Max Schmallegger, Mathias Wiech, Sebastian Soritz, Miriam de J Velásquez-Hernández, Brigitte Bitschnau, Heidrun Gruber-Woelfler, Georg Gescheidt
Tetrazole moieties are components of various pharmacologically active molecules. Several synthetic protocols for the synthesis of tetrazoles have been developed. Among those, the reaction of organic nitriles with azides catalyzed by Lewis acids (LAs) provides a convenient access. Nevertheless, generally rather harsh reaction conditions have to be utilized for such syntheses. We have developed a simple, solvent-free procedure which allows a convenient isolation of tetrazoles using a heterogeneous catalyst: we show that polystyrene/AlCl3 composites produce tetrazoles at reasonable yields and allow a simple work-up procedure. We have characterized the AlCl3/polystyrene composite (gas sorption, XRD, IR) and investigated its efficacy in the preparation of aryl-substituted tetrazoles. We also have evaluated MgCl2, CuCl2, and ZnCl2 as Lewis-acid catalysts, but they are clearly outperformed by AlCl3 correlating with the Lewis-acid strength on the Gutmann-Beckett scale.
{"title":"Polystyrene-bound AlCl<sub>3</sub> - a catalyst for the solvent-free synthesis of aryl-substituted tetrazoles.","authors":"Max Schmallegger, Mathias Wiech, Sebastian Soritz, Miriam de J Velásquez-Hernández, Brigitte Bitschnau, Heidrun Gruber-Woelfler, Georg Gescheidt","doi":"10.1039/d4cy01215a","DOIUrl":"10.1039/d4cy01215a","url":null,"abstract":"<p><p>Tetrazole moieties are components of various pharmacologically active molecules. Several synthetic protocols for the synthesis of tetrazoles have been developed. Among those, the reaction of organic nitriles with azides catalyzed by Lewis acids (LAs) provides a convenient access. Nevertheless, generally rather harsh reaction conditions have to be utilized for such syntheses. We have developed a simple, solvent-free procedure which allows a convenient isolation of tetrazoles using a heterogeneous catalyst: we show that polystyrene/AlCl<sub>3</sub> composites produce tetrazoles at reasonable yields and allow a simple work-up procedure. We have characterized the AlCl<sub>3</sub>/polystyrene composite (gas sorption, XRD, IR) and investigated its efficacy in the preparation of aryl-substituted tetrazoles. We also have evaluated MgCl<sub>2</sub>, CuCl<sub>2</sub>, and ZnCl<sub>2</sub> as Lewis-acid catalysts, but they are clearly outperformed by AlCl<sub>3</sub> correlating with the Lewis-acid strength on the Gutmann-Beckett scale.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" ","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11815551/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143431921","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Haitao Huang , Zhijie Chen , Haijin Li , Yongtao Li , Xiaolong Deng
The creation of efficient non-precious metals is crucial for advancing electrochemical systems used in energy conversion and storage technologies. This work introduces an exceptionally potent and durable electrocatalyst, a trimetallic nitrogen-enriched carbon nanotube composite (FeCoNi@CNTs-NC-2), synthesized through a process of pyrolysis followed by acid treatment. Electrochemical tests have demonstrated that this catalyst displays remarkable performance and longevity in facilitating the oxygen reduction reaction. Furthermore, when integrated into Zn–air batteries, it delivers outstanding open-circuit voltage, power output, and specific energy capacity. These discoveries offer valuable insights for the engineering of effective and reliable electrocatalysts based on non-precious metal alloys.
{"title":"Fe, Co, and Ni co-doped nitrogen-doped carbon nanotubes for the electrocatalytic oxygen reduction reaction†","authors":"Haitao Huang , Zhijie Chen , Haijin Li , Yongtao Li , Xiaolong Deng","doi":"10.1039/d4cy01507j","DOIUrl":"10.1039/d4cy01507j","url":null,"abstract":"<div><div>The creation of efficient non-precious metals is crucial for advancing electrochemical systems used in energy conversion and storage technologies. This work introduces an exceptionally potent and durable electrocatalyst, a trimetallic nitrogen-enriched carbon nanotube composite (FeCoNi@CNTs-NC-2), synthesized through a process of pyrolysis followed by acid treatment. Electrochemical tests have demonstrated that this catalyst displays remarkable performance and longevity in facilitating the oxygen reduction reaction. Furthermore, when integrated into Zn–air batteries, it delivers outstanding open-circuit voltage, power output, and specific energy capacity. These discoveries offer valuable insights for the engineering of effective and reliable electrocatalysts based on non-precious metal alloys.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1238-1246"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430667","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Amer Alhaj Zen , Zaman Abdalhussein Ibadi Alaridhee , Rafid Kamal Jameel , Morug Salih Mahdi , Aseel Salah Mansoor , Usama Kadem Radi , Ameer Hassan Idan , Hala Bahai , Elyor Berdimurodov , Ilyos Eliboev , Abdulrahman A. Almehizia
Researchers have developed a novel electrode for the enantioselective electro-organic Grignard carboxylation of (1-bromoethyl)benzenes with carbon dioxide (CO2) . This study focuses on using Mg nanoparticle-catalyzed graphene oxide modified with Prl-tacd@Mg, with a surface area of 95.3 [m2 g−1] which, when combined with a choline chloride acetamide (ChCl/Ac) deep eutectic solvent, significantly enhances electrochemical performance. The goal is to achieve high selectivity and efficiency in the carboxylation process, contributing to sustainable chemical transformations. This innovative approach allows for the electro-organic synthesis of (R)-2-phenylpropanoic acid derivatives at a current of 15 mA for 30 min at room temperature, achieving yields between 88% and 96%. The ChCl/Ac system serves as a cost-effective electrolyte and solvent, facilitating an increased reaction rate. The synthesized products were characterized through various analytical techniques, including melting point analysis, 1HNMR spectroscopy, and CHN composition analysis. The electrode's performance was thoroughly evaluated using techniques such as X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), energy-dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) surface area analysis, cyclic voltammetry (CV), and Fourier-transform infrared spectroscopy (FT-IR). Its affordability and environmentally friendly characteristics highlight its potential for advancing sustainable electro-organic synthesis processes.
{"title":"Designing a reusable chiral SPE electrode with Mg nanoparticles on graphene oxide for efficient enantioselective Grignard carboxylation of (1-bromoethyl)benzenes in a deep eutectic solvent","authors":"Amer Alhaj Zen , Zaman Abdalhussein Ibadi Alaridhee , Rafid Kamal Jameel , Morug Salih Mahdi , Aseel Salah Mansoor , Usama Kadem Radi , Ameer Hassan Idan , Hala Bahai , Elyor Berdimurodov , Ilyos Eliboev , Abdulrahman A. Almehizia","doi":"10.1039/d4cy01324g","DOIUrl":"10.1039/d4cy01324g","url":null,"abstract":"<div><div>Researchers have developed a novel electrode for the enantioselective electro-organic Grignard carboxylation of (1-bromoethyl)benzenes with carbon dioxide (CO<sub>2</sub>) . This study focuses on using Mg nanoparticle-catalyzed graphene oxide modified with Prl-tacd@Mg, with a surface area of 95.3 [m<sup>2</sup> g<sup>−1</sup>] which, when combined with a choline chloride acetamide (ChCl/Ac) deep eutectic solvent, significantly enhances electrochemical performance. The goal is to achieve high selectivity and efficiency in the carboxylation process, contributing to sustainable chemical transformations. This innovative approach allows for the electro-organic synthesis of (<em>R</em>)-2-phenylpropanoic acid derivatives at a current of 15 mA for 30 min at room temperature, achieving yields between 88% and 96%. The ChCl/Ac system serves as a cost-effective electrolyte and solvent, facilitating an increased reaction rate. The synthesized products were characterized through various analytical techniques, including melting point analysis, 1HNMR spectroscopy, and CHN composition analysis. The electrode's performance was thoroughly evaluated using techniques such as X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), energy-dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) surface area analysis, cyclic voltammetry (CV), and Fourier-transform infrared spectroscopy (FT-IR). Its affordability and environmentally friendly characteristics highlight its potential for advancing sustainable electro-organic synthesis processes.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1185-1202"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430649","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Guoliang Wu , Qiang Bao , Jian Zhang , Mingjian Luo , Zhirui Chen , Xue Qiao , Yi Hu , Wenlin Wang , Yunfeng Hu
A coke detection strategy based on iodide-modified Ag NPs was established coupled with the release and dispersion of coke species. This method can selectively acquire group-based structural characteristics of coke species deposited on industrially deactivated zeolite catalysts with strong fluorescence within complex systems.
{"title":"Surface-enhanced Raman scattering technique for comprehensive group-based structural identification of coke deposits on deactivated zeolite catalysts†","authors":"Guoliang Wu , Qiang Bao , Jian Zhang , Mingjian Luo , Zhirui Chen , Xue Qiao , Yi Hu , Wenlin Wang , Yunfeng Hu","doi":"10.1039/d4cy01361a","DOIUrl":"10.1039/d4cy01361a","url":null,"abstract":"<div><div>A coke detection strategy based on iodide-modified Ag NPs was established coupled with the release and dispersion of coke species. This method can selectively acquire group-based structural characteristics of coke species deposited on industrially deactivated zeolite catalysts with strong fluorescence within complex systems.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1003-1008"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430621","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Saba Didarataee , Julia Ong , Anastasiia Suprun , Neeraj Joshi , Juan C. Scaiano
We report absolute rate constants for the reaction of triplet decatungstate (3DT*) with hydroperoxides using laser techniques and taking advantage of its recently discovered NIR phosphorescence. This allows an understanding of kinetic and mechanistic details on 3DT* catalyzed oxidation, and the role of O2 and hydroperoxides. We find that the DTH· radical is less reactive towards oxygen than usually assumed. We find that temporary accumulation of DTH· enables the persistent free radical mechanism to operate making DTH· an excellent disproportionation partner, which likely contributes to the good selectivity frequently observed when DT is used as a photoredox catalyst.
{"title":"Kinetics, quantum yield and mechanism of the decatungstate-catalyzed photooxidation of C–H hydrogen donors: role of the persistent radical effect†","authors":"Saba Didarataee , Julia Ong , Anastasiia Suprun , Neeraj Joshi , Juan C. Scaiano","doi":"10.1039/d4cy01358a","DOIUrl":"10.1039/d4cy01358a","url":null,"abstract":"<div><div>We report absolute rate constants for the reaction of triplet decatungstate (<sup>3</sup>DT*) with hydroperoxides using laser techniques and taking advantage of its recently discovered NIR phosphorescence. This allows an understanding of kinetic and mechanistic details on <sup>3</sup>DT* catalyzed oxidation, and the role of O<sub>2</sub> and hydroperoxides. We find that the DTH· radical is less reactive towards oxygen than usually assumed. We find that temporary accumulation of DTH· enables the persistent free radical mechanism to operate making DTH· an excellent disproportionation partner, which likely contributes to the good selectivity frequently observed when DT is used as a photoredox catalyst.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1149-1156"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430646","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Leoni-Franziska Klingelhöfer , Joakim Kattelus , Emma Verkama , Jorge A. Velasco , Leonhard Iser , Marcus Rose , Reetta Karinen , Riikka L. Puurunen
In this work, the hydrodenitrogenation (HDN) of a primary amine (dodecylamine), a secondary amine (didodecylamine), and a tertiary amine (tridodecylamine) over a Pt/ZrO2 catalyst was compared in a batch reactor. The main product of the amine hydrotreating was dodecane, but significant amounts of secondary amine were also formed as an intermediate during HDN of the primary and the tertiary amine. It was found that the primary amine is the only species for which direct HDN is possible; HDN of the secondary amine thus proceeds through a primary amine intermediate and HDN of the tertiary amine involves formation of the secondary amine, which decomposes to the primary amine. Consequently, HDN of the tertiary and secondary amines is slower than that of the primary amine. Kinetic modeling indicated that bimolecular condensation reactions of the primary amine, as well as potentially of the primary amine and the secondary amine, have a significant effect on the HDN process. Formation of the secondary amine from the primary amine increases the initial conversion and nitrogen removal rate but appeared to slow down the overall rate of nitrogen removal. The results thus demonstrate how condensation reactions affect amine HDN, which has implications for catalyst design for HDN of renewable feeds containing aliphatic amines.
{"title":"Catalytic hydrodenitrogenation of primary, secondary, and tertiary C12-alkyl amines over a platinum on zirconia catalyst†","authors":"Leoni-Franziska Klingelhöfer , Joakim Kattelus , Emma Verkama , Jorge A. Velasco , Leonhard Iser , Marcus Rose , Reetta Karinen , Riikka L. Puurunen","doi":"10.1039/d4cy01099j","DOIUrl":"10.1039/d4cy01099j","url":null,"abstract":"<div><div>In this work, the hydrodenitrogenation (HDN) of a primary amine (dodecylamine), a secondary amine (didodecylamine), and a tertiary amine (tridodecylamine) over a Pt/ZrO<sub>2</sub> catalyst was compared in a batch reactor. The main product of the amine hydrotreating was dodecane, but significant amounts of secondary amine were also formed as an intermediate during HDN of the primary and the tertiary amine. It was found that the primary amine is the only species for which direct HDN is possible; HDN of the secondary amine thus proceeds through a primary amine intermediate and HDN of the tertiary amine involves formation of the secondary amine, which decomposes to the primary amine. Consequently, HDN of the tertiary and secondary amines is slower than that of the primary amine. Kinetic modeling indicated that bimolecular condensation reactions of the primary amine, as well as potentially of the primary amine and the secondary amine, have a significant effect on the HDN process. Formation of the secondary amine from the primary amine increases the initial conversion and nitrogen removal rate but appeared to slow down the overall rate of nitrogen removal. The results thus demonstrate how condensation reactions affect amine HDN, which has implications for catalyst design for HDN of renewable feeds containing aliphatic amines.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1259-1271"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cy/d4cy01099j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430668","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiaoxue Yu , Junkai Xu , Yunhao Wang , Jianjun Fang , Xianfang Yue , Breno R. L. Galvão , Jing Li
Developing bifunctional electrocatalysts for efficiently catalyzing the oxygen evolution/reduction reaction (OER/ORR) is essential for water electrolysis and other processes. Herein, we have investigated the OER and ORR performance of monolayered TM-C13N3 by first-principles calculations, where TM includes Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, and Au. The results show that Pt-C13N3 has excellent bifunctional OER/ORR activity with overpotentials of 0.27 V for the OER and 0.39 V for the ORR. In addition, volcano plots and contour maps based on the linear relationship between the adsorption energies of oxygenated intermediates were established to characterize the OER/ORR activity trends of TM-C13N3. The origin of the OER/ORR activity is revealed by analyzing Bader charges, the d-band center, and the crystal orbital Hamiltonian population (COHP).
{"title":"Transition metal atoms embedded in monolayer C13N3 as OER/ORR bifunctional electrocatalysts†","authors":"Xiaoxue Yu , Junkai Xu , Yunhao Wang , Jianjun Fang , Xianfang Yue , Breno R. L. Galvão , Jing Li","doi":"10.1039/d4cy01160k","DOIUrl":"10.1039/d4cy01160k","url":null,"abstract":"<div><div>Developing bifunctional electrocatalysts for efficiently catalyzing the oxygen evolution/reduction reaction (OER/ORR) is essential for water electrolysis and other processes. Herein, we have investigated the OER and ORR performance of monolayered TM-C<sub>13</sub>N<sub>3</sub> by first-principles calculations, where TM includes Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, and Au. The results show that Pt-C<sub>13</sub>N<sub>3</sub> has excellent bifunctional OER/ORR activity with overpotentials of 0.27 V for the OER and 0.39 V for the ORR. In addition, volcano plots and contour maps based on the linear relationship between the adsorption energies of oxygenated intermediates were established to characterize the OER/ORR activity trends of TM-C<sub>13</sub>N<sub>3</sub>. The origin of the OER/ORR activity is revealed by analyzing Bader charges, the d-band center, and the crystal orbital Hamiltonian population (COHP).</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1122-1133"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430644","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Visible light-induced photocatalysis has attracted significant attention as a sustainable strategy to mitigate climate change by reducing CO2. This process uses semiconductor materials to convert CO2 into valuable chemicals and fuels under visible light, providing an environmentally friendly alternative to traditional energy-intensive methods. This review explores the fundamental principles and innovative photocatalysts, including metal-based, metal-free and hybrid systems, aimed at enhancing photocatalytic efficiency and selectivity. It begins with an overview of the basic mechanisms of photocatalysis, including charge generation, separation, and recombination, and examines the thermodynamic factors that influence CO2 reduction, such as temperature, light intensity, and the properties of the semiconductor material. Key challenges are explored, such as improving light absorption properties, increasing reaction rates, and optimizing charge carrier dynamics. Recent advancements in material design, nanostructuring, and doping techniques have shown promising results in improving photocatalytic CO2 conversion. Future research will focus on addressing the scalability, stability, and efficiency of photocatalytic systems, as well as exploring the potential for coupling CO2 reduction with renewable energy sources for practical applications.
{"title":"Innovations and fundamentals in visible light-driven photocatalysis for CO2 reduction","authors":"Rajesh Sahu , Tarun Patodia , Sakshi Juyal , Fateh Singh Gill , Brijesh Prasad , Ankur Jain","doi":"10.1039/d4cy01305k","DOIUrl":"10.1039/d4cy01305k","url":null,"abstract":"<div><div>Visible light-induced photocatalysis has attracted significant attention as a sustainable strategy to mitigate climate change by reducing CO<sub>2</sub>. This process uses semiconductor materials to convert CO<sub>2</sub> into valuable chemicals and fuels under visible light, providing an environmentally friendly alternative to traditional energy-intensive methods. This review explores the fundamental principles and innovative photocatalysts, including metal-based, metal-free and hybrid systems, aimed at enhancing photocatalytic efficiency and selectivity. It begins with an overview of the basic mechanisms of photocatalysis, including charge generation, separation, and recombination, and examines the thermodynamic factors that influence CO<sub>2</sub> reduction, such as temperature, light intensity, and the properties of the semiconductor material. Key challenges are explored, such as improving light absorption properties, increasing reaction rates, and optimizing charge carrier dynamics. Recent advancements in material design, nanostructuring, and doping techniques have shown promising results in improving photocatalytic CO<sub>2</sub> conversion. Future research will focus on addressing the scalability, stability, and efficiency of photocatalytic systems, as well as exploring the potential for coupling CO<sub>2</sub> reduction with renewable energy sources for practical applications.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 988-1002"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430671","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xingyang Feng , Changmei Zhao , Junjie Zhou , Fangzhu Shi , Rui Yan , Zhiqiang Wang
4P-5NT/CN nanocomposites with high O2 activation and charge separation properties were synthesized via wet chemistry and calcination for photocatalytic degradation of ametryn (AME). With their wide visible light absorption range, the 4P-5NT/CN nanocomposites exhibited excellent charge transfer and separation properties, which significantly improved the photocatalytic degradation of AME by CN photocatalysts. The Z-type charge transfer mechanism between N-doped TiO2 (NT) and g-C3N4 (CN) and the high oxygen adsorption oxygen activation function of surface-modified phosphoric acid were crucial to the improved photocatalytic performance. The improved oxygen activation performance further induced the generation of more active species and accelerated the interaction with AME to initiate degradation. Results showed that the photocatalytic degradation of AME by 4P-5NT/CN was 25.8 times greater than that by pure CN under optimal loading conditions. Oxygen temperature-programmed desorption (O2-TPD) experiments showed that H3PO4 promoted the physical adsorption of O2 on the surface of the material, effectively facilitating oxygen activation and inducing ·O2− generation. Reactive oxide species (ROS) were determined through ESR and free radical capture detection. The intermediate fragmentation products of AME degradation were detected using liquid chromatography-tandem mass spectrometry (LC-MS/MS), and the synergistic degradation pathways of ·O2− and ·OH were obtained. The synergistic effect is reflected in the fact that ·O2− tends to attack the ethyl chain, triggering the degradation reaction, whereas ·OH tends to attack the sulfur methyl group, ultimately leading to better mineralisation. This work reveals the selection pattern of AME active sites by ROS during photocatalytic degradation and provides a new idea for the design of visible-light-driven high-oxygen-activity photocatalysts for the efficient treatment of environmental pollutants with effective mineralisation.
{"title":"Phosphate modulated nitrogen-doped titanium dioxide/carbon nitride heterogeneous photocatalysts with efficient O2 activation for ametryn degradation†","authors":"Xingyang Feng , Changmei Zhao , Junjie Zhou , Fangzhu Shi , Rui Yan , Zhiqiang Wang","doi":"10.1039/d4cy01167h","DOIUrl":"10.1039/d4cy01167h","url":null,"abstract":"<div><div>4P-5NT/CN nanocomposites with high O<sub>2</sub> activation and charge separation properties were synthesized <em>via</em> wet chemistry and calcination for photocatalytic degradation of ametryn (AME). With their wide visible light absorption range, the 4P-5NT/CN nanocomposites exhibited excellent charge transfer and separation properties, which significantly improved the photocatalytic degradation of AME by CN photocatalysts. The Z-type charge transfer mechanism between N-doped TiO<sub>2</sub> (NT) and g-C<sub>3</sub>N<sub>4</sub> (CN) and the high oxygen adsorption oxygen activation function of surface-modified phosphoric acid were crucial to the improved photocatalytic performance. The improved oxygen activation performance further induced the generation of more active species and accelerated the interaction with AME to initiate degradation. Results showed that the photocatalytic degradation of AME by 4P-5NT/CN was 25.8 times greater than that by pure CN under optimal loading conditions. Oxygen temperature-programmed desorption (O<sub>2</sub>-TPD) experiments showed that H<sub>3</sub>PO<sub>4</sub> promoted the physical adsorption of O<sub>2</sub> on the surface of the material, effectively facilitating oxygen activation and inducing ·O<sub>2</sub><sup>−</sup> generation. Reactive oxide species (ROS) were determined through ESR and free radical capture detection. The intermediate fragmentation products of AME degradation were detected using liquid chromatography-tandem mass spectrometry (LC-MS/MS), and the synergistic degradation pathways of ·O<sub>2</sub><sup>−</sup> and ·OH were obtained. The synergistic effect is reflected in the fact that ·O<sub>2</sub><sup>−</sup> tends to attack the ethyl chain, triggering the degradation reaction, whereas ·OH tends to attack the sulfur methyl group, ultimately leading to better mineralisation. This work reveals the selection pattern of AME active sites by ROS during photocatalytic degradation and provides a new idea for the design of visible-light-driven high-oxygen-activity photocatalysts for the efficient treatment of environmental pollutants with effective mineralisation.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1174-1184"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430648","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kai Zhao , Qiutong Han , Zhe Lu , Yubin Zheng , Boye Zhou , Haoqiang Chi , Dawei Liu , Lu Wang , Zhigang Zou , Yong Zhou
Harnessing solar energy to catalytically reduce CO2 into chemical fuels represents a promising solution to simultaneously address the energy crisis and global warming. However, the efficient and selective synthesis of high value-added products under relatively mild conditions remains a challenge. Herein, a catalyst composed of hexagonal In2O3 (abbrev. as h-In2O3) short nanorods with a high specific surface area was synthesized via a straightforward solvothermal method. Compared to commercial cubic In2O3 (abbrev. as com-In2O3), the h-In2O3 short nanorods exhibited high yield in the photothermal reduction of CO2 to CO, CH4, CH3OH, and C2H5OH, using water vapor as the reducing agent. With oxygen vacancies being introduced into h-In2O3 through H2 treatment, C2H5OH yield rate represents a remarkable 5.89 times and 13.22 times higher than h-In2O3 and com-In2O3, respectively. The product selectivity of C2H5OH for VO-In2O3 reached an impressive 47.07%, far surpassing 11.37% for com-In2O3 and 12.84% for h-In2O3. Electrochemical measurement and in situ DRIFTS spectra indicate that the introduction of O vacancies could contribute to the reduced recombination of photogenerated carriers and the enhanced dissociation of H2O, which may be beneficial to the improvement of C2H5OH yield and selectivity.
{"title":"Hexagonal In2O3 short nanorods rich in O vacancy-defects toward promoting highly efficient photothermal CO2 reduction into C2H5OH†","authors":"Kai Zhao , Qiutong Han , Zhe Lu , Yubin Zheng , Boye Zhou , Haoqiang Chi , Dawei Liu , Lu Wang , Zhigang Zou , Yong Zhou","doi":"10.1039/d4cy01376j","DOIUrl":"10.1039/d4cy01376j","url":null,"abstract":"<div><div>Harnessing solar energy to catalytically reduce CO<sub>2</sub> into chemical fuels represents a promising solution to simultaneously address the energy crisis and global warming. However, the efficient and selective synthesis of high value-added products under relatively mild conditions remains a challenge. Herein, a catalyst composed of hexagonal In<sub>2</sub>O<sub>3</sub> (abbrev. as h-In<sub>2</sub>O<sub>3</sub>) short nanorods with a high specific surface area was synthesized <em>via</em> a straightforward solvothermal method. Compared to commercial cubic In<sub>2</sub>O<sub>3</sub> (abbrev. as com-In<sub>2</sub>O<sub>3</sub>), the h-In<sub>2</sub>O<sub>3</sub> short nanorods exhibited high yield in the photothermal reduction of CO<sub>2</sub> to CO, CH<sub>4</sub>, CH<sub>3</sub>OH, and C<sub>2</sub>H<sub>5</sub>OH, using water vapor as the reducing agent. With oxygen vacancies being introduced into h-In<sub>2</sub>O<sub>3</sub> through H<sub>2</sub> treatment, C<sub>2</sub>H<sub>5</sub>OH yield rate represents a remarkable 5.89 times and 13.22 times higher than h-In<sub>2</sub>O<sub>3</sub> and com-In<sub>2</sub>O<sub>3</sub>, respectively. The product selectivity of C<sub>2</sub>H<sub>5</sub>OH for V<sub>O</sub>-In<sub>2</sub>O<sub>3</sub> reached an impressive 47.07%, far surpassing 11.37% for com-In<sub>2</sub>O<sub>3</sub> and 12.84% for h-In<sub>2</sub>O<sub>3</sub>. Electrochemical measurement and <em>in situ</em> DRIFTS spectra indicate that the introduction of O vacancies could contribute to the reduced recombination of photogenerated carriers and the enhanced dissociation of H<sub>2</sub>O, which may be beneficial to the improvement of C<sub>2</sub>H<sub>5</sub>OH yield and selectivity.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 4","pages":"Pages 1090-1095"},"PeriodicalIF":4.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143430591","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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