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Review

Photocatalysis as an Alternative for the Remediation of Wastewater: A Scientometric Review

by
Jhoan Mauricio Moreno-Vargas
1,
Laura Maria Echeverry-Cardona
1,
Darwin Augusto Torres-Ceron
1,2,3,*,
Sebastian Amaya-Roncancio
4,5,
Elisabeth Restrepo-Parra
1 and
Kevin Jair Castillo-Delgado
1
1
Plasma Physics Laboratory, Universidad Nacional de Colombia Sede Manizales, Manizales 170003, Colombia
2
Facultad de Ciencias Básicas, Universidad Tecnológica de Pereira, Pereira 660003, Colombia
3
Gestión & Medio Ambiente, Manizales 170004, Colombia
4
Natural and Exact Sciences Department, Universidad de la Costa, Barranquilla 080002, Colombia
5
PCM Computational Applications, Universidad Nacional de Colombia Sede Manizales, Manizales 170003, Colombia
*
Author to whom correspondence should be addressed.
ChemEngineering 2024, 8(5), 95; https://doi.org/10.3390/chemengineering8050095
Submission received: 27 May 2024 / Revised: 23 July 2024 / Accepted: 13 August 2024 / Published: 13 September 2024
Browse Figures
Versions Notes

Abstract

:
The objective of this study is to map, describe, and identify “water treatment using catalysts and/or nanomaterials” and their derivable aspects. A comprehensive search was conducted in academic databases such as WoS and Scopus, following the PRISMA methodology, to identify relevant studies published between 2010 and 2024. Inclusion and exclusion criteria were applied to select articles that address both experimental and theoretical aspects of photocatalysis in wastewater treatment. The methodology is developed through exploratory data analysis and the use of the Tree of Science algorithm. The first results indicate the roots, in which it is possible to gain knowledge of the environment for the implementation of a photoreactor it uses as a photocatalyst agent. A total of 94 relevant articles were identified. The results show that most studies focus on the degradation of organic pollutants using TiO2 as a photocatalyst. Additionally, there has been a significant increase in the number of publications and citations in recent years, indicating growing interest in this field. Then, in the trunk, some more solid ideas in terms of basic concepts, techniques and possible variations for the application of knowledge and development of future research related to the initial topic are indicated. Finally, through the leaves, new modifications and combinations of the photocatalytic materials are obtained, in search of improving their performance in terms of reduction in water contaminants. From the above, centrality in photocatalysis is identified as an alternative for water remediation using different photocatalysts. It is concluded that the total citation network contains, within the most important nodes, articles of high interest in the community, such as those authored by Zhang, Xiaofei; Nezamzadeh-Ejhieh, Alireza; or Li, Jingyi, from countries in the Middle East and the Asian continent, justified not only by the research capabilities of these countries, but also by the needs and problems that these regions face in terms of water scarcity. Future work indicates the need for and interest in improving various characteristics such as photocatalytic performance, the number of cycles that the material supports, and its reduction capacity in the presence of high concentrations of contaminants, with the intention of maximizing the benefits of its applicability in water treatment.

1. Introduction

Currently, there is a growing global problem due to the contamination of water sources, as a consequence of the presence of contaminants of various kinds such as emerging biological contaminants and heavy metals that generate great environmental, health, and economic impacts [1,2,3,4]. This contamination is generated by crude oil spills [5], poor disposal of waste [6], biological contamination transferred by maritime traffic, illegal refinery, and dyes used in the textile industry, among others, where many of these problems can be solved through scientific and technological research and development.
From the R + D + I system, the implementation of treatment technologies that reduce the number of contaminants present in water resources is generated. Currently there are different alternatives to treat various contaminants such as organic waste [7,8,9,10], pollutants in petroleum [11,12], heavy metals [13,14,15], microbiological contaminants found in bodies of water [16,17] and drug treatments [18,19,20]. However, many of these treatment systems are conventional and are not efficient due to the structural complexity or relative stability of many of these types of contaminants. This makes it necessary to develop and implement new modern treatment systems that combine conventional processes with physicochemical processes that seek the chemical transformation of contaminants. One of these treatments is heterogeneous photocatalysis, which belongs to the so-called advanced oxidation processes. (AOPs) [21,22,23,24].
For this process, different materials with suitable properties to act as catalysts are used, such as, for example, TiO2 [25,26,27] ZnO [28,29], CdO [30], SnO2 [31], iron oxides [32,33,34,35], and WO3 [25,36] ZnS [37]. Many of these materials have the ability to be excited with not very high energy light, absorbing part of the radiation of the solar spectrum that reaches the surface of the Earth (λ > 310 nm), which increases the interest in the possible use of sunshine. The most researched photocatalysts so far are broadband semiconductor metal oxides and especially TiO2, which is the most commonly used semiconductor in these types of processes, because it is low cost, non-toxic, insoluble in water and has a high chemical stability that makes it capable of producing electronic transitions by absorption of light in the closest ultraviolet (UV), allowing a reduction in the forbidden energy bandwidth (GAP) or by incorporating ions to improve the conductivity at active sites.
Taking this context into account, this article addresses the treatment of contaminated water using catalysts and nanomaterials. This treatment is carried out through a scientometric review, due to a large amount of research that has been carried out on this topic and in order to analyze the publications with the most impact in the Web of Science (WoS) and Scopus databases. The Tree of Science (ToS) is a methodological and systematic tool that, through a process analogous to that undertaken by trees in their development, classifies articles and the type of information provided by them into an initial, pioneering, and supportive group like the roots of the tree; into another central, strong, and highly relevant group like the trunk; and finally presents the branches of the tree, which represent the group of articles that bring novelty to the topic and set new trends and research lines around the treated subject, yet are supported and nourished by the work developed in the other components of the tree. This approach is widely used and versatile across different fields of knowledge, applicable in thematic areas such as education, marketing, administration, health, entrepreneurship, and natural sciences. The utility and versatility of ToS have been supported by previous research [38,39,40,41].
The ToS was applied to review the contributions of this topic over time and, finally, a cluster analysis was performed to study articles in different subareas. The rest of the article is organized as follows: first, a methodological part, where the process of selecting the published works is explained; this is followed by the results, showing the documents that are part of the root, trunk and leaves; and finally, the conclusion.

2. Methodology

In order to understand the scientific structure of the research field, a scientometric analysis was carried out in 2024, using Web of Science (WoS) (from 2004 to 2024) and Scopus (from 2004 to 2023). To identify the relevant articles in the remediation of contaminated water through physicochemical treatments, the search was divided into four parts according to the sections of the process: for the application part, the search commands ((remov* OR decomposition OR reducti* OR degrad* OR mineralization) were used; in the process variables, the search commands used were (chemical AND oxygen AND demand OR cod); for the synthesis method part, the search command was photocatal*; and finally, for the alternative solution, the search commands were (nanoparticles AND TiO2). It should be noted that, to execute these search parameters, it was necessary to merge and measure these databases through the development of exploratory data analysis (EDA) using scientometric tools such as Bibliometrix, thus facilitating the grouping of relevant data and references, as well as a complete description of the recent studies that allows a more efficient development of bibliometric analysis around the variable studied.
Table 1 outlines the primary parameters used. For example, to identify articles related to the role of the academic as a researcher, particular search terms were used in the title, abstract and keywords. WoS’s performance was 470 entries, while Scopus produced 167 entries. Although WoS returns a greater number of entries, it is still essential to incorporate Scopus due to the inclusion of 63 documents that are not present in WoS. The ‘bibliometrix’ and ‘tosr’ packages were used to consolidate data from both databases.
Figure 1 shows the general process to select the most relevant literature on the topic. Next, the PRISMA (Preferred Reporting Items for Systematic reviews and Meta-Analyses) flow proposed by Liberati et al. (2009) [42], where the refinement process of the documents to reach a highly useful and convenient sample for the analysis included in this article is described.
The network has 881 nodes (articles) and 2962 edges (links), and 60 relevant articles using in-degree and page rank metrics were identified. Then, 28 articles related to this research topic were manually selected. After removing duplicate documents, two authors reviewed the documents to identify reviews and unrelated documents to remove them from the list. A total of 22 articles not related to the main topic and 53 reviews were found. Unrelated documents were removed from this step because they collect documents that create new knowledge, but reviews do not generate new knowledge. Finally, there is a data set with 91,087 coded articles. The coded process is explained below.

3. Results

This section will provide a general overview of annual scientific production, production by country, authorship analysis, and journal analysis.

3.1. Scientometric Mapping and Scientific Production

Figure 2 shows the articles published per year in both Web of Science (WoS) and Scopus, as well as an analysis of total publications per year and total citations. In order to understand the different moments of the development of the topic over time [43,44], at least three stages that stand out for the productivity and its corresponding citation are shown in Figure 2, as follows:

3.1.1. (2000–2007) Initial Growth Phase

The initial growth phase, which goes from 2000 to 2007, is marked by the influential article by Chen et al. (2003) [45] that reports a study centered around the implementation of a photoreactor that uses nanostructured TiO2 materials as a photocatalyst agent, which, combined with an electrolysis system, allowed good performance in terms of a reduction in rhodamine 6G as a water contaminant. This article has had a substantial impact on the academic community, obtaining the highest number of citations in this phase with 130 mentions in other documents, and marking a trend or thematic segment in this chronological phase of the research development in this bibliometric report, since the majority of interactions carried out occurred around the application of TiO2 as a catalyst in water decontamination processes, thus evaluating different treatments that modify the base material already mentioned to improve its performance and photocatalytic behavior. Another notable contribution comes from Chen et al. (2004) [46] with 60 citations and from Li et al. (2007) [47] with 56 citations, who develop research regarding the decontamination and treatment of water contaminated with organic and inorganic products through the implementation of photocatalytic techniques developed with TiO2 base materials and enhanced by electrochemical processes with good performance. This phase represents a period of origin and thematic development, which justifies the low production of articles and perhaps the low citation of these in future works, due to their lack of academic maturity. However, they behave as a seed for the future development of research and academic production related to photocatalytic processes mediated by TiO2 as a base semiconductor.

3.1.2. (2008–2014) Thematic Development Phase

This second phase, between 2008 and 2014, presents a time period with much stronger growth in terms of scientific production than that presented in the first stage. Likewise, the research topic was reaching greater maturity, laying even more solid foundations in terms of basic concepts, techniques, and possible variations for the application of knowledge and development of future research related to the initial topic. The previous statements are supported by the fact that it is in this stage where the years with the highest number of citations are found, in relation to the number of publications carried out, as can be seen in Figure 2. In this chronological stage, the work developed by Maeda et al. (2009) [48] is found, which corresponds to the most cited article in this bibliometric report, with 648 citations. It addresses research related to photocatalytic processes mediated by a semiconductor material different from titanium dioxide, titanium nitride, and graphitic carbon, whose band gap is energetically lower than that of TiO2, and when doped with platinum or rhodium oxide, increases the performance and stability in the oxidation–reduction processes of water to obtain O2 or H2. Starting from the research reported in previously mentioned publications, the works published at this stage explore the application of different semiconductors for photocatalytic applications in water treatment, as conducted by Subash et al. (2013) [49], who synthesized a co-doped zirconium structure with silver and zinc oxide, trying to take advantage of the energetic interactions carried out between its valence and conduction bands, to favor photocatalytic processes of reduction in the contaminant Reactive Red 120 as a water contaminant; other relevant researches could be found in [50,51,52,53,54]. Better performances than those presented by other commercial materials were found, showing relevant and important results for the academic community, which led to it being cited 284 times by other authors.

3.1.3. (2015–2022) High Productivity Phase

In this stage, maximum productivity and thematic maturity are reached. The years with the greatest number of publications occur, which results in the years with the greatest number of citations. However, at this moment, the impact of these publications is lower, if the data from the existing relationship between the number of publications and the number of citations associated with them is analyzed. Nonetheless, this does not imply that, in the future, the number of citations of these articles will not increase, since they will be the basis and starting point for new and innovative research related to this field of knowledge.
At this stage, research reports predominate, in which the photocatalytic properties of materials used previously are studied and evaluated, but applied to new reduction processes or with modifications that aim at improving their response in the implemented processes. Likewise, the growing interest and relevance that the application of photocatalytic techniques has gained in the reduction in contaminants from the pharmaceutical industry is observed, taking into account that the articles with the greatest impact and with the greatest number of citations in this chronological stage of thematic development are referring to this topic. Such is the case of W-K. Jo [55] and T.S. Natarajan (2015) [56] who evaluated the impact of the morphology of TiO2-based nanostructured materials in interaction with graphitic carbon nitride for the reduction in isoniazid. They determined that the titanium dioxide nanotube morphology increases the surface area of the material and, at the same time, the photocatalytic response of the composite material. The studies carried out by Ahmadi et al. (2017) [57] and Deng et al. (2017) [58], are in this same thematic line. They report two different research projects focused on the treatment of water contaminated with tetracycline, some using a dioxide titanium structure as photocatalytic material with multi-walled carbon nanotubes. The others, using the AgIn5S8 structure with silver nanoparticles deposited on its surface to form a photocatalytic nanohybrid, obtained positive results in terms of photocatalytic reduction in the pharmaceutical contaminant; other relevant published information can be found in [55,56,57,58]. The reported documents report 269, 244, and 213 citations, respectively.
Figure 2 shows the annual distribution of publications and their respective citations from 2010 to 2024. Each bar represents the number of publications per year, while the superimposed line indicates the total citations received by these publications until the date of the search. This graph illustrates both the evolution of academic interest in the field and the cumulative impact of research over time.

3.2. Production by Countries

Country analysis is becoming a common scientometric technique for identifying the most productive places in the world on a specific topic. It is important to understand the dynamics of scientific production, and the quality and impact of research in the countries. This study shows the production (number of articles), the quality (according to Scimago metrics), and the impact (citations received) of research in a country. In addition, a collaboration network is created to understand the communities generated through interactions between researchers.
There are 45 countries that research and publish on the topic of photocatalysis as an alternative for water remediation. The first 10 are listed in Table 2. This list is organized according to the number of publications that represent the production of each country regarding the total number of records obtained in this search. These 10 countries represent 74.8% of scientific production on the subject, with Iran, India, and China being the countries that have the most significant contributions. This behavior can be explained because one of the most reported articles in these countries deals with the treatment of pharmaceutical wastewater with nanomaterials, especially contaminants such as tetracycline, binary mixture of dyes and 4-nitrophenol, presenting a high relationship with the proposed topic. In China, a behavior similar to what happens in Iran is reflected, where pharmaceutical waste has a great impact, but in this case conductive and semiconductor materials are used in order to evaluate the chemical reduction of oxygen, which is one of the response variables evaluated in the most cited articles in this country [45,58,59].
Finally, from the 14.53% of scientific production on the subject in India, according to the three articles with the most impact [45,60,61], it can be deduced that the main wastes to be intervened are those derived from tannery, which have been treated using nanomaterials that guarantee highly efficient, active, and reusable solar use. In the same line, other papers related to this subject can be found in [59,62,63].
The inter-relationships between countries and authors have been analyzed to understand the dynamics of collaboration in the field of photocatalysis applied to wastewater treatment. These inter-relationships are presented in Figure 3, which shows the co-authorship networks and international collaborations, respectively. Figure 3 illustrates the connections between authors who have collaborated on publications within this field. Nodes in the network represent authors, while the lines between them indicate co-authorships in scientific articles. The density of connections and the size of nodes are determined by the number of collaborations and the centrality of the author in the network, respectively. Figure 3 presents four subgroups of countries, and the inset figure of clusters by size shows a similar size among the four clusters. The internal figure of nodes and links over time shows the interaction between new countries and new relationships over time.

3.3. Production by Authors

Table 3 details the scientific production by authors in the field of photocatalysis for wastewater treatment, highlighting the main contributors and their impacts on research. It provides essential analysis of how individuals and groups have influenced trends and developments in this area. In the analysis of the production by authors (see Table 3) it is possible to notice that Nezamzadeh is the most relevant author in the topic addressed by this review. He holds number one in a number of publications and citations by other prominent authors in this field of knowledge. As an example of his work, the articles published in 2013 [64,65] are highlighted, in which he reports a pair of research works where he synthesized and characterized structures of nano-zeolite doped with nanostructured copper oxide, and cyclonoptilolite zeolite doped with copper sulfide. He evaluated their photocatalytic behavior in the reduction in methylene blue and rhodamine B for the first material, and methyl Orange and green bromocresol, one of the largest water pollutants from the textile industry. These research works allowed for a conclusion that the synthesized materials have photocatalytic potential for decontamination applications of industrial wastewater with the presence of dyes, and that the temperature and drying process of the material have an effect on the capacity to reduce contaminants.
Nezamzadeh continued his research on the topic of photocatalytic materials, and in 2014, he published another of his research works [66] in which, in a process similar to previous research, he synthesized a photocatalytic material and evaluated its performance in the reduction in water pollutants. On this occasion, he used a zeolite cyclonoptilolite structure doped with zinc oxide for the photoreduction of 4-nitrophenol, obtaining good results in terms of photocatalytic capacity and demonstrating the influence on the contaminant reduction process of parameters such as pH, the addition of electron acceptors, and the concentration of the contaminant in the aqueous medium to be treated. Furthermore, from the point of view of the impact of his publications (H-Index), Nezamzadeh also takes first place thanks to the fact that the number of publications carried out by this author is also accompanied by a significant number of citations.
Another relevant author with a high research impact on the topic related to this review is Krishnakumar, who, together with Subash, has a large number of citations and a high rate of co-authorships and research collaborations as well as published scientific articles. These authors have developed high-impact research that has already accumulated a significant number of citations. Among them, different works stand out in which they synthesized photocatalytic materials based on zinc and silver oxide nanostructures, doped with other metallic materials that generate modifications and energetic interactions in the photocatalyst, thus improving its performance in terms of reducing dyes present in wastewater from different industries [45,67,68]. In 2012, they synthesized a structure in which they added bromine to its base material and evaluated its performance in the reduction in the contaminant black acid-1. In 2013, they added zirconium to its base structure and evaluated its photocatalytic capacity in the reduction in the red reagent 120. In 2014, they synthesized zinc oxide by co-opting it with silver and gold, to be used as a photocatalyst in the mineralization of methylene blue. Finally, they concluded from their research that the addition of these metals to its base structure improves the performance of the photocatalyst in the reduction in contaminants, and also that factors such as the concentration of the contaminant in the aqueous medium can modify the performance of the mineralization process.
The approach to the key authors of research on the topic of this document can be obtained from Table 3, by identifying highly cited and collaborative communities. Two communities of research collaboration between highly related authors can be identified through citations in their works.
Community number one (olive color) appears as the larger in terms of the number of authors and impact with at least eight members. In this community, there are hegemonic surnames of recognized authors such as Wang and Li, with a high degree of impact on the community and who are highly connected even with other classic and seminal authors such as Zhang and Chen who have the highest degree of impact and belong to community 2 (lime green).

3.4. Production by Journals

In Table 4, regarding the publication of articles related to research on the topic addressed in this review, an important group of journals was found that concentrates a high number of publications associated with photocatalytic processes. Among the most relevant journals is DESALINATION AND WATER TREATMENT, a journal focused on the research and application of technologies related to water treatment, integrated water management, water reuse, wastewater, and topics related to environmental and energy problems. However, despite having the largest number of publications on the subject of the review, this journal, according to SRJ, is located in Q3 with an H-index of 83 (2009–2023), an impact factor of 1.0 (2023), and a CiteScore of 2.2. It has the most publications on the topic discussed. In this sense, the JOURNAL OF HAZARDOUS MATERIALS, according to SRJ, is located in Q1 with an H-index of 352 (1975–2024), and an impact factor of 12.2 (2023), and a CiteScore of 25.4. This journal can be cited, which occupies the highest position in terms of impact factor, and the second position in terms of the number of publications related to the topic under study. This is a journal that focuses on topics related to the areas of environmental science and engineering through the publication of complete research papers, review articles, and research perspectives that allow dangers and risks to be reduced. Finally, the CHEMICAL ENGINEERING JOURNAL, according to SRJ, is located in Q1 with an H-index of 309 (1992–2023), an impact factor of 13.3 (2023), and a CiteScore of 21.7. This journal can be mentioned, which is a journal focused on topics related to catalysis, chemical reaction engineering, environmental chemical engineering, ecological and sustainable science and engineering, and novel materials. Although this journal does not have the greatest number of publications or H-index, it does present the greatest impact factor among the journals that top the list of greatest bibliographic production on the related topic.

3.5. Tree of Science (ToS)

Figure 4 provides a graphical representation of the application of the literature recommendation algorithm (ToS) [41]. Specifically, for the field of photocatalytic processes, the development of the metaphor allows for identifying the thematic trends that are popular in the academic community. In this way, an exploration of the thematic branches proposed in the leaves, as recent studies, is developed. These connect with the documents that highlight the structure of the field coming from the trunk and in turn are connected with the foundational articles from the roots.

3.5.1. Classic Documents (Root)

The first results allow for identifying that the study and development around photocatalytic processes has attracted the attention of the research community, due to the diversity of applications that this physicochemical process has in the contemporary needs of humanity. Semiconductors appear as the preferred type of material to mediate photocatalytic processes, due to their properties and optoelectronic characteristics [76]. Photocatalytic processes are currently studied and applied in fields such as water decontamination, greenhouse gas reduction, organic compound elimination, and carbon dioxide methanation [64,66,73].
TiO2 is a semiconductor widely used to mediate photocatalytic processes due to its morphological, optical, and energetic properties. In this sense, studies are found, such as the one carried out by Konstantinou and Albanis (2004) [75], in which the behavior of TiO2 as a photocatalyst in the reduction in textile dyes was evaluated, identifying the influence on the process of parameters such as pH, concentration of catalyst, the concentration of the substrate, and the presence of electron acceptors such as hydrogen peroxide and ammonium persulfate, in addition to molecular oxygen. Likewise, Konstantinou and Albanis (2004) [75], studied the reactions and intermediate products in the photocatalytic reaction for pesticide removal, in which the evaluation of byproducts and toxicity measurements were the key actions to evaluate the overall process.
Although TiO2 presents good photocatalytic behavior due to its electronic and energetic properties, an effective relationship between its rutile and anatase phases and high surface area presents certain limitations for its use with sunlight because the prohibited energy of its band is greater than the energy that the visible range of radiation can provide. However, alternatives have been implemented such as the functionalization of nanometric-scale TiO2 with other materials. The studies developed by Pelaez et al. (2012) [77] and Asahi et al. (2001) [78] are an example of the alternative mentioned above. In these works, the best efficiency in terms of the photocatalytic properties of nitrogen doped with TiO2 nanoparticles was demonstrated, compared to pure TiO2 when mediating water decontamination processes.

3.5.2. Structural Documents (Trunk)

The study of photocatalytic materials has had great relevance in the field of technological research, mainly due to their application in water-cleaning and purification processes. In this sense, within the most relevant articles and works on this topic, studies can be found that evaluate performance, effectiveness, physicochemical processes, and different parameters that can influence the application of a variety of semiconductor materials as photocatalytic materials in water-cleaning processes and contaminant removal.
Nezamzadeh-Ejhieh and Salimi, (2010) [79] developed a work in which the efficiency of an aqueous CuO/X zeolite solution is evaluated in terms of photo-reduction of o-phenylenediamine (OPD), which is a contaminating aromatic amine, used as a component of polymers, drugs, glucose biosensing, as a mediator, and as a substrate for dyeing natural and synthetic fibers, including textiles. Furthermore, in search of counteracting the rapid recombination of electron–hole pairs in the photocatalytic material, they analyzed the effect of adding hydrogen peroxide and potassium bromate. They determined that the CuO/X zeolite, in the presence of ultraviolet light, presents a better degradation rate of o-phenylenediamine compared to pure CuO or pure zeolite X, thanks to the electronic and energetic interaction generated between these materials. Likewise, they verified the positive influence of hydrogen peroxide or potassium bromate on the photo-reduction of o-phenylenediamine, by increasing the number of electrons trapped by zeolite X, the generation of radicals, and other oxidizing species.
Subsequently, Nezamzadeh-Ejhieh and Karimi-Shamsabadi, (2013) [68] continued researching using the same photocatalytic material, CuO/X zeolite, for the reduction in other chemical contaminants, methylene blue and rhodamine B. Similar results to those found with o-phenylenediamine were obtained in this research, in which the CuO/X zeolite, in the presence of hydrogen peroxide or potassium bromate, presents good performance in the reduction in contaminants, as well as a depletion of less than 5% after four catalysis cycles. Likewise, they found a direct relationship between the drying temperature of the photocatalyst and its capacity to reduce contaminants, concluding that, at 200 °C, it presents better catalytic behavior.
Continuing with the same thematic trend around research in which semiconductor materials are intended to be used as catalysts in water-cleaning and decontamination processes, Krishnakumar et al. (2012) [73] carried out research in which they synthesized zinc oxide doped with silver bromide (AgBr-ZnO) through a simultaneous precipitation process from zinc oxalate and silver bromide. This material was used as a photocatalyst in the degradation of the Acid Black dye, in a process assisted by ultraviolet light, demonstrating better behavior in terms of reduction capacity than commercial materials such as ZnO. In addition, the parameters that influence the reduction process were analyzed. For example, they determined that the pH with the best results in the reduction of the dye was 12, and that, with an amount of 4g per liter, better results were also obtained. In this study it was found that the degradation of the dye occurs mainly on the surface of the synthesized catalyst material.
Finally, but with the same thematic approach, is the study developed by Subash et al. (2013) [49], in which they developed an active and reusable solar catalyst, Zr-loaded Ag-ZnO, for the degradation of the Reactive Red 120 dye. (RR 120). The catalyst was prepared by precipitation–thermal decomposition and was compared with other catalysts doped with a single metal and commercial catalysts, finding better performance for this material.
It can then be concluded that the strong, robust, and leading part of the research in this thematic field has focused on the study of the synthesis of compound semiconductor materials with photocatalytic properties that can be used in the purification and cleaning processes of water contaminated with dyes and other chemical elements from the industrial sector.

3.5.3. Emerging Trends Documents (Leaves and Branches)

In this section, where there are studies and publications that mark the most current and innovative trends in terms of the thematic section that is being analyzed, research in which a general overview is made of the conditions of the photocatalytic processes and possible materials to be used for the treatment of contaminated water during industrial processes that involve palm oil can be found. Nawaz et al. (2021) [70] developed a review article that seeks to collect information about how problems regarding inefficient sunlight or visible light can be used in photocatalytic processes, in the incomplete recovery of the photocatalysts after treatment, in the lack of understanding of the photocatalysis process, as well as in the parametric optimization of this process used for water purification, using the specific removal rate (mg of COD removed/g of catalyst h) to quantitatively compare the results obtained by different researchers.
Likewise, different research works, in which the synthesis, characterization, and evaluation of the photocatalytic behavior of some compound semiconductor materials in the cleaning and purification processes of contaminated water from the textile, pharmaceutical, and hospital industries, among others, are studied and compared. Such is the case of Suresh et al. (2014) [80] and Suresh et al. (2016) [81] who, through a simple microwave combustion process, were able to first synthesize zirconium oxide nanoparticles on an activated carbon structure. Then, they synthesized nanoparticles of nickel oxide on the same structure, to evaluate their potential as a catalyst in the ultraviolet light photo-reduction process of wastewater contaminated with dyes from the textile industry. It was demonstrated that the coordinated combination of the oxygen vacancy sites, the structural defects of the nanoparticles supported on the activated carbon, together with the electronic and energetic properties that these composite materials exhibit, and along with the presence of oxygen on the surface of the activated carbon, has led to long-lasting light absorption and delayed charge recombination.
In this same sense are the works carried out by Hemmatpour et al. (2022) [82] and Mehrabanpour et al. (2023) [69], who develop their research around the synthesis of cadmium sulfide nanoparticles coupled with bismuth vanadate nanoparticles and lead sulfide, respectively, in order to evaluate their properties as photocatalysts in the reduction in contaminated water. Hemmatpour et al. (2022) [82] evaluated their material in the reduction in contaminated water with Eriochrome Black T dye, determining better photocatalytic behavior in the compound than in the components separately from their matter. It was also found that for ratios from 3–4 to 1 of BiVO4 and CdS, there is a greater performance in reducing the contaminant. For its part, Mehrabanpour et al. (2023) [69] evaluated their material supported by clinoptilolite in a reduction in water contaminated by cefotaxime from the pharmacological or hospital industry; it showed enhanced photocatalytic activity compared to pure materials measured through the decrease in the chemical oxygen demand of the treated waters.
A study similar to the previous one, which intended to reduce contaminants from the pharmacological or hospital industry, was carried out by Yousefi et al. (2021) [83] in which they synthesized and characterized SnO2 and CuO nanoparticles through a hydrothermal process and coupled mechanically. These nanoparticles were implemented as a photocatalyst in the process of reducing water contaminated with phenazopyridine, varying the relationship between the molar concentration of its components, finding greater efficiency for the following conditions: Cpp: 5.5 ppm at pH = 7; irradiation time: 180 min; catalyst dose: 0.8 g/L. The efficiency of the process was measured by the variation in the intensity of the main peak of the HPLC measurement carried out on contaminated water, before and after treatment.
In addition to the studies mentioned above, the documents that report research in which titanium dioxide is used in different presentations to develop photocatalysis processes stand out. Wang et al. (2020) [84], for example, carried out a research in which they reviewed existing advances around the design and methods to improve the performance and possible application of electro-photocatalysis devices for the treatment of contaminated water at an industrial level, evaluating possible variations that modify the interfacial interaction of the materials, in addition to the energetic and electronic conditions that facilitate the catalytic process, such as the reduction in the gap of the materials, or the shift of the maximum absorption of radiation to wavelengths within the visible range.
There is also the research carried out by Kaur et al. (2018) [85] in which, to treat water contaminated with the benzimidazole fungicide Carbendazim, different ceramic materials were synthesized in the form of beads immobilized with titanium dioxide and titanium dioxide doped with iron. Five materials were used to make the ceramic beads: cement, white cement, plaster of Paris, clay, and sand mixed with Portland cement. After the ceramic beads were obtained, the TiO2 and TiO2-Fe particles were immobilized on them through heat fixation, and they were placed in a flat plate reactor. It was found that the ceramic material increased the surface area of the catalyst, significantly benefiting the photocatalysis process. In addition, the Fe-TiO2-coated clay beads had maximum photoactivity under sunlight 87 ± 1% average. The high stability of the materials was also observed, supporting up to 40 cycles of photocatalysis.
In line with the trend in terms of the most frequent applications of catalytic materials in this bibliographic review, the use of composite or TiO2-based materials for the purification or cleaning processes of water contaminated by dyes or products from the textile industry was also found. Natarajan et al. (2013) [86] utilized titanium oxide-based nanomaterials with tubular shapes, with bismuth doping, through sol–gel and hydrothermal methods. This composite nanomaterial was used as a mediator in the photo-degradation of the Rhodamine B dye, demonstrating the following: high effectiveness in terms of reducing this contaminant compared to pure titanium oxide; an increase in the surface area with the addition of bismuth, explained by the change in firm from titanium oxide nanoparticles to titanium nanotubes; and a complete reduction in the contaminant after 3 h of reaction.
Likewise, the research developed by Zarrin and Heshmatpour, (2020) [87] and Bashir et al. (2021) [88] was found, in which they synthesize TiO2-based materials combined with different materials in order to modify their electronic structure, energy behavior, surface area, and consequently its photocatalytic capacity in reducing water contaminated by dyes. Zarrin and Heshmatpour, (2020) [87] on the other hand, designed nanohybrids of graphene dioxide doped with different additives such as niobium oxide, tin (IV) oxide (SnO2), reduced graphene oxide, and ceramics (SiO2/Fe3O4/ZrO2), through the hydrothermal and sol–gel methods already mentioned in other research works. Moreover, Bashir et al. (2021) [88] added nickel (Ni) and praseodymium (Pr3+) ions to titanium dioxide, generating a decrease to almost half of the initial size of the material particles, which benefits the catalytic processes that titanium can develop, by increasing its total surface area. Finally, both research works obtained encouraging results regarding the photoreduction of the organic dyes crystal violet and methyl orange for the materials synthesized by Zarrin and Heshmatpour, (2020) [87], and of the reactive blue-19, reactive orange-13, and reactive blue-13 dyes, for which reductions of 99.0%, 70.0% and 85.0% were obtained, respectively, by the material synthesized by Bashir et al. (2021) [88].
In the section corresponding to the branches of the tree or thematic lines (see Figure 5), four communities can be found that are related through citations and references between articles. These communities can be classified into four topics with relevant key words, such as water, hazard, photobio, and environmental. Among the articles from all the communities, the document published by Fujishima and Honda (1971) [89] stands out. This article corresponds to community 4; it is the article with the highest number of historical citations on the topic covered. It addresses the thematic basis of the phenomenon of photo-generation of the electron–hole pair in semiconductors such as TiO2, without the need to imprint a potential difference in the electronic conduction process. Another research that needs to be highlighted, due to its number of citations and general relevance to the communities, corresponds to the work presented by Hoffmann et al. (1995) [74] belonging to community 1, who developed a very complete report in which different topics are related to the application of semiconductors, such as TiO2 as catalysts. In this article, they discuss topics that include generalities and theoretical bases of photocatalysis in semiconductors, photocatalytic properties of quantum semiconductors, modifications to semiconductors in search of improving their photocatalytic properties, doping with nanomaterials, important process variables in catalytic reactions, and a general review of the reactors implemented to develop photocatalysis with a semiconductor. This is an article of utmost importance and a mandatory reference for anyone carrying out research on this topic.
With great relevance to the level of interactions and citations, the research article carried out by Shannon et al. (2008) [90] is found in community 2. They develop a thematic review regarding the techniques, treatments, and alternatives developed or put into practice for the treatment of contaminated water, a topic closely related to one of the main applications of semiconductor materials with photocatalytic characteristics studied in this bibliometric analysis. As the main exponent of community 3 is the work by Neppolian (2002) [91], who carried out a very consistent study of the topic around which this bibliographic review and analysis is developed. In this article, a comparison is made in terms of photoreduction performance between TiO2 and other semiconductors such as ZnO, ZrO2, and WO3, which also present photocatalytic characteristics, but none with better results than TiO2. In order to analyze this behavior, the materials were tested as catalysts in the reduction process of three dyes from the textile industry: yellow reagent 17, blue reagent 4 and red reagent 2, all in the presence of solar irradiation. In this research, greater photo-degradation is reported for the red reactive dye, in addition to an optimal pH for the process ranging between 11 and 13, and ideal catalyst concentrations of m 8 × 10−4 to 1.2 × 10−3 M for the yellow reagent, 4.16 × 10−4 to 1.25 × 10−3 M for the red reagent, and 1 × 10−4 to 5 × 10−4 M for the blue reagent.
Chemengineering 08 00095 g005
Figure 5. Citation network. Source: Authors’ construction based on Gephi and RStudio [74,76,89,90,92].
Figure 5. Citation network. Source: Authors’ construction based on Gephi and RStudio [74,76,89,90,92].
Chemengineering 08 00095 g005

4. Conclusions

A bibliographic review was developed that allows the scientific community to obtain an idea of the current state and trajectory of research on the topic related to this article. For this purpose, it all started with a seed that provided results in two scientific databases, Web of Science and Scopus, yielding a series of results that were analyzed using ‘bibliometrix’ and ‘tosr’. From the results, an evolutionary trend in the subject was identified based on the root documents, which address topics related to basic concepts of the photocatalytic process as an alternative for the treatment of contaminated water, transcending the application of structures based on titanium dioxide with different doping, for its application mainly in the reduction in water contaminated with dyes and dyes from the textile industry, to finally reach a final stage in which new modifications and combinations in photocatalytic materials are researched, with the aim of improving their performance in terms of reducing water contaminants.
Likewise, the thematic–chronological maturation process was evident, which was divided into three stages, from 2000 to 2007, from 2008 to 2014, and from 2015 to 2024. These stages are divided into an initial period of low production but a high number of citations for the few published articles that served as a theoretical basis and starting point for future research; followed by a period in which, although the number of publications increased, the increase in citations associated with these documents was substantially greater; and concluding with a stage in which the increase in scientific production around this topic was much greater, but the relationship between the number of publications and the number of citations was lower. Moreover, it was possible to demonstrate the important contributions in terms of scientific production from countries in the Middle East and the Asian continent, justified not only by the research capabilities of these countries, but also by the needs and problems faced by these regions regarding water scarcity.
All this research production allows for noticing a marked trend in future research, towards studying the synthesis and application of new combinations of photocatalytic materials or different treatments to materials that already work, to improve their performance and diversify the water contaminants that can be treated with these photocatalysts.

Author Contributions

J.M.M.-V.: interpreted, conceptualized, corrected, and completed the final manuscript, L.M.E.-C.: interpreted, conceptualized, corrected, and completed the final manuscript, D.A.T.-C.: writing—original draft, review and editing, S.A.-R.: writing—original draft, review and editing, E.R.-P.: provided technical corrections and suggestions for the final manuscript and K.J.C.-D.: writing—original draft. All authors have read and agreed to the published version of the manuscript.

Funding

This work was carried out using internal resources of the laboratory and with the support of the National University of Colombia.

Data Availability Statement

The original contributions presented in the study are included in the article, further inquiries can be directed to the corresponding authors.

Acknowledgments

The authors thank Universidad Nacional de Colombia, Manizales Campus for the financial support of Minciencias within the framework of the program “Convocatoria nacional para el fortalecimiento de la investigación, la creación y la innovación en las sedes de presencia nacional de la Universidad Nacional de Colombia 2019–2021 (Sede Tumaco)”, and D.A. Torres-Ceron thanks to Universidad Nacional de Colombia, Manizales Campus for the financial support of the “Implementación de tecnologías limpias para el tratamiento de superficies para el sector de la galvanotecnia, con énfasis en la gestión de residuos y eficiencia hídrica y ambiental para la industria en Caldas, Código BPIN: 2021000100388”.

Conflicts of Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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Chemengineering 08 00095 g001
Figure 1. PRISMA Flow. Source: authors’ construction based on Liberati et al. (2009) [42].
Figure 1. PRISMA Flow. Source: authors’ construction based on Liberati et al. (2009) [42].
Chemengineering 08 00095 g001
Chemengineering 08 00095 g002
Figure 2. Annual trends in publications and citations in photocatalysis for wastewater treatment. Measurement of scientific production. Source: authors’ construction based on AED.
Figure 2. Annual trends in publications and citations in photocatalysis for wastewater treatment. Measurement of scientific production. Source: authors’ construction based on AED.
Chemengineering 08 00095 g002
Chemengineering 08 00095 g003
Figure 3. Collaboration between countries. Source: authors’ construction based on Biblioshiny and AED.
Figure 3. Collaboration between countries. Source: authors’ construction based on Biblioshiny and AED.
Chemengineering 08 00095 g003
Chemengineering 08 00095 g004
Figure 4. Tree of Science. Source: authors’ construction based on AED and ToS [68,69,70,71,72,73,74,75,76].
Figure 4. Tree of Science. Source: authors’ construction based on AED and ToS [68,69,70,71,72,73,74,75,76].
Chemengineering 08 00095 g004
Table 1. Search parameters. * Note 104 duplicates.
Table 1. Search parameters. * Note 104 duplicates.
DatabasesWeb of ScienceScopus
Consultation Period (in Years)2004–20242003–2023
Consultation date16 June 2024
Document TypeArticle, book, chapter and review.
Magazine TypeAll types
Search FieldsTITLE-ABS-KEY
Search Terms(((remov* OR decomposition OR reducti* OR degrad* OR mineralization) AND (chemical AND oxygen AND demand OR cod) AND photocatal* AND (nanoparticles AND tio2)))
Results529196
Total Results645
Table 2. Most productive countries.
Table 2. Most productive countries.
CountriesProductionCitationQ1Q2Q3Q4
Iran132(20.4%)4409(22.47%)552261
India125(19.32%)3307(16.85%)432743
China94(14.53%)2992(15.25%)481383
Egypt26(4.02%)667(3.4%)8620
Korea24(3.71%)957(4.88%)10400
Malaysia21(3.25%)790(4.03%)7910
USA18(2.78%)1081(5.51%)11113
Pakistan16(2.47%)215(1.1%)2531
Saudi Arabia14(2.16%)538(2.74%)8100
South Africa14(2.16%)219(1.12%)4410
Source: authors’ construction based on RStudio and AED.
Table 3. Top production by author. Source: authors’ construction based on RStudio, Biblioshiny, and EDA.
Table 3. Top production by author. Source: authors’ construction based on RStudio, Biblioshiny, and EDA.
N°ResearcherFiles in SeedScopus ArticlesCo-AuthorsTopicsTotal Citation
Documents		Scopus H-IndexAffiliation
1Nezamzadeh-Ejhieh, Alireza172011573110,18766Islamic Azad University, Shahreza Branch, Shahreza, Iran
2Balu, Krishnakumar139310515318930Universidad de Sevilla, Sevilla, Spain
3Subash, Balu1346475167020St. Joseph’s College of Engineering, Chennai, India
4Shanthi, Manohar1261529197523Annamalai University, Chidambaram, India
5Swaminathan, Meenakshisundaram1225219534993352Kalasalingam Academy of Research and Education, Krishnankoil, India
6Zhang, Xiaofei1119661191414Shandong University, Jinan, China
7Arami, Mokhtar71521028910256Amirkabir University of Technology, Tehran, Iran
8Li, Jingyi731555124415Inner Mongolia University China, Hohhot, China
9Li, Yancai734479102719Fujian Province Key Laboratory of Modern Analytical Science and Separation Technology, Zhangzhou, China
10Suganthi, Ayyadurai R.Baby7706229215729Thaiyaharajar College, Madurai, India
Table 4. Ranking of journals.
Table 4. Ranking of journals.
JournalWosScopusTotal%H-Index/CoverageSJR_QImpact Factor/Year
Desalination and water treatment257260.0583 (2009–2023)Q31.20 (2023)
Journal of hazardous materials188190.04352 (1975–2024)Q112.20 (2023)
Environmental science and pollution research183170.03179 (1994–2023)Q15.80 (2022)
Journal of environmental chemical engineering134150.03127 (2013–2023)Q17.40 (2023)
Chemical engineering journal133140.03309 (1992–2023)Q113.30 (2023)
Chemosphere95130.02311 (1972–2023)Q18.10 (2023)
Journal of materials science-materials in electronics10-100.0297 (1990–2023)Q22.80 (2023)
Journal of water process engineering93100.0289 (2014–2023)Q16.30 (2023)
Journal of environmental management83100.02243 (1977–2023)Q18.00 (2023)
Journal of photochemistry and photobiology a-chemistry9-80.02176 (1987–2024)Q24.10 (2023)
Source: Scimago Journal Ranking and AED.
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Moreno-Vargas, J.M.; Echeverry-Cardona, L.M.; Torres-Ceron, D.A.; Amaya-Roncancio, S.; Restrepo-Parra, E.; Castillo-Delgado, K.J. Photocatalysis as an Alternative for the Remediation of Wastewater: A Scientometric Review. ChemEngineering 2024, 8, 95. https://doi.org/10.3390/chemengineering8050095

AMA Style

Moreno-Vargas JM, Echeverry-Cardona LM, Torres-Ceron DA, Amaya-Roncancio S, Restrepo-Parra E, Castillo-Delgado KJ. Photocatalysis as an Alternative for the Remediation of Wastewater: A Scientometric Review. ChemEngineering. 2024; 8(5):95. https://doi.org/10.3390/chemengineering8050095

Chicago/Turabian Style

Moreno-Vargas, Jhoan Mauricio, Laura Maria Echeverry-Cardona, Darwin Augusto Torres-Ceron, Sebastian Amaya-Roncancio, Elisabeth Restrepo-Parra, and Kevin Jair Castillo-Delgado. 2024. "Photocatalysis as an Alternative for the Remediation of Wastewater: A Scientometric Review" ChemEngineering 8, no. 5: 95. https://doi.org/10.3390/chemengineering8050095

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