Journal of Catalysis最新文献

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Kinetics of hydrogen release from ammonia borane and role of the support for supported Ru catalysts in methanol solvent

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-25 DOI: 10.1016/j.jcat.2025.116041

Adam T. Twombly, James W. Harris

Ruthenium catalysts are promising for the catalytic release of H₂ from ammonia borane (AB). The reaction kinetics and the role of the support in the release of H₂ from AB in methanol solvent were studied using a series of Ru nanoparticle catalysts on various supports (SiO₂, carbon, γ-Al₂O₃, and TiO₂). Catalysts were synthesized using incipient wetness impregnation and solution deposition (SD) methods and characterized using N₂ physisorption, X-ray diffraction, inductively coupled plasma-optical emission spectroscopy, CO diffuse reflectance infrared Fourier transform spectroscopy, and transmission electron microscopy. The reaction kinetics were examined by measuring initial rates using a semi-batch reactor with a constant flow through the headspace analyzed by online mass spectrometry. The Ru/TiO₂-SD and Ru/C catalysts had the highest measured initial rates compared to the Ru/SiO₂ and Ru/Al₂O₃. Measured apparent activation energies were relatively similar between all catalysts. Regression of initial rates as a function of AB concentration was done for two different rate equations derived from two different proposed mechanisms for AB methanolysis. Both mechanisms were able to sufficiently describe trends in H₂ formation rate versus concentration at low AB concentrations. However, determination of which of the two proposed mechanisms best captures the trends in the data trends was inconclusive due to the lack of a statistically significant difference between degree-of-fit of the two models. Stability tests showed that Ru/C was less prone to deactivation over repeated use compared to Ru supported on the oxides. This study presents a comprehensive examination of the kinetics of AB methanolysis on different supported Ru catalysts; analysis of reaction mechanisms on all catalysts revealed similar apparent first order rate constants from either proposed kinetic models. This study demonstrates that while the support has relatively little influence on the measured reaction rates, carbon may be a preferred support given the decreased deactivation observed relative to the other supports tested.

{"title":"Kinetics of hydrogen release from ammonia borane and role of the support for supported Ru catalysts in methanol solvent","authors":"Adam T. Twombly, James W. Harris","doi":"10.1016/j.jcat.2025.116041","DOIUrl":"10.1016/j.jcat.2025.116041","url":null,"abstract":"<div><div>Ruthenium catalysts are promising for the catalytic release of H<sub>2</sub> from ammonia borane (AB). The reaction kinetics and the role of the support in the release of H<sub>2</sub> from AB in methanol solvent were studied using a series of Ru nanoparticle catalysts on various supports (SiO<sub>2</sub>, carbon, γ-Al<sub>2</sub>O<sub>3</sub>, and TiO<sub>2</sub>). Catalysts were synthesized using incipient wetness impregnation and solution deposition (SD) methods and characterized using N<sub>2</sub> physisorption, X-ray diffraction, inductively coupled plasma-optical emission spectroscopy, CO diffuse reflectance infrared Fourier transform spectroscopy, and transmission electron microscopy. The reaction kinetics were examined by measuring initial rates using a semi-batch reactor with a constant flow through the headspace analyzed by online mass spectrometry. The Ru/TiO<sub>2</sub>-SD and Ru/C catalysts had the highest measured initial rates compared to the Ru/SiO<sub>2</sub> and Ru/Al<sub>2</sub>O<sub>3</sub>. Measured apparent activation energies were relatively similar between all catalysts. Regression of initial rates as a function of AB concentration was done for two different rate equations derived from two different proposed mechanisms for AB methanolysis. Both mechanisms were able to sufficiently describe trends in H<sub>2</sub> formation rate versus concentration at low AB concentrations. However, determination of which of the two proposed mechanisms best captures the trends in the data trends was inconclusive due to the lack of a statistically significant difference between degree-of-fit of the two models. Stability tests showed that Ru/C was less prone to deactivation over repeated use compared to Ru supported on the oxides. This study presents a comprehensive examination of the kinetics of AB methanolysis on different supported Ru catalysts; analysis of reaction mechanisms on all catalysts revealed similar apparent first order rate constants from either proposed kinetic models. This study demonstrates that while the support has relatively little influence on the measured reaction rates, carbon may be a preferred support given the decreased deactivation observed relative to the other supports tested.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116041"},"PeriodicalIF":6.5,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486066","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Palladium-NHC mediated telomerization of aromatic alcohols

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-25 DOI: 10.1016/j.jcat.2025.116048

Lorenzo Palio , Lucas Piglialepre , Tiphaine Richard , Clément Dumont , Isabelle Suisse , Catherine S.J. Cazin , Steven P. Nolan , Mathieu Sauthier

The telomerization reaction of dienes with alcohols mediated by organopalladium complexes represents a versatile method to convert butadiene into value-added chemicals. The use of aromatic alcohols in the telomerization is still an under-explored area that has attracted increased interest in recent years. In this contribution, we examine the catalytic behaviour of a series of well-defined palladium N-heterocyclic carbene precatalysts (Pd-NHC) in the telomerization of butadiene with aromatic alcohols. The process was optimized by studying the influence of Pd/L ratio, of the base and of the pre-catalyst structure. The versatility of the method was tested employing a series of aromatic alcohols, including lignin-type phenols. In the context of biomass valorisation, an explorative study on the telomerization with lignin was carried out.

引用次数: 0

CuPt dual-atom synergistic catalyst boost carbon-oxygen bonds hydrogenation

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-24 DOI: 10.1016/j.jcat.2025.116047

Ziheng Zhen , Antai Li , Tiantian Xiao , Maoshuai Li , Jing Lv , Shouying Huang , Yue Wang , Xinbin Ma

Bimetallic catalyst with dual-atom pairs has drawn much attention in heterogeneous catalysis due to their unique synergistic effects. In this work, we prepared a series CeO₂ supported Cu-Pt dual sites catalysts and found the optimized one of 2Cu0.025Pt/CeO₂ exhibited excellent performance in the hydrogenation of methyl acetate (MA). Its product yield of ethanol was as 4 times as that of 2Cu/CeO₂ catalyst under the same reaction conditions, with only 0.025 wt% Pt addition. Combined with various characterizations and contrast samples, it is demonstrated that the post-deposited trace Pt species preferentially located besides the copper atoms and formed Cu-Pt atomic pairs. But when further increasing the loading of Pt, the aggregation of Cu happened, leading to a rapid decrease of activity. To reveal the role of Cu-Pt atom pairs in the hydrogenation of carbon–oxygen bonds reactions, we conducted chemisorption experiments and DFT simulations. It is suggested that Cu-Pt atomic pairs significantly enhanced the adsorption and activation capability of both the MA and H₂ molecules during the reaction. These insights may provide synthesis and design strategy for high-performance dual-atom sites catalysts for the carbon–oxygen bonds hydrogenation reactions.

{"title":"CuPt dual-atom synergistic catalyst boost carbon-oxygen bonds hydrogenation","authors":"Ziheng Zhen , Antai Li , Tiantian Xiao , Maoshuai Li , Jing Lv , Shouying Huang , Yue Wang , Xinbin Ma","doi":"10.1016/j.jcat.2025.116047","DOIUrl":"10.1016/j.jcat.2025.116047","url":null,"abstract":"<div><div>Bimetallic catalyst with dual-atom pairs has drawn much attention in heterogeneous catalysis due to their unique synergistic effects. In this work, we prepared a series CeO<sub>2</sub> supported Cu-Pt dual sites catalysts and found the optimized one of 2Cu0.025Pt/CeO<sub>2</sub> exhibited excellent performance in the hydrogenation of methyl acetate (MA). Its product yield of ethanol was as 4 times as that of 2Cu/CeO<sub>2</sub> catalyst under the same reaction conditions, with only 0.025 wt% Pt addition. Combined with various characterizations and contrast samples, it is demonstrated that the post-deposited trace Pt species preferentially located besides the copper atoms and formed Cu-Pt atomic pairs. But when further increasing the loading of Pt, the aggregation of Cu happened, leading to a rapid decrease of activity. To reveal the role of Cu-Pt atom pairs in the hydrogenation of carbon–oxygen bonds reactions, we conducted chemisorption experiments and DFT simulations. It is suggested that Cu-Pt atomic pairs significantly enhanced the adsorption and activation capability of both the MA and H<sub>2</sub> molecules during the reaction. These insights may provide synthesis and design strategy for high-performance dual-atom sites catalysts for the carbon–oxygen bonds hydrogenation reactions.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116047"},"PeriodicalIF":6.5,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143477550","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Direct synthesis of amides from nitroarenes and carboxylic acids via CO-mediated reduction

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-22 DOI: 10.1016/j.jcat.2025.116042

Mikhail A. Losev , Oleg I. Afanasyev , Denis Chusov

A highly efficient direct carbon monoxide-mediated protocol for converting nitroarenes and carboxylic acids to amides was developed. Investigation of the reaction kinetics and a Hammett study allowed us to reveal the reaction mechanism and the best reaction conditions. An observed apparent partial reaction order by nitroarene in this reaction is 0.5 indicating the switch of the rate-determining step during the course of the reaction. A highly valuable Vorinostat precursor with 99% purity was synthesized in a quantitative yield without any purification; the E-factor of the process was 0.35, which fits to the multiton chemistry reactions. All substrate scope was prepared using the simple Ru₃(CO)₁₂ as a catalyst, and TON up to 44,400 was achieved.

我们开发了一种一氧化碳介导的将硝基烯烃和羧酸转化为酰胺的高效直接方案。通过对反应动力学的研究和 Hammett 研究，我们揭示了反应机理和最佳反应条件。在该反应中，观察到硝基烯烃的明显部分反应顺序为 0.5，这表明在反应过程中决定速率的步骤发生了转换。在不进行任何纯化的情况下，我们定量合成了纯度为 99% 的高价值伏立诺司他前体；该过程的 E 因子为 0.35，符合多子化学反应。以简单的 Ru3(CO)12 为催化剂制备了所有底物范围，并实现了高达 44,400 吨的吨位。

引用次数: 0

Exhaustive reduction of aromatic esters and carboxylic acids with a homogeneous cobalt catalyst

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-21 DOI: 10.1016/j.jcat.2025.116034

Zi-Heng Zhang , Rui Sun , Yuan-Yuan Jiang , Jin-Qing Lin , Yan-Qiang Zhang , Bao-Hua Xu

A one-step procedure to exhaustively reduce aromatic esters and carboxylic acids to their corresponding tolyl derivatives is a significant transformation in organic synthesis, which remains challenging in homogeneous catalysis. In this study, it’s achieved by using the well-defined phosphinesulfonate chelated cobalt-based catalyst (Co(dppbsa)), along with NaBAr^F₄ as the basic additive and (MeO)₂MeSiH as the reductant. Particularly, this cobalt catalysis proceeds through ether intermediates. Experimental combined theoretical results support it follows an outer-sphere ionic hydrosilylation mechanism and the in situ formed cationic siloxane species are involved in the rate-limiting hydride transfer. The same system also enables the catalytic deoxygenation of aliphatic esters, aliphatic acids, and amides but terminating at the corresponding ethers, alkanols and secondary amines, respectively. These findings open up novel avenues for the catalytic application of phosphinesulfonate chelated complexes, potentially serving as the foundation for the exhaustive reduction of carboxylic skeletons with cobalt.

{"title":"Exhaustive reduction of aromatic esters and carboxylic acids with a homogeneous cobalt catalyst","authors":"Zi-Heng Zhang , Rui Sun , Yuan-Yuan Jiang , Jin-Qing Lin , Yan-Qiang Zhang , Bao-Hua Xu","doi":"10.1016/j.jcat.2025.116034","DOIUrl":"10.1016/j.jcat.2025.116034","url":null,"abstract":"<div><div>A one-step procedure to exhaustively reduce aromatic esters and carboxylic acids to their corresponding tolyl derivatives is a significant transformation in organic synthesis, which remains challenging in homogeneous catalysis. In this study, it’s achieved by using the well-defined phosphinesulfonate chelated cobalt-based catalyst (Co(dppbsa)), along with NaBAr<sup>F</sup><sub>4</sub> as the basic additive and (MeO)<sub>2</sub>MeSiH as the reductant. Particularly, this cobalt catalysis proceeds through ether intermediates. Experimental combined theoretical results support it follows an outer-sphere ionic hydrosilylation mechanism and the in situ formed cationic siloxane species are involved in the rate-limiting hydride transfer. The same system also enables the catalytic deoxygenation of aliphatic esters, aliphatic acids, and amides but terminating at the corresponding ethers, alkanols and secondary amines, respectively. These findings open up novel avenues for the catalytic application of phosphinesulfonate chelated complexes, potentially serving as the foundation for the exhaustive reduction of carboxylic skeletons with cobalt.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116034"},"PeriodicalIF":6.5,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462321","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The enhanced reactivity of graphitic supports for Pd catalyzed toluene hydrogenation

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-20 DOI: 10.1016/j.jcat.2025.116029

Alaba U. Ojo , Deependra M. Shakya , Julian Stetzler , Musbau Gbadamosi , Rahman Md. Masudur , Narayan Acharya , Nathan Thornburg , John Tengco , Santosh Kiran Balijepalli , John R. Monnier , Donna A. Chen , John R. Regalbuto

The hydrogenation of toluene to methylcyclohexane has recently been explored as a potential liquid hydrogen carrier system whereby methylcyclohexane can be safely and efficiently transported. Supported metal catalysts are currently being studied and optimized for this application. In this work, a pronounced support effect is demonstrated. Palladium catalysts on graphitic carbons were found to exhibit significantly enhanced toluene hydrogenation rates versus activated carbons and silica supports. Hydrogen temperature programmed desorption results appear to rule out the role of intercalated hydrogen. Using characterization by powder XRD, Raman and x-ray photoelectron spectroscopies, it is suggested that the enhancement in activity arises when a critical degree of crystallinity at the support surface enhances toluene adsorption and opens parallel reaction pathways.

引用次数: 0

Divergent photoreduction of nitroaromatic compounds catalysed by dithienoquinoxaline

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-19 DOI: 10.1016/j.jcat.2025.116033

Zuzana Burešová , Monika Grygarová , Eva Prokopová , Milan Klikar , Oldřich Pytela , Jiří Váňa , Abul Mansur Muhammed Fahim , Kanyashree Jana , Ekaterina Zubova , Jan Bartáček , Jiří Tydlitát , Zdeňka Růžičková , Radek Cibulka , Kirk S. Schanze , Filip Bureš

Nitroaromatic compounds can be conveniently reduced to anilines with the aid of a variety of chemical reductants. However, chemodivergent and chemoselective reduction of functionalized nitroaromatics into valuable nitroso, azo(xy), (hydr)azo and (hydroxyl)amino derivatives remains rather elusive. Electro- and photochemical strategies utilizing various catalytic systems and reaction media have been tested but most have been directed towards individual reduction products. Here, we present the photoredox-enabled chemodivergent reduction of nitroaromatics to nitroso, bis-(N,O-diacetyl)-N-arylhydroxylamine, azoxy, azo and amino derivatives. The developed protocol utilizes a novel photocatalyst, 6,9-dimethoxydithieno[2,3-f:3′,2′-h]quinoxaline-2,3-dicarbonitrile, and Hantzsch ester/triethanolamine as reductants. With the single organic photocatalyst, the reaction environment, temperature, time and catalyst loading can be varied to achieve chemodivergent photoreduction of nitroaromatics bearing various functional groups and to access a library of valuable products. The application of this methodology to multigram preparations of molecules of pharmaceutical and industrial relevance highlights its practical utility.

{"title":"Divergent photoreduction of nitroaromatic compounds catalysed by dithienoquinoxaline","authors":"Zuzana Burešová , Monika Grygarová , Eva Prokopová , Milan Klikar , Oldřich Pytela , Jiří Váňa , Abul Mansur Muhammed Fahim , Kanyashree Jana , Ekaterina Zubova , Jan Bartáček , Jiří Tydlitát , Zdeňka Růžičková , Radek Cibulka , Kirk S. Schanze , Filip Bureš","doi":"10.1016/j.jcat.2025.116033","DOIUrl":"10.1016/j.jcat.2025.116033","url":null,"abstract":"<div><div>Nitroaromatic compounds can be conveniently reduced to anilines with the aid of a variety of chemical reductants. However, chemodivergent and chemoselective reduction of functionalized nitroaromatics into valuable nitroso, azo(xy), (hydr)azo and (hydroxyl)amino derivatives remains rather elusive. Electro- and photochemical strategies utilizing various catalytic systems and reaction media have been tested but most have been directed towards individual reduction products. Here, we present the photoredox-enabled chemodivergent reduction of nitroaromatics to nitroso, bis-(<em>N</em>,<em>O</em>-diacetyl)-<em>N</em>-arylhydroxylamine, azoxy, azo and amino derivatives. The developed protocol utilizes a novel photocatalyst, 6,9-dimethoxydithieno[2,3-<em>f</em>:3′,2′-<em>h</em>]quinoxaline-2,3-dicarbonitrile, and Hantzsch ester/triethanolamine as reductants. With the single organic photocatalyst, the reaction environment, temperature, time and catalyst loading can be varied to achieve chemodivergent photoreduction of nitroaromatics bearing various functional groups and to access a library of valuable products. The application of this methodology to multigram preparations of molecules of pharmaceutical and industrial relevance highlights its practical utility.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116033"},"PeriodicalIF":6.5,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451572","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Boosting low-concentration toluene oxidation by decorating ultrasmall Pt nanoparticles on La0.8Sr0.2MnO3-δ with hydrogen plasma treatment

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-18 DOI: 10.1016/j.jcat.2025.116031

Bin Zhu , Xin He , Lingze Liu , Jinglin Liu , Xiaomin Zhang , Ben W.-L. Jang

Perovskite is one of the most promising materials for catalytic oxidation of volatile organic compounds (VOCs) because of its special tunable structure and properties as well as high stability. However, it commonly suffers from relatively low catalytic activity due to the low specific surface area and limited numbers of active sites caused by high synthesis temperature required. To improve the reactivity of the perovskite catalyst, a promising strategy is to construct highly dispersed noble metal sites on surfaces perovskite. However, generating highly active metallic sites while exhibiting good thermal stability remains a formidable challenge. Here, it’s demonstrated that the construction of highly efficient and robust platinum (Pt) sites on La_0.8Sr_0.2MnO_3-δ (Pt/LSMO) for toluene oxidation resulted in an almost three-fold increase in toluene conversion with a good stability. The key to the construction of these Pt sites is treating the oxidized Pt species on LSMO with hydrogen (H₂) plasma at low temperatures, which leads to the formation of high metallic Pt (Pt⁰), ultrasmall Pt nanoparticles (∼1.3 nm), and high concentration of oxygen vacancy (O_v). These features facilitate the generation of a large number of highly active and stable Pt⁰-Mn³⁺-O_v sites on Pt/LSMO, which contribute to the activation of toluene and oxygen species and, therefore, the catalytic reaction. This investigation demonstrates a promising approach of using the cold plasma technique to design and construct high-performing noble-based perovskite catalysts for toluene oxidation.

{"title":"Boosting low-concentration toluene oxidation by decorating ultrasmall Pt nanoparticles on La0.8Sr0.2MnO3-δ with hydrogen plasma treatment","authors":"Bin Zhu , Xin He , Lingze Liu , Jinglin Liu , Xiaomin Zhang , Ben W.-L. Jang","doi":"10.1016/j.jcat.2025.116031","DOIUrl":"10.1016/j.jcat.2025.116031","url":null,"abstract":"<div><div>Perovskite is one of the most promising materials for catalytic oxidation of volatile organic compounds (VOCs) because of its special tunable structure and properties as well as high stability. However, it commonly suffers from relatively low catalytic activity due to the low specific surface area and limited numbers of active sites caused by high synthesis temperature required. To improve thereactivity of the perovskite catalyst, a promising strategy is to construct highly dispersed noble metal sites on surfaces perovskite. However, generating highly active metallic sites while exhibiting good thermal stability remains a formidable challenge. Here, it’s demonstrated that the construction of highly efficient and robust platinum (Pt) sites on La<sub>0.8</sub>Sr<sub>0.2</sub>MnO<sub>3-δ</sub> (Pt/LSMO) for toluene oxidation resulted in an almost three-fold increase in toluene conversion with a good stability. The key to the construction of these Pt sites is treating the oxidized Pt species on LSMO with hydrogen (H<sub>2</sub>) plasma at low temperatures, which leads to the formation of high metallic Pt (Pt<sup>0</sup>), ultrasmall Pt nanoparticles (∼1.3 nm), and high concentration of oxygen vacancy (O<sub>v</sub>). These features facilitate the generation of a large number of highly active and stable Pt<sup>0</sup>-Mn<sup>3+</sup>-O<sub>v</sub> sites on Pt/LSMO, which contribute to the activation of toluene and oxygen species and, therefore, the catalytic reaction. This investigation demonstrates a promising approach of using the cold plasma technique to design and construct high-performing noble-based perovskite catalysts for toluene oxidation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116031"},"PeriodicalIF":6.5,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443797","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Insight into the role of Na distribution in Cu-SSZ-39 catalysts

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-18 DOI: 10.1016/j.jcat.2025.116032

Na Zhu, Lingyu Yu, Lisen Hou, Siying Wang

Cu-SSZ-39 has garnered significant attention because of its outstanding NH₃-SCR activity and hydrothermal stability. To facilitate commercial application of Cu-SSZ-39, it is crucial to streamline the synthesis process, adopt eco-friendly synthesis methods, enhance the catalytic performance, and explore the underlying catalytic mechanisms. Herein, ammonia exchange was skipped and Cu-SSZ-39 was directly synthesized via Cu-exchange of Na-SSZ-39. This approach yielded a Cu-SSZ-39 with superior catalytic performance compared to that prepared using the conventional NH₄-SSZ-39. Comparative characterization of the Cu-SSZ-39 catalysts, derived from both Na-SSZ-39 and NH₄-SSZ-39 exchanges demonstrated that the positioning of Na cations affected Cu distribution, and controlling Na distribution can enhance deNO_x activity. It was also found that while cation locations did not alter the reaction mechanism of Cu-SSZ-39 at low temperature, they did increase the concentration of active NO_x intermediates, thereby boosting catalytic performance. This study facilitates a more sustainable synthesis of Cu-SSZ-39 and provides deeper insights into how cations’ distribution in zeolites affects catalytic efficiency.

{"title":"Insight into the role of Na distribution in Cu-SSZ-39 catalysts","authors":"Na Zhu, Lingyu Yu, Lisen Hou, Siying Wang","doi":"10.1016/j.jcat.2025.116032","DOIUrl":"10.1016/j.jcat.2025.116032","url":null,"abstract":"<div><div>Cu-SSZ-39 has garnered significant attention because of its outstanding NH<sub>3</sub>-SCR activity and hydrothermal stability. To facilitate commercial application of Cu-SSZ-39, it is crucial to streamline the synthesis process, adopt eco-friendly synthesis methods, enhance the catalytic performance, and explore the underlying catalytic mechanisms. Herein, ammonia exchange was skipped and Cu-SSZ-39 was directly synthesized via Cu-exchange of Na-SSZ-39. This approach yielded a Cu-SSZ-39 with superior catalytic performance compared to that prepared using the conventional NH<sub>4</sub>-SSZ-39. Comparative characterization of the Cu-SSZ-39 catalysts, derived from both Na-SSZ-39 and NH<sub>4</sub>-SSZ-39 exchanges demonstrated that the positioning of Na cations affected Cu distribution, and controlling Na distribution can enhance deNO<em><sub>x</sub></em> activity. It was also found that while cation locations did not alter the reaction mechanism of Cu-SSZ-39 at low temperature, they did increase the concentration of active NO<em><sub>x</sub></em> intermediates, thereby boosting catalytic performance. This study facilitates a more sustainable synthesis of Cu-SSZ-39 and provides deeper insights into how cations’ distribution in zeolites affects catalytic efficiency.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116032"},"PeriodicalIF":6.5,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143443798","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Catalysts for ethanol dry reforming based on high-entropy perovskites

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-17 DOI: 10.1016/j.jcat.2025.116028

Nikita F. Eremeev , Semon A. Hanna , Ekaterina M. Sadovskaya , Aleksandra A. Leonova , Olga A. Bulavchenko , Arcady V. Ishchenko , Igor P. Prosvirin , Vladislav A. Sadykov , Yuliya N. Bespalko

Ethanol dry reforming is a promising way to produce syngas and hydrogen due to utilization of carbon dioxide and ability to produce ethanol using renewable sources. Main problem associated with ethanol dry reforming reaction is coke formation. Coking suppression can be achieved in a few ways including use of catalysts possessing required oxygen transport properties. High entropy oxides are of interest in application as catalysts for ethanol dry reforming and other reactions due to their structural stability, disordering features and tunability of functional properties. In this work, the catalysts based on Ni and multiple doped La manganites are studied. The oxides are synthesized by modified Pechini and citrate techniques, and the catalysts are prepared by wetness impregnation. The samples are characterized by XRD, TEM with EDX analysis, XPS. Oxygen transport and redox properties are studied by temperature-programmed isotope exchange of oxygen and reduction. According to structural and morphological studies, the samples are nanosized and form perovskite-like structure. The surface features of samples were characterized by XPS. The samples demonstrate a moderate oxygen mobility (D* up to ∼10^–12 cm²/s at 700 °C) required for catalytic operation and coking suppression. Tests in ethanol dry reforming demonstrated fine performance and good stability in the reaction conditions.

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