation
process followed a pseudo-first order reaction, with k = 0.048 ± 0.002 min−1 . This value is
significantly lower than the corresponding value for the degradation of methylene blue
(0.173 ± 0.019 min−1 ); this is due to the nonplanar structure of AO. The higher photocat-
alytic efficiency was found to be 96%, and it decreased nonlinearly with an increase in the
initial concentration and catalyst dosage. Finally, the authors confirmed the superiority of
titania nanoparticles compared to the use of micro-sized powders.
The degradation process is more complicated when more than one dye is present in the
solution; however, this scenario is also more realistic. Therefore, there are numerous studies
in which binary or ternary solutions of dyes are used in photocatalytic degradation. In
this recent review [4], the photocatalytic behavior of methylene, rhodamine B, and methyl
orange in their binary or ternary solutions was summarized. In this review, the importance
of diffusion was discussed. It was revealed that smaller dyes with a planar conformation
are easier to degrade and dominate in photocatalytic degradation in their binary or ternary
solutions.
Although titania is likely the better photocatalyst, it has some limitations, among
which is its limited optical adsorption in the visible light spectrum. Many methods have
been used to further expand the optical UV–Vis absorption region of TiO2 and to enhance
the efficient light-induced charge separation. The best option reported is to combine TiO2
with typical narrow-bandgap quantum dots (QDs) of different semiconductors and carbon
quantum dots (CQDs). In the work of Rawal et. al., [5] nitrogen (N) and sulfur (S) co-doped
graphene quantum dots (GQDs) were used. This material has a narrowed Eg value that
improves photogenerated electron transfer due to π-conjugation. The activity was found
to be 2.3–3 times higher than that of TiO2 . The photocatalyst was stable for at least three
cycles, and the formation of C-O-Ti bonds provided a charge transfer pathway.
BaTiO3 is another promising material, especially when it is combined with the double-
hole coupling of anion–anion combinations. Barium titanate has a perovskite structure
and large band gap of 3.0–3.3 eV; it has the appropriate band positions to split water
into hydrogen and oxygen, although the band gap should be regulated in lower values to
provide the ability to absorb more visible light. It has also been reported that by substituting
a metal dopant at a Ba or Ti site, a direct effect on the band gap energy (Eg), the stability,
and the formation of oxygen vacancies can be achieved. On this basis, the electronic
properties and optical absorption characteristics of BaTiO3 , with the double-hole coupling
of anion–anion combinations using first-principles methods, were studied. It was found
that the N–N co-doped BaTiO3 exhibited a more favorable formation energy under an
O-poor condition, and all the co-doping configurations reduced the value of Eg. The tuning
of the Eg makes the photocatalyst a promising candidate for visible-light water splitting [6].
Due to the importance of photocatalysis, as it is one of the most innovative advanced
oxidation techniques used, many materials have been tested for their photocatalytic activity.
A photocatalytic process should present a high efficiency, low cost, and avoid the produc-
tion of intermediate products with a high toxicity. The selection of a photocatalyst is very
important, as it must be cheap, stable, environmentally friendly, and have high activity.
Usually, a photocatalyst is a semiconductor with a high degree of absorption of light, prefer-
2
Catalysts 2023, 13, 677
ably solar light, and high rate of photogenerated charge carriers. One review summarized
the application of CuS as a photocatalyst [7]. CuS is a p-type semiconductor with different
nanostructures, such as nanoparticles and quantum dots or heterojunctions with carbon
materials, organic materials, or metal oxides. The recent developments in organic pollutant
photodegradation with a CuS as catalyst are discussed on the basis of different synthesis
parameters (Cu:S molar ratios, surfactant concentration etc.) and properties (particle size,
morphology, bandgap energy, and surface properties)
In the study by Le Pivert et. al., [8], ZnO nanoparticles were synthesized onto Zn
and used as roof for the photocatalytic removal of organic contaminants in rainwater.
The authors prepared the ZnO nanoparticles on the Zn roof with a hydrothermal growth
method in 2 h. The presence of Zn (II) ions and the native oxide film on the Zn surface
acted as active sites for the growth of ZnO nanoparticles. The photocatalytic activity was
determined using Methylene Blue under UV irradiation and Acid Red 14 with solar light.
The removal of Methyl Tert Butyl Ether (MTBE) using Fe2 O3 /MgO as a catalyst was
studied in the presence of arsenic under UV irradiation [9]. The catalyst contained 33.06%
Fe2 O3 and 45.06% MgO. The main parameters of the degradation process, including the
effect of arsenic and MTBE concentrations, catalyst mass, pH, etc., were studied. It was
found that the concentration of MTBE influenced the most the photocatalytic process.
The higher performance in the removal of MTBE was achieved at pH = 5 and an initial
concentration of MTBe equal to 37.5 mg/L, with a catalyst dose of1.58 mg/L without
the presence of As. The presence of arsenic decreased the removal efficiency remarkably.
Therefore, pretreatment for the removal of arsenic and more details of this interference
effect are suggested.
Psychiatric drugs, including amisulpride, a typical antipsychotic drug, are a class
of pharmaceuticals that are often prescribed and used in a wide range of mental health
problems. Their use is increasing worldwide. Graphitic carbon nitride (g-C3 N4 ) can be used
as photocatalyst for the degradation of this type of drug. In the work of Antonopoulou et.
al. [10], the application of g-C3 N4 catalysts for the degradation of amisulpride was studied.
Particularly, in the degradation process of amisulpride under UV-A irradiation with the
application of g-C3 N4 , the transformation products and the ecotoxicological assessment
were investigated. It was found that the degradation pathways of amisulpride included
mainly oxidation, dealkylation, and the cleavage of the methoxy group. The main reactive
species were found to be h+ and O2 •− . In ultrapure water, the transformation products had
a low toxicity, while an increased toxicity was observed when wastewater was used as a
matrix, especially at the beginning of the process.
g-C3 N4 is an interesting material with a graphene-like structure, chemical and thermal
stability, and a low cost. Is a good visible light absorber and can be used in a wide variety
of photocatalytic applications. It has a narrow band gap of ~2.7 eV, but it exhibits a high
recombination process and thus limited activity. This drawback can be overcome with the
combination of g-C3 N4 and MoS2 , since heterostructuring can decrease the recombination
effects between electrons and holes. The photocatalytic removal of psychiatric drugs
in secondary effluents of hospital wastewater with g-C3 N4 or 1% MoS2 /g-C3 N4 was
studied [11] in a laboratory-scale pilot plant and in a solar simulator apparatus. The results
showed that the 1% MoS2 /g-C3 N4 was more active than the g-C3 N4 , with 54% and 30%
removal, respectively. The degradation followed first order kinetics, and six transformation
products were generated during degradation; these were totally degraded at the end
of the treatment.
As previously noted, research on new materials is always challenging. These materials
should be active, selective, and of a low cost. It is also desirable that they are ecofriendly,
and, if possible, they should originate from the valorization of waste. Biochar is such a
materials. It can be produced from any kind of biomass through a pyrolysis process under
a limited- or no-oxygen atmosphere. Generally, biochar has a moderate or high specific
surface area, a hierarchical pore structure, and active surface groups. The utilization
of biochar and biochar-based nanocomposites for dye removal from wastewater was
3
Catalysts 2023, 13, 677
reviewed [12]. The removal of dyes from wastewater via natural and modified biochar
follows numerous mechanisms, such as precipitation, surface complexation, ion exchange,
cation–π interactions, and electrostatic attraction. The preparation parameters and the post
treatment of biochar can alter the surface speciation, and the modified biochar can exhibit
better performance in the removal of dyes. A framework for artificial neural networking
and machine learning to model the dye removal efficiency of biochar from wastewater was
also proposed.
In addition to the excellent adsorption properties of the biochar, it can also act as
a catalyst for the activation of persulfate ions and the oxidation of organic compounds.
Biochar from lemon stalks, pyrolyzed at 850 ◦ C under a limited oxygen atmosphere,
produced a highly active and selective biochar for the oxidation of sulfamethoxazole (SMX),
using sodium persulfate as oxidant [13]. The biochar had a significant amount of carbonates
and could completely degrade 0.5 mg L−1 SMX within 20 min using 500 mg L−1 sodium
persulfate (SPS) and 100 mg L−1 biochar in ultrapure water (UPW). The degradation
process is favored at a low pH and in the presence of chlorides. The complexity of the water
matrices usually has a negative impact on the degradation. The mechanism follows radicals
with hydroxyl radicals as the main active species and non-radical pathways; electron
transfer pathway was proven with electrochemical characterization. The biochar from
lemon stalks is stable and active.
The combination of more than one advanced oxidation process often leads to synergis-
tic effects and has proved to be a more efficient strategy. In this respect, the degradation
of SMX was studied using a CuOx–BiVO4 catalyst as either a photocatalyst or persulfate
(sodium persulfate, SPS) activator [14]. This hybrid process (catalyst/SPS/Solar System)
was found to be synergetic for copper-promoted BiVO4 photocatalysts. Specifically, dif-
ferent loadings of CuOx (0.75–10% wt.) were deposited on BiVO4 and tested under solar
irradiation for the degradation of SMX. The most active catalyst was found to be the
0.75 CuOx–BiVO4 , while a higher loading of CuOx delayed the degradation process. The
complexity of the water matrix (from ultrapure to bottled, BW, and wastewater, WW) also
has a negative effect on the degradation process. The addition of SPS is beneficial for the
degradation process, and the two processes exhibit a synergistic effect. Specifically, in a
BW matrix, the application of SPS results in complete elimination after 60 min, while in the
absence of SPS, an SMX degradation of only 40% took place in 120 min under solar light.
For the WW, ~37%, 45%, and 66% degrees of symmetry were determined using 0.75, 3.0,
and 10.0 CuOx–BiVO4 , respectively.
Catalytic processes for water and wastewater treatment are a promising approach
to improving the quality of the water. Although photocatalysis is the most popular and
attractive process due to its simplicity and utilization of the abundant solar light, the com-
bination of other advanced oxidation processes can lead to effective systems. Interestingly,
the presented experimental results highlight that it is difficult to decide which catalyst
or process is better, and the determination of the activity must be performed in a wide
window of operating parameters.
Conflicts of Interest: The author declares no conflict of interest.
References
1. Neelgund, G.M.; Aguilar, S.F.; Jimenez, E.A.; Ray, R.L. Adsorption Efficiency and Photocatalytic Activity of Silver Sulfide
Nanoparticles Deposited on Carbon Nanotubes. Catalysts 2023, 13, 476. [CrossRef]
2. Khan, S.; Noor, A.; Khan, I.; Muhammad, M.; Sadiq, M.; Muhammad, N. Photocatalytic Degradation of Organic Dyes Contami-
nated Aqueous Solution Using Binary CdTiO2 and Ternary NiCdTiO2 Nanocomposites. Catalysts 2023, 13, 44. [CrossRef]
3. Kong, C.P.Y.; Suhaimi, N.A.A.; Shahri, N.N.M.; Lim, J.-W.; Nur, M.; Hobley, J.; Usman, A. Auramine O UV Photocatalytic
Degradation on TiO2 Nanoparticles in a Heterogeneous Aqueous Solution. Catalysts 2022, 12, 975. [CrossRef]
4. Suhaimi, N.A.A.; Kong, C.P.Y.; Shahri, N.N.M.; Nur, M.; Hobley, J.; Usman, A. Dynamics of Diffusion- and Immobilization-Limited
Photocatalytic Degradation of Dyes by Metal Oxide Nanoparticles in Binary or Ternary Solutions. Catalysts 2022, 12, 1254. [CrossRef]
5. Rawal, J.; Kamran, U.; Park, M.; Pant, B.; Park, S.-J. Nitrogen and Sulfur Co-Doped Graphene Quantum Dots Anchored TiO2
Nanocomposites for Enhanced Photocatalytic Activity. Catalysts 2022, 12, 548. [CrossRef]
4
Catalysts 2023, 13, 677
6. Goumri-Said, S.; Kanoun, M.B. Insight into the Effect of Anionic–Anionic Co-Doping on BaTiO3 for Visible Light Photocatalytic
Water Splitting: A First-Principles Hybrid Computational Study. Catalysts 2022, 12, 1672. [CrossRef]
7. Isac, L.; Cazan, C.; Andronic, L.; Enesca, A. CuS-Based Nanostructures as Catalysts for Organic Pollutants Photodegradation.
Catalysts 2022, 12, 1135. [CrossRef]
8. Le Pivert, M.; Piebourg, A.; Bastide, S.; Duc, M.; Leprince-Wang, Y. Direct One-Step Seedless Hydrothermal Growth of ZnO
Nanostructures on Zinc: Primary Study for Photocatalytic Roof Development for Rainwater Purification. Catalysts 2022, 12, 1231.
[CrossRef]
9. Mehdizadeh, A.; Derakhshan, Z.; Abbasi, F.; Samaei, M.R.; Baghapour, M.A.; Hoseini, M.; Lima, E.C.; Bilal, M. The Effect of
Arsenic on the Photocatalytic Removal of Methyl Tet Butyl Ether (MTBE) Using Fe2 O3 /MgO Catalyst, Modeling, and Process
Optimization. Catalysts 2022, 12, 927. [CrossRef]
10. Antonopoulou, M.; Papadaki, M.; Rapti, I.; Konstantinou, I. Photocatalytic Degradation of Pharmaceutical Amisulpride Using
g-C3 N4 Catalyst and UV-A Irradiation. Catalysts 2023, 13, 226. [CrossRef]
11. Rapti, I.; Boti, V.; Albanis, T.; Konstantinou, I. Photocatalytic Degradation of Psychiatric Pharmaceuticals in Hospital WWTP
Secondary Effluents Using g-C3 N4 and g-C3 N4 /MoS2 Catalysts in Laboratory-Scale Pilot. Catalysts 2023, 13, 252. [CrossRef]
12. Goswami, L.; Kushwaha, A.; Kafle, S.R.; Kim, B.-S. Surface Modification of Biochar for Dye Removal from Wastewater. Catalysts
2022, 12, 817. [CrossRef]
13. Giannakopoulos, S.; Vakros, J.; Frontistis, Z.; Manariotis, I.D.; Venieri, D.; Poulopoulos, S.G.; Mantzavinos, D. Biochar from
Lemon Stalks: A Highly Active and Selective Carbocatalyst for the Oxidation of Sulfamethoxazole with Persulfate. Catalysts 2023,
13, 233. [CrossRef]
14. Kouvelis, K.; Kampioti, A.A.; Petala, A.; Frontistis, Z. Degradation of Sulfamethoxazole Using a Hybrid CuOx –BiVO4 /SPS/Solar
System. Catalysts 2022, 12, 882. [CrossRef]
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5
catalysts
Article
Adsorption Efficiency and Photocatalytic Activity of Silver
Sulfide Nanoparticles Deposited on Carbon Nanotubes
Gururaj M. Neelgund 1, * , Sanjuana Fabiola Aguilar 1 , Erica A. Jimenez 1 and Ram L. Ray 2
1 Department of Chemistry, Prairie View A&M University, Prairie View, TX 77446, USA
2 College of Agriculture and Human Sciences, Prairie View A&M University, Prairie View, TX 77446, USA
* Correspondence: gmneelgund@pvamu.edu
Abstract: A multimode, dual functional nanomaterial, CNTs-Ag2 S, comprised of carbon nanotubes

(CNTs) and silver sulfide (Ag2 S) nanoparticles, was prepared through the facile hydrothermal process.
Before the deposition of Ag2 S nanoparticles, hydrophobic CNTs were modified to become hydrophilic
through refluxing with a mixture of concentrated nitric and sulfuric acids. The oxidized CNTs were
employed to deposit the Ag2 S nanoparticles for their efficient immobilization and homogenous
distribution. The CNTs-Ag2 S could adsorb toxic Cd(II) and completely degrade the hazardous
Alizarin yellow R present in water. The adsorption efficiency of CNTs-Ag2 S was evaluated by
estimating the Cd(II) adsorption at different concentrations and contact times. The CNTs-Ag2 S could
adsorb Cd(II) entirely within 80 min of the contact time, while CNTs and Ag2S could not pursue it. The
Cd(II) adsorption followed the pseudo-second-order, and chemisorption was the rate-determining
step in the adsorption process. The Weber−Morris intraparticle pore diffusion model revealed that
intraparticle diffusion was not the sole rate-controlling step in the Cd(II) adsorption. Instead, it was
contributed by the boundary layer effect. In addition, CNTs-Ag2 S could completely degrade alizarin
yellow R in water under the illumination of natural sunlight. The Langmuir-Hinshelwood (L-H)
model showed that the degradation of alizarin yellow R proceeded with pseudo-first-order kinetics.
Overall, CNTs-Ag2 S performed as an efficient adsorbent and a competent photocatalyst.
Keywords: CNTs; Ag2 S; cadmium; adsorption; alizarin yellow R

Citation: Neelgund, G.M.; Aguilar,
S.F.; Jimenez, E.A.; Ray, R.L.
Adsorption Efficiency and
Photocatalytic Activity of Silver
1. Introduction
Sulfide Nanoparticles Deposited on
Carbon Nanotubes. Catalysts 2023, 13, Water pollution engrossed by heavy metals is a primary environmental, ecological,
476. https://doi.org/10.3390/ and public health concern [1]. Heavy metals are highly soluble in water and are toxic,
catal13030476 carcinogenic, and non-degradable [2,3]. Rapid industrialization and technological develop-
ment have resulted in the discharge of heavy metal-containing effluents into surface and
Academic Editor: John Vakros
groundwater [4]. The discharged heavy metals are adsorbed by soil and enter the human
Received: 31 December 2022 body through the food chain. Heavy metals accumulate in various organs and body tissues
Revised: 21 February 2023 and can cause irreparable damage, including death [5]. Among the heavy metals, cadmium
Accepted: 21 February 2023 is enormously used and highly toxic [6]. The source for discharging the cadmium into the
Published: 26 February 2023 environment is industrial activities, such as electroplating, smelting, alloy manufacturing,
pigments, plastic, battery, fertilizers, pesticides, pigments, dyes, textile operations, and
refining [7]. In water, cadmium exists as bivalent, Cd(II), which is responsible for several
adverse effects, such as kidney dysfunction, nephritis, hypertension, renal dysfunction,
Copyright: © 2023 by the authors.
nervous system dysfunction, bone lesions, digestive system dysfunction, cancer, and repro-
Licensee MDPI, Basel, Switzerland.
ductive organ damage [8–10]. The itai-itai disease, caused by Cd(II)-contaminated water
This article is an open access article
from the Jinzu river in Japan, has instigated severe pain, bone fractures, proteinuria, and
distributed under the terms and
osteomalacia [11]. The Cd2+ ions have a high affinity for binding to sulfhydryl (-SH) groups
conditions of the Creative Commons
Attribution (CC BY) license (https://
of proteins in biological systems [12]. The presence of Cd(II) in water can lead to severe
creativecommons.org/licenses/by/
health and environmental problems. Therefore, its elimination is critically needed. The
4.0/).
Cd(II) present in water could be eradicated through chemical precipitation, ion exchange,
7
Catalysts 2023, 13, 476
solvent extraction, membrane separation, electrochemical removal, coagulation, and ad-

sorption [13–21]. In these techniques, adsorption is superior because of its high efficiency,
relative simplicity in design, easy operation, and low operational cost [20,21]. Because of
this, many adsorbents have been developed and tested for their efficiency [20–22].
Another class of pollutants that also causes major environmental problems, such as
heavy metals, is azo dyes. Azo dyes have attractive colors and are enormously used in
industries due to their availability and stability [23]. These dyes contain azo bonds (-N=N-)
and substituted aromatic rings [24]. The complex molecular structure of azo dyes has made
them recalcitrant and resistant to biodegradation [25]. Azo dyes are mutagenic, teratogenic,
and carcinogenic [25]. Moreover, azo dyes can decompose into potentially carcinogenic
polychlorinated naphthalenes, benzidine, and amines [26,27]. The toxicity of azo dyes can
result in lung cancer, heart diseases, chromosomal aberrations, neurotoxicity, skin disease,
and respiratory problems in humans [25]. These dyes can cause disorders of the central
nervous system and the inactivation of enzymatic activities [28]. Beyond toxicity, azo dyes
are abundantly used in industries because of their cost and advancement in colors that
cover the entire spectrum. After their use in industries, about 10-15% of the azo dyes are dis-
charged into the environment through water effluents [29,30]. Releasing azo dyes content
water can result in several environmental problems including reduced light penetration in
water bodies, which leads to diminished photosynthetic activities, lessened growth and
reproduction of aquatic creatures, and aesthetic damage [30,31]. The consequences of the
xenobiotic and recalcitrant azo dyes impact the ecosystem’s structure and functioning.
Considering the adverse effects, it is essential to completely obliterate azo dyes to prevent
severe damage and protect health and the environment. Different techniques have been
developed to remove the azo dyes in water, viz., coagulation/flocculation, ultrafiltration
and membrane processing, chemical precipitation, electrochemical degradation, and ozona-
tion [32–37]. In comparison, photocatalysis is an excellent method for eradicating azo dyes
from water in an environmentally friendly approach as the end products of this process are
harmless [38,39]. Due to its efficiency in degrading azo dyes, many photocatalysts have
been developed to eliminate dyes [37–45]. Among azo dyes, alizarin yellow R (AYR) is
a prominently used dye in industries. It is a highly water-soluble anionic dye that con-
tains polycyclic aromatic hydrocarbons [25]. AYR is a derivative of salicylic acid and was
prepared in 1887 by Rudolf Nietzki through the reaction of m-nitroaniline and salicylic
acid [46]. AYR is an industrially important dye and is vastly used in the textile, leather,
plastics, paints, and lacquer industries [24]. Furthermore, it is used as an acid-base indicator
and employed in histology, stains, and nutrient media preparations [47].
Considering the health and environmental problems associated with Cd(II) and AYR,
we designed the dual applicable nanocomposite, CNTs-Ag2 S for efficient Cd(II) adsorption
and photodegradation of AYR. The multimode CNTs-Ag2 S was produced through the
facile deposition process of Ag2 S nanoparticles over oxidized carbon nanotubes (CNTs)
using the hydrothermal method. The adsorption efficiency of CNTs-Ag2 S was estimated
by evaluating the adsorption rate of Cd(II) from water. The dynamics and controlling
mechanisms of Cd(II) adsorption were assessed by pseudo-first- and second-order kinetic
models. The reaction pathways and the rate-controlling step underlying Cd(II) adsorption
were evaluated using the Weber−Morris intraparticle pore diffusion model. The adsorption
equilibrium was determined by fitting the experimental results with Langmuir, Freundlich,
and Temkin isotherm models. Furthermore, the catalytic activity of CNTs-Ag2 S was
determined through the degradation of AYR under exposure to natural sunlight. The
photocatalytic activity of CNTs-Ag2 S was quantified using the Langmuir-Hinshelwood
(L-H) model.
2. Results and Discussion

The ATR-FTIR spectrum of CNTs-COOH, shown in Figure 1a, demonstrated a band
at 3427 cm−1 corresponding to the O-H bond. The band for the C=O bond of the -COOH
groups appeared at 1699 cm−1 , and the band for the C=C bonds of CNTs was found at
8
Catalysts 2023, 13, 476
1554 cm−1 [48–50]. The spectrum of Ag2 S (Figure 1b) displayed the peak of the Ag-S
bond at 552 cm−1 [51]. The spectrum of CNTs-Ag2 S (Figure 1c) revealed the characteristic
absorption bands related to CNTs and Ag2 S. The prominent peaks observed at 1066 and
1096 cm−1 in Figure 1c were attributed to C-O stretching. The peak at 3574 cm−1 , was
due to the −OH stretching vibrations of adsorbed water molecules. The band due to C=O
was observed at 1693 cm−1 , and the peak, at 1517 cm−1 , was attributed to C-H. The peak
related to Ag-S was situated around 550 cm−1 . The XRD pattern of CNTs-Ag2 S (Figure 2)
showed a characteristic (0 0 2) reflection of hexagonal graphite of CNTs at 26.1◦ [52].
It revealed the reflections related to Ag2 S at 22.7 (−1 0 1), 25.2 (−1 1 1), 26.5 (0 1 2),
29.2 (1 1 1), 31.7 (−1 1 2), 33.8 (1 2 0), 34.6 (−1 2 1), 34.9 (0 2 2), 36.8 (1 1 1), 37.0 (1 2 1),
37.3 (0 1 3), 37.9 (−1 0 3), 40.9 (0 3 1), 43.6 (0 2 3), 44.4 (−1 3 1), 46.4 (−1 2 3), 48.0 (−2 1 2),
48.9 (0 1 4), 53.0 (0 4 0), 53.5 (−2 1 3), 58.3 (−1 4 1), 58.4 (−2 2 3), 60.2 (−1 0 5), 61.4 (0 1 5),
62.8 (2 3 1), 63.4 (2 1 3), 63.9 (−1, 3 4), and 68.0◦ (2 3 2). These values agree with the
values found in the standard pattern of acanthite Ag2 S (JCPDS file 14-0072) [52]. The TEM
images of CNTs-Ag2 S presented in Figure 3 explored the deposition of spherical-resembling
Ag2 S nanoparticles over the surface of tubular-structured CNTs. The proportion of Ag2 S
nanoparticles was low, possibly due to the low quantity of precursor AgNO3 used in the
preparation compared to the ratio of CNTs. The presence of Ag2 S nanoparticles over the
surface of CNTs is perceptible in Figure 3a–f. It is noticeable in Figure 3a that the few
Ag2 S nanoparticles have combined and formed clusters. Figure 3b,d reveal the ruptured
surface of some CNTs. It could have happened through the harsh treatment of CNTs with
the mixture of concentrated HNO3 and H2 SO4 . This process was required to make the
CNTs hydrophilic and provide a suitable environment for the effective deposition of Ag2 S
nanoparticles. However, the entire surface of the CNTs was not distracted and the smooth
surface of the CNT is perceptible in Figure 3e,f. Overall, a few defective sites were formed
in CNTs. Figure 3d-f reveals the strong adherence of Ag2 S nanoparticles to the smooth-
surfaced CNT. The absence of leached or free-standing nanoparticles in the void area shows
the strong adherence of Ag2 S nanoparticles to the surface of CNTs. The size of the Ag2 S
nanoparticle present in Figure 3d,e, was around 38 and 15 nm, respectively. Therefore,
Ag2 S nanoparticles have broad size distribution. The average size of Ag2 S nanoparticles,
calculated from XRD, was around 29 nm, which agrees with the size determined from the
TEM images. The core of the Ag2 S nanoparticles (Figure 3d) appears denser than the edge.
The CNTs have a width of around 110 nm and a length of several micrometers. Overall,
CNTs have effectively exfoliated. Further, the EDS of CNTs-Ag2 S (Figure S1, Supplementary
Catalysts 2023, 13, 476 4 of 23
Materials) demonstrated the presence of O, Ag, and S in CNTs-Ag2 S. The peaks for Cu and
Ca were found in Figure S1, those are by the copper grid used in the TEM measurement.
60
50
Transmittance (%)
40
(c)
30
(b)
20
10 (a)
0
4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumber (cm )
Figure
Figure 1. 1. ATR-FTIR
ATR‐FTIR spectra
spectra of (a) CNTs-COOH,
of (a) CNTs‐COOH, (b) Ag
(b) Ag2S, and 2 S, and (c)
(c) CNTs‐Ag 2S. CNTs-Ag2 S.
(-121)
25 9
2)
)
0
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1)
Catalysts 2023, 13, 476
Figure 1. ATR‐FTIR spectra of (a) CNTs‐COOH, (b) Ag2S, and (c) CNTs‐Ag2S.
(-121)
25
(-112)
(121)
20
(-103)
(111)
Intensity
15
(031)
(120)
(023)
10
(-213)
(-123)
(012)
(-134)
(-223)
(014)
(-101)
(015)
0
10 20 30 40 50 60 70 80
2 (degree)
Catalysts 2023, 13, 476 5 of 23
Figure 2. XRD of CNTs-Ag2 S.
Figure 2. XRD of CNTs‐Ag2S.
Figure3.3.(a–f)
Figure (a–f)TEM
TEMimages
imagesof
ofCNTs-Ag
CNTs‐Ag2S.
S.
2
The
The TGA
TGA pattern
pattern ofof CNTs‐Ag
CNTs-Ag22SS(Figure
(Figure4)4)displayed
displayedfourfour weight
weight loss
loss steps.
steps. TheThe
ini‐
initial weight
tial weight loss
loss of of 6.5%
6.5% that
that occurred
occurred before
before 100 C◦ C
100 was
was attributed
attributed to to
thethe desorption
desorption of
of physically
physically adsorbedwater
adsorbed watermolecules
moleculesover
overthe
the surface
surface of
of CNTs-Ag
CNTs‐Ag22S. S. The
The following
following
weight
weightloss
lossof
of15%
15%ensued
ensuedwithin
withinthe
therange 100‐490◦C
rangeofof100–490 C was
was due
due to
to the
the detachment
detachmentand and
decomposition
decompositionofofoxygen-containing
oxygen‐containing functional groups
functional existing
groups on the
existing onsurface of the CNTs.
the surface of the
The
CNTs.subsequent weight loss
The subsequent of 10.5%
weight loss transpired within the within
of 10.5% transpired range ofthe range◦of
500–540 C, 500‐540
was owing C,
was owing to the breaking of the bond between silver and sulfide in Ag2S nanoparticles
and releasing sulfur. The successive sharp and significant weight loss of 31.5% taken place
within the range of 540‐550 10 C was by the decomposition of sulfur and the formation of
metallic silver and silver oxide. The residual weight remained was about 64%. The broad
Catalysts 2023, 13, 476
to the breaking of the bond between silver and sulfide in Ag2 S nanoparticles and releasing
sulfur. The successive sharp and significant weight loss of 31.5% taken place within the
range of 540–550 ◦ C was by the decomposition of sulfur and the formation of metallic silver
and silver oxide. The residual weight remained was about 64%. The broad endothermic
peak found in the DTA curve around 80 ◦ C was because of the dehydration of the sample.
The small endothermic peak found at 170 ◦ C accounted for the removal of functional groups
from the surface of the CNTs. The intense exothermic peak at 545 ◦ C was assigned to release
sulfur by breaking the bond between silver and sulfide. The UV-vis absorption spectrum
of CNTs-Ag2 S, shown in Figure 5, exhibited a characteristic absorption band of the C=C
bonds of CNTs at 232 nm [52]. In addition, the broad absorption tail corresponding to Ag2 S
nanoparticles was observed in the visible region [52,53]. If semiconductor nanoparticles
Catalysts 2023, 13, 476 are conjugated to CNTs, it shows the charge-transfer band [52,54]. However,6 no such band
of 23
Catalysts 2023, 13, 476 6 of 23
was observed in Figure 5, illustrating that the conjugation of Ag2 S nanoparticles to CNTs
has not altered their energy states [52,54].
100
100
60
60
90 50
90 50
80 40
(V)
80 40
flow(V)
(%)
Weight(%)
30
70 30
Heatflow
70
Weight
20
20
Heat
60
60 10
10
50 0
50 0
-10
40 -10
40
-20
-20
100 200 300 400 500 600 700 800
100 200 300 400 500 600 700 800
Temperature(o(oC)
Temperature C)
Figure 4.4.TG/DTA
TG/DTAof CNTs‐Ag 2S.
of CNTs-Ag
Figure
Figure 4. TG/DTA of CNTs‐Ag2S. 2 S.
C=C
C=C
0.7
0.7
0.6
0.6
Absorbance
Absorbance
0.5
0.5
0.4
0.4
0.3
0.3
200 300 400 500 600 700 800

200 300 400 500 600 700 800
Wavelength(nm)
Wavelength (nm)
Figure UV-visabsorption
Figure 5.5.UV‐vis absorption spectrum
spectrum of CNTs-Ag
of CNTs‐Ag2S. 2 S.
Figure 5. UV‐vis absorption spectrum of CNTs‐Ag2S.
The XPS survey spectrum of CNTs‐Ag2S, shown in Figure 6a, confirmed the presence
The XPS survey spectrum of CNTs‐Ag2S, shown in Figure 6a, confirmed the presence
of C, O, Ag, and S. The high‐resolution spectrum of C1s (Figure 6b) divulged four distinct
of C, O, Ag, and S. The high‐resolution spectrum of C1s (Figure 6b) divulged four distinct
11 at 284.5,
peaks by Gaussian fitting situated 285.5, 286.4, and 287.8 eV. Among these, peaks
peaks by Gaussian fitting situated at 284.5, 285.5, 286.4, and 287.8 eV. Among these, peaks
at 284.5 and 285.5 eV were assigned to the C‐C bonds of the sp 2 and sp3 hybridized carbon
at 284.5 and 285.5 eV were assigned to the C‐C bonds of the sp2 and sp3 hybridized carbon
Catalysts 2023, 13, 476
The XPS survey spectrum of CNTs-Ag2 S, shown in Figure 6a, confirmed the presence
of C, O, Ag, and S. The high-resolution spectrum of C1s (Figure 6b) divulged four distinct
peaks by Gaussian fitting situated at 284.5, 285.5, 286.4, and 287.8 eV. Among these, peaks
at 284.5 and 285.5 eV were assigned to the C-C bonds of the sp2 and sp3 hybridized carbon
atoms of CNTs, respectively [55]. The peaks at 286.4 and 287.8 eV were due to the C-O and
Catalysts 2023, 13, 476 C=O bonds of CNTs, respectively [55]. The deconvoluted O 1s peak (Figure 6c) 7exhibited of 23 a
peak at 531.3 eV for the lattice oxygen and a peak at 532.4 eV corresponding to the carbonyl
(=C-O) functional groups of the CNTs [56]. The core-electron binding energy of Ag 3d3/2
was
presence offound at 373.9
Ag 3d3/2 andeV,
Agand that
3d5/2 of Ag
peaks 3d5/2
and theirwas at 367.9
positions eV (Figure
confirm the Ag6d). Theofpresence
+ state silver of
Ag 3d3/2 and Ag 3d5/2 peaks and their positions confirm the Ag + state of silver [57]. The
[57]. The difference in the position of Ag 3d5/2 and Ag 3d3/2 peaks was 6 eV, and no
difference
shoulder in thepeaks
or satellite position
wereof observed
Ag 3d5/2between
and Ag 3d3/2 peaks
them. The was 6 eV, and Sno2pshoulder
high‐resolution spec‐ or
trumsatellite
(Figurepeaks
6e) forwere
the observed
spin‐orbitbetween
splittingthem.
of S2+The
washigh-resolution
deconvoluted Sinto 2p spectrum
the 2p3/2(Figure
level 6e)
for the spin-orbit splitting of S 2+ was deconvoluted into the 2p3/2 level peak at 161.2 eV,
peak at 161.2 eV, and the 2p1/2 peak at 162.3 eV. These peaks occurred by the Ag‐S bonds
of theand
Ag2the 2p1/2 peak at
S nanoparticles 162.3
[58]. TheeV. These peaks
additional peak occurred
at 163.9 eV byisthe Ag-Stobonds
related of the Ag2 S
the presence
nanoparticles [58].
of sulfur in CNTs‐Ag2S [58]. The additional peak at 163.9 eV is related to the presence of sulfur in
CNTs-Ag2 S [58].
(a)
C KLL
C 1s
Ag 3d5
Ag MNN
Intensity (a.u.)
N 1s
Ag 3p3
O 1s
Ag 3p1
O KLL
Ag 4d
Ag 4p
S 2p
S 2s
1000 800 600 400 200 0

Binding energy (eV)
(b) C 1s
Intensity (a.u.)
280 282 284 286 288 290
Binding energy (eV)

Figure 6. Cont.
12
Catalysts
Catalysts 2023,
2023, 476 476
13, 13, 8 of 23
(c) O 1s
Intensity (a.u.)
525 528 531 534 537

Binding energy (eV)
(d) Ag 3d
3d5/2
Intensity (a.u.)
3d1/2
Catalysts 2023, 13, 476 9 of 23

363 366 369 372 375 378
Binding energy (eV)
(e) S 2p
Intensity (a.u.)
156 159 162 165 168

Binding energy (eV)
Figure
Figure 6. (a)
6. (a) XPSXPS survey
survey spectrum
spectrum of CNTs-Ag
of CNTs‐Ag 2 S.High‐resolution
2S. (b) (b) High-resolution spectrum
spectrum of C1s.
of C1s. (c) High-resolution
(c) High‐
spectrum of O1s. (d) High-resolution spectrum of Ag3d. (e) High-resolution spectrum of S2p.
resolution spectrum of O1s. (d) High‐resolution spectrum of Ag3d. (e) High‐resolution spectrum
of S2p.
The adsorption ability of CNTs‐Ag2S was determined by estimating the Cd(II) ad‐
sorption present in water. The contact time between adsorbent and adsorbate is critical
13 the Cd(II) adsorption was determined by allowing
and it controls adsorption. Therefore,
for contact with CNTs‐Ag2S at different times and compared with that of CNTs and Ag2S
Catalysts 2023, 13, 476
The adsorption ability of CNTs-Ag2 S was determined by estimating the Cd(II) ad-
sorption present in water. The contact time between adsorbent and adsorbate is critical
and it controls adsorption. Therefore, the Cd(II) adsorption was determined by allowing
for contact with CNTs-Ag2 S at different times and compared with that of CNTs and Ag2 S
(Figure 7). The plot of the adsorption capacity, qt versus t, is presented in Figure S2. Cd(II)
adsorption is time dependent and occurs as a gradient function of time. Hence, contact
time is crucial in controlling the Cd(II) adsorption. The tendency in Cd(II) adsorption by
CNTs, Ag2 S, and CNTs-Ag2 S was identical like the adsorption was rapid, then gradually
reduced, and finally attained equilibrium. The initial rapid Cd(II) adsorption could have
occurred due to the difference in the concentration of Cd2+ ions in the solution and over the
surface of the CNTs-Ag2 S, which facilitated the movement of Cd2+ ions from the solution to
the surface of the CNTs-Ag2 S [8]. Also, in the beginning, many active sites were available
on the surface of CNTs-Ag2 S to occupy by Cd2+ ions [8]. With the elapsed contact time, the
active sites of the CNTs-Ag2 S were predominantly occupied by Cd2+ ions. Apart, there is a
possibility of repulsion between Cd2+ ions in the solution and Cd2+ ions exist over the sur-
face of CNTs-Ag2 S. Owing to these reasons, the adsorption rate could gradually decrease
and eventually attain equilibrium [8]. Within 80 min of the contact time, CNTs-Ag2 S could
adsorb the Cd(II) completely; however, under identical conditions, the adsorption rates of
CNTs and Ag2 S were 79 and 53%, respectively. Thus, the adsorption efficiency of CNTs and
Ag2 S was significantly improved by their conjugation in CNTs-Ag2 S. Further, to identify
the adsorption kinetics of CNTs-Ag2 S, the data were simulated with the pseudo-first-order
kinetic model using the expression presented in Equation (1).
ln(qe − qt ) = lnqe − k1 t (1)

Catalysts 2023, 13, 476 10 of 23
where qe and qt are the quantity of adsorbate (mg/g) at equilibrium and particular time,
t (min), respectively, and k1 (min−1 ) is the pseudo-first-order rate constant.
100
Removal efficiency (%)
80
60
40
20 CNTs-Ag2S
CNTs
Ag2S
0
0 20 40 60 80 100 120
t (min)
Figure 7. Adsorption kinetics of Cd(II) over CNTs, Ag S, and CNTs-Ag S.
2 2
Figure 7. Adsorption kinetics of Cd(II) over CNTs, Ag 2S, and CNTs‐Ag2S.
The pseudo-first-order plot obtained for Cd(II) adsorption over CNTs, Ag2 S, and
The pseudo‐first‐order
CNTs-Ag plot obtained for Cd(II) adsorption2 over CNTs, Ag2S, and
2 S is shown in Figure 8. The correlation coefficients (R ) perceived for CNTs, Ag2 S,
CNTs‐Ag S is shown in Figure 8. The correlation coefficients (R2) perceived for CNTs,
and CNTs-Ag2 S were 0.9906, 0.9540, and 0.9930, respectively. The k1 and qe were computed
2
Ag2S, and CNTs‐Ag2S were 0.9906, 0.9540, and 0.9930, respectively. The k1 and qe were
computed using the slope and intercept values of the straight lines acquired in Figure 8.
The estimated values of k1 and qe is summarized in Table 1. The calculated qe(cal) could
14 value qe(exp) for all samples. Thus, the experimental data
not agree with the experimental
for the Cd(II) adsorption could not be projected by the pseudo‐first‐order kinetic model.
Catalysts 2023, 13, 476
using the slope and intercept values of the straight lines acquired in Figure 8. The estimated
values of k1 and qe is summarized in Table 1. The calculated qe (cal) could not agree with
the experimental value qe (exp) for all samples. Thus, the experimental data for the Cd(II)
adsorption could not be projected by the pseudo-first-order kinetic model. Alternatively, it
was analyzed using the pseudo-second-order kinetic model using Equation (2).
t 1 t
= + (2)
Catalysts 2023, 13, 476 qt k2 q2e qe 11 of 23
where k2 [g/(mg.min)] is the pseudo-second-order rate constant.
5 CNTs-Ag2S
CNTs
4 Ag2S
3
ln(qe-qt)
−1
0 10 20 30 40 50 60 70 80
t (min)
Figure 8. Pseudo-first-order kinetics for Cd(II) adsorption over CNTs, Ag2 S, and CNTs-Ag2 S.
Figure 8. Pseudo‐first‐order kinetics for Cd(II) adsorption over CNTs, Ag2S, and CNTs‐Ag2S.
Table 1. Parameters calculated for the Cd(II) adsorption using adsorption kinetic models.
Table 1. Parameters calculated for the Cd(II) adsorption using adsorption kinetic models.
Pseudo-First-Order Kinetic Model Pseudo-Second-Order Kinetic Model
Adsorbent
Pseudo‐First‐Order Kinetic Pseudo‐Second‐Order Kinetic
qe (exp) mg g−1 k2 × 10−3
qe (cal) mgqg −1
e (exp) k1 (min )
−1 R2
Model qe (cal) mg g−1 1 Model1 R2
(g mg min )
− −
Adsorbent
CNTs-Ag2 S 125.0 5.0633 mg g −1 qe (cal) mg
0.0778 0.9930 −1 133.2 q e (cal) k2 × 10−3 (g0.9980 2
1.2140
k 1(min ) R 2 R
CNTs 98.75 4.7785 0.0608
g−1 0.9906 109.8 mg g−1 0.8360
mg−1 min−1)0.9963
Ag2 S 67.50 4.0970 0.0519 0.9540 72.62
CNTs‐Ag 2S 125.0 5.0633 0.0778 0.9930 133.2 1.7750 1.2140 0.9985 0.9980
CNTs 98.75 4.7785 0.0608 0.9906 109.8 0.8360 0.9963
The pseudo-second-order model plot is illustrated in Figure 9, and the determined
Ag 2S 67.50 4.0970 0.0519 2 0.9540 72.62 1.7750 0.9985
parameters are presented in Table 1. The R values derived from the pseudo-second-
order plots for CNTs, Ag2 S, and CNTs-Ag2 S were 0.9963, 0.9985, and 0.9980, respectively.
The RThe pseudo‐second‐order
2 value of the second-order plotmodel wasplot is illustrated
relatively in Figure
higher than 9, and
that found for the determined
the first-
parameters are presented
order plot, which was closeintoTable 1. The
1. The R values
2
qe (cal) derived frommodel
of the second-order the pseudo‐second‐order
matched the
qe (exp) for all samples. The linearity of the pseudo-second-order plot and therespectively.
plots for CNTs, Ag 2 S, and CNTs‐Ag 2S were 0.9963, 0.9985, and 0.9980, agreeing The
values
R 2 valueof of
qe (exp) and qe (cal) show
the second‐order plotthat
wastherelatively
Cd(II) adsorption couldthat
higher than be analyzed
found for using
the the
first‐order
pseudo-second-order
plot, which was close kinetics rather
to 1. The than of
qe(cal) thethe
pseudo-first-order kinetics.
second‐order model The agreement
matched the qe(exp) for
of the
all second-order
samples. kinetics demonstrates
The linearity that chemisorptionplot
of the pseudo‐second‐order wasand
the rate-determining
the agreeing values of
step in the Cd(II) adsorption [9]. Moreover, it represents the rapid transfer of Cd(II)
qe(exp) and qe(cal) show that the Cd(II) adsorption could be analyzed using the pseudo‐
from a solution with a lower initial concentration to the surface of the CNTs-Ag2 S due to
second‐order kinetics rather than the pseudo‐first‐order kinetics. The agreement of the
second‐order kinetics demonstrates that chemisorption was the rate‐determining step in
the Cd(II) adsorption [9]. Moreover, it represents the rapid transfer of Cd(II) from a solu‐
15
tion with a lower initial concentration to the surface of the CNTs‐Ag2S due to the concen‐
Catalysts 2023, 13, 476
the concentration gradient [9]. Further, the experimental data were explored using the
Weber−Morris intraparticle pore diffusion model to evaluate the diffusion mechanism
using Equation (3).
Catalysts 2023, 13, 476 qt = k id t0.5 + C (3)of 23
12
where kid (mg/g.min) is the intraparticle diffusion rate constant, which can be calculated
from the linear plot of qt versus t0.5 . c (mg/g) is the intraparticle diffusion constant,
estimated
surface from the intercept
adsorption and directly proportional
in the rate‐controlling to regression
step. If the the boundary of layer
the qtthickness.
versus t0.5Itplot
is is
assumed that the higher the intercept value, the more significant
linear and passes through the origin, intraparticle diffusion plays a significant role the contribution of the
in con‐
surface adsorption in the rate-controlling step. If the regression of the qt versus t0.5 plot
trolling the kinetics of the adsorption process. If it does not pass through the origin, intra‐
is linear and passes through the origin, intraparticle diffusion plays a significant role in
particle diffusion is not the only rate‐limiting step. Instead, it is contributed by the bound‐
controlling the kinetics of the adsorption process. If it does not pass through the origin,
ary layer effect [59]. The intraparticle diffusion plot of qt versus t0.5 acquired for the Cd(II)
intraparticle diffusion is not the only rate-limiting step. Instead, it is contributed by the
adsorption
boundary layer on CNTs‐Ag
effect [59]. 2S is demonstrated in Figure 10. The plot in Figure
The intraparticle diffusion plot of qt versus t0.5 acquired 10 doesfor not
pass through
the Cd(II) the origin
adsorption on of the coordinates
CNTs-Ag (Figure S3). So, intraparticle diffusion is not the
2 S is demonstrated in Figure 10. The plot in Figure 10
sole rate‐limiting step in Cd(II) adsorption
does not pass through the origin of the coordinates over (Figure
CNTs‐Ag S3).2S.So,
The association
intraparticle of the two
diffusion
is not the sole rate-limiting step in Cd(II) adsorption over CNTs-Ag2 S. The association
straight lines in the intraparticle diffusion plot (Figure S3) and the intercept values (Table
of the
S1) two straight
support that thelines in the intraparticle
intraparticle diffusiondiffusion
was notplotonly(Figure S3) and the intercept
a rate‐controlling step in the
values adsorption;
Cd(II) (Table S1) support
it also that the intraparticle
contributed throughdiffusion was not
the boundary onlyeffect
layer a rate-controlling
[59]. The multi‐
step in the
linearity ofCd(II) adsorption;
the plot in Figureit10 also contributed
(Figure through
S3) shows thatthe
theboundary layer effect
Cd(II) adsorption [59].
transpires
The multilinearity of the plot in Figure 10 (Figure S3) shows that
through multiple phases [60]. Among these, the initial stage occurred through the rapid the Cd(II) adsorption
transpires through
adsorption of Cd2+ multiple
ions, thephases
second[60].phaseAmong these, the
was owing initial
to the stage occurred
diffusion through
of Cd2+ ions into the
the rapid adsorption of Cd 2+ ions, the second phase was owing to the diffusion of Cd2+ ions
pores of CNTs‐Ag2S, and the third phase was due to equilibrium of the adsorption that
into the apores
caused of CNTs-Ag
chemical 2 S, and the third
reaction/bonding [60].phase was due to equilibrium of the adsorption
that caused a chemical reaction/bonding [60].
1.8 CNTs-Ag2S
CNTs
1.6 Ag2S
1.4
1.2
t/qt
1.0
0.8
0.6
0.4
0.2
20 40 60 80 100 120
t (min)
Figure 9. Pseudo-second-order kinetics for Cd(II) adsorption over CNTs, Ag2 S, and CNTs-Ag2 S.
Figure 9. Pseudo‐second‐order kinetics for Cd(II) adsorption over CNTs, Ag2S, and CNTs‐Ag2S.
16
Catalysts 2023, 13, 476
Catalysts 2023, 13, 476 13 of 23
120
100
80
qt (mg/g)
60
Phase-III
40
Phase-II
20
Phase-I
0
2 4 6 8 10 12
0.5 0.5
t (min )
Figure
Figure 10.10. Weber-Morris
Weber‐Morris intraparticle
intraparticle diffusion
diffusion plot plot for
for the Cd(II) the Cd(II)
adsorption adsorption
over CNTs‐Ag2S. over CNTs-Ag2 S.
TheThe experimental
experimental equilibrium
equilibrium parametersparameters for Cd(II)
for Cd(II) adsorption adsorption
were determined by were determined
applying three isotherm models: Langmuir, Freundlich, and Temkin. The Langmuir
by applying three isotherm models: Langmuir, Freundlich, and Temkin. The Langmuir
model predicts that the adsorbed molecules form a monolayer and adsorption emerges at
amodel predicts
static number that the sites,
of adsorption adsorbed
each ofmolecules form ainmonolayer
which is equivalent and adsorption emerges
efficiency. Moreover,
at amolecule
each static number of adsorption
has a constant enthalpy and sites, each activation
adsorption of whichenergy,
is equivalent in efficiency.
it means that all Moreover,
each molecule
molecules has a constant
have an affinity enthalpy
equal to entire andsites
adsorption adsorption activation
[61]. With the energy, it means that all
help of Langmuir
isotherm
moleculesmodel,
haveit could be find equal
an affinity the value
to of the maximum
entire adsorption adsorption capacity
sites [61]. Withof the
the help of Langmuir
adsorbent using Equation (4) [62]:
isotherm model, it could be find the value of the maximum adsorption capacity of the
adsorbent using Equation𝐶(4) [62]:
𝐶 1
(4)
𝑞 𝑞 Ce 𝐾 C𝑞e 1
= + (4)
qe qm K L qm
where qe (mg/g) is the amount of adsorbed Cd(II) per unit mass of CNTs‐Ag2S; Ce (mg/L)
is the concentration of Cd(II) at equilibrium; qm is the maximum amount of the Cd(II)
where qe (mg/g)
adsorbed per
is the amount of adsorbed Cd(II) per unit mass of CNTs-Ag2 S; Ce (mg/L)
unit mass of CNTs‐Ag2S to form a complete monolayer on the surface‐bound
is the concentration
at high Ce. KL is the Langmuirof adsorption
Cd(II) atconstant
equilibrium; m is
related toqthe freethe maximum
energy amount of the Cd(II)
of adsorption.
adsorbed
The Langmuir per unit
plot for mass of CNTs-Ag
Cd(II) adsorption 2 SCNTs‐Ag
over to form2Saiscomplete monolayer
presented in on the surface-bound
Figure 11. The
at high Cparameters
estimated e . KL is the Langmuir adsorption constant related to the free energy of adsorption.
are shown in Table 2. The maximum adsorption capacity (qm) cal‐
culated for Cd(II) adsorption over CNTs‐Ag2S was 256.4 mg/g.
The Langmuir plot for Cd(II) adsorption over CNTs-Ag2 S is presented in Figure 11. The
Catalysts 2023, 13, 476
estimated parameters are shown in Table 2. The maximum adsorption
14 of 23
capacity (qm )
calculated for Cd(II) adsorption over CNTs-Ag2 S was 256.4 mg/g.
0.40
0.35
0.30
0.25
Ce/qe (g/L)
0.20
0.15
0.10
0.05
0.00
0 20 40 60 80 100
Ce (mg/L)
Figure 11.
Figure 11. Langmuir
Langmuir isotherm
isotherm plot forplot
Cd(II)for Cd(II) adsorption
adsorption over CNTs‐Agover
2S. CNTs-Ag2 S.
Table 2. Parameters calculated for Cd(II) adsorption over CNTs‐Ag2S using Langmuir, Freundlich,
and Temkin adsorption isotherm models.
Langmuir Isotherm 17
Freundlich Isotherm Temkin Isotherm
qm (mg KL (L KF (mg
R2Lan n R2Fre A B R2Tem
Catalysts 2023, 13, 476
Table 2. Parameters calculated for Cd(II) adsorption over CNTs-Ag2 S using Langmuir, Freundlich,
and Temkin adsorption isotherm models.
Langmuir Isotherm Freundlich Isotherm Temkin Isotherm

qm (mg g−1 ) KL (L mg−1 ) R2 Lan KF (mg g−1 ) n R2 Fre A B R2 Tem
256.4 −0.6830 0.9972 305.0 −31.21 0.3562 1.1 × 10256 0.4565 0.0019
The Freundlich isotherm is developed based on the assumption that the adsorption
sites are distributed exponentially concerning the heat of adsorption [62,63]. It provides
the relationship between the equilibrium of liquid and solid phase capacities with multi-
layer adsorption properties consisting of the heterogeneous surface of the adsorbent. The
Freundlich isotherm that supports multilayer adsorption agrees with the Langmuir model
over moderate ranges of concentrations but differs at low and high concentrations. The
linear form of the Freundlich isotherm can be represented b Equation (5):
ln Ce
ln qe = ln K F + (5)
n
where qe (mg/g) is the amount of Cd(II) adsorbed at equilibrium. KF and n are Freundlich
constants. KF symbolizes the affinity of the adsorbent, and n signifies the adsorption
intensity. Ce (mg/L) is the Cd(II) concentration at equilibrium. The Freundlich isotherm
plot attained for Cd(II) adsorption is shown in Figure S4, and the calculated parameters are
included in Table 2.
The Temkin isotherm model is based on the fact that, during adsorption, the heat of
all molecules decreases linearly with an increase in the coverage of the adsorbent surface
and that adsorption is characterized by the uniform distribution of binding energies up
to the maximum binding energy [62,64]. The linear form of the Temkin isotherm model is
shown in Equation (6):
qe = B lnA + B ln Ce (6)
where B = RT/KT , KT is the Temkin constant related to the heat of adsorption (J/mol); A
is the Temkin isotherm constant (L/g), R is the gas constant (8.314 J/mol K), and T is the
absolute temperature (K). The Temkin isotherm fitting plot for the Cd(II) adsorption is
shown in Figure S5. The values estimated from Figure S5 are illustrated in Table 2.
The R2 Lan value found for the Langmuir isotherm plot was 0.9972; for Freundlich and
Temkin isotherm plots, the R2 Fre and R2 Tem values were 0.3562 and 0.0019, respectively. The
Freundlich and Temkin isotherm models provided scattered points and failed to accomplish
linearity. Therefore, the Freundlich and Temkin isotherm models were unsuitable for
explaining Cd(II) adsorption over CNTs-Ag2 S. However, the Langmuir isotherm model
produced linearity. Therefore, the Langmuir model is appropriate for elucidating the Cd(II)
adsorption. The validation of the Langmuir model indicates that the Cd(II) adsorption over
CNTs-Ag2 S ensued with monolayer molecular covering and chemisorption, together [65].
Further, the photocatalytic activity of CNTs-Ag2 S was investigated through the degra-
dation of AYR under exposure to sunlight. The degradation of AYR by CNTs-Ag2 S is
presented in Figure 12. The activity of CNTs-Ag2 S was compared with that of CNTs and
Ag2 S. The CNTs-Ag2 S could degrade the AYR completely within 120 min of illumination.
However, CNTs and Ag2 S were capable to degrade 77.3 and 41% of AYR, respectively, in
120 min. Hence, the conjugation of CNTs and Ag2 S was substantially improved the photo-
catalytic activity in CNTs-Ag2 S. The degradation of AYR was quantified by the reduction in
the electronic absorption band located at 373 nm (Figure 13). The hybrid nano-architecture
of CNTs-Ag2 S was proficient in adsorbing higher number of AYR molecules and capable
in absorption of sunlight. In addition, the effectual hindrance of recombining of electrons
and holes during photocatalysis facilitated the degradation process. The photocatalytic
activity of CNTs-Ag2 S was further explored by finding the apparent rate constants using
18
120 min. Hence, the conjugation of CNTs and Ag2S was substantially improved the pho‐
tocatalytic activity in CNTs‐Ag2S. The degradation of AYR was quantified by the reduc‐
tion in the electronic absorption band located at 373 nm (Figure 13). The hybrid nano‐
architecture of CNTs‐Ag2S was proficient in adsorbing higher number of AYR molecules
Catalysts 2023, 13, 476 and capable in absorption of sunlight. In addition, the effectual hindrance of recombining
of electrons and holes during photocatalysis facilitated the degradation process. The pho‐
tocatalytic activity of CNTs‐Ag2S was further explored by finding the apparent rate con‐
stants using the Langmuir‐Hinshelwood (L‐H) model and with the help of Equation (7)
the Langmuir-Hinshelwood (L-H) model and with the help of Equation (7) that could be
that could be applicable for low concentrations of dyes [38,39,44,45].
applicable for low concentrations of dyes [38,39,44,45].
𝐶
𝑙𝑛ln C0 = k𝑘app t 𝑡 (7)
(7)
𝐶C
where C
where C00 is
is the
the initial
initial concentration
concentration of
of AYR and C
AYR and C is
is the
the concentration
concentration at at aa particular
particular time
time
of irradiation. k is the apparent rate constant of the reaction, and t is the irradiation
of irradiation. kapp is the apparent rate constant of the reaction, and t is the irradiation time.
app time.
1.0
Ag2S
CNTs
0.8 CNTs-Ag2S
0.6
C/C0
0.4
0.2
0.0
0 20 40 60 80 100 120
t (min)
Catalysts 2023, 13, 476 12. The degradation of alizarin yellow R in the
Figure 12. the presence
presence of
of CNTs,
CNTs, Ag
Ag22S,
S, and
and CNTs-Ag
16 of 23 22S
CNTs‐Ag
under the
under the illumination
illumination to
to sunlight.
sunlight.
0.3
0 min
110 min
Absorbance
0.2
0.1
0.0
300 350 400 450 500
Wavelength (nm)
Figure13.
Figure Reductionininthe
13.Reduction theelectronic
electronicabsorption
absorptionofof alizarin
alizarin yellow
yellow RRin in
thethe presence
presence of of CNTs-Ag
CNTs‐Ag 2S 2
S
underthe
under theirradiation
irradiationtotosunlight.
sunlight.
TheL‐H
The L-H plots
plots perceived
perceived for
for the
thedegradation
degradationofofAYR
AYRwere
werelinear, as as
linear, depicted in Figure
depicted in Fig‐14.
The14.
ure linearity of the L-H
The linearity plots
of the L‐Hreveals that the
plots reveals degradation
that of AYRofensue
the degradation with pseudo-
AYR ensue with
first-order kinetics. The apparent rate constants determined
pseudo‐first‐order kinetics. The apparent rate constants determined by the
by L-H
the plots
L‐H for CNTs,
plots for
Ag2 S, Ag
CNTs, and CNTs-Ag2 S were
2S, and CNTs‐Ag
0.0108, 0.0035, and 0.0378 min−1 , respectively. The value
2S were 0.0108, 0.0035, and 0.0378 min‐1, respectively. The value
determinedfor
determined forCNTs‐Ag
CNTs-Ag2S2 Swas
wasabout
aboutfour‐fold
four-fold higher
higher than
than CNTs
CNTs and
and eleven-fold
eleven‐fold greater
greater
than Ag2S. Therefore, the conjugation of CNTs and Ag2S has magnificently improved the
photocatalytic activity in CNTs‐Ag2S. Due to the conjugated structure, containing aro‐
matic, carbonyl, and azo groups, 19 the AYR solution possessed an intense color in water.
Accordingly, AYR degradation could happen by breaking the conjugated system in the
Catalysts 2023, 13, 476
than Ag2 S. Therefore, the conjugation of CNTs and Ag2S has magnificently improved
the photocatalytic activity in CNTs-Ag2 S. Due to the conjugated structure, containing
aromatic, carbonyl, and azo groups, the AYR solution possessed an intense color in water.
Accordingly, AYR degradation could happen by breaking the conjugated system in the
presence of CNTs-Ag2 S under sunlight irradiation. With this assumption, the possible
mechanism for the rapid degradation of AYR by CNTs-Ag2 S could be explained as follows
(Figure 15).
CNTs-Ag2 S + hν → e− + h+
h+ + H2 O → HO− + H+
Catalysts 2023, 13, 476 17 of 23
e− + O2 → O2 •−
O2 •− + H+ →HO2 •
Catalysts 2023, 13, 476 17 of 23
HO2 • + H2 O → H2 O2 + HO•
AYR5+ HO• → H2 O + CO2 + nontoxic products
Ag2S
5 CNTs
AgCNTs-Ag
2S 2S
4 CNTs
CNTs-Ag2S
4
3
0/C) /C)
3
ln(C 0
ln(C
2
2
1
1
00
00 2020 40 40 60 60 80 80100 100
120 120
t (min)
t (min)
Figure14.
Figure Langmuir-Hinshelwood
14.Langmuir‐Hinshelwood plot plot
for fordegradation
the degradation of alizarin
yellow Ryellow R in the of
presence of
Figure 14. Langmuir‐Hinshelwood plotthefor of alizarin
the degradation of alizarin in the presence
yellow R in the presence of
CNTs-Ag
CNTs‐Ag
CNTs‐Ag2S2 2Sunder
Sunder illumination
illumination
under to
tosunlight.
to sunlight.
illumination sunlight.
Figure 15. A possible mechanism for the degradation of alizarin yellow R in the presence of CNTs‐
Ag2S under exposure to sunlight.
Figure
Figure 15.A
15. Apossible
Further, possible
to
mechanism
find themechanism for the
stability offor the degradation
degradation
CNTs‐Ag
of
of alizarin
alizarin yellow
yellow RR in
in the
the presence
presence of
2S, it was recovered by centrifugation after
of CNTs-
CNTs‐
Ag
Ag22SS under
under exposure
exposure to
tosunlight.
sunlight.
photocatalysis. It was washed with DI water, dried and used in further two cycles of the
photocatalysis. The reused CNTs‐Ag2S was able to degrade AYR completely in further
Further,
two cycles to find
without any the stability
significant of CNTs‐Ag
reduction 2S, it (Figure
in activity was recovered by centrifugation
S6). The XRD of CNTs‐ after
photocatalysis. It was washed
Ag2S recorded before and after 20 with DI water, dried and used in further
using in the three degradation cycles of AYR could not two cycles of the
photocatalysis.
show any structuralThe reused CNTs‐Ag
modification or rapture 2S (Figure
was ableS7).to degrade AYR
Consequently, completely
CNTs‐Ag 2S is ta‐in further
Catalysts 2023, 13, 476
Further, to find the stability of CNTs-Ag2 S, it was recovered by centrifugation after

photocatalysis. It was washed with DI water, dried and used in further two cycles of the
photocatalysis. The reused CNTs-Ag2 S was able to degrade AYR completely in further two
cycles without any significant reduction in activity (Figure S6). The XRD of CNTs-Ag2 S
recorded before and after using in the three degradation cycles of AYR could not show
any structural modification or rapture (Figure S7). Consequently, CNTs-Ag2 S is table and
suitable for reuse.
The CNT/Ag2 S nanocomposite prepared by Di et al. and applied it to the degradation
of rhodamine B revealed its higher activity than bare Ag2 S nanoparticles under illumi-
nation to visible and near-infrared (NIR) light [57]. In addition, the recycled CNT/Ag2 S
nanocomposite could not lost the activity [57]. The Ag2 S-CNT nanocomposite, reported
by Meng et al. [66], efficiently degraded texbrite BA-L in presence of visible light. In this
study, the Ag2 S-CNT nanocomposite was for four degradation cycles of texbrite BA-L [66].
Further, the photocatalytic activity of CNTs-Ag2 S in the degradation of AYR was compared
with different photocatalysts and presented in Table 3 [24,25,46,67–69].
Table 3. Comparison of the degradation rate of AYR by CNTs-Ag2 S with reported photocatalysts.
Photocatalyst Source of Irradiation Degradation Rate (%) Ref

CNTs-Ag2 S Sunlight 100 This work
Fe nanoparticles Sunlight 93.7 25
H2 O2 UV 100 24
Zinc oxide UV 92.5 46
β-MnO2 nanowires Mercury lamp 98.0 69
Mn3 O4 Mercury lamp 62.0 69
MnO(OH) nanorods Mercury lamp 54.0 69
Bi2 O3 @RGO Sunlight 41.5 70
ZnO nanoparticles UV 95.0 71
ZnO nanoparticles Sunlight 13.2 71
ZnO nanoparticles Visible 06.2 71
3. Experimental
3.1. Materials
The chemicals and CNTs were purchased from Millipore Sigma and used as received.
The aqueous solutions were prepared using ultrapure water obtained by the Milli-Q Plus
system (Millipore; Burlington, MA, USA).
3.2. Preparation of CNTs-Ag2 S

The hydrophobic pristine CNTs were modified to hydrophilic through the oxidization
by refluxing in a mixture of 1:3 (v/v) concentrated HNO3 and H2 SO4 at 70 ◦ C for 24 h. The
resulting oxidized CNTs were collected through centrifugation and purified by washing
them with DI water [70,71]. The resulting oxidized CNTs were dried under a vacuum and
used to deposit Ag2 S nanoparticles. About 40 mg of oxidized CNTs (CNTs-COOH) were
dispersed in 40 mL of DI water using sonicator, and a solution of 0.04 mol/L of AgNO3 in
40 mL of DI water was added. The mixture was allowed to stir in room temperature for
30 min, and a freshly prepared 40 mL aqueous solution of 0.02 mol/L sodium sulfide was
added slowly. This suspension was stirred for 10 min and transferred to an autoclave. The
autoclave was heated at 180 ◦ C for 6 h to yield CNTs-Ag2 S. Thus, the formed CNTs-Ag2 S
was collected by centrifugation and purified with washing with DI water.
3.3. Preparation of Ag2 S

For control experiments, Ag2 S nanoparticles were prepared using the procedures used
for CNTs-Ag2 S without CNTs.
21
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"She's saying 'Good morning,'" declared May. "Oh, dear, dear
Jenny!"
Dropping Billy's hand she ran to the donkey, clasped her around the
neck, and talked to her in a whisper so low that the little boy could
not hear a word. Then Scout came up, and he, too, had to be
noticed. He looked at May with a wealth of love in his brown eyes,
and kept close to her side when, having said all she wanted to say to
Jenny, she beckoned Billy to follow her across the orchard. In a
sheltered corner she paused, and pointed at the ground.
"This is where the snowdrops are, underneath the grass," she said
gravely. Then suddenly, to Billy's astonishment, she dropped on her
knees, bent her head low, and cried softly: "Little snowdrops, little
snowdrops, are you still asleep?" She listened a minute, then rose, a
finger on her lips.
"Still asleep!" she murmured, "still asleep!"
"Asleep?" Billy echoed wonderingly. "Snowdrops don't go asleep,

May!" He smiled at the idea.
"Oh, yes, they do!" she corrected. "Didn't you know? Mr. Singleton
told me. I was, oh, so sorry when they died! Then Mr. Singleton told
me they'd gone deep, deep into the ground, and would sleep, sleep,
sleep till the spring came again, and God would say: 'Little
snowdrops, awake!' It's so sunny and warm to-day, I thought p'r'aps
the spring had come."
"Why, it's November, May!" exclaimed Billy, full of amazement. "It

won't be spring for months and months."
The little girl heaved a gentle sigh and rose from her knees. For a
minute her face wore a slightly clouded expression, then it smiled
and became contented again.
"Never mind," she said, "never mind! Mr. Singleton says God'll
remember them—He never forgets."
They returned to the garden, where William Brown had stirred up the
bonfire which had smouldered through the night. May clapped her
hands with delight when she saw the flames, and she and Billy set to
work collecting more rubbish to keep the bonfire burning.
At one o'clock Mrs. Brown came and called them in to dinner. She
was evidently pleased to see May. Billy noticed that her face
softened as she kissed the little girl and inquired if her mother knew
where she was.
"Oh, yes!" the child answered, adding: "I can stay till Harold fetches
me, Granny."
Harold did not arrive at Rowley Cottage till half-past four o'clock. He
had been told he must not stop to tea, he said, as it got dark so early
now, so May must please come at once. May told him of Billy's
gardening tools, and he lingered to have a look at them. The sight of
them evidently made him a little envious, for he did not express the
admiration Billy had expected he would.
"Oh, they'll do," he said, "but they've had a good bit of wear."
"Grandfer says they're none the worse for that," replied Billy. "See
how sharp the spade is! That's from use, Grandfer says. I think
they're beautiful tools."
"What made Master Tom give them to you?" asked Harold.
"Oh, he thought they would be just the right weight for me,"
explained Billy, "and so they are."
"He never gave me anything," remarked Harold, in a decidedly

grudgeful tone, "and he's always known me, whilst you—why, you're
almost a stranger to him! However, I don't want gardening tools; I've
some of my own that father gave me last birthday."
"But they're not such nice ones as yours," May told Billy.
Harold glanced at his little sister with a frown, and flushed angrily.
"I wouldn't change my tools for Billy's!" he exclaimed.
"Of course you wouldn't, as your father gave them to you," Billy said
quickly. "I suppose you know all about gardening?" he suggested.
"Rather!" Harold replied. "Father's got an allotment, and I help him

work it. We won several prizes at the vegetable and flower show last
August—the show's held in the Vicarage grounds every year. You
haven't seen the allotment gardens yet, I suppose? No? Well, you'd
better come and have a look at them on Saturday—there's no school
then, and I can show you about."
"Oh, thank you!" cried Billy. "I'll come—that is if Grandfer and Granny
will let me."
"Oh, they'll let you," declared Harold.
"Grandfer's so good-natured he generally lets people do as they like;

and Granny—well, I expect she'll be glad to get you out of her way.
She was vexed you had to come here, you know."
"I didn't know," said Billy. He felt hurt, but somehow he was not in the
least surprised. "How do you know?" he inquired.
"Oh, I heard her talking about you to mother before you came,"
Harold replied; "she said you'd be more trouble than enough, she
expected."
"Why should she have said that?" cried Billy indignantly, adding, as
Harold shook his head, "I think it was an unkind thing to say, and—
and an unkind thing to repeat!"
Harold looked rather ashamed.
"Now you're angry," he said, "and won't come on Saturday, I

suppose. Well, do as you like!"
He went off, leading May, who had listened to the conversation
between the two boys in puzzled silence. Billy watched them through
the orchard with a swelling heart. As they passed through the
gateway into the pathfields May looked back and waved her hand.
"Good-bye, Billy!" she cried; "I'll come again to-morrow if mother'll let
me! I like you, Billy, I do!"
Billy nodded and smiled. Then a cold nose touched his hand, and
Scout rubbed against him. He bent to caress the dog, and as he did
so, heard his grandfather's voice calling him to come in to tea. It
sounded so hearty that he felt quite cheered by it.
"At any rate he isn't vexed I had to come here!" he said to himself.
CHAPTER VII.
"COME LIFE, COME DEATH, THEY'RE SAFE."
DURING the next few days, the weather continuing fine, May was a
constant visitor at Rowley Cottage, coming and going as she
pleased. She spent most of her time with her grandfather and Billy in
the garden, but sometimes she would leave them and wander about
the orchard with the live-stock there. She had no fear of any living
creature, and even the big, grey gander, which hissed so fiercely,
would eat from her hand.
"She's not like any other little girl I ever knew," Billy remarked to his
grandfather one evening, as they sat on the settle by the kitchen fire,
Scout asleep at their feet, discussing May, who had gone home
shortly before tea.
"I expect not," William Brown answered, "she's different from most
children, poor dear! She learns nothing at school, but—"
"She's only backward," his wife broke in sharply. She was seated
near the table, sewing by the light of an oil lamp. "You needn't speak
as though she's stupid," she added, in a tone full of resentment, "for
she can learn some things quick enough."
"Just what I was going to say when you interrupted me," William
Brown said mildly. "She can't remember if you try to teach her to
read or add up figures, but tell her anything about an animal or a
bird, or a flower, and she'll remember it. Oh, yes! If she's a bad
memory for some things—"
"Oh, her memory will be all right by-and-by!" broke in Mrs. Brown
again. "It'll strengthen as she grows older, you'll find!"
"I hope so, I'm sure," her husband muttered to himself. Aloud he
said: "I suppose you've no objection to Billy's spending to-morrow
with his cousins, Maria? Being Saturday, Harold will have a holiday. I
saw Elizabeth when I went to the post office this afternoon, and she
asked if Billy might come. Of course, I said 'yes.'"
"Then why ask me anything about it?" questioned Mrs. Brown tartly.
"You said 'yes,' so that's enough. Billy and his cousins indeed!"
"Aunt Elizabeth said I was to look on May and Harold as cousins,"

explained Billy, adding in a disappointed tone, "If you don't want me
to go, Granny, of course I won't."
"Oh, go!" said Mrs. Brown impatiently. "Why should I want to keep
you here?"
Accordingly Billy went. He consulted his grandfather as to the time

he ought to go, and was told as early after breakfast as he pleased.
So soon after nine o'clock found him at the top of the hill, hastening
in the direction of the village. At the first turn of the road he met May
and Harold.
"Oh, here you are!" exclaimed Harold. "We were coming to meet
you. She—" nodding at his sister—"would come too! Now what
would you like to do before dinner? I thought we wouldn't go to the
allotment field till this afternoon, then father'll be there. Father can't
leave the post office in the morning, because mother's too busy
about the house to attend to the shop. I say, don't you think it would
be nice to go down to the bridge by the railway-station? We might sit
on it and watch the Canadians."
"The Canadians?" echoed Billy, inquiringly.
"Yes—the Canadian lumbermen. They've been taking down trees in

the valley, and they've got a steam saw near the station cutting them
up. It's great fun looking on. You'd like it, wouldn't you?"
"Yes," agreed Billy, "I expect I should."
So the children spent the morning seated on top of one of the arches
of an old stone bridge close to the railway-station, watching a great
steam saw at work, and a lot of khaki-clad Canadian lumbermen
loading trucks with timber. Some of the men spoke to them good-
naturedly in passing, and one, a grey-headed, middle-aged man who
seemed to be in command of the others, stopped, and, after
exchanging a few words with the boys, addressed himself to May.
"I've a little daughter at home in Canada with fair hair like yours," he
told her, with a smile. "Guess she's about your age, my dear. Real
smart she is. See!"
He took a letter from his pocket, opened it, looked at it admiringly for
a few moments, then showed it to May.
"Her own handwriting," he said proudly; "her own spelling too.

Guess, now, you can't write or spell much better than that yourself."
"May can't either write or spell," Harold said, as his little sister did not
attempt to answer; "she goes to school, but she can't learn—it's not
her fault."
The Canadian put his great brown hand under May's chin, lifted her
face and looked long and earnestly into the depths of her dark-blue
eyes. What he saw there brought a very tender expression into his
own eyes.
"No," he said gently, "it's not her fault. What's your name, little one?"
he asked May.
When she had told him, he remarked that it was a very pretty name.
Then he asked for a kiss, and, having received it, went across the
bridge and away.
"Nice man!" May exclaimed. "Where's Canada, Harold?"
"Oh, ever so far off," he answered.
"Further away than Exeter?" questioned the little girl.
Her brother nodded, laughing. "It's across the sea," he explained. "To
get there you've to go in a ship."
"Oh, how lovely!" cried May, clasping her hands.
"She stayed by the sea once," Harold told Billy. "Mother took her to
Teignmouth for a week because she'd been ill; that was two years
ago, but she's never forgotten it. Now, what do you say to making a
move? I'm getting so hungry that I'm sure it must be nearly dinner-
time."
Dinner was being dished when the children reached the post office.
Billy, who was quite at his ease with his adopted relations, enjoyed
his dinner—a share of a large rabbit-pie, which was the nicest he
had ever tasted, he thought. He did not talk much himself, but
listened to the conversation of the others. He learnt that on Saturday
afternoons Mrs. Varcoe came to "scrub up," and that Aunt Elizabeth
took charge of the post office so that her husband might go
gardening.
As soon as ever dinner was over Uncle John said, "Now then, boys!"
and a start was made for the allotment gardens.
The allotment gardens were in a field which sloped right down to the
river. Many of their owners were there on this sunny November
afternoon, tidying their patches of ground against the coming winter.
Several large bonfires were burning finely, and it was not long before
Harold and Billy were busily engaged making a bonfire of their own.
Meanwhile John Dingle was weeding the ground between his winter
greens, pausing now and again to exchange a few words with other
allotment holders.
"There's going to be a change in the weather before long," Billy

overheard him say by-and-by to a man who was passing.
"Aye, aye!" was the answer; "the wind's changing—veering round to

the west."
"Does a west wind bring rain, Uncle John?" Billy inquired.
"Very often. But there are other signs the fine weather's going to
break up. See those long fleecy clouds? Mares' tails we call 'em.
They mean wind—high wind. It wouldn't surprise me if there was a
westerly gale before morning. Where's May?"
May had followed her father and the boys to the allotment field, but
had wandered away from her father's garden. She was now seen
returning with the Vicar—he often came there on Saturday
afternoons, Billy afterwards learnt.
"Oh, she's with Mr. Singleton!" John Dingle exclaimed; "that's all
right! I don't like her to get away to the river by herself for fear she
should fall in. You haven't spoken to our Vicar yet, have you, Billy?
He was in the post office this morning and spoke of you—he noticed
you on Sunday."
"Yes," said Mr. Singleton, who had come up with May and heard the
postmaster's last words; "and I want to make the acquaintance of my
new parishioner."
He shook hands with Billy. Although he was really old his eyes
looked young, the little boy noticed. Those eyes were smiling at him
now in the kindliest, friendliest fashion. "So you've come to live with
your grandfather," he said. "I hope you'll like the country. You're
going in for gardening, I understand! Ah, you wonder how I know
that! A friend of yours told me—Mr. Tom Turpin."
"Oh!" cried Billy, flushing. So the Vicar considered Mr. Tom Turpin his
friend! His heart swelled with happiness at that thought.
"He came to see me to say 'good-bye,'" the Vicar continued;

"dropped in for a few minutes with his father on his way to the
railway-station. He's gone to-day."
"Ah, poor lad!" sighed the postmaster. "I hope God will keep him
safe."
"He will," the Vicar answered; "be sure He will. We know the Lord is
mindful of His own—come life, come death, they're safe."
Come life, come death, they're safe! Those words, spoken by the old
man with child-like faith and conviction, sounded in Billy's ears again
and again during the remainder of the day, bringing joy and
consolation with them. They eased the ache there was always in his
heart when he thought of his mother, the innocent victim of the cruel
war, and he murmured them to himself that night, as he lay in bed in
the darkness, listening to the rising wind which was beginning to
moan and to sob around the house.
The postmaster had been a true prophet. The fine weather had
broken up. The after-glow of summer had gone.
CHAPTER VIII.
GRANDFER'S SECRET.
BILLY started up in bed uttering shriek after shriek, his forehead

damp with perspiration, his limbs a tremble, his heart cold with fear.
What had happened? A terrible noise had wakened him from tranquil
sleep, a noise right overhead it had seemed. He had opened his
eyes to find himself in pitch darkness; but now, all of a sudden, a
great light almost blinded him, and, springing out of bed, he made a
rush across the room for the door. As he reached it, it was opened,
and Mrs. Brown, carrying a lighted candle, caught him by the arm.
"What's the matter, child?" she asked crossly. "Oh, stop that noise!
Do you hear? Stop that noise, you little coward, you!"
Billy obeyed. The room was in darkness again but for the flickering
light of the candle which Mrs. Brown placed on the top of a chest of
drawers.
"Get back to bed!" she commanded, giving the boy a little shake,
then letting him go. "You ought to be ashamed of yourself for
shrieking like that just because there's a thunderstorm."
"A thunderstorm!" faltered Billy. "Oh, was it only thunder I heard? I

thought—oh, that's lightning!" He crept into bed and lay down.
For a moment the room had been illuminated brilliantly. Now a series
of low, crackling reports sounded right overhead.
"What did you think?" asked Mrs. Brown, when her voice could be
heard.
"That—that there was an air raid," the little boy admitted.
"The Germans haven't ventured over Devonshire yet," Mrs. Brown

remarked, "and maybe they never will. But if they came you'd do no
good by shrieking."
"I know," Billy answered. "I couldn't help it, Granny! I couldn't,
indeed! Oh!—" as another flash of lightning lit up the room. "Now we
shall have thunder again!"
He was right. This time, however, it did not sound directly over the
house, but further away. Mrs. Brown sat down on the edge of the
bed and looked at him gravely. She had thrown on a grey flannel
dressing-gown, which she now proceeded to button up.
"I'll stay with you a little while," she said, her voice sounding kinder;
"if I'd known you'd have been so scared I'd have come to you before.
But I thought perhaps you'd sleep on like your grandfather. He's such
a heavy sleeper nothing disturbs him, yet he always wakes up sharp
at six o'clock. It's been a wild night, but the thunder's passing, I
think."
"Yes," agreed Billy. He listened, then went on, "But hark to the rain!
It's coming down in torrents! It must have put out all the bonfires, and
they were burning so beautifully. Oh, Granny, poor Jenny! How
dreadful to think of her out in the orchard."
"Jenny's all right," Mrs. Brown assured him. "Your grandfather put
her in her stable the last thing before he went to bed; she won't sleep
out again this winter, I reckon. Why, you're trembling still, child!"
"But I'm not frightened any longer. I'm not afraid of thunder and
lightning; it was only—that I didn't know—"
"Oh, yes, I understand now," Mrs. Brown broke in; "but I didn't at
first. I'm sorry I didn't."
"Oh, never mind, Granny," Billy murmured. "I oughtn't to have been
afraid; I shouldn't have been if I'd stopped to think—to remember
God was with me and that He'd keep me safe."
"He didn't keep your mother safe!"
The little boy started up in bed.
"Yes, He did!" he cried. "He took her to be with Him for ever and
ever! That's being safe, isn't it?"
Mrs. Brown was silent. She was not religious in the true sense of the
word. She called herself a Christian, of course, but she had never
opened her heart to the Saviour—never known that love which
passeth knowledge. Indeed, she had never felt the need of that love;
but now, as she looked at Billy's glowing face and shining eyes, she
had a feeling that the little boy possessed something of which she
was lacking.
"When I miss her—and, oh! I miss her always, every minute of the
day," he continued, "it makes my heart ache less when I remember
she's safe. Oh, mother!" He caught his breath with a sob.
"You mustn't grieve, child," Mrs. Brown said, with unusual

gentleness; "by your own telling you know that she's better off where
she's gone. I daresay she had a troublous life."
Billy nodded. "But we were very happy," he said, "just mother and
me. Of course we were poor, but Grandfer helped us. He used to
write such nice letters—short, but ever so kind. We used to look
forward to getting his letters, not so much because of the money—"
"What money?" interposed Mrs. Brown with a start.

"The money he used to send us," the little boy explained. "Oh, didn't
you know about it?"
Mrs. Brown hesitated, but only momentarily. Her face was flushed
and her brows were knitted in a frown.
"No," she replied, "I did not. Perhaps your grandfather thought it no
business of mine." She rose as she spoke and took her candle.
"Well, I suppose I can leave you now," she remarked; "you're not
likely to have a shrieking fit again."
"Oh, no, Granny! And thank you for coming to me. I—"
Billy ceased speaking abruptly, for Mrs. Brown had gone, closing the
door behind her. He did not feel at all sleepy, but he closed his eyes
and tried to sleep. He wished he had not spoken of the money his
grandfather had given his mother. He supposed, now, that Grandfer
had not wished Granny to know about it—that that was the reason
why he had always been so anxious not to be thanked. Then would
Granny have been against the money having been sent?
"That must be it!" Billy decided. "Oh, how mean of her! Yes, I do call
it mean! She is mean."
Though he had been so short a time at Rowley Cottage, he had

discovered that Mrs. Brown had but one aim and ambition in life—to
make and save money. Only the day before she had shown temper
because her husband had become a subscriber to some war charity.
"You can't afford it!" she had declared. "We're only working people!
Don't I slave from dawn to dusk over the housework and poultry,
doing without a servant to save money? And you—why, you'd give
the coat off your back, I believe, if anyone asked you for it! What's
going to become of us in our old age if we don't put by now? Oh, we
ought to trust Providence a bit, ought we? What cant! 'Look-out for
yourself' is my motto, and it will take some beating! Don't talk to me!"
William Brown had not done so, but had allowed her to rage on. Billy
was thinking how sad and ashamed he had looked, when he heard
raised voices in the next room. Evidently a quarrel was taking place.
He sat up in bed and listened, then, unable to make out what was
being said, slipped out of bed and opened the door. Only one voice
was speaking now—Granny's, shrill and excited.
"You kept it a secret from me to avoid unpleasantness?" it cried. "A

fine excuse! And now you won't even tell me how much you sent
her! It's too bad—too bad! And I had to admit to the boy you kept me
in the dark! A nice position to have put your wife in! Shame on you,
William Brown!"
"The shame's on you who were always so against the boy's father!—
on you who begrudged the little money I spent on bringing him up
and educating him!" Billy heard his grandfather retort. "You were
never fair to my son—your own daughter knows it!"
Billy shut the door heavily and went back to bed. He had suddenly
remembered that he ought not to be listening. Oh, how he wished he
had not mentioned his grandfather's secret! But he had not known it
was a secret till Mrs. Brown's flushed face and frowning brows had
enlightened him.
The lightning was coming in only occasional flashes now, and the
thunder had nearly stopped. By-and-by the angry voices in the next
room ceased. Still Billy could not sleep. Though no longer frightened
he could not quiet his nerves; he felt them throbbing all over him,
even to his finger-tips. At last came dawn—a wintry dawn, chill and
mournful, and it was time to rise.
The little boy was nearly dressed when Mrs. Brown, looking much as
usual, opened the door and popped her head in.
"Oh, you're getting up!" she said. "Your grandfather's been out this
long while, and'll be in to breakfast soon. Hurry! I want you to feed
the fowls, and—but how white you look! Didn't you sleep again?"
"No," Billy admitted, "I couldn't—I was too unhappy. Oh, Granny, I
heard you and Grandfer quarrelling," and his voice choked. "My
head's dizzy," he faltered; "I feel—"
The room seemed to be swimming about him. He saw everything

through a mist. The mist thickened and closed in around him, and
had not Mrs. Brown rushed into the room and caught him as he
staggered, he would have fallen, unconscious, upon the floor.
CHAPTER IX.
THE BIRD PICTURE BOOK.
FOR several days Billy was ill, so ill that he kept his bed, and the
doctor who attended him insisted he should have a night nurse.
Accordingly Mrs. Varcoe was engaged to fill that position.
"Such an expense!" Billy overheard Mrs. Brown grumbling to her

daughter, who came to Rowley Cottage, greatly concerned, as soon
as she heard of his illness. "The doctor says he's still suffering from
shock to some extent, and his nerves are unstrung. I never
bargained he would be as delicate as this."
"Oh, I expect he'll be all right after a bit," was the hasty response. "I
can understand how the thunderstorm upset him. Of course, you
can't work by day and nurse by night, mother; you've done wisely in
getting Mrs. Varcoe."
At first Billy was rather in awe of Mrs. Varcoe. He felt as though a
giantess had taken possession of him. But he soon discovered that
the giantess, in spite of her big, work-roughened hands, had the
gentlest touch possible, and that her shrewd green eyes often had a
very tender mother-look in them.
She was a silent watcher at his bedside as a rule, but one night,
when Billy was too feverish and restless to sleep, she proved that
she could be a good talker. He questioned her about her sons, and
she told him a great deal that interested him concerning them, and
spoke of a letter she had received after the eldest had been killed.
"It was from his captain," she explained; "just a few words, saying my
boy had been a good soldier and had done his duty. I ought to be a
proud mother, he said. And I am!"
Billy was deeply moved.
"Oh, Mrs. Varcoe, how brave you are!" he exclaimed.
He felt there was a link between him and Mrs. Varcoe, for both of
them had suffered through the war. He began to talk to her of his
mother, and that led to tears. She did not try to stop him, as Granny
would have done, when he began to weep. No! she put her strong
arms around him, and hushed him upon her breast. There, by-and-
by, he fell asleep.
During the days he was in bed Billy was kept very quiet, but directly
he came downstairs again he was allowed to see visitors. The Vicar
was the first who called to see him; then each of the members of the
Dingle family came at different times, delighted that he was about
again. After that little May came every afternoon, and sat beside him
on the settle, talking to him about the animals and birds she noticed
on her daily journey from the village to Rowley Cottage.
"Get well quickly, Billy," she would say, "then I'll take you to the
woods to see the squirrels. Oh, they are the dearest, sweetest
things! You'll love them, you will!"
A wonderfully happy time followed. After the heavy rains a spell of
dry, clear weather set in. Every day now found Billy either in the
garden with his grandfather or roaming about the woods and lanes
with May. He never tired of watching the squirrels springing from tree
to tree, and he soon grew accustomed to the sounds which at first
startled him—the rustle of birds and the scuttle of rabbits in the
undergrowth, the discordant cries of cock-pheasants as they rose
from the ground and took wing, and the mournful hoot of the owls.
Once, on a misty day, he saw an owl quite close. It was white, save
for a few light golden-brown feathers in its wings, and had a round,
solemn, baby face.
Then he learnt to ride Jenny, and to drive her in the market cart, too.
One never-to-be-forgotten day he drove his grandfather nearly to
Exeter. As they neared the city they began to meet other vehicles,
and his grandfather changed seats with him and took the reins. He
was rather glad of this, not as yet being an experienced driver.
The first stop they made when Exeter was reached was before a
large fruit and poultry shop in High Street. Here William Brown
unloaded the contents of his cart—a quantity of winter greens and
potatoes, and two baskets, one containing dead poultry, the other
some golden apples called "Blenheim Oranges," the crop of one of
his best apple-trees which had been gathered carefully before the
gales, and hoarded. Then they drove to various other shops and did
a lot of shopping, for Mrs. Brown had given them a long list of
errands to execute; and, later, their purchases having been stored
away in the market cart, they drove down a narrow side-street into a
yard, where they left Jenny and her load in the care of a stable boy
who seemed to know her and smacked her fat sides familiarly.
"Nov for the market!" said William Brown. He dived his hand into his
trouser-pocket, and the next minute slipped half-a-crown into his
grandson's palm. "A trifle for pocket-money," he explained, with his
good-natured smile.
"Oh, grandfather, thank you, thank you!" cried Billy.

He had never had a half-crown in his life before.
"May I do what I like with it?" he asked eagerly, his eyes sparkling.
"Certainly," agreed his grandfather. "Spend it, or, if you like, you can
open an account with it in the Post Office Savings Bank."
"I think I'd like to spend it, grandfather." The market reached, William
Brown met several acquaintances who claimed his attention. He
suggested that Billy should go and look at the shops and come back
to him, adding that he would be there for an hour at least. Billy
jumped at the suggestion, for he wanted to spend his half-crown. He
thought he would buy himself a pocket-knife. It would be such a
useful thing to have.
He wandered from shop to shop, gazing into the windows. At last he

came to one in which were all sorts of fancy articles.
"I should think they'd sell pocket-knives here," he thought. "I'll ask,
anyway."
There were several customers in the shop when he entered it, so the
little boy had to wait a few minutes before he could be attended to.
He passed the time in looking at some picture books on the counter.
One, in particular, excited his admiration. It contained coloured prints
of all sorts of birds, wild and tame. "How May would like that!" he
thought. "I'll buy it for her!—that is, if it is not too expensive." Turning
to an assistant who had come to him, he inquired: "What is the price
of this picture book, please?"
"Two shillings," was the reply.
"Oh!" exclaimed Billy. "I can't afford that." He had hoped it might not
be more than a shilling. If he bought it he would have only sixpence
left. "What are the prices of your pocket-knives?" he asked.
"We have none less than eighteen-pence," he was told.

He stood undecided, thinking. May knew nothing about the book,
and he wanted a pocket-knife so much. Harold had one, and it was
most useful. But the book would be a great joy to May. Oh, she must
have it!
When he returned to the market to his grandfather the bird picture

book was in his possession.
"Spent all your money?" William Brown inquired, smiling.
Billy shook his head.
"No," he replied. "I've sixpence left that I'm going to save towards
buying a pocket-knife."
He did not tell his grandfather then what he had purchased, but on
the way home, some hours later, he told him.
"It's all pictures of birds," he explained. "I'm sure May'll be pleased

with it."
"Aye, I reckon!" William Brown nodded. He had refused to allow Billy

to drive on the homeward journey, saying that it would be dark very
soon. But Billy was not nervous to-day, as he had been during his
first drive from Exeter. He knew now how sure-footed Jenny was,
and that his grandfather was a careful driver. By-and-by his
grandfather began to talk of the plans his Exeter acquaintances were
making for growing big crops of vegetables and corn next year.
"Every one's as keen as pepper to get as much as possible out of

the land," he said. "We men at home mean to show our fighting men
we can do our bit as well as they can. And may God prosper our
labours! After all's said and done, we can't do anything without Him!
The harvest's in His hands, you know, Billy! Ah! those who work on
the land need to put a deal of faith in th' Almighty."
They had nearly reached home now. A few minutes later Jenny was
picking her way down the cart track at the back of the house, her
master at her head. Then she drew up with a satisfied snort before
the back door. Billy jumped out, and ran into the kitchen, his
purchase under his arm. He had hoped to see May. But she was not
there. Having known he would be absent she had not been near
Rowley Cottage for the day. No one was there but Mrs. Brown.
"Oh, Granny!" cried the little boy, "look here! Grandfer gave me half-
a-crown, and I bought this."
He pulled off the paper from the picture book, which he put into her
hands, never doubting but that she would admire it. She glanced at it
with a darkening face.
"A baby's book!" she exclaimed scornfully. "The idea of a boy your
age wasting money on such a book as this! Your grandfather should
have known better than to let you!"
"I bought it for May," faltered Billy. "It all pictures—pictures of birds.
She loves birds, so I thought she'd be pleased—"
"Oh, it's for May, is it?" Mrs. Brown broke in, with a sudden change of
tone. "That alters the case. She'll be pleased, of course, and—and it
was good of you to remember the poor child, Billy."
She had never spoken to Billy so cordially before.
CHAPTER X.
SPRING.

Catalytic Processes For Water and Wastewater Treatment John Vakros Full Chapter

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Catalytic Processes for Water and

Wastewater Treatment John Vakros

ISBN 978-3-0365-7299-4 (Hbk)

About the Editor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii

Preface to ”Catalytic Processes for Water and Wastewater Treatment” . . . . . . . . . . . . . . . ix

Souraya Goumri-Said and Mohammed Benali Kanoun

Luminita Isac, Cristina Cazan, Luminita Andronic and Alexandru Enesca

Maria Antonopoulou, Maria Papadaki, Ilaeira Rapti and Ioannis Konstantinou

Ilaeira Rapti, Vasiliki Boti, Triantafyllos Albanis and Ioannis Konstantinou

Spyridon Giannakopoulos, John Vakros, Zacharias Frontistis, Ioannis D. Manariotis, Danae

Konstantinos Kouvelis, Adamantia A. Kampioti, Athanasia Petala and Zacharias Frontistis

1 Department of Chemical Engineering, University of Patras, Caratheodory 1, University Campus,

Conflicts of Interest: The author declares no conflict of interest.

Abstract: A multimode, dual functional nanomaterial, CNTs-Ag2 S, comprised of carbon nanotubes

Keywords: CNTs; Ag2 S; cadmium; adsorption; alizarin yellow R

solvent extraction, membrane separation, electrochemical removal, coagulation, and ad-

2. Results and Discussion

200 300 400 500 600 700 800

1000 800 600 400 200 0

280 282 284 286 288 290

Binding energy (eV)

525 528 531 534 537

Catalysts 2023, 13, 476 9 of 23

156 159 162 165 168

ln(qe − qt ) = lnqe − k1 t (1)

where k2 [g/(mg.min)] is the pseudo-second-order rate constant.

Langmuir Isotherm Freundlich Isotherm Temkin Isotherm

Further, to find the stability of CNTs-Ag2 S, it was recovered by centrifugation after

Photocatalyst Source of Irradiation Degradation Rate (%) Ref

3.2. Preparation of CNTs-Ag2 S

3.3. Preparation of Ag2 S

"Still asleep!" she murmured, "still asleep!"

"Asleep?" Billy echoed wonderingly. "Snowdrops don't go asleep,

"Why, it's November, May!" exclaimed Billy, full of amazement. "It

"What made Master Tom give them to you?" asked Harold.

"He never gave me anything," remarked Harold, in a decidedly

"I wouldn't change my tools for Billy's!" he exclaimed.

"Rather!" Harold replied. "Father's got an allotment, and I help him

"Oh, they'll let you," declared Harold.

"Grandfer's so good-natured he generally lets people do as they like;

Harold looked rather ashamed.

"Now you're angry," he said, "and won't come on Saturday, I

"Aunt Elizabeth said I was to look on May and Harold as cousins,"

Accordingly Billy went. He consulted his grandfather as to the time

"The Canadians?" echoed Billy, inquiringly.

"Yes—the Canadian lumbermen. They've been taking down trees in

"Yes," agreed Billy, "I expect I should."

"Her own handwriting," he said proudly; "her own spelling too.

"Nice man!" May exclaimed. "Where's Canada, Harold?"

"Oh, ever so far off," he answered.

"Further away than Exeter?" questioned the little girl.

"Oh, how lovely!" cried May, clasping her hands.

"There's going to be a change in the weather before long," Billy

"Aye, aye!" was the answer; "the wind's changing—veering round to

"Does a west wind bring rain, Uncle John?" Billy inquired.

"He came to see me to say 'good-bye,'" the Vicar continued;

BILLY started up in bed uttering shriek after shriek, his forehead

"A thunderstorm!" faltered Billy. "Oh, was it only thunder I heard? I

"That—that there was an air raid," the little boy admitted.

"The Germans haven't ventured over Devonshire yet," Mrs. Brown

"He didn't keep your mother safe!"

The little boy started up in bed.

"You mustn't grieve, child," Mrs. Brown said, with unusual