The 1,2,3,4-tetrahydroquinoline (py-THQL) is a crucial intermediate and fragment in chemical synthesis, but its production from quinoline (QL) selective hydrogenation in heterogeneous catalysis mainly relies on noble-metal-based catalysts. Therefore, the design of catalysts composed of earth-abundant elements for this reaction is meaningful. In this work, using density functional theory (DFT) calculations, we found the binding energy of QL to be a suitable descriptor to illustrate the general activity trend of metallic catalysts for QL hydrogenation. Among the screened bimetallic alloys composed of Fe, Co, Ni, and Cu, we computationally identified Ni3Fe as a promising candidate catalyst with high stability, while our systematic mechanistic calculations showed the low energy barriers for each hydrogenation step. Our established DFT-based mean-field microkinetic model indicates a much higher turnover frequency for py-THQL production on the Ni3Fe(111) surface than on the experimentally reported high-performance AuPd3(111) surface. This work not only identified a valuable descriptor for the rational catalyst screening for the complex QL hydrogenation reaction but also theoretically predicted a cost-effective Ni3Fe catalyst for the hydrogenation reaction.
{"title":"Identification of Ni3Fe alloy as a candidate catalyst for quinoline selective hydrogenation with computations†","authors":"Zhaochun He , Yonghua Liu , Tao Wang","doi":"10.1039/d4cy01076k","DOIUrl":"10.1039/d4cy01076k","url":null,"abstract":"<div><div>The 1,2,3,4-tetrahydroquinoline (py-THQL) is a crucial intermediate and fragment in chemical synthesis, but its production from quinoline (QL) selective hydrogenation in heterogeneous catalysis mainly relies on noble-metal-based catalysts. Therefore, the design of catalysts composed of earth-abundant elements for this reaction is meaningful. In this work, using density functional theory (DFT) calculations, we found the binding energy of QL to be a suitable descriptor to illustrate the general activity trend of metallic catalysts for QL hydrogenation. Among the screened bimetallic alloys composed of Fe, Co, Ni, and Cu, we computationally identified Ni<sub>3</sub>Fe as a promising candidate catalyst with high stability, while our systematic mechanistic calculations showed the low energy barriers for each hydrogenation step. Our established DFT-based mean-field microkinetic model indicates a much higher turnover frequency for py-THQL production on the Ni<sub>3</sub>Fe(111) surface than on the experimentally reported high-performance AuPd<sub>3</sub>(111) surface. This work not only identified a valuable descriptor for the rational catalyst screening for the complex QL hydrogenation reaction but also theoretically predicted a cost-effective Ni<sub>3</sub>Fe catalyst for the hydrogenation reaction.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 24","pages":"Pages 7134-7139"},"PeriodicalIF":4.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798123","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ettore Bianco , Fabrizio Sordello , Francesco Pellegrino , Valter Maurino
In hydrogen production through water splitting, two reactions are involved: the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), both with efficiency issues. In previous works, our group demonstrated the possibility of enhancing H2 production by conducting HCOOH photocatalytic reforming on metal–TiO2 nanoparticles under controlled periodic illumination (CPI) rather than continuous illumination performed at the same average incident photon flux. The enhancement was observed only over specific metals, including Pt, Pd and Rh, due to their low Tafel slopes. Hydrogen adsorption and desorption energies are strongly dependent on the potential at the metal nanoparticles, and we demonstrated the ability to use CPI to induce oscillations in the potential of the catalyst. In this work, by modulating the duty cycle and the frequency of the CPI, we observed both of these playing a key role in boosting HER. Experimental evidence suggest that the relaxation of the photopotential during the dark period is the key factor for increasing the photonic efficiency of the reaction.
{"title":"Enhancing the HER rate over Pt–TiO2 nanoparticles under controlled periodic illumination: role of light modulation†","authors":"Ettore Bianco , Fabrizio Sordello , Francesco Pellegrino , Valter Maurino","doi":"10.1039/d4cy00775a","DOIUrl":"10.1039/d4cy00775a","url":null,"abstract":"<div><div>In hydrogen production through water splitting, two reactions are involved: the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), both with efficiency issues. In previous works, our group demonstrated the possibility of enhancing H<sub>2</sub> production by conducting HCOOH photocatalytic reforming on metal–TiO<sub>2</sub> nanoparticles under controlled periodic illumination (CPI) rather than continuous illumination performed at the same average incident photon flux. The enhancement was observed only over specific metals, including Pt, Pd and Rh, due to their low Tafel slopes. Hydrogen adsorption and desorption energies are strongly dependent on the potential at the metal nanoparticles, and we demonstrated the ability to use CPI to induce oscillations in the potential of the catalyst. In this work, by modulating the duty cycle and the frequency of the CPI, we observed both of these playing a key role in boosting HER. Experimental evidence suggest that the relaxation of the photopotential during the dark period is the key factor for increasing the photonic efficiency of the reaction.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 24","pages":"Pages 7205-7211"},"PeriodicalIF":4.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy00775a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798142","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Marlena Kardela , Błażej Dziuk , Roman Szostak , Michal Szostak , Elwira Bisz
Iron-catalyzed cross-coupling has emerged as a pivotal concept for the synthesis of valuable products across various facets of chemical research, including pharmaceuticals, organic materials and biological probes. In this respect, the use of N-heterocyclic carbenes (NHCs) as ancillary ligands to iron has been particularly effective. However, the major limitation is that the successful iron-catalytic systems have been almost exclusively limited to N-aryl-N-heterocyclic carbenes, which significantly restricts future developments of this commanding catalysis platform. Herein, we report IBzH (IBenzhydryl), a class of N-heterocyclic carbenes that are based on benzhydryl substitution of the imidazole ring. We demonstrate that this N-alkyl yet sterically-flexible ligand class promote the challenging C(sp3)–C(sp2) iron-catalyzed cross-coupling of unactivated haloalkanes, superseding the performance of other NHC ligands. Alkyl–alkyl cross-coupling is also described. Large scale synthesis and the evaluation of steric and electronic properties is presented. Considering the major advantages of sterically-flexible N-heterocyclic carbenes, we anticipate that this class of N-alkyl NHC ligands will have broad application.
{"title":"IBzH (IBenzhydryl): sterically-flexible N-aliphatic N-heterocyclic carbenes (NHCs) for iron-catalyzed C(sp3)–C(sp2) cross-coupling of unactivated haloalkanes†","authors":"Marlena Kardela , Błażej Dziuk , Roman Szostak , Michal Szostak , Elwira Bisz","doi":"10.1039/d4cy01315h","DOIUrl":"10.1039/d4cy01315h","url":null,"abstract":"<div><div>Iron-catalyzed cross-coupling has emerged as a pivotal concept for the synthesis of valuable products across various facets of chemical research, including pharmaceuticals, organic materials and biological probes. In this respect, the use of <em>N</em>-heterocyclic carbenes (NHCs) as ancillary ligands to iron has been particularly effective. However, the major limitation is that the successful iron-catalytic systems have been almost exclusively limited to <em>N</em>-aryl-<em>N</em>-heterocyclic carbenes, which significantly restricts future developments of this commanding catalysis platform. Herein, we report IBzH (IBenzhydryl), a class of <em>N</em>-heterocyclic carbenes that are based on benzhydryl substitution of the imidazole ring. We demonstrate that this <em>N</em>-alkyl yet sterically-flexible ligand class promote the challenging C(sp<sup>3</sup>)–C(sp<sup>2</sup>) iron-catalyzed cross-coupling of unactivated haloalkanes, superseding the performance of other NHC ligands. Alkyl–alkyl cross-coupling is also described. Large scale synthesis and the evaluation of steric and electronic properties is presented. Considering the major advantages of sterically-flexible <em>N</em>-heterocyclic carbenes, we anticipate that this class of <em>N</em>-alkyl NHC ligands will have broad application.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 24","pages":"Pages 7002-7008"},"PeriodicalIF":4.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798102","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The synthesis of renewable bio-based monomers, like 2,5-furandicarboxylic acid (FDCA), is of high interest in the shift toward a circular economy. Bimetallic catalysts offer the variation of different properties, enabling the design of tailor-made catalysts. The combination of silver and palladium, both highly active for specific liquid-phase oxidation reactions, shows promise for superior performance in the selective oxidation of 5-(hydroxymethyl)furfural (HMF) to FDCA. While Ag/CBA and Ag3Pd1/CBA, supported on carbon black acetylene (CBA), were active only for the oxidation of the aldehyde group of HMF, increasing the Pd-fraction allowed for the oxidation of the alcohol group as well. In-depth characterization by X-ray diffraction, electron microscopy, and X-ray absorption spectroscopy revealed a synergistic effect between Ag and Pd in Pd-rich alloys, leading to an enhanced performance. Pd is particularly effective in activating oxygen, the oxidizing agent, while Ag ensures a high selectivity in the dehydrogenation reaction. Moreover, removing residual surfactants from the synthesized catalysts by increasing the calcination temperature further enhanced the activity. This study demonstrates the potential of tuning the catalytic properties of noble metal-based catalysts for optimizing liquid-phase oxidation reactions.
{"title":"Synergy of Ag and Pd in bimetallic catalysts for the selective oxidation of 5-(hydroxymethyl)furfural†","authors":"Dominik Neukum , Maya Eyleen Ludwig , Georgios Uzunidis , Ajai Raj Lakshmi Nilayam , Bärbel Krause , Silke Behrens , Jan-Dierk Grunwaldt , Erisa Saraçi","doi":"10.1039/d4cy01028k","DOIUrl":"10.1039/d4cy01028k","url":null,"abstract":"<div><div>The synthesis of renewable bio-based monomers, like 2,5-furandicarboxylic acid (FDCA), is of high interest in the shift toward a circular economy. Bimetallic catalysts offer the variation of different properties, enabling the design of tailor-made catalysts. The combination of silver and palladium, both highly active for specific liquid-phase oxidation reactions, shows promise for superior performance in the selective oxidation of 5-(hydroxymethyl)furfural (HMF) to FDCA. While Ag/CBA and Ag<sub>3</sub>Pd<sub>1</sub>/CBA, supported on carbon black acetylene (CBA), were active only for the oxidation of the aldehyde group of HMF, increasing the Pd-fraction allowed for the oxidation of the alcohol group as well. In-depth characterization by X-ray diffraction, electron microscopy, and X-ray absorption spectroscopy revealed a synergistic effect between Ag and Pd in Pd-rich alloys, leading to an enhanced performance. Pd is particularly effective in activating oxygen, the oxidizing agent, while Ag ensures a high selectivity in the dehydrogenation reaction. Moreover, removing residual surfactants from the synthesized catalysts by increasing the calcination temperature further enhanced the activity. This study demonstrates the potential of tuning the catalytic properties of noble metal-based catalysts for optimizing liquid-phase oxidation reactions.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 24","pages":"Pages 7163-7171"},"PeriodicalIF":4.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy01028k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798126","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Matthew E. Potter , Lucas Spiske , Philipp N. Plessow , Evangeline B. McShane , Marina Carravetta , Alice E. Oakley , Takudzwa Bere , James H. Carter , Bart D. Vandegehuchte , Kamila M. Kaźmierczak , Felix Studt , Robert Raja
Microporous solid acid catalysts are widely used in industrial hydrocarbon transformations in both the fuels and petrochemical industries. The specific choice of microporous framework often dictates the acidic properties of the system, such as acid site strength and concentration. In this work we have explored the influence of acid site concentration on butane isomerisation activity and the mechanistic pathway by controlling the quantity of magnesium doped into an aluminophosphate, keeping the acid site strength and framework topology constant. By combining experimental kinetic studies, and theoretical mechanistic studies, we conclude that isobutane formation, from n-butane, predominantly proceeds through a bimolecular pathway. Specifically, the activity of the system is strongly linked to the presence of alkenes, and herein the precise mechanistic roles of the alkenes are explored.
{"title":"Combining computational and experimental studies to gain mechanistic insights for n-butane isomerisation with a model microporous catalyst†","authors":"Matthew E. Potter , Lucas Spiske , Philipp N. Plessow , Evangeline B. McShane , Marina Carravetta , Alice E. Oakley , Takudzwa Bere , James H. Carter , Bart D. Vandegehuchte , Kamila M. Kaźmierczak , Felix Studt , Robert Raja","doi":"10.1039/d4cy01035c","DOIUrl":"10.1039/d4cy01035c","url":null,"abstract":"<div><div>Microporous solid acid catalysts are widely used in industrial hydrocarbon transformations in both the fuels and petrochemical industries. The specific choice of microporous framework often dictates the acidic properties of the system, such as acid site strength and concentration. In this work we have explored the influence of acid site concentration on butane isomerisation activity and the mechanistic pathway by controlling the quantity of magnesium doped into an aluminophosphate, keeping the acid site strength and framework topology constant. By combining experimental kinetic studies, and theoretical mechanistic studies, we conclude that isobutane formation, from <em>n</em>-butane, predominantly proceeds through a bimolecular pathway. Specifically, the activity of the system is strongly linked to the presence of alkenes, and herein the precise mechanistic roles of the alkenes are explored.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 24","pages":"Pages 7140-7151"},"PeriodicalIF":4.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cy/d4cy01035c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798124","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Majd Tabbara , Zhiyuan Zong , Hugo Dignoes Ricart , Sarah Chfira , D. Chester Upham
The commercial, CO2-intensive, propylene generation process is challenged by a low equilibrium yield, costly separation processes, and severe carbon deposition. Oxidative dehydrogenation (ODH) of propane offers a promising alternative; however, its potential is hampered by the undesirable over-oxidation of propylene to carbon oxides. Chemical looping approaches have been used, where a metal oxide reacts with propane and/or hydrogen – instead of O2 – which can avoid over-oxidation of the hydrocarbons to carbon oxides. Oxygen can then react with the reduced solid product to regenerate it to a stoichiometric oxide. However, solid chemical looping catalysts have a low oxygen carrying capacity, often less than 1% in order to avoid cyclic deactivation, arising from changes to the lattice structure in each cycle. Herein, we report the use of molten metals as chemical looping catalysts, where the catalyst completely reduces to metallic form and melts each half-cycle. A high oxygen capacity is possible, and melting reduces lattice strain upon reduction. Thermodynamic calculations indicate that 21 individual metal candidates could be viable, and the most promising 14 are experimentally compared. Bi–Sn had the highest conversion, and 50–50 mol% Bi–Sn was supported in a fixed-bed reactor. This resulted in 22% propylene yield at 600 °C, compared to a 20% yield from the reference using borosilicate beads at the same temperature. After 10 cycles with separate flows of O2 followed by C3H8, totaling 37 hours on stream, no deactivation was observed. Enhanced propylene selectivity was observed using a 50–50 mol% Bi–Sn molten mixture, surpassing the performance of Bi or Sn alone, and leading to reduced carbon oxide formation. This improved selectivity occurred with both co-fed and pre-oxidized catalysts, suggesting the creation of a unique metal oxide selectively generating propylene while minimizing overoxidation to carbon oxides. Additionally, the oxygen conversion over the Bi–Sn alloy was lower than over Bi or Sn separately when co-feeding propane and oxygen. Selectivity to cracked products was high for most of the active melts tested, especially above 550 °C.
{"title":"Propane oxidative dehydrogenation catalyzed by molten metal alloys†","authors":"Majd Tabbara , Zhiyuan Zong , Hugo Dignoes Ricart , Sarah Chfira , D. Chester Upham","doi":"10.1039/d4cy00976b","DOIUrl":"10.1039/d4cy00976b","url":null,"abstract":"<div><div>The commercial, CO<sub>2</sub>-intensive, propylene generation process is challenged by a low equilibrium yield, costly separation processes, and severe carbon deposition. Oxidative dehydrogenation (ODH) of propane offers a promising alternative; however, its potential is hampered by the undesirable over-oxidation of propylene to carbon oxides. Chemical looping approaches have been used, where a metal oxide reacts with propane and/or hydrogen – instead of O<sub>2</sub> – which can avoid over-oxidation of the hydrocarbons to carbon oxides. Oxygen can then react with the reduced solid product to regenerate it to a stoichiometric oxide. However, solid chemical looping catalysts have a low oxygen carrying capacity, often less than 1% in order to avoid cyclic deactivation, arising from changes to the lattice structure in each cycle. Herein, we report the use of molten metals as chemical looping catalysts, where the catalyst completely reduces to metallic form and melts each half-cycle. A high oxygen capacity is possible, and melting reduces lattice strain upon reduction. Thermodynamic calculations indicate that 21 individual metal candidates could be viable, and the most promising 14 are experimentally compared. Bi–Sn had the highest conversion, and 50–50 mol% Bi–Sn was supported in a fixed-bed reactor. This resulted in 22% propylene yield at 600 °C, compared to a 20% yield from the reference using borosilicate beads at the same temperature. After 10 cycles with separate flows of O<sub>2</sub> followed by C<sub>3</sub>H<sub>8</sub>, totaling 37 hours on stream, no deactivation was observed. Enhanced propylene selectivity was observed using a 50–50 mol% Bi–Sn molten mixture, surpassing the performance of Bi or Sn alone, and leading to reduced carbon oxide formation. This improved selectivity occurred with both co-fed and pre-oxidized catalysts, suggesting the creation of a unique metal oxide selectively generating propylene while minimizing overoxidation to carbon oxides. Additionally, the oxygen conversion over the Bi–Sn alloy was lower than over Bi or Sn separately when co-feeding propane and oxygen. Selectivity to cracked products was high for most of the active melts tested, especially above 550 °C.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 24","pages":"Pages 7009-7019"},"PeriodicalIF":4.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205461","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Deyu Chu , Jinjing Ma , Qishun Liu , Jie Fu , Heng Yin
Optimizing the production process of high value-added chemicals derived from renewable biomass holds immense promise for clean energy utilization and environmental sustainability. The abundant acidic sites and distinctive pore structures of zeolites serve as critical catalysts in improving the effectiveness of carbohydrates conversion and enabling the selective preparation of bio-based chemicals. This approach not only maximizes the utilization of renewable resources but also aligns with the imperative of environmental protection. This review presents an extensive overview of the latest advancements in utilizing zeolites as catalysts for converting carbohydrate biomass into bio-based chemicals. Emphasis is placed on elucidating the acidic properties and pore structures of zeolites and their profound impact on the carbohydrates conversion process. Furthermore, the review evaluates future directions for developing zeolite-catalyzed biomass conversion, aiming to offer insights into achieving sustainable and efficient utilization of biomass resources.
{"title":"Effects of zeolite porosity and acidity on catalytic conversion of carbohydrates to bio-based chemicals: a review","authors":"Deyu Chu , Jinjing Ma , Qishun Liu , Jie Fu , Heng Yin","doi":"10.1039/d4cy01070a","DOIUrl":"10.1039/d4cy01070a","url":null,"abstract":"<div><div>Optimizing the production process of high value-added chemicals derived from renewable biomass holds immense promise for clean energy utilization and environmental sustainability. The abundant acidic sites and distinctive pore structures of zeolites serve as critical catalysts in improving the effectiveness of carbohydrates conversion and enabling the selective preparation of bio-based chemicals. This approach not only maximizes the utilization of renewable resources but also aligns with the imperative of environmental protection. This review presents an extensive overview of the latest advancements in utilizing zeolites as catalysts for converting carbohydrate biomass into bio-based chemicals. Emphasis is placed on elucidating the acidic properties and pore structures of zeolites and their profound impact on the carbohydrates conversion process. Furthermore, the review evaluates future directions for developing zeolite-catalyzed biomass conversion, aiming to offer insights into achieving sustainable and efficient utilization of biomass resources.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 24","pages":"Pages 6980-7001"},"PeriodicalIF":4.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798101","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kai Cui , Jiaming Yang , Yuli Jing , Junwen Chen , Chen Zhao , Peng Wu , Xiaohong Li
Sustainability issues have led to a gradual market expansion for the 1,4-butanediol (BDO) monomer of the biodegradable plastics to replace conventional plastics. Maleic anhydride (MA) can be derived from the oxidation of bio-based furfural or fructose. Although the hydrogenation of MA can produce a series of products, including succinic anhydride (SA), γ-butyrolactone (GBL), BDO and tetrahydrofuran (THF), the one-pot deep hydrogenation of MA to BDO or THF under mild conditions has been rarely reported in the literature until now. Herein, we report the production of BDO from the one-pot deep hydrogenation of MA over a Cu–0.03Mo/SiO2 catalyst, achieving 100% MA conversion and 88.3% BDO yield. The Cu–0.03Mo/SiO2 catalyst also showed good long-term stability without obvious loss in activity or BDO selectivity during a 160 h time-on-stream test. Doping Mo to Cu/SiO2 catalysts in an optimal amount adjusted the distribution of Cu0/Cu+ species and modulated the interaction of Cu–SiO2 and surface acidity, so that the activation of hydrogen, MA and relevant intermediates can become balanced, in addition to the restriction of side-reactions. This study provides potential for the green synthesis of BDO with non-precious Cu-based catalysts.
{"title":"One-pot synthesis of 1,4-butanediol via the deep hydrogenation of maleic anhydride over Cu–xMo/SiO2 catalysts†","authors":"Kai Cui , Jiaming Yang , Yuli Jing , Junwen Chen , Chen Zhao , Peng Wu , Xiaohong Li","doi":"10.1039/d4cy01006j","DOIUrl":"10.1039/d4cy01006j","url":null,"abstract":"<div><div>Sustainability issues have led to a gradual market expansion for the 1,4-butanediol (BDO) monomer of the biodegradable plastics to replace conventional plastics. Maleic anhydride (MA) can be derived from the oxidation of bio-based furfural or fructose. Although the hydrogenation of MA can produce a series of products, including succinic anhydride (SA), γ-butyrolactone (GBL), BDO and tetrahydrofuran (THF), the one-pot deep hydrogenation of MA to BDO or THF under mild conditions has been rarely reported in the literature until now. Herein, we report the production of BDO from the one-pot deep hydrogenation of MA over a Cu–0.03Mo/SiO<sub>2</sub> catalyst, achieving 100% MA conversion and 88.3% BDO yield. The Cu–0.03Mo/SiO<sub>2</sub> catalyst also showed good long-term stability without obvious loss in activity or BDO selectivity during a 160 h time-on-stream test. Doping Mo to Cu/SiO<sub>2</sub> catalysts in an optimal amount adjusted the distribution of Cu<sup>0</sup>/Cu<sup>+</sup> species and modulated the interaction of Cu–SiO<sub>2</sub> and surface acidity, so that the activation of hydrogen, MA and relevant intermediates can become balanced, in addition to the restriction of side-reactions. This study provides potential for the green synthesis of BDO with non-precious Cu-based catalysts.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 24","pages":"Pages 7081-7092"},"PeriodicalIF":4.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798119","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jelle W. Bos , Job G. A. Vloedgraven , Sophie C. C. Wiedemann , Leo van Dongen , Roel C. J. Moonen , Bas Wels , Peter H. Berben , Bennie H. Reesink , Peter de Peinder , Eelco T. C. Vogt , Bert M. Weckhuysen
C18 branched saturated fatty acids (BSFA) are used as ingredients in cosmetics and lubricants and are produced via the hydrogenation of C18 branched unsaturated fatty acids (BUFA). Industrial-grade C18 BUFA contain the odorous by-product γ-stearolactone (GSL), which must be removed by acid-catalysed ring-opening of GSL into oleic acid. Zeolites such as Y and beta can facilitate the ring-opening, but due to the dimensions of GSL the activity is expected to be limited by diffusion into the micropores. Hence, zeolites Y and beta were modified via hydrothermal treatment and acid leaching and used in the GSL ring-opening reaction. While modification of zeolite beta led to a reduction in acidity of more than 50%, the material displayed much-enhanced activity compared to the parent material. In a batch reactor steamed beta zeolites were able to convert all GSL within 2 h, compared to 5 h for the parent zeolite. Infrared spectroscopy studies of adsorbed pyridine reveal that likely a beneficial change in Brønsted/Lewis acid site ratio is responsible for the increased activity. Lewis acid sites in zeolites are known to catalyse double bond isomerisation, which could greatly enhance GSL conversion by reducing the reverse formation of GSL from oleic acid. We believe that these insights can be used to further improve GSL ring-opening activity and inspire research on the ring-opening of other biomass derived lactones.
{"title":"γ-Stearolactone ring-opening by zeolites for the production of branched saturated fatty acids†","authors":"Jelle W. Bos , Job G. A. Vloedgraven , Sophie C. C. Wiedemann , Leo van Dongen , Roel C. J. Moonen , Bas Wels , Peter H. Berben , Bennie H. Reesink , Peter de Peinder , Eelco T. C. Vogt , Bert M. Weckhuysen","doi":"10.1039/d4cy00782d","DOIUrl":"10.1039/d4cy00782d","url":null,"abstract":"<div><div>C<sub>18</sub> branched saturated fatty acids (BSFA) are used as ingredients in cosmetics and lubricants and are produced <em>via</em> the hydrogenation of C<sub>18</sub> branched unsaturated fatty acids (BUFA). Industrial-grade C<sub>18</sub> BUFA contain the odorous by-product γ-stearolactone (GSL), which must be removed by acid-catalysed ring-opening of GSL into oleic acid. Zeolites such as Y and beta can facilitate the ring-opening, but due to the dimensions of GSL the activity is expected to be limited by diffusion into the micropores. Hence, zeolites Y and beta were modified <em>via</em> hydrothermal treatment and acid leaching and used in the GSL ring-opening reaction. While modification of zeolite beta led to a reduction in acidity of more than 50%, the material displayed much-enhanced activity compared to the parent material. In a batch reactor steamed beta zeolites were able to convert all GSL within 2 h, compared to 5 h for the parent zeolite. Infrared spectroscopy studies of adsorbed pyridine reveal that likely a beneficial change in Brønsted/Lewis acid site ratio is responsible for the increased activity. Lewis acid sites in zeolites are known to catalyse double bond isomerisation, which could greatly enhance GSL conversion by reducing the reverse formation of GSL from oleic acid. We believe that these insights can be used to further improve GSL ring-opening activity and inspire research on the ring-opening of other biomass derived lactones.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 24","pages":"Pages 7037-7047"},"PeriodicalIF":4.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11589803/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142749412","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Meiyan Guo , Wanxiang Yang , Yi Li , Yongfan Zhang , Wei Lin
Cadmium sulfide (CdS) exhibits remarkable light absorption capabilities and is widely employed in photocatalytic reduction of CO2. Nevertheless, the crystal facet effects on the micro-scale mechanisms governing CO2 conversion on CdS remain elusive. This study theoretically investigates the electronic properties of hexagonal-phase (101), (001), and cubic-phase (111) CdS surfaces modified with diethylenetriamine (DETA). From a microscopic viewpoint, it elucidates the unique bonding characteristics of CO2 on different exposed facets of DETA/CdS and the formation mechanisms leading to products such as CO, HCOOH, CH2O, CH3OH, and CH4. Our findings reveal that the DETA/CdS(101) surface is the most stable, effectively adsorbing hydrogen and CO2 at varied Cd sites with a high selectivity towards CO production, thereby showing promise for syngas generation, albeit with potential yields of formic acid and methane. Conversely, DETA/CdS(001) and (111) primarily facilitate the reduction of CO2 to CH4. These discoveries offer theoretical insights into photochemical experiments involving CO2 reduction on CdS, shedding light on the influence of crystal facets on reaction pathways.
{"title":"Mechanistic study of DETA-modified CdS for carbon dioxide reduction†","authors":"Meiyan Guo , Wanxiang Yang , Yi Li , Yongfan Zhang , Wei Lin","doi":"10.1039/d4cy01140f","DOIUrl":"10.1039/d4cy01140f","url":null,"abstract":"<div><div>Cadmium sulfide (CdS) exhibits remarkable light absorption capabilities and is widely employed in photocatalytic reduction of CO<sub>2</sub>. Nevertheless, the crystal facet effects on the micro-scale mechanisms governing CO<sub>2</sub> conversion on CdS remain elusive. This study theoretically investigates the electronic properties of hexagonal-phase (101), (001), and cubic-phase (111) CdS surfaces modified with diethylenetriamine (DETA). From a microscopic viewpoint, it elucidates the unique bonding characteristics of CO<sub>2</sub> on different exposed facets of DETA/CdS and the formation mechanisms leading to products such as CO, HCOOH, CH<sub>2</sub>O, CH<sub>3</sub>OH, and CH<sub>4</sub>. Our findings reveal that the DETA/CdS(101) surface is the most stable, effectively adsorbing hydrogen and CO<sub>2</sub> at varied Cd sites with a high selectivity towards CO production, thereby showing promise for syngas generation, albeit with potential yields of formic acid and methane. Conversely, DETA/CdS(001) and (111) primarily facilitate the reduction of CO<sub>2</sub> to CH<sub>4</sub>. These discoveries offer theoretical insights into photochemical experiments involving CO<sub>2</sub> reduction on CdS, shedding light on the influence of crystal facets on reaction pathways.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"14 24","pages":"Pages 7172-7181"},"PeriodicalIF":4.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142798127","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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