Pub Date : 2025-01-13DOI: 10.1016/j.cattod.2025.115187
Fahimeh Forouzeshfar , M.R. Coleman , Joseph G. Lawrence
This research investigated depolymerization of poly (ethylene terephthalate) (PET) via glycolysis using a series of ionic liquid (IL) catalysts. Organic acids were paired with 1,8-Diazabicyclo [5.4.0] undec-7-ene (DBU) to produce ionic liquids (DBU-ILs). The study explored the effect of structural variations in the organic acids on PET conversion and bis (2-hydroxyethyl) terephthalate (BHET) yield under optimized reaction conditions (specifically, EG:PET ratio of 5:1, temperature of 190 °C, reaction time of 120 min, and 5 mol% DBU in the catalyst relative to PET). The organic acids were selected to include variation in the (i) number of carboxylic acids available to complex with DBU and (ii) structure of the linker and pendant groups to adjust the lipophilicity of the catalyst. The catalytic activity of the DBU-IL increased with increasing lipophilicity of organic acid. Catalysts with organic acids with aromatic linkers (i.e. terephthalic acid) exhibited lower activities than aliphatic linkers at similar lipophilicity. Notably, a linear relationship was observed between the catalytic activity and lipophilicity for diacids with aliphatic linker of increasing chain length. The apparent rate constant for the DBU-azelaic acid was 32 % greater than for DBU-oxalic acid. Reusability studies showed that there was minimal degradation of the catalytic activity of the DBU-ILs over five reaction cycles.
{"title":"Glycolysis of poly (ethylene terephthalate) using DBU-based ionic liquid catalysts","authors":"Fahimeh Forouzeshfar , M.R. Coleman , Joseph G. Lawrence","doi":"10.1016/j.cattod.2025.115187","DOIUrl":"10.1016/j.cattod.2025.115187","url":null,"abstract":"<div><div>This research investigated depolymerization of poly (ethylene terephthalate) (PET) via glycolysis using a series of ionic liquid (IL) catalysts. Organic acids were paired with 1,8-Diazabicyclo [5.4.0] undec-7-ene (DBU) to produce ionic liquids (DBU-ILs). The study explored the effect of structural variations in the organic acids on PET conversion and bis (2-hydroxyethyl) terephthalate (BHET) yield under optimized reaction conditions (specifically, EG:PET ratio of 5:1, temperature of 190 °C, reaction time of 120 min, and 5 mol% DBU in the catalyst relative to PET). The organic acids were selected to include variation in the (i) number of carboxylic acids available to complex with DBU and (ii) structure of the linker and pendant groups to adjust the lipophilicity of the catalyst. The catalytic activity of the DBU-IL increased with increasing lipophilicity of organic acid. Catalysts with organic acids with aromatic linkers (i.e. terephthalic acid) exhibited lower activities than aliphatic linkers at similar lipophilicity. Notably, a linear relationship was observed between the catalytic activity and lipophilicity for diacids with aliphatic linker of increasing chain length. The apparent rate constant for the DBU-azelaic acid was 32 % greater than for DBU-oxalic acid. Reusability studies showed that there was minimal degradation of the catalytic activity of the DBU-ILs over five reaction cycles.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"450 ","pages":"Article 115187"},"PeriodicalIF":5.2,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143172527","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 : 2025-01-12DOI: 10.1016/j.cattod.2025.115203
Luoyu Gao , Yanqi Shi , Zhenjiang Li, Ziqi Liu, Min Zhang, Yue Xu, Xin Zou, Xin Yuan, Yongzhu Hu, Kai Guo
Solvolysis of postconsumer poly(ethylene terephthalate) (PET) into monomeric feedstocks that can be recycled contributes value-added strategy to waste plastic management. Chemical route for PET recycling with sets of diols, diamines, and amino alcohols as the solvolytic reagents by endogenous basic ionic pair phosphonium organocatalyst was established. Methylation of tertiary phosphine with dimethyl carbonate produced quaternary phosphonium methyl carbonate (QPMC) catalyst of strong basic character. QPMC depolymerized PET by virtually complete conversion with 78 % up isolated yield of monomers under optimal reaction conditions of 160 °C, 2 mol% catalyst loading, and 4 h. Catalytic solvolysis mechanism with ethylene glycol was probed by NMR titrations where methyl carbonate anion coordinated to hydroxyl of ethylene glycol by H-bonding, rather than H-abstraction by the basic methyl carbonate anion, was validated.
{"title":"Endogenous base phosphine/dimethyl carbonate catalyzed depolymerization of poly(ethylene terephthalate)","authors":"Luoyu Gao , Yanqi Shi , Zhenjiang Li, Ziqi Liu, Min Zhang, Yue Xu, Xin Zou, Xin Yuan, Yongzhu Hu, Kai Guo","doi":"10.1016/j.cattod.2025.115203","DOIUrl":"10.1016/j.cattod.2025.115203","url":null,"abstract":"<div><div>Solvolysis of postconsumer poly(ethylene terephthalate) (PET) into monomeric feedstocks that can be recycled contributes value-added strategy to waste plastic management. Chemical route for PET recycling with sets of diols, diamines, and amino alcohols as the solvolytic reagents by endogenous basic ionic pair phosphonium organocatalyst was established. Methylation of tertiary phosphine with dimethyl carbonate produced <strong>q</strong>uaternary <strong>p</strong>hosphonium <strong>m</strong>ethyl <strong>c</strong>arbonate (QPMC) catalyst of strong basic character. QPMC depolymerized PET by virtually complete conversion with 78 % up isolated yield of monomers under optimal reaction conditions of 160 °C, 2 mol% catalyst loading, and 4 h. Catalytic solvolysis mechanism with ethylene glycol was probed by NMR titrations where methyl carbonate anion coordinated to hydroxyl of ethylene glycol by H-bonding, rather than H-abstraction by the basic methyl carbonate anion, was validated.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"450 ","pages":"Article 115203"},"PeriodicalIF":5.2,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143172526","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 : 2025-01-10DOI: 10.1016/j.cattod.2025.115197
Nadia Larumbe , Samuel Moles , M. Carmen Hidalgo , Encarnación Rubio , Pilar Goñi , Rosa Mosteo
Access to clean water is crucial for human health, yet microbial contamination poses significant challenges. This study investigates the effectiveness of novel photocatalytic catalysts: heterostructured TiO2/AgBr and faceted titanium dioxide, for microbial inactivation under ultraviolet and visible light. Both catalysts were synthesized and characterized. Performance was evaluated using real wastewater samples and saline solutions, targeting gram-positive and gram-negative bacteria. The experimental approach included testing the photocatalysts with and without the addition of peroxydisulfate to assess its impact on inactivation effectiveness. Results indicated that the TiO2/AgBr catalyst outperformed the faceted titanium dioxide one due to its superior visible light absorption and enhanced charge separation, achieving complete inactivation of environmental strains of Escherichia coli and significant inactivation for Enterococcus faecalis in real wastewater. The inclusion of peroxodisulfate with TiO2/AgBr significantly improved inactivation rates, demonstrating a synergistic effect. Regarding wastewater composition, the treatment achieves a significant COD removal while the rest of studied parameters remain stable. Both catalysts effectively prevented bacterial regrowth for up to 48 hours, underscoring its long-term efficacy. Overall, these findings highlight the potential application of TiO2/AgBr combined with peroxodisulfate as an effective strategy for microbial inactivation, contributing to the advancement in water treatment technologies across real environmental contexts.
{"title":"Towards the effective removal of environmental strains of bacteria from real wastewater by heterostructured photocatalysts","authors":"Nadia Larumbe , Samuel Moles , M. Carmen Hidalgo , Encarnación Rubio , Pilar Goñi , Rosa Mosteo","doi":"10.1016/j.cattod.2025.115197","DOIUrl":"10.1016/j.cattod.2025.115197","url":null,"abstract":"<div><div>Access to clean water is crucial for human health, yet microbial contamination poses significant challenges. This study investigates the effectiveness of novel photocatalytic catalysts: heterostructured TiO<sub>2</sub>/AgBr and faceted titanium dioxide, for microbial inactivation under ultraviolet and visible light. Both catalysts were synthesized and characterized. Performance was evaluated using real wastewater samples and saline solutions, targeting gram-positive and gram-negative bacteria. The experimental approach included testing the photocatalysts with and without the addition of peroxydisulfate to assess its impact on inactivation effectiveness. Results indicated that the TiO<sub>2</sub>/AgBr catalyst outperformed the faceted titanium dioxide one due to its superior visible light absorption and enhanced charge separation, achieving complete inactivation of environmental strains of <em>Escherichia coli</em> and significant inactivation for <em>Enterococcus faecalis</em> in real wastewater. The inclusion of peroxodisulfate with TiO<sub>2</sub>/AgBr significantly improved inactivation rates, demonstrating a synergistic effect. Regarding wastewater composition, the treatment achieves a significant COD removal while the rest of studied parameters remain stable. Both catalysts effectively prevented bacterial regrowth for up to 48 hours, underscoring its long-term efficacy. Overall, these findings highlight the potential application of TiO<sub>2</sub>/AgBr combined with peroxodisulfate as an effective strategy for microbial inactivation, contributing to the advancement in water treatment technologies across real environmental contexts.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"449 ","pages":"Article 115197"},"PeriodicalIF":5.2,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143141079","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 : 2025-01-10DOI: 10.1016/j.cattod.2025.115199
Tonglin Yang , Fangqi Yang , Fangqiang Yang , Yang Ding , Fa Cao , Quan Zhang
Electrochemical reduction of carbon dioxide (CO2) to valuable fuels or feedstocks holds great promise for zero-emission carbon recycling and renewable energy storage. However, it remains a great challenge to prepare high-performance rare earth single-atom catalysts (SACs) for electroreduction of CO2. In this work, we reported the facile synthesis of Nd SACs with atomically dispersed Nd-N6 active sites by using g-C3N4 as support (Nd1/NC) for efficient electroreduction of CO2 to CO. Nd1/NC exhibited a maximum FE of 83 % and a CO partial current density of 7.0 mA cm−2, and a stability of 50 h at −0.8 V in an H-cell. Notably, a dramatically improved CO partial current density of 50.6 mA cm−2 with FECO of up to 93 % was obtained in the flow cell. DFT calculations revealed that the Nd-N6 sites facilitate the transfer of electrons from g-C3N4 to Nd, which strengthens the adsorption of the *COOH intermediate, contributing to the enhanced catalytic activity.
{"title":"Rare-earth neodymium single atom catalyst for efficient electrochemical CO2 reduction","authors":"Tonglin Yang , Fangqi Yang , Fangqiang Yang , Yang Ding , Fa Cao , Quan Zhang","doi":"10.1016/j.cattod.2025.115199","DOIUrl":"10.1016/j.cattod.2025.115199","url":null,"abstract":"<div><div>Electrochemical reduction of carbon dioxide (CO<sub>2</sub>) to valuable fuels or feedstocks holds great promise for zero-emission carbon recycling and renewable energy storage. However, it remains a great challenge to prepare high-performance rare earth single-atom catalysts (SACs) for electroreduction of CO<sub>2</sub>. In this work, we reported the facile synthesis of Nd SACs with atomically dispersed Nd-N<sub>6</sub> active sites by using g-C<sub>3</sub>N<sub>4</sub> as support (Nd<sub>1</sub>/NC) for efficient electroreduction of CO<sub>2</sub> to CO. Nd<sub>1</sub>/NC exhibited a maximum FE of 83 % and a CO partial current density of 7.0 mA cm<sup>−2</sup>, and a stability of 50 h at −0.8 V in an H-cell. Notably, a dramatically improved CO partial current density of 50.6 mA cm<sup>−2</sup> with FE<sub>CO</sub> of up to 93 % was obtained in the flow cell. DFT calculations revealed that the Nd-N<sub>6</sub> sites facilitate the transfer of electrons from g-C<sub>3</sub>N<sub>4</sub> to Nd, which strengthens the adsorption of the *COOH intermediate, contributing to the enhanced catalytic activity.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"449 ","pages":"Article 115199"},"PeriodicalIF":5.2,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143141381","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 : 2025-01-10DOI: 10.1016/j.cattod.2025.115200
Andrea Osti , Simone Costa , Lorenzo Rizzato , Beatrice Senoner , Antonella Glisenti
The Dry Reforming of Methane (DRM) is an intriguing process to convert two greenhouse gases, CH4 and CO2, into syngas (CO+H2) and to upgrade biogas into biosyngas. However, the challenges of high operating temperatures and catalyst deactivation have hindered its large-scale implementation so far. Recently, photothermal catalysis has emerged as a sustainable alternative to conventional thermocatalysis, enabling a reduction of the required temperature and improvement of catalyst stability. This approach necessitates the development of a suitable photocatalyst. Herein, we proposed the use of active Ni nanoparticles (NPs) with plasmonic features, supported over semiconductive perovskites LaFeO3 or LaMnO3 with La-deficiency. The incorporation of Ni was achieved through either B-site substitution within the perovskite lattice or surface loading via Ammonia Deposition Precipitation (ADP), followed by a reductive treatment under H2 to yield Ni0 NPs. The prepared samples were extensively characterized by XRD, N2 physisorption, H2-TPR, SEM-EDX, HAADF STEM-EDX, XPS, UV-Vis DRS. The pre-reduced catalysts were then tested for thermal and photothermal DRM under visible light illumination (3 suns) at 600 °C. The Fe-based samples were poorly active because of Ni0 reoxidation, whereas a good activity and stability were ensured by Mn-perovskites, preserving the Ni0 active species. Among the Ni loading procedures, only ADP ensured improved activity in photothermal conditions thanks to high Ni NPs concentration, while the B-site doped catalyst showed better thermal than photo-activity because of low surface Ni concentration. Interestingly, light illumination was found to reduce perovskite decomposition and coke deposition. A Ni/Al2O3 reference catalyst demonstrated slightly higher activity than Ni/LaMnO3 but suffered from much faster deactivation due to coking and reoxidation.
{"title":"Photothermal activation of methane dry reforming on perovskite-supported Ni-catalysts: Impact of support composition and Ni loading method","authors":"Andrea Osti , Simone Costa , Lorenzo Rizzato , Beatrice Senoner , Antonella Glisenti","doi":"10.1016/j.cattod.2025.115200","DOIUrl":"10.1016/j.cattod.2025.115200","url":null,"abstract":"<div><div>The Dry Reforming of Methane (DRM) is an intriguing process to convert two greenhouse gases, CH<sub>4</sub> and CO<sub>2</sub>, into syngas (CO+H<sub>2</sub>) and to upgrade biogas into biosyngas. However, the challenges of high operating temperatures and catalyst deactivation have hindered its large-scale implementation so far. Recently, photothermal catalysis has emerged as a sustainable alternative to conventional thermocatalysis, enabling a reduction of the required temperature and improvement of catalyst stability. This approach necessitates the development of a suitable photocatalyst. Herein, we proposed the use of active Ni nanoparticles (NPs) with plasmonic features, supported over semiconductive perovskites LaFeO<sub>3</sub> or LaMnO<sub>3</sub> with La-deficiency. The incorporation of Ni was achieved through either B-site substitution within the perovskite lattice or surface loading via Ammonia Deposition Precipitation (ADP), followed by a reductive treatment under H<sub>2</sub> to yield Ni<sup>0</sup> NPs. The prepared samples were extensively characterized by XRD, N<sub>2</sub> physisorption, H<sub>2</sub>-TPR, SEM-EDX, HAADF STEM-EDX, XPS, UV-Vis DRS. The pre-reduced catalysts were then tested for thermal and photothermal DRM under visible light illumination (3 suns) at 600 °C. The Fe-based samples were poorly active because of Ni<sup>0</sup> reoxidation, whereas a good activity and stability were ensured by Mn-perovskites, preserving the Ni<sup>0</sup> active species. Among the Ni loading procedures, only ADP ensured improved activity in photothermal conditions thanks to high Ni NPs concentration, while the B-site doped catalyst showed better thermal than photo-activity because of low surface Ni concentration. Interestingly, light illumination was found to reduce perovskite decomposition and coke deposition. A Ni/Al<sub>2</sub>O<sub>3</sub> reference catalyst demonstrated slightly higher activity than Ni/LaMnO<sub>3</sub> but suffered from much faster deactivation due to coking and reoxidation.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"449 ","pages":"Article 115200"},"PeriodicalIF":5.2,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143141082","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-10DOI: 10.1016/j.cattod.2025.115185
Hannah K. Hennig , Jacob R. Schare , Reilly P. Lynch , Alex Bullock , Michael S. Baldwin , Mark E. Bussell
The CO2 hydrogenation (HYD) reaction was investigated over Ni phosphide (Ni3P, Ni12P5, Ni2P) catalysts to probe the effect of the NixPy phase on photo-thermal catalytic properties in comparison to Ni metal. The light absorption properties of 2.5 wt% NixPy/SiO2 catalysts differ substantially, with the extent of light absorption decreasing as the P/Ni molar ratio of the Ni phosphide phase increases. This finding directly impacts the photo-thermal catalytic properties as the photo-enhancement (light activity / dark activity) correlates linearly with the extent of light absorption. For comparison purposes, 2.5 wt% Ni/SiO2 catalysts were also investigated and showed high activity but suffered from low CO selectivity (57–68 %). A Ni3P/SiO2 catalyst was the most active of the Ni phosphides with high CO selectivity (>95 %), while Ni12P5/SiO2 and Ni2P/SiO2 catalysts had lower CO2 HYD activities but CO selectivities above 98 %. Upon light exposure, the NixPy/SiO2 (and Ni/SiO2) catalysts exhibited significant rises of temperature (∼200 K increase from room temperature), indicating the importance of photothermal heating in increasing the CO2 HYD rate. The findings highlight how a non-metal element (i.e., P) plays a crucial role in tailoring the photo-thermal catalytic properties of earth abundant nickel metal.
{"title":"Effect of nickel phosphide phase on the photo-thermal catalytic hydrogenation of carbon dioxide","authors":"Hannah K. Hennig , Jacob R. Schare , Reilly P. Lynch , Alex Bullock , Michael S. Baldwin , Mark E. Bussell","doi":"10.1016/j.cattod.2025.115185","DOIUrl":"10.1016/j.cattod.2025.115185","url":null,"abstract":"<div><div>The CO<sub>2</sub> hydrogenation (HYD) reaction was investigated over Ni phosphide (Ni<sub>3</sub>P, Ni<sub>12</sub>P<sub>5</sub>, Ni<sub>2</sub>P) catalysts to probe the effect of the Ni<sub>x</sub>P<sub>y</sub> phase on photo-thermal catalytic properties in comparison to Ni metal. The light absorption properties of 2.5 wt% Ni<sub>x</sub>P<sub>y</sub>/SiO<sub>2</sub> catalysts differ substantially, with the extent of light absorption decreasing as the P/Ni molar ratio of the Ni phosphide phase increases. This finding directly impacts the photo-thermal catalytic properties as the photo-enhancement (light activity / dark activity) correlates linearly with the extent of light absorption. For comparison purposes, 2.5 wt% Ni/SiO<sub>2</sub> catalysts were also investigated and showed high activity but suffered from low CO selectivity (57–68 %). A Ni<sub>3</sub>P/SiO<sub>2</sub> catalyst was the most active of the Ni phosphides with high CO selectivity (>95 %), while Ni<sub>12</sub>P<sub>5</sub>/SiO<sub>2</sub> and Ni<sub>2</sub>P/SiO<sub>2</sub> catalysts had lower CO<sub>2</sub> HYD activities but CO selectivities above 98 %. Upon light exposure, the Ni<sub>x</sub>P<sub>y</sub>/SiO<sub>2</sub> (and Ni/SiO<sub>2</sub>) catalysts exhibited significant rises of temperature (∼200 K increase from room temperature), indicating the importance of photothermal heating in increasing the CO<sub>2</sub> HYD rate. The findings highlight how a non-metal element (i.e., P) plays a crucial role in tailoring the photo-thermal catalytic properties of earth abundant nickel metal.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"449 ","pages":"Article 115185"},"PeriodicalIF":5.2,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143141446","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 : 2025-01-07DOI: 10.1016/j.cattod.2025.115186
Francieli Martins Mayer , Mateus da Silva Carvalho , Amanda Ramos Mallmann , Ana Paula Stelzer de Oliveira , Dóris Ruiz , Ana Carla Specht Boeira , Dirléia dos Santos Lima , Maria do Carmo Rangel
The increasing demand for clean energy and for the environmental protection has driven the search for new technologies that minimize the impacts of the excessive consumption of fossil fuel. Catalytic pyrolysis emerges as a promising alternative route for producing energy and chemicals from biomass, because of its flexibility, low cost and simplicity. However, the process still requires active catalysts that can be tailored for each application. With this goal in mind, catalysts based on platinum (1 %) supported on beta zeolite with different SAR (30, 60 and 90) were evaluated in the fast pyrolysis of pre-treated medium density fiber (MDF) residues in this work. Beta zeolite was prepared using silica extracted from coal ash came from a thermoelectric plant. Non-oxygenated compounds, such as BTEX (benzene, toluene, ethylbenzene and xylenes), other monoaromatics (21.2–26.5 %), naphthalene derivatives (5–29.2 %), polyaromatics (0–6.1 %) and linear hydrocarbon (0.4–11.9 %), as well as oxygenates (1.0–11.8 %), were produced over the catalysts in contrast with oxygenates (80.2 %) and linear hydrocarbons (6.6 %) formed without any catalyst. The catalysts changed the products distribution, the amount varying according to SAR and platinum. The platinum-containing catalysts with SAR 30 and 60 produced the highest amount of BTEX (41.1 and 42.0 %, respectively), the most valuable compounds among the products and formed negligible amounts of polyaromatics (0.3 %), the main coke precursor. They also produced low amounts of oxygenates (5.3: SAR 30 and 1.4 %: SAR 60). Among the BTEX compounds, the catalyst with SAR 30 produced more benzene, toluene and xylenes than that with SAR 60 which in turn formed more ethylbenzene. The catalyst with SAR 90 was the least selective to BTEX. This work showed that platinum supported on beta zeolites (SAR 30 and 60) are promising options to produce BTEX from MDF fast pyrolysis, with the advantage of tailoring the catalysts to obtain high yields of benzene, toluene, xylenes and ethylbenzene. Moreover, the process used two kinds of residues (MDF and coal ash), contributing to environmental protection.
{"title":"Catalytic pyrolysis of MDF wastes over beta zeolite-supported platinum","authors":"Francieli Martins Mayer , Mateus da Silva Carvalho , Amanda Ramos Mallmann , Ana Paula Stelzer de Oliveira , Dóris Ruiz , Ana Carla Specht Boeira , Dirléia dos Santos Lima , Maria do Carmo Rangel","doi":"10.1016/j.cattod.2025.115186","DOIUrl":"10.1016/j.cattod.2025.115186","url":null,"abstract":"<div><div>The increasing demand for clean energy and for the environmental protection has driven the search for new technologies that minimize the impacts of the excessive consumption of fossil fuel. Catalytic pyrolysis emerges as a promising alternative route for producing energy and chemicals from biomass, because of its flexibility, low cost and simplicity. However, the process still requires active catalysts that can be tailored for each application. With this goal in mind, catalysts based on platinum (1 %) supported on beta zeolite with different SAR (30, 60 and 90) were evaluated in the fast pyrolysis of pre-treated medium density fiber (MDF) residues in this work. Beta zeolite was prepared using silica extracted from coal ash came from a thermoelectric plant. Non-oxygenated compounds, such as BTEX (benzene, toluene, ethylbenzene and xylenes), other monoaromatics (21.2–26.5 %), naphthalene derivatives (5–29.2 %), polyaromatics (0–6.1 %) and linear hydrocarbon (0.4–11.9 %), as well as oxygenates (1.0–11.8 %), were produced over the catalysts in contrast with oxygenates (80.2 %) and linear hydrocarbons (6.6 %) formed without any catalyst. The catalysts changed the products distribution, the amount varying according to SAR and platinum. The platinum-containing catalysts with SAR 30 and 60 produced the highest amount of BTEX (41.1 and 42.0 %, respectively), the most valuable compounds among the products and formed negligible amounts of polyaromatics (0.3 %), the main coke precursor. They also produced low amounts of oxygenates (5.3: SAR 30 and 1.4 %: SAR 60). Among the BTEX compounds, the catalyst with SAR 30 produced more benzene, toluene and xylenes than that with SAR 60 which in turn formed more ethylbenzene. The catalyst with SAR 90 was the least selective to BTEX. This work showed that platinum supported on beta zeolites (SAR 30 and 60) are promising options to produce BTEX from MDF fast pyrolysis, with the advantage of tailoring the catalysts to obtain high yields of benzene, toluene, xylenes and ethylbenzene. Moreover, the process used two kinds of residues (MDF and coal ash), contributing to environmental protection.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"449 ","pages":"Article 115186"},"PeriodicalIF":5.2,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143141447","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 : 2025-01-07DOI: 10.1016/j.cattod.2025.115189
M.V. Morales , J.M. Conesa , A. Guerrero-Ruiz , I. Rodríguez-Ramos
2,5-Dimethylfuran (DMF), which is one of the most promising liquid biofuels, has garnered significant attention due to its potential to develop the utilization of biomass energy. In this work, its synthesis through the hydrodeoxygenation reaction (HDO) of 5-hydroxymethylfurfural (HMF) has been studied on Ni catalysts supported on various metal oxides and a high surface graphite (HSAG), in a batch reactor, using 1-butanol as a solvent. At 180 °C and under 30 bar H2, the catalytic activity and the predominant reaction route were found to be strongly conditioned by the nature of the support, as well as by the presence of impurities depending on the commercial HMF feedstock employed. The HSAG support turned out to be the most suitable for the HDO of HMF leading to the formation of DMF, via rupture of the C-O bonds. Additionally, the catalytic performance of Co and Cu supported on this graphitic material was studied, being Cu the one that offers the best yields to DMF (95 %), even in the absence of external hydrogen (84 %), confirming that butanol acts as a hydrogen donor in addition of solvent.
{"title":"Carbon-supported non-noble metal catalysts for efficient synthesis of the biofuel 2,5-dimethylfurfural from 5‑hydroxymethylfurfural in 1-butanol under mild conditions","authors":"M.V. Morales , J.M. Conesa , A. Guerrero-Ruiz , I. Rodríguez-Ramos","doi":"10.1016/j.cattod.2025.115189","DOIUrl":"10.1016/j.cattod.2025.115189","url":null,"abstract":"<div><div>2,5-Dimethylfuran (DMF), which is one of the most promising liquid biofuels, has garnered significant attention due to its potential to develop the utilization of biomass energy. In this work, its synthesis through the hydrodeoxygenation reaction (HDO) of 5-hydroxymethylfurfural (HMF) has been studied on Ni catalysts supported on various metal oxides and a high surface graphite (HSAG), in a batch reactor, using 1-butanol as a solvent. At 180 °C and under 30 bar H<sub>2</sub>, the catalytic activity and the predominant reaction route were found to be strongly conditioned by the nature of the support, as well as by the presence of impurities depending on the commercial HMF feedstock employed. The HSAG support turned out to be the most suitable for the HDO of HMF leading to the formation of DMF, via rupture of the C-O bonds. Additionally, the catalytic performance of Co and Cu supported on this graphitic material was studied, being Cu the one that offers the best yields to DMF (95 %), even in the absence of external hydrogen (84 %), confirming that butanol acts as a hydrogen donor in addition of solvent.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"449 ","pages":"Article 115189"},"PeriodicalIF":5.2,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143141445","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 : 2025-01-04DOI: 10.1016/j.cattod.2025.115188
Fangwei Liu , Yilin Zhao , Kunkun Wei , Jingbo Hu , Chengyuan Liu , Yang Pan , Jianzhou Wu , Xutao Chen , Shihui Zou , Jie Fan
Methyl radicals (·CH3) are crucial intermediates in the oxidative coupling of methane (OCM) reaction mechanism, involving both heterogeneous and homogeneous processes. We quantitatively determined the concentrations of desorbed ·CH3 from meticulously synthesized Er2O3 catalysts using in situ synchrotron-based vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). Our findings corroborate that the generation capacity of ·CH3 serves as a robust metric for describing the catalytic performance of OCM. This investigation revealed that the modulation of reactive oxygen species (O- and O2-) on the surface of various Er2O3 catalysts significantly influences the generation capability of ·CH3 radicals. Notably, the ratio of these reactive oxygen species demonstrates a positive correlation with both the concentration of ·CH3 radicals and the C2 yield. Consequently, the generation potential of ·CH3 serves as a critical linkage between the reaction performance of OCM and the surface structure of the catalyst, thereby enriching our comprehension of the intrinsic relationship between structure and performance in catalysts based on metal oxide during the OCM reaction.
{"title":"Regulating surface reactive oxygen species to promote ·CH3 generation on Er2O3 catalysts","authors":"Fangwei Liu , Yilin Zhao , Kunkun Wei , Jingbo Hu , Chengyuan Liu , Yang Pan , Jianzhou Wu , Xutao Chen , Shihui Zou , Jie Fan","doi":"10.1016/j.cattod.2025.115188","DOIUrl":"10.1016/j.cattod.2025.115188","url":null,"abstract":"<div><div>Methyl radicals (·CH<sub>3</sub>) are crucial intermediates in the oxidative coupling of methane (OCM) reaction mechanism, involving both heterogeneous and homogeneous processes. We quantitatively determined the concentrations of desorbed ·CH<sub>3</sub> from meticulously synthesized Er<sub>2</sub>O<sub>3</sub> catalysts using in situ synchrotron-based vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). Our findings corroborate that the generation capacity of ·CH<sub>3</sub> serves as a robust metric for describing the catalytic performance of OCM. This investigation revealed that the modulation of reactive oxygen species (O<sup>-</sup> and O<sub>2</sub><sup>-</sup>) on the surface of various Er<sub>2</sub>O<sub>3</sub> catalysts significantly influences the generation capability of ·CH<sub>3</sub> radicals. Notably, the ratio of these reactive oxygen species demonstrates a positive correlation with both the concentration of ·CH<sub>3</sub> radicals and the C<sub>2</sub> yield. Consequently, the generation potential of ·CH<sub>3</sub> serves as a critical linkage between the reaction performance of OCM and the surface structure of the catalyst, thereby enriching our comprehension of the intrinsic relationship between structure and performance in catalysts based on metal oxide during the OCM reaction.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"449 ","pages":"Article 115188"},"PeriodicalIF":5.2,"publicationDate":"2025-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143097919","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 : 2025-01-04DOI: 10.1016/j.cattod.2024.115178
Sounak Roy , Benjaram M. Reddy , Jennifer Strunk
{"title":"Preface: Catalysis for circular economy towards sustainable energy (Indo-German conference on catalysis, BITS Pilani – Hyderabad, 20–23 September 2023)","authors":"Sounak Roy , Benjaram M. Reddy , Jennifer Strunk","doi":"10.1016/j.cattod.2024.115178","DOIUrl":"10.1016/j.cattod.2024.115178","url":null,"abstract":"","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"449 ","pages":"Article 115178"},"PeriodicalIF":5.2,"publicationDate":"2025-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143097461","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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