Pub Date : 2025-02-03DOI: 10.1016/j.ceja.2025.100713
Martin Keller , Shih-Yuan Chen , Atul Sharma
NH3 and CO2 can react to produce syngas (H2 + CO), which serves as a feedstock for the production of chemicals or synthetic fuels. Combining NH3 cracking (NH3 → 0.5N2 + 1.5H2) and the redox-mediated reverse water gas shift reaction (RWGS, CO2 + H2 → CO + H2O), we propose the “NH3-RWGS” process in a two-reactor system that can produce N2-free syngas without requiring a downstream gas separation step. We investigate the role of La0.75Sr0.25Cr0.5Mn0.5O3−δ (LSCM) in the redox-mediated RWGS, combined with a stabilized Ni catalyst to impart NH3 cracking functionality. The mixture of LSCM and Ni catalyst at a weight ratio of 10:1 increases the NH3 cracking activity fivefold compared to using only LSCM. Because the reduction of LSCM proceeds through a two-step mechanism that requires the prior cracking of NH3, it also substantially increases the redox reactivity of LSCM. The Ni catalyst exhibits undesirable nitrogen uptake at ∼500 °C, and the redox capacity of LSCM with NH3 and CO2 decreases with temperature. Therefore, the process is best implemented at ∼600 °C. Under these conditions, the application of the “NH3-RWGS” process with mixtures of LSCM and Ni catalyst is promising to produce high-quality, N2-free syngas directly from NH3 and CO2.
{"title":"Redox-mediated reverse water gas shift integrated with ammonia cracking over Ni/La0.75Sr0.25Cr0.5Mn0.5O3−δ","authors":"Martin Keller , Shih-Yuan Chen , Atul Sharma","doi":"10.1016/j.ceja.2025.100713","DOIUrl":"10.1016/j.ceja.2025.100713","url":null,"abstract":"<div><div>NH<sub>3</sub> and CO<sub>2</sub> can react to produce syngas (H<sub>2</sub> + CO), which serves as a feedstock for the production of chemicals or synthetic fuels. Combining NH<sub>3</sub> cracking (NH<sub>3</sub> → 0.5N<sub>2</sub> + 1.5H<sub>2</sub>) and the redox-mediated reverse water gas shift reaction (RWGS, CO<sub>2</sub> + H<sub>2</sub> → CO + H<sub>2</sub>O), we propose the “NH<sub>3</sub>-RWGS” process in a two-reactor system that can produce N<sub>2</sub>-free syngas without requiring a downstream gas separation step. We investigate the role of La<sub>0.75</sub>Sr<sub>0.25</sub>Cr<sub>0.5</sub>Mn<sub>0.5</sub>O<sub>3−δ</sub> (LSCM) in the redox-mediated RWGS, combined with a stabilized Ni catalyst to impart NH<sub>3</sub> cracking functionality. The mixture of LSCM and Ni catalyst at a weight ratio of 10:1 increases the NH<sub>3</sub> cracking activity fivefold compared to using only LSCM. Because the reduction of LSCM proceeds through a two-step mechanism that requires the prior cracking of NH<sub>3</sub>, it also substantially increases the redox reactivity of LSCM. The Ni catalyst exhibits undesirable nitrogen uptake at ∼500 °C, and the redox capacity of LSCM with NH<sub>3</sub> and CO<sub>2</sub> decreases with temperature. Therefore, the process is best implemented at ∼600 °C. Under these conditions, the application of the “NH<sub>3</sub>-RWGS” process with mixtures of LSCM and Ni catalyst is promising to produce high-quality, N<sub>2</sub>-free syngas directly from NH<sub>3</sub> and CO<sub>2</sub>.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"22 ","pages":"Article 100713"},"PeriodicalIF":5.5,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143373018","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-02DOI: 10.1016/j.ceja.2025.100712
Josef Marousek , Beata Gavurova , Anna Marouskova , Babak Minofar
Portland cement (PC) production is a major contributor to environmental pollution due to its resource and energy – intensive nature, ranking as the 3rd largest source. Humans excrete approximately 5 g of phosphorus (P) day-1, which is often precipitated by salts into hardly applicable minerals such as struvite (in developed countries) or contributes to eutrophication (in developing countries). Worldwide, biogas plants produce a billion tons of digestate daily. Proposed solutions involve dewatering, charring and activation of digestate that is subsequently used to sorb P from wastewater and used as a PC substitute. Unique laboratory findings indicate that iron phosphates (FeP) on charred digestate can enhance concrete strength parameters (up to 80 %); reducing weight (- 18 %) and production cost (- 4 %) while turning carbon emissions into carbon sequestration. The mechanisms behind the experimental results are investigated through molecular modeling. It is revealed that interactions of char and FeP enhance aggregates, forming stronger contact ion pairs and increasing concrete strength and durability. Although the concept brings many technical, economic, and environmental improvements, further analyses are needed, especially regarding scaling up and the durability of the concrete.
{"title":"Techno-economic aspects of concrete lightweighting by char enrichment with phosphates from wastewater","authors":"Josef Marousek , Beata Gavurova , Anna Marouskova , Babak Minofar","doi":"10.1016/j.ceja.2025.100712","DOIUrl":"10.1016/j.ceja.2025.100712","url":null,"abstract":"<div><div>Portland cement (PC) production is a major contributor to environmental pollution due to its resource and energy – intensive nature, ranking as the 3rd largest source. Humans excrete approximately 5 g of phosphorus (P) day<sup>-1</sup>, which is often precipitated by salts into hardly applicable minerals such as struvite (in developed countries) or contributes to eutrophication (in developing countries). Worldwide, biogas plants produce a billion tons of digestate daily. Proposed solutions involve dewatering, charring and activation of digestate that is subsequently used to sorb P from wastewater and used as a PC substitute. Unique laboratory findings indicate that iron phosphates (FeP) on charred digestate can enhance concrete strength parameters (up to 80 %); reducing weight (- 18 %) and production cost (- 4 %) while turning carbon emissions into carbon sequestration. The mechanisms behind the experimental results are investigated through molecular modeling. It is revealed that interactions of char and FeP enhance aggregates, forming stronger contact ion pairs and increasing concrete strength and durability. Although the concept brings many technical, economic, and environmental improvements, further analyses are needed, especially regarding scaling up and the durability of the concrete.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"22 ","pages":"Article 100712"},"PeriodicalIF":5.5,"publicationDate":"2025-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143378660","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-29DOI: 10.1016/j.ceja.2025.100711
Congshu Huang , Jiu-Long Li , Tongli Liu , Xiyu Yang , Zhipeng Xie , Jingjing Wang , Haiyan Zhuang , Junhao Xue , Weifeng Bu
Spiropyran is a well-established photochromic material. However, its intrinsic structural limitations render it challenging to exhibit ideal photochromic properties in its pure solid state. Typically, the photochromic properties in its solid state can only be achieved by introducing large steric hindrance groups, which may impede their further development. In this article, we proposed a novel design strategy by embedding several electron-deficient aza-aromatic rings to construct serial donor-acceptor (D-A) conjugated spiropyran derivatives (SP-3Py, SP-Py, and SP-Md). This approach not only provides sufficient free space for effective photoisomerization in the solid state but also effectively improves their π-electron delocalization ability via the electron-deficient nitrogen heterocyclic properties, which can significantly enhance their photochromic rate. The three aza-aromatic spiropyran derivatives exhibited rapid solid-state photoresponsivity (5–10 s) and excellent photochromic performance through the above synergistic strategies. Moreover, the D-A building block of the aza-aromatic spiropyrans can markedly tune their color-switching range. Following irradiation, all the aza-aromatic spiropyrans exhibited a blue color, potentially expanding their application fields. Our investigation indicates that introducing aza-aromatic rings to construct D-A-type spiropyrans can significantly enhance their solid-state photochromic performance, even without strong electron-deficient moieties or large steric hindrance groups, providing a concise and efficient strategy for the design of high-performance solid-state photochromic spiropyran derivatives.
{"title":"Aza-aromatic spiropyrans: An efficient strategy to achieve rapid solid state photochromic response by the synergistic effect of enhanced π-electron delocalization ability and free volume","authors":"Congshu Huang , Jiu-Long Li , Tongli Liu , Xiyu Yang , Zhipeng Xie , Jingjing Wang , Haiyan Zhuang , Junhao Xue , Weifeng Bu","doi":"10.1016/j.ceja.2025.100711","DOIUrl":"10.1016/j.ceja.2025.100711","url":null,"abstract":"<div><div>Spiropyran is a well-established photochromic material. However, its intrinsic structural limitations render it challenging to exhibit ideal photochromic properties in its pure solid state. Typically, the photochromic properties in its solid state can only be achieved by introducing large steric hindrance groups, which may impede their further development. In this article, we proposed a novel design strategy by embedding several electron-deficient aza-aromatic rings to construct serial donor-acceptor (D-A) conjugated spiropyran derivatives (SP-3Py, SP-Py, and SP-Md). This approach not only provides sufficient free space for effective photoisomerization in the solid state but also effectively improves their π-electron delocalization ability via the electron-deficient nitrogen heterocyclic properties, which can significantly enhance their photochromic rate. The three aza-aromatic spiropyran derivatives exhibited rapid solid-state photoresponsivity (5–10 s) and excellent photochromic performance through the above synergistic strategies. Moreover, the D-A building block of the aza-aromatic spiropyrans can markedly tune their color-switching range. Following irradiation, all the aza-aromatic spiropyrans exhibited a blue color, potentially expanding their application fields. Our investigation indicates that introducing aza-aromatic rings to construct D-A-type spiropyrans can significantly enhance their solid-state photochromic performance, even without strong electron-deficient moieties or large steric hindrance groups, providing a concise and efficient strategy for the design of high-performance solid-state photochromic spiropyran derivatives.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"22 ","pages":"Article 100711"},"PeriodicalIF":5.5,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142947","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-27DOI: 10.1016/j.ceja.2025.100710
Tibo De Saegher , Jonas Elmroth Nordlander , Filip Hallböök , Boyana Atanasova , Pieter Vermeir , Kevin M. Van Geem , Jeriffa De Clercq , An Verberckmoes , Christian Hulteberg , Jeroen Lauwaert
Mild reductive catalytic depolymerization (MRCD) of lignin offers a sustainable route to produce functionalized aromatic compounds. However, the economic viability is hindered by the need for expensive palladium (Pd) catalysts and the limited exploration of continuous flow reactors (CFRs), which are essential to achieve an adequate production scale. This study examines the impact of partial replacement of Pd with copper (Cu) on the performance, selectivity, active site characteristics, and deactivation of a γ-Al2O3 supported Pd catalyst in MRCD of lignin using a CFR. Despite containing 49 % less Pd, the PdCu catalyst achieves the same depolymerization degree as the Pd catalyst over 200 min of time on stream. During the reaction, metallic Pd is formed within the Pd catalyst and both a smaller (unordered) and larger (ordered FCC) metallic PdCu phase within the PdCu catalyst. The enhanced performance of the PdCu catalyst is attributed to synergistic effects between Pd and Cu and presence of differently sized metallic phases. A minimal impact of Cu on the selectivity, even in monomer yields, was observed. For both catalysts, the primary cause of deactivation is the hydration of the γ-Al2O3 support to boehmite, leading to loss of its acidity and morphological changes. Metal leaching and poisoning are insignificant, while nanoparticle growth likely arises from the reduction of the metallic phases during reaction. Only a very small amount of coke deposition is observed. Overall, the cost-effective partial replacement of Pd with of Cu forms metallic PdCu alloys during the reaction, enhancing activity without adversely affecting selectivity or deactivation.
{"title":"Mild reductive catalytic depolymerization of lignin in a continuous flow reactor using a Cu-enhanced Pd catalyst","authors":"Tibo De Saegher , Jonas Elmroth Nordlander , Filip Hallböök , Boyana Atanasova , Pieter Vermeir , Kevin M. Van Geem , Jeriffa De Clercq , An Verberckmoes , Christian Hulteberg , Jeroen Lauwaert","doi":"10.1016/j.ceja.2025.100710","DOIUrl":"10.1016/j.ceja.2025.100710","url":null,"abstract":"<div><div>Mild reductive catalytic depolymerization (MRCD) of lignin offers a sustainable route to produce functionalized aromatic compounds. However, the economic viability is hindered by the need for expensive palladium (Pd) catalysts and the limited exploration of continuous flow reactors (CFRs), which are essential to achieve an adequate production scale. This study examines the impact of partial replacement of Pd with copper (Cu) on the performance, selectivity, active site characteristics, and deactivation of a γ-Al<sub>2</sub>O<sub>3</sub> supported Pd catalyst in MRCD of lignin using a CFR. Despite containing 49 % less Pd, the PdCu catalyst achieves the same depolymerization degree as the Pd catalyst over 200 min of time on stream. During the reaction, metallic Pd is formed within the Pd catalyst and both a smaller (unordered) and larger (ordered FCC) metallic PdCu phase within the PdCu catalyst. The enhanced performance of the PdCu catalyst is attributed to synergistic effects between Pd and Cu and presence of differently sized metallic phases. A minimal impact of Cu on the selectivity, even in monomer yields, was observed. For both catalysts, the primary cause of deactivation is the hydration of the γ-Al<sub>2</sub>O<sub>3</sub> support to boehmite, leading to loss of its acidity and morphological changes. Metal leaching and poisoning are insignificant, while nanoparticle growth likely arises from the reduction of the metallic phases during reaction. Only a very small amount of coke deposition is observed. Overall, the cost-effective partial replacement of Pd with of Cu forms metallic PdCu alloys during the reaction, enhancing activity without adversely affecting selectivity or deactivation.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"22 ","pages":"Article 100710"},"PeriodicalIF":5.5,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142946","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-21DOI: 10.1016/j.ceja.2025.100709
Zhendong Li , Wei Ye , Huiting Li , Jianzhe Qiao , Yunyi Du , Zhujun Dong , Lichun Fu , Yuwei Pan
Zero-valent iron (ZVI) is a widely employed material for environmental remediation due to its capability to effectively degrade or reduce various pollutants. The enhancement of its reactivity and applicability can be achieved through chemical surface modification. Chemical surface modification involves introducing specific chemical functional groups onto the surface of ZVI, altering its surface chemical properties and structural morphology. This article provides an overview of the advancements made in four commonly used chemical modifications of ZVI, namely ZVI sulfide, ZVI silicide, ZVI oxalate, and ZVI phosphate. The review examines the impacts of these four different modified compounds on the surface structure and reactivity of ZVI, as well as elucidates the mechanisms by which modified ZVI interacts with and removes pollutants. Furthermore, the article discusses the prospects and challenges associated with modified ZVI, offering valuable insights for future research and the application of environmental remediation technologies.
{"title":"Recent research on chemically modifying the surface of zero-valent iron: A mini review","authors":"Zhendong Li , Wei Ye , Huiting Li , Jianzhe Qiao , Yunyi Du , Zhujun Dong , Lichun Fu , Yuwei Pan","doi":"10.1016/j.ceja.2025.100709","DOIUrl":"10.1016/j.ceja.2025.100709","url":null,"abstract":"<div><div>Zero-valent iron (ZVI) is a widely employed material for environmental remediation due to its capability to effectively degrade or reduce various pollutants. The enhancement of its reactivity and applicability can be achieved through chemical surface modification. Chemical surface modification involves introducing specific chemical functional groups onto the surface of ZVI, altering its surface chemical properties and structural morphology. This article provides an overview of the advancements made in four commonly used chemical modifications of ZVI, namely ZVI sulfide, ZVI silicide, ZVI oxalate, and ZVI phosphate. The review examines the impacts of these four different modified compounds on the surface structure and reactivity of ZVI, as well as elucidates the mechanisms by which modified ZVI interacts with and removes pollutants. Furthermore, the article discusses the prospects and challenges associated with modified ZVI, offering valuable insights for future research and the application of environmental remediation technologies.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"21 ","pages":"Article 100709"},"PeriodicalIF":5.5,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143174992","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-20DOI: 10.1016/j.ceja.2025.100708
Arun S R, George Jacob
High entropy materials have grabbed more attention in recent years on account of their unique crystal structure, large compositional design space, and complex chemistry enabling the enormous and unexplored properties in the different fields. Among the entropy-stabilized materials, high entropy oxide nanoparticles (HEO NPs) have attracted the scientific community owing to their superior energy storage applications. This research anticipates an approach for unleashing the charge storage properties of HEO NPs for supercapacitor applications. The spinel-type (MnFeCoNiZn)3O4 HEO NPs were prepared by the solution combustion method. This (MnFeCoNiZn)3O4 HEO NPs electrode exhibited 288.7 Fg-1 (3 Ag-1) of specific capacitance (Csp). It maintained a 52% rate capability from 3 to 30 Ag-1. Furthermore, after a cyclic stability test for 5000 cycles, this (MnFeCoNiZn)3O4 HEO NPs maintained 50% capacity retention at 10 Ag-1. Additionally, an asymmetric supercapacitor (ASC) was constructed of ((MnFeCoNiZn)3O4 HEO NPs // activated carbon (AC)) which exhibited a 1.5 V voltage window. It delivered a good energy density of 7.9 Whkg-1 with a power density of 746 WKg-1. This research has paved the way for preparing the HEO NPs by simple synthesizing methods and exploration of high entropy materials in the field of supercapacitors.
{"title":"Exploring the charge storage ability of the spinel-type high entropy oxide (MnFeCoNiZn)3O4 nanoparticles for supercapacitor applications","authors":"Arun S R, George Jacob","doi":"10.1016/j.ceja.2025.100708","DOIUrl":"10.1016/j.ceja.2025.100708","url":null,"abstract":"<div><div>High entropy materials have grabbed more attention in recent years on account of their unique crystal structure, large compositional design space, and complex chemistry enabling the enormous and unexplored properties in the different fields. Among the entropy-stabilized materials, high entropy oxide nanoparticles (HEO NPs) have attracted the scientific community owing to their superior energy storage applications. This research anticipates an approach for unleashing the charge storage properties of HEO NPs for supercapacitor applications. The spinel-type (MnFeCoNiZn)<sub>3</sub>O<sub>4</sub> HEO NPs were prepared by the solution combustion method. This (MnFeCoNiZn)<sub>3</sub>O<sub>4</sub> HEO NPs electrode exhibited 288.7 Fg<sup>-1</sup> (3 Ag<sup>-1</sup>) of specific capacitance (<em>C<sub>sp</sub></em>). It maintained a 52% rate capability from 3 to 30 Ag<sup>-1</sup>. Furthermore, after a cyclic stability test for 5000 cycles, this (MnFeCoNiZn)<sub>3</sub>O<sub>4</sub> HEO NPs maintained 50% capacity retention at 10 Ag<sup>-1</sup>. Additionally, an asymmetric supercapacitor (ASC) was constructed of ((MnFeCoNiZn)<sub>3</sub>O<sub>4</sub> HEO NPs // activated carbon (AC)) which exhibited a 1.5 V voltage window. It delivered a good energy density of 7.9 Whkg<sup>-1</sup> with a power density of 746 WKg<sup>-1</sup>. This research has paved the way for preparing the HEO NPs by simple synthesizing methods and exploration of high entropy materials in the field of supercapacitors.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"21 ","pages":"Article 100708"},"PeriodicalIF":5.5,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143174991","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-12DOI: 10.1016/j.ceja.2025.100706
Ajit Kumar Dhanka , Emerson C. Kohlrausch , Raghabendra Samantray , Vinod Kumar , Balaram Pani , Nityananda Agasti
A highly efficient and stable CeO2-based material has been developed for photocatalytic degradation of antibiotics in water. In this study, we investigated the defects due to metal-support interaction between Ag and CeO2 in the Ag/CeO2 nanocomposites. Here we introduced oxygen vacancies in CeO2 by incorporating Ag on the surface of CeO2. Notably, the addition of Ag to CeO2 reduces the band gap energy to 2.90 eV, accompanied by an increase in Ce3+ content which is correlated with an increase in oxygen vacancies. X-ray photoelectron spectroscopy (XPS), Raman and EPR studies substantiated the increase in surface oxygen vacancies in CeO2 induced by the interaction between Ag and CeO2. Oxygen vacancies in Ag/CeO2 act as trapping sites for photogenerated electrons and successfully restrain the recombination of photogenerated electron and hole pairs, thereby exhibiting improved catalytic activity of Ag/CeO2 nanocomposites. Ag/CeO2 nanocomposites exhibited better catalytic performance than pristine CeO2, which is attributed to the enhanced oxygen vacancies in the nanocomposites. We investigated the effect of silver (Ag) on increasing oxygen vacancies in Ag/CeO2.Trapping experiments were conducted to identify the reactive species participating in the photocatalytic degradation process. A plausible mechanism is proposed based on critical analysis of the results from the characterization techniques of the nanocomposites and photocatalytic experiments. The possible degradation pathways for Ciprofloxacin along with the degradation intermediates have been proposed based on High resolution mass spectroscopy (HRMS) analysis. This study provides insights on structural characteristics of defective CeO2, in-depth photocatalytic mechanism and degradation pathway of ciprofloxacin, that could facilitate the exploration of other ceria-based nanocomposites for catalytic applications.
{"title":"Harnessing defects in Ag/CeO2 for enhanced photocatalytic degradation of antibiotic in water: Structural characteristics, in-depth insights on mechanism, degradation pathway","authors":"Ajit Kumar Dhanka , Emerson C. Kohlrausch , Raghabendra Samantray , Vinod Kumar , Balaram Pani , Nityananda Agasti","doi":"10.1016/j.ceja.2025.100706","DOIUrl":"10.1016/j.ceja.2025.100706","url":null,"abstract":"<div><div>A highly efficient and stable CeO<sub>2</sub>-based material has been developed for photocatalytic degradation of antibiotics in water. In this study, we investigated the defects due to metal-support interaction between Ag and CeO<sub>2</sub> in the Ag/CeO<sub>2</sub> nanocomposites. Here we introduced oxygen vacancies in CeO<sub>2</sub> by incorporating Ag on the surface of CeO<sub>2.</sub> Notably, the addition of Ag to CeO<sub>2</sub> reduces the band gap energy to 2.90 eV, accompanied by an increase in Ce<sup>3</sup><sup>+</sup> content which is correlated with an increase in oxygen vacancies. X-ray photoelectron spectroscopy (XPS), Raman and EPR studies substantiated the increase in surface oxygen vacancies in CeO<sub>2</sub> induced by the interaction between Ag and CeO<sub>2</sub>. Oxygen vacancies in Ag/CeO<sub>2</sub> act as trapping sites for photogenerated electrons and successfully restrain the recombination of photogenerated electron and hole pairs, thereby exhibiting improved catalytic activity of Ag/CeO<sub>2</sub> nanocomposites. Ag/CeO<sub>2</sub> nanocomposites exhibited better catalytic performance than pristine CeO<sub>2</sub>, which is attributed to the enhanced oxygen vacancies in the nanocomposites. We investigated the effect of silver (Ag) on increasing oxygen vacancies in Ag/CeO<sub>2</sub>.Trapping experiments were conducted to identify the reactive species participating in the photocatalytic degradation process. A plausible mechanism is proposed based on critical analysis of the results from the characterization techniques of the nanocomposites and photocatalytic experiments. The possible degradation pathways for Ciprofloxacin along with the degradation intermediates have been proposed based on High resolution mass spectroscopy (HRMS) analysis. This study provides insights on structural characteristics of defective CeO<sub>2</sub>, in-depth photocatalytic mechanism and degradation pathway of ciprofloxacin, that could facilitate the exploration of other ceria-based nanocomposites for catalytic applications.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"21 ","pages":"Article 100706"},"PeriodicalIF":5.5,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143174988","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-10DOI: 10.1016/j.ceja.2025.100707
Adriano S. Silva , Paulo Zadra Filho , Ana Paula Ferreira , Fernanda F. Roman , Arthur P. Baldo , Madeleine Rauhauser , Jose L. Diaz de Tuesta , Ana I. Pereira , Adrián M.T. Silva , Juliana M.T. Pietrobelli , Marzhan S. Kalmakhanova , Daniel D. Snow , Helder T. Gomes
Monitoring campaigns of contaminants of emerging concern (CECs) in surface waters is of utmost importance in evaluating the anthropogenic impact on riparian ecosystems. Beyond identifying pollutants and threats, treatment solutions are also needed to mitigate the adverse effects caused by polluted water discharged into the environment. For years, grab samples have been used to assess water quality, but the results can be misleading since contaminants are not always found due to the low and highly variable concentrations at which they are present in these matrices. Even in such small concentrations, the contaminants can be harmful to aquatic life. Therefore, for about three months, passive samplers were used to monitor the presence of pharmaceuticals in river water up- and downstream the discharge of a wastewater treatment plant (WWTP). Passive samplers were extracted, analyzed and the results were used to identify possible pollution composition and potential sources. Our campaign enabled the identification and quantification of 28 contaminants and showed that 27 increased in amount after WWTP discharge entered the river. The statistical analysis revealed the correlation between the pollutants, showed the oscillation in their amounts, and enabled the identification of specific pollutant groups that deserve attention for treatment, such as antibiotics and antidepressants. Moreover, an innovative catalytic wet peroxide oxidation (CWPO) intensified filtration process was investigated as a possible water treatment solution, using composite polymeric membranes loaded with carbon nanotubes (CNTs). Sulfamethoxazole (SMX) was selected as a model pollutant, and 85–90 % removals were achieved in continuous flow mode during 8 h (equivalent to 2255–2315 mg m-2 h-1).
{"title":"Occurrence of micropollutants in surface water and removal by catalytic wet peroxide oxidation enhanced filtration using polymeric membranes loaded with carbon nanotubes","authors":"Adriano S. Silva , Paulo Zadra Filho , Ana Paula Ferreira , Fernanda F. Roman , Arthur P. Baldo , Madeleine Rauhauser , Jose L. Diaz de Tuesta , Ana I. Pereira , Adrián M.T. Silva , Juliana M.T. Pietrobelli , Marzhan S. Kalmakhanova , Daniel D. Snow , Helder T. Gomes","doi":"10.1016/j.ceja.2025.100707","DOIUrl":"10.1016/j.ceja.2025.100707","url":null,"abstract":"<div><div>Monitoring campaigns of contaminants of emerging concern (CECs) in surface waters is of utmost importance in evaluating the anthropogenic impact on riparian ecosystems. Beyond identifying pollutants and threats, treatment solutions are also needed to mitigate the adverse effects caused by polluted water discharged into the environment. For years, grab samples have been used to assess water quality, but the results can be misleading since contaminants are not always found due to the low and highly variable concentrations at which they are present in these matrices. Even in such small concentrations, the contaminants can be harmful to aquatic life. Therefore, for about three months, passive samplers were used to monitor the presence of pharmaceuticals in river water up- and downstream the discharge of a wastewater treatment plant (WWTP). Passive samplers were extracted, analyzed and the results were used to identify possible pollution composition and potential sources. Our campaign enabled the identification and quantification of 28 contaminants and showed that 27 increased in amount after WWTP discharge entered the river. The statistical analysis revealed the correlation between the pollutants, showed the oscillation in their amounts, and enabled the identification of specific pollutant groups that deserve attention for treatment, such as antibiotics and antidepressants. Moreover, an innovative catalytic wet peroxide oxidation (CWPO) intensified filtration process was investigated as a possible water treatment solution, using composite polymeric membranes loaded with carbon nanotubes (CNTs). Sulfamethoxazole (SMX) was selected as a model pollutant, and 85–90 % removals were achieved in continuous flow mode during 8 h (equivalent to 2255–2315 mg m<sup>-2</sup> h<sup>-1</sup>).</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"21 ","pages":"Article 100707"},"PeriodicalIF":5.5,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143174987","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Fischer-Tropsch synthesis (FTS) offers a promising route for producing sustainable jet fuels from syngas. However, optimizing catalyst design and operating conditions for the ideal C8-C16 jet fuel range is challenging. Thus, this work introduces a machine learning (ML) framework to enhance Co/Fe-supported FTS catalysts and optimize their operating conditions for a better jet fuel selectivity. For this purpose, a dataset was implemented with 21 features, including catalyst structure, preparation method, activation procedure, and FTS operating parameters. Moreover, various machine-learning models (Random Forest (RF), Gradient Boosted, CatBoost, and artificial neural networks (ANN)) were evaluated to predict CO conversion and C8-C16 selectivity. Among these, the CatBoost model achieved the highest accuracy (R2 = 0.99). Feature analysis revealed that FTS operational conditions mainly affect CO conversion (37.9 %), while catalyst properties were primarily crucial for C8-C16 selectivity (40.6 %). The proposed ML framework provides a first powerful tool for the rational design of FTS catalysts and operating conditions to maximize jet fuel productivity.
{"title":"Improving catalysts and operating conditions using machine learning in Fischer-Tropsch synthesis of jet fuels (C8-C16)","authors":"Parisa Shafiee, Bogdan Dorneanu, Harvey Arellano-Garcia","doi":"10.1016/j.ceja.2024.100702","DOIUrl":"10.1016/j.ceja.2024.100702","url":null,"abstract":"<div><div>Fischer-Tropsch synthesis (FTS) offers a promising route for producing sustainable jet fuels from syngas. However, optimizing catalyst design and operating conditions for the ideal C8-C16 jet fuel range is challenging. Thus, this work introduces a machine learning (ML) framework to enhance Co/Fe-supported FTS catalysts and optimize their operating conditions for a better jet fuel selectivity. For this purpose, a dataset was implemented with 21 features, including catalyst structure, preparation method, activation procedure, and FTS operating parameters. Moreover, various machine-learning models (Random Forest (RF), Gradient Boosted, CatBoost, and artificial neural networks (ANN)) were evaluated to predict CO conversion and C8-C16 selectivity. Among these, the CatBoost model achieved the highest accuracy (R<sup>2</sup> = 0.99). Feature analysis revealed that FTS operational conditions mainly affect CO conversion (37.9 %), while catalyst properties were primarily crucial for C8-C16 selectivity (40.6 %). The proposed ML framework provides a first powerful tool for the rational design of FTS catalysts and operating conditions to maximize jet fuel productivity.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"21 ","pages":"Article 100702"},"PeriodicalIF":5.5,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143173988","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-08DOI: 10.1016/j.ceja.2025.100705
José Juan Bolívar Caballero , Fereshteh Talkhab , Hanmin Yang , Samina Gulshan , Pengcheng Cao , Thomas Lewin , Pär G. Jönsson , Weihong Yang
Pyrolysis of biomass plus catalytic reforming of its pyrolysis volatiles is a green alternative to produce solid (biochar) and gaseous (syngas) fuels that have several valuable applications; however, this catalytic process suffers from fast deactivation, and its energy consumption is yet to be studied, factors that determine the process’s feasibility in industrialisation. To address these issues, the direct electrification of a 3D-printed FeCrAl heater coated with 15.5 % Ni/AlO was tested in a parametric study in the catalytic steam reforming of biomass pyrolysis volatiles, in order to investigate the effect of the S/B ratio and space–time on the syngas yield and composition. Complete bio-oil reforming was obtained at a biomass feed rate of 1 g min−1 and a S/B ratio of 2, and stability close to 100 % was estimated after over four hours of operation. Nonetheless, the produced syngas is rich in C – C gases and moderately low in H ( 2 wt %). The effect of the catalyst’s structure on the bio-oil reforming and heat efficiency was complemented using CFD simulations and compared to a simple geometry based on commercial extruded monoliths. Finally, the biomass-derived syngas upgrading to H production was assessed using different process simulations and compared to existing H-producing technologies in terms of energy efficiency and emissions.
{"title":"Renewable syngas production from electrified catalytic steam reforming of biomass pyrolysis volatiles","authors":"José Juan Bolívar Caballero , Fereshteh Talkhab , Hanmin Yang , Samina Gulshan , Pengcheng Cao , Thomas Lewin , Pär G. Jönsson , Weihong Yang","doi":"10.1016/j.ceja.2025.100705","DOIUrl":"10.1016/j.ceja.2025.100705","url":null,"abstract":"<div><div>Pyrolysis of biomass plus catalytic reforming of its pyrolysis volatiles is a green alternative to produce solid (biochar) and gaseous (syngas) fuels that have several valuable applications; however, this catalytic process suffers from fast deactivation, and its energy consumption is yet to be studied, factors that determine the process’s feasibility in industrialisation. To address these issues, the direct electrification of a 3D-printed FeCrAl heater coated with 15.5 % Ni/Al<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>O<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span> was tested in a parametric study in the catalytic steam reforming of biomass pyrolysis volatiles, in order to investigate the effect of the S/B ratio and space–time on the syngas yield and composition. Complete bio-oil reforming was obtained at a biomass feed rate of <span><math><mo>≤</mo></math></span> 1 g min<sup>−1</sup> and a S/B ratio of <span><math><mo>≥</mo></math></span> 2, and stability close to 100 % was estimated after over four hours of operation. Nonetheless, the produced syngas is rich in C<span><math><msub><mrow></mrow><mrow><mn>1</mn></mrow></msub></math></span> – C<span><math><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub></math></span> gases and moderately low in H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> (<span><math><mo>≈</mo></math></span> 2 wt %). The effect of the catalyst’s structure on the bio-oil reforming and heat efficiency was complemented using CFD simulations and compared to a simple geometry based on commercial extruded monoliths. Finally, the biomass-derived syngas upgrading to H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> production was assessed using different process simulations and compared to existing H<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>-producing technologies in terms of energy efficiency and emissions.</div></div>","PeriodicalId":9749,"journal":{"name":"Chemical Engineering Journal Advances","volume":"21 ","pages":"Article 100705"},"PeriodicalIF":5.5,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143174989","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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