Pub Date : 2025-11-29DOI: 10.1016/j.apcata.2025.120731
Qiang Zhang , Hao Kang , LI Jian-xiang , Yan-hong Chen , Ye-qi Song , Yue-lin Wang
A novel sulfate-based catalytic system was developed for the oxidative cracking of n-butane to high-value olefins under oxygen-free conditions. Leveraging the S⁶⁺/S²⁻ (SO₄²⁻/S²⁻) redox couple, the catalyst efficiently promotes lattice-oxygen transport and storage, enabling selective C–C bond scission in the absence of gaseous O₂. The catalyst was characterized by multiple analytical techniques including XRD, TPR, XRF, and XPS to analyze its phase structure, redox properties, elemental composition, and surface chemical state. The 10 % LaS/Si catalyst exhibited excellent catalytic performance: A total ethylene and propylene yield was 50.9 wt%, while a COx (CO+CO2) yield was only 6.8 wt% at the conditions of 650 ℃. Deactivation was primarily attributed to sulfur loss, accompanied by a phase transition from La₂(SO₄)₃ to (LaO)₂SO₄ and La₂O₂S. A two-step regeneration process of carbon burning followed by sulfur replenishment using SO2 was therefore developed. Incorporation of CeO₂ further enhanced cyclic regeneration stability, and the catalyst retained near-fresh activity after 17 regeneration cycles.
{"title":"Catalytic-oxidative cracking of n-butane and regeneration durability over La₂(SO₄)₃/SiO₂: Sulfur-loss mechanism and CeO₂-promoted two-step regeneration","authors":"Qiang Zhang , Hao Kang , LI Jian-xiang , Yan-hong Chen , Ye-qi Song , Yue-lin Wang","doi":"10.1016/j.apcata.2025.120731","DOIUrl":"10.1016/j.apcata.2025.120731","url":null,"abstract":"<div><div>A novel sulfate-based catalytic system was developed for the oxidative cracking of n-butane to high-value olefins under oxygen-free conditions. Leveraging the S⁶⁺/S²⁻ (SO₄²⁻/S²⁻) redox couple, the catalyst efficiently promotes lattice-oxygen transport and storage, enabling selective C–C bond scission in the absence of gaseous O₂. The catalyst was characterized by multiple analytical techniques including XRD, TPR, XRF, and XPS to analyze its phase structure, redox properties, elemental composition, and surface chemical state. The 10 % LaS/Si catalyst exhibited excellent catalytic performance: A total ethylene and propylene yield was 50.9 wt%, while a CO<sub>x</sub> (CO+CO<sub>2</sub>) yield was only 6.8 wt% at the conditions of 650 ℃. Deactivation was primarily attributed to sulfur loss, accompanied by a phase transition from La₂(SO₄)₃ to (LaO)₂SO₄ and La₂O₂S. A two-step regeneration process of carbon burning followed by sulfur replenishment using SO<sub>2</sub> was therefore developed. Incorporation of CeO₂ further enhanced cyclic regeneration stability, and the catalyst retained near-fresh activity after 17 regeneration cycles.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120731"},"PeriodicalIF":4.8,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682630","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-29DOI: 10.1016/j.apcata.2025.120728
Heike Plendl , Patrick Schlachta , Tim Kratky , Kristína Krahulíková , Olaf Hinrichsen
CeO2-doped NiAlOx mixed oxide catalysts with molar Ce/Ni ratios of 0.05, 0.1 and 0.3 were prepared via coprecipitation and analyzed in detail regarding structure and activity in CO2 methanation. A cerium-free NiAlOx, a CeO2 and a NiCe-based sample served as references. Characterization revealed a two-phase composition of the doped materials consisting of a NiAlOx mixed oxide and a CeO2 phase. The latter features highly reactive oxygen vacancies upon reduction with hydrogen, which provide additional binding sites for CO2. Reduction of the CeO2 phase (and with that the formation of oxygen vacancies in the doped catalysts) was demonstrated to be only feasible in the presence of Ni which, in this context, acts as a hydrogenation catalyst providing dissociated hydrogen. The detection of completely reversible reduction-oxidation-reduction cycles of CeO2-doped NiAlOx by quasi in-situ XPS suggested diminutively-sized Ni particles provided by synthesis via coprecipitation. Catalytic testing of the CeO2-doped samples in CO2methanation revealed up to three times higher turnover frequencies and CH4weight-time yields compared to undoped NiAlOx. An optimum in catalytic activity at Ce/Ni = 0.1 indicated the prerequisite of a balance between Ni and Ce amounts in the catalyst to avoid undesired byproduct formation.
{"title":"Synthesis, characterization and activity of CeO2-doped coprecipitated NiAlOx catalysts for CO2 methanation","authors":"Heike Plendl , Patrick Schlachta , Tim Kratky , Kristína Krahulíková , Olaf Hinrichsen","doi":"10.1016/j.apcata.2025.120728","DOIUrl":"10.1016/j.apcata.2025.120728","url":null,"abstract":"<div><div>CeO<sub>2</sub>-doped NiAlO<sub>x</sub> mixed oxide catalysts with molar Ce/Ni ratios of 0.05, 0.1 and 0.3 were prepared <em>via</em> coprecipitation and analyzed in detail regarding structure and activity in CO<sub>2</sub> methanation. A cerium-free NiAlO<sub>x</sub>, a CeO<sub>2</sub> and a NiCe-based sample served as references. Characterization revealed a two-phase composition of the doped materials consisting of a NiAlO<sub>x</sub> mixed oxide and a CeO<sub>2</sub> phase. The latter features highly reactive oxygen vacancies upon reduction with hydrogen, which provide additional binding sites for CO<sub>2</sub>. Reduction of the CeO<sub>2</sub> phase (and with that the formation of oxygen vacancies in the doped catalysts) was demonstrated to be only feasible in the presence of Ni which, in this context, acts as a hydrogenation catalyst providing dissociated hydrogen. The detection of completely reversible reduction-oxidation-reduction cycles of CeO<sub>2</sub>-doped NiAlO<sub>x</sub> by quasi <em>in-situ</em> XPS suggested diminutively-sized Ni particles provided by synthesis <em>via</em> coprecipitation. <em>Catalytic testing of the CeO</em><sub><em>2</em></sub><em>-doped samples in CO</em><sub><em>2</em></sub> <em>methanation revealed up to three times higher turnover frequencies and CH</em><sub><em>4</em></sub> <em>weight-time yields compared to undoped NiAlO</em><sub><em>x</em></sub><em>.</em> An optimum in catalytic activity at Ce/Ni = 0.1 indicated the prerequisite of a balance between Ni and Ce amounts in the catalyst to avoid undesired byproduct formation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120728"},"PeriodicalIF":4.8,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145733761","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-29DOI: 10.1016/j.apcata.2025.120730
Hina Mehjabeen , Fuping Tian , Li Rui , Jicong Yan , Tao Hu , Xiang Wang
Chemical recycling provides a route for closed-loop recycling of polyethylene terephthalate (PET), in which post-consumer PET is depolymerized to bis(2-hydroxyethyl) terephthalate (BHET) via glycolysis and can subsequently be repolymerized to produce recycled PET (rPET). Herein, we have developed a heterogeneous catalytic approach using MgO/Y2O3, the first reported use of Y2O3 for polyester depolymerization to facilitate the glycolysis of PET. The catalyst provides strong and stable basic sites, enabling the depolymerization of 10 g PET with 0.1 g catalyst in 20 mL ethylene glycol (EG) at 185 °C for 2.25 h, achieving 88 ± 3 % PET conversion and 85 ± 3 % BHET yield. In addition, this work demonstrates high PET conversion and BHET yield under relatively mild conditions using a low amount of EG.
{"title":"Catalytic glycolysis of polyethylene terephthalate over MgO/Y2O3 with reduced ethylene glycol consumption","authors":"Hina Mehjabeen , Fuping Tian , Li Rui , Jicong Yan , Tao Hu , Xiang Wang","doi":"10.1016/j.apcata.2025.120730","DOIUrl":"10.1016/j.apcata.2025.120730","url":null,"abstract":"<div><div>Chemical recycling provides a route for closed-loop recycling of polyethylene terephthalate (PET), in which post-consumer PET is depolymerized to bis(2-hydroxyethyl) terephthalate (BHET) via glycolysis and can subsequently be repolymerized to produce recycled PET (rPET). Herein, we have developed a heterogeneous catalytic approach using MgO/Y<sub>2</sub>O<sub>3</sub>, the first reported use of Y<sub>2</sub>O<sub>3</sub> for polyester depolymerization to facilitate the glycolysis of PET. The catalyst provides strong and stable basic sites, enabling the depolymerization of 10 g PET with 0.1 g catalyst in 20 mL ethylene glycol (EG) at 185 °C for 2.25 h, achieving 88 ± 3 % PET conversion and 85 ± 3 % BHET yield. In addition, this work demonstrates high PET conversion and BHET yield under relatively mild conditions using a low amount of EG.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120730"},"PeriodicalIF":4.8,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682624","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-27DOI: 10.1016/j.apcata.2025.120721
Xue Liu , Wenmiao Chen , Guang Li , Mingyue Xue , Zhi Li , Qiang Liu , Hongyan Zhuo , Yanli Chen
Seawater electrolysis has emerged as a sustainable approach for energy production, but the presence of chloride ions induces severe corrosion and competitive chlorine evolution, significantly impairing oxygen evolution reaction (OER) efficiency. To address this challenge, we developed a phosphate-engineered CoFe2O4-NF-P (200) electrocatalyst with precisely controlled oxygen vacancies for efficient and stable seawater oxidation. During synthesis, PH3 gas not only reduces Co/Fe cations and generates oxygen vacancies, but its residual POx species also facilitate the in-situ formation of active MOOH-P phases. This promotion effect can be attributed to the POx-induced localized charge imbalance on the CoFe2O4 surface, which triggers protonation and creates a highly hydrated and hydroxylated environment conducive to MOOH-P transformation. Undoubtedly, the CoFe2O4-NF-P (200) electrode demonstrated outstanding OER activity, achieving a current density of 500 mA cm⁻² at a low overpotential of 350 mV (1.580 V) in seawater. Density functional theory (DFT) calculations demonstrate that the formation of MOOH-P following surface reconstruction under phosphidation effectively reduces the bandgap, optimizes the adsorption energy of *O intermediates, and consequently significantly lowers the kinetic barrier of the OER. This work establishes oxygen vacancy engineering as an effective strategy for designing robust seawater oxidation electrocatalysts.
海水电解已成为一种可持续的能源生产方法，但氯离子的存在会导致严重的腐蚀和竞争性氯析出，显著降低析氧反应（OER）效率。为了解决这一挑战，我们开发了一种磷酸盐工程CoFe2O4-NF-P（200）电催化剂，具有精确控制的氧空位，可实现高效稳定的海水氧化。在合成过程中，PH3气体不仅降低了Co/Fe阳离子，产生了氧空位，而且其残留的POx也促进了活性MOOH-P相的原位形成。这种促进作用可归因于pox诱导的CoFe2O4表面局部电荷不平衡，从而触发质子化，创造了一个高度水化和羟基化的环境，有利于MOOH-P转化。毫无疑问，CoFe2O4-NF-P（200）电极表现出出色的OER活性，在海水中以350 mV （1.580 V）的低过电位实现500 mA cm⁻²的电流密度。密度泛函理论（DFT）计算表明，在磷化作用下，表面重构后形成的MOOH-P有效地减小了带隙，优化了*O中间体的吸附能，从而显著降低了OER的动力学势垒。本研究建立了氧空位工程作为设计强效海水氧化电催化剂的有效策略。
{"title":"Phosphate-Induced oxygen vacancies and surface reconstruction of CoFe2O4 for industrial-grade seawater oxidation","authors":"Xue Liu , Wenmiao Chen , Guang Li , Mingyue Xue , Zhi Li , Qiang Liu , Hongyan Zhuo , Yanli Chen","doi":"10.1016/j.apcata.2025.120721","DOIUrl":"10.1016/j.apcata.2025.120721","url":null,"abstract":"<div><div>Seawater electrolysis has emerged as a sustainable approach for energy production, but the presence of chloride ions induces severe corrosion and competitive chlorine evolution, significantly impairing oxygen evolution reaction (OER) efficiency. To address this challenge, we developed a phosphate-engineered CoFe<sub>2</sub>O<sub>4</sub>-NF-P (200) electrocatalyst with precisely controlled oxygen vacancies for efficient and stable seawater oxidation. During synthesis, PH<sub>3</sub> gas not only reduces Co/Fe cations and generates oxygen vacancies, but its residual PO<sub>x</sub> species also facilitate the in-situ formation of active MOOH-P phases. This promotion effect can be attributed to the PO<sub>x</sub>-induced localized charge imbalance on the CoFe<sub>2</sub>O<sub>4</sub> surface, which triggers protonation and creates a highly hydrated and hydroxylated environment conducive to MOOH-P transformation. Undoubtedly, the CoFe<sub>2</sub>O<sub>4</sub>-NF-P (200) electrode demonstrated outstanding OER activity, achieving a current density of 500 mA cm⁻² at a low overpotential of 350 mV (1.580 V) in seawater. Density functional theory (DFT) calculations demonstrate that the formation of MOOH-P following surface reconstruction under phosphidation effectively reduces the bandgap, optimizes the adsorption energy of *O intermediates, and consequently significantly lowers the kinetic barrier of the OER. This work establishes oxygen vacancy engineering as an effective strategy for designing robust seawater oxidation electrocatalysts.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120721"},"PeriodicalIF":4.8,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145617377","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this work, an investigation of methane pyrolysis over Fe/Al-based catalysts has been carried out to optimize the formulation, that is to obtain structural features suitable to high C/Fe ratios before the catalyst is fully deactivated. At this scope, Fe-Al2O3 catalysts at different Fe-Al ratios were prepared by the fusion-decomposition method and reduction in H2; fresh and reduced samples were extensively characterized by N2 adsorption/desorption, electron microscopies, X-Ray Diffraction and Raman spectroscopy. As a general feature, the reduced catalyst structures are characterized by mesoporous Fe aggregates dispersed in microporous alumina, with presence of FeAl2O4 at the interface; however, several textural parameters (including specific surface area, pore size distribution, Fe crystallite size, FeAl2O4 abundance) change importantly with increasing Fe/Al ratio. Close to the equimolar Fe-Al ratio, such textural properties appear optimal to guarantee high Fe dispersion and accessibility. All the formulations were first screened in methane pyrolysis in a thermobalance; a selected subset of formulations was then tested in a packed bed reactor. The study reveals that formulations with Fe-Al molar ratios from 50–50 to 75–25 are all characterized by high initial activity and lower deactivation rate, thus achieving the maximum C-accumulation capacity. Among them, the equimolar formulation achieved the highest C/Fe ratio, reaching 2.5 gC/gFe after 1 h testing with 40 % CH4 at 800°C. The spent catalysts were characterized by electron microscopies, X-Ray Diffraction and Raman spectroscopy to better comprehend the effects of extent of reaction and Fe-Al ratio on the characteristics of the solid. In all the samples, after reaction, the Fe3C was the main iron-containing phase and a progressive decrease of the residual Fe phase was observed at increasing C-accumulation. Concerning the nature of C-structures, a large variety of them was observed depending on Fe content and crystalline size.
{"title":"Methane pyrolysis on fused Fe-Al2O3 catalysts: Characterization of catalyst structure, performance and carbon formation","authors":"Chiara Negri , Veronica Piazza , Marco Orsenigo, Matteo Maestri, Gianpiero Groppi, Lidia Castoldi, Alessandra Beretta","doi":"10.1016/j.apcata.2025.120719","DOIUrl":"10.1016/j.apcata.2025.120719","url":null,"abstract":"<div><div>In this work, an investigation of methane pyrolysis over Fe/Al-based catalysts has been carried out to optimize the formulation, that is to obtain structural features suitable to high C/Fe ratios before the catalyst is fully deactivated. At this scope, Fe-Al<sub>2</sub>O<sub>3</sub> catalysts at different Fe-Al ratios were prepared by the fusion-decomposition method and reduction in H<sub>2</sub>; fresh and reduced samples were extensively characterized by N<sub>2</sub> adsorption/desorption, electron microscopies, X-Ray Diffraction and Raman spectroscopy. As a general feature, the reduced catalyst structures are characterized by mesoporous Fe aggregates dispersed in microporous alumina, with presence of FeAl<sub>2</sub>O<sub>4</sub> at the interface; however, several textural parameters (including specific surface area, pore size distribution, Fe crystallite size, FeAl<sub>2</sub>O<sub>4</sub> abundance) change importantly with increasing Fe/Al ratio. Close to the equimolar Fe-Al ratio, such textural properties appear optimal to guarantee high Fe dispersion and accessibility. All the formulations were first screened in methane pyrolysis in a thermobalance; a selected subset of formulations was then tested in a packed bed reactor. The study reveals that formulations with Fe-Al molar ratios from 50–50 to 75–25 are all characterized by high initial activity and lower deactivation rate, thus achieving the maximum C-accumulation capacity. Among them, the equimolar formulation achieved the highest C/Fe ratio, reaching 2.5 g<sub>C</sub>/g<sub>Fe</sub> after 1 h testing with 40 % CH<sub>4</sub> at 800°C. The spent catalysts were characterized by electron microscopies, X-Ray Diffraction and Raman spectroscopy to better comprehend the effects of extent of reaction and Fe-Al ratio on the characteristics of the solid. In all the samples, after reaction, the Fe<sub>3</sub>C was the main iron-containing phase and a progressive decrease of the residual Fe phase was observed at increasing C-accumulation. Concerning the nature of C-structures, a large variety of them was observed depending on Fe content and crystalline size.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120719"},"PeriodicalIF":4.8,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145617330","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
An imperative cornerstone of modern organic synthesis lies in the ability to actively shape molecular frameworks through selective bond formation. Carbon–carbon (C–C) bonds provide the fundamental backbone of organic molecules, whereas carbon–heteroatom linkages, particularly C–N, C–O, and C–S bonds, impart essential structural and functional diversity that underpins chemical reactivity, bioactivity, and material properties. Over the past few decades, the evolution from classical strategies such as Wurtz coupling, Grignard addition, aldol condensation, and nucleophilic substitutions towards catalytic methodologies has transformed the synthetic landscape. Transition-metal catalysis, exemplified by Suzuki, Heck, and Negishi cross-couplings, has enabled highly efficient, selective, and mild routes for C–C and carbon–heteroatom bond construction. Parallel developments in photocatalysis and organocatalysis have expanded the synthetic toolbox by offering environmentally benign and metal-free alternatives with broad substrate tolerance. These advances have not only enhanced regio- and stereocontrol but also facilitated late-stage functionalization of complex molecules, thereby streamlining the synthesis of bioactive compounds and functional materials. Increasing emphasis on sustainability has further driven the integration of green chemistry principles, including renewable feedstocks, recyclable catalysts, and energy-efficient conditions. This review highlights recent catalytic innovations in C–C, C–N, C–O, and C–S bond formation, discusses their mechanistic foundations, and underscores their implications in medicinal chemistry, materials science, and sustainable synthesis.
{"title":"Sustainable catalytic strategies for carbon–carbon and carbon–heteroatom (C–S, C–N, C–O, C–Se) bond formation: Green pathways to advanced molecules","authors":"Aeyaz Ahmad Bhat , Noureddine Elboughdiri , Abhinav Kumar , Ankit Dilipkumar Oza , Karim Kriaa , Chemseddine Maatki , Bilel Hadrich , Anjuman Ayub , Meraj Ahmed , Atif Khurshid Wani","doi":"10.1016/j.apcata.2025.120714","DOIUrl":"10.1016/j.apcata.2025.120714","url":null,"abstract":"<div><div>An imperative cornerstone of modern organic synthesis lies in the ability to actively shape molecular frameworks through selective bond formation. Carbon–carbon (C–C) bonds provide the fundamental backbone of organic molecules, whereas carbon–heteroatom linkages, particularly C–N, C–O, and C–S bonds, impart essential structural and functional diversity that underpins chemical reactivity, bioactivity, and material properties. Over the past few decades, the evolution from classical strategies such as Wurtz coupling, Grignard addition, aldol condensation, and nucleophilic substitutions towards catalytic methodologies has transformed the synthetic landscape. Transition-metal catalysis, exemplified by Suzuki, Heck, and Negishi cross-couplings, has enabled highly efficient, selective, and mild routes for C–C and carbon–heteroatom bond construction. Parallel developments in photocatalysis and organocatalysis have expanded the synthetic toolbox by offering environmentally benign and metal-free alternatives with broad substrate tolerance. These advances have not only enhanced regio- and stereocontrol but also facilitated late-stage functionalization of complex molecules, thereby streamlining the synthesis of bioactive compounds and functional materials. Increasing emphasis on sustainability has further driven the integration of green chemistry principles, including renewable feedstocks, recyclable catalysts, and energy-efficient conditions. This review highlights recent catalytic innovations in C–C, C–N, C–O, and C–S bond formation, discusses their mechanistic foundations, and underscores their implications in medicinal chemistry, materials science, and sustainable synthesis.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120714"},"PeriodicalIF":4.8,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682631","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-25DOI: 10.1016/j.apcata.2025.120718
Francesco Sandri , Jennifer Cueto , Christoph Schmidt , Anssi Peuronen , Pia Damlin , Teija Tirri , Kari Eränen , Mika Lastusaari , Narendra Kumar , David P. Serrano , Päivi Mäki-Arvela , Dmitry Yu. Murzin
The production of aromatics, specifically benzene, toluene and xylenes (BTX), from bio-derived feedstock such as ethanol and furfural can be achieved by zeolite catalysts. However, the formation of coke strongly limits this reaction leading to catalyst deactivation. In-depth understanding of the relationship between the catalyst characteristics and the mechanism of carbon deposit is needed to improve potential applicability of this novel approach for BTX production. Evaluation of the catalytic activity of β and ZSM-5 zeolites in the aromatization of ethanol and furfural, coupled with the characterization of the spent catalysts, gave important insights on the structure and features that are required to increase the aromatics formation. With these investigations it was possible to determine the location of the catalytic sites that are active in the aromatization reaction, defining at the same time the mechanism of deactivation by coke formation. These findings give important advances for the future design of efficient catalysts for the aromatics production.
{"title":"Production of aromatics from furfural and ethanol over zeolite catalysts: Reaction and deactivation mechanisms, effect of acidity and zeolite structures","authors":"Francesco Sandri , Jennifer Cueto , Christoph Schmidt , Anssi Peuronen , Pia Damlin , Teija Tirri , Kari Eränen , Mika Lastusaari , Narendra Kumar , David P. Serrano , Päivi Mäki-Arvela , Dmitry Yu. Murzin","doi":"10.1016/j.apcata.2025.120718","DOIUrl":"10.1016/j.apcata.2025.120718","url":null,"abstract":"<div><div>The production of aromatics, specifically benzene, toluene and xylenes (BTX), from bio-derived feedstock such as ethanol and furfural can be achieved by zeolite catalysts. However, the formation of coke strongly limits this reaction leading to catalyst deactivation. In-depth understanding of the relationship between the catalyst characteristics and the mechanism of carbon deposit is needed to improve potential applicability of this novel approach for BTX production. Evaluation of the catalytic activity of β and ZSM-5 zeolites in the aromatization of ethanol and furfural, coupled with the characterization of the spent catalysts, gave important insights on the structure and features that are required to increase the aromatics formation. With these investigations it was possible to determine the location of the catalytic sites that are active in the aromatization reaction, defining at the same time the mechanism of deactivation by coke formation. These findings give important advances for the future design of efficient catalysts for the aromatics production.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120718"},"PeriodicalIF":4.8,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682622","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In the industrial production of high value-added polyethylene, the efficient removal of trace acetylene impurities from raw ethylene is a key step to ensure the quality of the polymer. However, current mainstream industrial technology relies on the thermally catalysed selective hydrogenation of acetylene under high-temperature and high-pressure conditions. Electrocatalytic acetylene semi-hydrogenation (EASH) is an alternative, environmentally friendly strategy that can be performed under mild reaction conditions. Herein, using density functional theory calculations, the performances of nine p-block single-metals (ie, Al, Ga, Ge, Tl, Sb, Sn, Bi, In and Pb) supported on a N-doped graphene (MN4-G) catalyst are studied to screen single-atom catalysts with high activity and selectivity for EASH. Firstly, comprehensive evaluations of binding, cohesive and formation energies confirm that MN4-G configurations are thermodynamically stable. Secondly, Gibbs free energy analysis shows that PbN4-G catalysts promote EASH and inhibit the side reaction of hydrogen evolution. Thirdly, the analysis and calculation results show that the adsorption energy of acetylene and ethylene can be used as characteristic descriptors to predict the EASH selectivity of the catalyst. Finally, the mechanism of its catalytic activity is explained from the electronic and orbital perspectives. Our results show that the directional coupling between Pz and C2H4- anti-bonding orbitals is the key to regulating ethylene desorption. Moderate electronic feedback can weaken C2H4 adsorption and avoid excessive hydrogenation, ensuring high selectivity. This study provides a preferred systems for designing high-performance EASH catalysts as well as a theoretical basis and a design strategy for EASH catalysts for industrial applications.
{"title":"Single-atom catalysts with p-block metals for the electrocatalytic semi-hydrogenation of acetylene: A DFT study","authors":"Xiaoqing Gong, Yi Yang, Yuanyuan Yu, Mingqiang Liu, Xiaohong Song, Kefeng Xie","doi":"10.1016/j.apcata.2025.120716","DOIUrl":"10.1016/j.apcata.2025.120716","url":null,"abstract":"<div><div>In the industrial production of high value-added polyethylene, the efficient removal of trace acetylene impurities from raw ethylene is a key step to ensure the quality of the polymer. However, current mainstream industrial technology relies on the thermally catalysed selective hydrogenation of acetylene under high-temperature and high-pressure conditions. Electrocatalytic acetylene semi-hydrogenation (EASH) is an alternative, environmentally friendly strategy that can be performed under mild reaction conditions. Herein, using density functional theory calculations, the performances of nine <em>p</em>-block single-metals (ie, Al, Ga, Ge, Tl, Sb, Sn, Bi, In and Pb) supported on a N-doped graphene (MN<sub>4</sub>-G) catalyst are studied to screen single-atom catalysts with high activity and selectivity for EASH. Firstly, comprehensive evaluations of binding, cohesive and formation energies confirm that MN<sub>4</sub>-G configurations are thermodynamically stable. Secondly, Gibbs free energy analysis shows that PbN<sub>4</sub>-G catalysts promote EASH and inhibit the side reaction of hydrogen evolution. Thirdly, the analysis and calculation results show that the adsorption energy of acetylene and ethylene can be used as characteristic descriptors to predict the EASH selectivity of the catalyst. Finally, the mechanism of its catalytic activity is explained from the electronic and orbital perspectives. Our results show that the directional coupling between <em>P</em><sub><em>z</em></sub> and C<sub>2</sub>H<sub>4</sub>-<span><math><msubsup><mrow><mi>π</mi></mrow><mrow><mi>z</mi></mrow><mrow><mo>*</mo></mrow></msubsup></math></span> anti-bonding orbitals is the key to regulating ethylene desorption. Moderate electronic feedback can weaken C<sub>2</sub>H<sub>4</sub> adsorption and avoid excessive hydrogenation, ensuring high selectivity. This study provides a preferred systems for designing high-performance EASH catalysts as well as a theoretical basis and a design strategy for EASH catalysts for industrial applications.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"710 ","pages":"Article 120716"},"PeriodicalIF":4.8,"publicationDate":"2025-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621177","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The persistent nature, toxicity, and resistance to traditional treatment procedures of antibiotics, pesticides, and phenols have made their growing presence in water bodies a major environmental and public health challenge. The degradation of these emerging pollutants has shown great promise using advanced oxidation processes (AOPs), particularly the photo-Fenton process. This review highlights the growing levels of contaminants in water, such as antibiotics, pesticides, and phenols, along with their sources, fate, and impacts on human health and the environment. The fundamentals and mechanistic processes of the photo-Fenton approach are briefly discussed. Under visible light, single-atom catalysts (SACs) offer greater efficiency, selectivity, and recyclability in pollutant degradation due to their atomically distributed metal sites, high catalytic activity, and variable coordination environments. The most recent developments in single-atom-based photo-Fenton catalysts, their design, synthesis strategies, and applications for the degradation of antibiotics, pesticides, and phenolic pollutants in water are thoroughly discussed and summarized in this review. A critical discussion of essential issues, including catalyst performance under actual water conditions, scalability, and stability, is provided. The article concludes by outlining potential directions for the sustainable implementation and logical design of SAC-based photo-Fenton systems in environmental remediation.
{"title":"Recent advances in single-atom-based photo-Fenton catalysts for the degradation of antibiotics, pesticides, and phenols","authors":"Sahil Rana , Pooja Dhiman , Pankaj Sharma , Mashallah Rezakazemi , Gaurav Sharma","doi":"10.1016/j.apcata.2025.120717","DOIUrl":"10.1016/j.apcata.2025.120717","url":null,"abstract":"<div><div>The persistent nature, toxicity, and resistance to traditional treatment procedures of antibiotics, pesticides, and phenols have made their growing presence in water bodies a major environmental and public health challenge. The degradation of these emerging pollutants has shown great promise using advanced oxidation processes (AOPs), particularly the photo-Fenton process. This review highlights the growing levels of contaminants in water, such as antibiotics, pesticides, and phenols, along with their sources, fate, and impacts on human health and the environment. The fundamentals and mechanistic processes of the photo-Fenton approach are briefly discussed. Under visible light, single-atom catalysts (SACs) offer greater efficiency, selectivity, and recyclability in pollutant degradation due to their atomically distributed metal sites, high catalytic activity, and variable coordination environments. The most recent developments in single-atom-based photo-Fenton catalysts, their design, synthesis strategies, and applications for the degradation of antibiotics, pesticides, and phenolic pollutants in water are thoroughly discussed and summarized in this review. A critical discussion of essential issues, including catalyst performance under actual water conditions, scalability, and stability, is provided. The article concludes by outlining potential directions for the sustainable implementation and logical design of SAC-based photo-Fenton systems in environmental remediation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120717"},"PeriodicalIF":4.8,"publicationDate":"2025-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682623","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-22DOI: 10.1016/j.apcata.2025.120715
Valmir B. Silva , Patrícia M. Soares, Elisa S. Orth
Understanding how substituents influence chemical reactivity is strategic when screening and predicting catalysts, especially towards the neutralization of toxic organophosphates, present in agrochemicals and chemical warfare. Herein, the substituent effects were concomitantly investigated on both nucleophilic and electrophilic centers in catalytic dephosphorylation reactions, focusing on imidazole-based nucleophiles and aryl organophosphates. Eight imidazole derivatives, bearing methyl, carboxylic acid, or hydroxyl groups, and two aryl organophosphates, were studied. High catalytic outcomes were obtained: nearly 2 min, that would take over 7 days in their absence. A simultaneous multianalysis approach (combining our data with the literature) was proposed with a novel trilinear Brønsted-type relationship correlating the reaction rate constants with the basicity of the imidazole nucleophiles and the pKa values of both the leaving and non-leaving groups of the organophosphates. While the nucleophile and leaving group exert major influences on reactivity, the non-leaving group's contribution is lower. Particularly, imidazoles display higher sensitivity to substituent variations compared to other nucleophiles, suggesting that structural tuning of the imidazole core can greatly enhance catalytic efficiency. As a proof of concept, the model accurately predicted the catalytic performance for a given reaction, compared to the one reported experimentally (∼3 % deviation). This approach offers a valuable framework for designing efficient catalysts and guiding safe, targeted experimentation in organophosphate degradation and related applications, avoiding unnecessary experiments with highly toxic agents. Such structure-reactivity relationships can foster chemical security and safety in the scope of organophosphate degradation and detection and be broaden to other classes of reactions.
{"title":"Simultaneous multianalysis of substituent effects in the catalytic degradation of organophosphates by imidazoles","authors":"Valmir B. Silva , Patrícia M. Soares, Elisa S. Orth","doi":"10.1016/j.apcata.2025.120715","DOIUrl":"10.1016/j.apcata.2025.120715","url":null,"abstract":"<div><div>Understanding how substituents influence chemical reactivity is strategic when screening and predicting catalysts, especially towards the neutralization of toxic organophosphates, present in agrochemicals and chemical warfare. Herein, the substituent effects were concomitantly investigated on both nucleophilic and electrophilic centers in catalytic dephosphorylation reactions, focusing on imidazole-based nucleophiles and aryl organophosphates. Eight imidazole derivatives, bearing methyl, carboxylic acid, or hydroxyl groups, and two aryl organophosphates, were studied. High catalytic outcomes were obtained: nearly 2 min, that would take over 7 days in their absence. A simultaneous multianalysis approach (combining our data with the literature) was proposed with a novel trilinear Brønsted-type relationship correlating the reaction rate constants with the basicity of the imidazole nucleophiles and the pK<sub>a</sub> values of both the leaving and non-leaving groups of the organophosphates. While the nucleophile and leaving group exert major influences on reactivity, the non-leaving group's contribution is lower. Particularly, imidazoles display higher sensitivity to substituent variations compared to other nucleophiles, suggesting that structural tuning of the imidazole core can greatly enhance catalytic efficiency. As a proof of concept, the model accurately predicted the catalytic performance for a given reaction, compared to the one reported experimentally (∼3 % deviation). This approach offers a valuable framework for designing efficient catalysts and guiding safe, targeted experimentation in organophosphate degradation and related applications, avoiding unnecessary experiments with highly toxic agents. Such structure-reactivity relationships can foster chemical security and safety in the scope of organophosphate degradation and detection and be broaden to other classes of reactions.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"710 ","pages":"Article 120715"},"PeriodicalIF":4.8,"publicationDate":"2025-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621178","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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