Pub Date : 2025-12-02DOI: 10.1016/j.apcata.2025.120734
Xu Jia , Jiaolong Qiao , Zhiqi Song , Jiaqi Zhang , Liuxue Zhang , Guomin Yu , Xiulian Wang , Shaokang Liu
In order to improve the efficiency of the phenol production process, a novel photocatalytic semiconductor material Fe-MOF/Eu-C3N4 was synthesized through an in-situ method. Compared with C3N4 and Fe-MOF, the photocatalytic performance of the heterojunction was significantly enhanced. The direct hydroxylation of benzene into phenol was effectively catalyzed under the visible light irradiation. The yield and selectivity of phenol reached 21.25 % and 95 % under the optimal experimental conditions, respectively. The photocatalytic activity of the Fe-MOF/Eu-C3N4 remained high after seven reaction cycles. Therefore, the explored photocatalytic self-Fenton system could be applied to the field of direct hydroxylation of benzene to phenol.
{"title":"Fe-MOF-mediated europium-modified graphitic carbon nitride composites: A route to efficient light-driven benzene hydroxylation","authors":"Xu Jia , Jiaolong Qiao , Zhiqi Song , Jiaqi Zhang , Liuxue Zhang , Guomin Yu , Xiulian Wang , Shaokang Liu","doi":"10.1016/j.apcata.2025.120734","DOIUrl":"10.1016/j.apcata.2025.120734","url":null,"abstract":"<div><div>In order to improve the efficiency of the phenol production process, a novel photocatalytic semiconductor material Fe-MOF/Eu-C<sub>3</sub>N<sub>4</sub> was synthesized through an in-situ method. Compared with C<sub>3</sub>N<sub>4</sub> and Fe-MOF, the photocatalytic performance of the heterojunction was significantly enhanced. The direct hydroxylation of benzene into phenol was effectively catalyzed under the visible light irradiation. The yield and selectivity of phenol reached 21.25 % and 95 % under the optimal experimental conditions, respectively. The photocatalytic activity of the Fe-MOF/Eu-C<sub>3</sub>N<sub>4</sub> remained high after seven reaction cycles. Therefore, the explored photocatalytic self-Fenton system could be applied to the field of direct hydroxylation of benzene to phenol.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120734"},"PeriodicalIF":4.8,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682632","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 : 2025-12-01DOI: 10.1016/j.apcata.2025.120739
Can Zhu , Yuehui Luo , Wanyun Tang , Nan Huang , Shiju Tao , Huan Yang , Hao Feng , Quanxin Li
The high value transformation of renewable lignocellulose is crucial for reducing carbon emissions and promoting sustainable development. This effort aims to demonstrate that bio-based cresol (an important high-value chemical) can be yielded from lignocellulosic biomass. This novel directed conversion was effectuated by coupling catalytic pyrolysis of lignocellulose into aromatic intermediates and catalytic hydroxylation of aromatic intermediates into bio-based cresol. We also developed a highly active and recyclable magnetic catalyst (Cu0-CuFe2O4@Biochar(HTR)), confirming that introducing Cu0 into the copper-iron composite metal oxide catalyst promotes hydroxyl radicals formation and the synthesis of bio-based cresol. The Cu0-CuFe2O4@Biochar(HTR) catalyst exhibited high cresol selectivity (81.1 %) and high cresol yield (54.3 %) in catalytic hydroxylation of aromatic intermediates into bio-based cresol. Based on catalyst characterizations and hydroxyl radicals analysis, the presumable reaction mechanism related to the bio-based cresol synthesis was proposed. Potentially, this strategy may provide a beneficial pathway for developing high-value bio-based chemical (cresol) using renewable lignocellulosic biomass.
{"title":"Selective catalytic transformation of lignocellulose into bio-based cresol using recyclable Cu0-CuFe2O4@Biochar composite catalyst","authors":"Can Zhu , Yuehui Luo , Wanyun Tang , Nan Huang , Shiju Tao , Huan Yang , Hao Feng , Quanxin Li","doi":"10.1016/j.apcata.2025.120739","DOIUrl":"10.1016/j.apcata.2025.120739","url":null,"abstract":"<div><div>The high value transformation of renewable lignocellulose is crucial for reducing carbon emissions and promoting sustainable development. This effort aims to demonstrate that bio-based cresol (an important high-value chemical) can be yielded from lignocellulosic biomass. This novel directed conversion was effectuated by coupling catalytic pyrolysis of lignocellulose into aromatic intermediates and catalytic hydroxylation of aromatic intermediates into bio-based cresol. We also developed a highly active and recyclable magnetic catalyst (Cu<sup>0</sup>-CuFe<sub>2</sub>O<sub>4</sub>@Biochar(HTR)), confirming that introducing Cu<sup>0</sup> into the copper-iron composite metal oxide catalyst promotes hydroxyl radicals formation and the synthesis of bio-based cresol. The Cu<sup>0</sup>-CuFe<sub>2</sub>O<sub>4</sub>@Biochar(HTR) catalyst exhibited high cresol selectivity (81.1 %) and high cresol yield (54.3 %) in catalytic hydroxylation of aromatic intermediates into bio-based cresol. Based on catalyst characterizations and hydroxyl radicals analysis, the presumable reaction mechanism related to the bio-based cresol synthesis was proposed. Potentially, this strategy may provide a beneficial pathway for developing high-value bio-based chemical (cresol) using renewable lignocellulosic biomass.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120739"},"PeriodicalIF":4.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682627","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 : 2025-12-01DOI: 10.1016/j.apcata.2025.120738
Mufudzi Chaza, Mohamed I. Fadlalla, Thulani M. Nyathi, Nico Fischer, Michael Claeys
The interaction between a support material and active metal influences the activity, selectivity, and physicochemical stability of a supported catalyst. In this study, the effect of support materials (viz., alumina (Al2O3) and silica-modified-alumina (SiOx-m-Al2O3)) on the performance of Ru-based catalysts for Power-to-Liquids Fischer-Tropsch synthesis (PtL-FTS) was investigated. The overarching aims of this study were to achieve high CO conversions (>85 %) to C5+ hydrocarbons and low selectivities to CH4 (<5 %) and CO2 (<1 %). Two catalysts of 20 wt.-% Ru loading were synthesised using Al2O3 and SiOx-m-Al2O3 supports. Catalyst evaluation was conducted at 220 ºC and 17.5 bar. The Ru/SiOx-m-Al2O3 catalyst achieved higher and more stable CO conversions (≥87 %) and C5+ selectivities (≥92 %) when compared with the Ru/Al2O3 catalyst (≥80 % and ≥88 %, respectively). Spent catalyst characterisation via XRD showed no changes in phases or crystallite sizes, thereby eliminating active metal oxidation or sintering as catalyst deactivation mechanisms. However, the translucent overlayers (observed in TEM micrographs) and the G- and D-bands (observed in Raman spectra) indicated the presence of carbon deposits in both catalysts, which may have led to the blocking of active sites and consequent loss of CO conversion over time. Thermogravimetric analysis revealed that more carbon was deposited in the Ru/Al2O3 catalyst (29 % weight loss measured) when compared with the Ru/SiOx-m-Al2O3 catalyst (11 % weight loss measured), in agreement with the contrasting CO conversion losses observed. Therefore, modifying Al2O3 using SiOx led to the inhibition of carbon deposition and, thus, greater catalytic performance.
{"title":"Fischer-Tropsch synthesis over supported Ru catalysts for high syngas conversions: A comparative study of Al2O3 and SiOx-modified-Al2O3 supports","authors":"Mufudzi Chaza, Mohamed I. Fadlalla, Thulani M. Nyathi, Nico Fischer, Michael Claeys","doi":"10.1016/j.apcata.2025.120738","DOIUrl":"10.1016/j.apcata.2025.120738","url":null,"abstract":"<div><div>The interaction between a support material and active metal influences the activity, selectivity, and physicochemical stability of a supported catalyst. In this study, the effect of support materials (<em>viz.</em>, alumina (Al<sub>2</sub>O<sub>3</sub>) and silica-modified-alumina (SiO<sub>x</sub>-m-Al<sub>2</sub>O<sub>3</sub>)) on the performance of Ru-based catalysts for Power-to-Liquids Fischer-Tropsch synthesis (PtL-FTS) was investigated. The overarching aims of this study were to achieve high CO conversions (>85 %) to C<sub>5+</sub> hydrocarbons and low selectivities to CH<sub>4</sub> (<5 %) and CO<sub>2</sub> (<1 %). Two catalysts of 20 wt.-% Ru loading were synthesised using Al<sub>2</sub>O<sub>3</sub> and SiO<sub>x</sub>-m-Al<sub>2</sub>O<sub>3</sub> supports. Catalyst evaluation was conducted at 220 ºC and 17.5 bar. The Ru/SiO<sub>x</sub>-m-Al<sub>2</sub>O<sub>3</sub> catalyst achieved higher and more stable CO conversions (≥87 %) and C<sub>5+</sub> selectivities (≥92 %) when compared with the Ru/Al<sub>2</sub>O<sub>3</sub> catalyst (≥80 % and ≥88 %, respectively). Spent catalyst characterisation <em>via</em> XRD showed no changes in phases or crystallite sizes, thereby eliminating active metal oxidation or sintering as catalyst deactivation mechanisms. However, the translucent overlayers (observed in TEM micrographs) and the G- and <span>D</span>-bands (observed in Raman spectra) indicated the presence of carbon deposits in both catalysts, which may have led to the blocking of active sites and consequent loss of CO conversion over time. Thermogravimetric analysis revealed that more carbon was deposited in the Ru/Al<sub>2</sub>O<sub>3</sub> catalyst (29 % weight loss measured) when compared with the Ru/SiO<sub>x</sub>-m-Al<sub>2</sub>O<sub>3</sub> catalyst (11 % weight loss measured), in agreement with the contrasting CO conversion losses observed. Therefore, modifying Al<sub>2</sub>O<sub>3</sub> using SiO<sub>x</sub> led to the inhibition of carbon deposition and, thus, greater catalytic performance.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120738"},"PeriodicalIF":4.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787035","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 construction of efficient interfacial active sites in metal oxides remains a major challenge for driving the CO2 cycloaddition under mild conditions. Herein, we engineered a CoxMg1-xO solid solution catalyst via a controlled reduction strategy, which achieves near-atomic dispersion within the MgO lattice. The catalyst delivers 96 % yield of cyclic carbonate from epichlorohydrin at 90 °C and 0.1 MPa CO2, surpassing the performance of benchmark MgO and Co3O4 catalysts and maintaining stability over five cycles. Structural and spectroscopic characterization (XRD, XPS, UV-Vis) combined with DFT calculations reveal that the high activity originates from synergistic Co-OV-Mg interfacial sites, where Lewis acidic Co2+ activates epoxides and adjacent oxygen vacancies facilitate CO2 adsorption. This synergistic effect lowers the energy barrier for the rate-determining ring-opening step to 0.37 eV. This work demonstrates the rational design of oxide solid solutions to create cooperative interfacial sites for efficient CO2 conversion under mild conditions.
{"title":"Interfacial Co-OV-Mg active centers in valence-tailored solid solutions for mild and efficient CO2 cycloaddition","authors":"Muhua Chen, Yuqing Wang, Mengting Li, Bo Fu, Jihuai Tan, Licheng Li, Meisi Chen","doi":"10.1016/j.apcata.2025.120729","DOIUrl":"10.1016/j.apcata.2025.120729","url":null,"abstract":"<div><div>The construction of efficient interfacial active sites in metal oxides remains a major challenge for driving the CO<sub>2</sub> cycloaddition under mild conditions. Herein, we engineered a Co<sub>x</sub>Mg<sub>1-x</sub>O solid solution catalyst via a controlled reduction strategy, which achieves near-atomic dispersion within the MgO lattice. The catalyst delivers 96 % yield of cyclic carbonate from epichlorohydrin at 90 °C and 0.1 MPa CO<sub>2</sub>, surpassing the performance of benchmark MgO and Co<sub>3</sub>O<sub>4</sub> catalysts and maintaining stability over five cycles. Structural and spectroscopic characterization (XRD, XPS, UV-Vis) combined with DFT calculations reveal that the high activity originates from synergistic Co-O<sub>V</sub>-Mg interfacial sites, where Lewis acidic Co<sup>2</sup><sup>+</sup> activates epoxides and adjacent oxygen vacancies facilitate CO<sub>2</sub> adsorption. This synergistic effect lowers the energy barrier for the rate-determining ring-opening step to 0.37 eV. This work demonstrates the rational design of oxide solid solutions to create cooperative interfacial sites for efficient CO<sub>2</sub> conversion under mild conditions.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120729"},"PeriodicalIF":4.8,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682628","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 : 2025-11-30DOI: 10.1016/j.apcata.2025.120735
Wijnand Marquart, Michael Claeys, Nico Fischer
The reverse water-gas shift (RWGS) reaction is thermodynamically limited due to its endothermic nature in terms of CO2 conversion. While higher reaction temperatures and increased H2/CO2 feed ratios can enhance CO2 conversion, a more efficient approach involves reaction intensification via the removal of the by-product (H2O), shifting the equilibrium per Le Chatelier’s principle. Ex situ H2O removal, combined with recycling of unreacted gases leads to CO-enriched feeds, which in turn promotes methanation, especially at lower temperatures. In this study, the origin of CH4 formation was investigated under both conventional and CO-enriched RWGS feed conditions using (isotopically labelled) transient, breakthrough, experiments over a Mo2C catalysts, known for its high RWGS activity. In CO-free feeds, methanation is highly suppressed, even under elevated pressure. In contrast, a CO enriched feed significantly enhanced CH4 formation, particularly during reaction initiation. Using isotopically labelled C13O2, two key insights were revealed: (1) CH4 is primarily formed via adsorbed *CO species (either adsorbed from the gas phase or via CO2 dissociation), and (2) in the presence of an extra reducing agent in the feed (CO), the activity of the catalysts is improved by facilitating the removal of surface *O species. These findings underscore the importance of improving the hydrogenation (or *O removal) capacity of Mo2C catalysts to boost performance under both conventional and intensified RWGS conditions.
{"title":"On the origin of methane in the RWGS: Insights into selectivity on Mo2C catalysts","authors":"Wijnand Marquart, Michael Claeys, Nico Fischer","doi":"10.1016/j.apcata.2025.120735","DOIUrl":"10.1016/j.apcata.2025.120735","url":null,"abstract":"<div><div>The reverse water-gas shift (RWGS) reaction is thermodynamically limited due to its endothermic nature in terms of CO<sub>2</sub> conversion. While higher reaction temperatures and increased H<sub>2</sub>/CO<sub>2</sub> feed ratios can enhance CO<sub>2</sub> conversion, a more efficient approach involves reaction intensification <em>via</em> the removal of the by-product (H<sub>2</sub>O), shifting the equilibrium per Le Chatelier’s principle. <em>Ex situ</em> H<sub>2</sub>O removal, combined with recycling of unreacted gases leads to CO-enriched feeds, which in turn promotes methanation, especially at lower temperatures. In this study, the origin of CH<sub>4</sub> formation was investigated under both conventional and CO-enriched RWGS feed conditions using (isotopically labelled) transient, breakthrough, experiments over a Mo<sub>2</sub>C catalysts, known for its high RWGS activity. In CO-free feeds, methanation is highly suppressed, even under elevated pressure. In contrast, a CO enriched feed significantly enhanced CH<sub>4</sub> formation, particularly during reaction initiation. Using isotopically labelled C<sup>13</sup>O<sub>2</sub>, two key insights were revealed: (1) CH<sub>4</sub> is primarily formed <em>via</em> adsorbed *CO species (either adsorbed from the gas phase or <em>via</em> CO<sub>2</sub> dissociation), and (2) in the presence of an extra reducing agent in the feed (CO), the activity of the catalysts is improved by facilitating the removal of surface *O species. These findings underscore the importance of improving the hydrogenation (or *O removal) capacity of Mo<sub>2</sub>C catalysts to boost performance under both conventional and intensified RWGS conditions.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120735"},"PeriodicalIF":4.8,"publicationDate":"2025-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682625","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 sustainable production of biofuels via residual and waste biomass is highly desirable, but the efficient catalytic hydrogenation remains a challenge. In this work, a novel strategy was developed for synthesizing Co-Ni alloy nanoparticles encapsulated in nitrogen-doped carbon nanotubes (NCNTs) anchored onto both sides of reduced graphene oxide (rGO) by direct pyrolysis of GO-wrapped core–shell bimetallic organic frameworks (MOFs). Under conditions of 270 ℃, 5 Mpa and 240 min, the CoNi@NCNTs/rGO catalyst achieved 94.6 % conversion efficiency in the hydrogenation of resin oil into hydrocarbon biofuels. This high performance was attributed to the significant synergistic effect between Co and Ni, the in-situ-formed NCNTs@rGO, and its hierarchical porous structure. The CoNi@NCNTs/rGO catalyst possessed a hierarchical porous structure with pores ranging from 1.8 nm to 190 nm, where NCNTs facilitated the dispersion and stabilization of Ni-Co alloy nanoparticles, while electron transfer from Ni to Co increased the electron density at Co sites, thereby enhancing the efficiency of hydrogen activation and dissociation. A reaction network was proposed based on the product distribution to elucidate the hydrogenation reaction pathways of monoterpenes, sesquiterpenes, and diterpenoid resin acids in rosin oil over the CoNi@NCNTs/rGO catalyst. Moreover, the obtained biofuel had a high density of 0.92 g/cm3 and a high heat value of 51.09 MJ/kg. The non-noble metal Co-Ni alloy catalyst offers a sustainable and cost-effective approach for converting bio-oil into biofuel, meeting the growing industry demand for more efficient catalytic processes.
{"title":"Highly efficient hydrogenation of waste resin oil into high-density hydrocarbon biofuel over MOF-derived CoNi@NCNTs/rGO catalyst","authors":"Xiaoxuan Liang, Hairong Mo, Chenghong Wu, Xiaopeng Chen, Mingda Zhang, Xu Wei, Jiezhen Liang, Linlin Wang","doi":"10.1016/j.apcata.2025.120732","DOIUrl":"10.1016/j.apcata.2025.120732","url":null,"abstract":"<div><div>The sustainable production of biofuels via residual and waste biomass is highly desirable, but the efficient catalytic hydrogenation remains a challenge. In this work, a novel strategy was developed for synthesizing Co-Ni alloy nanoparticles encapsulated in nitrogen-doped carbon nanotubes (NCNTs) anchored onto both sides of reduced graphene oxide (rGO) by direct pyrolysis of GO-wrapped core–shell bimetallic organic frameworks (MOFs). Under conditions of 270 ℃, 5 Mpa and 240 min, the CoNi@NCNTs/rGO catalyst achieved 94.6 % conversion efficiency in the hydrogenation of resin oil into hydrocarbon biofuels. This high performance was attributed to the significant synergistic effect between Co and Ni, the in-situ-formed NCNTs@rGO, and its hierarchical porous structure. The CoNi@NCNTs/rGO catalyst possessed a hierarchical porous structure with pores ranging from 1.8 nm to 190 nm, where NCNTs facilitated the dispersion and stabilization of Ni-Co alloy nanoparticles, while electron transfer from Ni to Co increased the electron density at Co sites, thereby enhancing the efficiency of hydrogen activation and dissociation. A reaction network was proposed based on the product distribution to elucidate the hydrogenation reaction pathways of monoterpenes, sesquiterpenes, and diterpenoid resin acids in rosin oil over the CoNi@NCNTs/rGO catalyst. Moreover, the obtained biofuel had a high density of 0.92 g/cm<sup>3</sup> and a high heat value of 51.09 MJ/kg. The non-noble metal Co-Ni alloy catalyst offers a sustainable and cost-effective approach for converting bio-oil into biofuel, meeting the growing industry demand for more efficient catalytic processes.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"711 ","pages":"Article 120732"},"PeriodicalIF":4.8,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145682626","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.2025.120731
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}
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