Home Novel in situ synthesis of quaternary core–shell metallic sulfide nanocomposites for degradation of organic dyes and hydrogen production
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Novel in situ synthesis of quaternary core–shell metallic sulfide nanocomposites for degradation of organic dyes and hydrogen production

  • Yousaf Khan EMAIL logo , Uzma Sharafat , Saima Gul , M. I. Khan EMAIL logo , Muhammad Ismail EMAIL logo , Murad Ali Khan , Rafia Younus and Sher Bahadar Khan
Published/Copyright: May 8, 2023
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Green Processing and Synthesis
From the journal Green Processing and Synthesis Volume 12 Issue 1

Abstract

Environmental remediation of toxic organic pollutants on catalytic degradation has gained much attention. Organic dyes and fossil fuels as pollutants are the two major problems nowadays. The efficient and targeted eradication of organic dye from water systems is a critical global concern for the treatment of both drinking water and wastewater. In this study, ZnO–ZnS–CdO–CdS quaternary core–shell nanocomposites (NCs) were synthesized using Ricinus communis as a stabilizing agent and hydrazine hydrate as a reducing agent. UV-visible spectroscopy and photoluminescence confirmed the formation of NCs. Fourier transform infrared spectroscopy confirmed the presence of functional groups, while scanning electron microscopy analysis revealed that the morphology of nanomaterials was spherical and poly distributed. X-ray powder diffraction confirmed the crystalline nature of prepared samples. The prepared nanocatalysts were used in the production of hydrogen gas from green sources of the Brassica campestris leaf extract and the degradation of Congo red and methyl red dyes. Overall, the photocatalytic performance of NCs and their design was successful. The prepared catalysts were not only active in the degradation of a single substrate but also in the degradation of a mixture of dyes.

Keywords: precipitation method; green synthesis; organic pollutants; hydrogen gas; Brassica campestris

1 Introduction

Environmental pollution, particularly water pollution, is increasing with each passing day as a result of massive industrial growth. Textile dyes, pharmaceutical metabolites, and discrete organic solvents make up the majority of industrial waste [1]. Large numbers of industrial effluents are poisonous, non-biodegradable, and harmful to living things. The accumulation of these contaminants in wastewater, particularly organic dyes, can cause both acute and chronic health problems [2,3].

Organic dyes are commonly used in the textile, printing, cosmetic, painting, baking, and plastic industries, as well as in acid–base titration and biological research as indicators and tracers [4]. During the coloring process, the textile and paint industries discharge a large number of organic dyes into wastewater [5]. Among the different dyes used in various industries, azo dyes are regarded to be the largest group of synthetic organic dyes. Because of the azo groups, azo dyes are exceptionally stable [6,7]. More than 2,000 different azo dyes in various natures and forms are in use, with about 1 million tons of planned global azo dye production per year [8,9]. During the painting and synthesizing process, 10–15% of dyes were nearly released into the wastewater. This wastewater containing colors raises concerns about public health and also disrupts aquatic life by lowering gas solubility and light penetration, thereby impacting phytoplankton photosynthetic activities [8,9]. At present, dyes are produced and used widely in many different industries, including printing, garments, paper and pulp, etc. However, large amounts of dyestuffs are discharged into aqueous habitats, endangering both human health and aquatic life [10]. As a result, wastewater containing industrial dyes must be cleaned using modern procedures before being discharged into the aquatic environment. Metallic nanoparticles (NPs) and nanocomposites (NCs) have been used as excellent photo-catalysts for the removal of organic dyes due to their distinctive localized surface plasmon resonance, increased surface area, and OH− generation. As a result, it is necessary to eliminate or convert these toxic contaminants into non-poisonous forms [11]. Adsorption, coagulation–flocculation, reverse osmosis, and oxidation are common wastewater treatment methods used, which are less effective for this purpose. Such processes turn dissolved pollutants into solid trash, which can then be released into the environment in one or the other form [12,13]. In this case, the photo-catalysis procedure has been shown to be quite effective in removing such dyes. The presence of a free electron–hole pair in photo-catalysis can generate free radical (OH˙) species with advanced oxidation properties, which can lead to the complete breakdown of organic pollutants into mineral acids, CO2, and H2O [14].

In recent years, in order to achieve long-term industrial benefits, there is a demand for a tremendous increase in clean and green energy production. An environmentally friendly, renewable, and green energy source can help not only to reduce environmental issues but also to alleviate the global energy crisis that is on the horizon. Recently, hydrogen production has received a lot of attention. However, during industrial hydrogen production, a lot of fossil fuels are wasted, resulting in large amounts of NO x and CO2 emissions, which are the main causes of the greenhouse effect and industrial smog. The use of photo-catalysts for hydrogen fuel production from green sources can solve this problem because it is a renewable, abundant, clean, and green sources of electricity [15].

The development of suitable photo-catalysts is a key research topic to attain higher photo-catalytic activity. Various types of photo-catalysts have been documented. Metal sulfides and semiconductor NPs, particularly those in groups II–VI, are noteworthy in this regard due to their outstanding chemical and physical features [16]. Generally, researchers are concerned not only with the nanocrystals, structural features, such as crystallography, composition, morphology, and mean size, but also with their surfaces, because nanostructures’ surfaces contain a wide range of atoms, the electronic states formed on their surfaces may be critical, influencing the physical properties of the nanostructures. Coating nano-crystals with a shell of an unusual species is one of the strategies for influencing their surface features [17]. Zinc oxide (ZnO), zinc sulfide (ZnS), cadmium oxide (CdO), and cadmium sulfide (CdS) NPs are essential semiconductors in this regard. At room temperature, ZnO has a band gap of 3.7 eV. Solar cells, light-emitting diodes (LED), gas sensors, and field emission are only a few of the technological applications [18]. Similarly, the band gap of ZnS is 3.3 eV, which is sufficient. ZnS has unique properties, such as resistance to high electric fields, large band-gap strength, and photo- and electroluminescence residents. UV LED, infrared purple windows, solar cells, sensors, bio-catalysis, and imaging are only a few of the applications of ZnS [19]. CdO has a band gap of ∼2.7 eV, making it a good candidate for photo-catalytic research when combined with other NPs from this group [20]. The band gap of CdS is 2.42 eV and due to its unique properties, CdS NPs have a wide range of applications, including solar cells, LED, photo-catalysis, and optical instruments [21].

Because of excellent optical characteristics, ZnO and ZnS nanomaterials have been extensively employed as photo-catalysts [22]. They are, however, only active in UV light. As a result, attempts have been made to make them active in the visible zone in order to make the best use of solar energy [23]. On the other hand, CdS is an excellent visible light photo-catalyst but it has poor quantum performance due to low stability charge recombination in solution. As a result, significant attempts have been made to increase the photo-catalytic stability of CdS, despite its relatively high photoactivity [24]. Controlling morphology, modifying the structural surface of CdS NPs, doping transition metal ions with CdS [25], applying CdS to graphene sheets or carbon nanotubes to obtain homogeneously allotted CdS QDs [26], and combining CdS with other semiconductors [27] are some of the methods used. In the foregoing attempts, a combination of various band gap semiconductors generating a continuous chain of electron–hole pair is accomplished. So, due to their optoelectronic and structural properties, ZnO, ZnS, and CdO NPs are good semiconductor materials for CdS, forming a series of chains of electron–hole pairs, where their efficiency is increasing [24]. The various methods used for the synthesis include precipitation, solvothermal, hydrothermal, co-precipitation, sol–gel, microwave-aided, and sono-chemical techniques. Over the other approaches, precipitation methods have a distinct advantage since it is easy, inexpensive, and more energetic [28,29]. Here, the successful fabrication of ZnO–ZnS–CdO–CdS core–shell quaternary NCs was demonstrated by using a novel method of chemical precipitation at 80°C.

Despite its low energy density and significant moisture content, biomass offers a potential sustainable fuel source for the production of H2. However, a number of processes, including gasification, pyrolysis, and super-/subcritical hydrothermal treatment, have been developed to efficiently convert biomass to hydrogen [30,31]. In this study, the prepared nanocatalysts were used in the production of hydrogen gas from green sources of the Brassica campestris leaf extract and the degradation of Congo red (CR) and methyl red (MR) dyes.

2 Experimental

2.1 Materials

The chemicals, zinc sulfate heptahydrate (ZnSO4·7H2O), cadmium sulfate octahydrate (CdSO4·8H2O), sodium sulfide (Na2S), and potassium hydroxide (KOH), were purchased from BDH Chemicals, England. Castor (Ricinus communis) oil was purchased from a local Kohat market and used as a capping agent. Hydrazine monohydrate was purchased from Daejung, Korea. Azo dyes, CR, MR, and methyl orange, were from Merck.

2.2 Synthesis of quaternary ZnO–ZnS–CdO–CdS NCs

First, 50 mL of 0.05 M aqueous ZnSO4·7H2O was taken in a round bottom flask and stirred with a magnetic stirrer. The capping agent solution was prepared by dissolving 1 mL of castor oil in 10 mL of absolute ethanol. Then, the castor oil solution was added dropwise in a round bottom flask containing zinc sulfate solution and mixed. For the synthesis of ZnO, 1 mL of hydrazine monohydrate was added dropwise to the zinc sulfate solution and mixed continuously with a magnetic stirrer until white precipitates were obtained. The formation of white precipitate confirmed the synthesis of ZnO NPs. After washing three times with distilled water, precipitates were suspended in 50 mL of distilled water.

In the second step, 50 mL of 0.05 M aqueous ZnSO4·7H2O was added to the ZnO suspension. Then, 50 mL of 0.05 M sodium sulfide pentahydrate and 5 mL of ethanolic castor oil were added dropwise. After that, 1 mL of hydrazine monohydrate was added dropwise and stirred until turbid white precipitates were obtained, which confirmed the formation of ZnO–ZnS NCs. The product was washed with distilled water, filtered, and suspended in 50 mL of distilled water.

The same experimental procedures were followed for the synthesis of ternary ZnO–ZnS–CdO and quaternary ZnO–ZnS–CdO–CdS NCs using CdSO4·8H2O as a precursor of cadmium. The NCs were washed with distilled water, followed by washing with ethanol, then dried, and calcined in a furnace at 300°C for 2 h, and stored for future use.

2.3 Photo-catalytic degradation of dyes

Organic dyes CR and MR degradation were carried out using synthesized NCs. First, 50 mL of 0.04 mM dye solution was taken in a round bottom flask, and its spectra were recorded using a UV-visible (UV-Vis) spectrophotometer in a quartz cuvette. Then, 50 mg of NCs was added and kept in the dark for 5 min to allow the system to reach equilibrium. Then, the reaction mixture in the flask was placed under the solar light and stirred. The spectra of the same solution were then recorded using a UV-Vis spectrophotometer at different time intervals. During the test, the dye concentrations were kept constant at 0.04 mM. The maximum drop in λ max was recorded at 500 nm for CR and 490 nm for MR. The following equation was used to compute the % degradation of the degraded dye:

(1) Degradation ( % ) = 100 − ( A t × 100 ) A 0

where the starting absorbance is denoted by A 0 and the absorbance at different time intervals is represented by A t .

2.4 Gas generation from the biomass

The biomass of Brassica campestris leaves was collected and dried at room temperature. The leaves were then pulverized into powder. Following that, 6 g of the leaf powder was dissolved in 0.05 M aqueous KOH solution. The extract was filtered through filter paper after 1 h. The production of gas (H2) from the biomass was carried out in a round bottom flask as a reaction vessel. Reactions were carried out both with and without a catalyst. In the presence of the catalyst, a specific amount of biomass was placed in a round-bottom flask and stirred using a magnetic stirrer. The flask was connected to a 500 mL graduated cylinder through a pipe. The entire reaction was carried out in the light (100 W tungsten lamp). After a few minutes, the generated gas started to cause a drop in the water level in the graduated cylinder. The amount of the alkaline biomass solution used in the experiment ranged from 10 to 50 mL, while the amount of the catalyst used ranged from 10 to 50 mg.

2.5 Characterization

A UV-Vis spectrophotometer (Shimadzu, UV-1800), with a wavelength range of 200–700 nm was used for optical absorption spectrum monitoring of ZnO–ZnS–CdO–CdS NCs. The photo-catalytic degradation analysis of the organic dyes was also performed using the same apparatus. A NICOLET iS50 Fourier transform infrared (FTIR) spectrophotometer was used to determine the different functional groups that act as stabilizers on the surface of NCs. Average crystalline structures of NPs were analyzed using powder X‐ray diffraction (XRD) with a PAN (JDX‐3532 JEOL, Japan) analytical diffractometer. An energy dispersive X-ray spectrometer (EDX) 6490 (LA) linked to a MIRA3-TESCAN scanning electron microscope (SEM) was used to examine the elemental composition of the prepared NCs. The DV 420_OE model was used to study the photoluminescence (PL).

3 Results and discussion

3.1 Synthesis of quaternary core–shell NCs

The synthesis of NPs and ZnO–ZnS–CdO–CdS NCs is presented in Figure 1. The formation of white precipitates (Figure A1 in Appendix) after mixing zinc sulfate with hydrazine hydrate confirmed the synthesis of ZnO NPs. Similarly, the formation of turbid white precipitates confirmed the formation of ZnO–ZnS NCs (Figure A1). The product was washed with distilled water, filtered, and suspended in 50 mL of distilled water. The chemical procedure for the configuration of ZnS and CdS NPs is as follows:

Na 2 S + H 2 O + ∆ → 2 Na + + S —

S 2 − + Cd 2 + → CdS

S 2 − + Zn 2 + → ZnS

Figure 1 Schematic representation of the NC synthesis.
Figure 1

Schematic representation of the NC synthesis.

In the first phase, sodium sulfide was converted to hydrogen sulfide, which then interacted with Cd2+ and Zn2+ to form CdS and ZnS, respectively. A pictorial representation is shown in Figure A1.

3.2 Characterization

3.2.1 UV-Vis analysis

The UV-Vis spectra of the prepared NPs and NC samples were recorded using a UV-Vis spectrophotometer. The UV-Vis spectra of the prepared samples are presented in Figure 2a.

Figure 2 (a) UV-Vis and (b) PL of the synthesized NPs and NCs.
Figure 2

(a) UV-Vis and (b) PL of the synthesized NPs and NCs.

The ZnO NPs showed a broad absorption band at around 280 nm. CdO NPs showed an absorption band at 285 nm and a small peak around 305–315 nm [32]. A small peak was observed in ZnS NPs near 280 nm. CdS NPs displayed an absorption band at 440 nm. The oil NCs displayed an absorption band at 420 nm, which indicated a blue shift in comparison to pure CdS NPs due to quantum confinement. The above absorption bands confirm the configuration of ZnO, ZnS, CdO, CdS NPs, and ZnO–ZnS–CdO–CdS NCs [27,28,33].

3.2.2 PL study

PL spectroscopy is an influential tool to calculate approximately the recombination of photo-induced charge carriers (e− and h+). PL not only explains the dependence of photo-catalytic activity but also on the transfer rate and separation efficiency of the photo-generated charges as well as improved surface chemistry characteristics of the photo-catalyst [34]. The PL spectra of the prepared NCs were recorded at room temperature in order to examine the optical properties. The electronic structure of the semiconductor nanomaterials may be very clearly seen in the PL spectra [35]. Thus, PL spectra are also very helpful in demonstrating the effective growth of ZnO, and also later the ZnS, CdO, and CdS shells on ZnO NPs to synthesize ZnO–ZnS–CdO–CdS NCs. Figure 2b displays the visible room-temperature PL spectra of ZnO–ZnS–CdO–CdS NCs [36,37].

3.2.3 FT-IR analysis of nanomaterials

Figure 3 shows the FT-IR spectra of the synthesized NPs and NCs, which demonstrate distinct peaks of the functional groups included in the stabilizer in the region 500–3,500 cm−1. The O–H vibration of stretching is visible in the sharp band between 3,200 and 3,600 cm−1 [38,39]. The C–H group stretching vibration has a peak at 2,900–3,100 cm−1. The R–N═C═S bonding is visible on the peaks from 2,086 to 2,093 cm−1 [40]. The peaks ranging from 1,009 to 1,150 cm−1 indicate stretching vibrations of C–O and C–N, whereas peaks at 1,220 and 1,140 cm−1 exhibited bending vibrations of aliphatic amines, respectively. The peaks between 600 and 800 cm−1 are attributed to the formation of ZnS and CdS. Furthermore, zinc and CdO vibrations were found to have high peaks at 600 and 500 cm−1, respectively [41,42,43]. Thus, from the above discussion, it can be concluded that biomolecules of castor oil (organic acids) serve as a stabilizing agent for the prepared nanomaterials.

Figure 3 FTIR spectra of the synthesized NPs and NCs.
Figure 3

FTIR spectra of the synthesized NPs and NCs.

3.2.4 XRD patterns of nanomaterials

Figure 3 shows the XRD patterns of prepared ZnO, ZnS, CdO, CdS NPs, and ZnO–ZnS–CdO–CdS NCs. It showed the main characteristic peaks with indices of 31.28 (101), 33.88 (002), 48.18 (102), and 63.88 (103), indicating that ZnO NPs had a hexagonal structure [44]. Similarly, major peaks with indices of 28.31 (111), 47.69 (220), and 56.69 (311) were identified, confirming the cubic zinc-blended structure of ZnS NPs [45,46]. Similarly, key feature peaks with indices of 33.37 (111), 38.8 (200), and 55.88 (220) are shown, indicating the cubic structure of CdO [47]. The [111], [220], and [311] diffraction peaks, indicative of the CdS cubic system [48], are also validated in Figure 4.

Figure 4 XRD pattern of the synthesized NPs and NCs.
Figure 4

XRD pattern of the synthesized NPs and NCs.

A mixed structure of ZnO–ZnS–CdO–CdS composites was synthesized, as shown in Figure 4. This validated the hexagonal structure of ZnO and the cubic structures of ZnS, CdO, and CdS, which were unaffected by the coating methods [49]. The Debye–Scherer formula, L = kλ/β ½cos θ, was used to calculate the size of nanocrystallites [50], where θ is the Bragg angle, and λ =1.5418 Å is the X-ray wavelength (Cu source utilized), β = 1/2 is the full width at half-maximum (FWHM) on a 2θ scale, and k is constant nearly equal to unity. According to Scherer’s equation, the average crystallite sizes of ZnO, ZnS, CdO, CdS NPs, and ZnO–ZnS–CdO–CdS NCs were 3, 3.87, 2.96, 3, and 4.72 nm, respectively.

3.2.5 EDX and SEM analyses of nanomaterials

Through energy dispersive X-ray analysis elemental compositions of ZnO NPs, ZnS NPs, CdO NPs, CdS NPs, and ZnO–ZnS–CdO–CdS NPs using castor oil as a catalyst were determined and are shown in Figure 5. The spectra revealed fine signals for Cd and O in CdO, Cd and S in CdS, Zn and O in ZnO, Zn and S in ZnS, and Zn, CdO, and S in ZnO–ZnS–CdO–CdS NPs, demonstrating the reduction of Zn2+ into ZnO and ZnS nanomaterials and Cd2+ into CdO and CdS nanomaterials. EDX examination revealed the presence of Zn, Cd, O, and S in the formed NPs and NCs [51].

Figure 5 EDX investigation of (a) NCs, (b) ZnS NPs, (c) ZnO NPs, (d) CdO NPs, and (e) CdS NPs.
Figure 5

EDX investigation of (a) NCs, (b) ZnS NPs, (c) ZnO NPs, (d) CdO NPs, and (e) CdS NPs.

SEM was used to examine the morphology and agglomerated sizes of ZnO, ZnS, CdO, CdS NPs, and ZnO–ZnS–CdO–CdS NCs produced with castor oil, as shown in Figure 6.

Figure 6 SEM analysis of (a) NCs, (b) ZnS NPs, (c) ZnO NPs, (d) CdO NPs, and (e) CdS NPs.
Figure 6

SEM analysis of (a) NCs, (b) ZnS NPs, (c) ZnO NPs, (d) CdO NPs, and (e) CdS NPs.

The electrical and optical characteristics of NPs and NCs are dependent on their forms [52]. SEM has been utilized by various researchers to determine the size and morphology, as well as to characterize NPs [53]. The synthesized ZnO, ZnS, CdO, CdS NPs, and ZnO–ZnS–CdO–CdS NCs were polydistributed and spherical in shape, according to SEM analysis, and the sizes of NPs and NCs ranged from 1–10 µm up to 100 nm.

3.3 Photo-catalytic degradation of dyes

In recent years, commercial dyes like CR and MR have been successfully degraded using nanomaterials [54]. Two different azo dye solutions (CR and MR) were utilized to investigate the photo-catalytic performance of ZnO, CdO, CdS, and ZnO–ZnS–CdO–CdS NCs.

First, control studies for the two different dyes were carried out without the use of a catalyst, using only 3 mL of each dye in a cuvette. It was exposed to sunlight for varied periods of time and its spectrum was recorded using a UV-Vis spectrophotometer. Figure 4 illustrates control studies that reveal a small fraction of dye degradation, a process known as photolysis response. Figures 5–8 show a decrease in absorption intensities with time exposure, indicating photo-catalytic degradation of CR and MR dyes [55]. With increasing irradiation time, the absorbance maximum (495 nm for CR and 488 nm for MR) gradually dropped. The degradation percentage and ln C t /C o of all the dyes in the presence of the produced NPs and NCs are also shown in Figures 7–10. The degradation percentage of the dyes was calculated by using the following equation:

(2) D egradation percentage = 100 − A t × 100 A 0

where A 0 represents the initial absorbance of the dye solution and A t represents the absorbance at different intervals [56].

Figure 7 UV-Vis spectra of the CR dye degradation in the presence of (a) ZnO, (b) CdO, (c) CdS, and (d) NCs.
Figure 7

UV-Vis spectra of the CR dye degradation in the presence of (a) ZnO, (b) CdO, (c) CdS, and (d) NCs.

Figure 8 Degradation percentage of the CR dye: (a) ZnO, (b) CdO, (c) CdS, and (d) NCs.
Figure 8

Degradation percentage of the CR dye: (a) ZnO, (b) CdO, (c) CdS, and (d) NCs.

Figure 9 UV-Vis spectra of the MR dye degradation in the presence of (a) ZnO, (b) CdO, (c) CdS, and (d) NCs.
Figure 9

UV-Vis spectra of the MR dye degradation in the presence of (a) ZnO, (b) CdO, (c) CdS, and (d) NCs.

Figure 10 Degradation percentage of the MR dye: (a) ZnO, (b) CdO, (c) CdS, and (d) NCs.
Figure 10

Degradation percentage of the MR dye: (a) ZnO, (b) CdO, (c) CdS, and (d) NCs.

As evident from Figure 7, the degradation percentage of the CR dye was 83% by ZnO NPs, 71% by CdO NPs, 68% by CdS NPs, and 86% by the prepared NCs.

In the case of MR degradation, the degradation percentage was 82% by ZnO NPs, 97% by CdO NPs, 77% by CdS NPs, and 93% by the prepared NCs (Figure 9).

It is noteworthy that the prepared NCs had the maximum efficiency in the case of CR and noticeable efficiency in the case of MR.

3.3.1 Kinetics of photodegradation

We can understand dye degradation behaviors using the Langmuir–Hinshelwood (L–H) model. Therefore, the pseudo‐first‐order equation can be expressed as follows:

(3) Rate ( r ) = d c /d t = ln ( C t / C 0 ) = − k app t

Since the reaction is colored, the rate of reaction can be determined and expressed in adsorption spectra at time t:

(4) Rate ( r ) = ln ( C t / C 0 ) = ln ( A t / A 0 ) = − k app t

where C o is the initial concentration and C t is the final concentration.

The half-life (t ½) is calculated from Eq. 5 as

(5) Half − life ( t ½ ) = 0.69 / k

where C 0 is the initial concentration and C t is the concentration at time (t) of the dye.

Figures A2 and A3 show a linear relationship in plots of ln (C t /C 0) versus time of degradation. So, the degradation of dyes followed the first-order kinetics. From Eq. 5, the slopes of ln(C t /C 0) vs time and half-life (t 1/2) of the degraded dye samples were calculated (in min) in the presence of ZnO, CdO, CdS NPs, and ZnO–ZnS–CdO–CdS NCs for CR and MR dyes, respectively [57,58].

The slope and half lifetime for CR dyes were 0.1112 and 6.2 in the presence of ZnO, 1.11 and 0.62 for CdO, 0.1335 and 5.16 for CdS, and 0.2425 and 2.85 for oil NCs, respectively. Similarly, for MR dyes, the slope and half lifetime were 0.4129 and 1.67 for ZnO, 0.9021 and 0.76 for CdO, 0.2231 and 3.10 for CdS, and 0.2231 and 3.10 for oil NCs, respectively.

Thus, the above kinetic study exposed that ZnO–ZnS–CdO–CdS NPs and NCs are efficient photo-catalysts for the removal of the given dyes. The synthesized NCs showed the highest efficiency for the degradation CR dyes and a well-defined result for MR. CR was chosen for further investigation because it had the highest efficiency when compared to MR.

3.3.2 Degradation of a mixture of MR and CR

In order to check the catalytic degradation activity of the prepared NCs, the catalyst was tested in this work against a solution of a mixture of dyes. For the degradation of the mixed solution of MR and CR, 25 mL of each 0.04 mM dye was mixed in a reaction beaker. Then, 50 mg of NCs was added into the reaction vessel, and its spectra were recorded using a UV-Vis spectrophotometer. The reaction mixture was placed under a magnetic stirrer in solar light. The spectra of the solution mixture were then recorded using a UV-Vis spectrophotometer. A strong absorption peak is observed at 491 nm for the aqueous MR and CR mixture, as shown in Figure A4.

It is well known that an absorption peak is observed at 495 nm for CR, while that of MR is observed at 488 nm. Thus, the appearance of the peak at 491 nm was due to the chemical interaction of the two dye solutions. The peak intensity at 491 nm decreases after the addition of 10 mg of the catalyst in sunlight. UV-Vis spectra were continuously recorded at a time interval of 15 min, as shown in Figure A4. With time, the intensity of the peak decreases at 491 nm. The decrease in the peak intensity at 491 nm after the addition of the catalyst was due to the initiation of dye degradation [59,60]. The prepared NCs show excellent catalytic degradation activity, and the 74% degradation of the mixture of CR and MR takes 105 min. Thus, the prepared NC catalyst has the best catalytic degradation activity not only for a single substrate but also for a mixture of dyes.

3.3.3 Reusability of NCs

The reusability of effective catalysts and their uses for the next cycle is a major concern in catalysis. The majority of catalysts are deactivated after just one or two cycles of usage. In addition to catalytic efficiency, other important factors to take into account when assessing catalysts’ performance include photocorrosion, versatility, compostability, and stability since they may significantly lower the overall expenses of the process [61]. Heterogeneous NP-based catalysts have been effectively documented in the literature due to their photocatalytic activity; however, the problem is that they must recover from the reaction media in order to be reused. Thus, stable and fully separable catalysts are essential to the processes of recycling and reuse.

The recyclability of catalysts was investigated using CR in this study. The degradation of CR was evaluated for 105 min for consecutive three cycles. The recyclability was tested after washing the catalyst three times in double distilled water when it was used for degradation and utilized for the next reaction at the same time.

As shown in Figure A5, ZnO degrades the CR dye by 83%, 75%, and 71% for the first, second, and third cycles, respectively. Similarly, CdO degrades the CR dye by 71%, 60%, and 65% for the first, second, and third cycles, respectively. Degradation percentage of CdS were 68%, 64%, and 59% for the first, second, and third cycles, respectively. However, degradation efficiencies of NCs were 86%, 80%, and 76% for the first, second, and third cycles, respectively.

3.3.4 Mechanism of degradation

A schematic representation of organic dye photocatalysis by the prepared NCs is illustrated in Scheme 1. It provides a plausible mechanism for the degradation reaction. The proposed degradation mechanism of the dye reaction is as follows. Photoelectrons are elevated from the valence band (VB) of the NC catalyst to the conduction band (CB), which often initiates photocatalytic activities. The energy of the absorbed light has now reached or exceeded the photocatalyst band gap energy. Photoelectron excitation causes a hole to form in the VB. As a result, a pair of electron and hole (e−/h+) is produced, as shown in the following equation:

(6) NCs + hν → NCs ( e − ( CB ) + h + ( VB ) )

Scheme 1 Possible mechanism of photodegradation of the dye for ZnO/ZnS/CdO/CdS NCs.
Scheme 1

Possible mechanism of photodegradation of the dye for ZnO/ZnS/CdO/CdS NCs.

The generation of hydroxyl radicals (OH˙) occurs when water ionizes and combines with the newly generated hole in the VB to produce a hydroxyl radical. This process is implicated in the destruction of the dye molecule:

(7) H 2 O + h + ( VB ) → OH ˙ ( ads ) + H + ( ads )

This OH˙ radical on the surface of NCs is a very potent oxidizing agent, and dye molecules that are close to the catalyst surface mineralize molecules to varying degrees depending on their structure and stability. These hydroxyl radicals can destroy any existing bacteria in the media in addition to attacking organic contaminants [62]. Similarly, the excited electrons in the conducting band now interact with the oxygen in the area to generate the anionic superoxide radical ( O 2 − ) at the same time:

(8) O 2 + e − ( CB ) → O 2 − ( ads )

Superoxide radicals contribute to the oxidation process while also preventing electron and hole recombination, preserving electron neutrality inside the catalyst.

Superoxide is protonated in this step, which results in the production of H2O2. This further splits apart and produces a hydroxyl radical, which is very reactive. The oxidation and reduction processes occur at the same time on the photo-excited catalyst surface in photo-catalysis. Scheme 1 shows the procedure and plausible mechanism of dye degradation.

3.4 Hydrogen gas generation from the biomass

The prepared nanocatalysts were used in the production of hydrogen gas from green sources of the Brassica campestris leaf extract. Hydrogen produced through gasification exhibits an economic efficiency compared to other renewable energy sources.

3.4.1 Gas generation from the biomass using ZnO NPs

The experiment for gas generation from the biomass was carried out in a round bottom flask used as a reaction container as presented in Figure A5, where in each case 100 W tungsten lamp is used as a source of radiation. In the absence of the prepared catalyst, the flask was filled with only 10 mL of 0.05 M KOH solution. Through rubber tubing, the flask was connected to a 500 mL graduating cylinder. The flask was placed on the magnetic stirrer to be stirred. The entire assembly was placed in a tungsten lamp, and the gas production was measured. After 1 h, 91 µmol·g−1·min−1 gas was generated. In another trial, 10 mL of the biomass extract alone was added, and 122 µmol·g−1·min−1 gas was generated in 1 h.

Similarly, in the presence of a catalyst, the round bottom flask was filled with 20 mL of the biomass extract and then 20 mg of ZnO NPs was added. The process was initiated and gas production started, and produced 550 µmol·g−1·min−1. The amount of the biomass extract was constant at 20 mL, while the catalyst amount increased from 20 to 50 mg. With an increase in the amount of catalyst, the gas production increased from 550 to 672 µmol·g−1·min−1 in 1 h (Figure 11a and b).

Figure 11 (a) H2 generation in the presence of ZnO NPs. (b) The rate of H2 evolution with various amounts of ZnO NPs. (c) H2 generation in the presence of CdS NPs. (d) The rate of H2 evolution with various amounts of CdS NPs. (From 10 mL 0.05 M KOH, 10 mL biomass extract, 20 mL biomass + 10 mg NPs, 20 mL biomass + 20 mg NPs, 30 mg NPs, and 20 mL biomass + 50 mg NPs, 60 min at 100 W tungsten lamp, respectively).
Figure 11

(a) H2 generation in the presence of ZnO NPs. (b) The rate of H2 evolution with various amounts of ZnO NPs. (c) H2 generation in the presence of CdS NPs. (d) The rate of H2 evolution with various amounts of CdS NPs. (From 10 mL 0.05 M KOH, 10 mL biomass extract, 20 mL biomass + 10 mg NPs, 20 mL biomass + 20 mg NPs, 30 mg NPs, and 20 mL biomass + 50 mg NPs, 60 min at 100 W tungsten lamp, respectively).

In order to increase H2 production, Reddy et al. have shown that sodium hydroxide can be utilized as an effective additive in glucose gasification and the supercritical water reaction of cellulose [63]. At a comparatively low temperature of 573 K, Ishida et al. showed that the addition of sodium hydroxide could greatly increase the H2 output from cellulose [64]. They proposed the following alkaline thermal treatment reaction stoichiometry:

(9) C 6 H 10 O 5 ( s ) + 12NaOH ( s ) + H 2 O ( g ) → 6Na 2 CO 3 ( s ) + 12H 2 ( g )

Sodium hydroxide's effectiveness in generating H2 is due to its capacity to promote the dissolving of cellulose [65] and the disintegration of cellulose [66]. Additionally, the solid carbonate formed during this reaction traps the carbon dioxide formed during it, producing H2 with little to no carbon dioxide. The hydroxyl group may enable H2 synthesis from cellulose at lower pressures and temperatures according to a comparison of the literature regarding the supercritical water reaction with sodium hydroxide and alkaline thermal treatment reaction [67].

The mechanisms of photo-electrochemical hydrogen production from the biomass (presented as C x H y O z ) and water over prepared NCs are shown in Eqs. 10–13. Under irradiation with sunlight (photon energy), the electrons (e ̄) from the VB will be excited and transferred to the CB, and then finally react with a proton (H+) to produce hydrogen gas. Photo-excited h+ generated in the VB of the NCs will oxidize the C x H y O z molecules to carbon dioxide and water. In actuality, the process by which C x H y O z degrades into CO2 and water is incredibly complicated, as explored in more detail below. The following equations succinctly describe the chemical processes [68]:

(10) CdS or ZnO or NCs + hv → CdS⁎ or ZnO⁎ or NCs⁎ + e − + h +

(11) C x H y O z + ( 4 x + y − 2 z ) h + + ( 4 x + y − 2 z ) OH − → x CO 2 + ( 2 x + y − z ) H 2 O

(12) 2 H 2 O + 2 e − → H 2 + 2 OH −

(13) Total: C x H y O z + ( 2 x − z ) H 2 O − → x CO 2 + ( 2 x – z + ( y / 2 ) ) H 2

3.4.2 Gas generation from the biomass by using CdS NPs

About 20 mL of the biomass extract prepared in 0.05 M KOH solution and 10 mg of CdS NPs were taken in a round bottom flask. The reaction was started; 216 µmol·g−1·min−1 H2 gas was collected in the graduated cylinder. Then, the amount of the biomass extract was kept constant at 20 mL, while the amount of the photo-catalyst was changed to 20, 30, 40, to 50 mg. The H2 gas concentrations collected were 274, 580, 641, and 733 µmol·g−1·min−1, respectively, in 60 min, while the rate of H2 evolution is shown in Figure 11c and d.

3.4.3 Hydrogen gas generation from the biomass by using oil NCs

About 10 mL of the biomass extract and 10 mg of oil NCs were taken in a round bottom flask. The process was initiated, and the graduated cylinder was filled with 214 µmol·g−1·min−1 H2. The catalyst concentration was kept constant at 10 mg, and the biomass extract concentration was varied from 20 to 50 mL, resulting in H2 gas concentrations of 305, 366, 550, and 580 µmol·g−1·min−1, respectively, in 60 min, as shown in Figure 12. In another experiment, the biomass value was held constant at 20 mL, while the oil NC values were adjusted to 10, 20, 30, 40, and 50 mg in that order. As shown in Figure 12, the H2 generated was 305 µmol·g−1·min−1 for 10 mg NCs, 397 µmol·g−1·min−1 for 20 mg, 458 µmol·g−1·min−1 for 30 mg, 611 µmol·g−1·min−1 for 40 mg, and 763 µmol·g−1·min−1 for 50 mg NCs.

Figure 12 (a) H2 generation from the biomass in the presence of oil NCs and NPs. (b) The rate of H2 evolution with various amounts of oil NCs.
Figure 12

(a) H2 generation from the biomass in the presence of oil NCs and NPs. (b) The rate of H2 evolution with various amounts of oil NCs.

4 Conclusions

In this work, quaternary NCs were successfully developed through an in situ precipitation method. Here, castor oil was used as a capping agent in deionized water. The synthesized pure NPs and NCs were characterized by UV-Vis, PL, FTIR, XRD, EDX, and SEM analyses to study their optical, structural, and morphological data. UV-Vis spectroscopy showed the redshift in the NCs as compared to CdS NPs. This indicates the presence of more CdS NPs in NCs and hence exhibits better visible light photo-catalytic activity. PL spectroscopy reveals evidence for interaction between ZnO, ZnS, CdO, and CdS. The photo-catalytic properties of NCs and hydrogen gas generation are encouraging as compared to pure ZnO, ZnS, CdO, and CdS NPs due to efficient charge separation in ZnO–ZnS–CdO–CdS NCs.

Acknowledgements

This study is based on the work conducted by Mr. Yousaf Khan as part of his PhD thesis under the supervision of Prof. Dr. M. I. Khan and Prof. Dr. Murad Ali Khan.

  1. Author contributions: Yousaf Khan, Uzma Sharafat, Rafia Younus, Saima Gul: conceptualization, investigation, formal analysis, methodology, visualization, and validation; Murad Ali Khan, Muhammad Ismail: formal analysis, investigation, writing – original draft, methodology, validation, writing – review and editing; Sher Bahadar Khan, M. I. Khan: project administration, visualization, supervision, resources, data curation, writing – review and editing.

  2. Conflict of interest: The authors state that there are no conflict of interest.

  3. Data availability statement: The authors confirm that the data supporting the findings of this study are available within the article.

Appendix

Figure A1 Synthesis of (a) ZnO NPs, (b) ZnO/ZnS NCs, (c) ZnO/ZnS/CdO NCs, and (d) ZnO/ZnS/CdO/CdS NCs.
Figure A1

Synthesis of (a) ZnO NPs, (b) ZnO/ZnS NCs, (c) ZnO/ZnS/CdO NCs, and (d) ZnO/ZnS/CdO/CdS NCs.

Figure A2 Plot of ln(C t /C o) versus time for the CR dye for (a) ZnO, (b) CdO (c), CdS, and (d) NCs.
Figure A2

Plot of ln(C t /C o) versus time for the CR dye for (a) ZnO, (b) CdO (c), CdS, and (d) NCs.

Figure A3 Plot of ln(C t /C o) versus time for the MR dye for (a) ZnO, (b) CdO, (c) CdS, and (d) NCs.
Figure A3

Plot of ln(C t /C o) versus time for the MR dye for (a) ZnO, (b) CdO, (c) CdS, and (d) NCs.

Figure A4 Photocatalytic degradation of a mixture of MR and CR dyes (25 mL of each 0.04 mM dye + 50 mg of NCs).
Figure A4

Photocatalytic degradation of a mixture of MR and CR dyes (25 mL of each 0.04 mM dye + 50 mg of NCs).

Figure A5 Reusability of the CR dye for ZnO, CdO, CdS, and NCs.
Figure A5

Reusability of the CR dye for ZnO, CdO, CdS, and NCs.

Figure A6 Set up for hydrogen generation from the biomass and photo-catalyst reaction.
Figure A6

Set up for hydrogen generation from the biomass and photo-catalyst reaction.

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Received: 2022-10-15
Revised: 2023-02-28
Accepted: 2023-03-07
Published Online: 2023-05-08

© 2023 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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  10. Optimization of apigenin nanoparticles prepared by planetary ball milling: In vitro and in vivo studies
  11. Synthesis and characterization of silver nanoparticles using Origanum onites leaves: Cytotoxic, apoptotic, and necrotic effects on Capan-1, L929, and Caco-2 cell lines
  12. Exergy analysis of a conceptual CO2 capture process with an amine-based DES
  13. Construction of fluorescence system of felodipine–tetracyanovinyl–2,2′-bipyridine complex
  14. Excellent photocatalytic degradation of rhodamine B over Bi2O3 supported on Zn-MOF nanocomposites under visible light
  15. Optimization-based control strategy for a large-scale polyhydroxyalkanoates production in a fed-batch bioreactor using a coupled PDE–ODE system
  16. Effectiveness of pH and amount of Artemia urumiana extract on physical, chemical, and biological attributes of UV-fabricated biogold nanoparticles
  17. Geranium leaf-mediated synthesis of silver nanoparticles and their transcriptomic effects on Candida albicans
  18. Synthesis, characterization, anticancer, anti-inflammatory activities, and docking studies of 3,5-disubstituted thiadiazine-2-thiones
  19. Synthesis and stability of phospholipid-encapsulated nano-selenium
  20. Putative anti-proliferative effect of Indian mustard (Brassica juncea) seed and its nano-formulation
  21. Enrichment of low-grade phosphorites by the selective leaching method
  22. Electrochemical analysis of the dissolution of gold in a copper–ethylenediamine–thiosulfate system
  23. Characterisation of carbonate lake sediments as a potential filler for polymer composites
  24. Evaluation of nano-selenium biofortification characteristics of alfalfa (Medicago sativa L.)
  25. Quality of oil extracted by cold press from Nigella sativa seeds incorporated with rosemary extracts and pretreated by microwaves
  26. Heteropolyacid-loaded MOF-derived mesoporous zirconia catalyst for chemical degradation of rhodamine B
  27. Recovery of critical metals from carbonatite-type mineral wastes: Geochemical modeling investigation of (bio)hydrometallurgical leaching of REEs
  28. Photocatalytic properties of ZnFe-mixed oxides synthesized via a simple route for water remediation
  29. Attenuation of di(2-ethylhexyl)phthalate-induced hepatic and renal toxicity by naringin nanoparticles in a rat model
  30. Novel in situ synthesis of quaternary core–shell metallic sulfide nanocomposites for degradation of organic dyes and hydrogen production
  31. Microfluidic steam-based synthesis of luminescent carbon quantum dots as sensing probes for nitrite detection
  32. Transformation of eggshell waste to egg white protein solution, calcium chloride dihydrate, and eggshell membrane powder
  33. Preparation of Zr-MOFs for the adsorption of doxycycline hydrochloride from wastewater
  34. Green nanoarchitectonics of the silver nanocrystal potential for treating malaria and their cytotoxic effects on the kidney Vero cell line
  35. Carbon emissions analysis of producing modified asphalt with natural asphalt
  36. An efficient and green synthesis of 2-phenylquinazolin-4(3H)-ones via t-BuONa-mediated oxidative condensation of 2-aminobenzamides and benzyl alcohols under solvent- and transition metal-free conditions
  37. Chitosan nanoparticles loaded with mesosulfuron methyl and mesosulfuron methyl + florasulam + MCPA isooctyl to manage weeds of wheat (Triticum aestivum L.)
  38. Synergism between lignite and high-sulfur petroleum coke in CO2 gasification
  39. Facile aqueous synthesis of ZnCuInS/ZnS–ZnS QDs with enhanced photoluminescence lifetime for selective detection of Cu(ii) ions
  40. Rapid synthesis of copper nanoparticles using Nepeta cataria leaves: An eco-friendly management of disease-causing vectors and bacterial pathogens
  41. Study on the photoelectrocatalytic activity of reduced TiO2 nanotube films for removal of methyl orange
  42. Development of a fuzzy logic model for the prediction of spark-ignition engine performance and emission for gasoline–ethanol blends
  43. Micro-impact-induced mechano-chemical synthesis of organic precursors from FeC/FeN and carbonates/nitrates in water and its extension to nucleobases
  44. Green synthesis of strontium-doped tin dioxide (SrSnO2) nanoparticles using the Mahonia bealei leaf extract and evaluation of their anticancer and antimicrobial activities
  45. A study on the larvicidal and adulticidal potential of Cladostepus spongiosus macroalgae and green-fabricated silver nanoparticles against mosquito vectors
  46. Catalysts based on nickel salt heteropolytungstates for selective oxidation of diphenyl sulfide
  47. Powerful antibacterial nanocomposites from Corallina officinalis-mediated nanometals and chitosan nanoparticles against fish-borne pathogens
  48. Removal behavior of Zn and alkalis from blast furnace dust in pre-reduction sinter process
  49. Environmentally friendly synthesis and computational studies of novel class of acridinedione integrated spirothiopyrrolizidines/indolizidines
  50. The mechanisms of inhibition and lubrication of clean fracturing flowback fluids in water-based drilling fluids
  51. Adsorption/desorption performance of cellulose membrane for Pb(ii)
  52. A one-pot, multicomponent tandem synthesis of fused polycyclic pyrrolo[3,2-c]quinolinone/pyrrolizino[2,3-c]quinolinone hybrid heterocycles via environmentally benign solid state melt reaction
  53. Green synthesis of silver nanoparticles using durian rind extract and optical characteristics of surface plasmon resonance-based optical sensor for the detection of hydrogen peroxide
  54. Electrochemical analysis of copper-EDTA-ammonia-gold thiosulfate dissolution system
  55. Characterization of bio-oil production by microwave pyrolysis from cashew nut shells and Cassia fistula pods
  56. Green synthesis methods and characterization of bacterial cellulose/silver nanoparticle composites
  57. Photocatalytic research performance of zinc oxide/graphite phase carbon nitride catalyst and its application in environment
  58. Effect of phytogenic iron nanoparticles on the bio-fortification of wheat varieties
  59. In vitro anti-cancer and antimicrobial effects of manganese oxide nanoparticles synthesized using the Glycyrrhiza uralensis leaf extract on breast cancer cell lines
  60. Preparation of Pd/Ce(F)-MCM-48 catalysts and their catalytic performance of n-heptane isomerization
  61. Green “one-pot” fluorescent bis-indolizine synthesis with whole-cell plant biocatalysis
  62. Silica-titania mesoporous silicas of MCM-41 type as effective catalysts and photocatalysts for selective oxidation of diphenyl sulfide by H2O2
  63. Biosynthesis of zinc oxide nanoparticles from molted feathers of Pavo cristatus and their antibiofilm and anticancer activities
  64. Clean preparation of rutile from Ti-containing mixed molten slag by CO2 oxidation
  65. Synthesis and characterization of Pluronic F-127-coated titanium dioxide nanoparticles synthesized from extracts of Atractylodes macrocephala leaf for antioxidant, antimicrobial, and anticancer properties
  66. Effect of pretreatment with alkali on the anaerobic digestion characteristics of kitchen waste and analysis of microbial diversity
  67. Ameliorated antimicrobial, antioxidant, and anticancer properties by Plectranthus vettiveroides root extract-mediated green synthesis of chitosan nanoparticles
  68. Microwave-accelerated pretreatment technique in green extraction of oil and bioactive compounds from camelina seeds: Effectiveness and characterization
  69. Studies on the extraction performance of phorate by aptamer-functionalized magnetic nanoparticles in plasma samples
  70. Investigation of structural properties and antibacterial activity of AgO nanoparticle extract from Solanum nigrum/Mentha leaf extracts by green synthesis method
  71. Green fabrication of chitosan from marine crustaceans and mushroom waste: Toward sustainable resource utilization
  72. Synthesis, characterization, and evaluation of nanoparticles of clodinofop propargyl and fenoxaprop-P-ethyl on weed control, growth, and yield of wheat (Triticum aestivum L.)
  73. The enhanced adsorption properties of phosphorus from aqueous solutions using lanthanum modified synthetic zeolites
  74. Separation of graphene oxides of different sizes by multi-layer dialysis and anti-friction and lubrication performance
  75. Visible-light-assisted base-catalyzed, one-pot synthesis of highly functionalized cinnolines
  76. The experimental study on the air oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid with Co–Mn–Br system
  77. Highly efficient removal of tetracycline and methyl violet 2B from aqueous solution using the bimetallic FeZn-ZIFs catalyst
  78. A thermo-tolerant cellulase enzyme produced by Bacillus amyloliquefaciens M7, an insight into synthesis, optimization, characterization, and bio-polishing activity
  79. Exploration of ketone derivatives of succinimide for their antidiabetic potential: In vitro and in vivo approaches
  80. Ultrasound-assisted green synthesis and in silico study of 6-(4-(butylamino)-6-(diethylamino)-1,3,5-triazin-2-yl)oxypyridazine derivatives
  81. A study of the anticancer potential of Pluronic F-127 encapsulated Fe2O3 nanoparticles derived from Berberis vulgaris extract
  82. Biogenic synthesis of silver nanoparticles using Consolida orientalis flowers: Identification, catalytic degradation, and biological effect
  83. Initial assessment of the presence of plastic waste in some coastal mangrove forests in Vietnam
  84. Adsorption synergy electrocatalytic degradation of phenol by active oxygen-containing species generated in Co-coal based cathode and graphite anode
  85. Antibacterial, antifungal, antioxidant, and cytotoxicity activities of the aqueous extract of Syzygium aromaticum-mediated synthesized novel silver nanoparticles
  86. Synthesis of a silica matrix with ZnO nanoparticles for the fabrication of a recyclable photodegradation system to eliminate methylene blue dye
  87. Natural polymer fillers instead of dye and pigments: Pumice and scoria in PDMS fluid and elastomer composites
  88. Study on the preparation of glycerylphosphorylcholine by transesterification under supported sodium methoxide
  89. Wireless network handheld terminal-based green ecological sustainable design evaluation system: Improved data communication and reduced packet loss rate
  90. The optimization of hydrogel strength from cassava starch using oxidized sucrose as a crosslinking agent
  91. Green synthesis of silver nanoparticles using Saccharum officinarum leaf extract for antiviral paint
  92. Study on the reliability of nano-silver-coated tin solder joints for flip chips
  93. Environmentally sustainable analytical quality by design aided RP-HPLC method for the estimation of brilliant blue in commercial food samples employing a green-ultrasound-assisted extraction technique
  94. Anticancer and antimicrobial potential of zinc/sodium alginate/polyethylene glycol/d-pinitol nanocomposites against osteosarcoma MG-63 cells
  95. Nanoporous carbon@CoFe2O4 nanocomposite as a green absorbent for the adsorptive removal of Hg(ii) from aqueous solutions
  96. Characterization of silver sulfide nanoparticles from actinobacterial strain (M10A62) and its toxicity against lepidopteran and dipterans insect species
  97. Phyto-fabrication and characterization of silver nanoparticles using Withania somnifera: Investigating antioxidant potential
  98. Effect of e-waste nanofillers on the mechanical, thermal, and wear properties of epoxy-blend sisal woven fiber-reinforced composites
  99. Magnesium nanohydroxide (2D brucite) as a host matrix for thymol and carvacrol: Synthesis, characterization, and inhibition of foodborne pathogens
  100. Synergistic inhibitive effect of a hybrid zinc oxide-benzalkonium chloride composite on the corrosion of carbon steel in a sulfuric acidic solution
  101. Review Articles
  102. Role and the importance of green approach in biosynthesis of nanopropolis and effectiveness of propolis in the treatment of COVID-19 pandemic
  103. Gum tragacanth-mediated synthesis of metal nanoparticles, characterization, and their applications as a bactericide, catalyst, antioxidant, and peroxidase mimic
  104. Green-processed nano-biocomposite (ZnO–TiO2): Potential candidates for biomedical applications
  105. Reaction mechanisms in microwave-assisted lignin depolymerisation in hydrogen-donating solvents
  106. Recent progress on non-noble metal catalysts for the deoxydehydration of biomass-derived oxygenates
  107. Rapid Communication
  108. Phosphorus removal by iron–carbon microelectrolysis: A new way to achieve phosphorus recovery
  109. Special Issue: Biomolecules-derived synthesis of nanomaterials for environmental and biological applications (Guest Editors: Arpita Roy and Fernanda Maria Policarpo Tonelli)
  110. Biomolecules-derived synthesis of nanomaterials for environmental and biological applications
  111. Nano-encapsulated tanshinone IIA in PLGA-PEG-COOH inhibits apoptosis and inflammation in cerebral ischemia/reperfusion injury
  112. Green fabrication of silver nanoparticles using Melia azedarach ripened fruit extract, their characterization, and biological properties
  113. Green-synthesized nanoparticles and their therapeutic applications: A review
  114. Antioxidant, antibacterial, and cytotoxicity potential of synthesized silver nanoparticles from the Cassia alata leaf aqueous extract
  115. Green synthesis of silver nanoparticles using Callisia fragrans leaf extract and its anticancer activity against MCF-7, HepG2, KB, LU-1, and MKN-7 cell lines
  116. Algae-based green AgNPs, AuNPs, and FeNPs as potential nanoremediators
  117. Green synthesis of Kickxia elatine-induced silver nanoparticles and their role as anti-acetylcholinesterase in the treatment of Alzheimer’s disease
  118. Phytocrystallization of silver nanoparticles using Cassia alata flower extract for effective control of fungal skin pathogens
  119. Antibacterial wound dressing with hydrogel from chitosan and polyvinyl alcohol from the red cabbage extract loaded with silver nanoparticles
  120. Leveraging of mycogenic copper oxide nanostructures for disease management of Alternaria blight of Brassica juncea
  121. Nanoscale molecular reactions in microbiological medicines in modern medical applications
  122. Synthesis and characterization of ZnO/β-cyclodextrin/nicotinic acid nanocomposite and its biological and environmental application
  123. Green synthesis of silver nanoparticles via Taxus wallichiana Zucc. plant-derived Taxol: Novel utilization as anticancer, antioxidation, anti-inflammation, and antiurolithic potential
  124. Recyclability and catalytic characteristics of copper oxide nanoparticles derived from bougainvillea plant flower extract for biomedical application
  125. Phytofabrication, characterization, and evaluation of novel bioinspired selenium–iron (Se–Fe) nanocomposites using Allium sativum extract for bio-potential applications
  126. Erratum
  127. Erratum to “Synthesis, characterization, and evaluation of nanoparticles of clodinofop propargyl and fenoxaprop-P-ethyl on weed control, growth, and yield of wheat (Triticum aestivum L.)”
https://doi.org/10.1515/gps-2022-8128
Keywords for this article
precipitation method; green synthesis; organic pollutants; hydrogen gas; Brassica campestris
Creative Commons
BY 4.0

Articles in the same Issue

  1. Research Articles
  2. Value-added utilization of coal fly ash and recycled polyvinyl chloride in door or window sub-frame composites
  3. High removal efficiency of volatile phenol from coking wastewater using coal gasification slag via optimized adsorption and multi-grade batch process
  4. Evolution of surface morphology and properties of diamond films by hydrogen plasma etching
  5. Removal efficiency of dibenzofuran using CuZn-zeolitic imidazole frameworks as a catalyst and adsorbent
  6. Rapid and efficient microwave-assisted extraction of Caesalpinia sappan Linn. heartwood and subsequent synthesis of gold nanoparticles
  7. The catalytic characteristics of 2-methylnaphthalene acylation with AlCl3 immobilized on Hβ as Lewis acid catalyst
  8. Biodegradation of synthetic PVP biofilms using natural materials and nanoparticles
  9. Rutin-loaded selenium nanoparticles modulated the redox status, inflammatory, and apoptotic pathways associated with pentylenetetrazole-induced epilepsy in mice
  10. Optimization of apigenin nanoparticles prepared by planetary ball milling: In vitro and in vivo studies
  11. Synthesis and characterization of silver nanoparticles using Origanum onites leaves: Cytotoxic, apoptotic, and necrotic effects on Capan-1, L929, and Caco-2 cell lines
  12. Exergy analysis of a conceptual CO2 capture process with an amine-based DES
  13. Construction of fluorescence system of felodipine–tetracyanovinyl–2,2′-bipyridine complex
  14. Excellent photocatalytic degradation of rhodamine B over Bi2O3 supported on Zn-MOF nanocomposites under visible light
  15. Optimization-based control strategy for a large-scale polyhydroxyalkanoates production in a fed-batch bioreactor using a coupled PDE–ODE system
  16. Effectiveness of pH and amount of Artemia urumiana extract on physical, chemical, and biological attributes of UV-fabricated biogold nanoparticles
  17. Geranium leaf-mediated synthesis of silver nanoparticles and their transcriptomic effects on Candida albicans
  18. Synthesis, characterization, anticancer, anti-inflammatory activities, and docking studies of 3,5-disubstituted thiadiazine-2-thiones
  19. Synthesis and stability of phospholipid-encapsulated nano-selenium
  20. Putative anti-proliferative effect of Indian mustard (Brassica juncea) seed and its nano-formulation
  21. Enrichment of low-grade phosphorites by the selective leaching method
  22. Electrochemical analysis of the dissolution of gold in a copper–ethylenediamine–thiosulfate system
  23. Characterisation of carbonate lake sediments as a potential filler for polymer composites
  24. Evaluation of nano-selenium biofortification characteristics of alfalfa (Medicago sativa L.)
  25. Quality of oil extracted by cold press from Nigella sativa seeds incorporated with rosemary extracts and pretreated by microwaves
  26. Heteropolyacid-loaded MOF-derived mesoporous zirconia catalyst for chemical degradation of rhodamine B
  27. Recovery of critical metals from carbonatite-type mineral wastes: Geochemical modeling investigation of (bio)hydrometallurgical leaching of REEs
  28. Photocatalytic properties of ZnFe-mixed oxides synthesized via a simple route for water remediation
  29. Attenuation of di(2-ethylhexyl)phthalate-induced hepatic and renal toxicity by naringin nanoparticles in a rat model
  30. Novel in situ synthesis of quaternary core–shell metallic sulfide nanocomposites for degradation of organic dyes and hydrogen production
  31. Microfluidic steam-based synthesis of luminescent carbon quantum dots as sensing probes for nitrite detection
  32. Transformation of eggshell waste to egg white protein solution, calcium chloride dihydrate, and eggshell membrane powder
  33. Preparation of Zr-MOFs for the adsorption of doxycycline hydrochloride from wastewater
  34. Green nanoarchitectonics of the silver nanocrystal potential for treating malaria and their cytotoxic effects on the kidney Vero cell line
  35. Carbon emissions analysis of producing modified asphalt with natural asphalt
  36. An efficient and green synthesis of 2-phenylquinazolin-4(3H)-ones via t-BuONa-mediated oxidative condensation of 2-aminobenzamides and benzyl alcohols under solvent- and transition metal-free conditions
  37. Chitosan nanoparticles loaded with mesosulfuron methyl and mesosulfuron methyl + florasulam + MCPA isooctyl to manage weeds of wheat (Triticum aestivum L.)
  38. Synergism between lignite and high-sulfur petroleum coke in CO2 gasification
  39. Facile aqueous synthesis of ZnCuInS/ZnS–ZnS QDs with enhanced photoluminescence lifetime for selective detection of Cu(ii) ions
  40. Rapid synthesis of copper nanoparticles using Nepeta cataria leaves: An eco-friendly management of disease-causing vectors and bacterial pathogens
  41. Study on the photoelectrocatalytic activity of reduced TiO2 nanotube films for removal of methyl orange
  42. Development of a fuzzy logic model for the prediction of spark-ignition engine performance and emission for gasoline–ethanol blends
  43. Micro-impact-induced mechano-chemical synthesis of organic precursors from FeC/FeN and carbonates/nitrates in water and its extension to nucleobases
  44. Green synthesis of strontium-doped tin dioxide (SrSnO2) nanoparticles using the Mahonia bealei leaf extract and evaluation of their anticancer and antimicrobial activities
  45. A study on the larvicidal and adulticidal potential of Cladostepus spongiosus macroalgae and green-fabricated silver nanoparticles against mosquito vectors
  46. Catalysts based on nickel salt heteropolytungstates for selective oxidation of diphenyl sulfide
  47. Powerful antibacterial nanocomposites from Corallina officinalis-mediated nanometals and chitosan nanoparticles against fish-borne pathogens
  48. Removal behavior of Zn and alkalis from blast furnace dust in pre-reduction sinter process
  49. Environmentally friendly synthesis and computational studies of novel class of acridinedione integrated spirothiopyrrolizidines/indolizidines
  50. The mechanisms of inhibition and lubrication of clean fracturing flowback fluids in water-based drilling fluids
  51. Adsorption/desorption performance of cellulose membrane for Pb(ii)
  52. A one-pot, multicomponent tandem synthesis of fused polycyclic pyrrolo[3,2-c]quinolinone/pyrrolizino[2,3-c]quinolinone hybrid heterocycles via environmentally benign solid state melt reaction
  53. Green synthesis of silver nanoparticles using durian rind extract and optical characteristics of surface plasmon resonance-based optical sensor for the detection of hydrogen peroxide
  54. Electrochemical analysis of copper-EDTA-ammonia-gold thiosulfate dissolution system
  55. Characterization of bio-oil production by microwave pyrolysis from cashew nut shells and Cassia fistula pods
  56. Green synthesis methods and characterization of bacterial cellulose/silver nanoparticle composites
  57. Photocatalytic research performance of zinc oxide/graphite phase carbon nitride catalyst and its application in environment
  58. Effect of phytogenic iron nanoparticles on the bio-fortification of wheat varieties
  59. In vitro anti-cancer and antimicrobial effects of manganese oxide nanoparticles synthesized using the Glycyrrhiza uralensis leaf extract on breast cancer cell lines
  60. Preparation of Pd/Ce(F)-MCM-48 catalysts and their catalytic performance of n-heptane isomerization
  61. Green “one-pot” fluorescent bis-indolizine synthesis with whole-cell plant biocatalysis
  62. Silica-titania mesoporous silicas of MCM-41 type as effective catalysts and photocatalysts for selective oxidation of diphenyl sulfide by H2O2
  63. Biosynthesis of zinc oxide nanoparticles from molted feathers of Pavo cristatus and their antibiofilm and anticancer activities
  64. Clean preparation of rutile from Ti-containing mixed molten slag by CO2 oxidation
  65. Synthesis and characterization of Pluronic F-127-coated titanium dioxide nanoparticles synthesized from extracts of Atractylodes macrocephala leaf for antioxidant, antimicrobial, and anticancer properties
  66. Effect of pretreatment with alkali on the anaerobic digestion characteristics of kitchen waste and analysis of microbial diversity
  67. Ameliorated antimicrobial, antioxidant, and anticancer properties by Plectranthus vettiveroides root extract-mediated green synthesis of chitosan nanoparticles
  68. Microwave-accelerated pretreatment technique in green extraction of oil and bioactive compounds from camelina seeds: Effectiveness and characterization
  69. Studies on the extraction performance of phorate by aptamer-functionalized magnetic nanoparticles in plasma samples
  70. Investigation of structural properties and antibacterial activity of AgO nanoparticle extract from Solanum nigrum/Mentha leaf extracts by green synthesis method
  71. Green fabrication of chitosan from marine crustaceans and mushroom waste: Toward sustainable resource utilization
  72. Synthesis, characterization, and evaluation of nanoparticles of clodinofop propargyl and fenoxaprop-P-ethyl on weed control, growth, and yield of wheat (Triticum aestivum L.)
  73. The enhanced adsorption properties of phosphorus from aqueous solutions using lanthanum modified synthetic zeolites
  74. Separation of graphene oxides of different sizes by multi-layer dialysis and anti-friction and lubrication performance
  75. Visible-light-assisted base-catalyzed, one-pot synthesis of highly functionalized cinnolines
  76. The experimental study on the air oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid with Co–Mn–Br system
  77. Highly efficient removal of tetracycline and methyl violet 2B from aqueous solution using the bimetallic FeZn-ZIFs catalyst
  78. A thermo-tolerant cellulase enzyme produced by Bacillus amyloliquefaciens M7, an insight into synthesis, optimization, characterization, and bio-polishing activity
  79. Exploration of ketone derivatives of succinimide for their antidiabetic potential: In vitro and in vivo approaches
  80. Ultrasound-assisted green synthesis and in silico study of 6-(4-(butylamino)-6-(diethylamino)-1,3,5-triazin-2-yl)oxypyridazine derivatives
  81. A study of the anticancer potential of Pluronic F-127 encapsulated Fe2O3 nanoparticles derived from Berberis vulgaris extract
  82. Biogenic synthesis of silver nanoparticles using Consolida orientalis flowers: Identification, catalytic degradation, and biological effect
  83. Initial assessment of the presence of plastic waste in some coastal mangrove forests in Vietnam
  84. Adsorption synergy electrocatalytic degradation of phenol by active oxygen-containing species generated in Co-coal based cathode and graphite anode
  85. Antibacterial, antifungal, antioxidant, and cytotoxicity activities of the aqueous extract of Syzygium aromaticum-mediated synthesized novel silver nanoparticles
  86. Synthesis of a silica matrix with ZnO nanoparticles for the fabrication of a recyclable photodegradation system to eliminate methylene blue dye
  87. Natural polymer fillers instead of dye and pigments: Pumice and scoria in PDMS fluid and elastomer composites
  88. Study on the preparation of glycerylphosphorylcholine by transesterification under supported sodium methoxide
  89. Wireless network handheld terminal-based green ecological sustainable design evaluation system: Improved data communication and reduced packet loss rate
  90. The optimization of hydrogel strength from cassava starch using oxidized sucrose as a crosslinking agent
  91. Green synthesis of silver nanoparticles using Saccharum officinarum leaf extract for antiviral paint
  92. Study on the reliability of nano-silver-coated tin solder joints for flip chips
  93. Environmentally sustainable analytical quality by design aided RP-HPLC method for the estimation of brilliant blue in commercial food samples employing a green-ultrasound-assisted extraction technique
  94. Anticancer and antimicrobial potential of zinc/sodium alginate/polyethylene glycol/d-pinitol nanocomposites against osteosarcoma MG-63 cells
  95. Nanoporous carbon@CoFe2O4 nanocomposite as a green absorbent for the adsorptive removal of Hg(ii) from aqueous solutions
  96. Characterization of silver sulfide nanoparticles from actinobacterial strain (M10A62) and its toxicity against lepidopteran and dipterans insect species
  97. Phyto-fabrication and characterization of silver nanoparticles using Withania somnifera: Investigating antioxidant potential
  98. Effect of e-waste nanofillers on the mechanical, thermal, and wear properties of epoxy-blend sisal woven fiber-reinforced composites
  99. Magnesium nanohydroxide (2D brucite) as a host matrix for thymol and carvacrol: Synthesis, characterization, and inhibition of foodborne pathogens
  100. Synergistic inhibitive effect of a hybrid zinc oxide-benzalkonium chloride composite on the corrosion of carbon steel in a sulfuric acidic solution
  101. Review Articles
  102. Role and the importance of green approach in biosynthesis of nanopropolis and effectiveness of propolis in the treatment of COVID-19 pandemic
  103. Gum tragacanth-mediated synthesis of metal nanoparticles, characterization, and their applications as a bactericide, catalyst, antioxidant, and peroxidase mimic
  104. Green-processed nano-biocomposite (ZnO–TiO2): Potential candidates for biomedical applications
  105. Reaction mechanisms in microwave-assisted lignin depolymerisation in hydrogen-donating solvents
  106. Recent progress on non-noble metal catalysts for the deoxydehydration of biomass-derived oxygenates
  107. Rapid Communication
  108. Phosphorus removal by iron–carbon microelectrolysis: A new way to achieve phosphorus recovery
  109. Special Issue: Biomolecules-derived synthesis of nanomaterials for environmental and biological applications (Guest Editors: Arpita Roy and Fernanda Maria Policarpo Tonelli)
  110. Biomolecules-derived synthesis of nanomaterials for environmental and biological applications
  111. Nano-encapsulated tanshinone IIA in PLGA-PEG-COOH inhibits apoptosis and inflammation in cerebral ischemia/reperfusion injury
  112. Green fabrication of silver nanoparticles using Melia azedarach ripened fruit extract, their characterization, and biological properties
  113. Green-synthesized nanoparticles and their therapeutic applications: A review
  114. Antioxidant, antibacterial, and cytotoxicity potential of synthesized silver nanoparticles from the Cassia alata leaf aqueous extract
  115. Green synthesis of silver nanoparticles using Callisia fragrans leaf extract and its anticancer activity against MCF-7, HepG2, KB, LU-1, and MKN-7 cell lines
  116. Algae-based green AgNPs, AuNPs, and FeNPs as potential nanoremediators
  117. Green synthesis of Kickxia elatine-induced silver nanoparticles and their role as anti-acetylcholinesterase in the treatment of Alzheimer’s disease
  118. Phytocrystallization of silver nanoparticles using Cassia alata flower extract for effective control of fungal skin pathogens
  119. Antibacterial wound dressing with hydrogel from chitosan and polyvinyl alcohol from the red cabbage extract loaded with silver nanoparticles
  120. Leveraging of mycogenic copper oxide nanostructures for disease management of Alternaria blight of Brassica juncea
  121. Nanoscale molecular reactions in microbiological medicines in modern medical applications
  122. Synthesis and characterization of ZnO/β-cyclodextrin/nicotinic acid nanocomposite and its biological and environmental application
  123. Green synthesis of silver nanoparticles via Taxus wallichiana Zucc. plant-derived Taxol: Novel utilization as anticancer, antioxidation, anti-inflammation, and antiurolithic potential
  124. Recyclability and catalytic characteristics of copper oxide nanoparticles derived from bougainvillea plant flower extract for biomedical application
  125. Phytofabrication, characterization, and evaluation of novel bioinspired selenium–iron (Se–Fe) nanocomposites using Allium sativum extract for bio-potential applications
  126. Erratum
  127. Erratum to “Synthesis, characterization, and evaluation of nanoparticles of clodinofop propargyl and fenoxaprop-P-ethyl on weed control, growth, and yield of wheat (Triticum aestivum L.)”
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