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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
St. Alban-Anlage 66
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
indicated below:
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Page Range.
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license CC BY-NC-ND.
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
60
Heat
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
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Provided she held her tongue as to her movements, suspicion was most
unlikely to fall upon her, at any rate for some time, and the danger of her
being sought for as Lady Holt was remote; and, if she were, she would
certainly not be a consenting party to the identification, because of the
consequent inevitable exposure of her bigamous marriage and the rupture
with Sir Ross Buchanan which that exposure would entail.
Melville looked at his companion lying huddled at the bottom of the

boat. Could he rely upon her not betraying him? What line should he take
with her when presently the scene that had to be got over between them
should begin? He could not quite decide; it was difficult to do so until he
saw her face. But for the moment he was glad that she should cower down
as she was doing; it rendered her chance of being recognised so much the
less, and already boat-loads of soaked holiday-makers were passing them.
Melville paused as a favourable opportunity offered, and surreptitiously
dropped his revolver into the river-bed. If—anything—should happen, that
must not be found amongst his possessions, for the bullet it had held would
certainly be kept, and such a coincidence as his possessing a weapon which
it fitted must be prevented. He kept his head down as he sculled and looked
neither to the right nor to the left. To the lock-keeper from whom he had
hired the boat he was a stranger, and all he had to do was to avoid being
recognised himself by any acquaintance who might chance to be in the
crowd that now was nearing the lock simultaneously.
He drew in to the left bank and let the lock fill up. The rain, which had
been savage and relentless while they were on the river, was abating now
they were within easy reach of shelter; the intervals between the peals of
thunder were lengthening, and, most noticeable of all, the terrible
oppression was relieved. Melville hooked the boat on to the stakes below
the lock and backed her gently up the stream until he came to a spot where
they could land easily.
"Sit up, Lavender," he said softly, but peremptorily.
She raised herself on one arm and looked round. Hopelessness stared
from her large eyes, but Melville saw with relief that the insane terror had
departed from them; he was anxious to get her into the train without
exciting remark, and it was something that she had regained her self-
control. That her frock was dripping wet and stained red from the cushions
would not attract attention here where everyone was wet, and before they
reached Waterloo she would not look so deplorable, however cold and
uncomfortable she might feel.
"We won't go through the lock," he said. "I'm going to pay the man for
the boat and say he'll find her here. Pull yourself together as much as you
can before I come back. If we are quick I think we can just catch a train,
and we shall get away before all the people get out of the lock and crowd up
the station. Do you feel better now?"
"Yes," she answered dully.
"I can depend upon you until we get home?" he asked, with some
anxiety.
She nodded a vacant assent, and with that he had to be satisfied. He got
out of the boat and went to the lock to pay for its hire and tell the man
where to find it. Meantime, Lavender, realising that whatever the future
might have in store for her, no good could be done by a scene at St. Martin's
Lock, made an effort to pull herself together, and tried to readjust her
bedraggled costume. With one of the napkins from the hamper she dried her
face and hands, and wringing some of the water from her skirts and rubbing
her patent shoes, she succeeded in making herself a little more presentable.
Melville was pleased. They hurried to the station and were fortunate enough
to catch an up train and secure an empty carriage.
But as soon as the train moved away his manner changed. Even if they
were left alone during the whole journey they only had fifty-five minutes in
which to arrive at an understanding, for he was quite clear he could not go
back with her to The Vale. He took the corner seat immediately opposite to
her.
"Why did you leave the boat at Fairbridge?"
The question sprang sharply from his lips, insisting on an immediate

reply.
"The storm was so awful—so appalling," she said faintly. "It was like
the end of the world."
It was obvious to Melville that she was frightened of him, and he was
content that it should be so, for only by terrorising her could he hope to
maintain his ascendency over her; any woman might be nervous at being
shut up in a railway carriage with a murderer, but it was not of that
precisely that she was afraid, for she stood in no fear of violence at his
hands. There was something despotic about him that compelled obedience,
and even if she had not been naturally as truthful as she was she would not
have attempted to prevaricate.
"Now tell me," Melville rapped out in the same peremptory way, "did
you hear what we were saying in that room?"
"Some of it," she replied; "enough, at any rate, to know what you have
been doing to get money."
"You don't know what my position was," Melville said. "You remember
my leaving Monte Carlo—ruined?" Lavender nodded. "I went down to see
my uncle a few days after I got home and he refused to help me. I don't
know why. He had always been lavish to my brother, and had never refused
me anything before. I was in absolute need of shillings, and had to get them
somehow. After I heard of your marriage with him, I told him I knew and
got something from him."
"But you got it on the ground that I was in need of it," she said
indignantly.
"It was the only way I could get it at all," he retorted.
"It was an outrage," she said, with suppressed passion. "I resent that as
much as anything else. After all the years I never touched a penny of his
money for you to tell him I was starving and pocket the money for yourself
is a thing you can't expect me not to be mad about."
Her eyes blazed from her white face, and Melville grew apprehensive.
"What do you think Sir Geoffrey's answer was?" he asked.
"What?"
"He gave me ten pounds as an act of charity, and said if you needed any
more you could apply to the people you'd been living with all those years.
So you see, if you had been starving, you need not have looked for much
help from him."
A flush shot over her neck and cheeks and ebbed again.
"It only makes it worse that your villainy provoked such a message—
such a gratuitous affront. Oh, what an incredible fool I have been! But I am
beginning to see you in your true colours now."
Melville looked at her, shading his eyes with his hand; it might not be
so easy to silence her after all.
"What are you going to do?"
"How can I say?" she protested. "I must have time. I can't even think
yet."
"You must think," he retorted curtly. "You must make up your mind
between this and Waterloo, and stick to it afterwards."
"I can't," she repeated. "What's more, I won't try." Her thoughts flashed
back from themselves to the dead man. "Why did you do it?" she sobbed.
"Why, in the name of heaven, did you do it?"
For just one moment a pang of remorse stabbed Melville's heart.
"Only the devil knows," he groaned; but the train was travelling rapidly,
and this was no time for vain reflection. "You must assure me, Lavender. I
must know that I can have confidence in you. After all, we're in this thing
together."
A look of fear came into her face, to be noted instantly by him.

"What have I to do with it?" she said defiantly.
"Nothing," he answered swiftly. "I want your oath that you know
nothing of it."
She threw out her hands with a pathetic gesture.
"I can't give it. I'm not sure of myself. I can't live and be sure of not
betraying it. I shall never sleep—never know peace again."
"I want your oath," Melville said doggedly. "After all, you stand to gain
more by Sir Geoffrey's death than I do."
"What do you mean?" she asked, surprised.
"You are free to marry Sir Ross."
She looked at him, not quite grasping the purport of his words, but even
as he said them they gave him confidence. If she was recalcitrant, he might
threaten her.
"Except yourself, no one can ever throw light upon Sir Geoffrey's death.
You must swear that you will throw none on it."
She did not answer, but sat like a statue of despair, as white as marble
and as motionless. Already they were drawing near to Clapham Junction;
ten or twelve minutes were all that were left for him to get the oath he must
obtain.
"Think," he said swiftly. "Think what it might mean if a living soul

knew that you were at that boathouse to-day. You—Sir Geoffrey's wife—
living on money derived from a man whom you had feloniously married,
engaged to be married again to a man who is twice a millionaire! What
would be said? That you had everything to gain by the death of Sir Geoffrey
Holt, supposing your identity became known, as it must be then: that you
could hope for no help or forgiveness from him, and that as the wife of Sir
Ross you would be rich beyond the dreams of avarice—and safe. They
would find there motive enough for the crime, and would say that your
hand fired the shot. And if you told the truth, and swore I did it, why should
they believe you? Why should I, who have lived all my life upon Sir
Geoffrey's bounty, kill the man upon whom I actually depend for my daily
bread?"
Lavender stared at him with increasing horror. Could he possibly intend

to shift suspicion on to her, or was he only putting into words what would
be the general opinion if her presence at Fairbridge that afternoon became
known? Melville read the doubt in her mind, and, with his fiendish
cleverness, allayed her first uncertainty. To let that rankle might be to goad
her too far, but he must appeal to her self-interest too.
"If it got to that, of course that would be the end of me," he said, "for I
should have to confess that the deed was only mine, and I could not be
taken alive. But think what you stand to lose: the income you have, the
fortune you may have, your name, your reputation, possibly your freedom.
You would be so involved in a scandal of bigamy and murder that in self-
defence you would have to disappear. Lavender, it isn't only for my sake
that I'm putting it all like this; I'm not asking you to do anything. I'm only
imploring you for both our sakes to do nothing. Will you give me your
solemn promise to hold your tongue for ever about to-day's work? Will you
swear not to say one word of where we have been, or anything else, to any
living soul? Will you, Lavender—will you?"
In sheer despair she retired from the unequal contest.
"I promise," she said. "I will be silent."
Melville could not repress a sigh of relief. It never occurred to him to

doubt her reliability. She would keep her promise, he knew, and he would
be safe. But there was no opportunity for further converse. They were at
Vauxhall, and the man who collected their tickets got into the compartment
and travelled with them to Waterloo.
At the terminus Melville put Lavender into a hansom.
"Don't write to me or call," he said. "I must go home at once, and I shall
probably have to go down again to Fairbridge. They are sure to send for me.
I will write to you as soon as I can and fix up an appointment."
She looked at him in wonder. He had courage of its kind, and courage of
any kind appeals to women.
"You need not be afraid," she murmured. "I will keep my promise," and
as he told the cabman where to go, she leaned back and closed her eyes in
utter exhaustion.
Left by himself, Melville, too, could have collapsed; there was a

physical reaction that left all his joints weak, and he shivered with cold. But
danger was not over yet; much would depend upon his getting into his
rooms unnoticed. So he hailed another hansom and drove to Piccadilly
Circus.
"What sort of storm have you had here?" he asked, as he paid the
cabman.
"Bad, sir; very heavy about four o'clock."
"Ah, well," Melville said, "it's good for your business, I daresay."
He walked round the corner into Jermyn Street erect and steady,
although he felt so excited. How would things work out? The street was
almost empty, for London was dressing for dinner, and the commissionaire
was not standing by the front door of the chambers. A swift glance into the
office showed Melville that that was empty too, and rapidly he walked
along the thickly-carpeted passage. Opposite the lift he paused to scan the
names upon the letters stuck in the letter rack, and his heart leaped as he
caught sight of the orange envelope of a telegram addressed to himself. So
it had come! He put out his hand involuntarily to take it, but checked the
impulse and silently ran up the staircase and gained his rooms. Once there
he tore off all his clothes and hung them in a wardrobe, which he locked.
He changed his linen, dried and brushed his hair, and then, putting on a pair
of flannel trousers and a smoking jacket, rang the bell and lay down on the
sofa, a cigarette in his mouth, a paper in his hand.
After an interval the bell was answered by the manager.

"Where's Jervis to-day, then?" Melville asked pleasantly.
"Went off duty, sir, at twelve. He'll be back at eight. Can I do anything
for you?"
"I wanted some tea," said Melville. "I'm ashamed to say I've been
asleep."
"I'll bring it to you," the manager said.
"Thanks," Melville answered. "You might see if there are any letters for
me," and he rose and stretched himself.
Tea arrived, and on the tray there lay a couple of letters and the
telegram. Melville tore it open, and an exclamation of surprise and horror
broke from him.
"When did this come?" he asked. "Half an hour ago! Oh, why wasn't it
brought up to me at once?"
"I'm very sorry," the manager said, "but I really didn't know you were
in."
"I've been in all the afternoon," said Melville. "Who would go out in
such a storm if they could help it? But, in any case, I think someone should
bring up telegrams to see if I am at home. It's awful—awful!"
"Bad news, sir?" asked the manager.
"Awful," said Melville again. "Sir Geoffrey Holt is dead. I must go

down at once."
CHAPTER XVI.
AN UNEXPECTED WILL.
That Sir Geoffrey's violent end should have an almost paralysing effect
upon the household that loved him so much was, of course, only to be
expected, but it is impossible to tell beforehand how great grief will
manifest itself in different people. Thus Ralph, who enjoyed a reputation of
being bright and frank and open-hearted beyond the common, became
morose and even sullen, nursing his wrath against the unknown murderer
and allowing the iron to enter into his soul. Melville, on the contrary,
hitherto self-centred and indifferent to the happiness of others, seemed to be
softened by the tragedy, and in many little ways displayed an eagerness to
comfort the rest and a regard for their sorrow that was very winning. The
inquest which was held two days after the outrage was ineffective: a verdict
of wilful murder was returned against some person unknown, and the case
was recommended by the coroner to the attention of the police. So far they
preserved a sphinx-like silence, and although conjecture was rife in the
neighbourhood it received no assistance or corroboration from the
detectives engaged.
The evidence given at the inquest was little more than formal; the
doctor's testimony was brevity itself, Ralph's was concise to the point of
curtness, and the police inspector had no suggestions to offer; the facts were
self-evident, and of the only details that seemed to promise any interest,
namely, the bloodstains upon Ralph's jacket and in the water in the basin,
his explanation was so obviously simple that comment was superfluous. Yet
upon the people in the court Ralph's manner had an effect not wholly
favourable. He appeared to resent their natural curiosity, was brusque, and
even in bowing to the coroner, when that functionary gave expression to the
sympathy felt by his court for Sir Geoffrey's relatives, did not err upon the
side of graciousness. But if Ralph thus failed to maintain the family
traditions of courtesy, Melville atoned for it. He was merely asked whether
he could throw any light upon the crime by suggesting any motive which
might have prompted it, and this, it is needless to say, he could not do. But
his quiet dignity in this moment of sorrow and his air of engaging candour
won all hearts, and he quitted the scene in full possession of the sympathy
of the audience.
There followed two most miserable days, during which Ralph smoked
in solitude upon his houseboat, and Melville, for the most part, idled at The
Grange. Music fits every mood, and there was no disrespect to the uncle by
the nephew turning to his Amati for comfort in this dark hour, and so he
played—played as if inspired by Saint Cecilia—and stole a little further into
Gwendolen's heart.
It was with a sense of genuine relief that the two brothers returned to the
Manor House after the funeral. There was a certain restraint between them
and an odd embarrassment as to their mutual attitude in the small matters of
daily life; thus Sir Geoffrey's chair at the head of the table was left empty
by consent, but it stood as a constant reminder that for one of them it
symbolised possession, and now that its late tenant was laid to rest with his
fathers, the question as to which of the two should sit in it by right was
about to be decided.
With the closing of the inquest Melville's first fears of detection were
allayed, and his mind was engaged almost exclusively with the problem of
his future. He took it for granted that his uncle had died intestate, and the
only complication he could foresee in the division of the estate was brought
about by the existence of Lavender, of which he believed he was the only
person who knew. Mr. Tracy might know, and if he did, Melville supposed
that half the estate would be held, pending Lady Holt's instructions, and that
the other half would be divided between his brother and himself without
undue delay. What action he should take with regard to Lavender it was too
early to decide, but in a vague way he was beginning to incline to the policy
of persuading her never to come forward, which he was confident he could
do, and, by-and-bye, her share, too, might be obtainable for himself, or, at
any rate, half of it.
The brothers were standing in the hall, both feeling rather aimless and
self-conscious, when Martin joined them.
"Mr. Tracy mentioned that he had to return to London soon after the
funeral, so I have taken some luncheon into the library. I thought, perhaps,
you would have business to do before he left."
The butler directed his remarks diplomatically between the two young
men. He assumed that the Manor House would be left to Ralph, as being the
elder, but he did not wish to make any invidious distinctions between them
at present. They looked at each other and went into the library, where they
found Mr. Tracy contemplating a substantial pie as if wondering what
description of animal food it might contain. The old lawyer looked up at
them with a smile, and settled all difficulties of precedence by sitting down
in the nearest chair, which happened to be at the head of the table. He knew
the utility of a meal as a preparation for an unpleasant discussion, and
although as Sir Geoffrey's solicitor he was only the mouthpiece by which
the dead man's disposition of his property was to be communicated, he felt
uncomfortable.
"I'm not ashamed to say that I am particularly hungry," he remarked.

"With your permission, I will discuss this pie before discussing business,"
and he proceeded to make an excellent luncheon, talking all the while of
everything except that which was uppermost in all their minds.
But, luncheon disposed of, his manner changed.
"I have had two copies of Sir Geoffrey's will prepared," he said, "and
perhaps you would like to look at them while I read the original. It is not a
long document, but the technical phraseology may, perhaps, seem confusing
to the lay mind."
He turned to a table in the window, where he had placed a bag

containing his papers, and so did not observe the slight start of surprise
which Melville could not repress. So there was a will after all! Was fortune
about to play him a scurvy trick after he had dared so much? He lighted a
cigarette and sat down in a chair where the light would not fall upon his
face.
"In its main features," continued Mr. Tracy, who seemed to be taking an
unconscionable time fumbling in his bag, "the will, as I have said, is
sufficiently simple, but it contains at least one element of surprise. I will
read it without further comment, and you can follow from the copies," and,
giving a type-written copy of the will to Ralph and another to Melville, he
read the original clearly and distinctly.
Beginning with legacies to the servants, ranging from a year's wages to
the youngest maid to life provision for Martin Somers, the will ordained
that a charge should be made upon the estate sufficient to give an annuity of
four hundred pounds a year to the testator's widow, Dame Lavinia Holt, to
be paid quarterly to her in person, on application at Mr. Tracy's office, the
first instalment to be paid upon her first making such personal application,
and not necessarily to accrue from the date of her husband's death; subject
only to these legacies and this one charge, everything real and personal was
bequeathed to "my dear nephew, Ralph Ashley," for his uncontrolled use
and enjoyment. Of Melville's name no mention whatever was made.
Mr. Tracy folded up the document and waited. The silence grew painful.
Ralph did not know what to say, and Melville could not trust himself to
speak. He was white with mortification and rage, and could have cursed
himself for having with his own hand destroyed his last chance for the
future. He cleared his throat and tried to speak, but the words would not
come. Ralph looked enquiringly at the solicitor.
"I suppose there can be no mistake," he said; "but this lady—who is

she? I have never heard until this minute that my uncle ever married."
"I can throw no light upon the mystery," Mr. Tracy said. "Sir Geoffrey
was not the man to give confidences. He drafted this will himself, less than
a month ago, and all I have done is to engross it and procure his signature. I
should like to say that I ventured to ask certain questions and even make
certain suggestions, but they were received with unmistakable disapproval,
and, of course, I could not pursue the matter."
"It is iniquitous," said Melville hoarsely. He rose abruptly from his chair
and faced his brother. "This is your work, you scoundrel! For years you
have left nothing undone to estrange Sir Geoffrey from me. You have
schemed and plotted for this, and at the last minute, curse you, you have
succeeded. Well, you may be hugging yourself now, but I swear you will
live to be sorry."
Mr. Tracy tried to pacify him, but in his heart he was not a little sorry
for him. It must be a terrible shock to find himself thus ignored by the uncle
from whom, for all the lawyer knew to the contrary, he had every right to
expect munificent provision. And the lawyer spoke the truth when he said
he had ventured to plead Melville's cause with Sir Geoffrey, although he
reduced to the lowest possible terms the substance of the old man's answer
to his pleading; yet even at that interview, when Sir Geoffrey might
reasonably have been expected to confide entirely in the lawyer engaged to
give legal effect to his last testament, he had refrained; his native pride
forbade him to dilate upon his story, and kindly, but quite firmly, he
declared his intention not to swerve from the course which he had chosen.
Now that the thing was done, however, Mr. Tracy preferred that the possible
quarrel between the two young men should be deferred until after his own
departure, so he reverted to the matter immediately in hand.
"Subject to your approval," he said, addressing Ralph, whom alone it

was now necessary to consult, "I will take steps to ascertain Lady Holt's
address. Sir Geoffrey told me he knew she was alive, but did not know
where she was to be found. I rather inferred that she was in London, and in
poor circumstances."
"Act as you think right," said Ralph. He was so surprised by the

revelation that he was impatient to learn the whole story. "Make all possible
enquiries, and if they fail, why not advertise a reward for information about
her? Why should Sir Geoffrey's wife be in poor circumstances at all?"
"Perhaps she was misrepresented to her husband," Melville said bitterly.
"Well, I will see about it," said Mr. Tracy, "and let you know the result.
Now I must really hurry away. I ventured to ask the butler to order a
conveyance to take me up to the station. Good-bye, Mr. Melville. I quite
understand your very natural disappointment, and I do not hesitate to say I
am sorry about it. If I can be of any service to you at any time do not
hesitate to command me."
Ralph walked to the door with Mr. Tracy.
"I'm all at sixes and sevens for the minute," he said, "but I should like to
see you again soon. Uncle Geoffrey may have left Melville nothing, but he
has made no conditions in leaving me so much. You can, doubtless, advise
me what would be the best thing to do about my brother."
"I shall be particularly glad to do so," the old lawyer replied heartily.
"Give me time to confirm any appointment, as I am very busy just now, but,
within reason, I can come here or see you in the Fields at any time."
"I suppose I'm in for a quarrel with Melville," Ralph continued

seriously, "so I should just like to add this. He's not likely to agree to accept
anything from me, but if he turns up later on to consult you, can't you let
him have a hundred or so without saying too precisely where it comes
from? You can make it right with me afterwards."
"Of course I can," said Mr. Tracy. "Very delicate of you, I'm sure. I shall
be delighted to take part in so amiable a conspiracy," and, shaking the new
master of the Manor House warmly by the hand, he got into the carriage
and drove away.
Ralph watched the carriage disappear, and turned back into the house
with a sigh. How was he to deal with his brother in this moment of
humiliation, which Melville would with difficulty be persuaded was not due
to him? Although they were brothers and so nearly of an age, the difference
in their temperaments was such that Ralph felt certain beforehand that he
could not hope to appeal successfully to the better part of Melville's
character, which surely must exist. If Sir Geoffrey, with all the authority of
age and wealth, could not control his younger nephew, how could Ralph
hope to succeed? He lingered in the hall, reluctant to open what would be a
painful interview, and as he looked at the familiar things, with their
evidence of wealth and cultured taste, and realised that they were all his, he
became conscious for the first time of the duties and responsibilities which
he had inherited with his rights and privileges. There was no mental
reservation in the inarticulate expression of regret at his uncle's death that
escaped him. Even if it had come in the ordinary course of nature, he would
fain have postponed the day, and lived content and happy with the dear old
man, as he had done for so many years; but for the end to come so
tragically, so treacherously, increased the bitterness a thousandfold, and
Ralph's first emotion as he looked upon his goodly heritage was one of
unmitigated grief at having thus entered upon his own.
But after a little while he raised his head with a new expression of peace
and high purpose on his face. He would strive to be as good a master of the
fine old Manor as Sir Geoffrey had ever been, and the moment to begin his
duties had arrived. He must offer the hand of brotherhood to Melville, and
enlist his help in tracking their uncle's murderer to his doom. More
hopefully he went slowly from the hall to join his brother in the library; but
as he opened the door a feeling of chill disappointment stole over him, for
Melville, too, had shirked the interview and the room was empty. As Ralph
turned to the window with a sigh he saw his brother, looking tall and slight
in his sombre mourning, moving slowly over the sunlit turf and making
evidently in the direction of The Grange.
CHAPTER XVII.
AN ARREST.
It was the fact that Melville shirked a conversation with his brother
immediately after the reading of the will; the mental strain had been so
great that he could not be sure of his temper or judgment, and that being so,
common prudence dictated a delay which would enable him to consider the
new situation in all its bearings before risking a final rupture with the new
lord of the Manor. He sought a temporary refuge at The Grange, where he
knew he would receive commiseration upon his terrible disappointment,
and where he might derive some sardonic satisfaction from the knowledge
that his presence by Gwendolen's side would involve Ralph's absence from
the same desirable spot. Mrs. Austen was quite frank in her condemnation
of Sir Geoffrey's action.
"Whatever Melville may or may not have done, it is unfair to allow a

young fellow to grow up without any profession or occupation, in the belief
that he will inherit a considerable fortune, and then to ignore his existence
in this way."
Gwendolen agreed with the abstract proposition, but could not believe
that Sir Geoffrey would have taken such drastic measures without good
reason; she hinted as much, but her mother would have none of it.
"I dare say Sir Geoffrey had plenty to put up with from Melville," she
said, "but that is the penalty of having children, whether they are your own
or adopted by you. What makes this will so inexplicable is that it was made
such a little while ago, for just lately Melville seemed to be on better terms
with his uncle than he had been for years. I'm sure there is some mischief-
maker at the bottom of it all, and if it had not been for this terrible murder
Sir Geoffrey would have got at the rights of the story, whatever it was, and
made a new will."
"Melville is fortunate in having such a brother as Ralph," said

Gwendolen; "it isn't as if the money were left to strangers. I don't suppose
there will be any difference really."
"What nonsense!" said Mrs. Austen testily. "Ralph is a very charming

young man, and I'm delighted you're going to be his wife, but I have a very
warm place in my heart for Melville, and I think it's quite possible he has
been misjudged; and your most excellent Ralph goes about with the
cheerful expression of a professional mute whenever Melville comes down.
Lately, for instance, since Melville has been here so frequently we haven't
seen half so much of Ralph."
Gwendolen sighed. She had not failed to observe the fact, but she could
throw no light upon the reason of it. Ralph resembled Sir Geoffrey in being
very taciturn where his private feelings were concerned; she remembered
the day when Sir Geoffrey said he had a bone to pick with Ralph. The
discussion ended satisfactorily, but she connected the slight trouble in some
way with Melville, who, as she afterwards learned, had seen his uncle the
previous night, and Ralph's championship of his brother's cause had been
discontinued from that time; since then, indeed, he never talked about him.
It was all very puzzling and sad.
In the meantime, Melville forsook the neighbourhood. He accepted Mrs.

Austen's hospitality for a couple of nights, and then, frankly confessing that
the proximity of the Manor House with its associations was intolerable to
him in his present frame of mind, returned to London, outwardly calm
enough, but inwardly consumed by a raging fire of evil passions. As he
paced his chambers, secure from prying eyes, hate and fear, chagrin and lust
for revenge swept across his pallid face, and sometimes, as he caught sight
of his reflection in the mirror, he thought the whole world must be able to
read his secret in the careworn lines, which in reality it ascribed to laudable
grief and natural disappointment. It is a kind-hearted place, this same world
of ours, provided its patience and generosity are not unduly taxed, and just
now it laid itself out to make things easier for Melville. He accepted the
proffered sympathy gratefully, and won a new sort of popularity by his
quiet pluck and his gentle air of resignation. Old people thought he was
chastened by his trouble; young ones thought he was to be pitied; and
Melville made the most of this occasion to make new friends among the
children of this world.
But he did not forget his vow that Ralph should live to be sorry for
having contributed, however indirectly, to his disinheritance, and wherever
he went he sowed scandal with both hands. It is an invisible seed, of which
the fruit is more deadly than the upas tree, and in sowing it as he did it is
possible that Melville himself had no idea of what the harvest would be.
Society knew little of Sir Geoffrey, who lived a comparatively retired life in
his fine old Surrey home, but the mystery attaching to the unknown Lady
Holt tickled its palate, and the murder of a man who was one of its order
was not lightly to be forgotten. Thus at many a dinner party, where the
subject was delicately broached, and at many a little luncheon in the clubs,
where the conversation veered upon the question of undetected criminals,
remarks were made—no one could afterwards precisely say by whom—
which went to direct the general suspicion towards one point.
"What is the good of all this parrot-talk about motives," he said on one
occasion. "When once you set to work imputing motives you need never
stop. Anybody can tell you that half the murders in the world are due to
drink or jealousy. Neither comes into this case. And England isn't like Sicily
or Corsica, where vendetta is an institution. Sir Geoffrey could not have had
an enemy in the world, so you may rule out revenge as well."
"How about the lady?" someone suggested, but Melville disposed of the
idea.
"She can't have got her knife into him, or she would not have lain so
low all these years. Besides, it looks as if Sir Geoffrey believed her to be
dead, for he made some funny arrangements about her annuity. Anyhow, all
that is pretty certain to come to light, for I believe there is a big reward
offered to anyone who will produce her. No; I don't see much use in fooling
after motives."
That was as far as he allowed himself to go then, but elsewhere, and to

another audience, he took a different line and seemed interested in hearing
the general opinion on this same subject of motives. He sat silent until the
end of the conversation, when he appeared disinclined to endorse the
verdict of the rest.
"It's too jolly dangerous," he said gravely, "to go about suggesting

people who might commit a crime, and then inventing reasons why they
should do it. It's very easy to vary the amusement, until you begin to believe
you have found the motive and the man by a process of exhaustion. Why,
Sir Geoffrey once told me he had made no will; is there sufficient motive
there for me to kill him so that I might benefit under an intestacy? On the
other hand, my brother knew he had made one, though I don't suppose he
knew its tenour. Is there sufficient motive there for him to kill the old man
on the chance of coming in? The thing is absurd on the face of it. We were
both dependent on him, and I venture to say that no two fellows were ever
fonder of their father than we were of our uncle."
It was not often he was as precise as that. For the most part he contented
himself with the vaguest remarks, all harmless individually, but totalling up
to an incredible strength when put together by skilful brains; and skilful
brains were doing it, brains owned by men who, in spite of all detractors,
are marvellously shrewd, and who do not often have to confess themselves
beaten in the end, although they may sometimes take a long time upon the
journey, and even make errors by the way. Whose business it was to gather
these rumours and carry them to the detectives engaged upon the case, it
matters not to enquire; popular opinion is no evidence, but it is often useful
as indicating where evidence may be found, and, Melville's expressed
opinion notwithstanding, all lawyers attach importance to motive in arguing
for or against the criminality of individuals. At any rate, they agreed in the
advisability of making an arrest upon suspicion, and their selection of the
individual was partly influenced by some of these random and irresponsible
remarks.
The Manor House was looking its best in the mellow light of an ideal
summer evening. It had been one of those days when it is impossible not to
feel delight in life, and Ralph awoke to full consciousness of the fact that he
had youth and love and wealth to comfort himself withal. He spent the
morning at The Grange, and after luncheon punted Gwendolen up the river,
arranging for Mrs. Austen to join them at the Manor House. There was no
flaw in his happiness that day, and, perhaps because of the violent contrast
between its morning and its night, it always stood out afterwards with
particular distinctness in his memory. Returning from Longbridge, he put
on his evening clothes and went to The Grange to fetch Gwendolen and her
mother; they strolled leisurely down to the Manor House and lingered over
dinner, discussing idly many little plans for alterations to be made in the old
place for the fuller satisfaction of its new mistress.
Martin hovered about them, anticipating their every want, and when at
last they left the dining-room they resumed the discontinued custom, and
decided to have their coffee brought to them on the houseboat. It seemed to
mark the closing of a tragedy and the resumption of the pleasant routine of
their country life.
And as on that evening—which now seemed so long ago—when the last

of the guests, summoned to congratulate them on their betrothal, had
departed, and Sir Geoffrey and Mrs. Austen joined Ralph and Gwendolen,
so now the sound of music was borne to them from other houseboats on the
river, so now a stray punt was poled swiftly down the stream, and the swans
floated out from their nooks under the willows and rocked gracefully in its
wake. Everything goes on just the same, although the best and greatest of us
die.
Mrs. Austen was dozing comfortably in her chair, and Ralph sat close to
Gwendolen, smoking in perfect content. Both were seeing visions of the
future, a future of unbroken peace and happiness spent in each other's
company, and the interruption of their waking dream by the sound of
footsteps coming on board was not unwelcome, as it only suggested another
little touch in the picture of material prosperity of which they themselves
furnished the human interest.
Martin deposited his tray in the kitchen in the tender, and came up to
Ralph.
"May I speak to you for a moment, sir?" he said almost in a whisper.
Ralph looked up surprised.
"What is it, Martin? Anything the matter?"
"I should like to speak to you alone, sir, if I may."
Martin followed him to the top of the ladder.
"A gentleman has come—in connection with the murder," he said, an

odd look of embarrassment upon his face, "and he says he must see you at
once; he won't be denied."
"Of course I must see him at once," said Ralph. "Why should he be
denied?"
The look on Martin's face was pitiful.
"I can't tell you what I mean, Mr. Ralph," he said, "but I'm sure there is
some hideous mistake. I think—I think he thinks you know something
about it."
Ralph stared at the old servant in blank astonishment, utterly failing to

comprehend his meaning.
"Where is the gentleman?" he said, but the question was answered for
Martin. A tall figure was standing at the foot of the stairway, and bowed to
Ralph as he reached the bottom step.
"Mr. Ralph Ashley?"

Catalytic Processes For Water and Wastewater Treatment John Vakros 2 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

Melville looked at his companion lying huddled at the bottom of the

"Sit up, Lavender," he said softly, but peremptorily.

"Yes," she answered dully.

"Why did you leave the boat at Fairbridge?"

The question sprang sharply from his lips, insisting on an immediate

"It was the only way I could get it at all," he retorted.

"What are you going to do?"

For just one moment a pang of remorse stabbed Melville's heart.

A look of fear came into her face, to be noted instantly by him.

She threw out her hands with a pathetic gesture.

"What do you mean?" she asked, surprised.

"You are free to marry Sir Ross."

"Think," he said swiftly. "Think what it might mean if a living soul

Lavender stared at him with increasing horror. Could he possibly intend

In sheer despair she retired from the unequal contest.

"I promise," she said. "I will be silent."

Melville could not repress a sigh of relief. It never occurred to him to

At the terminus Melville put Lavender into a hansom.

Left by himself, Melville, too, could have collapsed; there was a

"Bad, sir; very heavy about four o'clock."

After an interval the bell was answered by the manager.

"I'll bring it to you," the manager said.

"Bad news, sir?" asked the manager.

"Awful," said Melville again. "Sir Geoffrey Holt is dead. I must go

"I'm not ashamed to say that I am particularly hungry," he remarked.

But, luncheon disposed of, his manner changed.

He turned to a table in the window, where he had placed a bag

"I suppose there can be no mistake," he said; "but this lady—who is

"Subject to your approval," he said, addressing Ralph, whom alone it

"Act as you think right," said Ralph. He was so surprised by the

"Perhaps she was misrepresented to her husband," Melville said bitterly.

Ralph walked to the door with Mr. Tracy.

"I suppose I'm in for a quarrel with Melville," Ralph continued

"Whatever Melville may or may not have done, it is unfair to allow a

"Melville is fortunate in having such a brother as Ralph," said

"What nonsense!" said Mrs. Austen testily. "Ralph is a very charming